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WO2021101078A1 - Procédé de fabrication de film polyimide et film polyimide ainsi fabriqué - Google Patents

Procédé de fabrication de film polyimide et film polyimide ainsi fabriqué Download PDF

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Publication number
WO2021101078A1
WO2021101078A1 PCT/KR2020/014239 KR2020014239W WO2021101078A1 WO 2021101078 A1 WO2021101078 A1 WO 2021101078A1 KR 2020014239 W KR2020014239 W KR 2020014239W WO 2021101078 A1 WO2021101078 A1 WO 2021101078A1
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Prior art keywords
polyimide film
mol
polyamic acid
mpa
gpa
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English (en)
Korean (ko)
Inventor
박세주
김동영
원동영
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PI Advanced Materials Co Ltd
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PI Advanced Materials Co Ltd
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Priority to CN202080081068.0A priority Critical patent/CN114729141B/zh
Priority to JP2022529519A priority patent/JP7367214B2/ja
Publication of WO2021101078A1 publication Critical patent/WO2021101078A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • It relates to a method for producing a polyimide film and a polyimide film produced thereby. More specifically, it relates to a method for producing a polyimide film having a high yield point and yield strength at a low modulus of elasticity, a high transmittance and a low haze, and a polyimide film produced thereby.
  • Flexible displays such as curved, bendable, foldable, and rollable, are the next generation displays that have recently attracted attention from both academia and industry.
  • functional film/coating material is an important polymer substrate material constituting a flexible display, and it can be said to be a key material essential for the successful implementation and development of a flexible display. It is attracting attention.
  • Polyimide is a polymer characterized by having a heteroimide ring in its main chain, and has excellent mechanical properties, flame retardancy, chemical resistance, and low dielectric constant, in addition to excellent heat resistance, and has been applied to a wide range of applications such as coating materials, molding materials, and composite materials.
  • a flexible display polymer substrate The most important physical property required for a flexible display polymer substrate is flexibility.
  • such a polymer substrate should not be damaged during the curving, bending, folding, rolling, and stretching processes in which the flexible display repeatedly deforms, and various initial physical properties should not be lost.
  • Such a flexible display polymer substrate is required to be transparent for various purposes, and therefore, optical properties such as high light transmittance and low haze are often required.
  • Another object of the present invention is to provide a method for producing a polyimide film having high transmittance and low haze.
  • Another object of the present invention is to provide a polyimide film prepared by the method for producing a polyimide film described above.
  • preparing a polyamic acid by reacting a dianhydride monomer and a diamine monomer; Preparing a polyimide precursor solution including the polyamic acid, an imidation catalyst, a dehydrating agent, a filler, and a solvent; And preparing a polyimide film by imidizing the polyamic acid, wherein the imidation catalyst is from about 0.8 mol to about 2.5 mol based on 1 mol of the amic acid group in the polyamic acid.
  • the dehydrating agent is included in a molar ratio of about 2.0 mol to about 4.0 mol with respect to 1 mol of the amic acid group in the polyamic acid, and the average particle diameter (D 50 ) of the filler is about 1.6 ⁇ m or less, and the There is provided a method for producing a polyimide film in which the modulus of the polyimide film is from about 2.5 GPa to about 4.0 GPa.
  • biphenyltetracarboxylic dianhydride may be included in an amount of about 10 mol% to about 90 mol% based on the total molar amount of dianhydride monomers.
  • pyromellitic dianhydride may be further included in an amount of about 10 mol% to about 90 mol% based on the total molar amount of dianhydride monomers.
  • the diamine monomer is m-tolidine (m-TD), 4,4'-oxydianiline (ODA), 1,3-bis(4-amino). Phenoxy)benzene (TPE-R), 2,2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP), or combinations thereof.
  • a polyimide film prepared by any one of the first to fourth embodiments is provided.
  • the polyimide film may have a yield point of about 2.3% to about 2.8%.
  • the polyimide film may have a yield strength of about 55 MPa to about 80 MPa.
  • the polyimide film may have a transmittance of about 43% or more in a visible light region.
  • the polyimide film may have a haze of about 7.5% or less.
  • the present invention may have an effect of providing a polyimide film production method having a high yield point and yield strength at a low elastic modulus, a high transmittance and a low haze, and a polyimide film prepared therefrom.
  • the inventors of the present invention control the content of the imidation catalyst and the dehydrating agent and the average particle diameter (D 50 ) of the filler to prepare a polyimide film, as low as about 2.0 GPa to about 4.0 GPa.
  • the present invention was completed by discovering that it is possible to manufacture a polyimide film having a high transmittance and low haze while having a high yield point and a yield strength even in a modulus, and a degree of damage is low even when repeated deformation is applied.
  • the present invention will be described in more detail.
  • a method of manufacturing a polyimide film comprises the steps of preparing a polyamic acid by reacting a dianhydride monomer and a diamine monomer; Preparing a polyimide precursor solution including the polyamic acid, an imidation catalyst, a dehydrating agent, a filler, and a solvent; And preparing a polyimide film by imidizing the polyamic acid; wherein the imidation catalyst is included in a molar ratio of about 0.8 mol to about 2.5 mol with respect to 1 mol of the amic acid group in the polyamic acid, and the The dehydrating agent is included in a molar ratio of about 2.0 mol to about 4.0 mol with respect to 1 mol of the amic acid group in the polyamic acid, the average particle diameter (D 50 ) of the filler is about 1.6 ⁇ m or less, and the modulus of the polyimide film is about From 2.5 GPa to about 4.0
  • a polyamic acid may be prepared by reacting a dianhydride monomer and a diamine monomer. More specifically, a polyamic acid solution may be prepared by polymerizing a dianhydride monomer and a diamine monomer in a solvent. At this time, all the monomers may be added at once, or each of the monomers may be added sequentially, and in this case, partial polymerization between the monomers may occur.
  • the type of the dianhydride monomer is not particularly limited, and may be variously selected within a range that does not adversely affect the effects of the present invention.
  • the dianhydride monomer may include biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), and the like, and these may be used alone or in combination.
  • the dianhydride monomer is about 10 mol% to about 90 mol% (e.g., 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol% based on the total molar amount of the dianhydride monomer). %, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol% or 90 mol%) Of biphenyltetracarboxylic acid dianhydride (BPDA).
  • BPDA biphenyltetracarboxylic acid dianhydride
  • the dianhydride monomer is from about 15 mol% to about 85 mol%, for example from about 20 mol% to about 80 mol%, another example from about 30 mol%, based on the total molar amount of the dianhydride monomer. It may be included in about 70 mol%, but is not limited thereto.
  • the dianhydride monomer may include biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA).
  • BPDA biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • Biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) are, for example, about 10:90 to about 90:10 (e.g., 10:90, 15:85 20:80, 25: 75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15 or 90:10), another example may be included in a molar ratio of about 20:80 to about 80:20, another example of about 30:70 to about 70:30, but is not limited thereto.
  • the dianhydride monomer is greater than about 10 mol% to about 100 mol% (e.g., 11 mol%, based on the total molar amount of the dianhydride monomer) of biphenyltetracarboxylic dianhydride and pyromellitic dianhydride. 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol %, 80 mol%, 85 mol%, 90 mol%, 95 mol%, or 100 mol%), but is not limited thereto.
  • the type of the diamine monomer is not particularly limited, and may be variously selected within a range that does not adversely affect the effects of the present invention.
  • the diamine monomer is m-tolidine (m-TD), 4,4'-oxydianiline (ODA), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 2, 2-bis(4-[4-aminophenoxy]-phenyl)propane (BAPP) and the like may be included, and these may be used alone or in combination of two or more.
  • the diamine monomer may include m-tolidine (m-TD) or 4,4'-oxydianiline (ODA).
  • the diamine monomer contains m-tolidine (m-TD) and 4,4'-oxydianiline (ODA) from about 1:99 to about 99:1 (e.g., 1:99, 5 :95, 10:90, 15:85 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5 or 99:1), such as about 1:99 to about 50:50, other such as about 1:99 To about 30:70, for another example, it may be included in a molar ratio of about 5:95 to about 20:80, but is not limited thereto.
  • m-TD m-tolidine
  • ODA 4,4'-oxydianiline
  • the organic solvent is not particularly limited as long as it is a solvent in which polyamic acid can be dissolved, and may be, for example, an aprotic polar organic solvent.
  • aprotic polar oil-borne solvents amide solvents such as N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAc), p-chlorophenol, o-chloro Phenolic solvents such as phenol, N-methylpyrrolidone (NMP), gamma-butyrolactone (GBL), Diglyme, and the like, and these may be used alone or in combination of two or more.
  • an auxiliary solvent such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, or water may be used to adjust the solubility of the polyamic acid.
  • the oil cover solvent may be an amide-based solvent, for example, N,N-dimethylformamide or N,N-dimethylacetamide, but is not limited thereto.
  • the polyamic acid is about 5% by weight to about 35% by weight (e.g., 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight) based on the total weight of the polyamic acid solution. %, 30% by weight or 35% by weight).
  • the polyamic acid solution may have a molecular weight and a solution viscosity suitable for forming a film.
  • the polyamic acid may be included in, for example, about 10% by weight to about 30% by weight, for example, about 15% by weight to about 25% by weight, but is not limited thereto.
  • a polyimide precursor solution including a polyamic acid, an imidation catalyst, a dehydrating agent, a filler, and a solvent may be prepared. More specifically, an imidation catalyst, a dehydrating agent, a filler, and optionally an additional solvent may be added to the polyamic acid solution to prepare a polyimide precursor solution.
  • an imidation catalyst, a dehydrating agent, a filler, and optionally an additional solvent may be added to the polyamic acid solution to prepare a polyimide precursor solution.
  • an additional solvent it may be understood with reference to the description of the solvent used when preparing the polyamic acid solution.
  • the imidation catalyst may mean a component having an effect of promoting a ring closure reaction with respect to polyamic acid, examples of which include tertiary amine compounds, more specifically aliphatic tertiary amines, aromatic tertiary amines, heterocyclic tertiary And amines.
  • a heterocyclic tertiary amine may be used, examples of which include quinoline, isoquinoline, ⁇ -picoline, and pyridine, and these may be used alone or in combination of two or more. .
  • the imidation catalyst is in a molar ratio of about 0.8 to about 2.5 moles (e.g., 0.8 moles, 0.9 moles, 1.0 moles, 1.1 moles, 1.2 moles, 1.3 moles, 1.4 moles, 1.5 moles of the amic acid group in the polyamic acid). Moles, 1.6 moles, 1.7 moles, 1.8 moles, 1.9 moles, 2.0 moles, 2.1 moles, 2.2 moles, 2.3 moles, 2.4 moles or 2.5 moles of mole ratio).
  • the content of the imidation catalyst is less than the above range, film formation is difficult, and when the content of the imidation catalyst exceeds the above range, the modulus becomes too large (e.g., exceeds about 4.0 GPa), and the transmittance decreases. There is. Accordingly, in the above range, it may be possible to manufacture a polyimide film having a high yield point and yield strength at a low elastic modulus, and a high transmittance and low haze.
  • the imidation catalyst may be included in a molar ratio of about 0.8 mol to about 2.4 mol with respect to 1 mol of the amic acid group in the polyamic acid, but is not limited thereto.
  • the dehydrating agent may mean promoting a ring closure reaction through a dehydration action on polyamic acid, for example, aliphatic acid anhydride, aromatic acid anhydride, N,N'-dialkylcarbodiimide, lower aliphatic halides, halogenation Lower fatty anhydrides, arylphosphonic acid dihalides, thionyl halides, and the like, and these may be used alone or in combination of two or more.
  • aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, and lactic anhydride may be used alone or in combination of two or more from the viewpoint of availability and cost.
  • the dehydrating agent is in a molar ratio of about 2.0 mol to about 4.0 mol with respect to 1 mol of the amic acid group in the polyamic acid (e.g., 2.0 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 moles, 2.9 moles, 3.0 moles, 3.1 moles, 3.2 moles, 3.3 moles, 3.4 moles, 3.5 moles, 3.6 moles, 3.7 moles, 3.8 moles, 3.9 moles or 4.0 moles of mole ratio).
  • the amic acid group in the polyamic acid e.g., 2.0 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 moles, 2.9 moles, 3.0 moles, 3.1 moles, 3.2 moles, 3.3 moles, 3.4 moles, 3.5 moles, 3.6
  • the dehydrating agent may be included in a molar ratio of about 2.5 mol to about 3.3 mol with respect to 1 mol of the amic acid group in the polyamic acid, but is not limited thereto.
  • the molar ratio of the imidation catalyst and the dehydrating agent is about 1:1 to about 1:10 (eg, 1:1, 1:1.1, 1:1.2, 1:1.3). , 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1 :8, 1:9 or 1:10).
  • the above range it may be possible to manufacture a polyimide film having a high yield point and yield strength at a low modulus of elasticity, and a high transmittance and low haze.
  • the molar ratio of the imidation catalyst and the dehydrating agent is from about 1:1.2 to about 1:6, for example from about 1:1.3 to about 1:5, for example from about 1:1.3 to about 1:4. It may be, but is not limited thereto.
  • the filler may impart roughness to the polyimide film, examples of which include inorganic fillers, more specifically dicalcium phosphate, barium sulfate, calcium carbonate, spherical silica, and the like, which may be used alone or in combination of two or more. Can be used.
  • inorganic fillers more specifically dicalcium phosphate, barium sulfate, calcium carbonate, spherical silica, and the like, which may be used alone or in combination of two or more. Can be used.
  • the filler may have an average particle diameter (D 50 ) of about 1.6 ⁇ m or less, specifically greater than 0 ⁇ m to about 1.6 ⁇ m. In the above range, it may be possible to manufacture a polyimide film having a high yield point and yield strength at a low elastic modulus, and a high transmittance and low haze.
  • D 50 average particle diameter
  • the average particle diameter (D 50 ) of the filler is 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, or 1.6 ⁇ m, for example, may be about 0.5 ⁇ m to about 1.6 ⁇ m, but is not limited thereto.
  • the content of the filler is not particularly limited, but based on the total weight of the polyimide film, about 0.05% by weight to about 0.5% by weight (e.g., 0.05% by weight, 0.1% by weight, 0.15% by weight, 0.2% by weight, 0.25 % By weight, 0.3% by weight, 0.35% by weight, 0.4% by weight, 0.45% by weight or 0.5% by weight), and in the above range, it has a high yield point and yield strength at a low modulus of elasticity, and has a high transmittance and low haze.
  • the production of polyimide films may be possible.
  • the content of the filler may be about 0.1% by weight to about 0.3% by weight, but is not limited thereto.
  • the polyimide precursor solution may contain various additives within a range that does not adversely affect the effects of the present invention.
  • additives include antioxidants, light stabilizers, antistatic agents, heat stabilizers, flame retardants, and the like, and these may be used alone or in combination of two or more.
  • a polyimide film can be prepared by imidizing the polyamic acid.
  • a polyimide precursor solution may be cast on a support and dried to prepare a gel film, and the gel film may be heat treated to be imidized to prepare a polyimide film.
  • a polyimide precursor solution cast on a support is prepared from about 40° C. to about 300. °C, for example about 80 °C to about 200 °C, for another example about 100 °C to about 180 °C, another example can be dried at a temperature range of about 100 °C to about 130 °C to obtain a gel film .
  • a gel film may be formed by partially curing and/or drying to occur.
  • the gel film is in an intermediate stage of curing from polyamic acid to polyimide, and may have self-supporting properties.
  • it may include the step of stretching the gel film to adjust the thickness and size of the finally obtained polyimide film and improve orientation, and the stretching may be performed in a machine transport direction (MD) and a transverse direction to the machine transport direction. It may be performed in at least one direction of (TD).
  • MD machine transport direction
  • TD transverse direction
  • the volatile content of the gel film may be, but is not limited to, about 5% by weight to about 500% by weight, for example, about 5% by weight to about 200% by weight, and for example, about 5 to about 150% by weight.
  • the volatile content of the gel film can be calculated using Equation 2 below.
  • Equation 1 A means the weight of the gel film, and B means the weight after heating the gel film at 450° C. for 20 minutes.
  • the gel film in the step of heat-treating the gel film, is varied in the range of about 50° C. to about 700° C., for example, about 150° C. to about 600° C., and other examples, about 200° C.
  • a polyimide film can be obtained by heat treatment at a phosphorus temperature to remove a solvent, etc. remaining in the gel film, and imidizing most of the remaining amic acid groups.
  • the polyimide film obtained as described above may be further cured by heating and finishing at a temperature of about 400° C. to about 650° C. for about 5 seconds to about 400 seconds to further cure the polyimide film. You may do this under a certain tension in order to alleviate the internal stress that may be.
  • a polyimide film manufactured by the above-described manufacturing method may have a high yield point at a low elastic modulus, and may also have a high transmittance.
  • Polyimide film is about 2.5 to about 4.0 GPa (e.g., 2.5 GPa, 2.6 GPa, 2.7 GPa, 2.8 GPa, 2.9 GPa, 3 GPa, 3.1 GPa, 3.2 GPa, 3.3 GPa, 3.4 GPa, 3.5 GPa, 3.6 GPa , 3.7 GPa, 3.8 GPa, 3.9 GPa or 4 GPa).
  • the modulus of the polyimide film may be about 2.7 GPa to about 3.7 GPa, but is not limited thereto.
  • the polyimide film may have a yield point of about 2.3% to about 2.8% (eg, 2.3%, 2.4%, 2.5%, 2.6%, 2.7% or 2.8%).
  • the polyimide film may have a yield point of about 2.4% to about 2.7%, but is not limited thereto.
  • the polyimide film is about 55 MPa to about 80 MPa (e.g., 55 MPa, 56 MPa, 57 MPa, 58 MPa, 59 MPa, 60 MPa, 61 MPa, 62 MPa, 63 MPa, 64 MPa, 65 MPa, 66 MPa, 67 MPa, 68 MPa, 69 MPa, 70 MPa, 71 MPa, 72 MPa, 73 MPa, 74 MPa, 75 MPa, 76 MPa, 77 MPa, 78 MPa, 79 MPa or 80 Mpa) It can have a yield strength of
  • the yield strength of the polyimide film may be about 55 MPa to about 75 MPa, for example, about 60 MPa to about 80 MPa, and for another example, about 60 MPa to about 75 Mpa, but is limited thereto. It is not.
  • the polyimide film may have a transmittance of about 43% or more (eg, about 43% to about 100%) in a visible light region, for example, about 380 nm to about 780 nm.
  • the transmittance of the polyimide film may be about 43% to about 90%, for example, about 45% to about 80%, but is not limited thereto.
  • the polyimide film may have a thickness of about 5 ⁇ m to about 100 ⁇ m.
  • the thickness of the polyimide film may be, for example, about 10 ⁇ m to about 80 ⁇ m, for example, about 20 ⁇ m to about 70 ⁇ m, and another example, about 25 ⁇ m to about 60 ⁇ m, but is limited thereto. no.
  • DMF dimethylformamide
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • m-TD lidine
  • ODA 4,4'-oxydianiline
  • the polyimide precursor solution was cast on a SUS plate (100SA, Sandvik) using a doctor blade, and dried at 110° C. for 10 minutes to prepare a gel film. After separating the gel film from the SUS plate, heat treatment was performed at 400° C. for 10 minutes to prepare a polyimide film having a thickness of 50 ⁇ m.
  • a polyimide film was prepared in the same manner as in Example 1, except that the content of the imidation catalyst, the dehydrating agent, and the average particle diameter of the filler were changed as described in Table 1.
  • Modulus (unit: GPa), yield point (unit: %), yield strength (unit: Mpa): A specimen was prepared by cutting the manufactured polyimide film into 15 mm ⁇ 50 mm, and according to ASTM D 882 standards. However, the modulus, yield point, and yield strength were measured at room temperature using a tensile tester (Instron 5564, Instron) at a tensile speed of 200 mm/min, and the results are shown in Table 1 below.
  • Example 1 0.8 2.5 1.5 2.70 2.53 67.26 62 6.8
  • Example 2 1.0 2.5 1.5 2.80 2.52 69.09 58 6.9
  • Example 3 1.2 3.0 1.5 2.90 2.54 70.01 54
  • Example 4 1.5 3.3 1.5 3.05 2.57 70.80 52
  • Example 5 2.0 3.3 1.5 3.40 2.54 71.8 48
  • Example 6 2.4 3.3 1.5 3.70 2.53 72.4 45
  • Comparative Example 1 1.2 3.3 1.8 2.92 2.56 70.12 52 9.2 Comparative Example 2 1.2 3.3 2.0 2.93 2.55 69.80 50 11.0 Comparative Example 3 3.0 3.3 1.5 4.10 2.52 72.5 40 7.8 Comparative Example 4 0.5 3.3 1.5 - Comparative Example 5 0.8 1.9 1.5 - Comparative Example 6 0.8 4.5 1.5 2.71
  • the modulus of the polyimide film is low and the yield point is high. , It can be seen that it has high transmittance and low haze.
  • the haze of the polyimide film was as high as 9.2% or more.
  • the modulus of the polyimide film was as high as 4.1 GPa, the transmittance was as low as 40%, and the content of the imidation catalyst was less than the scope of the present invention In the case of Comparative Example 4, film formation was not possible.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

L'invention concerne un procédé de fabrication de film polyimide et un film de polyimide ainsi fabriqué, le procédé de fabrication de film polyimide comprenant les étapes suivantes : préparation d'un acide polyamique par réaction d'un monomère de dianhydride et d'un monomère de diamine ; préparation d'une solution de précurseur de polyimide comprenant l'acide polyamique, un catalyseur d'imidisation, un agent de déshydratation, une charge et un solvant ; et fabrication d'un film polyimide par imidisation de l'acide polyamique, le catalyseur d'imidisation étant inclus dans une quantité allant d'environ 0,8 à 2,5 moles sur la base de 1 mole d'un groupe acide amique dans l'acide polyamique, l'agent déshydratant étant inclus dans une quantité allant d'environ 2,0 à 4,0 moles sur la base de 1 mole d'un groupe acide amique dans l'acide polyamique, le diamètre moyen (D50) de la charge étant inférieur ou égal à environ 1,6 µm et le module du film de polyimide étant d'environ 2,5 à 4,0 GPa.
PCT/KR2020/014239 2019-11-22 2020-10-19 Procédé de fabrication de film polyimide et film polyimide ainsi fabriqué Ceased WO2021101078A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160081041A (ko) * 2014-12-30 2016-07-08 에스케이씨코오롱피아이 주식회사 가교형 수용성 열가소성 폴리아믹산 및 이의 제조방법
KR20170049912A (ko) * 2015-10-29 2017-05-11 에스케이씨코오롱피아이 주식회사 폴리이미드 필름 및 이의 제조방법
KR20190039180A (ko) * 2016-08-10 2019-04-10 다이니폰 인사츠 가부시키가이샤 폴리이미드 필름, 적층체 및 디스플레이용 표면재
KR20190065977A (ko) * 2017-12-04 2019-06-12 코오롱인더스트리 주식회사 폴리이미드계 필름의 제조방법 및 이로부터 제조된 폴리이미드계 필름
KR102013534B1 (ko) * 2018-12-24 2019-08-22 에스케이씨코오롱피아이 주식회사 디스플레이 기판 제조용 폴리아믹산 조성물 및 이를 이용하여 디스플레이용 기판을 제조하는 방법
KR20190116724A (ko) * 2018-04-05 2019-10-15 에스케이씨코오롱피아이 주식회사 연성금속박적층판 제조용 폴리이미드 필름 및 이를 포함하는 연성금속박적층판

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006093027A1 (fr) * 2005-02-28 2006-09-08 Kaneka Corporation Procédé de fabrication de film polyimide
JP2009021350A (ja) * 2007-07-11 2009-01-29 Du Pont Toray Co Ltd カバーレイ
KR101404093B1 (ko) * 2009-01-13 2014-06-09 에스케이씨코오롱피아이 주식회사 폴리이미드 필름
JP2012102216A (ja) * 2010-11-09 2012-05-31 Kaneka Corp ポリイミドフィルムの製造方法及びポリイミドフィルム
KR102044260B1 (ko) * 2011-10-05 2019-11-13 히다치 가세이듀퐁 마이쿠로시스데무즈 가부시키가이샤 고투명 폴리이미드
KR102277807B1 (ko) * 2014-10-17 2021-07-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 폴리이미드 수지 조성물, 폴리이미드 필름 및 적층체

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160081041A (ko) * 2014-12-30 2016-07-08 에스케이씨코오롱피아이 주식회사 가교형 수용성 열가소성 폴리아믹산 및 이의 제조방법
KR20170049912A (ko) * 2015-10-29 2017-05-11 에스케이씨코오롱피아이 주식회사 폴리이미드 필름 및 이의 제조방법
KR20190039180A (ko) * 2016-08-10 2019-04-10 다이니폰 인사츠 가부시키가이샤 폴리이미드 필름, 적층체 및 디스플레이용 표면재
KR20190065977A (ko) * 2017-12-04 2019-06-12 코오롱인더스트리 주식회사 폴리이미드계 필름의 제조방법 및 이로부터 제조된 폴리이미드계 필름
KR20190116724A (ko) * 2018-04-05 2019-10-15 에스케이씨코오롱피아이 주식회사 연성금속박적층판 제조용 폴리이미드 필름 및 이를 포함하는 연성금속박적층판
KR102013534B1 (ko) * 2018-12-24 2019-08-22 에스케이씨코오롱피아이 주식회사 디스플레이 기판 제조용 폴리아믹산 조성물 및 이를 이용하여 디스플레이용 기판을 제조하는 방법

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CN114729141B (zh) 2023-11-21
CN114729141A (zh) 2022-07-08
TW202126729A (zh) 2021-07-16
KR20210062999A (ko) 2021-06-01

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