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WO2021117961A1 - Film de polyimide présentant une excellente résistance aux intempéries - Google Patents

Film de polyimide présentant une excellente résistance aux intempéries Download PDF

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Publication number
WO2021117961A1
WO2021117961A1 PCT/KR2019/018376 KR2019018376W WO2021117961A1 WO 2021117961 A1 WO2021117961 A1 WO 2021117961A1 KR 2019018376 W KR2019018376 W KR 2019018376W WO 2021117961 A1 WO2021117961 A1 WO 2021117961A1
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Prior art keywords
diamine
polyimide film
acid dianhydride
present
mol
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English (en)
Korean (ko)
Inventor
안경일
이호용
김원겸
심재현
김동연
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Doosan Corp
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Doosan Corp
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Priority to CN201980004567.7A priority Critical patent/CN113260676B/zh
Publication of WO2021117961A1 publication Critical patent/WO2021117961A1/fr
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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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133308—Support structures for LCD panels, e.g. frames or bezels
    • G02F1/133331—Cover glasses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide film, and more particularly, to a polyimide film having excellent transparency and preventing color change due to external ultraviolet exposure, thereby securing excellent weather resistance and excellent visibility at the same time.
  • a cover window for protecting a panel is applied to a surface of a display device such as a liquid crystal display (LCD) or an organic light emitting display (OLED).
  • a display device such as a liquid crystal display (LCD) or an organic light emitting display (OLED).
  • LCD liquid crystal display
  • OLED organic light emitting display
  • tempered glass having excellent flatness, heat resistance, chemical resistance and barrier performance against moisture or gas, a small coefficient of linear expansion (CTE), and high light transmittance has been mainly used.
  • cover window In order to be applied to such a flexible display, the cover window must also have flexibility, but the conventional glass cover window is generally heavy and fragile, and is not suitable for the flexible display due to poor flexibility.
  • cover windows using a plastic material having relatively free formability have advantages of being light, not easily broken, and implementing various designs.
  • polycarbonate, polyethylene terephthalate, polymethyl methacrylate, etc. having excellent transparency are mainly used as plastic materials for cover windows.
  • Tg glass transition temperature
  • the cover window is disposed at the outermost portion of the flexible display device.
  • the present invention has been devised to solve the above problems, and the amount of change in the CIE Lab color space a* and b* values caused by exposure to external ultraviolet (UV-B) is minimized to achieve high weather resistance and excellent visibility at the same time. It aims at providing a mid film.
  • the present invention provides at least one diamine; And as a polyimide film copolymerized including at least one acid dianhydride, the change value of a* in the CIE Lab color space measured with a spectrophotometer through a 72-hour exposure test in a UV-B wavelength region of 280 to 315 nm ( ⁇ a*) and the change value of b* ( ⁇ b*) provide a polyimide film that simultaneously satisfies Equations 1 and 2 below.
  • a* 1 and b* 1 are the a* and b* values of the CIE Lab color space measured after 72 hours of exposure in the UV-B wavelength region, respectively,
  • a* 0 and b* 0 are the a* and b* values of the CIE Lab color space measured before exposure in the UV-B wavelength region, respectively.
  • ⁇ a* measured by a colorimeter through a 72-hour exposure test in a UV-B wavelength region of 280 to 315 nm is in the range of -0.4 to 0, and ⁇ b* is in the range of 0 to 1.0. can be a range.
  • the polyimide film has a light transmittance of 85% or more at a wavelength of 550 nm at a thickness of 10 to 100 ⁇ m, a yellowness of 5 or less according to ASTM E313-73 standard, and a glass transition temperature ( Tg) may be 250 to 450 °C.
  • the polyimide film has an average coefficient of linear expansion (CTE) of 100 ppm/°C or less, measured at a thickness of 10 to 100 ⁇ m at 50 to 250° C., and a Young’s Modulus of 2 to 8 GPa.
  • CTE average coefficient of linear expansion
  • the at least one diamine is a fluorinated primary diamine; It may include at least one selected from the group consisting of a sulfone-based second diamine, a hydroxy-based third diamine, an ether-based fourth diamine, an alicyclic fifth diamine, and a non-fluorine-based sixth diamine.
  • the content of the first to sixth diamines may be 10 to 100 mol%, respectively, based on 100 mol% of the total diamine.
  • the at least one acid dianhydride is a fluorinated aromatic primary acid dianhydride, an alicyclic secondary acid dianhydride, a non-fluorinated aromatic tertiary acid dianhydride, and a sulfone-based aromatic quaternary acid dianhydride. It may include one or more selected from.
  • the content of the first acid dianhydride to the fourth acid dianhydride may be 10 to 100 mol%, respectively, based on 100 mol% of the total acid dianhydride.
  • the ratio (a/b) of the number of moles of the diamine (a) and the acid dianhydride (b) may be in the range of 0.7 to 1.3.
  • the polyimide film may be used as a cover window of a display device.
  • the ⁇ a* and ⁇ b* characteristic values of the CIE Lab color space are controlled by adopting a predetermined component constituting the polyimide film and controlling the content thereof, thereby minimizing the change in color coordinates due to external UV exposure and high weather resistance. and excellent visibility can be realized at the same time.
  • the present invention exhibits high light transmittance, low yellowness, excellent modulus and low coefficient of linear expansion (CTE), thereby improving workability and reliability of the final product.
  • the polyimide film of the present invention can be usefully applied as a cover window for display devices and flexible displays in the art, including flat panel display panels, and other IT products, electronic products, home appliances, etc. known in the art. is also applicable.
  • the effect according to the present invention is not limited by the contents exemplified above, and more various effects are included in the present specification.
  • 1 is a graph showing the CIE Lab color space (L*, a*, b*).
  • the polyimide resin film according to an embodiment of the present invention is a transparent film that can be provided in a display device, and more specifically, can be used as a cover window of a flexible display.
  • the cover window refers to a film disposed on the outermost surface of the flexible display device to protect the display device.
  • the cover window may be a window film alone or a film in which a window coating layer is formed on a separate substrate made of an optically transparent resin.
  • the cover window disposed at the outermost portion of the display device is made of a conventional plastic material
  • the initial transparency or light transmittance is relatively excellent
  • yellowing occurs inevitably due to damage. , which leads to a decrease in visibility.
  • ⁇ a* and ⁇ b* values which are color coordinate values of the CIE Lab color space
  • the color change increases, which adversely affects the visibility of the display.
  • the polyimide film according to the present invention is the amount of change in color coordinates (L*, a*, b*) in the CIE Lab color space according to the external UV exposure test compared to the conventionally known plastic film, such as the change in a* It is characterized in that the value ( ⁇ a*) and the change value of b* ( ⁇ b*) are each minimized to within a specific range. Accordingly, when the polyimide film is applied as a cover window of a flexible display device continuously exposed to external ultraviolet rays in daily life, specifically, a cover window of a foldable mobile phone, excellent weather resistance and visibility effects can be continuously exhibited.
  • the polyimide film may include at least one diamine; and at least one acid dianhydride, the change value of a* in the CIE Lab color space measured with a spectrophotometer through a 72-hour exposure test in a UV-B wavelength region of 280 to 315 nm ( ⁇ a*) and the change value ( ⁇ b*) of b* may simultaneously satisfy Equations 1 and 2 below.
  • a* 1 and b* 1 are the a* and b* values of the CIE Lab color space measured after 72 hours of exposure in the UV-B wavelength region, respectively,
  • a* 0 and b* 0 are the a* and b* values of the CIE Lab color space measured before exposure in the UV-B wavelength region, respectively.
  • the L* a* b* color space means a color value defined in the CIE Lab color space.
  • L* represents lightness
  • a*b* represents hue and saturation.
  • a*b* indicates a color direction
  • a* indicates a red direction
  • -a* indicates a green direction
  • b* indicates a yellow direction
  • -b* indicates a blue direction (see FIG. 1 below).
  • ⁇ a* measured with a spectrophotometer through a 72-hour exposure test in a UV-B wavelength region of 280 to 315 nm is in the range of -0.5 to 0.5, and ⁇ b* is - It may range from 1.5 to 1.5.
  • ?a* is preferably in the range of -0.4 to 0, and ?b* is preferably in the range of 0 to 1.0.
  • the change values of a* and b* may be affected by the thickness of the film.
  • the numerical values of these color coordinate change amounts may be measured based on the thickness of the polyimide film of 10 to 100 ⁇ m, specifically 30 to 80 ⁇ m, and more specifically 80 ⁇ 5 ⁇ m.
  • the change values of a* and b* mean values measured based on a predetermined thickness of the polyimide film, but are not particularly limited thereto, and the thickness of the polyimide film It is also within the scope of the present invention to express a ratio of the change values of a* and b* according to the change (eg, ⁇ a*, ⁇ b*).
  • the polyimide film according to the present invention should have excellent optical properties such as high transparency and light transmittance in order to increase the visibility of the display screen as well as control the amount of change in color coordinates described above.
  • the polyimide film may have a light transmittance of 85% or more at a wavelength of 550 nm at a thickness of 10 to 100 ⁇ m, specifically 89% or more, and more specifically 90% to 99%. have.
  • the yellowness (Y.I.) according to the ASTM E313-73 standard may be 5 or less, specifically 4.5 or less.
  • the polyimide film may have a Young's Modulus of 2 to 8 GPa, and may be 3 to 6 GPa in terms of simultaneously exhibiting mechanical hardness and excellent flexibility.
  • Young's modulus means a value measured according to the ISO 527-3 standard. When the modulus is smaller than the above-mentioned value, it is difficult to exhibit sufficient hardness, and when the modulus is larger than the above-mentioned value, the flexibility is lowered and the foldability may be deteriorated.
  • the polyimide film may have an average coefficient of linear expansion (CTE) of 100 ppm/°C or less, specifically 70 ppm/°C, measured at a thickness of 10 to 100 ⁇ m and at 50 to 250°C.
  • CTE average coefficient of linear expansion
  • the polyimide film may have a glass transition temperature (Tg) of 250°C or higher, specifically, 250 to 450°C.
  • the above-described physical properties of the polyimide film are based on a thickness of 10 to 100 ⁇ m of the film, and specifically may be 30 to 80 ⁇ m, unless otherwise specified. However, it is not limited to the above-described thickness range, and may be appropriately adjusted within a typical thickness range known in the art.
  • components constituting the polyimide resin and/or its The composition is not particularly limited.
  • the polyimide film may include at least one at least one diamine; and at least one acid dianhydride.
  • the polyamic acid composition including the aforementioned diamine, acid dianhydride, and, if necessary, a solvent may be imidized and heat-treated at a high temperature.
  • polyimide (PI) resin refers to a high heat-resistant resin manufactured by preparing a polyamic acid derivative by solution polymerization of an aromatic acid dianhydride and an aromatic diamine or aromatic diisocyanate, and then imidizing it by ring-closing dehydration at a high temperature.
  • the polyimide resin is a polymer material containing an imide ring, and has excellent heat resistance, chemical resistance, abrasion resistance and electrical properties based on the chemical stability of the imide ring.
  • the polyimide resin may be in the form of a random copolymer or a block copolymer.
  • the diamine (a) component constituting the polyimide film of the present invention is not limited as long as it is a compound having an intramolecular diamine structure, and common diamine compounds known in the art may be used without limitation. As an example, there is an aromatic, alicyclic, or aliphatic compound having a diamine structure, or a combination thereof.
  • the amount of color coordinate change ( ⁇ a*, ⁇ b*) in the CIE Lab color space measured according to the external UV exposure test of the polyimide film is minimized, high light transmittance (High Transmittance), low YI, low haze, etc. optical properties of; thermal properties such as high glass transition temperature (High Tg) and low coefficient of linear expansion (Low CTE); Considering mechanical properties such as modulus, fluorine-based, sulfone-based, hydroxy-based, ether-based, ether-based, alicyclic, and non-fluorine-based diamines having a fluorinated substituent are used alone Alternatively, one or more of them may be used in combination as appropriate.
  • a fluorinated aromatic first diamine, a sulfone-based second diamine, a hydroxy-based diamine, an etheric fourth diamine, an alicyclic fifth diamine, and a non-fluorine-based sixth diamine are introduced as diamine compounds.
  • Each of the diamines may be used alone, or two or more thereof may be mixed.
  • Non-limiting examples of diamine monomers (a) that can be used include oxydianiline (ODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-TFDB) ), 2,2'-bis (trifluoromethyl) -4,3'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,3'-Diaminobiphenyl), 2,2'-bis ( Trifluoromethyl)-5,5'-diaminobiphenyl (2,2'-Bis(trifluoromethyl) -5,5'-Diaminobiphenyl), 2,2'-bis(trifluoromethyl)-4,4 '-diaminophenyl ether (2,2'-Bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 6-FODA), bisaminohydroxyphenyl hexafluoropropane (DBOH), bisamin
  • fluorinated primary diamine can induce linear polymerization of 2,2'-bis(trifluoromethyl)-4,4 '-diaminobiphenyl (2,2'-TFDB), 1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene (6-FAPB) may be used.
  • 2,2'-bis(trifluoromethyl)-4,4 '-diaminobiphenyl (2,2'-TFDB) 1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene
  • 6-FAPB 1,4-Bis(4-amino-2-trifluoromethylphenoxy)benzene
  • sulfone-based second diamine bis(4-aminophenyl)sulfone (4,4'-DDS) or 3,3'-DDS may be used.
  • the hydroxyl-based tertiary diamine is 2,2-bis (3-amino-4-methylphenyl)-hexafluoropropane (2,2-Bis (3-amino-4-methylphenyl)-hexafluoropropane, BIS-AT-AF ), 2,2-bis(3-amino-4-hydroxycyclohexyl)hexafluoropropane can be used.
  • 2,2-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6-FODA) or oxydianiline (ODA) may be used.
  • alicyclic fifth diamine 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), 4,4'-methylenebicyclohexylamine (PACM), 1,3-bis (Aminomethyl) cyclohexane (1,3-BAC), 1,4-bis (aminomethyl) cyclohexane (1,4-BAC), cis-1,2-cyclohexanedimethanamine, trans-1,2 -Cyclohexanedimethanamine, bis(4-aminocyclohexyl)ether (H-ODA), N-(4-aminocyclohexyl)-1,4-cyclohexanediamine can be used.
  • H-ODA bis(4-aminocyclohexyl)ether
  • N-(4-aminocyclohexyl)-1,4-cyclohexanediamine can be used.
  • non-fluorine-based sixth diamine
  • the content of the fluorinated first diamine, sulfone-based second diamine, hydroxy-based diamine, ether-based fourth diamine, alicyclic fifth diamine, non-fluorine-based sixth diamine, etc. is although not particularly limited, each may be 10 to 100 mol% based on 100 mol% of the total diamine, specifically 20 to 90 mol%, and more specifically 20 to 80 mol%.
  • a fluorinated first diamine and an etheric fourth diamine may be mixed.
  • their use ratio is not particularly limited, and for example, may be 50 to 90: 10 to 50 mol% ratio.
  • At least one kind of fluorinated primary diamine may be mixed as the diamine monomer (a). At this time, their ratio may be 50 to 90: 10 to 50 mol%, but is not particularly limited thereto.
  • acid dianhydride (b) monomer constituting the polyimide film of the present invention conventional compounds known in the art having an intramolecular acid dianhydride structure may be used without limitation.
  • an aromatic, alicyclic, or aliphatic compound having an acid dianhydride structure, or a combination thereof may be used, and specifically, fluorinated aromatic primary acid dianhydride, alicyclic secondary acid dianhydride, non-fluorinated aromatic agent
  • the triacid dianhydride and the sulfonic aromatic quaternary acid dianhydride may be used alone, or may be in the form of a combination of at least two or more thereof.
  • the fluorinated first acid dianhydride monomer is not particularly limited as long as it is an aromatic acid dianhydride into which a fluorine substituent is introduced.
  • Non-limiting examples of the fluorinated first acid dianhydride that can be used include 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydrid, 6-FDA), and 4-(trifluoromethyl)pyromellitic dianhydride (4-(trifluoromethyl)pyromellitic dianhydride, 4-TFPMDA). These may be used alone or in combination of two or more.
  • 6-FDA is a very suitable compound for transparency because it has a very high property of limiting the formation of a change transfer complex (CTC) between and within molecular chains.
  • the alicyclic second acid dianhydride is not particularly limited as long as it is a compound having an acid dianhydride structure while having an alicyclic ring rather than an aromatic ring in the compound.
  • Non-limiting examples of the alicyclic second acid dianhydride that can be used include cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA), Bicyclo[2,2,2]-7-octene-2,3,5,6-tetracarboxylic acid dianhydride (BCDA), (2,5-dioxotetrahydrofuran-3-yl)-1 ,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 1,1'-bicyclohexane-3,3',4,4'-tetracarboxylic dian Hydride (H-BPDA), 1,2,4,5-cyclohe
  • the non-fluorinated tertiary acid dianhydride monomer is not particularly limited as long as it is a non-fluorinated aromatic acid dianhydride into which a fluorine substituent is not introduced.
  • Non-limiting examples of non-fluorinated tertiary acid dianhydride monomers that can be used include Pyromellitic Dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3 ,3′,4,4′-Biphenyl tetracarboxylic acid dianhydride, BPDA), benzophenone tetracarboxylic dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), 4,4-(4,4-Isopropylidenediphenoxy) )bis(phthalic anhydride) (BPADA) and the like. These may be used alone, or two or more thereof may be used in combination.
  • the sulfone-based fourth acid dianhydride monomer is not particularly limited as long as it is an acid dianhydride introduced with a sulfone group.
  • 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (3,3', 4,4'-DIPHENYLSULFONETETRACARBOXYLIC DIANHYDRIDE (DSDA).
  • the content of the fluorinated aromatic first acid dianhydride, alicyclic second acid dianhydride, non-fluorinated aromatic tertiary acid dianhydride, sulfonic aromatic quaternary acid dianhydride, etc. is not particularly limited. For example, they may be included in the range of 10 to 100 mol%, specifically 10 to 90 mol%, and more specifically, 20 to 80 mol%, based on 100 mol% of the total acid dianhydride.
  • a fluorinated first acid dianhydride, an alicyclic second acid dianhydride, and a non-fluorinated tertiary acid dianhydride may be mixed.
  • their use ratio is not particularly limited, and for example, may be 5 to 20: 50 to 90: 5 to 15 mol% ratio.
  • an alicyclic secondary acid dianhydride and a non-fluorinated tertiary acid dianhydride may be mixed. At this time, their ratio may be 30-80: 20-70 mol%, but is not particularly limited thereto.
  • At least one non-fluorinated tertiary acid dianhydride may be mixed as the acid dianhydride (b). At this time, their use ratio may be 50 to 80: 20 to 50 mol%, but is not particularly limited thereto.
  • the ratio (a/b) of the number of moles of the diamine component (a) to the number of moles of the acid dianhydride component (b) may be 0.7 to 1.3, preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.
  • the polyamic acid composition of the present invention may use, without limitation, an organic solvent known in the art as a solvent for the solution polymerization of the above-mentioned monomers.
  • organic solvent known in the art as a solvent for the solution polymerization of the above-mentioned monomers.
  • usable solvents include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl
  • NMP N-methyl-2-pyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • DMSO dimethyl sulfoxide
  • acetone diethyl
  • a low-boiling solution such as tetrahydrofuran (THF), chloroform, or a solvent such as ⁇ -butyrolactone may be used.
  • the content of the solvent is not particularly limited, but is preferably 50 to 95% by weight based on the total weight of the polyamic acid composition in order to obtain an appropriate molecular weight and viscosity of the polyamic acid composition (polyamic acid solution). , More preferably, it may be included in the range of 70 to 90% by weight.
  • the polyamic acid composition described above can be prepared by adding at least one kind of acid dianhydride and at least one kind of diamine to an organic solvent and then reacting, for example, diamine (a) and acid dianhydride (b) to improve the physical properties of polyimide. ) can be adjusted to an equivalence ratio of approximately 1:1.
  • the composition of the polyamic acid composition is not particularly limited, and for example, based on 100% by weight of the total weight of the polyamic acid composition, 2.5 to 25.0% by weight of acid dianhydride, 2.5 to 25.0% by weight of diamine, and the remaining amount satisfying 100% by weight of the composition It may be composed of an organic solvent.
  • the content of the organic solvent may be 70 to 90% by weight.
  • the polyamic acid composition may be included in the range of 30 to 70 wt% of acid dianhydride, and 30 to 70 wt% of diamine, based on 100 wt% of the solid content, but is not particularly limited thereto.
  • the polyamic acid composition constituted as described above may have a viscosity in the range of about 1,000 to 200,000 cps, preferably about 5,000 to 50,000 cps. When the viscosity of the polyamic acid composition falls within the above-mentioned range, thickness control during coating of the polyamic acid composition is easy, and the coating surface can be uniformly exhibited.
  • the polyamic acid composition may contain a small amount of at least one additive such as a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, a leveling agent, etc. within a range that does not significantly impair the purpose and effect of the present invention.
  • the polyimide resin film according to the present invention may be prepared according to a conventional method known in the art, for example, 30 to 350 after coating (casting) the above-described polyamic acid composition on a substrate, for example, a glass substrate. It can be prepared by inducing the imide ring closure reaction (Imidazation) for 0.5 to 8 hours while gradually increasing the temperature in the range of °C.
  • Imidazation imide ring closure reaction
  • the coating method can be used without limitation a conventional method known in the art, for example, spin coating (Spin coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating (Slot die coating) and It may be made by at least one method selected from the group consisting of spray coating.
  • the polyamic acid composition may be coated at least once or more so that the colorless and transparent polyimide resin layer has a thickness of several hundred nm to several tens of ⁇ m.
  • the imidization method applied to the imidization step by casting the polymerized polyamic acid to a support is thermal imidization method, chemical imidization method, or thermal imidization method and chemical It can be applied in combination with the imidization method.
  • the thermal imidization method is a method of obtaining a polyimide film by casting a polyamic acid composition (polyamic acid solution) on a support and heating it for 1 to 10 hours while gradually increasing the temperature in a temperature range of 30 to 400°C.
  • the chemical imidization method is a method of adding a dehydrating agent represented by an acid anhydride such as acetic anhydride and an imidization catalyst represented by amines such as isoquinoline, ⁇ -picoline, and pyridine to the polyamic acid composition.
  • a dehydrating agent represented by an acid anhydride such as acetic anhydride
  • an imidization catalyst represented by amines such as isoquinoline, ⁇ -picoline, and pyridine
  • the heating conditions of the polyamic acid composition may vary depending on the type of the polyamic acid composition, the thickness of the polyimide film to be prepared, and the like.
  • a dehydrating agent and an imidization catalyst are added to the polyamic acid composition and cast on a support, then 80 to 300° C., preferably 150 to 250 After partial curing and drying by heating at °C to activate the dehydrating agent and imidization catalyst, a polyimide film can be obtained.
  • the thickness of the polyimide film thus formed is not particularly limited and may be appropriately adjusted according to the field to which it is applied. For example, it may be in the range of 10 to 150 ⁇ m, preferably in the range of 10 to 100 ⁇ m.
  • the polyimide film and modifications thereof of the present invention prepared as described above can be usefully used in various fields requiring minimization of color coordinate changes ( ⁇ a*, ⁇ b*) according to external UV exposure test, excellent optical properties, etc. have.
  • it is applied as a cover window of the display device to prevent surface abrasion and to continuously provide excellent weather resistance and visibility to the flexible display device.
  • a display device refers to a flexible display device or a non-flexible display device that displays an image, and includes not only a flat panel display device (FPD), but also a curved display device, a foldable display device, and the like. It includes a display device (Foldable Display Device), a flexible display device (Flexible Display Device), a foldable mobile phone, a smart phone, a mobile communication terminal or a tablet PC.
  • the display device includes a liquid crystal display, an electrophoretic display, an organic light emitting display, an inorganic EL display, and a field emission display.
  • the polyimide film of the present invention may be applied to a conventional display device known in the art, and may be utilized as a substrate or a protective film for other flexible displays.
  • a specific example of the display device provided with the above-described polyimide film includes a display unit, a polarizing plate, a touch screen panel, a cover window, and a protective film, wherein the cover window is a polyimide according to an embodiment of the present invention. It may include a film.
  • each component constituting the display device is not particularly limited, and may include conventional components known in the art.
  • a polyamic acid composition was prepared using a composition including diamine and acid dianhydride shown in Table 1 below.
  • the polyamic acid composition on glass for LCD After spin-coating the polyamic acid composition on glass for LCD, it is dried while gradually increasing the temperature stepwise in a convection oven in a nitrogen atmosphere for 30 minutes at 80° C., 30 minutes at 150° C., 1 hour at 200° C., and 1 hour at 300° C. And imide ring closure reaction (Imidazation) was carried out. Thus, a polyimide film having a film thickness of 80 ⁇ m having an imidization ratio of 85% or more was produced. Thereafter, the glass was etched with hydrofluoric acid to obtain a polyimide film.
  • Measurements were made using a UV-Vis NIR Spectrophotometer (Shimadzu, model name: uv-3150) at a wavelength of 550 nm.
  • the thickness of the film was measured with a thickness meter (Mitutoyo, model name: 293-140).
  • A* and b* were measured according to ASTM E313-73 standard using a spectrophotometer (Konica Minolta, model name: CM-3700d).
  • Example 1 Light transmittance (%) Yellowness (YI) Modulus (GPa) CTE (ppm) Tg(°C) a* 0 a* 1 ⁇ *a b* 0 b* 1 ⁇ b* Example 1 -0.1 -0.3 -0.2 1.2 1.5 0.3 89.2 1.7 5.6 39 381
  • Example 2 -0.2 -0.4 -0.2 2.8 2.9 0.1 88.6 4.1 4.3 46 337
  • Example 3 -0.4 -0.6 -0.2 1.6 2.2 0.6 88.8 2.3 3.4 58 283
  • Example 4 -0.3 -0.4 -0.1 1.4 1.9 0.5 89.3 2.0 3.7 49 323
  • Example 5 -0.2 -0.6 -0.4 2.5 3.2 0.7 88.7 3.7 3.6 53 318
  • Example 6 -0.2 -0.5 -0.3 1.8 2.4 0.6 88.4 2.5 3.8 62 314
  • Example 7 -0.1 -0.4 -0.3 2.6 3.3
  • the polyimide film according to the present invention minimized the amount of change in color coordinates ( ⁇ a*, ⁇ b*) of the CIE Lab color space due to external ultraviolet rays, so it was found that excellent weather resistance and excellent visibility were secured at the same time. . Accordingly, it was confirmed that the polyimide film of the present invention can be usefully applied as a cover window of a display device.

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Abstract

La présente invention concerne un film de polyimide dans lequel au moins une diamine et au moins un dianhydride d'acide sont polymérisés, et plus particulièrement, un film de polyimide qui présente une excellente transparence, en plus de présenter une excellente résistance aux intempéries et une excellente visibilité en raison du fait qu'il est sujet à un changement de couleur minimal après exposition aux UV externes, et peut ainsi être utilisé pour des couvertures transparentes.
PCT/KR2019/018376 2019-12-13 2019-12-24 Film de polyimide présentant une excellente résistance aux intempéries Ceased WO2021117961A1 (fr)

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