WO2019066368A1 - Film souple - Google Patents

Film souple Download PDF

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Publication number
WO2019066368A1
WO2019066368A1 PCT/KR2018/011060 KR2018011060W WO2019066368A1 WO 2019066368 A1 WO2019066368 A1 WO 2019066368A1 KR 2018011060 W KR2018011060 W KR 2018011060W WO 2019066368 A1 WO2019066368 A1 WO 2019066368A1
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WO
WIPO (PCT)
Prior art keywords
coating layer
flexible film
thickness
weight
acrylate
Prior art date
Application number
PCT/KR2018/011060
Other languages
English (en)
Korean (ko)
Inventor
이진국
박진영
정순화
장영래
서정현
김혜민
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180111632A external-priority patent/KR102095004B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/482,419 priority Critical patent/US11591498B2/en
Priority to CN201880005467.1A priority patent/CN110114396B/zh
Priority to JP2019536045A priority patent/JP6772418B2/ja
Publication of WO2019066368A1 publication Critical patent/WO2019066368A1/fr

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Classifications

    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present invention relates to a flexible film. More particularly, the present invention relates to a flexible film having excellent flexibility and inner layer rigidity while exhibiting high hardness.
  • Glass or tempered glass is generally used as a material having excellent mechanical properties on a display window or a front plate of such a mobile device.
  • glass causes a weight of the mobile device due to its own weight to be heavy, and there is a problem of breakage due to external stiffness.
  • Plastic resins are being studied as a substitute for glass. Plastic resin films are lightweight and less susceptible to breakage, making them suitable for trends toward lighter mobile devices. In particular, a film for coating a hard coating layer made of a plastic resin on a supporting substrate to achieve a film having properties of hardness and abrasion resistance has been proposed.
  • a method of increasing the thickness of the hard coat layer by a method of improving the surface hardness of the hard coat layer can be considered.
  • the surface hardness can be increased.
  • the hard coat layer hardens and shrinks to form wrinkles and curls And at the same time, cracking or peeling of the hard coat layer tends to easily occur, so that it is not easy to apply it practically.
  • Korean Patent Publication No. 2010-0041992 discloses a plastic film composition using a binder resin containing an ultraviolet ray-curable polyurethane acrylate oligomer excluding a monomer.
  • the plastic film disclosed above is not superimposed on the strength to replace the glass panel of the display with a pencil hardness of about 3H.
  • the present invention provides a flexible film having excellent flexibility and inner layer rigidity while exhibiting high hardness.
  • the elastic modulus of the second coating layer measured in accordance with ASTM D882 in the state where the crab 2 coating layer is peeled from the supporting substrate is 400 to 650 MPa, the thickness of the first coating layer is 20 to 20, the thickness of the second coating layer is 20 to 150,
  • the ratio of the thickness of the first coating layer to the thickness of the second coating layer is 1: 1 to 1: 5.
  • flexibility, flexibility, hardness, scratch resistance he represents the transparency, repetitive, continuous bending and less damage to the film in a long time folded state Ventura Double (bendable), the flexible (flexible), the It can be applied to a rollable or foldable mobile device, a display device, a front plate of various instrument panels, a display portion, and the like.
  • FIG. 1 is a schematic view illustrating a method of performing a dynamic folding test on a film according to an embodiment of the present invention.
  • FIG. 2 is a schematic illustration of a method of performing a dent test on a film according to one embodiment of the present invention.
  • a support substrate A first coating layer formed on one surface of the support substrate, the first coating layer comprising a first crosslinked copolymer of one or more different 3 to 6 functional acrylate binders, and inorganic fine particles; And a second crosslinking agent which is formed on the back surface of the supporting substrate and comprises at least one kind of a different 3 to 6 functional acrylate binder, a bifunctional acrylate binder, and a 2 to 4 functional urethane acrylate binder, And a second coating layer comprising a copolymer, wherein the second coating layer is peeled off from the support substrate ,
  • the elastic modulus of the second coating layer measured in accordance with ASTM D882 is 400 to 650 MPa, the thickness of the first coating layer is 20 to 70 m and the thickness of the second coating layer is 20 to 150 /
  • the ratio of the thicknesses of the first coating layer and the crab coating layer is 1: 1 to 1: 5.
  • acrylate egg acrylate as well as methacrylate, or a derivative having a substituent introduced into acrylate or methacrylate are all included.
  • a flexible film according to an embodiment of the present invention includes: a support substrate; A first coating layer formed on one side of the supporting substrate, the first coating layer comprising at least one first crosslinked copolymer having 3 to 6 functional acrylate bridges crosslinked, and inorganic fine particles; And at least one kind of 3 to 6 functional acrylate binder, at least one difunctional Acrylate binder, and a second crosslinked copolymer comprising a crosslinked 2 to 4-functional urethane acrylate binder, wherein the crab 2 coating layer is peeled from the supporting substrate, and ASTM D882 Wherein the thickness of the first coating layer is 20 to 150 m, the elastic modulus of the second coating layer measured based on the first coating layer is 400 to 650 MPa, the thickness of the first coating layer is 20 to 20, The ratio of the thickness of the coating layer is 1: 1 to 1: 5.
  • flexible refers to a state in which a crack is not generated at a length of 3 cm or more when a folding apparatus is repeated 100,000 times in a folding facility having a curvature radius of 2.5 mm And thus the flexible film of the present invention is applicable to a cover film of a bendable, flexible, rollable, or foldable display.
  • the supporting substrate on which the coating layer is formed preferably has an elastic modulus of about 4 GPa or more as measured according to ASTM D882 so as to secure flexibility and hardness, 100
  • the transparent plastic resin for optical use can be used without any particular limitation in the production method and material of the supporting substrate such as stretched film or non-stretched film.
  • the elastic modulus of the condition of the supporting substrate is about 4 GPa or more
  • the upper limit value may be about 9 GPa or less, or about 8 GPa or less. If the elastic modulus is less than 4 GPa, the layered hardness may not be achieved, and if it is more than 9 GPa, it may be difficult to form a flexible film.
  • the thickness of the support substrate may be about 10 or more, or about 20 or more, or about 30 or more, and the upper limit may be about 100 or less, or about 80 or less. If the thickness of the supporting substrate is less than 10 / m, there is a risk of breakage or curl in the coating layer forming step, and it may be difficult to attain the failure degree. On the other hand, if the thickness exceeds 100 / ml, flexibility may be reduced and formation of a flexible film may be difficult.
  • the plastic film of the present invention has elastic modulus of not less than 4 GPa and not more than 9 GPa and a thickness of 10 to 100 ffli A substrate can be used.
  • the supporting substrate may be formed of a material such as polyimide (PI), polyimideamide, poly (PEEK), polyetheretherketone (PEEK), cyclic olefin polymer (PEEK), polyethylene terephthalate (PET), polyethylenenaphthalate , COP), polyacrylate (PAC), polymethylmethacrylate (PMMA), or triacetylcellulose (TAC).
  • PI polyimide
  • PEEK polyimideamide
  • PEEK polyetheretherketone
  • PEEK cyclic olefin polymer
  • PET polyethylene terephthalate
  • PET polyethylenenaphthalate
  • COP polyacrylate
  • PMMA polymethylmethacrylate
  • TAC triacetylcellulose
  • the supporting substrate may be a single layer or a multi-layer structure including two or more substrates made of the same or different materials as needed, and is not particularly limited.
  • the supporting substrate may be formed of a material selected from the group consisting of polyimide (PI), polyimideamide, polyamide, polyimide (PI), polyimideamide polyimideamide, polyamide, and the like.
  • the flexible film of the present invention includes a first coating layer formed on one side of the supporting substrate and a second coating layer formed on the back side of the supporting substrate, that is, the opposite side where the crazing coating layer is formed.
  • the first coating layer comprises a crosslinked first crosslinked copolymer of one or more different 3 to 6 functional acrylate binders, and inorganic fine particles. It is preferable that the first coating layer is disposed on the upper side, that is, on the side closer to the user side when the flexible film of the present invention is applied to the other device or device alone.
  • the first coating layer contains the first crosslinked polymer and the inorganic fine particles, which are crosslinked and polymerized with each other, of the three to six functional acrylate binders, so that the high hardness property can be imparted to the flexible film of the present invention.
  • the modulus of elasticity measured in accordance with ASTM D882 in the state that the coating layer is peeled from the supporting substrate is not particularly limited, but it may be lGPa or more.
  • the 3 to 6 functional acrylate binder is selected from the group consisting of trimethylolpropane triacrylate (TMPTA), trimethylolpropane trioxytriacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PET A), dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate (DPHA) and the like. It is not.
  • TMPTA trimethylolpropane triacrylate
  • TMPEOTA trimethylolpropane trioxytriacrylate
  • GPTA glycerin propoxylated triacrylate
  • PET A pentaerythritol tetraacrylate
  • DPEPA dipentaerythritol pentaacrylate
  • DPHA dipentaerythritol hexaacrylate
  • the first crosslinked polymer is a polymer obtained by polymerizing at least one kind, or at least two kinds, or at least three kinds of these three or more functional acrylate binders.
  • the first crosslinked polymer is a copolymer of trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETA), and dipentaerythritol pentaacrylate (DPEPA) And may be cross-linked.
  • TMPTA trimethylolpropane triacrylate
  • PETA pentaerythritol tetraacrylate
  • DPEPA dipentaerythritol pentaacrylate
  • the 3- to 6-functional acrylate binder has a weight average molecular weight (Mw) of about 200 to about 2,000 g / mol, or about 200 to about 1,000 g / mol, And can range from about 600 g / m 2 to about 600 g / m 2.
  • Mw weight average molecular weight
  • the 3- to 6-functional acrylate binder has an acrylate equivalent weight of about 50 to about 300 g / mol, or about 50 to about 200 g / mol, counter 50 to about 150 g / m • can range.
  • a first coating layer can be formed.
  • the first coating layer includes inorganic microparticles in addition to the first crosslinked copolymer.
  • the inorganic fine particles there may be used inorganic fine particles having a nanoscale particle size, for example, nanoparticles having an average particle diameter (d50) of about 100 nm or less, about 10 to about 100 nm, or about 10 to about 50 nm.
  • d50 average particle diameter
  • silica fine particles, aluminum oxide particles, titanium oxide particles, zirconia oxide particles, or zinc oxide particles can be used.
  • the hardness of the first coating layer can be further improved.
  • the first coating layer may contain 40 to 80 parts by weight of the first crosslinked copolymer and 20 to 60 parts by weight of the inorganic fine particles with respect to 100 parts by weight of the first coating layer.
  • the thickness of the first coating layer may be from about 20 to about 70 [mu] m, or from about 20 to about 60 / [Lambda] P, or from about 30 to about 50. If the thickness of the first coating layer is less than 20 1, the surface hardness may be lowered. If the thickness of the first coating layer is more than 70, the flexibility of the flexible film of the present invention may not be good.
  • the first coating layer having a composition and a thickness as described above exhibits a high hardness so that the flexible film of the present invention including it can exhibit sufficient surface hardness.
  • the second coating layer is provided on the back surface of the supporting substrate, that is, on the opposite surface where the first coating layer is formed.
  • the second coating layer comprises a second crosslinked copolymer having at least one different from 3 to 6 functional acrylate binders, a bifunctional acrylate binder, and a 2 to 4 functional urethane acrylate binder cross-linked, , Flexibility and impact resistance properties can be imparted to the flexible film of the present invention.
  • the second coating layer may have a modulus of elasticity of about 400 to about 650, as measured according to ASTM D882, MPa, or from about 450 to about 650 MPa, or from about 500 to about 650 MPa, or from about 500 to about 600 MPa.
  • the coefficient of elasticity of the second coating layer is less than 400 MPa, strong curling may occur in the direction of the first coating layer during the production of the film. If the elastic modulus of the second coating layer is more than 650 MPa, A crack may occur when folding 100,000 folds. Therefore, when the elastic modulus of the second coating layer is in the above-mentioned range, more optimized physical properties can be secured in terms of hardness and flexibility.
  • the second coating layer is disposed on the lower side, that is, the side closer to the other device side when the flexible film of the present invention is applied to the other device or device alone.
  • the binder of the second crosslinked copolymer of the second coating layer includes a 3 to 6 functional acrylate binder, a bifunctional acrylate binder, and a 2 to 4 functional urethane acrylate binder.
  • the 3 to 6 functional acrylate binders may be the same as or different from those used in the first coating layer.
  • the 3 to 6-functional acrylate-based binder propane triacrylate to trimethylolpropane acrylate (TMPTA), hydroxy triacrylate to trimethylolpropane (TMPEOTA), glycerol propoxylated triacrylate (GPTA): pentaerythrityl (PETA), dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate (DPHA), and the like, but the present invention is not limited thereto.
  • the second crosslinked polymer is a 3- to 6-functional acrylate-based binder, and may include one or more kinds of different kinds, or two or more types, or three or more types.
  • the second crosslinked polymer is obtained by reacting trimethylolpropane triacrylate (TMPTA), pentaerythritol with tetraacrylate (PETA) as the 3- to 6-functional acrylate binder, ,
  • TMPTA trimethylolpropane triacrylate
  • PETA tetraacrylate
  • the dipentaerythritol may include pentacrylylate (DPEPA), but the present invention is not limited thereto.
  • the bifunctional acrylate binder may be selected from the group consisting of triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTEGDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA) But are not limited to, polyethylene glycol diacrylate (PEGDA), ethoxylated neopentyl glycol diacrylate (NPEOGDA), propoxylated neopentyl glycol diacrylate (NPPOGDA), diethylene glycol diacrylate (DEGDA), butanediol diacrylate (BDDA) or nucleic acid diol diacrylate (HDDA), but the present invention is not limited thereto.
  • TAGDA triethylene glycol diacrylate
  • TTEGDA tetraethylene glycol diacrylate
  • TPGDA tripropylene glycol diacrylate
  • DPGDA dipropylene glycol diacrylate
  • PEGDA polyethylene glycol diacryl
  • the 2- to 4-functional urethane acrylate binder has a weight average molecular weight (Mw) of about 400 to about 20,000 g / mol, or about 400 to about 15,000 g / mol, or about 1,000 To about 3,000 g / mc > l.
  • Mw weight average molecular weight
  • the 2- to 4-functional urethane acrylate binder may have an acrylate equivalent weight of about 100 to about 10,000 g / mol, or about 200 to about 5,000 g / mol, or A range of from about 200 to about 4,000 g / mol or from about 500 to about 1,000 g / m 2 may be desirable for optimization of the properties of the second coating layer.
  • TA-604AU manufactured by NOF CORPORATION
  • PU2100, PU210, PU3200, PU3400, PU3450 PU series, manufacturer: Miwon
  • PU3450 PU series, manufacturer: Miwon
  • the second crosslinked copolymer may contain at least one of the above-mentioned three to six functional acrylate binders, a bifunctional acrylate binder, and two to four functionalities Urethane acrylate binder is a polymer crosslinked with.
  • the second coating layer includes the crosslinked polymer of the three kinds of binders, so that it is possible to impart excellent flexibility and inner layer rigidity to the flexible film of the present invention.
  • the 3 to 6 functional acrylate binder may be used in an amount of 20 to 80 parts by weight and the bifunctional acrylate binder may be used in an amount of 10 to 40 parts by weight per 100 parts by weight of the second crosslinked copolymer. And 10 to 70 parts by weight of the 2 to 4 functional urethane acrylate binder. .
  • the second coating layer contains a second crosslinked copolymer in which one or more of a 3 to 6 functional acrylate binder, a bifunctional acrylate binder, and a 2 to 4 functional urethane acrylate binder are cross-linked with each other ,
  • the flexible film of the present invention can achieve sufficient flexibility and impact resistance.
  • the thickness of the second coating layer may be from about 20 to about 150, or from about 30 to about 120 [mu] m, or from about 30 to about 100.
  • compositions, thickness, and elastic modulus range of the crab coating layer are in the above-mentioned ranges, particularly when the film is repeatedly warped or folded for a long time due to high durability against bending, rolling or folding, It is possible to secure a very good folding property with less risk of damage to the substrate.
  • the ratio of the thicknesses of the first coating layer and the second coating layer is from about 1: 1 to about 1: 5, or from about 1: 1 to about 1: 4, About 1: 3. If the ratio of the thicknesses of the crab coating layer and the second coating layer is less than 1: 1, strong curling may occur in the direction of the first coating layer, and if it exceeds 1: 5, curling may occur in the direction of the second coating layer have.
  • the above-mentioned curl phenomenon causes defects in the point / adhesion with other devices, films, and layers that contact the other films, films, layers, etc., of the film of the present invention Therefore, when the ratio of the thicknesses of the first coating layer and the second coating layer is in the above-mentioned range, more optimized physical properties can be secured in terms of processability.
  • the first and second coating layers may contain a surfactant, a UV absorber, a UV stabilizer, a yellowing inhibitor, a leveling agent, an antifouling agent, a dye for improving the color value, etc., in addition to the binder, the inorganic fine particles, the photoinitiator, May further comprise additives commonly used in the art.
  • the content is not particularly limited as it can be variously controlled within a range that does not deteriorate the physical properties of the coating layer of the present invention. For example, about 100 to about 100 parts by weight of each of the first and second coating layers is about 0.01 to about 10 By weight.
  • the first and second coating layers may contain a surfactant as an additive, and the surfactant may be selected from the group consisting of 1 to 2 functional blend-based acrylates, fluorinated surfactants, May be active. At this time, the surfactant may be dispersed or crosslinked in the first and second coating layers.
  • the UV absorber may include a benzophenone-based compound, a benzotriazole-based compound, or a triazine-based compound.
  • examples of the UV stabilizer include tetramethylpiperazine Tetramethyl piperidine, and the like.
  • the first and second coating layers of the present invention as described above can be formed by applying a coating composition containing the above-described components onto a substrate and photo-curing the coating composition.
  • photoinitiator examples include 1-hydroxy-cyclohexyl-p-ketone,
  • Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • Products currently on the market include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907 and Esacure KIP 100F.
  • These photoinitiators may be used alone or in combination of two or more. remind.
  • organic solvent examples include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, 2-methoxyethane, 2-ethoxyethane, alkoxy alcohol solvents such as 1-methoxy-2-propanol, Ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone methyl propyl ketone and cyclohexanone, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethyl ethyleneneglycolicol monomonoethyl ethyl ether ether, ethylene Glycol monopropyl ether ethylene glycol monobutyl ether diethylene glycol monomethyl ether diethyl glycol monoethyl ether diethyl glycol monopropyl ether diethyl glycol monobutyl ether solvents such as diethylene glycol-2-ethyl n-butyl ether,
  • the content of the organic solvent may be varied within a range that does not deteriorate the physical properties of the coating composition, so that the weight ratio of the solid content: organic solvent to the solid content of the components contained in the coating composition is about 30: 70 to about 99: 1. And may have appropriate fluidity and applicability when the organic solvent is in the above range.
  • the coating composition may be sequentially coated on the front and back surfaces of the support substrate, or simultaneously on both sides of the support substrate.
  • a flexible film of the present invention can be obtained by coating a coating composition containing the above-mentioned components on both sides of the above-mentioned support substrate and then photo-curing to form a coating layer.
  • the method of applying the coating composition is not particularly limited as long as it can be used in the art to which the present technology belongs. For example, a bar coating method, a knife coating method, a coating method, a blade coating method, Gravure coating method, comma coating method, slot die coating method, lip coating method, and solution casting method.
  • the flexible film may include a plastic film, an adhesive film, a release film, a conductive film, a conductive layer, a liquid crystal material, and the like between at least one coating layer of at least one of the first and second coating layers, Layer, a coating layer, a cured resin layer, a non-conductive film, a metal mesh layer or a layer such as a patterned metal layer, a film, or a film.
  • the layer, film, film or the like may be in any form of a single layer, a double layer or a laminate type.
  • the layer, film, or film may be laminated on the coating layer by a method such as lamination, coating, deposition, or sputtering using an adhesive or an adhesive film.
  • the flexible film according to the present invention can be produced, for example, by the following method.
  • first coating and first photocuring of the coating composition for forming the first coating layer is performed on one side of the supporting substrate, and then coating is performed on the other side of the supporting substrate, And the second coating and the second photocuring of the composition.
  • the curl balance may be adjusted by forming the coating composition on both sides of the supporting substrate at the same time and curing the coating composition.
  • the flexible film of the present invention exhibits excellent durability and stability for excellent flexibility, flexibility, hardness, scratch resistance, high transparency, bending, curling or folding and is excellent in bendable, flexible,
  • a cover film of a next generation display having rollable or foldable characteristics, and the like can be used.
  • the first coating layer is coated with a pencil
  • the pencil hardness of the first coating layer may be 6H or more, or 7H or more.
  • both sides of the flexible film were folded at 80 to 90 degrees with respect to the bottom surface at intervals of 5 mm in the middle of the film with the second coating layer facing the bottom, repeated 100,000 times at room temperature , It is possible to exhibit excellent dynamic folding characteristics to such an extent that no more than 3 cm of clearance is generated.
  • the flexible film of the present invention is more than the light transmittance 88.0%, or more than 90.0%, the haze can be less than 1.5%, or 1.0 0/0 or less, or 0.5%.
  • Such a flexible film of the present invention can be utilized in various fields. For example, it is possible to use not only a flat shape but also a curved, bendable : flexible, rollable or foldable mobile communication terminal, a touch of a smartphone or a tablet PC Panels, and cover substrates or element substrates of various displays.
  • TMPTA trimethylolpropane triacrylate
  • PETA pentaerythritol tetraacrylate
  • DPEPA dipentaerythritol pentacrylate
  • MEK-AC-2140z silica particles
  • surfactant manufactured by Nissan Chemical Co., Ltd.
  • F 4 T7 surfactant
  • Irgacurel 27 photoinitiator Irgacurel 27
  • Production Example 1 the kind and / The components of Preparation Examples 1 to 10 and their contents are summarized in Table 1 below.
  • the coating composition was prepared by varying the kind and / or content of each component in Production Example 1.
  • the silica fine particles SI, S2, and S3 added at the time of production were obtained by using the laser light diffraction method (dynamic laser scattering, refractive index, viscosity, and dielectric constant of the solvent in which the inorganic fine particles were dispersed and the inorganic fine particles, , A particle diameter of cumulative 10% was dlO, a particle diameter of cumulative 50% was d50, and a particle diameter of cumulative 90% was d90, when the cumulative particle diameter distribution along the particle diameter was measured according to the device name: Malvern Zetasizer Nano-ZS90.
  • the modulus of elasticity of the first and second coating layers refers to a value measured according to ASTM D882 in a state where each coating layer is peeled from the supporting substrate, and the characteristics of each component are as follows:
  • TEGDA triethyleneglycol diacrylate
  • TPGDA tripropyleneglycol diacrylate
  • the coating composition of Preparation Example 1 was applied on both sides of a polyimide support substrate (size: 20 cm x 20 cm, thickness: 50 ml) having an elastic modulus value of 6 GPa measured according to ASTM D882 by bar coating method,
  • the first coating layer (thickness: 30) was formed by photocuring with a metal halide lamp having a wavelength of -320 nm.
  • a second coating layer (thickness: 30) was formed by applying the coating composition to the backside of the supporting substrate of the coating composition of Production Example 6 and photo-curing in the same manner to produce a flexible film.
  • a flexible film was prepared in the same manner as in Example 1, except that the coating composition and / or thickness used for the second coating layer in Example 1 were different. Comparative Examples 1 to 26 The same procedure as in Example 1 was carried out except that the kind and / or thickness of the coating composition used in the first coating layer, the kind of the coating composition used in the second coating layer, and / or the thickness of the coating layer were changed in Example 1 To prepare a flexible film.
  • the types of the coating compositions and the thicknesses of the coating layers of Examples 1 to 5 and Comparative Examples 1 to 42 are summarized in Tables 3 to 5, respectively.
  • the surface of the first coating layer was reciprocated once at a load of 750 g and at an angle of 45 degrees in accordance with the measurement standard JIS K5400-5-4, and the maximum hardness without a groove was confirmed.
  • FIG. 1 is a view schematically showing a method of performing a dynamic folding test on a film according to an embodiment of the present invention.
  • Each of the films of the examples and comparative examples was cut and laser cut to a size of 80 X 140 mm so as to minimize micro cracks at edge portions.
  • the laser cut film was placed on the measuring equipment so that the second coating layer was directed to the bottom surface.
  • the film was folded at 80 to 90 degrees with respect to the bottom surface at room temperature so that the gap was 5 mm.
  • the folding speed was once per 1.5 seconds), and the maximum number of repetitions in which a crack of 3 cm or more occurred was measured.
  • the films of the examples and comparative examples were cut into a square of 10 cm x 10 cm, and the outer surface of the film curvature (dried surface) was placed on the bottom of the experimental table.
  • the four corner points of the square were measured as a distance from the floor, Respectively. + Curl when the first coating layer is the inner surface of Curl, and Curl when the second coating layer is the inner surface of Curl. 4) Dent test
  • Fig . 1 is a schematic view showing a method of performing a dent test on a film according to an embodiment of the present invention.
  • An adhesive layer material: OCA, thickness and polyimide film (thickness: 50) was laminated on each of the films of Examples and Comparative Examples on the second coating layer. The laminated film was laminated on the bottom I left it.
  • the surface of the first coating layer was reciprocated once at an angle of 45 degrees while adding a load of 100 g, and then the maximum weight without damages such as pressing marks was confirmed on all the layers. We checked up to 1500g and did not proceed if damage did not occur.
  • Comparative Example 1 9H 300g 0mm Comparative Example 2 9H 0.1k or less 1500g or more 0mm Comparative Example 3 8H 0.1k or less 300g 0mm Comparative Example 4 8H 0.1k or less 1500g or more 0mm Comparative Example 5H 100k or more Less than lOOg 0mm Comparative Example 6 H 100k or more Less than lOOg 0mm Comparative Example 7 F 100k or more Less than lOOg 0mm
  • Comparative Example 8 F 100k or more Less than lOOg 0mm Comparative Example 9 4H 100k or more 400g + 2mm Comparative Example 10 4H 100k or more 800g to 5mm Comparative Example 11 3H 100k or more 1200g to 10mm Comparative Example 12 3H 100k or more 1500g or more -15mm Comparative Example 13 3H 100k or more 800g + lmm Comparative Example 14 3H 100k or more 1200g -4mm Comparative Example 15 3H 100k or more 1500g or more -8mm Comparative Example 16 3H 100k or more 1500g or more -13mm Comparative Example 17 9H 40k 500g + 25mm Comparative Example 18 9H 60k lOOOg + 15mm Comparative Example 19 8H 50k 1500g or more + 8mm Comparative Example 20 8H 40k 1500g or more + 4mm Comparative Example 21 8H 20k 1500g or more -3mm Comparative Example 22 8H 30k 1500g or more -2mm Comparative Example 23 8H 70k 1500g or more -2mm Comparative
  • the film of the present invention exhibited good properties in all properties, and exhibited excellent flexibility and impact resistance particularly in dynamic folding test, dent test and curl test as well as high hardness of 7H or more.
  • the films of the comparative examples did not exhibit a pencil hardness or exhibited flexibility and inner layer rigidity suitable for a flexible film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film souple, et plus précisément un film souple présentant une excellente flexibilité tout en présentant une grande dureté. Le film souple de la présente invention présente des propriétés de flexibilité, d'aptitude à la flexion, de grande dureté, de résistance à l'abrasion et de transparence élevée, et est moins susceptible d'être endommagé même après un gauchissement ou pliage de longue durée de manière répétée, de sorte que le film souple peut être appliqué de manière utile à un dispositif mobile flexible, un dispositif d'affichage, un panneau avant de tableau de bord, une unité d'affichage, etc.
PCT/KR2018/011060 2017-09-28 2018-09-19 Film souple WO2019066368A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/482,419 US11591498B2 (en) 2017-09-28 2018-09-19 Flexible film
CN201880005467.1A CN110114396B (zh) 2017-09-28 2018-09-19 柔性膜
JP2019536045A JP6772418B2 (ja) 2017-09-28 2018-09-19 フレキシブルフィルム

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170126592 2017-09-28
KR10-2017-0126592 2017-09-28
KR10-2018-0111632 2018-09-18
KR1020180111632A KR102095004B1 (ko) 2017-09-28 2018-09-18 플렉시블 필름

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WO2019066368A1 true WO2019066368A1 (fr) 2019-04-04

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CN112239623A (zh) * 2019-07-17 2021-01-19 罗门哈斯电子材料有限责任公司 用于显示设备的聚合物
JP2021532003A (ja) * 2019-05-20 2021-11-25 エルジー・ケム・リミテッド フレキシブルディスプレイ装置のカバーウィンドウおよびディスプレイ装置

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JP2010085760A (ja) * 2008-09-30 2010-04-15 Fujifilm Corp 防眩フィルム、偏光板、および画像表示装置
KR20100055160A (ko) * 2008-11-17 2010-05-26 웅진케미칼 주식회사 하드코팅액, 이를 사용한 하드코팅 필름 및 화상표시장치
JP2012030532A (ja) * 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐候ハードコートフィルム
KR20140027023A (ko) * 2012-08-23 2014-03-06 주식회사 엘지화학 하드코팅 필름
KR20150058067A (ko) * 2013-11-19 2015-05-28 주식회사 엘지화학 플라스틱 필름

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JP2010085760A (ja) * 2008-09-30 2010-04-15 Fujifilm Corp 防眩フィルム、偏光板、および画像表示装置
KR20100055160A (ko) * 2008-11-17 2010-05-26 웅진케미칼 주식회사 하드코팅액, 이를 사용한 하드코팅 필름 및 화상표시장치
JP2012030532A (ja) * 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐候ハードコートフィルム
KR20140027023A (ko) * 2012-08-23 2014-03-06 주식회사 엘지화학 하드코팅 필름
KR20150058067A (ko) * 2013-11-19 2015-05-28 주식회사 엘지화학 플라스틱 필름

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Publication number Priority date Publication date Assignee Title
JP2021532003A (ja) * 2019-05-20 2021-11-25 エルジー・ケム・リミテッド フレキシブルディスプレイ装置のカバーウィンドウおよびディスプレイ装置
EP3974183A4 (fr) * 2019-05-20 2022-08-03 Lg Chem, Ltd. Fenêtre de couverture pour dispositif d'affichage flexible et dispositif d'affichage flexible
JP7156591B2 (ja) 2019-05-20 2022-10-19 エルジー・ケム・リミテッド フレキシブルディスプレイ装置のカバーウィンドウおよびディスプレイ装置
CN112239623A (zh) * 2019-07-17 2021-01-19 罗门哈斯电子材料有限责任公司 用于显示设备的聚合物
JP2021017584A (ja) * 2019-07-17 2021-02-15 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ ディスプレイデバイス用のポリマー
JP7063942B2 (ja) 2019-07-17 2022-05-09 ローム アンド ハース エレクトロニック マテリアルズ エルエルシー ディスプレイデバイス用のポリマー
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CN112239623B (zh) * 2019-07-17 2022-10-04 罗门哈斯电子材料有限责任公司 用于显示设备的聚合物

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