WO2017023119A1 - Film plastique souple - Google Patents

Film plastique souple Download PDF

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Publication number
WO2017023119A1
WO2017023119A1 PCT/KR2016/008572 KR2016008572W WO2017023119A1 WO 2017023119 A1 WO2017023119 A1 WO 2017023119A1 KR 2016008572 W KR2016008572 W KR 2016008572W WO 2017023119 A1 WO2017023119 A1 WO 2017023119A1
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WO
WIPO (PCT)
Prior art keywords
plastic film
inorganic fine
flexible plastic
coating layer
fine particle
Prior art date
Application number
PCT/KR2016/008572
Other languages
English (en)
Korean (ko)
Inventor
김혜민
정혁
장영래
정순화
박진영
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 KR1020160098073A external-priority patent/KR102094450B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201680045556.XA priority Critical patent/CN107922778B/zh
Priority to US15/744,693 priority patent/US10118371B2/en
Priority to JP2018502141A priority patent/JP6384701B1/ja
Priority to EP16833355.7A priority patent/EP3309230B1/fr
Publication of WO2017023119A1 publication Critical patent/WO2017023119A1/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
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Definitions

  • the present invention relates to a flexible plastic film. More specifically, the present invention relates to a flexible plastic film that exhibits high hardness and has excellent flexibility.
  • Glass or tempered glass is generally used as a material having excellent mechanical properties in the display window or the front plate of the mobile device.
  • the glass causes the mobile device to be heavier due to its weight and there is a problem of breakage due to external impact.
  • plastic resin is being researched as a substitute material for glass.
  • Plastic resin films are lightweight and less prone to break, making them suitable for the trend toward lighter mobile devices.
  • a film for coating a hard coating worm made of a plastic resin on a supporting substrate has been proposed.
  • a method of increasing the thickness of the hard coating layer may be considered.
  • the surface hardness may be increased, but wrinkles or curls may be caused by hardening shrinkage of the hard coat layer. It is not easy to apply practically, since it becomes large and cracks or peeling of a hard coat layer easily occur.
  • Korean Patent Publication No. 2010-0041992 discloses a plastic film composition excluding a monomer and using a binder resin including an ultraviolet curable polyurethane acrylate oligomer.
  • the plastic film disclosed above is not strong enough to replace the glass panel of the display with a pencil hardness of 3H.
  • the present invention provides a flexible plastic film having high flexibility while having a high hardness.
  • a support substrate having an elastic modulus of at least 4 GPa and measured in accordance with ASTM D882 and having a thickness in the range of 20 to 200 m; And a coating layer formed on at least one surface of the support substrate,
  • the coating layer may be a crosslinked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder; And inorganic fine particles having a bi-modal particle distribution, including a first group of inorganic fine particles having a d 50 of 20 to 35 nm and a second group of inorganic fine particles having a d 50 of 40 to 130 nm.
  • inorganic fine particles having a bi-modal particle distribution including a first group of inorganic fine particles having a d 50 of 20 to 35 nm and a second group of inorganic fine particles having a d 50 of 40 to 130 nm.
  • flexibility, flexibility, High hardness, scratch resistance, high transparency, and less damage to the film under repeated, continuous bending or prolonged folding, resulting in bendable, flexible, rollable, or foldable mobile devices It can be usefully applied to display devices, front panels of various instrument panels, and display units.
  • FIG. 1 is a view schematically showing a method for performing bending durability and bending stability test for a film according to an embodiment of the present invention.
  • Figure 2 is a graph showing the distribution according to the particle diameter of the inorganic fine particles according to an embodiment of the present invention.
  • 3 is a graph showing the distribution according to the particle diameter of the inorganic fine particles according to the comparative example of the present invention.
  • the flexible plastic film of the present invention includes a support substrate having an elastic modulus of 4 GPa or more and a thickness in the range of 20 to 200 im as measured according to ASTM D882; And a coating layer formed on at least one surface of the support substrate, wherein the coating layer comprises a crosslinked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder; And inorganic fine particles having a bi-modal particle distribution including a first inorganic fine particle group having d 50 of 20 to 35 nm and a second inorganic fine particle group of d 50 of 40 to 130 nm.
  • first and second are used to describe various components, which terms are used only for the purpose of distinguishing one component from other components.
  • the support substrate having an elastic modulus of 4 GPa or more and a thickness in the range of 20 to 200 / im as measured according to ASTM D882; And a coating layer formed on at least one surface of the support substrate, wherein the coating layer comprises a crosslinked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder; And inorganic fine particles having a bi-modal particle distribution including a first inorganic fine particle group having d 50 of 20 to 35 nm and a second inorganic fine particle group having d 50 of 40 to 130 nm.
  • the term "flexible” means a state having flexibility such that no crack occurs over 3 mm in length when wound on a cylindrical mandrel having a diameter of 4 mm, and thus
  • the flexible full plastic film of the invention is applicable to bendable, flexible, rollable, cover films of foldable displays and the like.
  • the support substrate on which the coating layer is formed has an elastic modulus of about 4 GPa or more when measured according to ASTM D882 so as to secure flexibility and hardness, and has a thickness of 20 If it is an optically transparent plastic resin of the range of to, it can be used without a restriction
  • the elastic modulus may be about 4 GPa or more, or about 5 GPa or more, or about 5.5 GPa, or about 6 GPa or more, and the upper limit may be about 9 GPa or less, or about 8 GPa or less, or about 7 GPa or less. Can be. If the elastic modulus is less than 4GPa, it does not achieve a layered hardness If not and too high above 9 GPa, it may be difficult to form a flexible film.
  • the thickness of the support substrate may be about or more, or about 25 or more, or about 30 or more, and the upper limit thereof may be about 200 or less, or about 150 or less, or about 100 or less, or about 60 or less. have.
  • the thickness of the supporting substrate is less than 20, there is a risk of curling or curling during the coating layer forming process, and it may be difficult to achieve high hardness.
  • the thickness exceeds, the flexibility may be difficult to form a flexible film.
  • the plastic film of the present invention has an elastic modulus of 4 GPa or more and 9 GPa or less and a thickness of 20 to 200 m.
  • Phosphorous support base material can be used.
  • the support substrate satisfies the above-described elastic modulus and thickness range, for example, polyimide (PI), polyimideamide, poly Polyetherimide (PEI), polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), polyetheretherketon (PEEK), cyclic olefin polymer (COP), polyacrylamide Film (polyacrylate, PAC), polymethylmethacrylate (PMMA), triacetylcellulose (TAC), or the like.
  • the support substrate may be a single layer or a multilayer structure including two or more substrates made of the same or different materials as necessary, but is not particularly limited.
  • the support substrate may be a substrate including polyimide (PI).
  • PI polyimide
  • the ratio of the thickness of the support substrate and the coating layer is about 1: 0.05 to about 1: 1, or about 1: 0.1 to about 1: 8 days Can be.
  • the ratio of the thickness of the support base material and the coating layer is in the above range, it is possible to more easily form a flexible plastic film exhibiting high hardness and flexibility.
  • the flexible plastic film of the present invention includes a coating layer formed on at least one surface of the supporting substrate.
  • the coating layer may be formed on both sides of the support substrate.
  • the coating layer is a crosslinked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder, and the first inorganic fine particles having a d 50 of 20 to 35 nm.
  • the eggs acrylate, acrylate as well as methacrylate, or acrylates or meth all of the substituents are introduced into the derivative methacrylate, mihanda throughout this specification.
  • the 3 to 6 functional acrylate-based binder is cross-polymerized with the 7 to 20 functional urethane acrylate-based binder to form a copolymer, and may impart high hardness to the coating layer formed after curing.
  • the 3 to 6 functional acrylate-based binder is trimethyl propane triacrylate (TMPTA), trimethyl propane hydroxy triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), penta Tetraacrylate (PETA) for an erythr or nuxaacrylate (DPHA) for a dipentaerythrite, etc. are mentioned.
  • TMPTA trimethyl propane triacrylate
  • TMPEOTA trimethyl propane hydroxy triacrylate
  • GPTA glycerin propoxylated triacrylate
  • PETA penta Tetraacrylate
  • DPHA nuxaacrylate
  • dipentaerythrite a dipentaerythrite
  • the 3 to 6 functional acrylate-based 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, or about 200 to About 500 g / m.
  • Mw weight average molecular weight
  • the acrylate-based binder may have an acrylate equivalent weight in the range of about 50 to about 300 g / mol, or about 50 to about 200 g / mol, or about 50 to about 150 g / m.
  • the 1 to 20 functional urethane acrylate-based binder is cross-polymerized with the 3 to 6 functional acrylate-based binder to form a copolymer, and may provide high hardness, flexibility, and layer resistance to the coating layer formed after curing. have.
  • the 7 to 20 functional urethane acrylate binders may be used alone or in combination with each other.
  • the cross-linked copolymer is a 3 to 6 functional acrylate-based binder and 7 to 20 functional urethane acrylate-based binder is about 1: 9: to about 5: 5: 5, preferably about 1: 9 to about 4: 6, and more preferably, it may be crosslinked-polymerized in the weight ratio of about 1: 9 to about 3.5: 6.5.
  • the cross-linked crosslinked copolymer of the 3 to 6 functional acrylate-based binder and the 7 to 20 functional urethane acrylate-based binder in the weight ratio, it is possible to achieve a high hardness and good physical properties while showing sufficient flexibility.
  • the 7-20 functional urethane acrylate-based binder has a weight average molecular weight of about 2,000 to about 8,000 g / mol, or about 3,000 to about 6,000 g mol, or about 3,000 to about 5,000 g / m may be in the range, for the optimization of the coating layer properties.
  • the 7 to 20 functional urethane acrylate-based binder has an acrylate equivalent weight of about 200 to about 1,500 g / mol, or about 200 to about 1,000 g / mol, or About 300 to about 600 g / mol, or about 300 to about 500 g / m. If the acrylate equivalent of the 7 to 20 functional urethane acrylate-based binder is too high, the hardness of the coating layer may not be sufficient. If the equivalent is low, the hardness may be improved but the flexibility may be inferior. In view of the combination of high hardness and flexibility as described above, The range of equivalents described above is preferred, with about 300 to about 500 g / m being most preferred.
  • the 7 to 20 functional urethane acrylate-based binder is advantageous in that the coating layer achieves high hardness because the bonding density is very high by including 7 or more acrylate groups in the molecule capable of crosslinking polymerization by ultraviolet rays.
  • the crosslink density increases, curling tends to occur and adhesion to the substrate decreases, which is not suitable for forming a flexible film.
  • the 7 to 20 functional urethane acrylate-based binder included in the coating layer of the present invention includes seven or more multi-functional acrylate groups and at the same time has a urethane bond in the molecule has excellent properties of elasticity and flexibility. Therefore, when crosslinked with a 3 to 6 functional acrylate-based binder in an appropriate weight ratio to form a copolymer, it serves to give the coating layer a high flexibility with high hardness.
  • the 7 to 20 functional urethane acrylate-based binder may include 2 to 20 urethane bonds in one molecule.
  • the coating layer of the present invention provides a high hardness and flexibility to the flexible plastic film by including a crosslinked copolymer in which the 3 to 6 functional acrylate binder and the 7 to 20 functional urethane acrylate binder are crosslinked.
  • a crosslinked copolymer in which the 3 to 6 functional acrylate binder and the 7 to 20 functional urethane acrylate binder are crosslinked.
  • the coating layer of the present invention includes inorganic fine particles having a bi-modal particle distribution including a first inorganic fine particle group having a d 50 of 20 to 35 nm and a second inorganic fine particle group having a d 50 of 40 to 130 nm.
  • the coating layer of the present invention uses the inorganic fine particles having a bimodal distribution including the first and second inorganic fine particle groups each having a specific range of d 50 , thereby providing flexible characteristics. It is possible to achieve both high hardness and flexibility of the coating layer while maintaining it.
  • the laser light diffraction method (Measurement method: Dynamic laser scattering, the size distribution by number is determined using the refractive index, viscosity, and dielectric constant of the solvent and inorganic fine particles are dispersed, 7] Name: Malvern According to the Zetasizer Nano-ZS90), the cumulative particle size distribution according to the particle diameter is measured as d 10 with a cumulative 10% particle size, d 50 with a cumulative particle size of 50% and d 90 with a cumulative particle size of 90%.
  • the particle size distribution according to the laser light diffraction method is substantially the same as that measured by SEM or TEM by diluting the dispersion in which the inorganic fine particles are dispersed in the solvent, or by analyzing the cross section of the coating layer containing the inorganic fine particles by SEM or TEM. The same distribution can be seen.
  • the first group of inorganic fine particles having a small particle size range contributes to the improvement of hardness
  • the second group of inorganic fine particles having a larger particle size range contributes to the improvement of flexibility and flexibility, so that the particle size range is different in addition to the above-mentioned crosslinked co-polymer.
  • the inorganic fine particle group in combination, it is possible to provide a coating layer having improved hardness and physical properties at the same time.
  • the degree of hardness and flexibility may vary depending on the particle size distribution of the first and second inorganic fine particle groups, and the hardness and flexibility of the coating layer when using the first and second inorganic fine particle groups satisfying a predetermined particle size distribution, respectively.
  • the present invention has been completed based on the fact that the balance of physical properties can be optimized.
  • first and second inorganic fine particle groups for example, silica fine particles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, or the like may be used independently.
  • the d 50 of the first inorganic fine particle group may be 20 nm or more, or about 21 nm or more, 35 nm or less, or 30 nm or less, or 25 nm or less, and d 50 of the second inorganic fine particle group. May be at least 40 nm, or at least about 42 nm, or at least about 45 nm, at most 130 nm, or at most 125 nm, or at most 120 nm.
  • the first inorganic fine particle group may have a d 10 of 10 to 19 nm, a d 50 of 20 to 35 nm, and a d 90 of 25 to 40 nm.
  • the second inorganic fine particle group is d 10 is 25 to lOnm
  • d 50 is 40 To 130 nm
  • d 90 may be 60 to 150 nm.
  • the content of the crab 1 inorganic fine particle group is about 5 parts by weight or more, or about 10 parts by weight or more, or about 15 parts by weight to 100 parts by weight of the total coating layer, in order to contribute to high hardness improvement.
  • the content of the second inorganic fine particle group is about 5 parts by weight or more, or about 10 parts by weight or more, or about 100 parts by weight of the total coating layer, in order to contribute to high hardness improvement. It may be 15 parts by weight or more, and about 50 parts by weight or less, or about 45 parts by weight or less, or about 40 parts by weight or less, or about 35 parts by weight or less to satisfy flexibility.
  • the second group of inorganic fine particles in the above weight range, it is possible to form a flexible plastic film having excellent physical properties satisfying high hardness and flexibility at the same time.
  • the total content of the inorganic fine particles including the first and the second inorganic fine particle groups is about 25 parts by weight or more, in order to contribute to high hardness improvement, based on 100 parts by weight of the total coating layer. Or about 30 parts by weight or more, or about 35 parts by weight or more, and can be ' adjusted to about 50 parts by weight or less, or about 45 parts by weight or less, or about 40 parts by weight or less to satisfy flexibility.
  • the first and second inorganic fine particle groups are each independently the same or different, the surface is
  • At least one silane coupling agent selected from the group consisting of (meth) acrylsilane, methacroxysilane, vinylsilane, epoxysilane and mercaptosilane May be modified.
  • the system 1 and the second inorganic surface-modified with a silane coupling agent Since the fine particle group can react with the acrylate group of the binder, it can be more advantageous because it has high adhesiveness with the substrate, can be uniformly dispersed in the coating layer, and the hardness can be improved without lowering the flexibility of the coating layer.
  • the crab 1 and the second inorganic particulate group is about 9: 1 to about 3: 7, or about 8: 2: 2 to about 4: 6, or about 7: 3 to about 5: 5: It may be included in the weight ratio of.
  • the first and second inorganic fine particle groups in the weight ratio range, it is possible to form a flexible plastic film having excellent physical properties, which is more improved in high hardness and flexibility.
  • the coating layer of the present invention in addition to the binder, inorganic fine particles, photoinitiator and organic solvent described above, surfactant, UV absorber, UV stabilizer, yellowing agent, leveling agent, antifouling agent, dye technology for improving the color value It may further include an additive commonly used in the field.
  • the content can be variously adjusted within a range that does not lower the physical properties of the coating layer of the present invention, it is not particularly limited, for example, may be included in about 0.01 to about 10 parts by weight based on 100 parts by weight of the coating layer.
  • the coating layer may include a surfactant as an additive
  • the surfactant may be a 1 to 2 functional fluorine-based acrylate, fluorine-based surfactant or silicone-based surfactant.
  • the surfactant may be included in the form of being dispersed or crosslinked in the coating layer.
  • the additive may include a UV absorber or a UV stabilizer, and the UV absorber may include a benzophenone compound, a benzotriazole compound, a triazine compound, and the like. Tetramethyl piperidine and the like.
  • photoinitiator examples include 1-hydroxy-cyclonuclear-phenyl ketone and 2-hydroxy-2- I-methyl-1-phenyl _1_ propanone, 2-hydroxy-_ _i- [4- (2- hydroxy hydroxy) phenyl] -2-methyl-1-propanone, methyl benzoyl formate, ⁇ , ⁇ - D meteuk - ⁇ -phenylacetophenone, 2-benzoyl-2- (dimethylamino) _1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methyl seed 5) phenyl] -2- (4 ⁇ morpholinyl propanone diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc.
  • 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, Esacure KIP 100F, etc.
  • These photoinitiators can be used individually or in mixture of 2 or more types.
  • the organic solvent is alcohol, such as methanol, ethane, isopropyl alcohol, butane.
  • Solvents alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone methyl propyl ketone, and cyclonucleanone
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone methyl propyl ketone
  • cyclonucleanone Propylene glycol monopropyl ether, propylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether ethylene glycol monobutyl ether, diethylene glycol monomethyl ether diethyl glycol monoethyl ether, diethyl glycol monopropyl ether diethyl glycol Ether solvents such as monobutyl ether and diethylene glycol-2-ethylnuclear
  • the content of the organic solvent is not particularly limited because it can be variously adjusted within a range that does not lower the physical properties of the coating composition, but with respect to the solid content of the components included in the coating composition, the weight ratio of solid content: organic solvent is about 30: 70 to about 99: 1. When the organic solvent is in the above range, it may have appropriate flowability and applicability.
  • the coating composition may be sequentially applied to the front and rear surfaces of the support substrate, or simultaneously applied to both sides of the support substrate.
  • the flexible plastic film of the present invention can be obtained by applying a coating composition including the above-described components on both sides of the support substrate and then photocuring 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, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, micro gravure coating Method, comma coating method, slot die coating method, lip coating method, solution casting (solution casting) method and the like can be used.
  • the coating layer may have a thickness of about 3 / m or more, for example, about 3 to about or about 3 to about 15 / m, or about 3 to about 10 / m, after curing completely. According to the present invention, when the coating layer having the thickness as described above can provide a flexible plastic film of high hardness.
  • the flexible plastic film has at least one coating layer on the top surface or between the base film and the coating layer, a plastic resin film, adhesive film, release film, conductive film, conductive layer, liquid crystal layer, coating layer, cured resin layer
  • the film may further include one or more layers, films, or films such as a non-conductive film, a metal mesh layer, or a patterned metal layer.
  • a conductive antistatic layer is first formed on a supporting substrate and then a coating layer is formed thereon to provide an anti-static function, or a low reflection layer is introduced by introducing a low refractive index layer on the coating layer. You can also implement
  • the layer, film, film or the like may be of any type, such as a single layer, a double layer or a laminate.
  • the layer, film, or film may be laminated on the coating layer by a method such as laminating a freestanding film using an adhesive or an adhesive film, or by coating, vapor deposition, sputtering, or the like. It is not limited to this.
  • the flexible plastic film according to the present invention can be produced, for example, by the following method.
  • first coating and first photocuring the first coating composition on one surface of the support substrate, and then the second coating and second coating composition on the other side of the support substrate, that is the back It can form by the two-step process of photocuring.
  • the first and second coating composition is the same as the above-described coating composition, it is to distinguish the composition to be applied only on one side and the back, respectively.
  • the ultraviolet irradiation is performed on the opposite side of the second photocuring step instead of the surface on which the first coating composition is applied, curls that may be caused by curing shrinkage in the first photocuring step are reversed. Offset can yield a flat flexible plastic film. Therefore, no additional planarization process is necessary.
  • the present invention is not limited thereto, and the curl balance may be matched by forming the coating composition on both sides of the supporting substrate at the same time and curing the coating composition.
  • the flexible plastic film of the present invention exhibits excellent flexibility, flexibility, high hardness, scratch resistance, high transparency, high durability and stability against bending, curling or folding, and is therefore bendable and flexible. ), Rollable, or as a cover film of a next-generation display having a foldable property.
  • the flexible plastic film of the present invention may exhibit flexibility to the extent that no crack occurs when wound on a cylindrical mandrel of 4 mm or 3 mm in diameter.
  • the pencil hardness at 750g load may be 6H or more, or 7H or more.
  • the flexible plastic film of the present invention is left at room temperature while folding both sides of the film at 90 degrees with respect to the bottom surface at intervals of 4 mm between the film thickness, and then the flat portion may be unfolded so that the folded portion goes downward.
  • the bending stability may be about 0.5 mm or less.
  • the flexible plastic film of the present invention may have a light transmittance of 88.0% or more, or 90.0% or more, and a haze of 1.5% or less, or 1.0% or less, or 0.5% or less.
  • Such flexible plastic films of the present invention can be utilized in various fields. For example, not only flat shapes, but also curved, bendable, flexible, rollable, or The present invention can be used for a foldable mobile communication terminal, a touch panel of a smartphone or a tablet PC, and a cover substrate or an element substrate of various displays.
  • TMPTA pro-pipe triacrylate
  • S1 dispersion solution 60 g
  • the elastic modulus value of the coating composition measured in accordance with ASTM D882 is a bar coating on both sides of a 6.0 GI 3 ⁇ 4] polyimide substrate (size: 20 cm ⁇ 30 cm, thickness: 35 / ⁇ ).
  • the coating layer was formed by coating in a manner and photocuring with a metal halide lamp having a wavelength of 290-320 nm.
  • Example 1 the coating layer was formed in the same manner as in Example 1, except that 83.3 g of the S2 dispersion solution was not included and a separate methyl ethyl ketone solvent was not included.
  • Example 3 the coating layer was formed in the same manner as in Example 1, except that 83.3 g of the S2 dispersion solution was not included and a separate methyl ethyl ketone solvent was not included.
  • solution which is 40 weight 0/0 dispersed in MEK (hereinafter, S3 dispersion solution) 3 combined that 5g common to prepare a coating composition.
  • Example 4 The subsequent process was the same as in Example 1 to form a coating layer.
  • Example 4 The subsequent process was the same as in Example 1 to form a coating layer.
  • the coating composition was prepared by mixing 60 g of S1 dispersion solution and 75 g of S3 dispersion solution in this acrylate solution.
  • Example 5 The subsequent process was the same as in Example 1 to form a coating layer.
  • Example 6 Except for using a polyimide substrate (size: 20cm X 30cm, thickness: 35 / zm) having an elastic modulus value of 4.2 GPa measured according to ASTM D882, the rest of the process was the same as in Example 1 to form a coating layer .
  • a polyimide substrate size: 20cm X 30cm, thickness: 35 / zm
  • ASTM D882 ASTM D882
  • Example 7 Except for using a polyimide substrate (size: 20 cm X 30 cm, thickness: 35 m) having an elastic modulus value of 7.6 GPa measured according to ASTM D882, the rest of the process was the same as in Example 1 to form a coating layer.
  • a polyimide substrate size: 20 cm X 30 cm, thickness: 35 m
  • ASTM D882 the rest of the process was the same as in Example 1 to form a coating layer.
  • photoinitiator Irgacure 184 (manufacturer: Ciba) lg, methylethyl 42 g of ketone (MEK) were mixed to prepare an acrylate solution.
  • the coating composition was prepared by mixing 60 g of S1 dispersion solution and 83.3 g of S2 dispersion solution in this acrylate solution.
  • Antistatic layer composition by mixing 20 g of AZO particle dispersion CX-610M (manufacturer: Nissan, solid content 6 0%), 10 g of pentaacrylate (DPHA) for dipentaerythr, 0.5 g of photoinitiator Irgacure 184 (manufacturer: Ciba), and 100 g of ethanol Was prepared.
  • AZO particle dispersion CX-610M manufactured by mixing 20 g of AZO particle dispersion CX-610M (manufacturer: Nissan, solid content 6 0%), 10 g of pentaacrylate (DPHA) for dipentaerythr, 0.5 g of photoinitiator Irgacure 184 (manufacturer: Ciba), and 100 g of ethanol Was prepared.
  • the antistatic layer composition was applied on one surface of the polyimide substrate used in Example 1 and photocured to form an antistatic layer having a thickness of 1 and a surface resistance of 10 9 ffi / sq.
  • the coating layer having a thickness of 6 // m was formed by coating and photocuring the coating composition of Example 1 on the upper surface of the antistatic layer and the other surface of the substrate on which the antistatic layer was not formed.
  • Hollow silica dispersion Thrulya 4320 (manufacturer: catalytic, 20% solids) 22 g, dipentaerythrene pentaacrylate (DPHA) 4 g, photoinitiator Irgacure 184 (manufacturer: Ciba) 0.5 g, fluorine-containing compound RS907 (manufacturer: DIC, 3 g of solid content 30%) was mixed to prepare a low refractive index layer composition.
  • the low refractive index layer composition was applied on one surface of the coating layer and then photocured to form a low refractive index layer having a thickness of 120 nm and an average reflectance of 2%. Comparative Example 1
  • Example 1 methyl ethyl ketone was 55 g, and the coating layer was formed in the same manner as in Example 1 except that the coating composition did not contain silica particles. Comparative Example 2
  • Example 1 methyl ethyl ketone is 12 g and silica particles are used.
  • Example 1 the coating layer was formed in the same manner as in Example 1 except that 35 g of methyl ethyl ketone was added and 110 g of only the S1 dispersion solution was included. Comparative Example 4
  • Example 1 the coating layer was formed in the same manner as in Example 1, except that 125 g of the S3 dispersion solution and 25 g of the S4 dispersion solution were not used and a separate methyl ethyl ketone solvent was not included. Comparative Example 5
  • the main components of the coating layers of Examples 1 to 7 and Comparative Examples 1 to 7 are summarized in Tables 1 and 2, respectively.
  • the distribution graph according to the particle size of the whole inorganic fine particles contained in the coating layers of Examples 1 to 4 is shown in FIG. 2, and the distribution graph according to the particle diameters of the whole inorganic fine particles included in the coating layers of Comparative Examples 2 to 4 is illustrated in FIG. 3.
  • the particle size distribution (d 10 , d 50 , d 90 ) of the inorganic fine particles was measured in a dispersion solution state using a Malvern Zetasizer Nano-ZS90 and determined as a size distribution by number. It was.
  • Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 1 2 3 4 5 6 7 Acrylate TMPTA 30 30 30 30 30 30 30 30 Yite MU9800 40 40 40 40 40 40 40-Binder MU9020 30 30 30 30 30 30-
  • the content of the inorganic fine particles is expressed as the net weight of only the inorganic fine particles (S 1 to S4) excluding the solvent according to the weight% of the inorganic fine particles dispersed in the solvent.
  • the maximum hardness without grooves was confirmed after reciprocating three times at a angle of 45 degrees with a load of 750 g according to the measurement standard JIS K5400-5-4 using a pencil hardness tester.
  • the standard diameter was measured according to the method of JIS K5600-5-1, after each film was wound in cylindrical mantelels of various diameters and no cracks of 3 mm or more in length were generated.
  • FIG. 1 is a view schematically showing a method for performing bending durability and bending stability test for a film according to an embodiment of the present invention.
  • Each film of Examples and Comparative Examples was cut, but laser cut to a size of 80 X 140mm to minimize the fine cracks of the edge (edge). Raise the laser cut film on the measuring device and place the fold at 4mm intervals, and fold both sides of the film at 90 degrees to the floor at room temperature. 10,000 repetitions were made with the action (the rate at which the film was folded once every 1.5 seconds).
  • each film of Examples and Comparative Examples was cut, but laser cut to a size of 80 x 140 mm to minimize fine cracks at the edge.
  • the laser cut film was placed on the fixing device and fixed so that the space between the folded portions was 4 mm. Both sides of the film were folded at 90 degrees with respect to the bottom surface, and allowed to stand at room temperature for 24 hours, and then the film was peeled upside down so that the folded portion went down, and a SUS shaped structure was placed on it to fix the film.
  • the shape of the film was measured with a non-contact surface curvature measuring instrument (PLUTO 681 (Dukin: 605nm laser, resolution 0.1)), and the maximum value of the height Z lifted from the bottom was measured by bending stability properties.
  • the films In order to measure the resilience of the film, the films, each of which measured bending durability and stability properties, were allowed to stand at room temperature for 1 hour, respectively. Visual observation was observed.
  • the film of the present invention exhibited good properties in all of the physical properties, in particular excellent durability and stability in the bending test, including high hardness.
  • the films of the comparative examples were inferior in pencil hardness or did not exhibit sufficient bending durability and stability for the flexible film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne un film plastique souple, et plus spécifiquement, un film plastique souple faisant preuve d'une dureté élevée tout en présentant une souplesse excellente. Selon le film plastique souple de la présente invention, le film plastique souple fait preuve de souplesse, d'aptitude à la flexion, d'une dureté élevée, d'une résistance à l'abrasion et d'une transparence élevées, et permet de réduire les préoccupations concernant les détériorations du film, même lorsqu'il est fléchi, ou plié de manière répétée sur une longue période, et ainsi peut être appliqué de manière utile aux faces avant, unités d'affichage, etc. de dispositifs mobiles souples, de dispositifs d'affichage et de divers tableaux de bord.
PCT/KR2016/008572 2015-08-03 2016-08-03 Film plastique souple WO2017023119A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201680045556.XA CN107922778B (zh) 2015-08-03 2016-08-03 柔性塑料膜
US15/744,693 US10118371B2 (en) 2015-08-03 2016-08-03 Flexible plastic film
JP2018502141A JP6384701B1 (ja) 2015-08-03 2016-08-03 フレキシブルプラスチックフィルム
EP16833355.7A EP3309230B1 (fr) 2015-08-03 2016-08-03 Film plastique souple

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20150109699 2015-08-03
KR10-2015-0109699 2015-08-03
KR20150160673 2015-11-16
KR10-2015-0160673 2015-11-16
KR1020160098073A KR102094450B1 (ko) 2015-08-03 2016-08-01 플렉시블 플라스틱 필름
KR10-2016-0098073 2016-08-01

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JP2020510707A (ja) * 2017-09-28 2020-04-09 エルジー・ケム・リミテッド フレキシブルフィルム
US20210240226A1 (en) * 2018-10-26 2021-08-05 Lg Chem, Ltd. Cover window for flexible display device and flexible display device

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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
JP2012030532A (ja) * 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐候ハードコートフィルム
KR20130135152A (ko) * 2012-05-31 2013-12-10 주식회사 엘지화학 하드코팅 필름
KR20140027024A (ko) * 2012-08-23 2014-03-06 주식회사 엘지화학 적층 하드코팅 필름
KR20140113423A (ko) * 2013-03-15 2014-09-24 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
JP2012030532A (ja) * 2010-07-30 2012-02-16 Dainippon Printing Co Ltd 耐候ハードコートフィルム
KR20130135152A (ko) * 2012-05-31 2013-12-10 주식회사 엘지화학 하드코팅 필름
KR20140027024A (ko) * 2012-08-23 2014-03-06 주식회사 엘지화학 적층 하드코팅 필름
KR20140113423A (ko) * 2013-03-15 2014-09-24 주식회사 엘지화학 플라스틱 필름

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020510707A (ja) * 2017-09-28 2020-04-09 エルジー・ケム・リミテッド フレキシブルフィルム
US11591498B2 (en) 2017-09-28 2023-02-28 Lg Chem, Ltd. Flexible film
US20210240226A1 (en) * 2018-10-26 2021-08-05 Lg Chem, Ltd. Cover window for flexible display device and flexible display device

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