WO2014030844A1 - 하드코팅 필름 - Google Patents
하드코팅 필름 Download PDFInfo
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- WO2014030844A1 WO2014030844A1 PCT/KR2013/006772 KR2013006772W WO2014030844A1 WO 2014030844 A1 WO2014030844 A1 WO 2014030844A1 KR 2013006772 W KR2013006772 W KR 2013006772W WO 2014030844 A1 WO2014030844 A1 WO 2014030844A1
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- hard coating
- film
- coating film
- hard
- photocurable
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
Definitions
- the present invention relates to a hard coat film. More specifically, the present invention relates to a hard coat film that exhibits high hardness and excellent properties without including a substrate.
- 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.
- films have been proposed in which a hard coat layer is coated on a resin substrate to achieve a film having properties of high hardness and wear resistance.
- a method of increasing the thickness of the hard coating layer may be considered.
- the surface hardness In order to secure the surface hardness to replace the glass it is necessary to implement the thickness of the hard coating layer.
- the thickness of the hard coating layer As the thickness of the hard coating layer is increased, the surface hardness can be increased.
- the wrinkles and curls increase due to the curing shrinkage of the hard coating layer, cracking or peeling of the hard coating layer is likely to occur. Is not easy.
- several methods have been proposed to realize high hardness of the hard coat film and to solve the problem of curling due to cracking and curing shrinkage of the hard coat layer.
- Korean Unexamined Patent Publication No. 2010-0041992 discloses a hard coating film composition excluding a monomer and using a binder resin including an ultraviolet curable polyurethane acrylate-based oligomer.
- the hard coat film disclosed above is not strong enough to replace the glass panel of the display with a pencil hardness of about 3H.
- the present invention provides a hard coating film exhibiting high hardness and excellent properties without including a supporting substrate.
- a monolayered substmte-less hard coating film comprising a photocurable crosslinked copolymer and inorganic fine particles dispersed in the photocurable crosslinked copolymer.
- the hard coating film of the present invention exhibits high hardness, scratch resistance, layer resistance, and high transparency even without a base film, and does not generate curl or crack due to its excellent workability, which is useful for mobile devices, display devices, front panels of various instrument panels, display parts, and the like. Can be applied.
- the hard coat film of the present invention is a single layer inorganic film containing a photocurable crosslinked copolymer and inorganic fine particles dispersed in the photocurable crosslinked copolymer.
- the hard coat film according to an embodiment of the present invention is a single layer inorganic material (substrate-less) film including a photocurable crosslinked copolymer and inorganic fine particles dispersed in the photocurable crosslinked copolymer.
- the substrate of the inorganic material is a support means for applying a hard coating composition for forming a hard coating layer, in a state that does not peel even after curing of the hard coating composition It means a support substrate which remains, and therefore, the inorganic material means not including such a support substrate.
- the hard coat film of the present invention is an inorganic film unlike the conventional hard coat film, that is, it does not include a support base material such as a plastic resin film, which is a support means for the hard coat layer and does not peel off after curing. Accordingly, the hard coat film of the present invention is a film of a substrate-less form.
- the hard coat film of the present invention is a single layer of inorganic film consisting of one hard coat layer.
- this does not exclude the case where another film, layer, or film is attached onto the hard coat film, but only a coating composition. It means that the hard coat layer formed by curing is a single layer.
- the hard coat film of the present invention has excellent curling properties without warping or cracking, but has high thickness and flatness, and exhibits high hardness, impact resistance, scratch resistance, and high transmittance.
- the hard coat film of the present invention comprises a photocurable crosslinked copolymer with a photocurable elastomer and a 3 to 6 functional acrylate monomer.
- the acrylate-based means not only acrylate but also methacrylate or a derivative in which a substituent is introduced into acrylate or methacrylate.
- the photocurable elastomer means a polymer material that exhibits elasticity and includes a functional group capable of crosslinking polymerization by ultraviolet irradiation.
- the photocurable elastomer is at least about 15%, for example from about 15 to about 200%, or from about 20 to about 200%, or from about 20 to about as measured by ASTM D638. It can have an elongation of 150%.
- the photocurable elastomer may be crosslinked with the 3 to 6 functional acrylate-based monomer to impart flexibility and layer resistance to the hard coat film formed by forming a hard coat film after curing.
- the photocurable crosslinked copolymer when the total weight of the photocurable crosslinked copolymer is 100 parts by weight, 5 to 20 parts by weight of the photocurable elastomer, the 3 to 6 functional acrylic 80 to 95 parts by weight of the rate monomer may be crosslinked.
- the hard coating film of the present invention by including the cross-linked copolymer of the 3-6 functional acrylate-based monomer and the photocurable elastomer cross-linked in the increase ratio, high hardness without deterioration of other physical properties such as curl properties and light resistance And high layer resistance.
- the photocurable elastomer may be a polymer or oligomer having a weight average molecular weight in the range of about 1,000 to about 600,000 g / mol, or about 10,000 to about 600,000 g / mol.
- the photocurable elastomer is, for example, polycaprolactone, urethane It may be at least one member selected from the group consisting of an acrylate polymer, and polyrotasein.
- polycaprolactone is formed by ring-opening polymerization of caprolactone and has excellent physical properties such as flexibility, layer resistance, and durability.
- the urethane acrylate polymer has excellent elasticity and durability, including urethane bonds.
- the polyrotaxane refers to a compound in which a dumbbell shaped molecule and a cyclic compound are structurally fitted.
- the dumbbell-shaped molecule includes a constant linear molecule and a blocking group disposed at both ends of the linear molecule, the linear molecule penetrates inside the cyclic compound, and the cyclic compound can move along the linear molecule. And the departure is prevented by the blocker.
- a cyclic compound in which a lactone compound having a (meth) acrylate compound introduced therein is bound; Linear molecules penetrating the cyclic compound; And a rotasein compound disposed at both ends of the linear molecule and including a blocking group to prevent the cyclic compound from being separated.
- the cyclic compound may be used without any limitation as long as it has a size enough to penetrate or surround the linear molecule, and may be a hydroxyl group, an amino group, a carboxyl group, a thiol group, or an aldehyde group that may react with other polymers or compounds. It may also contain a functional group. Specific examples of such cyclic compounds include ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, or a combination thereof.
- a compound having a straight chain form having a molecular weight of a predetermined or more may be used without great limitation, but a polyalkylene compound or a polylactone compound may be used.
- a polyoxyalkylene compound containing a oxyalkylene repeating unit having 1 to 8 carbon atoms or a polylactone compound having a lactone repeating unit having 3 to 10 carbon atoms may be used.
- the containment group according to the properties of the rotasein compound to be produced can adjust suitably, For example, 1 type (s) or 2 or more types chosen from the group which consists of a dinitrophenyl group, a cyclodextrin group, an ammantane group, a triryl group, a fluorescein group, and a pyrene group can be used.
- Such polyrotaxane compounds may have excellent scratch resistance and may exhibit self-healing ability when scratches or external damages occur.
- the hard coat film of the present invention by providing a light-curable elastomer including a light cured to give a high hardness and flexibility to the hard coat film, it is possible to prevent damage due to the outer layer lattice in particular to ensure excellent impact resistance.
- the 3- to 6-functional acrylate monomers are trimethyl to propane triacrylate (TMPTA), trimethyl to propane specific triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA) : pentaerythritol tetra Acrylate (PETA) or dipentaerythrite nucleacrylate (DPHA).
- TMPTA propane triacrylate
- TMPEOTA trimethyl to propane specific triacrylate
- GPTA glycerin propoxylated triacrylate
- PETA pentaerythritol tetra Acrylate
- DPHA dipent
- the hard coat film of the present invention contains inorganic fine particles dispersed in the photocurable crosslinked copolymer.
- the inorganic fine particles are nano-scale inorganic particles, for example, about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm nanoparticles Can be used.
- the inorganic fine particles for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles can be used.
- the hardness of the hard coat film can be further improved.
- the hard coat film is about 40 to about 90 parts by weight of the photocurable crosslinked copolymer and about 10 to about 60 parts by weight of the inorganic fine particles when the total weight of the hard coating film is 100 parts by weight Or may comprise about 50 to about 80 parts by weight of the photocurable crosslinked copolymer and about 20 to about 50 parts by weight of the inorganic fine particles.
- the hard coat film has at least 50, for example about 50 to about 500.
- the hard coating film of the present invention may have a thickness of about 50 / zm, about 75, about ⁇ , about 125, about 188 / m, about 200 ⁇ , about 250im, about 300 ⁇ , about 450 ⁇ , or about 500jm It can have Since the hard coating film of the present invention does not include a supporting substrate, the hard coating film is not affected by shrinkage of the substrate in the photocuring process, and thus there is no fear of curling or cracking.
- the hard coating film of the present invention in addition to the photocurable cross-linked copolymer and the inorganic fine particles described above, further includes additives commonly used in the technical field to which the present invention belongs, such as surfactants, anti-yellowing agents, leveling agents, antifouling agents, etc. can do.
- the content can be variously adjusted within a range that does not lower the physical properties of the hard coat film of the present invention, it is not particularly limited, for example, about 0.1 to about 10 with respect to 100 parts by weight of the photocurable crosslinked copolymer It may be included in parts by weight.
- the hard coating film may include a surfactant as an additive, and the surfactant may be a 1 to 2 functional fluorine acrylate, a fluorine surfactant or a silicone surfactant.
- the surfactant may be included in the form of being dispersed or crosslinked in the crosslinked copolymer.
- the additive may include a yellowing inhibitor
- the yellowing inhibitor may include a benzophenone compound or a benzotriazole compound.
- the hard coat film may be formed by photocuring a hard coating composition including the 3 to 6 functional acrylate monomer, a photocurable elastomer, an inorganic fine particle, a photoinitiator, optionally an additive, and an organic solvent.
- photoinitiator examples include 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1_phenyl-1-propanone and 2-hydroxy-1- [4- (2-hydroxy).
- Methoxy) phenyl] -2-methyl-1-propanone, methylbenzoylformate, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4 -Morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- (4'-morpholinyl) -1_propane may include diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc.
- Irgacure 184 Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F.
- photoinitiators can be used individually or in mixture of 2 or more types different from each other.
- organic solvent examples include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butane, 2-methoxyethanol and 2-ethoxyethane, alkoxy alcohol solvents such as 1-methoxy-2-propane, Ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl propyl phyll ketone, and cyclyl chloronucleus nucleus hexanonone, 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, diethethyl butyl glycol glycol monomonobutybutyl ether ether, , Ether solvents
- the hard coat film may be formed by applying and curing a hard coat composition including the above-described components on a release film for convenience during transportation, storage, processing or use.
- the method of applying the hard coating composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, for example, bar coating method, knife coating method, coating method, blade coating method, die coating method, Micro gravure coating, comma coating, slot die coating, lip coating, or solution casting (solution casting) method and the like can be used.
- the hard coating composition is completely cured, the thickness of the hard coating film is about 50 to about 500 / im, for example about 50 / / m, about 75 / ⁇ , about 100, about ⁇ 25 ⁇ ⁇ , about 188 / ⁇ , About 200 // m, about 300, about 450, or about 500; TM.
- the hard coating film of the present invention even if formed in a high thickness as described above, hard coating of high hardness without curl or crack generation Films can be produced.
- the release film may be used without limitation as long as it is commonly used in the art to which the present invention pertains.
- the release film may be a polyolefin-based film, such as a polyester film, polyethylene film, polyethylene terephthalate film, polypropylene film, or teflon-based film, preferably silicon to facilitate peeling Or a film release-treated with acrylsilicon.
- the release film may be removed by peeling after curing of the hard coating composition. Alternatively, it may be peeled off immediately before use and not removed after curing to favor transportation and storage.
- the hard coating film is formed by irradiating the applied hard coating composition with ultraviolet light to photocuring the same.
- the irradiation amount of ultraviolet light may be, for example, about 20 to about 600 mJ / cm 2 , or about 50 to about 500 mJ / cm 2 .
- the light source for ultraviolet irradiation is not particularly limited as long as it can be used in the art to which the present technology belongs, and for example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp, or the like can be used.
- Photocuring may be performed by irradiating for about 30 seconds to about 15 minutes, or about 1 minute to about 10 minutes, with the above dosage.
- the acrylate-based monomer due to shrinkage due to curing in the photocuring step may cause a curing shrinkage, or curl (curl) phenomenon that the resin substrate is rolled up with the coating layer.
- the curl phenomenon refers to a phenomenon in which a corner or the like is curved or curled when the film having a flat structure is laid out on a flat surface, which is a phenomenon that occurs when the acrylate shrinks during photocuring by ultraviolet rays.
- a hard coating film to be used as a cover for a mobile communication terminal such as a smartphone or a tablet PC
- the thickness of the hard coating layer must be increased to a predetermined thickness or more, for example, 50 ⁇ or more.
- the hard coating layer As the thickness increases, the curl phenomenon due to curing shrinkage also increases, thereby reducing the adhesive force and curling of the hard coat film. Therefore, it is not easy to manufacture a hard coating film of high hardness to the extent that glass can be replaced without deteriorating film properties.
- the hard coat film of the present invention when forming a hard coat film is applied to a thin release film that does not use a resin substrate without being affected by the shrinkage of the substrate without curing, so there is no fear of curl or cracks, 50 or more, eg Turn to form a hard coat film with a high thickness of 50 to 500.
- the resin substrate is not used, it is possible to provide a hard coating film having a high hardness without deterioration of physical properties required for the hard coating film such as hardness and layer resistance.
- a hard coating film formed as a single layer without a supporting substrate may be obtained.
- the hard coat film of the present invention exhibits excellent high hardness, layer resistance, scratch resistance, high transparency, durability, light resistance, light transmittance, and the like, and can be usefully used in various fields.
- the hard coat film of the present invention may have a good impact resistance to replace the glass.
- the hard coat film of the present invention may be free from cracking when 22g of iron ball is repeatedly dropped freely at a height of 50 cm 10 times.
- the hard coating film is formed by the hard coating film,
- the maximum value of the distance of each corner or one side of the hard coating film from the plane is about 1.0 mm or less, or about 0.6 or less than about mm, or about 0.3 mm or less. More specifically, after exposure to 70 to 100 hours at a temperature of 50 to 90 ° C and a humidity of 80 to 90% to be placed on a flat surface At this time, the maximum value of the distance of each corner or one side of the hard coating film from the plane may be about 1.0 mm or less, or about 0.6 mm or less, or about 0.3 mm or less.
- pencil hardness at 1kg load may be 7H or more, or 8H or more, or 9H or more.
- the hard coat film of the present invention may have a light transmittance of 91.0% or more or 92.0% or more, haze of 1.0% or less, or 5% or less, or 4% or less.
- the hard coating film of the present invention may have an initial color b value of 1.0 or less.
- the difference between the initial color b value and the color b value after 72 hours or more exposure to the UV lamp in the UVB wavelength region may be 0.5 or less, or 0.4 or less.
- Such a hard coat film of the present invention can be utilized in various fields. For example, it can be used for a touch panel of a mobile communication terminal, a smartphone or a tablet PC, and a cover substrate or an element substrate of various displays.
- a touch panel of a mobile communication terminal a smartphone or a tablet PC
- a cover substrate or an element substrate of various displays a cover substrate or an element substrate of various displays.
- the weight average molecular weight of the obtained polyrotasein was 600,000 g / mol, and elongation measured by ASTM D638 was 20%.
- DPHA silicon- dipentaerythrine nucleoacrylate
- the hard coating composition was applied onto a silicone treated PET film of 15 cm X 20 cm, thickness 100.
- photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp.
- Example 3 Except for the use of lg urethane acrylate-based polymer (trade name: UA200PA, Shinnakamura Chemical, weight average molecular weight 2,600 g / mol, elongation 170% according to ASTM D638) instead of polylotasein lg of Preparation Example 1 in the hard coating composition. And to prepare a hard coat film in the same manner as in Example 1.
- lg urethane acrylate-based polymer trade name: UA200PA, Shinnakamura Chemical, weight average molecular weight 2,600 g / mol, elongation 170% according to ASTM D638
- Example 4 Except for the use of lg urethane acrylate-based polymer (trade name: UA340P, Shinnakamura Chemical, weight average molecular weight 13,000 g / mol, elongation according to ASTM D638) lg instead of polyrotasein lg of Preparation Example 1 in the hard coating composition. And to prepare a hard coat film in the same manner as in Example 1.
- lg urethane acrylate-based polymer trade name: UA340P, Shinnakamura Chemical, weight average molecular weight 13,000 g / mol, elongation according to ASTM D638
- a hard coat film was prepared in the same manner as in Example 1, except that the thickness of the hard coat film was 250.
- Example 5
- a hard coat film was manufactured in the same manner as in Example 1, except that the hard coat film had a thickness of 300 after curing was completed in Example 1.
- a hard coat film was prepared in the same manner as in Example 1, except that the hard coat film had a thickness of 450 after curing was completed in Example 1. Comparative Example 1
- silica-dipentaerythri (DPHA) complexes containing about 40% by weight of nano-silica particles having a particle diameter of 20-30 nm (silica 4 g, DPHA 6 g), photoinitiator (trade name: Darocur TPO) 0.2 g, benzo Triazole-based yellowing inhibitor (trade name: Tinuvin 400) O.lg, fluorine-based surfactant (trade name: FC4430) 0.05g, methyl ethyl ketone lg was mixed to prepare a hard coating composition.
- DPHA silica-dipentaerythri
- the hardcoat composition was applied onto a 15 cm X 20 cm, 100 / m thick silicone treated PET film. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp.
- the PET film was peeled off.
- the thickness of the peeled hard coat film was 188.
- Major components and thicknesses of the hard coat films of Examples 1 to 6 and Comparative Example 1 are shown in Table 1 below.
- the number of grooves was evaluated after reciprocating 400 times with a load of 0.5 kg. O for 2 or less homes, ⁇ for 2 or more and 5 or less homes, and X for 5 or more homes.
- Each hard coating film was cut into 10 cm ⁇ 10 cm, stored in a chamber at a temperature of 85 ° C. and a humidity of 85% for 72 hours, and the maximum value of the distance at which one side of each corner was spaced apart from the plane was measured.
- Each hard-coating film is wrapped in a cylindrical mantel with a diameter of 3cm, and it is OK to determine if a crack has occurred. The case was evaluated by X. 7) Layer resistance
- Comparative Example 1 which does not include a photocurable elastomer, was found to have no impact resistance.
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Abstract
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JP2015528382A JP6110494B2 (ja) | 2012-08-23 | 2013-07-29 | ハードコーティングフィルム |
CN201380055244.3A CN104736612B (zh) | 2012-08-23 | 2013-07-29 | 硬涂膜 |
US14/423,418 US10280330B2 (en) | 2012-08-23 | 2013-07-29 | Hard coating film |
EP13830608.9A EP2873689B1 (en) | 2012-08-23 | 2013-07-29 | Hard coating film |
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KR20120092527 | 2012-08-23 | ||
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KR1020130089100A KR101436616B1 (ko) | 2012-08-23 | 2013-07-26 | 하드코팅 필름 |
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US (1) | US10280330B2 (ko) |
EP (1) | EP2873689B1 (ko) |
JP (1) | JP6110494B2 (ko) |
KR (1) | KR101436616B1 (ko) |
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EP2857440B1 (en) * | 2012-05-25 | 2021-11-10 | LG Chem, Ltd. | Hard coating film |
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JP6455993B2 (ja) | 2013-03-27 | 2019-01-23 | エルジー・ケム・リミテッド | 偏光子保護フィルム用樹脂組成物、偏光子保護フィルム、これを含む偏光板および偏光板の製造方法 |
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JP6110494B2 (ja) | 2017-04-05 |
JP2015533865A (ja) | 2015-11-26 |
TW201431914A (zh) | 2014-08-16 |
KR101436616B1 (ko) | 2014-09-03 |
EP2873689A4 (en) | 2016-01-20 |
US20150240109A1 (en) | 2015-08-27 |
KR20140027020A (ko) | 2014-03-06 |
TWI500668B (zh) | 2015-09-21 |
CN104736612A (zh) | 2015-06-24 |
EP2873689B1 (en) | 2020-03-04 |
US10280330B2 (en) | 2019-05-07 |
CN104736612B (zh) | 2018-03-02 |
EP2873689A1 (en) | 2015-05-20 |
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