[go: up one dir, main page]

WO2014171678A1 - Photocurable coating composition, coating film using same and polarizing plate - Google Patents

Photocurable coating composition, coating film using same and polarizing plate Download PDF

Info

Publication number
WO2014171678A1
WO2014171678A1 PCT/KR2014/003180 KR2014003180W WO2014171678A1 WO 2014171678 A1 WO2014171678 A1 WO 2014171678A1 KR 2014003180 W KR2014003180 W KR 2014003180W WO 2014171678 A1 WO2014171678 A1 WO 2014171678A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
coating composition
photocurable
photocurable coating
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2014/003180
Other languages
French (fr)
Korean (ko)
Other versions
WO2014171678A9 (en
Inventor
정병선
이두봉
임거산
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
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
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Priority to CN201480022058.4A priority Critical patent/CN105121565B/en
Priority to JP2016508860A priority patent/JP6348972B2/en
Publication of WO2014171678A1 publication Critical patent/WO2014171678A1/en
Publication of WO2014171678A9 publication Critical patent/WO2014171678A9/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate

Definitions

  • the present invention relates to a photocurable coating composition, a coating film, a polarizing plate, and a display device using the same, and more particularly, a photocurable coating composition which can be used in the manufacture of a coating film having excellent optical properties and mechanical properties, and excellent crack characteristics, It relates to a coating film formed using the same, a polarizing plate and a display device provided with the coating film.
  • the polarizing film used for image display apparatuses such as a liquid crystal display device, an electroluminescence (EL) display apparatus, a plasma display (PD), a field emission display (FED: field emission display), is generally iodine which is a dichroic dye, or The dichroic dye is manufactured by adsorption orientation of the polyvinyl alcohol-type resin film.
  • a protective film containing triacetyl cellulose or the like is bonded to at least one surface of the polarizing film to form a polarizing plate and used for a liquid crystal display device or the like.
  • the polarizing plate may include a coating film such as a hard coating film, an anti-glare film, an antireflection film, etc. to improve the function, and the coating film should not only have high transparency and low haze, but also have high hardness and good scratch resistance. In addition, it is desirable that no cracks occur during work or post-processing.
  • a coating film such as a hard coating film, an anti-glare film, an antireflection film, etc. to improve the function
  • the coating film should not only have high transparency and low haze, but also have high hardness and good scratch resistance. In addition, it is desirable that no cracks occur during work or post-processing.
  • an optical hard coating film having excellent optical properties and mechanical properties while having flexibility, a transparent plastic film or substrate as a base layer, and ethylene glycol on at least one side of the base layer Bifunctional or higher acrylate monomers having; At least one of a polyfunctional acrylate monomer and a polyfunctional urethane acrylate oligomer; And a hard coating film for optics provided with a hard coating layer on which a UV curable resin composition comprising silica fine particles is cured.
  • the optical hard coating film has a problem that a decrease in physical properties in the acrylic film substrate.
  • the present invention is to solve the above problems, an object of the present invention is excellent optical properties and mechanical properties and excellent cracking properties, photocurable coating composition that can be used in the production of a coating film using an acrylic film substrate To provide.
  • Another object of the present invention is to provide a coating film formed using the photocurable coating composition.
  • Still another object of the present invention is to provide a polarizing plate provided with the coating film.
  • Still another object of the present invention is to provide a display device provided with the coating film.
  • the present invention provides a photocurable coating composition having a storage modulus (G ′) of 4.0E + 07 to 7.0E + 07 Pa.
  • the present invention provides a coating film in which a coating layer including a cured product of the photocurable coating composition is formed on one or both surfaces of a transparent substrate.
  • the present invention provides a polarizing plate provided with the coating film.
  • the present invention provides a display device provided with the coating film.
  • the coating film formed using the photocurable coating composition according to the present invention has high transparency, low haze, high hardness, excellent scratch resistance, and excellent cracking properties, so that the coating film can be effectively used as a protective film of a polarizing plate. have.
  • One embodiment of the invention relates to a photocurable coating composition having a storage modulus (G ′) of 4.0E + 07 to 7.0E + 07 Pa.
  • the storage modulus refers to a storage modulus measured in a semi-cured state of the photocurable coating composition, specifically, just before UV curing is completed and immediately before UV irradiation is completed.
  • the method for measuring the storage modulus of the photocurable coating composition is not particularly limited, and may be measured by, for example, the method shown in the experimental example described later.
  • the coating film formed from the photocurable coating composition has excellent optical properties It can be made to exhibit excellent cracking properties while having and mechanical properties.
  • the composition of the photocurable coating composition is not particularly limited as long as it is formulated to have a storage modulus of 4.0E + 07 to 7.0E + 07 Pa.
  • the photocurable coating composition may comprise a photocurable (meth) acrylate oligomer.
  • the photocurable (meth) acrylate oligomer may be used at least one selected from the group consisting of epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate, specifically, urethane (meth) An acrylate and polyester (meth) acrylate can be mixed and used, or 2 types of polyester (meth) acrylate can be mixed and used.
  • the urethane (meth) acrylate may be prepared by reacting a polyfunctional (meth) acrylate having a hydroxyl group in a molecule with a compound having an isocyanate group in the presence of a catalyst according to methods known in the art.
  • polyfunctional (meth) acrylate having a hydroxy group in the molecule examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, and 4-hydroxybutyl (meth) acryl At least one selected from the group consisting of latex, caprolactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, and dipentaerythritol penta / hexa (meth) acrylate mixture.
  • the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2,4-diisocyanate,
  • the polyester (meth) acrylate may be prepared by reacting polyester polyol and acrylic acid according to methods known in the art.
  • the polyester (meth) acrylate is, for example, polyester acrylate, polyester diacrylate, polyester tetraacrylate, polyester hexaacrylate, polyester pentaerythritol triacrylate, polyester pentaerythritol tetraacrylic It may be selected from the group consisting of the rate, and polyester pentaerythritol hexaacrylate, but is not limited thereto.
  • the photocurable (meth) acrylate oligomer is preferably included in the photocurable coating composition of the present invention, based on 100 parts by weight, 92 to 99 parts by weight. If the content of the oligomer is less than 92 parts by weight, cracks may occur due to overcuring. If the content of the oligomer is more than 99 parts by weight, physical properties may be degraded due to uncuring.
  • the photocurable coating composition according to one embodiment of the present invention is a photocurable (meth) acrylate oligomer, which is a mixture of a tetrafunctional polyester (meth) acrylate and a monofunctional polyester (meth) acrylate or a tetrafunctional polyester ( And mixtures of meta) acrylates and 4- to 6-functional urethane (meth) acrylates.
  • the tetrafunctional polyester (meth) acrylate is preferably included in the photocurable coating composition of the present invention, 20 to 50 parts by weight based on 100 parts by weight of the solid content. If the content of the tetrafunctional polyester (meth) acrylate is less than 20 parts by weight, the cracking property is lowered, and if it exceeds 50 parts by weight, mechanical properties may be lowered.
  • the six-functional polyester (meth) acrylate is preferably included 45 to 75 parts by weight based on 100 parts by weight of the solids content of the photocurable coating composition of the present invention. If the content of the six-functional polyester (meth) acrylate is less than 45 parts by weight, the mechanical properties are lowered, and if it exceeds 75 parts by weight, the cracking property may occur.
  • the 4 to 6 functional urethane (meth) acrylate is preferably included in the photocurable coating composition of the present invention, 45 to 85 parts by weight based on 100 parts by weight of the solid content.
  • the content of the 4 to 6 functional urethane (meth) acrylate is less than 45 parts by weight, the mechanical properties are lowered, and when it exceeds 85 parts by weight, cracking property may occur.
  • the photocurable coating composition according to one embodiment of the present invention may be used including a photocurable monomer.
  • a monomer used in the art having a unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, and the like in a molecule can be used without limitation, and specifically (meth) The monomer which has an acryloyl group can be used.
  • the monomer having the (meth) acryloyl group is, for example, neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylic Rate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate , 1,2,4-cyclohexane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythr
  • the photocurable coating composition according to one embodiment of the present invention may further include a photoinitiator and a solvent.
  • the photoinitiator can be used without limitation so long as it is used in the art. Specifically, the photoinitiator may be used at least one selected from the group consisting of hydroxy ketones, amino ketones and hydrogen decyclic photoinitiator.
  • the photoinitiator is 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1 -Phenyl-1-one, 4-hydroxycyclophenylketone, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4- Knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, benzophenone, and diphenyl (2,4,6-trimethylbenzoyl) phosphine
  • One or more selected from the group consisting of oxides can be used.
  • the photoinitiator is preferably included from 0.05 to 10 parts by weight based on 100 parts by weight of the photocurable coating composition of the present invention. If the content of the photoinitiator is less than 0.05 parts by weight, the curing rate of the composition is slow and uncured to cause mechanical properties, and if more than 10 parts by weight, cracks may occur due to over curing.
  • the solvent is not particularly limited and may be used without limitation as long as it is used in the art. Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate and butyl acetate; nitromethane and N-methyl Nitrogen-containing compounds such as pyrrolidone and N, N-dimethylformamide; ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dioxolane; methylene chloride, chloroform, trichloroethane, tetrachloroethane and the like; Halogenated hydrocarbons; and other substances such as dimethyl sulfoxide, propylene carbonate and 2-methoxyethanol.
  • ketones such as acetone, methyl e
  • Solvents illustrated above can be used individually or in combination of 2 types or more, respectively. More specifically, one or more selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-methoxyethanol can be used.
  • the solvent is preferably included 0.1 to 85 parts by weight based on 100 parts by weight of the photocurable coating composition of the present invention.
  • the content of the solvent is less than 0.1 parts by weight, the viscosity is high, workability is lowered, and when it exceeds 85 parts by weight, there is a disadvantage in that it takes a lot of time in the drying and curing process.
  • the photocurable coating composition according to one embodiment of the present invention is a component generally used in the art, for example, an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a labeling agent. , Surfactants, lubricants, antifouling agents and the like may be additionally included.
  • Coating film according to an embodiment of the present invention is characterized in that the coating layer containing the cured product of the above-mentioned photocurable coating composition is formed on one side or both sides of the transparent substrate.
  • any plastic film having transparency can be used.
  • a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, cellulose (diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, Propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose), ethylene vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, Polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, poly
  • the uniaxial or biaxially stretched polyester film excellent in transparency and heat resistance among the above-described transparent substrates, or a cycloolefin derivative film capable of coping with the enlargement of the film while being excellent in transparency and heat resistance, transparency and optically anisotropy Triacetyl cellulose film free, high transparency and low cost acrylic copolymer film can be suitably used.
  • the thickness of the transparent substrate is not particularly limited, but may be 8 to 1000 ⁇ m, specifically 20 to 150 ⁇ m. If the thickness of the transparent substrate is less than 8 ⁇ m, the strength of the film is lowered, resulting in poor workability. If the thickness is greater than 1000 ⁇ m, the transparency is reduced or the weight of the polarizing plate is increased.
  • the coating film according to an embodiment of the present invention can be prepared by applying the photocurable coating composition of the present invention on one or both sides of the transparent substrate and curing to form a coating layer.
  • the photocurable coating composition according to one embodiment of the present invention is coated on a transparent substrate by appropriately using a known method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, spin coating, etc. Process) is possible.
  • the volatiles are dried by evaporation at a temperature of 30 to 150 °C for 10 seconds to 1 hour, more specifically for 30 seconds to 30 minutes, and then UV light Irradiate and harden.
  • the irradiation amount of the UV light may be specifically about 0.01 to 10J / cm2, more specifically 0.1 to 2J / cm2.
  • the thickness of the coating layer formed may be specifically 2 to 30um, more specifically 3 to 15um.
  • the thickness of the coating layer is included in the range can be obtained an excellent hardness effect.
  • Polarizing plate according to an embodiment of the present invention relates to a polarizing plate with a coating film described above.
  • Polarizing plate according to an embodiment of the present invention can be produced by laminating the above-described coating film on at least one side of the polarizing film.
  • the polarizing film is not particularly limited, and for example, a biaxial material such as iodine or a dichroic dye is adsorbed onto a hydrophilic polymer film such as a polyvinyl alcohol film or an ethylene-vinyl acetate copolymerized partial saponified film.
  • a hydrophilic polymer film such as a polyvinyl alcohol film or an ethylene-vinyl acetate copolymerized partial saponified film.
  • a stretched film, a polyene oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochloric acid processed product of polyvinyl chloride, or the like can be used.
  • those made of a dichroic substance such as a polyvinyl alcohol film and iodine can be used.
  • the thickness of these polarizing films is not specifically limited, Generally, it is about 5-80 micrometers.
  • One embodiment of the present invention relates to a display device provided with the above-described coating film.
  • a display device provided with the above-described coating film.
  • various display devices having excellent visibility can be manufactured.
  • the coating film of the present invention may be attached to the window of the display device.
  • the coating film according to an embodiment of the present invention can be used in a reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type.
  • the coating film according to one embodiment of the present invention can also be used in various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and an electronic paper.
  • Each component was mixed at a ratio (unit; wt%) as shown in Table 1 to prepare a photocurable coating composition.
  • Urethane acrylate urethane hexaacrylate (PU610)
  • Polyester acrylate (4-functional) polyester tetraacrylate (PS420)
  • Photoinitiator 1-hydroxycyclohexylphenyl ketone
  • the thickness of the Myerba so as to have a thickness of 6 ⁇ m on the transparent substrate film (80 ⁇ m, PMMA) After coating), and dried for 1 minute at 70 °C, and cured at 500mJ / cm 2 to prepare a coating film.
  • the storage modulus (G ′) of the composition was measured with a rheometer (Physica MCR-3xx, Anton Paar).
  • the prepared photocurable coating composition was placed in a 100 ° C. oven for 2 hours to completely dry the solvent, and then the residue was prepared as a measurement sample, and the prepared residue was placed on a bottom plate of a rheometer system, having a diameter of 8 mm.
  • the measuring spindle was placed 100 ⁇ m away from the bottom plate. Then, fix the spot-type UV illuminance to 33.3 MW / cm 2 (irradiation distance 57 mm, spot UV output 30%), and 20 points (20 points / 12 seconds) for 12 seconds at a frequency of 10 Hz at a strain of 0.01%. ) was measured to take the storage modulus value immediately before curing was completed.
  • the total light transmittance and total haze were measured with the spectrophotometer (HZ-1, Suga, Japan) facing the PMMA plane toward the light source D65.
  • the surface of the prepared coating film was subjected to a 500g load with a pencil hardness tester (PHT, Korea Seokbo Science Co., Ltd.) and the pencil hardness was measured. Pencils were made using Mitsubishi products, and were carried out five times for each pencil hardness. If there were two or more gases, it was determined to be defective, and pencil hardness was indicated by a pencil before the failure occurred.
  • PHT pencil hardness tester
  • the scratch resistance was tested by using a steel wool tester (WT-LCM100, Korea Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm ⁇ 2 cm). Steel wool used # 0000.
  • n number of rectangles not peeled off
  • the crack resistance judgment recorded the critical Mandrerel ⁇ in which no crack occurred.
  • the coating film exhibited excellent crack resistance while maintaining optical and mechanical properties.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention provides a photocurable coating composition having a storage elastic modulus (G') of 4.0E+07 to 7.0E+07 Pa, a coating film formed using same, a polarizing plate having the coating film and a display device. The coating film formed using the photocurable coating composition according to the invention can be effectively used as a protective film of the polarizing plate, etc. due to having excellent optical and mechanical physical properties, and thus having an excellent crack resistance property.

Description

광경화 코팅 조성물, 이를 이용한 코팅 필름 및 편광판 Photocurable coating composition, coating film and polarizing plate using the same

본 발명은 광경화 코팅 조성물, 이를 이용한 코팅 필름, 편광판 및 표시장치에 관한 것으로, 보다 상세하게는 광학적 물성과 기계적 물성이 우수하면서 크랙 특성이 우수한 코팅 필름의 제조에 사용될 수 있는 광경화 코팅 조성물, 이를 이용하여 형성되는 코팅 필름, 상기 코팅 필름이 구비된 편광판 및 표시장치에 관한 것이다.The present invention relates to a photocurable coating composition, a coating film, a polarizing plate, and a display device using the same, and more particularly, a photocurable coating composition which can be used in the manufacture of a coating film having excellent optical properties and mechanical properties, and excellent crack characteristics, It relates to a coating film formed using the same, a polarizing plate and a display device provided with the coating film.

액정 표시장치, 일렉트로루미네센스(EL) 표시장치, 플라즈마 디스플레이(PD), 전계 방출 디스플레이(FED: Field Emission Display) 등의 화상 표시장치에 사용하는 편광 필름은 일반적으로, 2색성 색소인 요오드 또는 2색성 염료를 폴리비닐알콜계 수지 필름에 흡착 배향시켜 제조되고 있다. 이 편광 필름의 적어도 한 면에 접착제층을 통해 트리아세틸셀룰로오스 등을 포함하는 보호 필름을 접합하여 편광판으로 만들어 액정 표시장치 등에 이용한다.The polarizing film used for image display apparatuses, such as a liquid crystal display device, an electroluminescence (EL) display apparatus, a plasma display (PD), a field emission display (FED: field emission display), is generally iodine which is a dichroic dye, or The dichroic dye is manufactured by adsorption orientation of the polyvinyl alcohol-type resin film. A protective film containing triacetyl cellulose or the like is bonded to at least one surface of the polarizing film to form a polarizing plate and used for a liquid crystal display device or the like.

편광판에는 기능 향상을 위해, 하드코팅 필름, 방현성 필름, 반사방지 필름 등의 코팅 필름이 포함될 수 있으며, 이러한 코팅 필름은 투명도가 높고 헤이즈가 낮아야 하며, 경도가 높고 내스크래치성이 좋아야 할 뿐만 아니라, 작업이나 후공정시 크랙이 발생하지 않는 것이 바람직하다.The polarizing plate may include a coating film such as a hard coating film, an anti-glare film, an antireflection film, etc. to improve the function, and the coating film should not only have high transparency and low haze, but also have high hardness and good scratch resistance. In addition, it is desirable that no cracks occur during work or post-processing.

대한민국 등록특허 제10-1127952호에는, 광학적 물성과 기계적 물성이 우수하면서도 유연성을 갖춘 광학용 하드코팅 필름으로서, 기재층으로서 투명성 플라스틱 필름 또는 기판, 및 상기 기재층의 적어도 한 면에, 에틸렌글리콜을 갖는 2관능 이상의 아크릴레이트계 모노머; 다관능 아크릴레이트계 모노머 및 다관능 우레탄 아크릴레이트계 올리고머 중 적어도 1종; 및 실리카 미립자를 포함하는 UV 경화형 수지 조성물이 경화된 하드코팅층이 구비된 광학용 하드코팅 필름이 개시되어 있다. 그러나, 상기 광학용 하드코팅 필름은 아크릴계 필름 기재에서 물성 저하가 발생하는 문제점이 있다.Republic of Korea Patent No. 10-1127952, an optical hard coating film having excellent optical properties and mechanical properties while having flexibility, a transparent plastic film or substrate as a base layer, and ethylene glycol on at least one side of the base layer Bifunctional or higher acrylate monomers having; At least one of a polyfunctional acrylate monomer and a polyfunctional urethane acrylate oligomer; And a hard coating film for optics provided with a hard coating layer on which a UV curable resin composition comprising silica fine particles is cured. However, the optical hard coating film has a problem that a decrease in physical properties in the acrylic film substrate.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 본 발명의 한 목적은 광학적 물성과 기계적 물성이 우수하면서 크랙 특성이 우수하며, 아크릴계 필름 기재를 사용한 코팅 필름의 제조에 사용될 수 있는 광경화 코팅 조성물을 제공하는 것이다.The present invention is to solve the above problems, an object of the present invention is excellent optical properties and mechanical properties and excellent cracking properties, photocurable coating composition that can be used in the production of a coating film using an acrylic film substrate To provide.

본 발명의 다른 목적은 상기 광경화 코팅 조성물을 이용하여 형성되는 코팅 필름를 제공하는 것이다.Another object of the present invention is to provide a coating film formed using the photocurable coating composition.

본 발명의 또 다른 목적은 상기 코팅 필름이 구비된 편광판을 제공하는 것이다.Still another object of the present invention is to provide a polarizing plate provided with the coating film.

본 발명의 또 다른 목적은 상기 코팅 필름이 구비된 표시장치를 제공하는 것이다.Still another object of the present invention is to provide a display device provided with the coating film.

한편으로, 본 발명은 저장탄성율(G')이 4.0E+07 내지 7.0E+07 Pa인 광경화 코팅 조성물을 제공한다.On the other hand, the present invention provides a photocurable coating composition having a storage modulus (G ′) of 4.0E + 07 to 7.0E + 07 Pa.

다른 한편으로, 본 발명은 투명기재의 한면 또는 양면에 상기 광경화 코팅 조성물의 경화물을 포함하는 코팅층이 형성되어 있는 코팅 필름을 제공한다.On the other hand, the present invention provides a coating film in which a coating layer including a cured product of the photocurable coating composition is formed on one or both surfaces of a transparent substrate.

또 다른 한편으로, 본 발명은 상기 코팅 필름이 구비된 편광판을 제공한다.On the other hand, the present invention provides a polarizing plate provided with the coating film.

또 다른 한편으로, 본 발명은 상기 코팅 필름이 구비된 표시장치를 제공한다.On the other hand, the present invention provides a display device provided with the coating film.

본 발명에 따른 광경화 코팅 조성물을 이용하여 형성되는 코팅 필름은 투명도가 높고 헤이즈가 낮으며, 경도가 높고 내스크래치성이 우수할 뿐만 아니라, 크랙 특성이 우수하므로 편광판의 보호 필름 등으로 효과적으로 사용될 수 있다.The coating film formed using the photocurable coating composition according to the present invention has high transparency, low haze, high hardness, excellent scratch resistance, and excellent cracking properties, so that the coating film can be effectively used as a protective film of a polarizing plate. have.

이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 일 실시형태는 저장탄성율(G')이 4.0E+07 내지 7.0E+07 Pa인 광경화 코팅 조성물에 관한 것이다.One embodiment of the invention relates to a photocurable coating composition having a storage modulus (G ′) of 4.0E + 07 to 7.0E + 07 Pa.

본 발명에서 저장탄성율은 광경화 코팅 조성물을 반경화시킨 상태, 구체적으로 경화가 완료되기 직전까지 UV를 조사하고 UV 조사가 완료되기 직전에 측정한 저장탄성율을 의미한다. 본 발명에서 광경화 코팅 조성물의 저장탄성율을 측정하는 방법은 특별히 제한되지 않으며, 예를 들면 후술하는 실험예에 제시된 방법으로 측정할 수 있다.In the present invention, the storage modulus refers to a storage modulus measured in a semi-cured state of the photocurable coating composition, specifically, just before UV curing is completed and immediately before UV irradiation is completed. In the present invention, the method for measuring the storage modulus of the photocurable coating composition is not particularly limited, and may be measured by, for example, the method shown in the experimental example described later.

본 발명의 일 실시형태에서는, 광경화 코팅 조성물의 반경화 상태에서의 저장탄성율을 4.0E+07 내지 7.0E+07 Pa의 범위로 조절함으로써, 광경화 코팅 조성물로부터 형성되는 코팅 필름이 우수한 광학적 물성과 기계적 물성을 가지면서 우수한 크랙 특성을 나타내도록 할 수 있다. In one embodiment of the present invention, by adjusting the storage modulus in the semi-cured state of the photocurable coating composition in the range of 4.0E + 07 to 7.0E + 07 Pa, the coating film formed from the photocurable coating composition has excellent optical properties It can be made to exhibit excellent cracking properties while having and mechanical properties.

본 발명의 일 실시형태에서, 광경화 코팅 조성물의 조성은, 4.0E+07 내지 7.0E+07 Pa의 저장탄성율을 가질 수 있도록 조성되는 한 특별히 제한되지 않는다.In one embodiment of the present invention, the composition of the photocurable coating composition is not particularly limited as long as it is formulated to have a storage modulus of 4.0E + 07 to 7.0E + 07 Pa.

본 발명의 일 실시형태에서, 광경화 코팅 조성물은 광경화형 (메타)아크릴레이트 올리고머를 포함할 수 있다.In one embodiment of the present invention, the photocurable coating composition may comprise a photocurable (meth) acrylate oligomer.

상기 광경화형 (메타)아크릴레이트 올리고머는 에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트 및 폴리에스테르 (메타)아크릴레이트로 구성된 군으로부터 선택된 1종 이상을 사용할 수 있으며, 구체적으로 우레탄 (메타)아크릴레이트와 폴리에스테르 (메타)아크릴레이트를 혼합하여 사용하거나, 2종의 폴리에스테르 (메타)아크릴레이트를 혼합하여 사용할 수 있다. The photocurable (meth) acrylate oligomer may be used at least one selected from the group consisting of epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate, specifically, urethane (meth) An acrylate and polyester (meth) acrylate can be mixed and used, or 2 types of polyester (meth) acrylate can be mixed and used.

상기 우레탄 (메타)아크릴레이트는 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트와 이소시아네이트기를 갖는 화합물을 당업계에 공지된 방법에 따라 촉매 존재 하에서 반응시켜 제조할 수 있다. 상기 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트의 구체적인 예는, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시이소프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 카프로락톤 개환 히드록시아크릴레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트 혼합물 및 디펜타에리스리톨펜타/헥사(메타)아크릴레이트 혼합물로 이루어진 군으로부터 선택되는 1종 이상일 수 있다. 또한 상기 이소시아네이트기를 갖는 화합물의 구체적인 예는, 1,4-디이소시아나토부탄, 1,6-디이소시아나토헥산, 1,8-디이소시아나토옥탄, 1,12-디이소시아나토도데칸, 1,5-디이소시아나토-2-메틸펜탄, 트리메틸-1,6-디이소시아나토헥산, 1,3-비스(이소시아나토메틸)시클로헥산, 트랜스-1,4-시클로헥센디이소시아네이트, 4,4'-메틸렌비스(시클로헥실이소시아네이트), 이소포론디이소시아네이트, 톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트, 자일렌-1,4-디이소시아네이트, 테트라메틸자일렌-1,3-디이소시아네이트, 1-클로로메틸-2,4-디이소시아네이트, 4,4'-메틸렌비스(2,6-디메틸페닐이소시아네이트), 4,4'-옥시비스(페닐이소시아네이트), 헥사메틸렌디이소시아네이트로부터 유도되는 3관능 이소시아네이트, 및 트리메탄프로판올어덕트톨루엔디이소시아네이트로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The urethane (meth) acrylate may be prepared by reacting a polyfunctional (meth) acrylate having a hydroxyl group in a molecule with a compound having an isocyanate group in the presence of a catalyst according to methods known in the art. Specific examples of the polyfunctional (meth) acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, and 4-hydroxybutyl (meth) acryl At least one selected from the group consisting of latex, caprolactone ring-opening hydroxyacrylate, pentaerythritol tri / tetra (meth) acrylate mixture, and dipentaerythritol penta / hexa (meth) acrylate mixture. Specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenylisocyanate), 4,4'-oxybis (phenylisocyanate), hexamethylene diisocyanate Trifunctional Isocyanates Derived from and Trimethane Propanol Adduct Toluene Diisosi It may be at least one member selected from the group consisting of a carbonate.

상기 폴리에스테르 (메타)아크릴레이트는 폴리에스테르 폴리올과 아크릴 산을 당업계에 공지된 방법에 따라 반응시켜 제조할 수 있다. 상기 폴리에스테르 (메타)아크릴레이트는 예를 들어, 폴리에스테르 아크릴레이트, 폴리에스테르 디아크릴레이트, 폴리에스테르 테트라아크릴레이트, 폴리에스테르 헥사아크릴레이트, 폴리에스테르 펜타에리스리톨 트리아크릴레이트, 폴리에스테르 펜타에리스리톨 테트라아크릴레이트, 및 폴리에스테르 펜타에리스리톨 헥사아크릴레이트로 이루어진 군에서 1종 이상 선택될 수 있으나, 이들만으로 한정되는 것은 아니다.The polyester (meth) acrylate may be prepared by reacting polyester polyol and acrylic acid according to methods known in the art. The polyester (meth) acrylate is, for example, polyester acrylate, polyester diacrylate, polyester tetraacrylate, polyester hexaacrylate, polyester pentaerythritol triacrylate, polyester pentaerythritol tetraacrylic It may be selected from the group consisting of the rate, and polyester pentaerythritol hexaacrylate, but is not limited thereto.

상기 광경화형 (메타)아크릴레이트 올리고머는 본 발명의 광경화 코팅 조성물 중 고형분 함량 기준 100 중량부에 대하여, 92 내지 99 중량부 포함되는 것이 바람직하다. 상기 올리고머의 함량이 92 중량부 미만이면 과경화로 인한 크랙이 발생할 수 있고, 99 중량부를 초과하면 미경화로 인해 물성 저하 문제가 발생할 수 있다.The photocurable (meth) acrylate oligomer is preferably included in the photocurable coating composition of the present invention, based on 100 parts by weight, 92 to 99 parts by weight. If the content of the oligomer is less than 92 parts by weight, cracks may occur due to overcuring. If the content of the oligomer is more than 99 parts by weight, physical properties may be degraded due to uncuring.

본 발명의 일 실시형태에 따른 광경화 코팅 조성물은 광경화형 (메타)아크릴레이트 올리고머로서, 4관능 폴리에스테르 (메타)아크릴레이트와 6관능 폴리에스테르 (메타)아크릴레이트의 혼합물 또는 4관능 폴리에스테르 (메타)아크릴레이트와 4내지 6관능 우레탄 (메타)아크릴레이트의 혼합물을 포함할 수 있다.The photocurable coating composition according to one embodiment of the present invention is a photocurable (meth) acrylate oligomer, which is a mixture of a tetrafunctional polyester (meth) acrylate and a monofunctional polyester (meth) acrylate or a tetrafunctional polyester ( And mixtures of meta) acrylates and 4- to 6-functional urethane (meth) acrylates.

상기 4관능 폴리에스테르 (메타)아크릴레이트는 본 발명의 광경화 코팅 조성물 중 고형분 함량 기준 100 중량부에 대하여, 20 내지 50 중량부 포함되는 것이 바람직하다. 상기 4관능 폴리에스테르 (메타)아크릴레이트의 함량이 20 중량부 미만이면 크랙 특성이 저하되고, 50 중량부를 초과하면 기계적 물성 저하가 발생할 수 있다.The tetrafunctional polyester (meth) acrylate is preferably included in the photocurable coating composition of the present invention, 20 to 50 parts by weight based on 100 parts by weight of the solid content. If the content of the tetrafunctional polyester (meth) acrylate is less than 20 parts by weight, the cracking property is lowered, and if it exceeds 50 parts by weight, mechanical properties may be lowered.

또한, 상기 6관능 폴리에스테르 (메타)아크릴레이트는 본 발명의 광경화 코팅 조성물 중 고형분 함량 기준 100 중량부에 대하여, 45 내지 75 중량부 포함되는 것이 바람직하다. 상기 6관능 폴리에스테르 (메타)아크릴레이트의 함량이 45 중량부 미만이면 기계적 물성이 저하되고, 75 중량부를 초과할 경우에는 크랙 특성의 저하가 발생할 수 있다.In addition, the six-functional polyester (meth) acrylate is preferably included 45 to 75 parts by weight based on 100 parts by weight of the solids content of the photocurable coating composition of the present invention. If the content of the six-functional polyester (meth) acrylate is less than 45 parts by weight, the mechanical properties are lowered, and if it exceeds 75 parts by weight, the cracking property may occur.

아울러, 상기 4 내지 6관능의 우레탄 (메타)아크릴레이트는 본 발명의 광경화 코팅 조성물 중 고형분 함량 기준 100 중량부에 대하여, 45 내지 85 중량부 포함되는 것이 바람직하다. 상기 4 내지 6관능의 우레탄 (메타)아크릴레이트의 함량이 45 중량부 미만이면 기계적 물성이 저하되고, 85 중량부를 초과할 경우 크랙 특성 저하가 발생할 수 있다In addition, the 4 to 6 functional urethane (meth) acrylate is preferably included in the photocurable coating composition of the present invention, 45 to 85 parts by weight based on 100 parts by weight of the solid content. When the content of the 4 to 6 functional urethane (meth) acrylate is less than 45 parts by weight, the mechanical properties are lowered, and when it exceeds 85 parts by weight, cracking property may occur.

본 발명의 일 실시형태에 따른 광경화 코팅 조성물은 광경화형 모노머를 포함하여 사용할 수 있다.The photocurable coating composition according to one embodiment of the present invention may be used including a photocurable monomer.

상기 모노머로는 광경화형 관능기로 (메타)아크릴로일기, 비닐기, 스티릴기, 알릴기 등의 불포화기를 분자내에 갖는, 당해 기술분야에서 사용되는 모노머를 제한 없이 사용할 수 있으며, 구체적으로 (메타)아크릴로일기를 갖는 모노머를 사용할 수 있다. As the monomer, a monomer used in the art having a unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, and the like in a molecule can be used without limitation, and specifically (meth) The monomer which has an acryloyl group can be used.

상기 (메타)아크릴로일기를 갖는 모노머는 예를 들어, 네오펜틸글리콜아크릴레이트, 1,6-헥산디올(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올에탄트리(메타)아크릴레이트, 1,2,4-시클로헥산테트라(메타)아크릴레이트, 펜타글리세롤트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 트리펜타에리스리톨트리(메타)아크릴레이트, 트리펜타에리스리톨헥사(메타)아크릴레이트, 비스(2-히드록시에틸)이소시아누레이트디(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 히드록시프로필(메타)아크릴레이트, 히드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소덱실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라히드로퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 및 이소보네올(메타)아크릴레이트로 이루어진 군으로부터 선택된 1종 이상일 수 있으나, 이들만으로 한정되는 것은 아니다.The monomer having the (meth) acryloyl group is, for example, neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylic Rate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate , 1,2,4-cyclohexane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate, hydrate Roxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Phenoxyethyl (meth) acrylate, and isobornol (meth) acrylate may be one or more selected from the group consisting of, but is not limited thereto.

특히, 상기 4관능 폴리에스테르 (메타)아크릴레이트와 혼합물 조성으로 포함되는 (메타)아크릴레이트의 함량 범위 내에서 광경화형 모노머를 대체하여 사용함으로써 광경화 코팅 조성물의 작업성 및 상용성을 증가시킬 수 있고, 동등 수준의 특성을 얻을 수 있다.In particular, by replacing the photocurable monomer within the content range of the (meth) acrylate contained in the mixture composition with the tetrafunctional polyester (meth) acrylate can increase the workability and compatibility of the photocurable coating composition And equivalent characteristics can be obtained.

본 발명의 일 실시형태에 따른 광경화 코팅 조성물은 광개시제 및 용제를 추가로 포함할 수 있다.The photocurable coating composition according to one embodiment of the present invention may further include a photoinitiator and a solvent.

상기 광개시제로는 당해 기술분야에서 사용되는 것이라면 제한 없이 사용할 수 있다. 구체적으로, 상기 광개시제로는 히드록시케톤류, 아미노케톤류 및 수소탈환형 광개시제로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.The photoinitiator can be used without limitation so long as it is used in the art. Specifically, the photoinitiator may be used at least one selected from the group consisting of hydroxy ketones, amino ketones and hydrogen decyclic photoinitiator.

예를 들어, 상기 광개시제로는 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1, 디페닐케톤, 벤질디메틸케탈, 2-히드록시-2-메틸-1-페닐-1-온, 4-히드록시시클로페닐케톤, 2,2-디메톡시-2-페닐-아세토페논, 안트라퀴논, 플루오렌, 트리페닐아민, 카바졸, 3-메틸아세토페논, 4-크놀로아세토페논, 4,4-디메톡시아세토페논, 4,4-디아미노벤조페논, 1-히드록시시클로헥실페닐케톤, 벤조페논, 및 디페닐(2,4,6-트리메틸벤조일)포스핀옥사이드로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. For example, the photoinitiator is 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenylketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1 -Phenyl-1-one, 4-hydroxycyclophenylketone, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4- Knoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, benzophenone, and diphenyl (2,4,6-trimethylbenzoyl) phosphine One or more selected from the group consisting of oxides can be used.

상기 광개시제는 본 발명의 광경화 코팅 조성물 100 중량부에 대하여 0.05 내지 10 중량부 포함되는 것이 바람직하다. 상기 광개시제의 함량이 0.05 중량부 미만이면 조성물의 경화 속도가 늦고 미경화가 발생하여 기계적 물성이 떨어지고, 10 중량부 이상이면 과경화로 크랙이 발생할 수 있다.The photoinitiator is preferably included from 0.05 to 10 parts by weight based on 100 parts by weight of the photocurable coating composition of the present invention. If the content of the photoinitiator is less than 0.05 parts by weight, the curing rate of the composition is slow and uncured to cause mechanical properties, and if more than 10 parts by weight, cracks may occur due to over curing.

상기 용제는 특별히 한정되지 않으며, 당해 기술분야에서 사용되는 것이라면 제한 없이 사용할 수 있다. 구체적으로, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논, 디아세톤알코올 등의 케톤류； 포름산메틸, 초산메틸, 초산에틸, 젖산에틸, 초산부틸 등의 에스테르류； 니트로메탄, N-메틸피롤리돈, N,N-디메틸포름아미드 등의 함질소 화합물； 디이소프로필에테르, 테트라히드로푸란, 디옥산, 디옥솔란 등의 에테르류； 염화메틸렌, 클로로포름, 트리클로로에탄, 테트라클로로에탄 등의 할로겐화 탄화수소； 디메틸술폭시드, 탄산프로필렌, 2-메톡시에탄올 등의 기타 물질을 들 수 있다. 상기 예시된 용제들은 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 보다 구체적으로, 초산메틸, 초산에틸, 초산부틸, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥사논 및 2-메톡시에탄올로 구성된 군으로부터 선택된 1종 이상을 사용할 수 있다.The solvent is not particularly limited and may be used without limitation as long as it is used in the art. Specifically, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate and butyl acetate; nitromethane and N-methyl Nitrogen-containing compounds such as pyrrolidone and N, N-dimethylformamide; ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dioxolane; methylene chloride, chloroform, trichloroethane, tetrachloroethane and the like; Halogenated hydrocarbons; and other substances such as dimethyl sulfoxide, propylene carbonate and 2-methoxyethanol. Solvents illustrated above can be used individually or in combination of 2 types or more, respectively. More specifically, one or more selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-methoxyethanol can be used.

상기 용제는 본 발명의 광경화 코팅 조성물 100 중량부에 대하여 0.1 내지 85 중량부 포함되는 것이 바람직하다. 상기 용제의 함량이 0.1 중량부 미만이면 점도가 높아 작업성이 떨어지고, 85 중량부를 초과할 경우에는 건조 및 경화 과정에서 많은 시간이 소요되는 단점이 있다. The solvent is preferably included 0.1 to 85 parts by weight based on 100 parts by weight of the photocurable coating composition of the present invention. When the content of the solvent is less than 0.1 parts by weight, the viscosity is high, workability is lowered, and when it exceeds 85 parts by weight, there is a disadvantage in that it takes a lot of time in the drying and curing process.

본 발명의 일 실시형태에 따른 광경화 코팅 조성물은 상기한 성분들 이외에도, 당해 기술분야에서 일반적으로 사용되는 성분들, 예를 들어 항산화제, UV 흡수제, 광안정제, 열적 고분자화 금지제, 레블링제, 계면활성제, 윤활제, 방오제 등이 추가적으로 포함될 수 있다.In addition to the above components, the photocurable coating composition according to one embodiment of the present invention is a component generally used in the art, for example, an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a labeling agent. , Surfactants, lubricants, antifouling agents and the like may be additionally included.

본 발명의 일 실시형태는 상술한 광경화 코팅 조성물을 이용하여 형성되는 코팅 필름에 관한 것이다. 본 발명의 일 실시형태에 따른 코팅 필름은 투명기재의 한면 또는 양면에 상술한 광경화 코팅 조성물의 경화물을 포함하는 코팅층이 형성되어 있는 것을 특징으로 한다.One embodiment of the present invention relates to a coating film formed using the photocurable coating composition described above. Coating film according to an embodiment of the present invention is characterized in that the coating layer containing the cured product of the above-mentioned photocurable coating composition is formed on one side or both sides of the transparent substrate.

상기 투명기재로는 투명성이 있는 플라스틱 필름이면 어떤 것이라도 사용 가능하다. 예를 들면, 노르보르넨이나 다환 노르보르넨계 단량체와 같은 시클로올레핀을 포함하는 단량체의 단위를 갖는 시클로올레핀계 유도체, 셀룰로오스(디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부틸레이트, 이소부틸에스테르셀룰로오스, 프로피오닐셀룰로오스, 부티릴셀룰로오스, 아세틸프로피오닐셀룰로오스), 에틸렌아세트산비닐공중합체, 폴리에스테르, 폴리스티렌, 폴리아미드, 폴리에테르이미드, 폴리아크릴, 폴리이미드, 폴리에테르술폰, 폴리술폰, 폴리에틸렌, 폴리프로필렌, 폴리메틸펜텐, 폴리염화비닐, 폴리염화비닐리덴, 폴리비닐알콜, 폴리비닐아세탈, 폴리에테르케톤, 폴리에테르에테르케톤, 폴리에테르술폰, 폴리메틸메타아크릴레이트, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리우레탄 및 에폭시 중에서 선택하여 사용할 수 있으며, 미연신, 1축 또는 2축 연신 필름을 사용할 수 있다.As the transparent substrate, any plastic film having transparency can be used. For example, a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene monomer, cellulose (diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl ester cellulose, Propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose), ethylene vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, Polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, Polyethylene naphthalene , Polycarbonate, polyurethane, and epoxy can be selected and used, and an unoriented, uniaxial or biaxially oriented film can be used.

구체적으로는, 상기 예시한 투명기재 중에서도 투명성 및 내열성이 우수한 1축 또는 2축 연신 폴리에스테르 필름이나, 투명성 및 내열성이 우수하면서 필름의 대형화에 대응할 수 있는 시클로올레핀계 유도체 필름, 투명성 및 광학적으로 이방성이 없는 트리아세틸셀룰로오스 필름, 높은 투명성과 저가인 아크릴계 공중합체 필름이 적합하게 사용될 수 있다. Specifically, the uniaxial or biaxially stretched polyester film excellent in transparency and heat resistance among the above-described transparent substrates, or a cycloolefin derivative film capable of coping with the enlargement of the film while being excellent in transparency and heat resistance, transparency and optically anisotropy Triacetyl cellulose film free, high transparency and low cost acrylic copolymer film can be suitably used.

상기 투명기재의 두께는 특별히 제한되지 않으나, 8 내지 1000㎛, 구체적으로는 20 내지 150㎛일 수 있다. 상기 투명기재의 두께가 8㎛ 미만이면 필름의 강도가 저하되어 가공성이 떨어지게 되고, 1000㎛ 초과이면 투명성이 저하되거나 편광판의 중량이 커지는 문제가 발생한다.The thickness of the transparent substrate is not particularly limited, but may be 8 to 1000 μm, specifically 20 to 150 μm. If the thickness of the transparent substrate is less than 8 μm, the strength of the film is lowered, resulting in poor workability. If the thickness is greater than 1000 μm, the transparency is reduced or the weight of the polarizing plate is increased.

본 발명의 일 실시형태에 따른 코팅 필름은 투명기재의 한면 또는 양면에 본 발명의 광경화 코팅 조성물을 도포하고 경화시켜 코팅층을 형성시킴으로써 제조할 수 있다.The coating film according to an embodiment of the present invention can be prepared by applying the photocurable coating composition of the present invention on one or both sides of the transparent substrate and curing to form a coating layer.

본 발명의 일 실시형태에 따른 광경화 코팅 조성물은 다이코터, 에어 나이프, 리버스 롤, 스프레이, 블레이드, 캐스팅, 그라비아, 마이크로 그라비아, 스핀코팅 등 공지된 방식을 적절히 사용하여, 투명기재에 도공(Coating Process)이 가능하다.The photocurable coating composition according to one embodiment of the present invention is coated on a transparent substrate by appropriately using a known method such as die coater, air knife, reverse roll, spray, blade, casting, gravure, micro gravure, spin coating, etc. Process) is possible.

상기 광경화 코팅 조성물을 투명기재에 도포한 후에는, 30 내지 150℃의 온도에서 10초 내지 1시간 동안, 보다 구체적으로는 30초 내지 30분 동안 휘발물을 증발시켜 건조시킨 다음, UV광을 조사하여 경화시킨다. 상기 UV광의 조사량은 구체적으로 약 0.01 내지 10J/㎠일 수 있으며, 보다 구체적으로 0.1 내지 2J/㎠일 수 있다.After applying the photocurable coating composition to a transparent substrate, the volatiles are dried by evaporation at a temperature of 30 to 150 ℃ for 10 seconds to 1 hour, more specifically for 30 seconds to 30 minutes, and then UV light Irradiate and harden. The irradiation amount of the UV light may be specifically about 0.01 to 10J / ㎠, more specifically 0.1 to 2J / ㎠.

이때, 형성되는 코팅층의 두께는 구체적으로 2 내지 30um, 보다 구체적으로 3 내지 15um일 수 있다. 상기 코팅층의 두께가 상기 범위 내에 포함될 경우 우수한 경도 효과를 얻을 수 있다.At this time, the thickness of the coating layer formed may be specifically 2 to 30um, more specifically 3 to 15um. When the thickness of the coating layer is included in the range can be obtained an excellent hardness effect.

본 발명의 일 실시형태는 상술한 코팅 필름이 구비된 편광판에 관한 것이다. 본 발명의 일 실시형태에 따른 편광판은 상술한 코팅 필름을 편광필름의 적어도 한면에 적층하여 제조할 수 있다.One embodiment of the present invention relates to a polarizing plate with a coating film described above. Polarizing plate according to an embodiment of the present invention can be produced by laminating the above-described coating film on at least one side of the polarizing film.

상기 편광필름은 특별하게 제한되지 않으며, 예를 들면 폴리비닐 알코올계 필름, 에틸렌-비닐 아세테이트 공중합체계 부분 비누화 필름 등의 친수성 고분자 필름에, 요오드나 2색성 염료 등의 2색성 물질을 흡착시켜 1축 연신한 필름, 폴리비닐 알코올의 탈수처리물이나 폴리염화비닐의 탈염산처리물 등 폴리엔계 배향 필름 등이 사용될 수 있다. 구체적으로는, 폴리비닐 알코올계 필름과 요오드 등의 2색성 물질로 이루어지는 것이 사용될 수 있다. 이들 편광필름의 두께는 특별하게 제한되지 않지만, 일반적으로는 5 내지 80㎛ 정도이다. The polarizing film is not particularly limited, and for example, a biaxial material such as iodine or a dichroic dye is adsorbed onto a hydrophilic polymer film such as a polyvinyl alcohol film or an ethylene-vinyl acetate copolymerized partial saponified film. A stretched film, a polyene oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochloric acid processed product of polyvinyl chloride, or the like can be used. Specifically, those made of a dichroic substance such as a polyvinyl alcohol film and iodine can be used. Although the thickness of these polarizing films is not specifically limited, Generally, it is about 5-80 micrometers.

본 발명의 일 실시형태는 상술한 코팅 필름이 구비된 표시장치에 관한 것이다. 일례로, 본 발명의 코팅 필름이 구비된 편광판을 표시장치에 내장함으로써, 가시성이 우수한 다양한 표시장치를 제조할 수 있다.　 또한, 본 발명의 코팅 필름을 표시장치의 윈도우에 부착시킬 수도 있다.One embodiment of the present invention relates to a display device provided with the above-described coating film. For example, by incorporating a polarizing plate with a coating film of the present invention into a display device, various display devices having excellent visibility can be manufactured. In addition, the coating film of the present invention may be attached to the window of the display device.

본 발명의 일 실시형태에 따른 코팅 필름은 반사형, 투과형, 반투과형 LCD 또는 TN형, STN형, OCB형, HAN형, VA형, IPS형 등의 각종 구동 방식의 LCD에 사용될 수 있다.　 또한, 본 발명의 일 실시형태에 따른 코팅 필름은 플라즈마 디스플레이, 필드 에미션 디스플레이, 유기 EL 디스플레이, 무기 EL 디스플레이, 전자 페이퍼 등의 각종 표시장치에도 사용될 수 있다.The coating film according to an embodiment of the present invention can be used in a reflective, transmissive, semi-transmissive LCD or LCD of various driving methods such as TN type, STN type, OCB type, HAN type, VA type, and IPS type. In addition, the coating film according to one embodiment of the present invention can also be used in various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and an electronic paper.

이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. These examples, comparative examples and experimental examples are only for illustrating the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.

실시예 1 내지 7 및 비교예 1 내지 6: 광경화 코팅 조성물의 제조Examples 1-7 and Comparative Examples 1-6: Preparation of Photocurable Coating Compositions

하기 표 1 에 나타낸 바와 같은 비율(단위; 중량%)로 각 성분들을 혼합하여 광경화 코팅 조성물을 제조하였다.Each component was mixed at a ratio (unit; wt%) as shown in Table 1 to prepare a photocurable coating composition.

표 1 우레탄아크릴레이트 폴리에스테르아크릴레이트 모노머 용제 광개시제 첨가제 6관능 6관능 4관능 3관능 실시예1 28 12 57.7 2.0 0.3 실시예2 24 16 57.7 2.0 0.3 실시예3 20 20 57.7 2.0 0.3 실시예4 4.8 8 27.2 57.7 2.0 0.3 실시예5 4.2 12 23.8 57.7 2.0 0.3 실시예6 3.6 16 20.4 57.7 2.0 0.3 실시예7 3 20 17 57.7 2.0 0.3 비교예1 2.4 24 13.6 57.7 2.0 0.3 비교예2 16 24 57.7 2.0 0.3 비교예3 40 57.7 2.0 0.3 비교예4 40 57.7 2.0 0.3 비교예5 40 57.7 2.0 0.3 비교예6 40 57.7 2.0 0.3 Table 1 Urethane Acrylate Polyester acrylate Monomer solvent Photoinitiator additive 6 sensuality 6 sensuality 4 sensuality Trifunctional Example 1 28 12 57.7 2.0 0.3 Example 2 24 16 57.7 2.0 0.3 Example 3 20 20 57.7 2.0 0.3 Example 4 4.8 8 27.2 57.7 2.0 0.3 Example 5 4.2 12 23.8 57.7 2.0 0.3 Example 6 3.6 16 20.4 57.7 2.0 0.3 Example 7 3 20 17 57.7 2.0 0.3 Comparative Example 1 2.4 24 13.6 57.7 2.0 0.3 Comparative Example 2 16 24 57.7 2.0 0.3 Comparative Example 3 40 57.7 2.0 0.3 Comparative Example 4 40 57.7 2.0 0.3 Comparative Example 5 40 57.7 2.0 0.3 Comparative Example 6 40 57.7 2.0 0.3

상기 표 1에서 사용된 각 성분은 다음과 같다. Each component used in Table 1 is as follows.

우레탄 아크릴레이트: 우레탄헥사아크릴레이트(PU610)Urethane acrylate: urethane hexaacrylate (PU610)

폴리에스테르 아크릴레이트(6관능): 폴리에스테르헥사아크릴레이트(PS610)Polyester acrylate (6-functional): polyester hexaacrylate (PS610)

폴리에스테르 아크릴레이트(4관능): 폴리에스테르테트라아크릴레이트(PS420)Polyester acrylate (4-functional): polyester tetraacrylate (PS420)

모노머: 펜타에리스리톨트리아크릴레이트(M340)Monomer: pentaerythritol triacrylate (m340)

용제: 메틸에틸케톤, 2-메톡시에탄올Solvent: Methyl ethyl ketone, 2-methoxyethanol

광개시제: 1-히드록시시클로헥실페닐케톤Photoinitiator: 1-hydroxycyclohexylphenyl ketone

첨가제: 변성 실리콘 폴리머(BYK-3530)Additive: Modified Silicone Polymer (BYK-3530)

실험예 1:Experimental Example 1:

상기 실시예 1-7과 비교예 1-6에서 제조한 광경화 코팅 조성물을 각각 1시간 동안 교반한 후, 투명기재 필름(80㎛, PMMA) 위에 두께가 6㎛가 되도록 마이어바(그라비어 코터의 일종)로 도포한 다음, 70℃에서 1분간 건조한 후, 500mJ/cm2으로 경화시켜 코팅 필름을 제조하였다. After stirring the photocurable coating composition prepared in Example 1-7 and Comparative Example 1-6 for 1 hour, respectively, the thickness of the Myerba (gravure coater) so as to have a thickness of 6㎛ on the transparent substrate film (80㎛, PMMA) After coating), and dried for 1 minute at 70 ℃, and cured at 500mJ / cm 2 to prepare a coating film.

(1) 저장탄성율(G')(1) Storage modulus (G ')

광경화 코팅 조성물을 UV 경화시키면서, 조성물의 저장탄성율(G')을 레오미터(Physica MCR-3xx, Anton Paar)로 측정하였다.While the photocured coating composition was UV cured, the storage modulus (G ′) of the composition was measured with a rheometer (Physica MCR-3xx, Anton Paar).

구체적으로, 제조한 광경화 코팅 조성물을 100℃ 오븐에 2시간 동안 두어 용제를 완전히 건조한 다음 잔존물을 측정 샘플로 준비하고, 준비된 잔존물을 레오미터 시스템의 바텀플레이트(bottom plate)에 놓고, 직경 8mm의 측정 스핀들을 바텀플레이트(bottom plate)로부터 100㎛ 떨어진 곳에 위치시켰다. 그런 다음, 스팟 타입의 UV 조도를 33.3MW/cm2(조사거리 57mm, spot UV 출력 30%)로 고정하고, 0.01%의 변형률에 10Hz의 주파수 조건으로 12초 동안 20 포인트(20포인트/12초)를 측정하여 경화 완료 직전의 저장탄성율 값을 취하였다.Specifically, the prepared photocurable coating composition was placed in a 100 ° C. oven for 2 hours to completely dry the solvent, and then the residue was prepared as a measurement sample, and the prepared residue was placed on a bottom plate of a rheometer system, having a diameter of 8 mm. The measuring spindle was placed 100 μm away from the bottom plate. Then, fix the spot-type UV illuminance to 33.3 MW / cm 2 (irradiation distance 57 mm, spot UV output 30%), and 20 points (20 points / 12 seconds) for 12 seconds at a frequency of 10 Hz at a strain of 0.01%. ) Was measured to take the storage modulus value immediately before curing was completed.

(2) 전광선투과율(2) total light transmittance

분광광도계(HZ-1, 일본 스가사)를 이용하여 PMMA 면을 광원(D65)으로 향해서 전광선투과율(Total Transmittance) 및 전체 헤이즈(Haze)를 측정하였다.The total light transmittance and total haze were measured with the spectrophotometer (HZ-1, Suga, Japan) facing the PMMA plane toward the light source D65.

(3) 연필경도(3) pencil hardness

제조된 코팅 필름의 표면을 연필경도 시험기(PHT, 한국 석보과학사)로 500g 하중을 걸고 연필경도를 측정하였다. 연필은 미쯔비시 제품을 사용하고 한 연필경도당 5회 실시하였다. 기스가 2개 이상이면 불량으로 판정하였으며, 불량이 발생하기 이전의 연필로 연필경도를 표시하였다. The surface of the prepared coating film was subjected to a 500g load with a pencil hardness tester (PHT, Korea Seokbo Science Co., Ltd.) and the pencil hardness was measured. Pencils were made using Mitsubishi products, and were carried out five times for each pencil hardness. If there were two or more gases, it was determined to be defective, and pencil hardness was indicated by a pencil before the failure occurred.

기스 0: OK Kis 0: OK

기스 1: OK Kiss 1: OK

기스 2 이상: NGKis 2 or higher: NG

(4) 내스크래치성 (4) scratch resistance

스틸울테스트기(WT-LCM100, 한국 프로텍사)를 이용하여 1kg/(2cm x 2cm)하에서 10회 왕복운동시켜 내스크래치성을 시험하였다. 스틸울은 #0000을 사용하였다. The scratch resistance was tested by using a steel wool tester (WT-LCM100, Korea Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm). Steel wool used # 0000.

A: 스크래치가 0개 A: 0 scratches

A': 스크래치가 1~10개 A ': 1 to 10 scratches

B: 스크래치가 11~20개 B: 11-20 scratches

C: 스크래치가 21~30개 C: 21-30 scratches

D: 스크래치가 31개 이상 D: 31 or more scratches

(5) 밀착성(5) adhesion

필름의 도포된 면에 1mm 간격으로 가로 세로 각각 11개의 직선을 그어 100개의 정사각형을 만든 후, 테이프(CT-24, 일본 니치방사)을 이용하여 3회 박리 테스트를 진행하였다. 100개의 사각형 3개를 테스트하여 평균치를 기록하였다. 밀착성은 다음과 같이 기록하였다. After eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm to make 100 squares, three peel tests were carried out using a tape (CT-24, Nichi-Shin, Japan). Three 100 squares were tested and averaged. The adhesion was recorded as follows.

밀착성 = n / 100 Adhesion = n / 100

n: 전체 사각형 중 박리되지 않는 사각형 수 n: number of rectangles not peeled off

100: 전체 사각형의 개수 100: total squares

따라서 하나도 박리되지 않았을 시 100 / 100으로 기록하였다.Therefore, when none of the peeling was recorded as 100/100.

(6) 내크랙성(6) Crack resistance

JIS-K5600-5-1에 따라 내굴곡성 측정법(Mandrel)을 사용하여, 만드렐 Φ(지름, mm)별 크랙 발생 여부를 측정하였다. 측정 시료 사이즈는 2.5cm x 20cm(가로 x 세로)로 준비하여, 필름의 도포된 면이 바깥으로 위치하게 하여 평가하였다.According to JIS-K5600-5-1, using the bend resistance measurement method (Mandrel), it was determined whether cracks by Mandrerel Φ (diameter, mm). The measurement sample size was prepared by 2.5 cm x 20 cm (width x length), and it evaluated by making the coated surface of the film outward.

내크랙성 판단은 크랙이 발생하지 않는 임계 만드렐 Φ를 기록하였다.The crack resistance judgment recorded the critical Mandrerel Φ in which no crack occurred.

상술한 방법으로 측정한 결과를 하기 표 2에 기재하였다.The results measured by the above-described method are shown in Table 2 below.

표 2 구분 저장탄성율(G') (Pa) 전광선투과율(%) 헤이즈(%) 연필경도(H) 내스크래치성 밀착성 만드렐(Φ) 실시예1 6.8E+07 91.8 0.3 2 A' 100/100 2 실시예2 6.0E+07 91.8 0.3 2 A' 100/100 2 실시예3 4.9E+07 91.7 0.3 2 A' 100/100 2 실시예4 6.9E+07 91.8 0.3 2 A' 100/100 2 실시예5 6.3E+07 91.9 0.3 2 A' 100/100 2 실시예6 5.4E+07 91.8 0.3 2 A' 100/100 2 실시예7 4.6E+07 91.8 0.3 2 A' 100/100 2 비교예1 3.8E+07 91.8 0.3 2 B 100/100 2 비교예2 3.9E+07 91.8 0.3 2 B 100/100 2 비교예3 8.5E+07 91.8 0.3 2 A 100/100 5 비교예4 7.2E+07 91.7 0.3 2 A' 100/100 4 비교예5 1.8E+07 91.9 0.3 1 D 100/100 1 비교예6 8.6E+07 91.8 0.3 2 A 100/100 5 TABLE 2 division Storage modulus (G ') (Pa) Total light transmittance (%) Haze (%) Pencil hardness (H) Scratch resistance Adhesiveness Mandrell (Φ) Example 1 6.8E + 07 91.8 0.3 2 A ' 100/100 2 Example 2 6.0E + 07 91.8 0.3 2 A ' 100/100 2 Example 3 4.9E + 07 91.7 0.3 2 A ' 100/100 2 Example 4 6.9E + 07 91.8 0.3 2 A ' 100/100 2 Example 5 6.3E + 07 91.9 0.3 2 A ' 100/100 2 Example 6 5.4E + 07 91.8 0.3 2 A ' 100/100 2 Example 7 4.6E + 07 91.8 0.3 2 A ' 100/100 2 Comparative Example 1 3.8E + 07 91.8 0.3 2 B 100/100 2 Comparative Example 2 3.9E + 07 91.8 0.3 2 B 100/100 2 Comparative Example 3 8.5E + 07 91.8 0.3 2 A 100/100 5 Comparative Example 4 7.2E + 07 91.7 0.3 2 A ' 100/100 4 Comparative Example 5 1.8E + 07 91.9 0.3 One D 100/100 One Comparative Example 6 8.6E + 07 91.8 0.3 2 A 100/100 5

상기 표 2에서 보는 바와 같이 본 발명의 실시예 1 내지 7의 광경화 코팅 조성물의 경우, 코팅 필름이 광학적 물성 및 기계적인 물성을 유지하면서, 우수한 내크랙성을 나타내었다.As shown in Table 2, in the photocurable coating compositions of Examples 1 to 7 of the present invention, the coating film exhibited excellent crack resistance while maintaining optical and mechanical properties.

반면, 광경화 코팅 조성물의 저장탄성율이 4.0E+07 Pa보다 작거나 7.0E+07 Pa보다 큰 비교예 1 내지 6의 경우에는 기계적 강도나 크랙 특성이 현저히 저하되는 것을 확인하였다.On the other hand, in the case of Comparative Examples 1 to 6 in which the storage modulus of the photocurable coating composition is smaller than 4.0E + 07 Pa or larger than 7.0E + 07 Pa, it was confirmed that the mechanical strength and crack characteristics were significantly reduced.

이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that this specific technology is only a preferred embodiment, which is not intended to limit the scope of the present invention. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.

따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (17)

저장탄성율(G')이 4.0E+07 내지 7.0E+07 Pa인 광경화 코팅 조성물.The photocurable coating composition having a storage modulus (G ′) of 4.0E + 07 to 7.0E + 07 Pa. 제1항에 있어서, 광경화형 (메타)아크릴레이트 올리고머를 포함하는 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition of claim 1 comprising a photocurable (meth) acrylate oligomer. 제2항에 있어서, 광경화형 (메타)아크릴레이트 올리고머가 우레탄 (메타)아크릴레이트와 폴리에스테르 (메타)아크릴레이트의 혼합물, 또는 2종의 폴리에스테르 (메타)아크릴레이트의 혼합물인 것을 특징으로 하는 광경화 코팅 조성물.The photocurable (meth) acrylate oligomer is a mixture of a urethane (meth) acrylate and a polyester (meth) acrylate, or a mixture of two polyester (meth) acrylates. Photocuring coating composition. 제2항에 있어서, 광경화형 (메타)아크릴레이트 올리고머가 광경화 코팅 조성물 중 고형분 기준 100 중량부에 대하여, 92 내지 99 중량부 포함되는 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition according to claim 2, wherein the photocurable (meth) acrylate oligomer is included in an amount of 92 to 99 parts by weight based on 100 parts by weight of the solid content of the photocurable coating composition. 제2항에 있어서, 광경화형 (메타)아크릴레이트 올리고머가 4관능 폴리에스테르 (메타)아크릴레이트와 6관능 폴리에스테르 (메타)아크릴레이트의 혼합물인 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition according to claim 2, wherein the photocurable (meth) acrylate oligomer is a mixture of a tetrafunctional polyester (meth) acrylate and a six functional polyester (meth) acrylate. 제5항에 있어서, 광경화 코팅 조성물 중 고형분 기준 100 중량부에 대하여, 4관능 폴리에스테르 (메타)아크릴레이트가 20 내지 50중량부 포함되고, 6관능 폴리에스테르 (메타)아크릴레이트는 45 내지 75 중량부 포함되는 것을 특징으로 광경화 코팅 조성물.The method according to claim 5, wherein the photocurable coating composition comprises 20 to 50 parts by weight of tetrafunctional polyester (meth) acrylate based on 100 parts by weight of solids, and the polyfunctional polyester (meth) acrylate is 45 to 75. A photocurable coating composition comprising a weight part. 제2항에 있어서, 광경화형 (메타)아크릴레이트 올리고머가 4관능 폴리에스테르 (메타)아크릴레이트와 4 내지 6관능 우레탄 (메타)아크릴레이트의 혼합물인 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition according to claim 2, wherein the photocurable (meth) acrylate oligomer is a mixture of tetrafunctional polyester (meth) acrylate and 4- to 6-functional urethane (meth) acrylate. 제7항에 있어서, 광경화 코팅 조성물 중 고형분 기준 100 중량부에 대하여, 4관능 폴리에스테르 (메타)아크릴레이트가 20 내지 50중량부 포함되고, 4 내지 6관능 우레탄 (메타)아크릴레이트는 45 내지 85 중량부 포함되는 것을 특징으로 광경화 코팅 조성물.The method according to claim 7, wherein 20 to 50 parts by weight of tetrafunctional polyester (meth) acrylate is included, based on 100 parts by weight of solids in the photocurable coating composition, 4 to 6 functional urethane (meth) acrylate is 45 to The photocurable coating composition, characterized in that it comprises 85 parts by weight. 제2항에 있어서, 광경화형 모노머를 추가로 포함하는 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition of claim 2, further comprising a photocurable monomer. 제9항에 있어서, 광경화형 모노머가 (메타)아크릴로일기를 갖는 모노머인 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition according to claim 9, wherein the photocurable monomer is a monomer having a (meth) acryloyl group. 제6항에 있어서, 혼합물 중 6관능 폴리에스테르 (메타)아크릴레이트의 일부를 광경화형 모노머로 대체하여 사용하는 것을 특징으로 하는 광경화 코팅 조성물.7. The photocurable coating composition of claim 6, wherein a portion of the six functional polyester (meth) acrylate in the mixture is used in place of the photocurable monomer. 제8항에 있어서, 혼합물 중 4내지 6관능 우레탄 (메타)아크릴레이트의 일부를 광경화형 모노머로 대체하여 사용하는 것을 특징으로 하는 광경화 코팅 조성물.9. The photocurable coating composition of claim 8, wherein a portion of the four to six functional urethane (meth) acrylates in the mixture are used in place of photocurable monomers. 제2항에 있어서, 광개시제 및 용제를 추가로 포함하는 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition of claim 2, further comprising a photoinitiator and a solvent. 제13항에 있어서, 광경화 코팅 조성물 100 중량부에 대하여, 광개시제가 0.05 내지 10 중량부 포함되고, 용제가 0.1 내지 85 중량부 포함되는 것을 특징으로 하는 광경화 코팅 조성물.The photocurable coating composition according to claim 13, wherein the photoinitiator is contained in an amount of 0.05 to 10 parts by weight and a solvent in an amount of 0.1 to 85 parts by weight based on 100 parts by weight of the photocurable coating composition. 투명기재의 한면 또는 양면에, 제1항 내지 제14항 중 어느 한 항에 따른 광경화 코팅 조성물의 경화물을 포함하는 코팅층이 형성되어 있는 코팅 필름.The coating film which is formed on one side or both sides of a transparent base material, The coating layer containing the hardened | cured material of the photocurable coating composition of any one of Claims 1-14. 제15항에 따른 코팅 필름이 구비되어 있는 것을 특징으로 하는 편광판.A coating film according to claim 15 is provided. 제15항에 따른 코팅 필름이 구비되어 있는 것을 특징으로 하는 표시장치.Display device according to claim 15 characterized in that the coating film is provided.
PCT/KR2014/003180 2013-04-15 2014-04-14 Photocurable coating composition, coating film using same and polarizing plate Ceased WO2014171678A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480022058.4A CN105121565B (en) 2013-04-15 2014-04-14 Photo-curable application composition, coat film and polarizing plate using the photo-curable application composition
JP2016508860A JP6348972B2 (en) 2013-04-15 2014-04-14 Photo-curing coating composition, coating film and polarizing plate using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130041047A KR20140123779A (en) 2013-04-15 2013-04-15 Photocurable Coating Composition, Coating Film and Polarizing Plate Using the Same
KR10-2013-0041047 2013-04-15

Publications (2)

Publication Number Publication Date
WO2014171678A1 true WO2014171678A1 (en) 2014-10-23
WO2014171678A9 WO2014171678A9 (en) 2014-12-11

Family

ID=51731564

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/003180 Ceased WO2014171678A1 (en) 2013-04-15 2014-04-14 Photocurable coating composition, coating film using same and polarizing plate

Country Status (5)

Country Link
JP (1) JP6348972B2 (en)
KR (1) KR20140123779A (en)
CN (1) CN105121565B (en)
TW (1) TWI627238B (en)
WO (1) WO2014171678A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019152102A1 (en) * 2018-02-02 2019-08-08 Pacific Light & Hologram, Inc. Photosensitive resin and manufacturing method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109575764B (en) * 2018-11-09 2021-08-17 宁波激智科技股份有限公司 Coating composition for diffusion brightening composite film laminating layer, diffusion brightening composite film and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000171804A (en) * 1998-12-05 2000-06-23 Dainippon Printing Co Ltd Liquid crystal display device and method of manufacturing the same
JP2000239333A (en) * 1998-12-21 2000-09-05 Jsr Corp Photocurable resin composition and optical member
US6838170B2 (en) * 1999-06-18 2005-01-04 Hitachi Chemical Company, Ltd. Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same
JP2010090204A (en) * 2008-10-04 2010-04-22 Three Bond Co Ltd Photocurable adhesive composition
KR20120040225A (en) * 2009-07-22 2012-04-26 히다치 가세고교 가부시끼가이샤 Photocurable resin composition and cured product of same; resin sheet and production method for same; and display device

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1014113A3 (en) * 1998-12-21 2001-05-09 Dsm N.V. Photo curable resin composition and optical parts
JP4429862B2 (en) * 2004-10-06 2010-03-10 日東電工株式会社 Hard coat film, antireflection hard coat film, optical element and image display device
JP5359137B2 (en) * 2007-09-12 2013-12-04 大日本印刷株式会社 OPTICAL LAMINATE, ITS MANUFACTURING METHOD, POLARIZING PLATE, AND IMAGE DISPLAY DEVICE
JP2009104002A (en) * 2007-10-24 2009-05-14 Three M Innovative Properties Co Protective film for image display device, and image display device including the same
JP2011162640A (en) * 2010-02-09 2011-08-25 Shin Etsu Polymer Co Ltd Photocurable resin composition and switch member containing cured product thereof
EP2527886B1 (en) * 2010-02-26 2014-11-26 LG Chem, Ltd. Polarizing plate comprising a pressure-sensitive adhesive layer
JP2011192342A (en) * 2010-03-12 2011-09-29 Nippon Shokubai Co Ltd Optical recording medium
JP2011210335A (en) * 2010-03-30 2011-10-20 Nippon Shokubai Co Ltd Photopolymerized resin composition for optical recording medium, cured material, and optical recoding medium
JP2012131900A (en) * 2010-12-21 2012-07-12 Sumitomo Bakelite Co Ltd Cured product of ultraviolet-curable resin composition, resin laminate and ultraviolet-curable resin composition
US8993114B2 (en) * 2010-12-24 2015-03-31 Dai Nippon Printing Co., Ltd. Hard coat film, polarizer and image display device
JP2012141459A (en) * 2010-12-28 2012-07-26 Fujifilm Corp Composition for forming hard coat layer, optical film, method for manufacturing optical film, polarizing plate, and image display device
JP2012252748A (en) * 2011-06-03 2012-12-20 Mitsubishi Rayon Co Ltd Active energy ray curable resin composition for optical recording medium and optical recording medium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000171804A (en) * 1998-12-05 2000-06-23 Dainippon Printing Co Ltd Liquid crystal display device and method of manufacturing the same
JP2000239333A (en) * 1998-12-21 2000-09-05 Jsr Corp Photocurable resin composition and optical member
US6838170B2 (en) * 1999-06-18 2005-01-04 Hitachi Chemical Company, Ltd. Adhesive, adhesive member, interconnecting substrate for semiconductor mounting having adhesive member, and semiconductor device containing the same
JP2010090204A (en) * 2008-10-04 2010-04-22 Three Bond Co Ltd Photocurable adhesive composition
KR20120040225A (en) * 2009-07-22 2012-04-26 히다치 가세고교 가부시끼가이샤 Photocurable resin composition and cured product of same; resin sheet and production method for same; and display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019152102A1 (en) * 2018-02-02 2019-08-08 Pacific Light & Hologram, Inc. Photosensitive resin and manufacturing method thereof
US10465029B2 (en) 2018-02-02 2019-11-05 Pacific Light & Hologram, Inc. Photosensitive resin and manufacturing method thereof

Also Published As

Publication number Publication date
JP6348972B2 (en) 2018-06-27
TW201500487A (en) 2015-01-01
CN105121565A (en) 2015-12-02
JP2016522277A (en) 2016-07-28
WO2014171678A9 (en) 2014-12-11
KR20140123779A (en) 2014-10-23
TWI627238B (en) 2018-06-21
CN105121565B (en) 2018-01-02

Similar Documents

Publication Publication Date Title
WO2014171679A1 (en) Photocurable coating film, polarizing plate, and display device
WO2014088272A1 (en) Hard coating film and flexible display using same
WO2012008757A2 (en) Anti-glare coating composition and anti-glare coating film having superior abrasion resistance and contamination resistance
WO2019045332A2 (en) Adhesive film, adhesive composition therefor and display member comprising same
KR20110114304A (en) Anti-glare hard coating composition, anti-glare film, polarizing plate and display device using the same
WO2016052883A1 (en) Polarizing plate and image display device having same
WO2018212545A1 (en) Hard coating film and image display apparatus comprising same
WO2019235769A1 (en) Hard coating film and image display device comprising same
WO2014098420A1 (en) Method for manufacturing hard-coated polarizing plate
WO2014171678A1 (en) Photocurable coating composition, coating film using same and polarizing plate
WO2014092384A1 (en) Anti-glare film and polarizing plate comprising same
WO2014051303A1 (en) Antiglare film, and polarizing plate and display device using same
WO2016137163A1 (en) Anti-glare film, and polarizing plate and display device using same
WO2014098421A1 (en) Method for manufacturing hard-coated polarizing plate
WO2016085072A1 (en) Polarizer protective layer composition, polarizer protective layer manufactured therefrom, polarizing plate comprising same and optical display device comprising same
WO2012128595A2 (en) Adhesive composition
WO2018155784A1 (en) Hard coating film and image display device comprising same
WO2018212547A1 (en) Hard coating film and image display apparatus comprising same
WO2016126047A1 (en) Anti-glare film
JP7318409B2 (en) Adhesive sheet for lamination, multi-layer body, and method for producing multi-layer body
WO2014104639A1 (en) Optical laminated film and polarizing plate including same
JP7318410B2 (en) Adhesive sheet for lamination, multi-layer body, and method for producing multi-layer body
US20250002746A1 (en) Hard coat film
WO2022182114A1 (en) Polarizing plate and image display device comprising same
WO2014065531A1 (en) Composition for use in anti-glare layer formation, anti-glare film, polarizer, and display device

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480022058.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14785818

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016508860

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14785818

Country of ref document: EP

Kind code of ref document: A1