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WO2014092388A1 - Organic-inorganic hybrid hard coating film, and polarizing plate including same - Google Patents

Organic-inorganic hybrid hard coating film, and polarizing plate including same Download PDF

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Publication number
WO2014092388A1
WO2014092388A1 PCT/KR2013/011258 KR2013011258W WO2014092388A1 WO 2014092388 A1 WO2014092388 A1 WO 2014092388A1 KR 2013011258 W KR2013011258 W KR 2013011258W WO 2014092388 A1 WO2014092388 A1 WO 2014092388A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
hard coating
organic
coating film
inorganic hybrid
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/KR2013/011258
Other languages
French (fr)
Korean (ko)
Inventor
임거산
김희봉
안명용
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
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Filing date
Publication date
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Publication of WO2014092388A1 publication Critical patent/WO2014092388A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C08J2433/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to an organic-inorganic hybrid hard coating film and a polarizing plate including the same.
  • Hard coating films are widely used to protect panel surfaces of various flat panel displays such as liquid crystal displays (TFT-LCDs), plasma displays (PDPs), organic electroluminescent displays (OLEDs), and CRTs.
  • TFT-LCDs liquid crystal displays
  • PDPs plasma displays
  • OLEDs organic electroluminescent displays
  • CRTs CRTs
  • the display panel employing a glass substrate has a weak impact resistance and has a problem in weight reduction, so that a film having a hard coating layer having a high hardness on the surface of a plastic transparent substrate is widely used to replace or supplement the disadvantage.
  • Korean Patent Publication No. 2009-0044089 discloses a composition for forming an organic-inorganic hybrid hard coating layer including a urethane acrylate oligomer, a polyfunctional acrylate monomer, and a silica having a molecular weight of 500 to 10,000.
  • the hard coating film has a pencil hardness of only 2H to 3H level, the hard coating film does not have sufficient surface protection characteristics that the hard coating film should have. Therefore, the organic-inorganic hybrid hard coating film having excellent optical properties and excellent surface hardness and wear resistance is It is required.
  • An object of the present invention is to provide an organic-inorganic hybrid hard coating film having a high surface hardness and excellent scratch resistance and scratch resistance and a polarizing plate including the same.
  • the hard coating layer formed by applying a composition for forming a hard coating layer containing an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive group and a photoinitiator on one surface of the transparent substrate film
  • the acrylate-based resin comprises at least 10% by weight of the tri-functional acrylate-based resin
  • the inorganic particles are characterized in that it comprises 80 to 120 parts by weight based on 100 parts by weight of acrylate-based resin It provides an organic-inorganic hybrid hard coating film.
  • the acrylate-based resin may have an average number of functional groups 6 to 14 functional.
  • the inorganic particles may have an average particle diameter of 1 to 100 nm.
  • the hard coating layer may have a thickness of 17 ⁇ 30 ⁇ m.
  • the hard coat film may have a surface hardness of 7H or more.
  • a polarizing plate including the organic-inorganic hybrid hard coating film.
  • the organic-inorganic hybrid hard coat film according to the present invention has a low haze and a high reflection sharpness, which is excellent in optical properties and has an excellent surface hardness, scratch resistance and scratch resistance.
  • the organic-inorganic hybrid hard coating film of the present invention is formed by applying a composition for forming a hard coating layer containing an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive group, and a photoinitiator to one surface of a transparent substrate film. It comprises a hard coating layer, wherein the acrylate-based resin comprises at least 10% by weight of the tri- or less functional acrylate-based resin, the inorganic particles containing 80 to 120 parts by weight based on 100 parts by weight of the acrylate-based resin will be.
  • the composition for forming a hard coat layer includes an acrylate resin having an average functional group number of 5 to 15, an inorganic particle having a UV reactive group, and a photoinitiator.
  • the acrylate-based resin having an average functional number of 5 to 15 is a photocurable resin, and may include a photocurable (meth) acrylate oligomer and a monomer.
  • Urethane (meth) acrylate can manufacture the polyfunctional (meth) acrylate which has a hydroxyl group in a molecule, and the compound which has an isocyanate group in presence of a catalyst.
  • the (meth) acrylate having a hydroxy group in the molecule examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and capro It may be selected from one or more selected from the group consisting of lactone ring-opened 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 monomer is usually used, and has a unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. in a photocurable functional group, and a (meth) acryloyl group is more preferable especially.
  • the monomer having a (meth) acryloyl group examples include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 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 , Dipentaeryth
  • Illustrative acrylate resin is a photocurable (meth) acrylate oligomer, and monomers can be used individually or in combination of 2 or more, respectively.
  • the acrylate resin of this invention is 5-15 average functional groups. If the average number of functional groups is less than 5, there is a problem that it is difficult to exhibit sufficient hardness due to low curing density, and when the average number of functional groups is greater than 15, cracking occurs due to large curing shrinkage due to poor reactivity due to poor reactivity or hardening. there is a problem.
  • the acrylate resin of this invention contains 10% or more of trifunctional or less acrylate resins.
  • the trifunctional or less acrylate-based resin is included in less than 10% of the entire acrylate-based resin, there is a problem that the curing reactivity is low and it is difficult to exhibit sufficient hardness.
  • trifunctional acrylate resins examples include caprolactone acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, ethoxyethoxyethyl acrylate stearyl acrylate and hexanediol diacrylate.
  • Dipropylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate can be used. have.
  • Inorganic particles having a UV reactive group include metal oxides or sulfides, and specifically, titanium dioxide (rutile, rutile / anatase mixed crystal, anatase amorphous structure), silicon oxide, indium oxide, tin oxide, zirconium oxide, zinc oxide, sulfide It may be zinc.
  • Colloidal inorganic oxides may also be used, including colloidal titanium dioxide, colloidal alumina, colloidal zirconia, colloidal vanadia, colloidal chromia, colloidal iron oxide, colloidal tin oxide, or mixtures thereof, preferably Silica can be used.
  • the average particle diameter of an inorganic particle is 1-100 nm.
  • the average particle diameter of the particles is less than 1 nm, the hardness may be lowered, and when the average particle diameter is greater than 100 nm, transparency may be reduced.
  • 80-120 weight part of inorganic particles are contained with respect to 100 weight part of acrylate resins. If the inorganic material is less than 80 parts by weight based on the above, the hardness may be lowered. If it is more than 120 parts by weight, the reaction rate may decrease, and transparency may be reduced.
  • Photoinitiators can be used without limitation, those used in the art. Specifically 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxy At least one selected from the group consisting of acetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, and benzophenone can be used.
  • the photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition for forming a hard coat layer. If the content of the photoinitiator is less than 0.1 parts by weight, the curing rate is slow, and if it exceeds 10 parts by weight, cracks may occur in the anti-glare hard coating layer due to over curing.
  • the composition for forming the hard coat layer may include a solvent.
  • the solvent can be used without limitation so long as it is known as a solvent of the composition for forming a coating layer in the art.
  • alcohols methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.
  • ketones methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexa
  • At least one selected from the group consisting of rice paddy, etc. hexane-based (hexane, heptane, octane, and the like), and benzene-based (benzene, toluene, xylene, and the like).
  • the solvent may be included in an amount of 10 to 95 parts by weight based on 100 parts by weight of the total composition for forming the hard coat layer.
  • the viscosity may be high and workability may be reduced. have.
  • the present invention provides a hard coating film including a hard coating layer formed using the above-described composition for forming a hard coating layer. That is, the anti-glare film of the present invention includes a hard coating layer formed by applying a hard coating layer-forming composition to at least one surface of a transparent substrate and then curing the composition.
  • the transparent substrate is not particularly limited as long as it is a film having transparency.
  • the transparent substrate may be cycloolefin derivatives having a unit of a monomer including a cycloolefin such as norbornene or a polycyclic norbornene monomer, cellulose (diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, iso Butyl ester cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose), ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, Polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone
  • the transparent substrate may have a thickness of about 8 ⁇ m to about 1000 ⁇ m, and preferably about 40 ⁇ m to about 100 ⁇ m.
  • the method of coating the antiglare layer forming composition on the transparent substrate is not particularly limited, and a method such as a die coater, an air knife, a reverse roll, a spray, a blade, a casting, a gravure, or a spin coating may be used.
  • the thickness after curing of the hard coat layer formed by the antiglare layer forming composition applied on the transparent substrate may be 17 to 30 ⁇ m preferably.
  • the curing step of the composition for forming a hard coating layer may be photocuring, wherein the irradiation amount of UV light may be about 0.01 ⁇ 10J / cm 2 , preferably 0.1 ⁇ 2J / cm 2 .
  • the hard coating layer manufactured through the above process may have a high hardness of 7H or more, and the organic-inorganic hybrid hard coating film including the hard coating layer may be included in a polarizing plate or a display device.
  • the present invention provides a polarizing plate equipped with an organic-inorganic hybrid hard coating film according to the present invention described above. That is, the polarizing plate of the present invention may be formed by laminating the anti-glare film according to the present invention described above on one side or both sides of a normal polarizer.
  • the polarizer may be provided with a protective film on at least one surface.
  • the hard coating layer-forming composition blended to have the composition and content (parts by weight) of Table 1 was filtered using a PP filter, and then cured on the upper surface of a triacetyl cellulose film (base film) having a thickness of 80 ⁇ m. It applied so that thickness might be 20 micrometers.
  • the content of the rake-based resin is calculated and shown in Table 2 below.
  • the hard coating layer-forming composition was applied onto an 80 ⁇ m triacetylcellulose (TAC) film, and then the solvent was dried for 2 minutes, and UV-cured at an accumulated light amount of 500 mJ / cm 2 to form a hard coating layer.
  • TAC triacetylcellulose
  • the thickness of the hard coating layer-forming composition and the hard coating layer after curing are used in Table 3 below.
  • JIS K5600 it measured using the Pencil Hardness Tester (pencil hardness tester, masonry science). After fixing the pencil at a load of 500g and an angle of 45, it was determined whether the surface was scratched visually by the pencil hardness.
  • Haze was measured using Suga's HZ-1 Haze Meter.
  • the transmission sharpness was determined by the sum of the transmission sharpness values of the slit intervals of 0.01 mm, 0.5 mm, 1.0 mm, and 2.0 mm.
  • the organic-inorganic hybrid hard coating film according to Examples 1 to 10 according to the present invention has excellent transparency and low haze, as well as excellent pencil hardness and scratch resistance.
  • Table 4 it is confirmed that the organic-inorganic hybrid hard coating film according to Examples 1 to 10 according to the present invention has excellent transparency and low haze, as well as excellent pencil hardness and scratch resistance.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

The present invention relates to an organic-inorganic hybrid hard coating film, and more particularly, to an organic-inorganic hybrid hard coating film comprising a hard coating layer formed by coating a composition for forming a hard coating layer including an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive functional group, and photoinitiator on one side of a transparent substrate film, wherein the acrylate-based resin includes at least 10 wt% of an acrylate-based resin having 3 or less functional groups, and the inorganic particles are included at 80 to 120 parts by weight based on 100 parts by weight of the acrylate-based resin.

Description

유기-무기 하이브리드 하드코팅 필름 및 이를 포함하는 편광판Organic-inorganic hybrid hard coating film and polarizing plate comprising the same

본 발명은 유기-무기 하이브리드 하드코팅 필름 및 이를 포함하는 편광판에 관한 것이다.The present invention relates to an organic-inorganic hybrid hard coating film and a polarizing plate including the same.

하드 코팅 필름은 각종 평판 디스플레이 패널, 예를 들어 액정 디스플레이(TFT-LCD), 플라즈마 디스플레이(PDP), 유기전자발광 디스플레이 (OLED), 브라운관(CRT) 등의 패널 표면을 보호하기 위하여 널리 사용되고 있다. Hard coating films are widely used to protect panel surfaces of various flat panel displays such as liquid crystal displays (TFT-LCDs), plasma displays (PDPs), organic electroluminescent displays (OLEDs), and CRTs.

유리기판을 채용한 디스플레이 패널은 내충격성이 약하고 경량화에 문제가 있으므로 이를 대체하거나 단점을 보완하기 위해서 플라스틱 투명 기재의 표면에 고경도의 하드코팅층을 형성된 필름이 널리 이용되고 있다. The display panel employing a glass substrate has a weak impact resistance and has a problem in weight reduction, so that a film having a hard coating layer having a high hardness on the surface of a plastic transparent substrate is widely used to replace or supplement the disadvantage.

한편. 하드코팅 필름의 경도 및 내마모성 향상을 위하여 유기 수지와 함께 무기 입자가 포함된 유-무기 하이브리드 하드코팅층 형성용 조성물이 공지되어 있다.Meanwhile. In order to improve the hardness and wear resistance of the hard coating film, a composition for forming an organic-inorganic hybrid hard coating layer containing inorganic particles together with an organic resin is known.

구체적으로 한국공개특허 제2009-0044089호는 분자량이 500~10,000인 우레탄 아크릴레이트 올리고머, 다관능성 아크릴레이트 모노머, 실리카를 포함하는 유기-무기 하이브리드 하드코팅층 형성용 조성물을 개시한다.Specifically, Korean Patent Publication No. 2009-0044089 discloses a composition for forming an organic-inorganic hybrid hard coating layer including a urethane acrylate oligomer, a polyfunctional acrylate monomer, and a silica having a molecular weight of 500 to 10,000.

그러나 상기 하드코팅 필름의 경우 연필경도가 2H~3H 수준에 그쳐 하드코팅 필름이 가져야 할 충분한 표면 보호 특성을 갖지 못하고 있어, 광학적 특성이 뛰어나면서도 표면경도 및 내마모성이 우수한 유-무기 하이브리드 하드코팅 필름이 요구되고 있다.However, since the hard coating film has a pencil hardness of only 2H to 3H level, the hard coating film does not have sufficient surface protection characteristics that the hard coating film should have. Therefore, the organic-inorganic hybrid hard coating film having excellent optical properties and excellent surface hardness and wear resistance is It is required.

본 발명의 목적은 표면경도가 높고 내스크레치성 및 내찰상성이 뛰어난 유기-무기 하이브리드 하드코팅 필름 및 이를 포함하는 편광판을 제공하는 것이다.An object of the present invention is to provide an organic-inorganic hybrid hard coating film having a high surface hardness and excellent scratch resistance and scratch resistance and a polarizing plate including the same.

본 발명의 목적을 달성하기 위하여, 평균 관능기수 5~15인 아크릴레이트계 수지, UV 반응성기를 가지는 무기입자 및 광개시제가 함유된 하드코팅층 형성용 조성물을 투명기재 필름의 일면에 도포하여 형성된 하드코팅층을 포함하여 이루어지고, 상기 아크릴레이트계 수지는 3관능 이하의 아크릴레이트계 수지를 10중량% 이상 포함하고, 상기 무기 입자는 아크릴레이트계 수지 100중량부에 대하여 80~120중량부를 포함하는 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름을 제공한다.In order to achieve the object of the present invention, the hard coating layer formed by applying a composition for forming a hard coating layer containing an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive group and a photoinitiator on one surface of the transparent substrate film It is made, the acrylate-based resin comprises at least 10% by weight of the tri-functional acrylate-based resin, the inorganic particles are characterized in that it comprises 80 to 120 parts by weight based on 100 parts by weight of acrylate-based resin It provides an organic-inorganic hybrid hard coating film.

바람직하게 상기 아크릴레이트계 수지는 평균 관능기수가 6~14 관능일 수 있다.Preferably the acrylate-based resin may have an average number of functional groups 6 to 14 functional.

상기 무기 입자는 평균 입경이 1~100㎚일 수 있다.The inorganic particles may have an average particle diameter of 1 to 100 nm.

상기 하드코팅층은 두께가 17~30㎛일 수 있다.The hard coating layer may have a thickness of 17 ~ 30㎛.

상기 하드코팅 필름은 표면경도가 7H 이상일 수 있다.The hard coat film may have a surface hardness of 7H or more.

본 발명의 또 다른 목적을 달성하기 위하여, 상기 유기-무기 하이브리드 하드코팅 필름을 포함하는 편광판을 제공한다.In order to achieve another object of the present invention, there is provided a polarizing plate including the organic-inorganic hybrid hard coating film.

본 발명에 따른 유기-무기 하이브리드 하드코팅 필름은 낮은 헤이즈 및 높은 반사선명도를 가져 광학적 특성이 우수함과 동시에, 우수한 표면경도, 내스크레치성 및 내찰상성을 갖는다는 장점이 있다. The organic-inorganic hybrid hard coat film according to the present invention has a low haze and a high reflection sharpness, which is excellent in optical properties and has an excellent surface hardness, scratch resistance and scratch resistance.

본 발명의 유기-무기 하이브리드 하드코팅 필름은, 평균 관능기수 5~15인 아크릴레이트계 수지, UV 반응성기를 가지는 무기 입자 및 광개시제가 함유된 하드코팅층 형성용 조성물을 투명기재 필름의 일면에 도포하여 형성된 하드코팅층을 포함하여 이루어지고, 상기 아크릴레이트계 수지는 3관능 이하의 아크릴레이트계 수지를 10중량% 이상 포함하고, 상기 무기 입자는 아크릴레이트계 수지 100중량부에 대하여 80~120중량부를 포함하는 것이다.The organic-inorganic hybrid hard coating film of the present invention is formed by applying a composition for forming a hard coating layer containing an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive group, and a photoinitiator to one surface of a transparent substrate film. It comprises a hard coating layer, wherein the acrylate-based resin comprises at least 10% by weight of the tri- or less functional acrylate-based resin, the inorganic particles containing 80 to 120 parts by weight based on 100 parts by weight of the acrylate-based resin will be.

이하, 본 발명을 더욱 상세하게 설명하나, 이는 본 발명의 설명을 위한 것이며, 본 발명의 범위를 제한하는 것이 아니다.Hereinafter, the present invention will be described in more detail, but for the purpose of illustrating the present invention, it is not intended to limit the scope of the present invention.

하드코팅층 형성용 조성물은 평균 관능기수가 5~15인 아크릴레이트계 수지, UV 반응성기를 가지는 무기 입자 및 광개시제를 포함한다.The composition for forming a hard coat layer includes an acrylate resin having an average functional group number of 5 to 15, an inorganic particle having a UV reactive group, and a photoinitiator.

평균 관능기수가 5~15인 아크릴레이트계 수지는 광경화성 수지이며, 광경화형(메타)아크릴레이트 올리고머, 모노머를 포함할 수 있다.The acrylate-based resin having an average functional number of 5 to 15 is a photocurable resin, and may include a photocurable (meth) acrylate oligomer and a monomer.

광경화형 (메타)아크릴레이트 올리고머는 에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트등을 통상적으로 사용하며 우레탄 (메타)아크릴레이트가 보다 바람직하다. 우레탄 (메타)아크릴레이트는 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트와 이소시아네이트기를 갖는 화합물을 촉매 존재 하에서 제조할 수 있다. 상기 분자내에 히드록시기를 갖는 (메타)아크릴레이트의 구체적인 예로는 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 이상 선택될 수 있다. 또한 상기 이소시아네이트기를 갖는 화합물의 구체적인 예로는, 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 1종 이상 선택될 수 있다.As a photocurable (meth) acrylate oligomer, epoxy (meth) acrylate, urethane (meth) acrylate, etc. are normally used, and urethane (meth) acrylate is more preferable. Urethane (meth) acrylate can manufacture the polyfunctional (meth) acrylate which has a hydroxyl group in a molecule, and the compound which has an isocyanate group in presence of a catalyst. Specific examples of the (meth) acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxyisopropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and capro It may be selected from one or more selected from the group consisting of lactone ring-opened 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 Toluenediiso O it may be one or more selected from the group consisting of carbonate.

모노머는 통상적으로 사용하는 것으로 광경화형 관능기로 (메타)아크릴로일기, 비닐기, 스티릴기, 알릴기 등의 불포화 기를 분자내 갖는 것으로, 그 중에서도 (메타)아크릴로일기가 보다 바람직하다. The monomer is usually used, and has a unsaturated group such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. in a photocurable functional group, and a (meth) acryloyl group is more preferable especially.

상기 (메타)아크릴로일기를 갖는 모노머는 구체적인 예로 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, 트리펜타에리스리톨헥사트리(메타)아크릴레이트, 비스(2-하이드록시에틸)이소시아누레이트디(메타)아크릴레이트, 하이드록시에틸(메타)아크릴레이트, 하이드록시프로필(메타)아크릴레이트, 하이드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소-덱실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라하이드로퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트,이소보네올(메타)아크릴레이트로 이루어진 군으로부터 1종 이상 선택될 수 있다.Specific examples of the monomer having a (meth) acryloyl group include neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 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 Yit, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexatri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth ) Acrylate, phenoxyethyl (meth) acrylate, isobornol (meth) acrylate may be selected from one or more kinds.

예시한 아크릴레이트계 수지는 광경화형 (메타)아크릴레이트 올리고머, 모노머는 각각 단독으로 또는 둘 이상을 조합하여 사용할 수 있다.Illustrative acrylate resin is a photocurable (meth) acrylate oligomer, and monomers can be used individually or in combination of 2 or more, respectively.

본 발명의 아크릴레이트계 수지는 평균 관능기 수가 5~15이다. 평균 관능기 수가 5 미만인 경우, 경화밀도가 낮아 충분한 경도를 발휘하기 어려운 문제가 있고, 15 초과인 경우, 반응성이 떨어져 경화 물성 불량이 발생하거나 경화가 충분히 진행되더라도 경화수축이 커서 필름에 크랙이 발생하는 문제가 있다. The acrylate resin of this invention is 5-15 average functional groups. If the average number of functional groups is less than 5, there is a problem that it is difficult to exhibit sufficient hardness due to low curing density, and when the average number of functional groups is greater than 15, cracking occurs due to large curing shrinkage due to poor reactivity due to poor reactivity or hardening. there is a problem.

또한 본 발명의 아크릴레이트계 수지는 3관능 이하의 아크릴레이트계 수지를 10% 이상 포함한다. 3관능 이하의 아크릴레이트계 수지가 아크릴레이트계 수지 전체에 대하여 10% 미만으로 포함될 경우 경화 반응성이 낮아져 충분한 경도를 발휘하기 어렵다는 문제가 있다.Moreover, the acrylate resin of this invention contains 10% or more of trifunctional or less acrylate resins. When the trifunctional or less acrylate-based resin is included in less than 10% of the entire acrylate-based resin, there is a problem that the curing reactivity is low and it is difficult to exhibit sufficient hardness.

3관능 이하의 아크릴레이트계 수지로는 예를 들면 카프로락톤 아크릴레이트, 옥틸 아크릴레이트, 아이소옥틸 아크릴레이트, 라우릴 아크릴레이트, 에톡시에톡시에틸 아크릴레이트 스테아릴 아크릴레이트, 헥산디올 다이아크릴레이트, 다이프로필렌글리콜 다이아크릴레이트, 트리프로필렌글리콜 다이아크릴레이트, 트리에틸렌글리콜 다이아크릴레이트, 테트라에틸렌글리콜 다이아크릴레이트, 폴리에틸렌글리콜 다이아크릴레이트, 트리메틸올프로판 트리아크릴레이트 및 펜타에리스리톨 트리아크릴레이트를 사용할 수 있다.Examples of the trifunctional acrylate resins include caprolactone acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate, ethoxyethoxyethyl acrylate stearyl acrylate and hexanediol diacrylate. , Dipropylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate can be used. have.

UV 반응성기를 가지는 무기입자는 금속산화물 또는 황화물등이 있으며, 구체적으로는 이산화티탄(루틸, 루틸/아나타제 혼합 결정, 아나타제 비정질 구조), 산화규소, 산화인듐, 산화주석, 산화지르코늄, 산화아연, 황화아연일 수 있다. 또한 콜로이드성 무기 산화물이 사용될 수 있는데, 콜로이드성 이산화티탄, 콜로이드성 알루미나, 콜로이드성 지르코니아, 콜로이드성 바나디아, 콜로이드성 크로미아, 콜로이드성 산화철, 콜로이드성 산화주석 또는 그 혼합물 등이 있으며, 바람직하게는 실리카를 사용할 수 있다.Inorganic particles having a UV reactive group include metal oxides or sulfides, and specifically, titanium dioxide (rutile, rutile / anatase mixed crystal, anatase amorphous structure), silicon oxide, indium oxide, tin oxide, zirconium oxide, zinc oxide, sulfide It may be zinc. Colloidal inorganic oxides may also be used, including colloidal titanium dioxide, colloidal alumina, colloidal zirconia, colloidal vanadia, colloidal chromia, colloidal iron oxide, colloidal tin oxide, or mixtures thereof, preferably Silica can be used.

무기 입자의 평균 입경은 1~100nm인 것이 바람직하다. 입자의 평균 입경이 1nm 미만인 경우에는 경도가 낮아질 수 있고, 100nm 초과인 경우 투명성이 저하될 수 있다.It is preferable that the average particle diameter of an inorganic particle is 1-100 nm. When the average particle diameter of the particles is less than 1 nm, the hardness may be lowered, and when the average particle diameter is greater than 100 nm, transparency may be reduced.

무기 입자는 아크릴레이트계 수지 100중량부에 대하여 80~120중량부 포함되는 것이 바람직하다. 상기 무기물이 상기의 기준으로 80중량부 미만인 경우 경도가 떨어질 수 있고, 120중량부를 초과할 경우 반응 속도가 떨어지고, 투명성이 저하될수 있다.It is preferable that 80-120 weight part of inorganic particles are contained with respect to 100 weight part of acrylate resins. If the inorganic material is less than 80 parts by weight based on the above, the hardness may be lowered. If it is more than 120 parts by weight, the reaction rate may decrease, and transparency may be reduced.

광개시제는 당해분야에서 사용되는 것을 제한 없이 사용할 수 있다. 구체적으로 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1, 디페닐케톤 벤질디메틸케탈, 2-히드록시-2-메틸-1-페닐-1-온, 4-히드록시시클로페닐케톤, 디메톡시-2-페닐아테토페논, 안트라퀴논, 플루오렌, 트리페닐아민, 카바졸, 3-메틸아세토페논, 4-크놀로아세토페논, 4,4-디메톡시아세토페논, 4,4-디아미노벤조페논, 1-히드록시시클로헥실페닐케톤 및 벤조페논으로 이루어진 군으로부터 선택된적어도 하나를 사용할 수 있다. Photoinitiators can be used without limitation, those used in the art. Specifically 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinepropanone-1, diphenyl ketone benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenylketone, dimethoxy-2-phenylatetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-knoloacetophenone, 4,4-dimethoxy At least one selected from the group consisting of acetophenone, 4,4-diaminobenzophenone, 1-hydroxycyclohexylphenylketone, and benzophenone can be used.

광개시제는 하드코팅층 형성용 조성물 전체 100중량부에 대하여 0.1 내지 10중량부 사용할 수 있다. 상기 광개시제의 함량이 0.1중량부 미만이면 경화 속도가 늦고, 10중량부를 초과 할 경우 과경화로 방현성 하드코팅층에 크랙이 발생할 수 있다.The photoinitiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition for forming a hard coat layer. If the content of the photoinitiator is less than 0.1 parts by weight, the curing rate is slow, and if it exceeds 10 parts by weight, cracks may occur in the anti-glare hard coating layer due to over curing.

하드코팅층 형성용 조성물에는 용제가 포함될 수 있다. 용제는 본 기술분야의 코팅층 형성용 조성물의 용제로 알려진 것이라면 제한되지 않고 사용할 수 있다.The composition for forming the hard coat layer may include a solvent. The solvent can be used without limitation so long as it is known as a solvent of the composition for forming a coating layer in the art.

구체적으로 알코올계(메탄올, 에탄올, 이소프로판올, 부탄올, 메틸셀루소브, 에틸솔루소브 등), 케톤계(메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 디에틸케톤, 디프로필케톤, 시클로헥사논 등), 헥산계(헥산, 헵탄, 옥탄 등), 벤젠계(벤젠, 톨루엔, 자일렌 등)로 이루어진 군으로부터 선택된 적어도 하나를 사용할 수 있다.Specifically, alcohols (methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexa) At least one selected from the group consisting of rice paddy, etc.), hexane-based (hexane, heptane, octane, and the like), and benzene-based (benzene, toluene, xylene, and the like).

용제는 하드코팅층 형성용 조성물 전체 100중량부에 대하여 10 내지 95중량부 포함될 수 있다. 상기 용제가 방현성 하드코팅층 형성용 조성물 100중량부에 대하여, 10중량부 미만이면 점도가 높아 작업성이 떨어질 수 있고, 95중량부를 초과할 경우에는 건조 과정에서 시간이 많이 소요되어 경제성이 떨어질 수 있다.The solvent may be included in an amount of 10 to 95 parts by weight based on 100 parts by weight of the total composition for forming the hard coat layer. When the solvent is less than 10 parts by weight based on 100 parts by weight of the composition for forming an anti-glare hard coating layer, the viscosity may be high and workability may be reduced. have.

본 발명에서는 상술한 하드코팅층 형성용 조성물을 이용하여 형성된 하드코팅층을 포함하는 하드코팅 필름을 제공한다. 즉 본 발명의 방현 필름은 투명기재의 적어도 일면에 하드코팅층 형성용 조성물을 도포시킨 다음 경화시켜 형성된 하드코팅층을 구비한다.The present invention provides a hard coating film including a hard coating layer formed using the above-described composition for forming a hard coating layer. That is, the anti-glare film of the present invention includes a hard coating layer formed by applying a hard coating layer-forming composition to at least one surface of a transparent substrate and then curing the composition.

상기 투명기재는 투명성이 있는 필름이면 특별히 제한되지 않는다. 예를 들면, 투명기재는 노르보르넨이나 다환 노르보르넨계 단량체와 같은 시클로올레핀을 포함하는 단량체의 단위를 갖는 시클로올레핀계 유도체들, 셀룰로오스(디아세틸셀룰로오스, 트리아세틸셀룰로오스, 아세틸셀룰로오스부틸레이트, 이소부틸에스테르셀룰로오스, 프로피오닐셀룰로오스, 부티릴셀룰로오스, 아세틸프로피오닐셀룰로오스), 에틸렌-아세트산비닐공중합체, 폴리에스테르, 폴리스티렌, 폴리아미드, 폴리에테르이미드, 폴리아크릴, 폴리이미드, 폴리에테르술폰, 폴리술폰, 폴리에틸렌, 폴리프로필렌, 폴리메틸펜텐, 폴리염화비닐, 폴리염화비닐리덴, 폴리비닐알콜, 폴리비닐아세탈, 폴리에테르케톤, 폴리에테르에테르케톤, 폴리에테르술폰, 폴리메틸메타아크릴레이트, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리우레탄, 에폭시 중에서 선택된 것을 사용할 수 있으며, 미연신, 1축 또는 2축 연신 필름을 사용할 수 있다.　 바람직하게는 투명성 및 내열성이 우수한 1축 또는 2축 연신 폴리에스테르 필름이나, 투명성 및 광학적으로 이방성이 없는 트리아세틸셀룰로오스 필름이 사용될 수 있다. The transparent substrate is not particularly limited as long as it is a film having transparency. For example, the transparent substrate may be cycloolefin derivatives having a unit of a monomer including a cycloolefin such as norbornene or a polycyclic norbornene monomer, cellulose (diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, iso Butyl ester cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose), ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacryl, polyimide, polyethersulfone, polysulfone, Polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, poly Butylene Terephthalate, Poly Renna phthalate, may be used polycarbonate, selected from polyurethane, epoxy, can be used an undrawn, uniaxially or biaxially stretched film. Preferably, a uniaxial or biaxially stretched polyester film having excellent transparency and heat resistance, but a triacetylcellulose film having no transparency and optically anisotropy may be used.

상기 투명기재의 두께는 8~1000㎛ 정도일 수 있고, 바람직하게 40~100㎛일 수 있다. The transparent substrate may have a thickness of about 8 μm to about 1000 μm, and preferably about 40 μm to about 100 μm.

방현층 형성용 조성물을 투명기재 상에 도포하는 방법은 특별히 제한되지 않으며, 다이코터, 에어 나이프, 리버스 롤, 스프레이, 블레이드, 캐스팅, 그라비아, 스핀코팅 등의 방식을 사용할 수 있다. The method of coating the antiglare layer forming composition on the transparent substrate is not particularly limited, and a method such as a die coater, an air knife, a reverse roll, a spray, a blade, a casting, a gravure, or a spin coating may be used.

투명기재 상에 도포된 방현층 형성용 조성물이 형성하는 하드코팅층의 경화 후 두께는 바람직하게는 17~30㎛일 수 있다. The thickness after curing of the hard coat layer formed by the antiglare layer forming composition applied on the transparent substrate may be 17 to 30㎛ preferably.

하드코팅층 형성용 조성물의 경화 단계는 광경화일 수 있으며, 이 때 UV광의 조사량은 약 0.01~10J/cm2, 바람직하게는 0.1~2J/cm2일 수 있다. The curing step of the composition for forming a hard coating layer may be photocuring, wherein the irradiation amount of UV light may be about 0.01 ~ 10J / cm 2 , preferably 0.1 ~ 2J / cm 2 .

상기의 과정을 거쳐 제조된 하드코팅층은 7H 이상의 고경도를 가질 수 있고, 이 하드코팅층을 포함하는 유기-무기 하이브리드 하드코팅 필름은 편광판 또는 표시장치에 포함될 수 있다.The hard coating layer manufactured through the above process may have a high hardness of 7H or more, and the organic-inorganic hybrid hard coating film including the hard coating layer may be included in a polarizing plate or a display device.

본 발명은 상술한 본 발명에 따른 유기-무기 하이브리드 하드코팅 필름이 구비된 편광판을 제공한다. 즉, 본 발명의 편광판은 통상의 편광자의 일면 또는 양면에 상술한 본 발명에 따른 방현 필름을 적층하여 형성된 것일 수 있다. 상기 편광자는 적어도 일면에 보호필름이 구비된 것일 수도 있다. The present invention provides a polarizing plate equipped with an organic-inorganic hybrid hard coating film according to the present invention described above. That is, the polarizing plate of the present invention may be formed by laminating the anti-glare film according to the present invention described above on one side or both sides of a normal polarizer. The polarizer may be provided with a protective film on at least one surface.

이하, 본 발명을 하기의 실시예 및 비교예에 의하여 보다 구체적으로 설명될 것이며, 하기의 실시예는 본 발명의 구체적인 일부 예시에 불과하고, 본 발명의 보호범위를 한정하거나 제한하고자 하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, and the following examples are only some specific examples of the present invention, and are not intended to limit or limit the protection scope of the present invention.

실시예 및 비교예Examples and Comparative Examples

(1) 하드코팅층 형성용 조성물의 제조(1) Preparation of a composition for forming a hard coat layer

표 1의 조성과 함량(중량부)을 갖도록 배합한 하드코팅층 형성용 조성물을 각각 PP재질의 필터를 이용하여 여과한 다음, 두께가 80㎛인 트리아세틸 셀룰로오스 필름(기재필름)의 상면에 경화 후 두께가 20㎛가 되도록 도포하였다.The hard coating layer-forming composition blended to have the composition and content (parts by weight) of Table 1 was filtered using a PP filter, and then cured on the upper surface of a triacetyl cellulose film (base film) having a thickness of 80 μm. It applied so that thickness might be 20 micrometers.

[표 1]TABLE 1

Figure PCTKR2013011258-appb-I000001
Figure PCTKR2013011258-appb-I000001

제조예 1 내지 7 6 및 비교제조예 1 내지 5에서 제조한 하드코팅층 형성용 조성물에 포함된 아크릴레이트계 수지의 평균 관능기수, 3관능 이하의 수지 함량 및 아크릴레이크계 수지 100중량부에 대하여 아크릴레이크계 수지의 함량을 계산하여 하기 표 2에 나타내었다.Acrylic based on the average number of functional groups, the resin content of trifunctional or less, and 100 parts by weight of the acrylic lake-based resin of the acrylate-based resin included in the composition for forming the hard coat layer prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 5 The content of the rake-based resin is calculated and shown in Table 2 below.

[표 2]TABLE 2

Figure PCTKR2013011258-appb-I000002
Figure PCTKR2013011258-appb-I000002

(2) 하드코팅층이 형성된 하드코팅 필름의 제조 (2) Preparation of a hard coat film having a hard coat layer

상기 하드코팅층 형성용 조성물을 80㎛의 트리아세틸셀룰로스(TAC) 필름 상에 도포한 후, 2분 동안 용제를 건조시키고, 500mJ/cm2의 적산광량으로 UV경화하여 하드코팅층을 형성시켰다. 이때 사용한 하드코팅층 형성용 조성물 및 경화 후 하드코팅층의 두께는 하기 표 3과 같다.The hard coating layer-forming composition was applied onto an 80 μm triacetylcellulose (TAC) film, and then the solvent was dried for 2 minutes, and UV-cured at an accumulated light amount of 500 mJ / cm 2 to form a hard coating layer. The thickness of the hard coating layer-forming composition and the hard coating layer after curing are used in Table 3 below.

[표 3]TABLE 3

Figure PCTKR2013011258-appb-I000003
Figure PCTKR2013011258-appb-I000003

실험예Experimental Example

상기 제조예 및 비교제조예에서 제조한 하드코팅층이 형성된 유기-무기 하이브리드 하드코팅 필름의 물성을 아래와 같은 방법으로 측정하고, 그 결과를 표 1에 나타내었다. 측정법 및 평가방법은 다음과 같다.The physical properties of the organic-inorganic hybrid hard coat film having the hard coat layer prepared in Preparation Examples and Comparative Preparation Examples were measured by the following method, and the results are shown in Table 1 below. Measurement and evaluation methods are as follows.

(1) 연필경도 평가(1) pencil hardness evaluation

JIS K5600에 의거, Pencil Hardness Tester(연필경도기, 석보과학)를 이용하여 측정하였다. 하중 500g, 각도 45로 연필을 고정시킨 후 표면을 연필 경도별로 긁어 육안으로 긁히는지 여부를 판단하였다.According to JIS K5600, it measured using the Pencil Hardness Tester (pencil hardness tester, masonry science). After fixing the pencil at a load of 500g and an angle of 45, it was determined whether the surface was scratched visually by the pencil hardness.

(2) 내스크레치성 평가 (2) scratch resistance evaluation

마찰시험기(rubbing tester, KPD-301, 기배이엔티사)에 강철솜을 장착한 후 1kg의 하중으로 10회 왕복시켜 발생하는 스크래치 개수를 평가하였다.The number of scratches generated by mounting the steel wool in a rubbing tester (KPD-301, Gibae ENT) and reciprocating 10 times under a load of 1 kg was evaluated.

(3) 헤이즈 측정(3) haze measurement

스가사의 HZ-1 Haze Meter를 이용하여 헤이즈를 측정하였다. Haze was measured using Suga's HZ-1 Haze Meter.

(4) 투과선명도 측정(4) Transmission sharpness measurement

투과선명도 측정기(ICM-1T, 스가사)를 이용하여 측정하였다. 투과선명도는 슬릿간격 0.01mm, 0.5mm, 1.0mm, 2.0mm의 투과선명도 수치의 합산으로 결정하였다.It measured using the transmission sharpness measuring instrument (ICM-1T, Suga Corporation). The transmission sharpness was determined by the sum of the transmission sharpness values of the slit intervals of 0.01 mm, 0.5 mm, 1.0 mm, and 2.0 mm.

[표 4]TABLE 4

Figure PCTKR2013011258-appb-I000004
Figure PCTKR2013011258-appb-I000004

상기 표 4를 통해 보는 바와 같이 본 발명에 따른 실시예 1 내지 10에 따른 유기-무기 하이브리드 하드코팅 필름은 투명도가 우수하고 헤이즈가 낮을 뿐만 아니라, 연필 경도 및 내스크래치성이 우수한 특성을 가짐을 확인할 수 있었다.As shown through Table 4, it is confirmed that the organic-inorganic hybrid hard coating film according to Examples 1 to 10 according to the present invention has excellent transparency and low haze, as well as excellent pencil hardness and scratch resistance. Could.

Claims (6)

평균 관능기수 5~15인 아크릴레이트계 수지, UV 반응성기를 가지는 무기입자 및 광개시제가 함유된 하드코팅층 형성용 조성물을 투명기재 필름의 일면에 도포하여 형성된 하드코팅층을 포함하여 이루어지고,It comprises a hard coating layer formed by applying a composition for forming a hard coating layer containing an acrylate-based resin having an average functional group of 5 to 15, inorganic particles having a UV reactive group and a photoinitiator on one surface of the transparent substrate film, 상기 아크릴레이트계 수지는 3관능 이하의 아크릴레이트계 수지를 10중량% 이상 포함하고,The acrylate-based resin comprises at least 10% by weight of acrylate-based resin of trifunctional or less, 상기 무기 입자는 아크릴레이트계 수지 100중량부에 대하여 80~120중량부를 포함하는 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름.The inorganic particles are organic-inorganic hybrid hard coating film, characterized in that it comprises 80 to 120 parts by weight based on 100 parts by weight of acrylate resin. 청구항 1에 있어서, 상기 아크릴레이트계 수지는 평균 관능기수가 6~14관능인 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름.The organic-inorganic hybrid hard coating film of claim 1, wherein the acrylate-based resin has an average number of functional groups of 6 to 14 functional groups. 청구항 1에 있어서, 상기 무기 입자는 평균 입경이 1~100㎚인 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름.The organic-inorganic hybrid hard coating film of claim 1, wherein the inorganic particles have an average particle diameter of 1 to 100 nm. 청구항 1에 있어서, 상기 하드코팅층은 두께가 17~30㎛인 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름.The organic-inorganic hybrid hard coating film of claim 1, wherein the hard coating layer has a thickness of 17 to 30 µm. 청구항 1에 있어서, 상기 하드코팅 필름은 표면경도가 7H 이상인 것을 특징으로 하는 유기-무기 하이브리드 하드코팅 필름.The organic-inorganic hybrid hard coating film of claim 1, wherein the hard coating film has a surface hardness of 7H or more. 청구항 1 내지 5중 어느 한 항의 유기-무기 하이브리드 하드코팅 필름을 포함하는 것을 특징으로 하는 편광판.Polarizing plate comprising the organic-inorganic hybrid hard coating film of any one of claims 1 to 5.
PCT/KR2013/011258 2012-12-13 2013-12-06 Organic-inorganic hybrid hard coating film, and polarizing plate including same Ceased WO2014092388A1 (en)

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