WO2020242117A1 - Anti-reflective film, polarizing plate, and display device - Google Patents
Anti-reflective film, polarizing plate, and display device Download PDFInfo
- Publication number
- WO2020242117A1 WO2020242117A1 PCT/KR2020/006581 KR2020006581W WO2020242117A1 WO 2020242117 A1 WO2020242117 A1 WO 2020242117A1 KR 2020006581 W KR2020006581 W KR 2020006581W WO 2020242117 A1 WO2020242117 A1 WO 2020242117A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- light
- film
- antireflection film
- transmitting substrate
- less
- Prior art date
Links
Images
Classifications
-
- 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
- G02B1/11—Anti-reflection coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to an antireflection film, a polarizing plate, and a display device.
- flat panel display devices such as PDPs and LCDs are equipped with antireflection films to minimize reflection of light incident from the outside.
- a method for minimizing reflection of light a method of coating a base film by dispersing a filler such as inorganic fine particles in a resin and providing irregularities (anti-glare: AG coating);
- a method of using interference of light by forming a plurality of layers having different refractive indices on the base film anti-reflection: AR coating
- the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using scattering of light through irregularities.
- the AG coating decreases the sharpness of the screen due to surface irregularities, many studies on AR coating have recently been conducted.
- a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, etc. are laminated on a light-transmitting base film is commercially available.
- the method of forming a plurality of layers has a disadvantage in that the scratch resistance is inferior because the interlayer adhesion (interface adhesion) is weak as the process of forming each layer is separately performed.
- a method of adding various particles of nanometer size for example, particles such as silica, alumina, zeolite, etc.
- the light-transmitting base film which is known to be commonly used in the anti-reflection film, has a limitation in that the optical property deviation is large.
- An object of the present invention is to provide an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectance and light transmittance deviation, and improving the clarity of a screen of a display device.
- the present invention is to provide a polarizing plate including the anti-reflection film.
- the present invention is to provide a display device including the anti-reflection film and providing high clarity of the screen.
- XRD X-ray diffraction
- a polarizing plate including the antireflection film is provided.
- a display device including the anti-reflection film may be provided.
- first and second terms are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
- the low refractive index layer may mean a layer having a low refractive index, and for example, may mean a layer exhibiting a refractive index of about 1.2 to 1.8 at a wavelength of 550 nm.
- the peak refers to a portion when the maximum value (or extreme value) of y appears when the value of x is changed and the value of y is recorded for the specific measured quantities x and y.
- the maximum value means the largest value at the periphery
- the extreme value means a value in which the instantaneous rate of change is 0.
- FWHM full width at half maximum
- hollow inorganic particles refer to particles in the form of an empty space present on the surface and/or inside of the inorganic particles.
- (meth)acrylate [(Meth)acrylate] is meant to include both acrylate and methacrylate.
- (co)polymer is meant to include both a copolymer (co-polymer) and a homopolymer (homo-polymer).
- the fluorinated compound means a compound containing at least one or more fluorine elements among the compounds.
- the photopolymerizable compound refers to a polymer compound polymerized by irradiation with light, for example, by irradiation with visible light or ultraviolet light.
- a light-transmitting substrate Hard coating layer; And a low refractive layer, and in an X-ray diffraction (XRD) pattern in a reflection mode, in an X-ray diffraction (XRD) pattern in a reflection mode, a peak appearing at a 2 ⁇ value of 22 to 24°
- XRD X-ray diffraction
- An antireflection film having a full half width (FWHM) of 1.5° or less may be provided.
- the present inventors conducted a study on the antireflection film, and in the X-ray diffraction pattern of the reflection mode, the full half width (FWHM) of the peak appearing at the 2 ⁇ value of 22 to 24° is 1.5° or less, It was confirmed through experiment that similar reflectance and light transmittance appeared throughout the antireflection film, so that the deviation of reflectance and light transmittance was small, as well as high scratch resistance and antifouling property, and that the display device has sharpness of the screen. Was completed.
- the antireflection film has a small variation in reflectance and light transmittance throughout the film, so that the clarity of the screen of the display device can be increased, but has excellent scratch resistance and high antifouling properties, so that it can be easily applied without great limitation to a display device or a polarizing plate manufacturing process.
- the X-ray diffraction pattern may be calculated using a reflection mode among X-ray irradiation modes.
- the full width at half maximum (FWHM) of the peak appearing at a 2 ⁇ value of 22 to 24° is 1.5° or less, 1.49 ° or less, may be 1.3 to 1.45 °. Accordingly, a similar reflectance and transmittance may be exhibited throughout the antireflection film, and an antireflection film having a low reflectance and transmittance deviation may be implemented, and scratch or antifouling properties may be improved.
- a peak at a 2 ⁇ value of 22 to 24° appears when the polymer chain contains a light-transmitting substrate in which the polymer chain is very well aligned (arranged).
- the antireflection film having may have excellent optical properties.
- the full width at half maximum of the peak is 1.5° or less, the crystallite size of the crystal plane of the light-transmitting substrate included in the antireflection film is large, and the antireflection film including the same has excellent optical properties, so that the reflectance deviation is low. I can.
- the polymer chains in the light-transmitting substrate included in the antireflection film may be arranged with low alignment,
- the full width at half maximum of the peak exceeds 1.5°, the crystallite size of the crystal plane of the light-transmitting substrate included in the anti-reflection film has grown very small, and the optical properties of the anti-reflection film including the light-transmitting substrate are lowered, resulting in a reflectance deviation. High problems can appear.
- the incidence angle ( ⁇ ) refers to the angle formed by the crystal plane and the X-ray when X-rays are irradiated on a specific crystal plane
- the diffraction peak refers to the incident angle of the X-ray incident on the horizontal axis (x-axis) in the xy plane.
- the first derivative value (the slope of the tangent line, dy/dx) of the double (2 ⁇ ) value of the incident angle of the X-ray which is the horizontal axis (x-axis) with respect to the diffraction intensity of the vertical axis (y-axis), from a positive value to a negative value. It refers to the point where the first derivative (the slope of the tangent line, dy/dx) is zero.
- the 2 ⁇ value of the peak is due to a specific interplanar distance (d-spacing) in the crystal of the polymer in the light-transmitting substrate, and the full width at half maximum of the peak may be due to the size of the polymer crystal in the light-transmitting substrate.
- the specific interplanar distance (d-spacing) in the light-transmitting substrate can be confirmed from the 2 ⁇ value of the peak appearing in the reflection mode X-ray diffraction (XRD) pattern. More specifically, at a Cu target and a wavelength ( ⁇ ) of 1.54 ⁇ , a (-110) crystal plane in the light-transmitting substrate may appear as a peak at a 2 ⁇ value of 22 to 24°.
- XRD reflection mode X-ray diffraction
- the size of the polymer crystal in the light-transmitting substrate may affect the full half width of the peak appearing at the 2 ⁇ value of 22 to 24°, and the smaller the full half width, the larger the size of the polymer crystal in the light-transmitting substrate. Accordingly, the crystal planes corresponding to the polymers in the light-transmitting substrate may be arranged with a high degree of alignment.
- the low refractive index layer included in the antireflection film according to the exemplary embodiment may include a binder resin and inorganic nanoparticles dispersed in the binder resin.
- the binder resin may include a (co)polymer of a photopolymerizable compound.
- the photopolymerizable compound forming the binder resin may include a monomer or oligomer including a (meth)acrylate group or a vinyl group.
- the photopolymerizable compound may include a monomer or oligomer including one or more, or two or more, or three or more (meth)acrylate groups or vinyl groups.
- the monomer or oligomer including the (meth)acrylate group include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate.
- )Acrylate tripentaerythritol hepta(meth)acrylate, triethylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylic Rate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or urethane-modified acrylate oligomer, epoxide Side acrylate oligomers, ether acrylate oligomers, dendritic acrylate oligomers, or mixtures of two or more thereof.
- the molecular weight of the oligomer may be 1,000 to 10,000.
- the monomer or oligomer including the vinyl group may include divinylbenzene, styrene, or paramethylstyrene.
- the content of the part derived from the photopolymerizable compound in the binder resin is not largely limited, the content of the photopolymerizable compound is 10% by weight to 80% by weight in consideration of the mechanical properties of the low-refractive-index layer or the antireflection film to be finally prepared. It may be weight %, 15 to 70 weight %, 20 to 60 weight %, or 30 to 50 weight %. If the content of the photopolymerizable compound is less than 10% by weight, scratch resistance and stain resistance of the low refractive layer may be greatly reduced, and if it exceeds 80% by weight, a problem of increasing reflectance may occur.
- the binder resin may further include a crosslinked polymer between a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.
- the antireflection film may have low interaction energy with respect to liquids or organic substances, and thus, the contaminants transferred to the antireflection film Not only can the amount be greatly reduced, it is possible to prevent a phenomenon in which the transferred contaminants remain on the surface, and the contaminants themselves can be easily removed.
- the reactive functional groups included in the fluorine-containing compound including the photoreactive functional group undergo a crosslinking action. Accordingly, the physical durability and resistance of the low refractive layer and the antireflection film Scratch properties and thermal stability can be improved.
- the fluorinated compound including the photoreactive functional group may contain or be substituted with one or more photoreactive functional groups, and the photoreactive functional group may participate in the polymerization reaction by irradiation with light, for example, irradiation with visible or ultraviolet light. It means a functional group.
- the photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl), or a thiol group ( Thiol).
- the fluorinated compound including the photoreactive functional group may have a weight average molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000 (a weight average molecular weight in terms of polystyrene measured by the GPC method).
- the fluorine-containing compounds cannot be uniformly and effectively arranged on the surface of the low refractive layer and are located inside, thereby preventing the low refractive layer and reflection
- the antifouling property of the surface of the film is deteriorated, and the crosslinking density inside the low refractive layer and the antireflection film is lowered, so that the overall strength and mechanical properties such as scratch resistance may be deteriorated.
- the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too high, the haze of the low refractive layer and the antireflection film may increase or the light transmittance may decrease, and the strength of the low refractive layer and the antireflection film may also be It can be degraded.
- the fluorinated compound including a photoreactive functional group is i) an aliphatic compound or an alicyclic compound in which at least one photoreactive functional group is substituted and at least one carbon is substituted with at least one fluorine; ii) a hetero aliphatic compound or a heteroaliphatic ring compound in which at least one photoreactive functional group is substituted, at least one hydrogen is substituted with fluorine, and at least one carbon is substituted with silicon; iii) a polydialkylsiloxane polymer (eg, polydimethylsiloxane polymer) in which at least one photoreactive functional group is substituted and at least one silicone is substituted with at least one fluorine; iv) It may contain at least one selected from the group consisting of polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine.
- a polydialkylsiloxane polymer eg, polydimethylsiloxane poly
- the binder resin included in the low refractive layer may include a crosslinked polymer between a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.
- the crosslinked polymer is 1 to 300 parts by weight, 2 to 250 parts by weight, 3 to 200 parts by weight, 5 parts derived from the fluorinated compound containing the photoreactive functional group, based on 100 parts by weight of the part derived from the photopolymerizable compound. To 190 parts by weight or 10 to 180 parts by weight.
- the content of the fluorinated compound including the photoreactive functional group relative to the photopolymerizable compound is based on the total content of the fluorinated compound including the photoreactive functional group.
- the fluorine-containing compound including the photoreactive functional group is added in an excessive amount compared to the photopolymerizable compound, the low refractive layer may not have sufficient durability or scratch resistance.
- the amount of the fluorine-containing compound including the photoreactive functional group is too small compared to the photopolymerizable compound, the low refractive layer may not have sufficient antifouling properties or mechanical properties such as scratch resistance.
- the fluorinated compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorinated compound including the photoreactive functional group may optionally contain silicon or a silicon compound therein, and specifically, the content of silicon in the fluorinated compound including the photoreactive functional group is 0.1% to 20% by weight. I can.
- the content of silicon or silicon compound contained in each of the fluorinated compounds including the photoreactive functional group can also be confirmed through a commonly known analysis method, for example, an ICP [Inductively Coupled Plasma] analysis method.
- Silicon contained in the fluorine-containing compound including the photoreactive functional group can increase compatibility with other components included in the low refractive layer of the embodiment, and accordingly, haze is generated in the low refractive layer finally produced. It can play a role of increasing transparency by preventing it, and in addition, it is possible to improve the scratch resistance by improving the slip property of the surface of the low refractive index layer or the antireflection film to be finally produced.
- the low refractive layer or the antireflection film may not have sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also decrease.
- the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and polysilsesquioxane having one or more substituted reactive functional groups.
- polysilsesquioxane in which one or more reactive functional groups are substituted has a reactive functional group on the surface, so that the mechanical properties of the low refractive layer, for example, scratch resistance can be improved, and previously known silica, alumina, zeolite, etc. Unlike the case of using fine particles of, it is possible to improve the alkali resistance of the low refractive layer, while improving the appearance characteristics such as average reflectance and color.
- the polysilsesquioxane may be expressed as (RSiO 1.5 ) n (where n is 4 to 30 or 8 to 20), and may have various structures such as random, ladder-shaped, cage, and partial cage.
- polysilsesquioxane having one or more reactive functional groups substituted with one or more reactive functional groups and a polyhedral oligomer having a cage structure Silsesquioxane (Polyhedral Oligomeric Silsesquioxane) can be used.
- the polyhedral oligomer silsesquioxane having one or more functional groups substituted and having a cage structure may include 8 to 20 silicones in a molecule.
- At least one of the silicones of the polyhedral oligomer silsesquioxane having a cage structure may be substituted with a reactive functional group, and silicones in which the reactive functional group is not substituted may be substituted with the aforementioned non-reactive functional group.
- the mechanical properties of the low refractive layer and the binder resin can be improved, and the remaining silicones
- a non-reactive functional group is substituted, a steric hindrance appears in the molecular structure, and the frequency or probability of exposure of the siloxane bond (-Si-O-) to the outside is greatly reduced, so that the alkali resistance of the low refractive layer and the binder resin Can be improved.
- the reactive functional groups substituted for the polysilsesquioxane are alcohols, amines, carboxylic acids, epoxides, imides, (meth)acrylates, nitriles, norbornene, olefins (ally, cycloalkenyl) Or vinyldimethylsilyl, etc.], polyethylene glycol, thiol, and may include one or more functional groups selected from the group consisting of vinyl groups, preferably epoxide or (meth)acrylate.
- the reactive functional group include (meth)acrylate, an alkyl (meth)acrylate having 1 to 20 carbon atoms, a cycloalkyl epoxide having 3 to 20 carbon atoms, an alkyl cycloalkane having 1 to 10 carbon atoms.
- Epoxide is mentioned.
- the alkyl (meth)acrylate means that the other part of'alkyl' that is not bonded to (meth)acrylate is a bonding position
- the cycloalkyl epoxide is another part of'cycloalkyl' that is not bonded to the epoxide. This refers to the bonding position
- the alkyl cycloalkane epoxide means that the other part of the'alkyl' that is not bonded to the cycloalkane epoxide is the bonding site.
- the polysilsesquioxane in which one or more reactive functional groups are substituted is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms other than the above-described reactive functional group.
- One or more unreactive functional groups selected from the group consisting of may further include one or more.
- a siloxane bond (-Si-O-) is located inside the molecule in the polysilsesquioxane in which one or more reactive functional groups are substituted. While not exposed to the outside, the alkali resistance and scratch resistance of the low refractive layer and the antireflection film can be further improved.
- polyhedral oligomeric silsesquioxane (POSS) having one or more reactive functional groups substituted and having a cage structure examples include TMP DiolIsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-PropanediolIsobutyl POSS, Octa(3 -hydroxy-3 methylbutyldimethylsiloxy) POSS substituted with one or more alcohols such as POSS; AminopropylIsobutyl POSS, AminopropylIsooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, AminophenylIsobutyl POSS, and other amine-
- the crosslinked polymer between the photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and a polysilsesquioxane substituted with one or more reactive functional groups is a poly(polysilsesquioxane) substituted with one or more reactive functional groups relative to 100 parts by weight of the photopolymerizable compound.
- Silsesquioxane may contain 0.5 to 60 parts by weight, 1.5 to 45 parts by weight, 3 to 40 parts by weight, or 5 to 30 parts by weight.
- the low refractive index layer included in the antireflection film according to the embodiment may include inorganic fine particles dispersed in the binder resin.
- the inorganic fine particles refer to inorganic particles having a diameter of nanometers or micrometers.
- the inorganic fine particles may include solid inorganic nanoparticles and/or hollow inorganic nanoparticles, and the solid inorganic nanoparticles have a diameter of 100 nm or less and no empty space exists therein. Means the particles of.
- the hollow inorganic nanoparticles refer to particles having a diameter of 200 nm or less and having an empty space on the surface and/or inside.
- the solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, 1 to 80 nm, 2 to 70 nm, or 5 to 60 nm.
- the hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, 10 to 150 nm, 20 to 130 nm, 30 to 110 nm, or 40 to 100 nm.
- each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one reactive group selected from the group consisting of a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl) and a thiol group (Thiol) on the surface. It may contain functional groups.
- the low refractive index layer may have a higher degree of crosslinking, thereby securing more improved scratch resistance and antifouling properties. can do.
- those coated with a fluorine-based compound may be used alone, or may be mixed with hollow inorganic nanoparticles whose surface is not coated with a fluorine-based compound.
- the surface energy may be lowered, and thus the durability and scratch resistance of the low refractive layer may be further improved.
- a conventionally known particle coating method or a polymerization method may be used without great limitation.
- the hollow inorganic nanoparticles and the fluorine-based compound are mixed with water and a catalyst.
- the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reactions.
- a specific example of the hollow inorganic nanoparticles may be hollow silica particles.
- the hollow silica may include a predetermined functional group substituted on the surface to be more easily dispersed in an organic solvent.
- Examples of the organic functional groups that can be substituted on the surface of the hollow silica particles are not largely limited, and for example, (meth)acrylate group, vinyl group, hydroxy group, amine group, allyl group, epoxy group, isocyanate group, amine group, Alternatively, fluorine or the like may be substituted on the hollow silica surface.
- the binder resin of the low refractive layer contains 10 to 600 parts by weight, 20 to 550 parts by weight, 50 to 500 parts by weight, 100 to 400 parts by weight, or 150 to 350 parts by weight of the inorganic fine particles based on 100 parts by weight of the photopolymerizable compound can do.
- the inorganic fine particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.
- the low refractive layer is a photopolymerizable compound, a fluorine-containing compound containing a reactive functional group, polysilsesquioxane having one or more reactive functional groups substituted, and a photocurable coating composition containing the inorganic fine particles is applied on the light-transmitting substrate And it can be obtained by photocuring the applied result.
- the photocurable coating composition may further include a photoinitiator. Accordingly, the photopolymerization initiator may remain in the low refractive layer prepared from the above-described photocurable coating composition.
- any compound known to be used in a photocurable resin composition may be used without limitation, and specifically, a benzophenone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or A mixture of two or more of these may be used.
- the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight, 5 to 90 parts by weight, 10 to 80 parts by weight, 20 to 70 parts by weight, or 30 to 60 parts by weight. If the amount of the photopolymerization initiator is too small, a material that remains uncured in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity or the crosslinking density is low, so that the mechanical properties of the produced film may be deteriorated or the reflectance may be greatly increased.
- the photocurable coating composition may further include an organic solvent.
- organic solvent include ketones, alcohols, acetates and ethers, or mixtures of two or more thereof.
- Such an organic solvent include ketones such as methyl ethylkenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these may be mentioned.
- ketones such as methyl ethylkenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone
- Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i
- the organic solvent may be added at the time of mixing each component included in the photocurable coating composition or may be included in the photocurable coating composition while each component is added in a dispersed or mixed state in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition decreases, and thus defects such as streaks may occur in the final film. In addition, when an excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not sufficiently performed, so that physical properties or surface properties of the film may be deteriorated, and defects may occur during drying and curing. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% to 50% by weight, or 2 to 20% by weight.
- methods and devices commonly used to apply the photocurable coating composition can be used without any other limitation.
- bar coating methods such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot Die coating method, 2 roll coating method, etc. can be used.
- ultraviolet or visible light having a wavelength of 200 to 400 nm may be irradiated, and the exposure amount at the time of irradiation is preferably 100 to 4,000 mJ/cm 2.
- the exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure.
- nitrogen purging may be performed to apply a nitrogen atmosphere.
- the hard coating layer included in the hard coating film in the above embodiment a commonly known hard coating layer may be used without great limitation.
- a binder resin including a photocurable resin As an example of the hard coating layer, a binder resin including a photocurable resin; And a hard coating layer comprising organic or inorganic fine particles dispersed in the binder resin.
- the photocurable resin included in the hard coating layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art.
- the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy tri At least one selected from the group of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated gly
- the organic or inorganic fine particles are not specifically limited in particle size, for example, the organic fine particles may have a particle diameter of 1 to 10 ⁇ m, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm Can have The particle diameter of the organic or inorganic fine particles may be defined as a volume average particle diameter.
- the organic or inorganic fine particles included in the hard coating layer is not limited, for example, the organic or inorganic fine particles are organic fine particles composed of acrylic resin, styrene resin, epoxide resin, and nylon resin, or silicon oxide, It may be inorganic fine particles composed of titanium dioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.
- the binder resin of the hard coating layer may further include a high molecular weight (co)polymer having a number average molecular weight of 10,000 or more, 13,000 or more, 15,000 to 100,000, or 20,000 to 80,000.
- the high molecular weight (co)polymer may be at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.
- the hard coating layer an organic polymer resin of a photocurable resin; And a hard coating layer comprising an antistatic agent dispersed in the organic polymer resin.
- the antistatic agent is a quaternary ammonium salt compound; Pyridinium salt; Cationic compounds having 1 to 3 amino groups; Anionic compounds such as a sulfonic acid base, a sulfuric acid ester base, a phosphoric acid ester base, and a phosphonic acid base; Amphoteric compounds such as amino acid or amino sulfuric acid ester compounds; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Reactants or polymers of two or more of these compounds; It may be a mixture of two or more of these compounds.
- the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium base groups in the molecule, and a low molecular or high molecular type may be used without limitation.
- a conductive polymer and metal oxide fine particles may be used as the antistatic agent.
- the conductive polymers include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, mixed conjugated poly( Phenylene vinylene), a conjugated multi-chain conjugated compound having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain onto a saturated polymer.
- the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, and the like.
- Organic polymer resin of the photopolymerizable resin; And the hard coating layer including the antistatic agent dispersed in the organic polymer resin may further include one or more compounds selected from the group consisting of alkoxy silane-based oligomers and metal alkoxide-based oligomers.
- the alkoxy silane compound may be conventional in the art, but, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be one or more compounds selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.
- the metal alkoxide oligomer may be prepared through a sol-gel reaction of a composition comprising a metal alkoxide compound and water.
- the sol-gel reaction may be performed in a manner similar to the method for preparing the alkoxysilane-based oligomer described above.
- the sol-gel reaction may be performed by slowly dropping water after diluting the metal alkoxide-based compound in an organic solvent.
- the molar ratio of the metal alkoxide compound to water (based on metal ions) may be adjusted within a range of 3 to 170.
- the metal alkoxide-based compound may be one or more compounds selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.
- the light-transmitting substrate included in the hard coating film according to the embodiment may be a transparent film having a light transmittance of 90% or more and a haze of 1% or less.
- the light-transmitting substrate may have a transmittance of 50% or more at a wavelength of 300 nm or more.
- the light-transmitting substrate is a polymer film having a low moisture permeability characteristic in which moisture permeation is hardly performed in which moisture moves from a high water vapor pressure to a low water vapor pressure through the film.
- the light-transmitting substrate is 30 to The moisture permeability is 50 g/m 2 ⁇ day or less, 30 g/m 2 ⁇ day or less, 20 g/m 2 ⁇ day or less or 15 g/m 2 ⁇ at a temperature of 40°C and 90 to 100% relative humidity. May be less than a day.
- the 2 ⁇ value of the peak is, It is due to the specific interplanar distance (d-spacing) in the crystal of the polymer, and may be due to the crystal state of the polymer in the light-transmitting substrate. It may be due to the size of the polymer crystal in the light-transmitting substrate.
- the specific interplanar distance (d-spacing) and size of the polymer crystal in the light-transmitting substrate is related to the stretching ratio, the stretching temperature, and the cooling rate after stretching in the manufacturing process of the light-transmitting substrate.
- the light-transmitting substrate It may be related to the ratio of the tensile strength between one direction of and a direction perpendicular to the one direction.
- the light-transmitting substrate has different values of tensile strength in one direction and a direction perpendicular to the one direction, for example, tensile strength in a direction perpendicular to the one direction relative to the tensile strength in one direction
- the ratio of may be 2 or more, 2 to 30, 2.1 to 20, 2.2 to 10, or 2.2 to 5.
- the tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction. If the tensile strength ratio is less than 2, a variation in reflectance and transmittance of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
- the light-transmitting substrate may have a tensile strength of 50 to 500 Mpa, 60 to 450 Mpa, or 70 to 400 Mpa in one direction.
- the tensile strength of the light-transmitting substrate in a direction perpendicular to the one direction may be 50 to 500 Mpa, 60 to 450 Mpa, or 70 to 400 Mpa.
- the light-transmitting substrate has a retardation (Rth) of 5,000 nm or more in the thickness direction measured at a wavelength of 400 nm to 800 nm, 5,200 to 50,000 nm, 5,400 to 40,000 nm, 5,600 to 30,000 nm, 5,800 to 20,000 nm, or 5,800 to Can be 10,000 nm.
- Rth retardation
- Specific examples of such a light-transmitting substrate include a uniaxially oriented polyethylene terephthalate film or a biaxially oriented polyethylene terephthalate film.
- the retardation (Rth) in the thickness direction of the light-transmitting substrate is less than 5,000 nm, the reflectance and transmittance variation of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
- the retardation in the thickness direction can be confirmed through a commonly known measuring method and measuring device.
- a commonly known measuring method and measuring device for example, as an apparatus for measuring retardation in the thickness direction, the brand name "AxoScan" manufactured by AXOMETRICS, etc. is mentioned.
- the film It can be calculated
- the size of the light-transmitting substrate of the measurement sample is not particularly limited, since it may be larger than the light metering portion (diameter: about 1 cm) of the stage of the measuring device, but it can be made into a size of 76 mm in length, 52 mm in width, and 13 ⁇ m in thickness. .
- the value of the ⁇ refractive index of the light-transmitting substrate (589 nm)'' used in the measurement of retardation in the thickness direction is unconventional including a resin film of the same type as the light-transmitting substrate forming the film to be measured for retardation.
- an unstretched film is used as a measurement sample (in addition, when the film to be measured is an unstretched film, the film can be used as a measurement sample as it is), and a refractive index measurement as a measuring device Using a device (trade name "NAR-1T SOLID” manufactured by Atago Co., Ltd.), using a light source of 589 nm, under a temperature condition of 23°C, in the in-plane direction (direction perpendicular to the thickness direction) of the measurement sample. It can be obtained by measuring the refractive index for light of 589 nm.
- the material of the light-transmitting polymer substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate, or the like.
- the thickness of the base film may be 10 to 300 ⁇ m in consideration of productivity, but is not limited thereto.
- the antireflection film of the embodiment may exhibit a low reflectance, thereby implementing high light transmittance and excellent optical properties.
- the antireflection film has an average reflectance of 2.0% or less, 1.6% or less, 1.2% or less, 0.05% to 0.9%, 0.10% to 0.70%, or 0.2% in the visible light wavelength range of 380 nm to 780 nm. It may have an average reflectivity of 0.5%.
- the antireflection film of the embodiment may exhibit low reflectance deviation and light transmittance deviation, thereby implementing excellent optical properties.
- the average reflectance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.18%p, or 0.02 to 0.17%p.
- the light transmittance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.15%p, or 0.01 to 0.10%p.
- the average reflectance deviation refers to the difference (absolute value) between the average reflectance in the visible light wavelength range of 380 to 780 nm of two or more specific portions (points) selected in the antireflection film and the average value of the average reflectance. .
- a method of calculating the average reflectance deviation specifically, 1) selecting two or more points in the antireflection film, 2) measuring the average reflectance at each of the two or more points, and 3) the average measured in step 2) By calculating the arithmetic mean of the reflectance, and 4) calculating the difference (absolute value) between the average reflectance of each point and the arithmetic mean of step 3), finally, a deviation of two or more average reflectances can be calculated.
- the average reflectance deviation having the largest value among the deviations of the two or more average reflectances may be 0.2%p or less.
- the light transmittance deviation refers to the difference (absolute value) between the transmittance of two or more specific portions (points) selected from the antireflection film and the average value of the transmittance. Instead of measuring the average reflectance, the transmittance is measured. Except for the point, the transmittance deviation may be calculated in the same manner as the method of calculating the average reflectance deviation. In this case, a light transmittance deviation having a largest value among the two or more light transmittance deviations may be 0.2%p or less.
- a polarizing plate including the antireflection film may be provided.
- the polarizing plate may include a polarizer and an antireflection film formed on at least one surface of the polarizer.
- a polarizing plate including a polarizer, a second hard coating layer having a thickness of 10 ⁇ m or less positioned so as to face the polarizer as a center, and an antireflection film according to the embodiment is provided Can be.
- the polarizing plate is manufactured using components and manufacturing methods known in the art, except that a second hard coating layer having a thickness of 10 ⁇ m or less, a polarizer, and the antireflection film are sequentially stacked.
- a second hard coating layer having a thickness of 10 ⁇ m or less, a polarizer, a light-transmitting substrate, a hard coating layer, and a low refractive index layer may be sequentially stacked.
- polarizing plates have a structure in which triacetyl cellulose (TAC) films are placed on both sides of the polarizer, but the triacetyl cellulose film has poor water resistance, so it can be distorted in a high temperature/high humidity environment and prevent defects such as light leakage. There is a problem that causes.
- TAC triacetyl cellulose
- a light-transmitting substrate having the above-described characteristics is positioned on one side of the polarizer, and a second hard coating layer having a thickness of 10 ⁇ m or less is positioned on the other side of the polarizer, so that the polarizing plate is Even if exposed to high temperature and high humidity for a long period of time, moisture transfer to the polarizer is blocked, thereby ensuring durability without significant changes in physical properties or shape.
- the polarizing plate uses a second hard coating layer having a thickness of 10 ⁇ m or less, it is possible to reduce the thickness of the entire polarizing plate with the effect of blocking moisture transfer and securing durability.
- the polarizer; The second hard coating layer; And a total thickness of the light-transmitting substrate may be 200 ⁇ m or less.
- the polarizer may have a thickness of 40 ⁇ m or less, or 1 to 40 ⁇ m
- the hard coating layer may have a thickness of 10 ⁇ m or less, or 1 to 10 ⁇ m
- the light-transmitting substrate may have a thickness of 150 ⁇ m or less Can have a thickness of. In this case, it is possible to reduce the thickness and weight of the polarizing plate and the display including the polarizing plate.
- a second hard coating layer having a thickness of 10 ⁇ m or less may be positioned on one surface of the polarizer, and a light-transmitting substrate included in the antireflection film may be positioned on the other surface of the polarizer.
- the light-transmitting substrate may have a retardation (Rth) of 5,000 nm or more, 7,000 to 50,000 nm, or 8,000 to 40,000 nm in a thickness direction measured at a wavelength of 400 nm to 800 nm.
- the retardation (Rth) in the thickness direction of the light-transmitting substrate included in the polarizing plate is less than 5,000 nm, the reflectance and transmittance variation of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light. Meanwhile, the method and apparatus for measuring the retardation are as described in the above-described antireflection film.
- the light-transmitting substrate has different values of tensile strength in one direction and a direction perpendicular to the one direction, for example, the ratio of the tensile strength in the one direction and the perpendicular direction to the tensile strength in one direction May be 2 or more, 3 or more, 4 to 30 or 5 to 20.
- the tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction. If the ratio of the tensile strength of the light-transmitting substrate included in the polarizing plate is less than 2, the variation in reflectance and transmittance of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
- the second hard coating layer having a thickness of 10 ⁇ m or less can be prepared using components and manufacturing methods known in the art to which the present invention pertains, for example, the same configuration as the hard coating layer included in the antireflection film. It may be a film having, etc.
- the polarizer vibrates in several directions and exhibits a characteristic capable of extracting only light vibrating in one direction from incident light.
- This characteristic can be achieved by stretching polyvinyl alcohol (PVA) absorbing iodine with strong tension.
- PVA polyvinyl alcohol
- the polarizer may be formed through a stretching step of arranging the dichroic dye materials side by side in a stretching direction, and a complementary color step of correcting the color of the PVA film passed through the stretching step, but is not limited thereto.
- the polyvinyl alcohol may be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof.
- examples of the polyvinyl alcohol resin derivative include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like.
- the dichroic dye an azo-based, anthraquinone-based, tetrazin-based, etc. may be used, but the present invention is not limited thereto.
- the polyvinyl alcohol film may be a commercially available polyvinyl alcohol film generally used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 of Kuraray, M3000, M6000 of Japanese Synthetic Company, etc. have.
- the polyvinyl alcohol film may have a degree of polymerization of 1000 to 10000 or 1500 to 5000, but is not limited thereto.
- the degree of polymerization satisfies the above range, molecular movement is free and can be flexibly mixed with iodine or a dichroic dye.
- the polarizing plate may be used as an upper polarizing plate of a display, for example, a liquid crystal display (LCD).
- the antireflection film may be positioned on the top, and specifically, the antireflection film may be positioned close to the viewer side of the display device. By controlling the anti-reflection film to be positioned close to the viewing side of the display, it is possible to improve durability by blocking moisture transfer toward the polarizer, and to minimize reflection of light incident from the outside, thereby improving the clarity of the screen.
- the second hard coating layer in contact with the polarizer and/or an adhesive layer may be further included on one surface of the light-transmitting substrate, and further, other functional layers, such as a fouling-resistant layer, may be further included between each layer or at the outermost side. .
- the second hard coating layer and the light-transmitting substrate positioned on each side of the polarizer may be bonded by lamination using an adhesive or the like.
- Usable adhesives are not particularly limited as long as they are known in the art, but for example, water-based adhesives, one- or two-component polyvinyl alcohol (PVA)-based adhesives, polyurethane-based adhesives, epoxy-based adhesives, styrene butadiene rubber-based adhesives (SBR-based) adhesives or hot melt adhesives.
- PVA polyvinyl alcohol
- SBR-based styrene butadiene rubber-based adhesives
- a second hard coating layer, a polarizer, a light-transmitting substrate, a hard coating layer, and a low refractive index layer may be sequentially stacked.
- the second hard coating layer in contact with the polarizer and/or an adhesive layer may be further included on one surface of the light-transmitting substrate, and further, other functional layers such as a contamination-resistant layer may be further included between each layer or at the outermost side. have.
- Triacetyl cellulose (TAC) film which is widely used as a polarizer protective film of a polarizing plate, has poor water resistance and can be distorted in a high temperature/high humidity environment and causes defects such as light leakage, whereas in the polarizing plate according to another embodiment, the polarizer Since the second hard coating layer and the antireflection film according to the embodiment are used on both sides, durability without significant change in physical properties or shape can be secured even when exposed to high temperature and high humidity for a long time.
- TAC Triacetyl cellulose
- the polarizing plate uses a second hard coating layer having a thickness of 10 ⁇ m or less, a solid structure can be implemented through a thinner thickness compared to other previously known polarizing plate structures.
- the polarizer; The second hard coating layer; And the total thickness of the light-transmitting substrate may be 200 ⁇ m or less.
- the polarizer may have a thickness of 40 ⁇ m or less, or 1 to 40 ⁇ m
- the hard coating layer may have a thickness of 10 ⁇ m or less, or 1 to 10 ⁇ m
- the light-transmitting substrate may have a thickness of 150 ⁇ m or less Can have a thickness of.
- a display device including the anti-reflection film described above may be provided.
- a specific example of the display device is not limited, and may be, for example, a liquid crystal display device, a plasma display device, or an organic light emitting diode device.
- the display device may include a pair of polarizing plates facing each other; A thin film transistor, a color filter, and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And it may be a liquid crystal display device including a backlight unit.
- the antireflection film may be provided on the outermost surface of the display panel on the viewer side or the backlight side.
- an anti-reflection film may be positioned on one surface of a polarizing plate that is relatively far from a backlight unit among a pair of polarizing plates.
- the display device may include a display panel, a polarizer provided on at least one surface of the panel, and an antireflection film provided on a surface opposite to the panel of the polarizer.
- an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having a low reflectance and light transmittance deviation and enhancing the clarity of a screen of a display device, a polarizing plate including the antireflection film, and the antireflection A display device including a film can be provided.
- Figure 1 It is an X-ray diffraction (XRD) pattern for the antireflection film of Example 1.
- the components shown in Table 1 were mixed to prepare a coating solution (B1, B2 and B3) for forming a hard coating layer.
- PETA pentaerythritol triacrylate
- IRG-184 initiator (Irgacure 184, Ciba company)
- BYK350 BYK leveling agent
- XX-103BQ (2.0 ⁇ m 1.515): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)
- XX-113BQ (2.0 ⁇ m 1.555): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)
- MA-ST (30% in MeOH): A dispersion in which nano silica particles with a size of 10 to 15 nm are dispersed in methyl alcohol (product of Nissan Chemical)
- TMPTA Trimethylolpropane triacrylate
- hollow silica nanoparticles (diameter range: about 42 nm to 66 nm, manufactured by JSC catalyst and chemicals) 283 g
- solid silica nanoparticles (diameter range: about 12 nm to 19 nm) 59 g
- the first fluorinated compound (X-71-1203M, ShinEtsu Corporation) 115 g
- the second fluorine-containing compound RS-537, DIC Corporation
- initiator Irgacure 127, Ciba Corporation
- MIBK A coating solution for forming a low refractive layer (photocurable coating composition) was prepared by diluting in a (methyl isobutyl ketone) solvent to a solid content concentration of 3% by weight.
- Preparation Example 2-2 Preparation of coating solution (C2) for forming a low refractive index layer
- MIBK methyl isobutyl ketone
- Example 1 to 3 and Comparative example 1 to 4 Preparation of antireflection film
- the coating solutions (C1, C2) for forming the low refractive layer were coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at a temperature of 40° C. for 1 minute. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating solution under nitrogen purging.
- Example 1 4.1 9300 Coating liquid (B1) Coating liquid (C1) Example 2 4.0 9200 Coating liquid (B2) Coating liquid (C1) Example 3 2.9 9230 Coating liquid (B2) Coating liquid (C1) Example 4 3.7 9300 Coating liquid (B3) Coating liquid (C1) Example 5 2.2 5800 Coating liquid (B1) Coating liquid (C2) Comparative Example 1 1.8 3500 Coating liquid (B3) Coating liquid (C1) Comparative Example 2 1.6 3000 Coating liquid (B2) Coating liquid (C1) Comparative Example 3 1.3 3200 Coating liquid (B2) Coating liquid (C1) Comparative Example 4 1.8 1500 Coating liquid (B1) Coating liquid (C2)
- a sample was prepared by fixing it so that it does not float on a low background Si holder (Bruker, Inc.), and a Bruker AXS D4 Endeavor XRD was used as a measurement equipment.
- the voltage and current used are 40 kV and 40 mA, respectively, and the devices and conditions such as optics and detector used are as follows.
- the measurement mode is a coupled 2 ⁇ / ⁇ mode, and using FDS (Fixed Divergence Slit) 0.3°, an area with a 2 ⁇ value of 6° to 70° was measured for 175 seconds every 0.04°.
- the full width at half maximum of the peak appearing between 2 ⁇ values of 22 to 24° in the X-ray diffraction (XRD) pattern was measured using the Bruker's TOPAS program. Specifically, specify the measurement range (fitting area) from 10 to 40° in the TOPAS program, and use the PV (pseudo-Voigt) function to input peaks around 17°, 19°, 23°, and 26° to be half-valued. I found the full width. Thereafter, the 2 ⁇ value of the peak appearing between the 2 ⁇ value of 22 to 24° and the full width at half maximum of the peak are shown in Table 3 below.
- FIG. 1 is an X-ray diffraction (XRD) pattern for the antireflection film of Example 1
- FIG. 2 is an X-ray diffraction (XRD) pattern for the antireflection film of Comparative Example 3.
- the anti-reflection film was measured for average transmittance in a wavelength range of 380 to 780 nm using the Transmittance mode of the Solidspec 3700 (SHIMADZU) equipment.
- the arithmetic average value of the measured transmittance of the 20 points was calculated. Thereafter, the difference (absolute value) between the transmittance and the arithmetic mean value at each point was defined as the transmittance deviation, and the transmittance deviation was calculated at each of the 20 points.
- the light transmittance deviation which has the largest value among the twenty light transmittance deviations, is shown in Table 3 below.
- the moisture permeability of the antireflection film obtained in Examples and Comparative Examples was measured using a MOCON test equipment (PERMATRAN-W, MODEL 3/61) under a temperature of 38°C and 100% relative humidity.
- Example 1 22.9 1.34 1.13 0.04 0.01 11.13
- Example 2 22.9 1.40 1.27 0.11 0.08 10.28
- Example 3 23.0 1.45 1.11 0.07 0.03 12.31
- Example 4 22.9 1.38 1.03 0.16 0.04 11.51
- Example 5 22.9 1.35 1.58 0.05 0.07 10.95 Comparative Example 1 23.0 1.73 1.15 0.31 0.29 11.33
- Comparative Example 2 2. 1.59 1.22 0.25 0.28 10.82 Comparative Example 3 23.2 1.81 1.0 0.28 0.3 11.18 Comparative Example 4 23.0 1.51 1.54 0.30 0.31 12.36
- the antireflection films of Examples 1 to 5 had an average reflectance deviation of 0.16%p or less, and a transmittance deviation of 0.08%p or less, and that there was little difference between the average reflectance and transmittance throughout the antireflection film. Confirmed. However, it was confirmed that the antireflection films of Comparative Examples 1 to 4, unlike the antireflection films of Examples 1 to 5, had a remarkably high deviation in average reflectance and deviation in transmittance.
- Trimethylloylpropane triacrylate 28g, KBE-403 2g, initiator KIP-100f, 0.1g, leveling agent (Tego wet 270) 0.06g was uniformly mixed to prepare a coating solution (A) for forming a second hard coating layer.
- the coating solution (A) for forming the second hard coating layer was applied to one side of a polarizer, a polyvinyl alcohol polarizer (thickness: 25 um, manufacturer: LG Chem), with a thickness of 7 um, and 500 mJ/mJ/ By irradiating ultraviolet rays of cm 2, a polarizer having a second hard coating layer formed on one surface thereof was manufactured.
- Example 6 to 10 and Comparative example 5 to 8 polarizing plate manufacturing
- a polarizing plate was manufactured by making the light-transmitting substrate of the anti-reflection film in direct contact with the polarizer, and the prepared polarizing plate includes a low refractive index layer, a hard coating layer, a light-transmitting substrate, a polarizer, and a second hard coating layer sequentially stacked. Has been.
- Example 6 Anti-reflection film Polarizer with a second hard coating layer formed
- Example 6 Example 1 Manufacturing Example 3
- Example 7 Example 2 Manufacturing Example 3
- Example 8 Example 3 Manufacturing Example 3
- Example 9 Example 4 Manufacturing Example 3
- Example 10 Example 5 Manufacturing Example 3 Comparative Example 5 Comparative Example 1 Manufacturing Example 3 Comparative Example 6 Comparative Example 2 Manufacturing Example 3 Comparative Example 7 Comparative Example 3 Manufacturing Example 3 Comparative Example 8 Comparative Example 4 Manufacturing Example 3
- a sample for thermal shock evaluation was prepared by cutting a square with a side of 10 cm and bonding to one side of a TV glass (12 cm wide, 12 cm long, and 0.7 mm thick). . At this time, the polarizing plate was cut so that the MD direction of the polarizer was parallel to one side of the square. Place the cut sample vertically in the thermal shock chamber, raise the temperature from room temperature to 80°C and leave for 30 minutes, then lower the temperature to -30°C and leave it for 30 minutes, then adjust the temperature to room temperature as 1 cycle. Repeated. After that, the cracks generated between the polarizers of the sample for evaluation and the gaps between the polarizers were visually checked to confirm the number of cracks having a length of 1 cm or more, and the results are shown in Table 5 below.
- the polarizing plates of Examples 6 to 10 had an average reflectance deviation of 0.13%p or less, and a light transmittance deviation of 0.06%p or less, and there was little difference between the average reflectance and light transmittance throughout the polarizing plate, and It was confirmed that there was no variation by site.
- the polarizing plates of Comparative Examples 5 to 8 unlike the polarizing plates of Examples 6 to 8, have remarkably high deviations in average reflectance and light transmittance, and thus, it can be predicted that a large deviation in visibility for each region will appear.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
The present invention relates to: an anti-reflective film which can achieve both high scratch resistance and smear resistance while having low reflectance and light transmissivity deviations, and can enhance the screen definition of a display device; and a polarizing plate and a display device each comprising same.
Description
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 5월 28일자 한국 특허 출원 제10-2019-0062633호 및 2020년 5월 7일자 한국 특허 출원 제10-2020-0054680호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0062633 filed May 28, 2019 and Korean Patent Application No. 10-2020-0054680 filed May 7, 2020. All contents disclosed in the literature are included as part of this specification.
본 발명은 반사 방지 필름, 편광판 및 디스플레이 장치에 관한 것이다.The present invention relates to an antireflection film, a polarizing plate, and a display device.
일반적으로 PDP, LCD 등의 평판 디스플레이 장치에는 외부로부터 입사되는 빛의 반사를 최소화하기 위한 반사 방지 필름이 장착된다. 빛의 반사를 최소화하기 위한 방법으로는 수지에 무기 미립자 등의 필러를 분산시켜 기재 필름 상에 코팅하고 요철을 부여하는 방법(anti-glare: AG 코팅); 기재 필름 상에 굴절율이 다른 다수의 층을 형성시켜 빛의 간섭을 이용하는 방법(anti-reflection: AR 코팅) 또는 이들을 혼용하는 방법 등이 있다.In general, flat panel display devices such as PDPs and LCDs are equipped with antireflection films to minimize reflection of light incident from the outside. As a method for minimizing reflection of light, a method of coating a base film by dispersing a filler such as inorganic fine particles in a resin and providing irregularities (anti-glare: AG coating); There is a method of using interference of light by forming a plurality of layers having different refractive indices on the base film (anti-reflection: AR coating) or a method of mixing them.
그 중, 상기 AG 코팅의 경우 반사되는 빛의 절대량은 일반적인 하드 코팅과 동등한 수준이지만, 요철을 통한 빛의 산란을 이용해 눈에 들어오는 빛의 양을 줄임으로써 저반사 효과를 얻을 수 있다. 그러나, 상기 AG 코팅은 표면 요철로 인해 화면의 선명도가 떨어지기 때문에, 최근에는 AR 코팅에 대한 많은 연구가 이루어지고 있다.Among them, in the case of the AG coating, the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using scattering of light through irregularities. However, since the AG coating decreases the sharpness of the screen due to surface irregularities, many studies on AR coating have recently been conducted.
상기 AR 코팅을 이용한 필름으로는 광투과성 기재 필름 상에 하드코팅층(고굴절율층), 저반사 코팅층 등이 적층된 다층 구조인 것이 상용화되고 있다. 그러나, 다수의 층을 형성시키는 방법은 각 층을 형성하는 공정을 별도로 수행함에 따라 층간 밀착력(계면 접착력)이 약해 내스크래치성이 떨어지는 단점이 있다. 이로 인해, 이전에는 반사 방지 필름에 포함되는 저굴절층의 내스크래치성을 향상시키기 위해서는 나노미터 사이즈의 다양한 입자(예를 들어, 실리카, 알루미나, 제올라이트 등의 입자)를 첨가하는 방법이 주로 시도되었다. 그러나, 상기와 같이 나노미터 사이즈의 입자를 사용하는 경우 저굴절층의 반사율을 낮추면서 내스크래치성을 동시에 높이기 어려운 한계가 있었으며, 나노미터의 사이즈의 입자로 인하여 저굴절층 표면이 갖는 방오성이 크게 저하되었다.As a film using the AR coating, a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, etc. are laminated on a light-transmitting base film is commercially available. However, the method of forming a plurality of layers has a disadvantage in that the scratch resistance is inferior because the interlayer adhesion (interface adhesion) is weak as the process of forming each layer is separately performed. For this reason, in the past, in order to improve the scratch resistance of the low refractive index layer included in the antireflection film, a method of adding various particles of nanometer size (for example, particles such as silica, alumina, zeolite, etc.) has been mainly attempted. . However, in the case of using nanometer-sized particles as described above, there is a limitation in that it is difficult to simultaneously increase scratch resistance while lowering the reflectance of the low refractive layer, and the antifouling properties of the surface of the low refractive layer are large due to nanometer-sized particles. Fell down.
한편, 반사 방지 필름에 통상적으로 사용되는 것으로 알려진 광투과성 기재 필름은 광학적 물성 편차가 크다는 한계가 있다. On the other hand, the light-transmitting base film, which is known to be commonly used in the anti-reflection film, has a limitation in that the optical property deviation is large.
본 발명은 낮은 반사율 및 투광율 편차를 가지면서 높은 내스크래치성 및 방오성을 동시에 구현할 수 있고 디스플레이 장치의 화면의 선명도를 높일 수 있는 반사 방지 필름을 제공하기 위한 것이다.An object of the present invention is to provide an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectance and light transmittance deviation, and improving the clarity of a screen of a display device.
또한, 본 발명은 상기 반사 방지 필름을 포함하는 편광판을 제공하기 위한 것이다.In addition, the present invention is to provide a polarizing plate including the anti-reflection film.
또한, 본 발명은 상기 반사 방지 필름을 포함하며 높은 화면의 선명도를 제공하는 디스플레이 장치를 제공하기 위한 것이다.In addition, the present invention is to provide a display device including the anti-reflection film and providing high clarity of the screen.
본 명세서에서는, 광투과성 기재; 하드코팅층; 및 저굴절층을 포함하고, 반사(Reflection) 모드의 X-선 회절(XRD) 패턴에서, 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭(FWHM)이 1.5° 이하인 반사 방지 필름이 제공된다.In this specification, the light-transmitting substrate; Hard coating layer; And a low refractive index layer, and in an X-ray diffraction (XRD) pattern in a reflection mode, an antireflection film having a full half width (FWHM) of 1.5° or less of a peak appearing at a 2θ value of 22 to 24° is provided. .
또한, 본 명세서에서는, 상기 반사 방지 필름을 포함하는 편광판이 제공된다. In addition, in the present specification, a polarizing plate including the antireflection film is provided.
또한, 본 명세서에서는, 상기 반사 방지 필름을 포함하는 디스플레이 장치가 제공될 수 있다.In addition, in the present specification, a display device including the anti-reflection film may be provided.
이하 발명의 구체적인 구현예에 따른 반사 방지 필름, 이를 포함하는 편광판 및 디스플레이 장치에 관하여 보다 상세하게 설명하기로 한다.Hereinafter, an antireflection film according to a specific embodiment of the present invention, a polarizing plate including the same, and a display device will be described in more detail.
본 명세서에서, 제1 및 제2의 용어는 다양한 구성요소들을 설명하는데 사용되며, 상기 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만 사용된다.In this specification, the first and second terms are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
또한, 저굴절층은 낮은 굴절률을 갖는 층을 의미할 수 있으며, 예를 들면, 550nm의 파장에서 약 1.2 내지 1.8의 굴절률을 나타내는 층을 의미할 수 있다.In addition, the low refractive index layer may mean a layer having a low refractive index, and for example, may mean a layer exhibiting a refractive index of about 1.2 to 1.8 at a wavelength of 550 nm.
또한, 피크는, 특정 측정량 x와 y에 대하여, x의 값을 변화시키고 그에 대해 y값을 기록하였을 때, y의 값이 최대값(또는 극값)이 나타나는 경우 그 부분을 의미한다. 이때, 최대값은 주변부에서 가장 큰 값을 의미하고, 극값은 순간변화율(instantaneous rate of change)이 0인 값을 의미한다.In addition, the peak refers to a portion when the maximum value (or extreme value) of y appears when the value of x is changed and the value of y is recorded for the specific measured quantities x and y. In this case, the maximum value means the largest value at the periphery, and the extreme value means a value in which the instantaneous rate of change is 0.
또한, 반치전폭(FWHM; Full Width at Half Maximum)은, 피크 높이의 y 좌표값의 1/2인 점을 통과하면서 x 좌표에 평행한 직선을 그었을 때, 직선이 곡선과 두점에서 교차하는 경우, 이 두점 사이의 거리를 의미한다.In addition, the full width at half maximum (FWHM) is when a straight line parallel to the x coordinate is drawn while passing through a point that is 1/2 of the y coordinate value of the peak height, when the straight line intersects the curve at two points, It means the distance between these two points.
또한, 중공형 무기 입자라 함은 무기 입자의 표면 및/또는 내부에 빈 공간이 존재하는 형태의 입자를 의미한다.In addition, hollow inorganic particles refer to particles in the form of an empty space present on the surface and/or inside of the inorganic particles.
또한, (메트)아크릴레이트[(Meth)acrylate]는 아크릴레이트(acrylate) 및 메타크릴레이트(Methacrylate) 양쪽 모두를 포함하는 의미이다.In addition, (meth)acrylate [(Meth)acrylate] is meant to include both acrylate and methacrylate.
또한, (공)중합체는 공중합체(co-polymer) 및 단독 중합체(homo-polymer) 양쪽 모두를 포함하는 의미이다.In addition, (co)polymer is meant to include both a copolymer (co-polymer) and a homopolymer (homo-polymer).
또한, 함불소 화합물은 화합물 중 적어도 1개 이상의 불소 원소가 포함된 화합물을 의미한다.In addition, the fluorinated compound means a compound containing at least one or more fluorine elements among the compounds.
또한, 광중합성 화합물은 빛의 조사에 의해, 예를 들어 가시 광선 또는 자외선의 조사에 의해 중합된 고분자 화합물을 통칭한다.In addition, the photopolymerizable compound refers to a polymer compound polymerized by irradiation with light, for example, by irradiation with visible light or ultraviolet light.
발명의 일 구현예에 따르면, 광투과성 기재; 하드코팅층; 및 저굴절층을 포함하고, 반사(Reflection) 모드의 X-선 회절(XRD) 패턴에서, 반사(Reflection) 모드의 X-선 회절(XRD) 패턴에서, 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭(FWHM)이 1.5° 이하인 반사 방지 필름이 제공될 수 있다.According to one embodiment of the invention, a light-transmitting substrate; Hard coating layer; And a low refractive layer, and in an X-ray diffraction (XRD) pattern in a reflection mode, in an X-ray diffraction (XRD) pattern in a reflection mode, a peak appearing at a 2θ value of 22 to 24° An antireflection film having a full half width (FWHM) of 1.5° or less may be provided.
이에, 본 발명자들은 반사 방지 필름에 관한 연구를 진행하여, 반사 모드의 X-선 회절 패턴에서, 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭(FWHM)이 1.5° 이하인 반사 방지 필름은, 반사방지 필름의 전체에서 유사한 반사율 및 투광율이 나타나 반사율 및 투광율의 편차가 적을 뿐만 아니라, 높은 내스크래치성 및 방오성을 동시에 구현할 수 있고 디스플레이 장치의 화면의 선명도를 갖는다는 점을 실험을 통하여 확인하고 발명을 완성하였다.Accordingly, the present inventors conducted a study on the antireflection film, and in the X-ray diffraction pattern of the reflection mode, the full half width (FWHM) of the peak appearing at the 2θ value of 22 to 24° is 1.5° or less, It was confirmed through experiment that similar reflectance and light transmittance appeared throughout the antireflection film, so that the deviation of reflectance and light transmittance was small, as well as high scratch resistance and antifouling property, and that the display device has sharpness of the screen. Was completed.
상기 반사 방지 필름은 필름 전반에 반사율 및 투광율의 편차가 적어 디스플레이 장치의 화면의 선명도를 높일 수 있으면서도 우수한 내스크래치성 및 높은 방오성을 가져서 디스플레이 장치 또는 편광판 제조 공정 등에 큰 제한 없이 용이하게 적용 가능하다.The antireflection film has a small variation in reflectance and light transmittance throughout the film, so that the clarity of the screen of the display device can be increased, but has excellent scratch resistance and high antifouling properties, so that it can be easily applied without great limitation to a display device or a polarizing plate manufacturing process.
구체적으로, 상기 X-선 회절 패턴은 X-선 조사 모드 중 반사 모드를 이용하여 산출할 수 있다.Specifically, the X-ray diffraction pattern may be calculated using a reflection mode among X-ray irradiation modes.
상기 일 구현예에 따른 반사 방지 필름으로부터 얻어진 상기 반사(Reflection) 모드의 X-선 회절(XRD) 패턴에서, 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭(FWHM)은 1.5° 이하, 1.49° 이하, 1.3 내지 1.45°일 수 있다. 이에 따라, 반사 방지 필름 전반에 유사한 반사율 및 투광율이 나타나 낮은 반사율 및 투광율 편차를 갖는 반사 방지 필름을 구현할 수 있으며, 스크래치 또는 방오성 향상도 함께 구현할 수 있다.In the X-ray diffraction (XRD) pattern in the reflection mode obtained from the antireflection film according to the embodiment, the full width at half maximum (FWHM) of the peak appearing at a 2θ value of 22 to 24° is 1.5° or less, 1.49 ° or less, may be 1.3 to 1.45 °. Accordingly, a similar reflectance and transmittance may be exhibited throughout the antireflection film, and an antireflection film having a low reflectance and transmittance deviation may be implemented, and scratch or antifouling properties may be improved.
상기 반사 방지 필름의 반사 모드의 X-선 회절 패턴에서, 22 내지 24°의 2θ 값에서 피크는, 고분자 사슬이 매우 잘 정렬(배열)된 광투과성 기재를 포함하는 경우에 나타나므로, 이러한 피크를 갖는 반사 방지 필름은 광학적 물성이 우수할 수 있다. 또한, 상기 피크의 반치전폭이 1.5° 이하로 나타나는 경우, 반사 방지 필름에 포함된 광투과성 기재의 결정면의 결정자 크기가 큰 것으로, 이를 포함하는 반사 방지 필름은 광학적 물성이 우수하여, 반사율 편차가 낮을 수 있다. In the X-ray diffraction pattern of the reflection mode of the antireflection film, a peak at a 2θ value of 22 to 24° appears when the polymer chain contains a light-transmitting substrate in which the polymer chain is very well aligned (arranged). The antireflection film having may have excellent optical properties. In addition, when the full width at half maximum of the peak is 1.5° or less, the crystallite size of the crystal plane of the light-transmitting substrate included in the antireflection film is large, and the antireflection film including the same has excellent optical properties, so that the reflectance deviation is low. I can.
상기 반사 방지 필름의 반사 모드의 X-선 회절 패턴에서, 22 내지 24°의 2θ 값에서 피크가 나타나지 않는 경우, 반사 방지 필름에 포함된 광투과성 기재 내의 고분자 사슬이 낮은 정렬도로 배열될 수 있고, 상기 피크의 반치전폭이 1.5° 초과하면 반사 방지 필름에 포함된 광투과성 기재의 결정면의 결정자 크기가 매우 작게 성장한 것으로, 이러한 광투과성 기재를 포함하는 반사 방지 필름의 광학적 물성이 저하되어, 반사율 편차가 높은 문제점이 나타날 수 있다.In the X-ray diffraction pattern of the reflection mode of the antireflection film, when the peak does not appear at the 2θ value of 22 to 24°, the polymer chains in the light-transmitting substrate included in the antireflection film may be arranged with low alignment, When the full width at half maximum of the peak exceeds 1.5°, the crystallite size of the crystal plane of the light-transmitting substrate included in the anti-reflection film has grown very small, and the optical properties of the anti-reflection film including the light-transmitting substrate are lowered, resulting in a reflectance deviation. High problems can appear.
한편, 상기 입사각(θ)이란 X선이 특정 결정면에 조사될 때, 결정면과 X선이 이루는 각도를 의미하며, 상기 회절 피크란, x-y 평면에서의 가로축(x축)이 입사되는 X선의 입사각의 2배(2θ)값이고, x-y 평면에서의 세로축(y축)이 회절 강도인 그래프 상에서, 가로축(x축)인 입사되는 X선의 입사각의 2배(2θ)값이 양의 방향으로 증가함에 따라, 세로축(y축)인 회절 강도에 대한 가로축(x축)인 X선의 입사각의 2배(2θ)값의 1차 미분값(접선의 기울기, dy/dx)이 양의 값에서 음의 값으로 변하는, 1차 미분값(접선의 기울기, dy/dx)이 0인 지점을 의미한다.Meanwhile, the incidence angle (θ) refers to the angle formed by the crystal plane and the X-ray when X-rays are irradiated on a specific crystal plane, and the diffraction peak refers to the incident angle of the X-ray incident on the horizontal axis (x-axis) in the xy plane. On the graph where the diffraction intensity is 2 times (2θ) and the vertical axis (y-axis) in the xy plane is diffraction intensity, as the horizontal axis (x-axis) doubles the incident angle (2θ) of the incident X-ray increases in the positive direction. , The first derivative value (the slope of the tangent line, dy/dx) of the double (2θ) value of the incident angle of the X-ray, which is the horizontal axis (x-axis) with respect to the diffraction intensity of the vertical axis (y-axis), from a positive value to a negative value. It refers to the point where the first derivative (the slope of the tangent line, dy/dx) is zero.
상기 피크의 2θ 값은 상기 광투과성 기재 내의 고분자의 결정 내 특정 면간 거리 (d-spacing)에 기인한 것이고, 상기 피크의 반치전폭은 상기 광투과성 기재 내의 고분자 결정의 크기에 기인한 것일 수 있다.The 2θ value of the peak is due to a specific interplanar distance (d-spacing) in the crystal of the polymer in the light-transmitting substrate, and the full width at half maximum of the peak may be due to the size of the polymer crystal in the light-transmitting substrate.
구체적으로, 광투과성 기재 내의 특정 면간 거리 (d-spacing)는, 반사(Reflection) 모드 X-선 회절 (XRD) 패턴에서의 나타나는 피크의 2θ 값으로부터 확인할 수 있다. 보다 구체적으로, Cu target 및 1.54 Å의 파장(λ)일 때, 상기 광투과성 기재 내에 (-110) 결정면은 22 내지 24°의 2θ 값에서 피크로 나타날 수 있다.Specifically, the specific interplanar distance (d-spacing) in the light-transmitting substrate can be confirmed from the 2θ value of the peak appearing in the reflection mode X-ray diffraction (XRD) pattern. More specifically, at a Cu target and a wavelength (λ) of 1.54 Å, a (-110) crystal plane in the light-transmitting substrate may appear as a peak at a 2θ value of 22 to 24°.
또한, 상기 광투과성 기재 내의 고분자 결정의 크기는, 상기 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭에 영향을 줄 수 있으며, 상기 반치전폭이 작을수록 광투과성 기재 내의 고분자 결정의 크기는 커지고, 이에 따라, 상기 광투과성 기재 내의 고분자 해당 결정면이 높은 정렬도로 배열될 수 있다.In addition, the size of the polymer crystal in the light-transmitting substrate may affect the full half width of the peak appearing at the 2θ value of 22 to 24°, and the smaller the full half width, the larger the size of the polymer crystal in the light-transmitting substrate. Accordingly, the crystal planes corresponding to the polymers in the light-transmitting substrate may be arranged with a high degree of alignment.
상기 일 구현예에 따른 반사 방지 필름에 포함된 저굴절층은, 바인더 수지 및 상기 바인더 수지에 분산된 무기 나노 입자를 포함할 수 있다.The low refractive index layer included in the antireflection film according to the exemplary embodiment may include a binder resin and inorganic nanoparticles dispersed in the binder resin.
한편, 상기 바인더 수지는 광중합성 화합물의 (공)중합체를 포함할 수 있다. 상기 바인더 수지를 형성하는 광중합성 화합물은 (메트)아크릴레이트기 또는 비닐기를 포함하는 단량체 또는 올리고머를 포함할 수 있다. 구체적으로, 상기 광중합성 화합물은 (메트)아크릴레이트기 또는 비닐기를 1 이상, 또는 2 이상, 또는 3 이상 포함하는 단량체 또는 올리고머를 포함할 수 있다. Meanwhile, the binder resin may include a (co)polymer of a photopolymerizable compound. The photopolymerizable compound forming the binder resin may include a monomer or oligomer including a (meth)acrylate group or a vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer including one or more, or two or more, or three or more (meth)acrylate groups or vinyl groups.
상기 (메트)아크릴레이트기를 포함한 단량체 또는 올리고머의 구체적인 예로는, 펜타에리스리톨 트리(메트)아크릴레이트, 펜타에리스리톨 테트라(메트)아크릴레이트, 디펜타에리스리톨 펜타(메트)아크릴레이트, 디펜타에리스리톨 헥사(메트)아크릴레이트, 트리펜타에리스리톨 헵타(메트)아크릴레이트, 트릴렌 디이소시아네이트, 자일렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트, 트리메틸올프로판 트리(메트)아크릴레이트, 트리메틸올프로판 폴리에톡시 트리(메트)아크릴레이트, 트리메틸롤프로판트리메타크릴레이트, 에틸렌글리콜 디메타크릴레이트, 부탄디올 디메타크릴레이트, 헥사에틸 메타크릴레이트, 부틸 메타크릴레이트 또는 이들의 2종 이상의 혼합물이나, 또는 우레탄 변성 아크릴레이트 올리고머, 에폭사이드 아크릴레이트 올리고머, 에테르아크릴레이트 올리고머, 덴드리틱 아크릴레이트 올리고머, 또는 이들의 2종 이상의 혼합물을 들 수 있다. 이때 상기 올리고머의 분자량은 1,000 내지 10,000일 수 있다.Specific examples of the monomer or oligomer including the (meth)acrylate group include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate. )Acrylate, tripentaerythritol hepta(meth)acrylate, triethylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylic Rate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or urethane-modified acrylate oligomer, epoxide Side acrylate oligomers, ether acrylate oligomers, dendritic acrylate oligomers, or mixtures of two or more thereof. At this time, the molecular weight of the oligomer may be 1,000 to 10,000.
상기 비닐기를 포함하는 단량체 또는 올리고머의 구체적인 예로는, 디비닐벤젠, 스티렌 또는 파라메틸스티렌을 들 수 있다.Specific examples of the monomer or oligomer including the vinyl group may include divinylbenzene, styrene, or paramethylstyrene.
상기 바인더 수지 중 상기 광중합성 화합물로부터 유래한 부분의 함량이 크게 한정되는 것은 아니나, 최종 제조되는 저굴절층이나 반사 방지 필름의 기계적 물성 등을 고려하여 상기 광중합성 화합물의 함량은 10중량% 내지 80중량%, 15 내지 70중량%, 20 내지 60중량%, 또는 30 내지 50중량%일 수 있다. 상기 광중합성 화합물의 함량이 10중량% 미만이면 저굴절층의 내스크래치성 및 방오성이 크게 저하될 수 있고, 80중량% 초과하면 반사율이 증가하는 문제점이 발생할 수 있다.Although the content of the part derived from the photopolymerizable compound in the binder resin is not largely limited, the content of the photopolymerizable compound is 10% by weight to 80% by weight in consideration of the mechanical properties of the low-refractive-index layer or the antireflection film to be finally prepared. It may be weight %, 15 to 70 weight %, 20 to 60 weight %, or 30 to 50 weight %. If the content of the photopolymerizable compound is less than 10% by weight, scratch resistance and stain resistance of the low refractive layer may be greatly reduced, and if it exceeds 80% by weight, a problem of increasing reflectance may occur.
한편, 상기 바인더 수지는 광중합성 화합물 및 광반응성 작용기를 포함한 함불소 화합물 간의 가교 중합체를 더 포함할 수 있다. Meanwhile, the binder resin may further include a crosslinked polymer between a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.
상기 광반응성 작용기를 포함한 함불소 화합물에 포함되는 불소 원소의 특성으로 인하여, 상기 반사 방지 필름은 액체들이나 유기 물질에 대하여 상호 작용 에너지가 낮아질 수 있으며, 이에 따라 상기 반사 방지 필름에 전사되는 오염 물질의 양을 크게 줄일 수 있을 뿐만 아니라 전사된 오염 물질이 표면에 잔류하는 현상을 방지할 수 있고, 상기 오염 물질 자체를 쉽게 제거할 수 있는 특성을 갖는다.Due to the characteristics of the fluorine element contained in the fluorine-containing compound including the photoreactive functional group, the antireflection film may have low interaction energy with respect to liquids or organic substances, and thus, the contaminants transferred to the antireflection film Not only can the amount be greatly reduced, it is possible to prevent a phenomenon in which the transferred contaminants remain on the surface, and the contaminants themselves can be easily removed.
또한, 상기 저굴절층 및 반사 방지 필름 형성 과정에서 상기 광반응성 작용기를 포함한 함불소 화합물에 포함된 반응성 작용기가 가교 작용을 하게 되고, 이에 따라 상기 저굴절층 및 반사 방지 필름이 갖는 물리적 내구성, 내스크래치성 및 열적 안정성을 높일 수 있다.In addition, in the process of forming the low refractive layer and the antireflection film, the reactive functional groups included in the fluorine-containing compound including the photoreactive functional group undergo a crosslinking action. Accordingly, the physical durability and resistance of the low refractive layer and the antireflection film Scratch properties and thermal stability can be improved.
상기 광반응성 작용기를 포함한 함불소 화합물에는 1 이상의 광반응성 작용기가 포함 또는 치환될 수 있으며, 상기 광반응성 작용기는 빛의 조사에 의하여, 예를 들어 가시 광선 또는 자외선의 조사에 의하여 중합 반응에 참여할 수 있는 작용기를 의미한다. 상기 광반응성 작용기는 빛의 조사에 의하여 중합 반응에 참여할 수 있는 것으로 알려진 다양한 작용기를 포함할 수 있으며, 이의 구체적인 예로는 (메트)아크릴레이트기, 에폭사이드기, 비닐기(Vinyl) 또는 싸이올기(Thiol)를 들 수 있다. The fluorinated compound including the photoreactive functional group may contain or be substituted with one or more photoreactive functional groups, and the photoreactive functional group may participate in the polymerization reaction by irradiation with light, for example, irradiation with visible or ultraviolet light. It means a functional group. The photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl), or a thiol group ( Thiol).
상기 광반응성 작용기를 포함한 함불소 화합물은 2,000 내지 200,000, 바람직하게는 5,000 내지 100,000의 중량평균분자량(GPC법에 의해 측정한 폴리스티렌 환산의 중량 평균 분자량)을 가질 수 있다. The fluorinated compound including the photoreactive functional group may have a weight average molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000 (a weight average molecular weight in terms of polystyrene measured by the GPC method).
상기 광반응성 작용기를 포함한 함불소 화합물의 중량평균분자량이 너무 작으면, 상기 함불소 화합물들이 상기 저굴절층 표면에 균일하고 효과적으로 배열하지 못하고 내부에 위치하게 되는데, 이에 따라 상기 저굴절층 및 반사 방지 필름의 표면이 갖는 방오성이 저하되고 상기 저굴절층 및 반사 방지 필름의 내부의 가교 밀도가 낮아져서 전체적인 강도나 내크스래치성 등의 기계적 물성이 저하될 수 있다. 또한, 상기 광반응성 작용기를 포함한 함불소 화합물의 중량평균분자량이 너무 높으면, 상기 저굴절층 및 반사 방지 필름의 헤이즈가 높아지거나 광투과도가 낮아질 수 있으며, 상기 저굴절층 및 반사 방지 필름의 강도 또한 저하될 수 있다. If the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too small, the fluorine-containing compounds cannot be uniformly and effectively arranged on the surface of the low refractive layer and are located inside, thereby preventing the low refractive layer and reflection The antifouling property of the surface of the film is deteriorated, and the crosslinking density inside the low refractive layer and the antireflection film is lowered, so that the overall strength and mechanical properties such as scratch resistance may be deteriorated. In addition, if the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too high, the haze of the low refractive layer and the antireflection film may increase or the light transmittance may decrease, and the strength of the low refractive layer and the antireflection film may also be It can be degraded.
구체적으로, 상기 광반응성 작용기를 포함한 함불소 화합물은 i) 하나 이상의 광반응성 작용기가 치환되고, 적어도 하나의 탄소에 1이상의 불소가 치환된 지방족 화합물 또는 지방족 고리 화합물; ii) 1 이상의 광반응성 작용기로 치환되고, 적어도 하나의 수소가 불소로 치환되고, 하나 이상의 탄소가 규소로 치환된 헤테로(hetero) 지방족 화합물 또는 헤테로(hetero)지방족 고리 화합물; iii) 하나 이상의 광반응성 작용기가 치환되고, 적어도 하나의 실리콘에 1이상의 불소가 치환된 폴리디알킬실록산계 고분자(예를 들어, 폴리디메틸실록산계 고분자); iv) 1 이상의 광반응성 작용기로 치환되고 적어도 하나의 수소가 불소로 치환된 폴리에테르 화합물로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다.Specifically, the fluorinated compound including a photoreactive functional group is i) an aliphatic compound or an alicyclic compound in which at least one photoreactive functional group is substituted and at least one carbon is substituted with at least one fluorine; ii) a hetero aliphatic compound or a heteroaliphatic ring compound in which at least one photoreactive functional group is substituted, at least one hydrogen is substituted with fluorine, and at least one carbon is substituted with silicon; iii) a polydialkylsiloxane polymer (eg, polydimethylsiloxane polymer) in which at least one photoreactive functional group is substituted and at least one silicone is substituted with at least one fluorine; iv) It may contain at least one selected from the group consisting of polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine.
상기 저굴절층에 포함되는 바인더 수지는 광중합성 화합물 및 광반응성 작용기를 포함한 함불소 화합물 간의 가교 중합체를 포함할 수 있다. The binder resin included in the low refractive layer may include a crosslinked polymer between a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.
상기 가교 중합체는, 상기 광중합성 화합물로부터 유래한 부분 100중량부에 대하여 상기 광반응성 작용기를 포함한 함불소 화합물로부터 유래한 부분 1 내지 300중량부, 2 내지 250중량부, 3 내지 200중량부, 5 내지 190중량부 또는 10 내지 180중량부를 포함할 수 있다. 상기 광중합성 화합물 대비 상기 광반응성 작용기를 포함한 함불소 화합물의 함량은 상기 광반응성 작용기를 포함한 함불소 화합물 전체 함량을 기준으로 한다. 상기 광중합성 화합물 대비 상기 광반응성 작용기를 포함한 함불소 화합물이 과량으로 첨가되는 경우 상기 저굴절층이 충분한 내구성이나 내스크래치성을 갖지 못할 수 있다. 또한, 상기 광중합성 화합물 대비 상기 광반응성 작용기를 포함한 함불소 화합물의 양이 너무 작으면, 상기 저굴절층이 충분한 방오성이나 내스크래치성 등의 기계적 물성을 갖지 못할 수 있다.The crosslinked polymer is 1 to 300 parts by weight, 2 to 250 parts by weight, 3 to 200 parts by weight, 5 parts derived from the fluorinated compound containing the photoreactive functional group, based on 100 parts by weight of the part derived from the photopolymerizable compound. To 190 parts by weight or 10 to 180 parts by weight. The content of the fluorinated compound including the photoreactive functional group relative to the photopolymerizable compound is based on the total content of the fluorinated compound including the photoreactive functional group. When the fluorine-containing compound including the photoreactive functional group is added in an excessive amount compared to the photopolymerizable compound, the low refractive layer may not have sufficient durability or scratch resistance. In addition, if the amount of the fluorine-containing compound including the photoreactive functional group is too small compared to the photopolymerizable compound, the low refractive layer may not have sufficient antifouling properties or mechanical properties such as scratch resistance.
상기 광반응성 작용기를 포함한 함불소 화합물은 규소 또는 규소 화합물을 더 포함할 수 있다. 즉, 상기 광반응성 작용기를 포함한 함불소 화합물은 선택적으로 내부에 규소 또는 규소 화합물을 함유할 수 있고, 구체적으로 상기 광반응성 작용기를 포함한 함불소 화합물 중 규소의 함량은 0.1 중량% 내지 20중량%일 수 있다.
The fluorinated compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorinated compound including the photoreactive functional group may optionally contain silicon or a silicon compound therein, and specifically, the content of silicon in the fluorinated compound including the photoreactive functional group is 0.1% to 20% by weight. I can.
상기 광반응성 작용기를 포함한 함불소 화합물 각각에 포함되는 규소 또는 규소 화합물의 함량 또한 통상적으로 알려진 분석 방법, 예를 들어 ICP [Inductively Coupled Plasma] 분석 방법을 통해서 확인할 수 있다.The content of silicon or silicon compound contained in each of the fluorinated compounds including the photoreactive functional group can also be confirmed through a commonly known analysis method, for example, an ICP [Inductively Coupled Plasma] analysis method.
상기 광반응성 작용기를 포함한 함불소 화합물에 포함되는 규소는 상기 구현예의 저굴절층에 포함되는 다른 성분과의 상용성을 높일 수 있으며 이에 따라 최종 제조되는 저굴절층에 헤이즈(haze)가 발생하는 것을 방지하여 투명도를 높이는 역할을 할 수 있으며, 아울러 최종 제조되는 저굴절층이나 반사 방지 필름의 표면의 슬립성을 향상시켜 내스크래치성을 높일 수 있다.Silicon contained in the fluorine-containing compound including the photoreactive functional group can increase compatibility with other components included in the low refractive layer of the embodiment, and accordingly, haze is generated in the low refractive layer finally produced. It can play a role of increasing transparency by preventing it, and in addition, it is possible to improve the scratch resistance by improving the slip property of the surface of the low refractive index layer or the antireflection film to be finally produced.
한편, 상기 광반응성 작용기를 포함한 함불소 화합물 중 규소의 함량이 너무 커지면, 상기 저굴절층이나 반사 방지 필름이 충분한 투광도나 반사 방지 성능을 갖지 못하며 표면의 방오성 또한 저하될 수 있다. On the other hand, if the content of silicon in the fluorine-containing compound including the photoreactive functional group is too large, the low refractive layer or the antireflection film may not have sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also decrease.
또한, 상기 바인더 수지는 광중합성 화합물, 광반응성 작용기를 포함한 함불소 화합물 및 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산(polysilsesquioxane) 간의 가교 중합체를 더 포함할 수 있다.In addition, the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and polysilsesquioxane having one or more substituted reactive functional groups.
한편, 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산은 표면에 반응성 작용기가 존재하여 상기 저굴절층의 기계적 물성, 예를 들어 내스크래치성을 높일 수 있고 이전에 알려진 실리카, 알루미나, 제올라이트 등의 미세 입자를 사용하는 경우와 달리 상기 저굴절층의 내알카리성을 향상시킬 수 있으면서, 평균 반사율이나 색상 등의 외관 특성을 향상시킬 수 있다. On the other hand, polysilsesquioxane in which one or more reactive functional groups are substituted has a reactive functional group on the surface, so that the mechanical properties of the low refractive layer, for example, scratch resistance can be improved, and previously known silica, alumina, zeolite, etc. Unlike the case of using fine particles of, it is possible to improve the alkali resistance of the low refractive layer, while improving the appearance characteristics such as average reflectance and color.
상기 폴리실세스퀴옥산은(RSiO
1.5)
n로 표기될 수 있으며(이때, n은 4 내지 30 또는 8 내지 20), 랜덤, 사다리형, cage 및 부분적인 cage 등의 다양한 구조를 가질 수 있다. 바람직하게는, 상기 저굴절층 및 반사 방지 필름의 물성 및 품질을 높이기 위하여, 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산으로 반응성 작용기가 1 이상 치환되고 케이지(cage)구조를 갖는 다면체 올리고머 실세스퀴옥산(Polyhedral Oligomeric Silsesquioxane)을 사용할 수 있다.The polysilsesquioxane may be expressed as (RSiO 1.5 ) n (where n is 4 to 30 or 8 to 20), and may have various structures such as random, ladder-shaped, cage, and partial cage. Preferably, in order to improve the physical properties and quality of the low refractive layer and the anti-reflection film, polysilsesquioxane having one or more reactive functional groups substituted with one or more reactive functional groups and a polyhedral oligomer having a cage structure Silsesquioxane (Polyhedral Oligomeric Silsesquioxane) can be used.
또한, 보다 바람직하게는, 상기 작용기가 1 이상 치환되고 케이지(cage)구조를 갖는 다면체 올리고머 실세스퀴옥산은 분자 중 실리콘 8 내지 20개를 포함할 수 있다. In addition, more preferably, the polyhedral oligomer silsesquioxane having one or more functional groups substituted and having a cage structure may include 8 to 20 silicones in a molecule.
또한, 상기 케이지(cage)구조를 갖는 다면체 올리고머 실세스퀴옥산의 실리콘들 중 적어도 1개 이상에는 반응성 작용기가 치환될 수 있으며, 반응성 작용기가 치환되지 않은 실리콘들에는 상술한 비반응성 작용기가 치환될 수 있다. In addition, at least one of the silicones of the polyhedral oligomer silsesquioxane having a cage structure may be substituted with a reactive functional group, and silicones in which the reactive functional group is not substituted may be substituted with the aforementioned non-reactive functional group. I can.
상기 케이지(cage)구조를 갖는 다면체 올리고머 실세스퀴옥산의 실리콘들 중 적어도 1개에 반응성 작용기가 치환됨에 따라서 상기 저굴절층 및 상기 바인더 수지의 기계적 물성을 향상시킬 수 있으며, 아울러 나머지 실리콘들에 비반응성 작용기가 치환됨에 따라서 분자 구조적으로 입체적인 장애(Steric hindrance)가 나타나서 실록산 결합(-Si-O-)이 외부로 노출되는 빈도나 확률을 크게 낮추어서 상기 저굴절층 및 상기 바인더 수지의 내알카리성을 향상시킬 수 있다. As a reactive functional group is substituted with at least one of the silicones of the polyhedral oligomer silsesquioxane having the cage structure, the mechanical properties of the low refractive layer and the binder resin can be improved, and the remaining silicones As a non-reactive functional group is substituted, a steric hindrance appears in the molecular structure, and the frequency or probability of exposure of the siloxane bond (-Si-O-) to the outside is greatly reduced, so that the alkali resistance of the low refractive layer and the binder resin Can be improved.
상기 폴리실세스퀴옥산에 치환되는 반응성 작용기는 알코올, 아민, 카르복실산, 에폭사이드, 이미드, (메트)아크릴레이트, 니트릴, 노보넨, 올레핀[알릴(ally), 사이클로알케닐(cycloalkenyl) 또는 비닐디메틸실릴 등], 폴리에틸렌글리콜, 싸이올 및 비닐기로 이루어진 군에서 선택된 1종 이상의 작용기를 포함할 수 있으며, 바람직하게는 에폭사이드 또는 (메트)아크릴레이트일 수 있다. The reactive functional groups substituted for the polysilsesquioxane are alcohols, amines, carboxylic acids, epoxides, imides, (meth)acrylates, nitriles, norbornene, olefins (ally, cycloalkenyl) Or vinyldimethylsilyl, etc.], polyethylene glycol, thiol, and may include one or more functional groups selected from the group consisting of vinyl groups, preferably epoxide or (meth)acrylate.
상기 반응성 작용기의 보다 구체적인 예로는 (메트)아크릴레이트, 탄소수 1 내지 20의 알킬 (메트)아크릴레이트, 탄소수 3 내지 20의 사이클로알킬(cycloalkyl) 에폭사이드, 탄소수 1 내지 10의 알킬 사이클로알케인(cycloalkane) 에폭사이드를 들 수 있다. 상기 알킬 (메트)아크릴레이트는 (메트)아크릴레이트와 결합하지 않은 '알킬'의 다른 한 부분이 결합 위치라는 의미이며, 상기 사이클로알킬 에폭사이드는 에폭사이드와 결합하지 않은 '사이클로알킬'의 다른 부분이 결합 위치라는 의미이며, 알킬 사이클로알케인(cycloalkane) 에폭사이드는 사이클로알케인(cycloalkane) 에폭사이드와 결합하지 않은 '알킬'의 다른 부분이 결합 위치라는 의미이다. More specific examples of the reactive functional group include (meth)acrylate, an alkyl (meth)acrylate having 1 to 20 carbon atoms, a cycloalkyl epoxide having 3 to 20 carbon atoms, an alkyl cycloalkane having 1 to 10 carbon atoms. ) Epoxide is mentioned. The alkyl (meth)acrylate means that the other part of'alkyl' that is not bonded to (meth)acrylate is a bonding position, and the cycloalkyl epoxide is another part of'cycloalkyl' that is not bonded to the epoxide. This refers to the bonding position, and the alkyl cycloalkane epoxide means that the other part of the'alkyl' that is not bonded to the cycloalkane epoxide is the bonding site.
한편, 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산은 상술한 반응성 작용기 이외로 탄소수 1 내지 20의 직쇄 또는 분지쇄의 알킬기, 탄소수 6 내지 20의 사이클로헥실기 및 탄소수 6 내지 20의 아릴기로 이루어진 군에서 선택된 1종 이상의 미반응성 작용기가 1이상 더 포함할 수 있다. 이와 같이 상기 폴리실세스퀴옥산에 반응성 작용기와 미반응성 작용기가 표면에 치환됨에 따라서, 상기 반응성 작용기가 1이상 치환된 폴리실세스퀴옥산에서 실록산 결합(-Si-O-)이 분자 내부에 위치하면서 외부로 노출되지 않게 되어 상기 저굴절층 및 반사 방지 필름의 내알카리성 및 내스크래치성을 보다 높일 수 있다. On the other hand, the polysilsesquioxane in which one or more reactive functional groups are substituted is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms other than the above-described reactive functional group. One or more unreactive functional groups selected from the group consisting of may further include one or more. As described above, as a reactive functional group and an unreactive functional group are substituted on the surface of the polysilsesquioxane, a siloxane bond (-Si-O-) is located inside the molecule in the polysilsesquioxane in which one or more reactive functional groups are substituted. While not exposed to the outside, the alkali resistance and scratch resistance of the low refractive layer and the antireflection film can be further improved.
이러한 반응성 작용기가 1 이상 치환되고 케이지(cage)구조를 갖는 다면체 올리고머 실세스퀴옥산(Polyhedral Oligomeric Silsesquioxane, POSS)의 예로는, TMP DiolIsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-PropanediolIsobutyl POSS, Octa(3-hydroxy-3 methylbutyldimethylsiloxy) POSS 등 알코올이 1이상 치환된 POSS; AminopropylIsobutyl POSS, AminopropylIsooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, AminophenylIsobutyl POSS 등 아민이 1이상 치환된 POSS; Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, Octa Maleamic Acid POSS 등 카르복실산이 1이상 치환된 POSS; EpoxyCyclohexylIsobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, GlycidylIsobutyl POSS, GlycidylIsooctyl POSS 등 에폭사이드가 1이상 치환된 POSS; POSS Maleimide Cyclohexyl, POSS Maleimide Isobutyl 등 이미드가 1이상 치환된 POSS; AcryloIsobutyl POSS, (Meth)acrylIsobutyl POSS, (Meth)acrylate Cyclohexyl POSS, (Meth)acrylate Isobutyl POSS, (Meth)acrylate Ethyl POSS, (Meth)acrylEthyl POSS, (Meth)acrylate Isooctyl POSS, (Meth)acrylIsooctyl POSS, (Meth)acrylPhenyl POSS, (Meth)acryl POSS, Acrylo POSS 등 (메트)아크릴레이트가 1이상 치환된 POSS; CyanopropylIsobutyl POSS 등의 니트릴기가 1이상 치환된 POSS; NorbornenylethylEthyl POSS, NorbornenylethylIsobutyl POSS, Norbornenylethyl DiSilanoIsobutyl POSS, Trisnorbornenyl Isobutyl POSS 등 노보넨기가 1이상 치환된 POSS; AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS 등 비닐기 1이상 치환된 POSS; AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS 등의 올레핀이 1이상 치환된 POSS; 탄소수 5 내지 30의 PEG가 치환된 POSS; 또는 MercaptopropylIsobutyl POSS 또는 MercaptopropylIsooctyl POSS 등의 싸이올기가 1이상 치환된 POSS; 등을 들 수 있다. Examples of polyhedral oligomeric silsesquioxane (POSS) having one or more reactive functional groups substituted and having a cage structure include TMP DiolIsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-PropanediolIsobutyl POSS, Octa(3 -hydroxy-3 methylbutyldimethylsiloxy) POSS substituted with one or more alcohols such as POSS; AminopropylIsobutyl POSS, AminopropylIsooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, AminophenylIsobutyl POSS, and other amine-substituted POSS; POSS in which one or more carboxylic acids are substituted, such as Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, and Octa Maleamic Acid POSS; POSS in which one or more epoxides are substituted such as EpoxyCyclohexylIsobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, GlycidylIsobutyl POSS, and GlycidylIsooctyl POSS; POSS with one or more imide substituted, such as POSS Maleimide Cyclohexyl and POSS Maleimide Isobutyl; AcryloIsobutyl POSS, (Meth)acrylIsobutyl POSS, (Meth)acrylate Cyclohexyl POSS, (Meth)acrylate Isobutyl POSS, (Meth)acrylate Ethyl POSS, (Meth)acrylEthyl POSS, (Meth)acrylate Isooctyl POSS, (Meth)acrylIsooctyl POSS, ( POSS in which one or more (meth)acrylates are substituted, such as Meth)acrylPhenyl POSS, (Meth)acryl POSS, and Acrylo POSS; POSS in which one or more nitrile groups are substituted, such as CyanopropylIsobutyl POSS; POSS with 1 or more substituted norbornene groups such as NorbornenylethylEthyl POSS, NorbornenylethylIsobutyl POSS, Norbornenylethyl DiSilanoIsobutyl POSS, and Trisnorbornenyl Isobutyl POSS; POSS substituted with one or more vinyl groups such as AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, and OctaVinyl POSS; POSS in which one or more olefins such as AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, and OctaVinyl POSS are substituted; POSS substituted with PEG having 5 to 30 carbon atoms; Or POSS in which one or more thiol groups such as MercaptopropylIsobutyl POSS or MercaptopropylIsooctyl POSS are substituted; And the like.
상기 광중합성 화합물, 광반응성 작용기를 포함한 함불소 화합물 및 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산(polysilsesquioxane) 간의 가교 중합체는 상기 광중합성 화합물 100중량부 대비 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산 0.5 내지 60중량부, 1.5 내지 45 중량부, 3 내지 40중량부, 또는 5 내지 30중량부를 포함할 수 있다.The crosslinked polymer between the photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and a polysilsesquioxane substituted with one or more reactive functional groups is a poly(polysilsesquioxane) substituted with one or more reactive functional groups relative to 100 parts by weight of the photopolymerizable compound. Silsesquioxane may contain 0.5 to 60 parts by weight, 1.5 to 45 parts by weight, 3 to 40 parts by weight, or 5 to 30 parts by weight.
상기 바인더 수지 중 광중합성 화합물로부터 유래한 부분 대비 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산(polysilsesquioxane)으로부터 유래한 부분의 함량이 너무 작은 경우, 상기 저굴절층의 내스크래치성을 충분히 확보하기 어려울 수 있다. 또한, 상기 바인더 수지 중 광중합성 화합물로부터 유래한 부분 대비 상기 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산(polysilsesquioxane)으로부터 유래한 부분의 함량이 너무 큰 경우에도, 상기 저굴절층이나 반사 방지 필름의 투명도가 저하될 수 있으며, 스크래치성이 오히려 저하될 수 있다. When the content of the portion derived from polysilsesquioxane in which the reactive functional group is substituted by one or more relative to the portion derived from the photopolymerizable compound in the binder resin is too small, sufficient scratch resistance of the low refractive layer is secured. It can be difficult to do. In addition, even when the content of the portion derived from polysilsesquioxane in which one or more reactive functional groups are substituted relative to the portion derived from the photopolymerizable compound in the binder resin is too large, the low refractive layer or the antireflection film The transparency of the material may be deteriorated, and the scratch property may be rather deteriorated.
한편, 상기 일 구현예에 따른 반사 방지 필름에 포함된 저굴절층은, 상기 바인더 수지에 분산된 무기 미립자를 포함할 수 있다. 상기 무기 미립자는 나노 미터 또는 마이크로 미터 단위의 직경을 갖는 무기 입자를 의미한다. Meanwhile, the low refractive index layer included in the antireflection film according to the embodiment may include inorganic fine particles dispersed in the binder resin. The inorganic fine particles refer to inorganic particles having a diameter of nanometers or micrometers.
구체적으로, 상기 무기 미립자는 솔리드형 무기 나노 입자 및/또는 중공형 무기 나노 입자를 포함할 수 있으며, 상기 솔리드형 무기 나노 입자는 100 ㎚ 이하의 직경을 가지며 그 내부에 빈 공간이 존재하지 않는 형태의 입자를 의미한다. Specifically, the inorganic fine particles may include solid inorganic nanoparticles and/or hollow inorganic nanoparticles, and the solid inorganic nanoparticles have a diameter of 100 nm or less and no empty space exists therein. Means the particles of.
또한, 상기 중공형 무기 나노 입자는 200 ㎚ 이하의 직경을 가지며 그 표면 및/또는 내부에 빈 공간이 존재하는 형태의 입자를 의미한다. In addition, the hollow inorganic nanoparticles refer to particles having a diameter of 200 nm or less and having an empty space on the surface and/or inside.
상기 솔리드형 무기 나노 입자는 0.5 내지 100㎚, 1 내지 80㎚, 2 내지 70nm 또는 5 내지 60nm 의 직경을 가질 수 있다. The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, 1 to 80 nm, 2 to 70 nm, or 5 to 60 nm.
상기 중공형 무기 나노 입자는 1 내지 200㎚, 10 내지 150㎚, 20 내지 130nm, 30 내지 110nm 또는 40 내지 100nm의 직경을 가질 수 있다.
The hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, 10 to 150 nm, 20 to 130 nm, 30 to 110 nm, or 40 to 100 nm.
한편, 상기 솔리드형 무기 나노 입자 및 상기 중공형 무기 나노 입자 각각은 표면에 (메트)아크릴레이트기, 에폭사이드기, 비닐기(Vinyl) 및 싸이올기(Thiol)로 이루어진 군에서 선택된 1종 이상의 반응성 작용기를 함유할 수 있다. 상기 솔리드형 무기 나노 입자 및 상기 중공형 무기 나노 입자 각각이 표면에 상술한 반응성 작용기를 함유함에 따라서, 상기 저굴절층은 보다 높은 가교도를 가질 수 있으며, 이에 따라 보다 향상된 내스크래치성 및 방오성을 확보할 수 있다.Meanwhile, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one reactive group selected from the group consisting of a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl) and a thiol group (Thiol) on the surface. It may contain functional groups. As each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles contains the above-described reactive functional groups on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby securing more improved scratch resistance and antifouling properties. can do.
상기 중공형 무기 나노 입자로는 그 표면이 불소계 화합물로 코팅된 것을 단독으로 사용하거나, 불소계 화합물로 표면이 코팅되지 않는 중공형 무기 나노 입자와 혼합하여 사용할 수 있다. 상기 중공형 무기 나노 입자의 표면을 불소계 화합물로 코팅하면 표면 에너지를 보다 낮출 수 있으며, 이에 따라 상기 저굴절층의 내구성이나 내스크래치성을 보다 높일 수 있다. As the hollow inorganic nanoparticles, those coated with a fluorine-based compound may be used alone, or may be mixed with hollow inorganic nanoparticles whose surface is not coated with a fluorine-based compound. When the surface of the hollow inorganic nanoparticles is coated with a fluorine-based compound, the surface energy may be lowered, and thus the durability and scratch resistance of the low refractive layer may be further improved.
상기 중공형 무기 나노 입자의 표면에 불소계 화합물을 코팅하는 방법으로 통상적으로 알려진 입자 코팅 방법이나 중합 방법 등을 큰 제한 없이 사용할 수 있으며, 예를 들어 상기 중공형 무기 나노 입자 및 불소계 화합물을 물과 촉매의 존재 하에서 졸-겔 반응 시켜서 가수 분해 및 축합 반응을 통하여 상기 중공형 무기 나노 입자의 표면에 불소계 화합물을 결합시킬 수 있다. As a method of coating a fluorine-based compound on the surface of the hollow inorganic nanoparticles, a conventionally known particle coating method or a polymerization method may be used without great limitation. For example, the hollow inorganic nanoparticles and the fluorine-based compound are mixed with water and a catalyst. In the presence of a sol-gel reaction, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reactions.
상기 중공형 무기 나노 입자의 구체적인 예로는 중공 실리카 입자를 들 수 있다. 상기 중공 실리카는 유기 용매에 보다 용이하게 분산되기 위해서 표면에 치환된 소정의 작용기를 포함할 수 있다. 상기 중공 실리카 입자 표면에 치환 가능한 유기 작용기의 예가 크게 한정되는 것은 아니며, 예를 들어 (메트)아크릴레이트기, 비닐기, 히드록시기, 아민기, 알릴기(allyl), 에폭시기, 이소시아네이트기, 아민기, 또는 불소 등이 상기 중공 실리카 표면에 치환될 수 있다.A specific example of the hollow inorganic nanoparticles may be hollow silica particles. The hollow silica may include a predetermined functional group substituted on the surface to be more easily dispersed in an organic solvent. Examples of the organic functional groups that can be substituted on the surface of the hollow silica particles are not largely limited, and for example, (meth)acrylate group, vinyl group, hydroxy group, amine group, allyl group, epoxy group, isocyanate group, amine group, Alternatively, fluorine or the like may be substituted on the hollow silica surface.
상기 저굴절층의 바인더 수지는 상기 광중합성 화합물 100중량부에 대하여 상기 무기 미립자 10 내지 600중량부, 20 내지 550중량부, 50 내지 500중량부, 100 내지 400중량부 또는 150 내지 350중량부를 포함할 수 있다. 상기 무기 미립자가 과량으로 첨가될 경우 바인더의 함량 저하로 인하여 코팅막의 내스크래치성이나 내마모성이 저하될 수 있다. The binder resin of the low refractive layer contains 10 to 600 parts by weight, 20 to 550 parts by weight, 50 to 500 parts by weight, 100 to 400 parts by weight, or 150 to 350 parts by weight of the inorganic fine particles based on 100 parts by weight of the photopolymerizable compound can do. When the inorganic fine particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.
한편, 상기 저굴절층은 광중합성 화합물, 반응성 작용기를 포함한 함불소 화합물, 반응성 작용기가 1 이상 치환된 폴리실세스퀴옥산 및 상기 무기 미립자를 포함하는 광경화성 코팅 조성물을 상기 광투과성 기재 상에 도포하고 도포된 결과물을 광경화함으로써 얻어질 수 있다. On the other hand, the low refractive layer is a photopolymerizable compound, a fluorine-containing compound containing a reactive functional group, polysilsesquioxane having one or more reactive functional groups substituted, and a photocurable coating composition containing the inorganic fine particles is applied on the light-transmitting substrate And it can be obtained by photocuring the applied result.
또한, 상기 광경화성 코팅 조성물은 광개시제를 더 포함할 수 있다. 이에 따라, 상술한 광경화성 코팅 조성물로부터 제조되는 저굴절층에는 상기 광중합 개시제가 잔류할 수 있다. In addition, the photocurable coating composition may further include a photoinitiator. Accordingly, the photopolymerization initiator may remain in the low refractive layer prepared from the above-described photocurable coating composition.
상기 광중합 개시제로는 광경화성 수지 조성물에 사용될 수 있는 것으로 알려진 화합물이면 크게 제한 없이 사용 가능하며, 구체적으로 벤조 페논계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물, 트리아진계 화합물, 옥심계 화합물 또는 이들의 2종 이상의 혼합물을 사용할 수 있다. As the photoinitiator, any compound known to be used in a photocurable resin composition may be used without limitation, and specifically, a benzophenone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or A mixture of two or more of these may be used.
상기 광중합성 화합물 100중량부에 대하여, 상기 광중합 개시제는 1 내지 100중량부, 5 내지 90중량부, 10 내지 80중량부, 20 내지 70중량부 또는 30 내지 60중량부의 함량으로 사용될 수 있다. 상기 광중합 개시제의 양이 너무 작으면, 상기 광경화성 코팅 조성물의 광경화 단계에서 미경화되어 잔류하는 물질이 발행할 수 있다. 상기 광중합 개시제의 양이 너무 많으면, 미반응 개시제가 불순물로 잔류하거나 가교 밀도가 낮아져서 제조되는 필름의 기계적 물성이 저하되거나 반사율이 크게 높아질 수 있다. With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight, 5 to 90 parts by weight, 10 to 80 parts by weight, 20 to 70 parts by weight, or 30 to 60 parts by weight. If the amount of the photopolymerization initiator is too small, a material that remains uncured in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity or the crosslinking density is low, so that the mechanical properties of the produced film may be deteriorated or the reflectance may be greatly increased.
또한, 상기 광경화성 코팅 조성물을 유기 용매를 더 포함할 수 있다. 상기 유기 용매의 비제한적인 예를 들면 케톤류, 알코올류, 아세테이트류 및 에테르류, 또는 이들의 2종 이상의 혼합물을 들 수 있다. In addition, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or mixtures of two or more thereof.
이러한 유기 용매의 구체적인 예로는, 메틸에틸케논, 메틸이소부틸케톤, 아세틸아세톤 또는 이소부틸케톤 등의 케톤류; 메탄올, 에탄올, n-프로판올, i-프로판올, n-부탄올, i-부탄올, 또는 t-부탄올 등의 알코올류; 에틸아세테이트, i-프로필아세테이트, 또는 폴리에틸렌글리콜 모노메틸에테르 아세테이트 등의 아세테이트류; 테트라하이드로퓨란 또는 프로필렌글라이콜 모노메틸에테르 등의 에테르류; 또는 이들의 2종 이상의 혼합물을 들 수 있다. Specific examples of such an organic solvent include ketones such as methyl ethylkenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these may be mentioned.
상기 유기 용매는 상기 광경화성 코팅 조성물에 포함되는 각 성분들을 혼합하는 시기에 첨가되거나 각 성분들이 유기 용매에 분산 또는 혼합된 상태로 첨가되면서 상기 광경화성 코팅 조성물에 포함될 수 있다. 상기 광경화성 코팅 조성물 중 유기 용매의 함량이 너무 작으면, 상기 광경화성 코팅 조성물의 흐름성이 저하되어 최종 제조되는 필름에 줄무늬가 생기는 등 불량이 발생할 수 있다. 또한, 상기 유기 용매의 과량 첨가시 고형분 함량이 낮아져, 코팅 및 성막이 충분히 되지 않아서 필름의 물성이나 표면 특성이 저하될 수 있고, 건조 및 경화 과정에서 불량이 발생할 수 있다. 이에 따라, 상기 광경화성 코팅 조성물은 포함되는 성분들의 전체 고형분의 농도가 1중량% 내지 50중량%, 또는 2 내지 20중량%가 되도록 유기 용매를 포함할 수 있다. The organic solvent may be added at the time of mixing each component included in the photocurable coating composition or may be included in the photocurable coating composition while each component is added in a dispersed or mixed state in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition decreases, and thus defects such as streaks may occur in the final film. In addition, when an excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not sufficiently performed, so that physical properties or surface properties of the film may be deteriorated, and defects may occur during drying and curing. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% to 50% by weight, or 2 to 20% by weight.
한편, 상기 광경화성 코팅 조성물을 도포하는데 통상적으로 사용되는 방법 및 장치를 별 다른 제한 없이 사용할 수 있으며, 예를 들어, Meyer bar 등의 바 코팅법, 그라비아 코팅법, 2 roll reverse 코팅법, vacuum slot die 코팅법, 2 roll 코팅법 등을 사용할 수 있다. On the other hand, methods and devices commonly used to apply the photocurable coating composition can be used without any other limitation. For example, bar coating methods such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot Die coating method, 2 roll coating method, etc. can be used.
상기 광경화성 코팅 조성물을 광경화 시키는 단계에서는 200 내지 400nm 파장의 자외선 또는 가시 광선을 조사할 수 있고, 조사시 노광량은 100 내지 4,000 mJ/㎠ 이 바람직하다. 노광 시간도 특별히 한정되는 것이 아니고, 사용 되는 노광 장치, 조사 광선의 파장 또는 노광량에 따라 적절히 변화시킬 수 있다.In the step of photocuring the photocurable coating composition, ultraviolet or visible light having a wavelength of 200 to 400 nm may be irradiated, and the exposure amount at the time of irradiation is preferably 100 to 4,000 mJ/cm 2. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure.
또한, 상기 광경화성 코팅 조성물을 광경화 시키는 단계에서는 질소 대기 조건을 적용하기 위하여 질소 퍼징 등을 할 수 있다. In addition, in the step of photocuring the photocurable coating composition, nitrogen purging may be performed to apply a nitrogen atmosphere.
상기 일 구현예에 하드 코팅 필름에 포함된 하드코팅층으로는 통상적으로 알려진 하드코팅층을 큰 제한 없이 사용할 수 있다. 상기 하드코팅층의 일 예로서, 광경화성 수지를 포함하는 바인더 수지; 및 상기 바인더 수지에 분산된 유기 또는 무기 미립자를 포함하는 하드코팅층을 들 수 있다.As the hard coating layer included in the hard coating film in the above embodiment, a commonly known hard coating layer may be used without great limitation. As an example of the hard coating layer, a binder resin including a photocurable resin; And a hard coating layer comprising organic or inorganic fine particles dispersed in the binder resin.
상기 하드코팅층에 포함되는 광경화성 수지는 자외선 등의 광이 조사되면 중합 반응을 일으킬 수 있는 광경화성 화합물의 중합체로서, 당업계에서 통상적인 것일 수 있다. 구체적으로, 상기 광경화성 수지는 우레탄 아크릴레이트 올리고머, 에폭사이드 아크릴레이트 올리고머, 폴리에스터 아크릴레이트, 및 폴리에테르 아크릴레이트로 이루어진 반응성 아크릴레이트 올리고머 군; 및 디펜타에리스리톨 헥사아크릴레이트, 디펜타에리스리톨 하이드록시 펜타아크릴레이트, 펜타에리스리톨 테트라아크릴레이트, 펜타에리스리톨 트리아크릴레이트, 트리메틸렌 프로필 트리아크릴레이트, 프로폭시레이티드 글리세롤 트리아크릴레이트, 트리메틸프로판 에톡시 트리아크릴레이트, 1,6-헥산디올디아크릴레이트, 프로폭시레이티드 글리세로 트리아크릴레이트, 트리프로필렌 글리콜 디아크릴레이트, 및 에틸렌글리콜 디아크릴레이트로 이루어진 다관능성 아크릴레이트 단량체 군에서 선택되는 1 종 이상을 포함할 수 있다.The photocurable resin included in the hard coating layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy tri At least one selected from the group of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include.
상기 유기 또는 무기 미립자는 입경의 구체적으로 한정되는 것은 아니나, 예를 들어 유기 미립자는 1 내지 10㎛의 입경을 가질 수 있으며, 상기 무기 입자는 1 ㎚ 내지 500 ㎚, 또는 1㎚ 내지 300㎚의 입경을 가질 수 있다. 상기 유기 또는 무기 미립자는 입경은 부피 평균 입경으로 정의될 수 있다.The organic or inorganic fine particles are not specifically limited in particle size, for example, the organic fine particles may have a particle diameter of 1 to 10 μm, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm Can have The particle diameter of the organic or inorganic fine particles may be defined as a volume average particle diameter.
또한, 상기 하드코팅층에 포함되는 유기 또는 무기 미립자의 구체적인 예가 한정되는 것은 아니나, 예를 들어 상기 유기 또는 무기 미립자는 아크릴계 수지, 스티렌계 수지, 에폭사이드 수지 및 나일론 수지로 이루어진 유기 미립자이거나 산화규소, 이산화티탄, 산화인듐, 산화주석, 산화지르코늄 및 산화아연으로 이루어진 무기 미립자일 수 있다.In addition, a specific example of the organic or inorganic fine particles included in the hard coating layer is not limited, for example, the organic or inorganic fine particles are organic fine particles composed of acrylic resin, styrene resin, epoxide resin, and nylon resin, or silicon oxide, It may be inorganic fine particles composed of titanium dioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.
상기 하드코팅층의 바인더 수지는 수평균분자량 10,000 이상, 13,000 이상, 15,000 내지 100,000 또는 20,000 내지 80,000의 고분자량 (공)중합체를 더 포함할 수 있다. 상기 고분자량 (공)중합체는 셀룰로스계 폴리머, 아크릴계 폴리머, 스티렌계 폴리머, 에폭사이드계 폴리머, 나일론계 폴리머, 우레탄계 폴리머, 및 폴리올레핀계 폴리머로 이루어진 군에서 선택되는 1 종 이상일 수 있다.The binder resin of the hard coating layer may further include a high molecular weight (co)polymer having a number average molecular weight of 10,000 or more, 13,000 or more, 15,000 to 100,000, or 20,000 to 80,000. The high molecular weight (co)polymer may be at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.
한편, 상기 하드코팅층의 또 다른 일 예로서, 광경화성 수지의 유기 고분자 수지; 및 상기 유기 고분자 수지에 분산된 대전 방지제를 포함하는 하드코팅층을 들 수 있다. Meanwhile, as another example of the hard coating layer, an organic polymer resin of a photocurable resin; And a hard coating layer comprising an antistatic agent dispersed in the organic polymer resin.
상기 대전 방지제는 4급 암모늄염 화합물; 피리디늄염; 1 내지 3개의 아미노기를 갖는 양이온성 화합물; 설폰산 염기, 황산 에스테르 염기, 인산 에스테르 염기, 포스폰산 염기 등의 음이온성 화합물; 아미노산계 또는 아미노 황산 에스테르계 화합물 등의 양성 화합물; 이미노 알코올계 화합물, 글리세린계 화합물, 폴리에틸렌 글리콜계 화합물 등의 비이온성 화합물; 주석 또는 티타늄 등을 포함한 금속 알콕사이드 화합물 등의 유기 금속 화합물; 상기 유기 금속 화합물의 아세틸아세토네이트 염 등의 금속 킬레이트 화합물; 이러한 화합물들의 2종 이상의 반응물 또는 고분자화물; 이러한 화합물들의 2종 이상의 혼합물일 수 있다. 여기서, 상기 4급 암모늄염 화합물은 분자 내에 1개 이상의 4급 암모늄염기를 가지는 화합물일 수 있으며, 저분자형 또는 고분자형을 제한 없이 사용할 수 있다. The antistatic agent is a quaternary ammonium salt compound; Pyridinium salt; Cationic compounds having 1 to 3 amino groups; Anionic compounds such as a sulfonic acid base, a sulfuric acid ester base, a phosphoric acid ester base, and a phosphonic acid base; Amphoteric compounds such as amino acid or amino sulfuric acid ester compounds; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Reactants or polymers of two or more of these compounds; It may be a mixture of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium base groups in the molecule, and a low molecular or high molecular type may be used without limitation.
또한, 상기 대전 방지제로는 도전성 고분자와 금속 산화물 미립자도 사용할 수 있다. 상기 도전성 고분자로는 방향족 공액계 폴리(파라페닐렌), 헤테로고리식 공액계의 폴리피롤, 폴리티오펜, 지방족 공액계의 폴리아세틸렌, 헤테로 원자를 함유한 공액예의 폴리아닐린, 혼합 형태 공액계의 폴리(페닐렌 비닐렌), 분자중에 복수의 공액 사슬을 갖는 공액계인 복쇄형 공액계 화합물, 공액 고분자 사슬을 포화 고분자에 그래프트 또는 블록 공중합시킨 도전성 복합체 등이 있다. 또한, 상기 금속 산화물 미립자로는 산화 아연, 산화 안티몬, 산화 주석, 산화 세륨, 인듐 주석 산화물, 산화 인듐, 산화 알루미늄, 안티몬 도핑된 산화 주석, 알루미늄 도핑된 산화 아연 등을 들 수 있다.In addition, a conductive polymer and metal oxide fine particles may be used as the antistatic agent. The conductive polymers include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, mixed conjugated poly( Phenylene vinylene), a conjugated multi-chain conjugated compound having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain onto a saturated polymer. In addition, the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, and the like.
상기 광중합성 수지의 유기 고분자 수지; 및 상기 유기 고분자 수지에 분산된 대전 방지제를 포함하는 하드코팅층은 알콕시 실란계 올리고머 및 금속 알콕사이드계 올리고머로 이루어진 군에서 선택되는 1종 이상의 화합물을 더 포함할 수 있다.Organic polymer resin of the photopolymerizable resin; And the hard coating layer including the antistatic agent dispersed in the organic polymer resin may further include one or more compounds selected from the group consisting of alkoxy silane-based oligomers and metal alkoxide-based oligomers.
상기 알콕시 실란계 화합물은 당업계에서 통상적인 것일 수 있으나, 예를 들어 테트라메톡시실란, 테트라에톡시실란, 테트라이소프로폭시실란, 메틸트리메톡시실란, 메틸트리에톡시실란, 메타크릴록시프로필트리메톡시실란, 글리시독시프로필 트리메톡시실란 및 글리시독시프로필 트리에톡시실란으로 이루어진 군에서 선택되는 1종 이상의 화합물일 수 있다.The alkoxy silane compound may be conventional in the art, but, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be one or more compounds selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.
또한, 상기 금속 알콕사이드계 올리고머는 금속 알콕사이드계 화합물 및 물을 포함하는 조성물의 졸-겔 반응을 통해 제조할 수 있다. 상기 졸-겔 반응은 전술한 알콕시 실란계 올리고머의 제조 방법에 준하는 방법으로 수행할 수 있다. 다만, 상기 금속 알콕사이드계 화합물은 물과 급격하게 반응할 수 있으므로, 상기 금속 알콕사이드계 화합물을 유기용매에 희석한 후 물을 천천히 드로핑하는 방법으로 상기 졸-겔 반응을 수행할 수 있다. 이때, 반응 효율 등을 감안하여, 물에 대한 금속 알콕사이드 화합물의 몰비(금속이온 기준)는 3 내지 170인 범위 내에서 조절하는 것일 수 있다.In addition, the metal alkoxide oligomer may be prepared through a sol-gel reaction of a composition comprising a metal alkoxide compound and water. The sol-gel reaction may be performed in a manner similar to the method for preparing the alkoxysilane-based oligomer described above. However, since the metal alkoxide-based compound may react rapidly with water, the sol-gel reaction may be performed by slowly dropping water after diluting the metal alkoxide-based compound in an organic solvent. In this case, in consideration of reaction efficiency, etc., the molar ratio of the metal alkoxide compound to water (based on metal ions) may be adjusted within a range of 3 to 170.
여기서, 상기 금속 알콕사이드계 화합물은 티타늄 테트라-이소프로폭사이드, 지르코늄 이소프로폭사이드 및 알루미늄 이소프로폭사이드로 이루어진 군에서 선택되는 1종 이상의 화합물일 수 있다.Here, the metal alkoxide-based compound may be one or more compounds selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.
상기 일 구현예에 따른 하드 코팅 필름에 포함된 광투과성 기재는 광 투과도가 90% 이상이고, 헤이즈 1% 이하인 투명 필름일 수 있다. The light-transmitting substrate included in the hard coating film according to the embodiment may be a transparent film having a light transmittance of 90% or more and a haze of 1% or less.
상기 광투과성 기재는300nm 이상의 파장에서 투과율이 50% 이상일 수 있다. 또한, 상기 광투과성 기재는, 필름을 통해 수증기압이 높은 곳에서 낮은 곳으로 습기가 이동하는 투습 현상이 거의 이루어지지 않는 저투습 특성을 갖는 고분자 필름으로, 예를 들어, 상기 광투과성 기재는 30 내지 40℃의 온도 및 90 내지 100% 상대습도의 조건에서 투습률이 50 g/m
2·day 이하, 30 g/m
2·day 이하, 20 g/m
2·day 이하 또는 15 g/m
2·day 이하일 수 있다. 상기 광투과성 기재의 투습률이 50g/m
2·day 초과하면 반사 방지 필름 내로 습기가 투습되어 고온 환경에서 상기 반사 방지 필름을 적용한 디스플레이의 열화 현상이 발생할 수 있다.The light-transmitting substrate may have a transmittance of 50% or more at a wavelength of 300 nm or more. In addition, the light-transmitting substrate is a polymer film having a low moisture permeability characteristic in which moisture permeation is hardly performed in which moisture moves from a high water vapor pressure to a low water vapor pressure through the film.For example, the light-transmitting substrate is 30 to The moisture permeability is 50 g/m 2 ·day or less, 30 g/m 2 ·day or less, 20 g/m 2 ·day or less or 15 g/m 2 · at a temperature of 40°C and 90 to 100% relative humidity. May be less than a day. When the moisture permeability of the light-transmitting substrate exceeds 50 g/m 2 ·day, moisture permeates into the anti-reflective film, and the display to which the anti-reflective film is applied may be deteriorated in a high temperature environment.
앞서 서술한 바와 같이, 상기 피크의 2θ 값은,
고분자의 결정 내 특정 면간 거리 (d-spacing)에 기인한 것이고, 상기 광투과성 기재 내의 고분자의 결정 상태에 기인한 것일 수 있고, 상기 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭은,
상기 광투과성 기재 내의 고분자 결정의 크기에 기인한 것일 수 있다.As previously described, the 2θ value of the peak is, It is due to the specific interplanar distance (d-spacing) in the crystal of the polymer, and may be due to the crystal state of the polymer in the light-transmitting substrate. It may be due to the size of the polymer crystal in the light-transmitting substrate.
또한, 상기 광투과성 기재 내의 고분자 결정의 특정 면간 거리 (d-spacing) 및 크기는, 광투과성 기재의 제조 과정에서의 연신비, 연신 온도 및 연신 후 냉각속도 등과 관련이 있으며, 또한, 상기 광투과성 기재의 일 방향 및 상기 일 방향과 수직한 방향 간의 인장강도 비율과 관련이 있을 수 있다.In addition, the specific interplanar distance (d-spacing) and size of the polymer crystal in the light-transmitting substrate is related to the stretching ratio, the stretching temperature, and the cooling rate after stretching in the manufacturing process of the light-transmitting substrate. In addition, the light-transmitting substrate It may be related to the ratio of the tensile strength between one direction of and a direction perpendicular to the one direction.
구체적으로, 상기 광투과성 기재는, 일 방향 및 상기 일 방향과 수직한 방향으로 상이한 인장강도의 값이 나타나며, 예를 들어, 일 방향의 인장강도에 대한, 상기 일 방향과 수직한 방향의 인장강도의 비율은 2 이상, 2 내지 30, 2.1 내지 20, 2.2 내지 10, 또는 2.2 내지 5일 수 있다. Specifically, the light-transmitting substrate has different values of tensile strength in one direction and a direction perpendicular to the one direction, for example, tensile strength in a direction perpendicular to the one direction relative to the tensile strength in one direction The ratio of may be 2 or more, 2 to 30, 2.1 to 20, 2.2 to 10, or 2.2 to 5.
이때, 상기 일 방향의 인장강도는 상기 일 방향과 수직한 방향의 인장강도 보다 작은 값을 갖는다. 상기 인장강도 비율이 2 미만이면 반사 방지 필름 부위별 반사율 및 투광율 편차가 클 수 있고, 가시광선의 간섭에 의한 레인보우 현상이 발생할 수 있다.In this case, the tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction. If the tensile strength ratio is less than 2, a variation in reflectance and transmittance of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
상기 광투과성 기재는 일 방향의 인장강도가 50 내지 500 Mpa, 60 내지 450 Mpa, 또는 70 내지 400 Mpa일 수 있다.The light-transmitting substrate may have a tensile strength of 50 to 500 Mpa, 60 to 450 Mpa, or 70 to 400 Mpa in one direction.
또한, 상기 광투과성 기재의 상기 일 방향과 수직한 방향의 인장강도는 50 내지 500 Mpa, 60 내지 450 Mpa, 또는 70 내지 400 Mpa일 수 있다.In addition, the tensile strength of the light-transmitting substrate in a direction perpendicular to the one direction may be 50 to 500 Mpa, 60 to 450 Mpa, or 70 to 400 Mpa.
상기 광투과성 기재는 파장 400 ㎚ 내지 800 ㎚에서 측정되는 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 이상, 5,200 내지 50,000 nm, 5,400 내지 40,000 nm, 5,600 내지 30,000 nm, 5,800 내지 20,000 nm, 또는 5,800 내지 10,000 nm일 수 있다. 이러한 광투과성 기재의 구체적인 예로는 일축 연신 폴리에틸렌 테레프탈레이트 필름 또는 이축 연신 폴리에틸렌 테레프탈레이트 필름을 들 수 있다.The light-transmitting substrate has a retardation (Rth) of 5,000 nm or more in the thickness direction measured at a wavelength of 400 nm to 800 nm, 5,200 to 50,000 nm, 5,400 to 40,000 nm, 5,600 to 30,000 nm, 5,800 to 20,000 nm, or 5,800 to Can be 10,000 nm. Specific examples of such a light-transmitting substrate include a uniaxially oriented polyethylene terephthalate film or a biaxially oriented polyethylene terephthalate film.
상기 광투과성 기재의 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 미만이면 반사 방지 필름 부위별 반사율 및 투광율 편차가 클 수 있고, 가시광선의 간섭에 의한 레인보우 현상이 발생할 수 있다.When the retardation (Rth) in the thickness direction of the light-transmitting substrate is less than 5,000 nm, the reflectance and transmittance variation of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
두께 방향의 리타데이션은 통상적으로 알려진 측정 방법 및 측정 장치를 통하여 확인할 수 있다. 예를 들어, 두께 방향의 리타데이션의 측정 장치로는 AXOMETRICS사제의 상품명 「엑소스캔(AxoScan) 등을 들 수 있다. The retardation in the thickness direction can be confirmed through a commonly known measuring method and measuring device. For example, as an apparatus for measuring retardation in the thickness direction, the brand name "AxoScan" manufactured by AXOMETRICS, etc. is mentioned.
예를 들어, 두께 방향의 리타데이션의 측정 조건으로는, 상기 광투과성 기재 필름에 대하여, 굴절률(589nm)값을 상기 측정 장치에 입력한 후, 온도: 25℃, 습도: 40%의 조건 하, 파장 590nm의 광을 사용하여, 광투과성 기재 필름의 두께 방향의 리타데이션을 측정하고, 구해진 두께 방향의 리타데이션 측정값(측정 장치의 자동 측정(자동 계산)에 의한 측정값)에 기초하여, 필름의 두께 10㎛당 리타데이션 값으로 환산함으로써 구할 수 있다. 또한, 측정 시료의 광투과성 기재의 사이즈는, 측정기의 스테이지의 측광부(직경: 약 1cm)보다도 크면 되기 때문에, 특별히 제한되지 않지만, 세로: 76mm, 가로 52mm, 두께 13㎛의 크기로 할 수 있다. For example, as a measurement condition for retardation in the thickness direction, after inputting a refractive index (589 nm) value into the measuring device for the light-transmitting base film, under the conditions of temperature: 25°C and humidity: 40%, Using light having a wavelength of 590 nm, the retardation in the thickness direction of the light-transmitting base film is measured, and based on the obtained retardation measurement value in the thickness direction (measured value by automatic measurement (automatic calculation) of the measuring device), the film It can be calculated|required by converting it to the retardation value per 10 micrometers of thickness of. In addition, the size of the light-transmitting substrate of the measurement sample is not particularly limited, since it may be larger than the light metering portion (diameter: about 1 cm) of the stage of the measuring device, but it can be made into a size of 76 mm in length, 52 mm in width, and 13 μm in thickness. .
또한, 두께 방향의 리타데이션의 측정에 이용하는 「상기 광투과성 기재의 굴절률(589nm)」의 값은, 리타데이션의 측정 대상이 되는 필름을 형성하는 광투과성 기재와 동일한 종류의 수지 필름을 포함하는 미연신 필름을 형성한 후, 이러한 미연신 필름을 측정 시료로서 사용하고(또한, 측정 대상이 되는 필름이 미연신 필름인 경우에는, 그 필름을 그대로 측정 시료로서 사용할 수 있음), 측정 장치로서 굴절률 측정 장치(가부시끼가이샤 아타고제의 상품명 「NAR-1T SOLID」)를 사용하며, 589nm의 광원을 사용하고, 23℃의 온도 조건에서, 측정 시료의 면 내 방향(두께 방향과는 수직인 방향)의 589nm의 광에 대한 굴절률을 측정하여 구할 수 있다. In addition, the value of the ``refractive index of the light-transmitting substrate (589 nm)'' used in the measurement of retardation in the thickness direction is unconventional including a resin film of the same type as the light-transmitting substrate forming the film to be measured for retardation. After forming a new film, such an unstretched film is used as a measurement sample (in addition, when the film to be measured is an unstretched film, the film can be used as a measurement sample as it is), and a refractive index measurement as a measuring device Using a device (trade name "NAR-1T SOLID" manufactured by Atago Co., Ltd.), using a light source of 589 nm, under a temperature condition of 23°C, in the in-plane direction (direction perpendicular to the thickness direction) of the measurement sample. It can be obtained by measuring the refractive index for light of 589 nm.
또한, 상기 광투과성 고분자 기재의 소재는 트리아세틸셀룰로오스, 사이클로올레핀중합체, 폴리아크릴레이트, 폴리카보네이트, 폴리에틸렌 테레프탈레이트 등일 수 있다. 또한, 상기 기재 필름의 두께는 생산성 등을 고려하여 10 내지 300㎛일 수 있으나, 이에 한정하는 것은 아니다.In addition, the material of the light-transmitting polymer substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate, or the like. In addition, the thickness of the base film may be 10 to 300 μm in consideration of productivity, but is not limited thereto.
상기 일 구현예의 반사 방지 필름은 낮은 반사율을 나타내어 높은 투광도 및 우수한 광학 특성을 구현할 수 있다. 구체적으로, 상기 반사 방지 필름은 380㎚ 내지 780㎚의 가시 광선 파장대 영역에서 평균 반사율이 2.0% 이하, 1.6% 이하, 1.2% 이하, 0.05% 내지 0.9%, 0.10% 내지 0.70%, 또는 0.2% 내지 0.5%의 평균 반사율을 가질 수 있다. The antireflection film of the embodiment may exhibit a low reflectance, thereby implementing high light transmittance and excellent optical properties. Specifically, the antireflection film has an average reflectance of 2.0% or less, 1.6% or less, 1.2% or less, 0.05% to 0.9%, 0.10% to 0.70%, or 0.2% in the visible light wavelength range of 380 nm to 780 nm. It may have an average reflectivity of 0.5%.
또한, 상기 일 구현예의 반사 방지 필름은 낮은 반사율 편차 및 투광율 편차를 나타내어 우수한 광학 특성을 구현할 수 있다. 구체적으로, 상기 반사 방지 필름의 평균 반사율 편차는 0.2%p 이하, 0.01 내지 0.18%p 또는 0.02 내지 0.17%p일 수 있다. 또한, 상기 반사 방지 필름의 투광율 편차는 0.2%p 이하, 0.01 내지 0.15%p 또는 0.01 내지 0.10%p일 수 있다.In addition, the antireflection film of the embodiment may exhibit low reflectance deviation and light transmittance deviation, thereby implementing excellent optical properties. Specifically, the average reflectance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.18%p, or 0.02 to 0.17%p. In addition, the light transmittance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.15%p, or 0.01 to 0.10%p.
상기 평균 반사율 편차는, 상기 반사 방지 필름에서 선정된 2개 이상의 특정 부분(포인트)의 380 내지 780nm의 가시 광선 파장대 영역에서의 평균 반사율과, 상기 평균 반사율의 평균값 간의 차이(절대값)를 의미한다. 상기 평균 반사율 편차를 산출하는 방법으로는, 구체적으로, 1) 반사 방지 필름 내에 2개 이상의 포인트 선정하고, 2) 상기 2개 이상의 포인트에서 평균 반사율 각각 측정하고, 3) 2)단계에서 측정된 평균 반사율의 산술 평균을 계산하고, 및 4) 각 포인트의 평균 반사율과 3)단계의 산술 평균의 차이(절대값)를 계산하여, 최종적으로 2개 이상의 평균 반사율의 편차를 산출할 수 있다. 이때, 2개 이상의 상기 평균 반사율의 편차 중 가장 큰 값을 갖는 평균 반사율 편차는 0.2%p 이하일 수 있다.The average reflectance deviation refers to the difference (absolute value) between the average reflectance in the visible light wavelength range of 380 to 780 nm of two or more specific portions (points) selected in the antireflection film and the average value of the average reflectance. . As a method of calculating the average reflectance deviation, specifically, 1) selecting two or more points in the antireflection film, 2) measuring the average reflectance at each of the two or more points, and 3) the average measured in step 2) By calculating the arithmetic mean of the reflectance, and 4) calculating the difference (absolute value) between the average reflectance of each point and the arithmetic mean of step 3), finally, a deviation of two or more average reflectances can be calculated. In this case, the average reflectance deviation having the largest value among the deviations of the two or more average reflectances may be 0.2%p or less.
한편, 상기 투광율 편차는 상기 반사 방지 필름에서 선정된 2개 이상의 특정 부분(포인트)의 투광율과, 상기 투광율의 평균값 간의 차이(절대값)를 의미하는 것으로, 평균 반사율을 측정하는 대신 투광율을 측정한다는 점을 제외하고, 상기 평균 반사율 편차를 산출하는 방법과 동일한 방법으로 투광율 편차를 산출할 수 있다. 이때, 2개 이상의 상기 투광율 편차 중 가장 큰 값은 갖는 투광율 편차는 0.2%p 이하일 수 있다.On the other hand, the light transmittance deviation refers to the difference (absolute value) between the transmittance of two or more specific portions (points) selected from the antireflection film and the average value of the transmittance. Instead of measuring the average reflectance, the transmittance is measured. Except for the point, the transmittance deviation may be calculated in the same manner as the method of calculating the average reflectance deviation. In this case, a light transmittance deviation having a largest value among the two or more light transmittance deviations may be 0.2%p or less.
발명의 다른 구현예에 따르면, 상기 반사 방지 필름을 포함하는 편광판이 제공될 수 있다. 상기 편광판은 편광자와 상기 편광자의 적어도 일면에 형성된 반사 방지 필름을 포함할 수 있다. According to another embodiment of the present invention, a polarizing plate including the antireflection film may be provided. The polarizing plate may include a polarizer and an antireflection film formed on at least one surface of the polarizer.
또한, 발명의 또 다른 구현예에 따르면, 편광자와, 상기 편광자를 중심으로 대향하도록 위치하는 10㎛ 이하의 두께를 갖는 제2하드 코팅층 및 상기 일 구현예에 따른 반사 방지 필름을 포함하는 편광판이 제공될 수 있다.In addition, according to another embodiment of the present invention, a polarizing plate including a polarizer, a second hard coating layer having a thickness of 10 μm or less positioned so as to face the polarizer as a center, and an antireflection film according to the embodiment is provided Can be.
상기 반사 방지 필름에 대한 상세한 설명 및 이에 포함되는 성분들에 대한 상세한 설명 및 구체적인 예시는 상술한 바와 같다. A detailed description of the antireflection film and a detailed description and specific examples of components included therein are as described above.
또한, 상기 편광판은 10㎛ 이하의 두께를 갖는 제2하드 코팅층, 편광자 및 상기 반사 방지 필름이 순차적으로 적층되는 것을 제외하고는, 본 발명이 속하는 기술분야에서 알려진 구성 성분 및 제조 방법을 이용하여 제조할 수 있으며, 예를 들어, 상기 편광판은 10㎛ 이하의 두께를 갖는 제2하드 코팅층, 편광자, 광투과성 기재, 하드코팅층 및 저굴절층이 순차적으로 적층되어 있을 수 있다. In addition, the polarizing plate is manufactured using components and manufacturing methods known in the art, except that a second hard coating layer having a thickness of 10 μm or less, a polarizer, and the antireflection film are sequentially stacked. For example, in the polarizing plate, a second hard coating layer having a thickness of 10 μm or less, a polarizer, a light-transmitting substrate, a hard coating layer, and a low refractive index layer may be sequentially stacked.
이전에 알려진 편광판들은 편광자를 중심으로 양쪽에 트리아세틸 셀룰로오스(TAC) 필름 등을 위치하는 구조를 가졌으나, 트리아세틸 셀룰로오스 필름의 경우 내수성이 약하여 고온/고습 환경에서 뒤틀릴 수 있고 빛샘 등의 불량을 유발하는 문제점이 있다.Previously known polarizing plates have a structure in which triacetyl cellulose (TAC) films are placed on both sides of the polarizer, but the triacetyl cellulose film has poor water resistance, so it can be distorted in a high temperature/high humidity environment and prevent defects such as light leakage. There is a problem that causes.
그러나, 상기 또 다른 구현예에 따른 편광판은, 편광자의 일면에 상술한 특성을 갖는 광투과성 기재가 위치하고, 편광자의 다른 일면에 10㎛ 이하의 두께를 갖는 제2 하드코팅층이 위치하여, 상기 편광판이 고온 고습 조건에서 장시간 노출되더라도 편광자 쪽으로의 수분 전달을 차단하여 물성이나 형태에 큰 변화가 없는 내구성을 확보할 수 있다.However, in the polarizing plate according to another embodiment, a light-transmitting substrate having the above-described characteristics is positioned on one side of the polarizer, and a second hard coating layer having a thickness of 10 μm or less is positioned on the other side of the polarizer, so that the polarizing plate is Even if exposed to high temperature and high humidity for a long period of time, moisture transfer to the polarizer is blocked, thereby ensuring durability without significant changes in physical properties or shape.
또한, 상기 편광판은 10㎛ 이하의 두께를 갖는 제2하드 코팅층을 사용함으로 인해, 상술한 수분 전달 차단 및 내구성 확보에 관한 효과와 함께, 편광판 전체의 두께를 낮출 수 있다. In addition, since the polarizing plate uses a second hard coating layer having a thickness of 10 μm or less, it is possible to reduce the thickness of the entire polarizing plate with the effect of blocking moisture transfer and securing durability.
구체적으로, 상기 편광자; 상기 제2하드 코팅층; 및 상기 광투과성 기재를 합한 총 두께는 200 ㎛ 이하일 수 있다. 예를 들어, 상기 편광자는 40 ㎛ 이하, 또는 1 내지 40 ㎛의 두께를 가질 수 있고, 상기 하드 코팅층은 10um 이하, 또는 1 내지 10 ㎛의 두께를 가질 수 있고, 상기 광투과성 기재는 150 ㎛ 이하의 두께를 가질 수 있다. 이 경우, 상기 편광판 및 상기 편광판을 포함하는 디스플레이의 박형 경량화가 가능하다.Specifically, the polarizer; The second hard coating layer; And a total thickness of the light-transmitting substrate may be 200 μm or less. For example, the polarizer may have a thickness of 40 μm or less, or 1 to 40 μm, the hard coating layer may have a thickness of 10 μm or less, or 1 to 10 μm, and the light-transmitting substrate may have a thickness of 150 μm or less Can have a thickness of. In this case, it is possible to reduce the thickness and weight of the polarizing plate and the display including the polarizing plate.
상기 편광자는 일면에 상기 10㎛ 이하의 두께를 갖는 제2 하드코팅층이 위치하고, 다른 일면에는 상기 반사 방지 필름에 포함되는 광투과성 기재가 위치할 수 있다. 상기 광투과성 기재는 파장 400㎚ 내지 800㎚에서 측정되는 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 이상, 7,000 내지 50,000nm, 또는 8,000 내지 40,000nm일 수 있다. 상기 편광판에 포함되는 광투과성 기재의 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 미만이면 반사 방지 필름 부위별 반사율 및 투광율 편차가 클 수 있고, 가시광선의 간섭에 의한 레인보우 현상이 발생할 수 있다. 한편, 상기 리타데이션의 측정 방법 및 장치는 상술한 반사 방지 필름에서 기재한 바와 같다.A second hard coating layer having a thickness of 10 μm or less may be positioned on one surface of the polarizer, and a light-transmitting substrate included in the antireflection film may be positioned on the other surface of the polarizer. The light-transmitting substrate may have a retardation (Rth) of 5,000 nm or more, 7,000 to 50,000 nm, or 8,000 to 40,000 nm in a thickness direction measured at a wavelength of 400 nm to 800 nm. When the retardation (Rth) in the thickness direction of the light-transmitting substrate included in the polarizing plate is less than 5,000 nm, the reflectance and transmittance variation of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light. Meanwhile, the method and apparatus for measuring the retardation are as described in the above-described antireflection film.
또한, 상기 광투과성 기재는 일 방향 및 상기 일 방향과 수직한 방향으로 상이한 인장강도의 값이 나타나며, 예를 들어, 일 방향의 인장강도에 대한, 상기 일 방향과 수직한 방향의 인장강도의 비율은 2 이상, 3 이상, 4 내지 30 또는 5 내지 20일 수 있다. 이때, 상기 일 방향의 인장강도는 상기 일 방향과 수직한 방향의 인장강도 보다 작은 값을 갖는다. 상기 편광판에 포함되는 광투과성 기재의 인장강도 비율이 2 미만이면 반사 방지 필름 부위별 반사율 및 투광율 편차가 클 수 있고, 가시광선의 간섭에 의한 레인보우 현상이 발생할 수 있다.In addition, the light-transmitting substrate has different values of tensile strength in one direction and a direction perpendicular to the one direction, for example, the ratio of the tensile strength in the one direction and the perpendicular direction to the tensile strength in one direction May be 2 or more, 3 or more, 4 to 30 or 5 to 20. In this case, the tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction. If the ratio of the tensile strength of the light-transmitting substrate included in the polarizing plate is less than 2, the variation in reflectance and transmittance of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.
상기 10㎛ 이하의 두께를 갖는 제2 하드코팅층은 본 발명이 속하는 기술분야에서 알려진 구성 성분 및 제조 방법을 이용하여 제조할 수 있으며, 예를 들어, 상기 반사 방지 필름에 포함된 하드코팅층과 동일한 구성 등을 갖는 필름일 수 있다.The second hard coating layer having a thickness of 10 μm or less can be prepared using components and manufacturing methods known in the art to which the present invention pertains, for example, the same configuration as the hard coating layer included in the antireflection film. It may be a film having, etc.
한편, 상기 편광자는 여러 방향으로 진동하면서 입사되는 빛으로부터 한쪽 방향으로 진동하는 빛만을 추출할 수 있는 특성을 나타낸다. 이러한 특성은 요오드를 흡수한 폴리 비닐 알코올(PVA, poly vinyl alcohol)를 강한 장력으로 연신하여 달성할 수 있다. 예를 들어, PVA 필름을 수용액에 담가 팽윤(swelling)시키는 팽윤하는 단계, 상기 팽윤된 PVA 필름에 편광성을 부여하는 이색성 염료 물질로 염색하는 단계, 상기 염색된 PVA 필름을 연신(stretch)하여 상기 이색성 염료 물질을 연신 방향으로 나란하게 배열시키는 연신 단계, 및 상기 연신 단계를 거친 PVA 필름의 색을 보정하는 보색 단계를 거쳐 편광자를 형성할 수 있으나, 이에 제한되는 것은 아니다.Meanwhile, the polarizer vibrates in several directions and exhibits a characteristic capable of extracting only light vibrating in one direction from incident light. This characteristic can be achieved by stretching polyvinyl alcohol (PVA) absorbing iodine with strong tension. For example, swelling of swelling by immersing a PVA film in an aqueous solution, dyeing with a dichroic dye material imparting polarization to the swollen PVA film, and stretching the dyed PVA film The polarizer may be formed through a stretching step of arranging the dichroic dye materials side by side in a stretching direction, and a complementary color step of correcting the color of the PVA film passed through the stretching step, but is not limited thereto.
상기 폴리 비닐 알코올은 폴리비닐알코올 수지 또는 그 유도체를 포함하는 것이면 특별한 제한 없이 사용이 가능하다. 이때, 상기 폴리비닐알코올 수지의 유도체로는, 이에 한정되는 것은 아니나, 폴리비닐포르말 수지, 폴리비닐아세탈 수지 등을 들 수 있다. 한편, 상기 이색성 염료로는, 아조(azo)계, 안트라퀴논(anthraquinone)계, 테트라진(tetrazin)계 등을 사용할 수 있으나, 이에 제한되는 것은 아니다. 또한, 상기 폴리비닐알코올 필름은 당해 기술분야에 있어서 편광자 제조에 일반적으로 사용되는 시판되는 폴리비닐알코올 필름, 예를 들어, 구라레 사의 P30, PE30, PE60, 일본합성사의 M3000, M6000 등을 사용할 수 있다.The polyvinyl alcohol may be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof. At this time, examples of the polyvinyl alcohol resin derivative include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like. Meanwhile, as the dichroic dye, an azo-based, anthraquinone-based, tetrazin-based, etc. may be used, but the present invention is not limited thereto. In addition, the polyvinyl alcohol film may be a commercially available polyvinyl alcohol film generally used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 of Kuraray, M3000, M6000 of Japanese Synthetic Company, etc. have.
한편, 상기 폴리비닐알코올 필름은, 이로써 한정되는 것은 아니나, 중합도가 1000 내지 10000 또는 1500 내지 5000일 수 있다. 중합도가 상기 범위를 만족할 때, 분자 움직임이 자유롭고, 요오드 또는 이색성 염료 등과 유연하게 혼합될 수 있다.Meanwhile, the polyvinyl alcohol film may have a degree of polymerization of 1000 to 10000 or 1500 to 5000, but is not limited thereto. When the degree of polymerization satisfies the above range, molecular movement is free and can be flexibly mixed with iodine or a dichroic dye.
상기 편광판은 디스플레이, 예를 들어, 액정표시장치(LCD)의 상부 편광판으로 사용될 수 있다. 또한, 적층구조에 있어서, 상기 반사 방지 필름이 상부에 위치할 수 있으며, 구체적으로, 상기 반사 방지 필름은 디스플레이 장치의 시인측에 가까이 위치할 수 있다. 상기 반사 방지 필름을 디스플레이의 시인측에 가까이 위치하도록 제어함으로 인하여, 편광자 쪽으로 수분 전달을 차단하여 내구성을 향상시키는 동시에, 외부로부터 입사되는 빛의 반사를 최소화시켜 화면의 선명도를 향상시킬 수 있다.The polarizing plate may be used as an upper polarizing plate of a display, for example, a liquid crystal display (LCD). In addition, in the laminated structure, the antireflection film may be positioned on the top, and specifically, the antireflection film may be positioned close to the viewer side of the display device. By controlling the anti-reflection film to be positioned close to the viewing side of the display, it is possible to improve durability by blocking moisture transfer toward the polarizer, and to minimize reflection of light incident from the outside, thereby improving the clarity of the screen.
한편, 상기 편광자와 접하는 제2하드 코팅층 및/또는 광투과성 기재의 일면에 접착층을 더 포함할 수 있으며, 나아가, 각 층 사이 또는 최외곽에는 내오염층 등의 기타 기능층을 더 포함할 수 있다.On the other hand, the second hard coating layer in contact with the polarizer and/or an adhesive layer may be further included on one surface of the light-transmitting substrate, and further, other functional layers, such as a fouling-resistant layer, may be further included between each layer or at the outermost side. .
예를 들어, 상기 편광자의 각 일면에 위치하는 제2하드 코팅층 및 광투과성 기재는, 접착제 등을 사용하여 라미네이션함으로써 접착시킬 수 있다. 사용 가능한 접착제로는 당 기술분야에 알려져 있는 것이면 특별히 제한되지 않으나, 예를 들면, 수계 접착제, 일액형 또는 이액형의 폴리비닐알콜(PVA)계 접착제, 폴리우레탄계 접착제, 에폭시계 접착제, 스티렌 부타디엔 고무계(SBR계) 접착제, 또는 핫멜트형 접착제 등이 있다.For example, the second hard coating layer and the light-transmitting substrate positioned on each side of the polarizer may be bonded by lamination using an adhesive or the like. Usable adhesives are not particularly limited as long as they are known in the art, but for example, water-based adhesives, one- or two-component polyvinyl alcohol (PVA)-based adhesives, polyurethane-based adhesives, epoxy-based adhesives, styrene butadiene rubber-based adhesives (SBR-based) adhesives or hot melt adhesives.
구체적으로, 상기 편광판은 제2하드 코팅층, 편광자, 광투과성 기재, 하드코팅층 및 저굴절층이 순차적으로 적층되어 있을 수 있다. 또한, 상기 편광자와 접하는 제2하드 코팅층 및/또는 광투과성 기재의 일면에 점착층을 더 포함할 수 있으며, 나아가, 각 층 사이 또는 최외곽에는 내오염층 등의 기타 기능층을 더 포함할 수 있다.Specifically, in the polarizing plate, a second hard coating layer, a polarizer, a light-transmitting substrate, a hard coating layer, and a low refractive index layer may be sequentially stacked. In addition, the second hard coating layer in contact with the polarizer and/or an adhesive layer may be further included on one surface of the light-transmitting substrate, and further, other functional layers such as a contamination-resistant layer may be further included between each layer or at the outermost side. have.
편광판의 편광자 보호필름으로 많이 사용중인 트리아세틸 셀룰로오스(TAC) 필름은 내수성이 약하여 고온/고습 환경에서 뒤틀릴 수 있고 빛샘 등의 불량을 유발하는데 반하여, 상기 또 다른 구현예에 따른 편광판에서는, 편광자의 양면에 각각 상기 제2하드 코팅층 및 상기 일 구현예에 따른 반사 방지 필름을 사용함에 따라서 고온 고습 조건에서 장시간 노출되어도 물성이나 형태에 큰 변화가 없는 내구성을 확보할 수 있다. Triacetyl cellulose (TAC) film, which is widely used as a polarizer protective film of a polarizing plate, has poor water resistance and can be distorted in a high temperature/high humidity environment and causes defects such as light leakage, whereas in the polarizing plate according to another embodiment, the polarizer Since the second hard coating layer and the antireflection film according to the embodiment are used on both sides, durability without significant change in physical properties or shape can be secured even when exposed to high temperature and high humidity for a long time.
또한, 상기 편광판은 10㎛ 이하의 두께를 갖는 제2하드 코팅층을 사용함으로 인해, 이전에 알려진 다른 편광판 구조에 비하여 보다 얇은 두께를 통해서도 견고한 구조를 구현할 수 있다.In addition, since the polarizing plate uses a second hard coating layer having a thickness of 10 μm or less, a solid structure can be implemented through a thinner thickness compared to other previously known polarizing plate structures.
보다 구체적으로, 상기 편광자; 상기 제2하드 코팅층; 및 상기 광투과성 기재를 합한 총 두께는 200 ㎛ 이하일 수 있다. 예를 들어, 상기 편광자는 40 ㎛ 이하, 또는 1 내지 40 ㎛의 두께를 가질 수 있고, 상기 하드 코팅층은 10um 이하, 또는 1 내지 10 ㎛의 두께를 가질 수 있고, 상기 광투과성 기재는 150 ㎛ 이하의 두께를 가질 수 있다.More specifically, the polarizer; The second hard coating layer; And the total thickness of the light-transmitting substrate may be 200 μm or less. For example, the polarizer may have a thickness of 40 μm or less, or 1 to 40 μm, the hard coating layer may have a thickness of 10 μm or less, or 1 to 10 μm, and the light-transmitting substrate may have a thickness of 150 μm or less Can have a thickness of.
발명의 또 다른 구현예에 따르면, 상술한 반사 방지 필름을 포함하는 디스플레이 장치가 제공될 수 있다. 상기 디스플레이 장치의 구체적인 예가 한정되는 것은 아니며, 예를 들어 액정표시장치 (Liquid Crystal Display), 플라즈마 디스플레이 장치, 유기발광 다이오드 장치(Organic Light Emitting Diodes) 등의 장치일 수 있다. According to another embodiment of the present invention, a display device including the anti-reflection film described above may be provided. A specific example of the display device is not limited, and may be, for example, a liquid crystal display device, a plasma display device, or an organic light emitting diode device.
하나의 일 예로, 상기 디스플레이 장치는 서로 대향하는 1쌍의 편광판; 상기 1쌍의 편광판 사이에 순차적으로 적층된 박막트랜지스터, 컬러필터 및 액정셀; 및 백라이트 유닛을 포함하는 액정디스플레이 장치일 수 있다.As an example, the display device may include a pair of polarizing plates facing each other; A thin film transistor, a color filter, and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And it may be a liquid crystal display device including a backlight unit.
상기 디스플레이 장치에서 상기 반사 방지 필름은 디스플레이 패널의 관측자측 또는 백라이트측의 최외각 표면에 구비될 수 있다. In the display device, the antireflection film may be provided on the outermost surface of the display panel on the viewer side or the backlight side.
상기 반사 방지 필름을 포함하는 디스플레이 장치는, 1쌍의 편광판 중에서 상대적으로 백라이트 유닛과 거리가 먼 편광판의 일면에 반사 방지 필름이 위치할 수 있다. In a display device including the anti-reflection film, an anti-reflection film may be positioned on one surface of a polarizing plate that is relatively far from a backlight unit among a pair of polarizing plates.
또한, 상기 디스플레이 장치는 디스플레이 패널, 상기 패널의 적어도 일면에 구비된 편광자 및 상기 편광자의 패널과 접하는 반대측 면에 구비된 반사방지 필름을 포함할 수 있다. In addition, the display device may include a display panel, a polarizer provided on at least one surface of the panel, and an antireflection film provided on a surface opposite to the panel of the polarizer.
본 발명에 따르면, 낮은 반사율 및 투광율 편차를 가지면서 높은 내스크래치성 및 방오성을 동시에 구현할 수 있고 디스플레이 장치의 화면의 선명도를 높일 수 있는 반사 방지 필름, 상기 반사 방지 필름을 포함한 편광판, 및 상기 반사 방지 필름을 포함하는 디스플레이 장치를 제공할 수 있다.According to the present invention, an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having a low reflectance and light transmittance deviation and enhancing the clarity of a screen of a display device, a polarizing plate including the antireflection film, and the antireflection A display device including a film can be provided.
도 1 은
실시예 1의 반사 방지 필름에 대한 X-선 회절(XRD) 패턴이다.Figure 1 It is an X-ray diffraction (XRD) pattern for the antireflection film of Example 1.
도 2는 비교예 3의 반사 방지 필름에 대한 X-선 회절(XRD) 패턴이다.2 is an X-ray diffraction (XRD) pattern of the antireflection film of Comparative Example 3.
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
제조예 1: 하드코팅층 형성용 코팅액의 제조 Preparation Example 1: Preparation of a coating solution for forming a hard coating layer
하기 표 1에 기재된 성분을 혼합하여 하드코팅층 형성용 코팅액(B1, B2 및 B3)을 제조하였다.The components shown in Table 1 were mixed to prepare a coating solution (B1, B2 and B3) for forming a hard coating layer.
(단위: g)(Unit: g) | B1B1 | B2B2 | B3B3 |
DPHADPHA | 6.237 6.237 | ||
PETAPETA | 16.421 16.421 | 10.728 10.728 | 13.413 13.413 |
UA-306TUA-306T | 3.079 3.079 | 2.069 2.069 | 6.114 6.114 |
8BR-5008BR-500 | 6.158 6.158 | 6.537 6.537 | 6.114 6.114 |
IRG-184IRG-184 | 1.026 1.026 | 1.023 1.023 | 1.026 1.026 |
Tego-270Tego-270 | 0.051 0.051 | 0.051 0.051 | 0.051 0.051 |
BYK350BYK350 | 0.051 0.051 | 0.051 0.051 | 0.051 0.051 |
2-butanol2-butanol | 25.92 25.92 | 32.80 32.80 | 36.10 36.10 |
IPAIPA | 45.92 45.92 | 38.80 38.80 | 35.70 35.70 |
XX-103BQ(2.0㎛ 1.515)XX-103BQ(2.0㎛ 1.515) | 0.318 0.318 | 0.460 0.460 | 0.600 0.600 |
XX-113BQ(2.0㎛ 1.555)XX-113BQ(2.0㎛ 1.555) | 0.708 0.708 | 0.563 0.563 | 0.300 0.300 |
MA-ST(30% in MeOH)MA-ST (30% in MeOH) | 0.342 0.342 | 0.682 0.682 | 0.542 0.542 |
DPHA: 다이펜타에리트리톨 헥사아크릴레이트DPHA: dipentaerythritol hexaacrylate
PETA: 펜타에리트리톨 트리아크릴레이트PETA: pentaerythritol triacrylate
UA-306T: 우레탄 아크릴레이트로 톨루엔 디이소시아네이트와 펜타 에리스리톨트리아크릴레이트의 반응물 (Kyoeisha제품)UA-306T: Reaction product of toluene diisocyanate and pentaerythritol triacrylate as urethane acrylate (Kyoeisha product)
8BR-500: 광경화형 우레탄 아크릴레이트 폴리머(Mw 200,000, Taisei Fine Chemical 제품) 8BR-500: Photo-curing urethane acrylate polymer (Mw 200,000, manufactured by Taisei Fine Chemical)
IRG-184: 개시제 (Irgacure 184, Ciba사)IRG-184: initiator (Irgacure 184, Ciba company)
Tego-270: Tego 사 레벨링제Tego-270: Tego's leveling agent
BYK350: BYK사 레벨링제BYK350: BYK leveling agent
IPA 이소프로필 알코올IPA isopropyl alcohol
XX-103BQ(2.0㎛ 1.515): 폴리스타이렌과 폴리메틸메타크릴레이트의 공중합 입자(Sekisui Plastic 제품)XX-103BQ (2.0㎛ 1.515): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)
XX-113BQ(2.0㎛ 1.555): 폴리스타이렌과 폴리메틸메타크릴레이트의 공중합 입자(Sekisui Plastic 제품)XX-113BQ (2.0㎛ 1.555): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)
MA-ST(30% in MeOH): 크기 10~15nm의 나노 실리카 입자가 메틸알코올에 분산된 분산액(Nissan Chemical제품)MA-ST (30% in MeOH): A dispersion in which nano silica particles with a size of 10 to 15 nm are dispersed in methyl alcohol (product of Nissan Chemical)
제조예 2-1: 저굴절층 형성용 코팅액(C1)의 제조Preparation Example 2-1: Preparation of coating solution (C1) for forming a low refractive index layer
트리메틸올프로페인 트리아크릴레이트(TMPTA) 100g, 중공형 실리카 나노 입자(직경범위: 약 42 ㎚ 내지 66 ㎚, JSC catalyst and chemicals사 제품) 283g, 솔리드형 실리카 나노 입자(직경범위: 약 12 ㎚ 내지 19 ㎚) 59g, 제1 함불소 화합물(X-71-1203M, ShinEtsu사) 115g, 제2 함불소 화합물 (RS-537, DIC사) 15.5g 및 개시제 (Irgacure 127, Ciba사) 10g를, MIBK(methyl isobutyl ketone)용매에 고형분 농도 3 중량%가 되도록 희석하여 저굴절층 형성용 코팅액(광경화성 코팅 조성물)을 제조하였다.Trimethylolpropane triacrylate (TMPTA) 100g, hollow silica nanoparticles (diameter range: about 42 nm to 66 nm, manufactured by JSC catalyst and chemicals) 283 g, solid silica nanoparticles (diameter range: about 12 nm to 19 nm) 59 g, the first fluorinated compound (X-71-1203M, ShinEtsu Corporation) 115 g, the second fluorine-containing compound (RS-537, DIC Corporation) 15.5 g and initiator (Irgacure 127, Ciba Corporation) 10 g, MIBK A coating solution for forming a low refractive layer (photocurable coating composition) was prepared by diluting in a (methyl isobutyl ketone) solvent to a solid content concentration of 3% by weight.
제조예 2-2: 저굴절층 형성용 코팅액(C2)의 제조Preparation Example 2-2: Preparation of coating solution (C2) for forming a low refractive index layer
디펜타에리스리톨 헥사아크릴레이트 (DPHA) 100g, 중공형 실리카 나노 입자(직경범위: 약 51 ㎚ 내지 72 ㎚, JSC catalyst and chemicals 사 제품) 143g, 솔리드형 실리카 나노 입자(직경범위: 약 12 ㎚ 내지 19 ㎚) 29g, 함불소 화합물 (RS-537, DIC 사) 56g 및 개시제 (Irgacure 127, Ciba 사) 3.1g 를, MIBK(methyl isobutyl ketone)용매에 고형분 농도 3.5 중량%가 되도록 희석하여 저굴절층 형성용 코팅액(광경화성 코팅 조성물)을 제조하였다.Dipentaerythritol hexaacrylate (DPHA) 100g, hollow silica nanoparticles (diameter range: about 51 nm to 72 nm, manufactured by JSC catalyst and chemicals) 143g, solid silica nanoparticles (diameter range: about 12 nm to 19) ㎚) 29g, fluorinated compound (RS-537, DIC) 56g and initiator (Irgacure 127, Ciba) 3.1g, diluted in MIBK (methyl isobutyl ketone) solvent to a solid content of 3.5% by weight to form a low refractive layer A coating solution (photocurable coating composition) was prepared.
실시예Example
1 내지 3 및 1 to 3 and
비교예Comparative example
1 내지 4: 반사 방지 필름의 제조 1 to 4: Preparation of antireflection film
하기 표 2에 기재된 각각의 광투과성 기재(두께 80㎛) 상에 상기 제조된 하드코팅층 형성용 코팅액(B1, B2, B3) 각각을 #12번 mayer bar로 코팅한 후 60℃의 온도에서 2분 건조하고, UV경화하여 하드코팅층(코팅 두께는 5㎛)을 형성했다. UV램프는 H bulb를 이용하였으며, 질소분위기 하에서 경화반응을 진행하였다. 경화 시 조사된 UV광량은 100mJ/cm
2이다. After coating each of the prepared hard coating layer forming coating solutions (B1, B2, B3) on each of the light-transmitting substrates (thickness 80 μm) listed in Table 2 with #12 mayer bar, at a temperature of 60° C. for 2 minutes It was dried and UV cured to form a hard coating layer (coating thickness of 5 μm). The UV lamp used an H bulb, and the curing reaction was carried out in a nitrogen atmosphere. The amount of UV light irradiated during curing is 100mJ/cm 2 .
상기 하드코팅층 상에, 상기 저굴절층 형성용 코팅액(C1, C2)을 #4 mayer bar로 두께가 약 110 내지 120㎚가 되도록 코팅하고, 40℃의 온도에서 1분 동안 건조 및 경화하였다. 상기 경화 시에는 질소 퍼징 하에서 상기 건조된 코팅액에 252mJ/㎠의 자외선을 조사하였다.On the hard coating layer, the coating solutions (C1, C2) for forming the low refractive layer were coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at a temperature of 40° C. for 1 minute. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating solution under nitrogen purging.
반사 방지 필름Anti-reflective film | ||||
광투과성 기재의 Light-transmitting | 하드코팅층Hard coating layer | 저굴절층Low refractive layer | ||
인장강도 비율*Tensile strength ratio* | 두께 방향 리타데이션 (Rth, nm)Thickness direction retardation (Rth, nm) | |||
실시예 1Example 1 | 4.14.1 | 93009300 | 코팅액 (B1)Coating liquid (B1) | 코팅액 (C1)Coating liquid (C1) |
실시예 2Example 2 | 4.04.0 | 92009200 | 코팅액 (B2)Coating liquid (B2) | 코팅액 (C1)Coating liquid (C1) |
실시예 3Example 3 | 2.92.9 | 92309230 | 코팅액 (B2)Coating liquid (B2) | 코팅액 (C1)Coating liquid (C1) |
실시예 4Example 4 | 3.73.7 | 93009300 | 코팅액 (B3)Coating liquid (B3) | 코팅액 (C1)Coating liquid (C1) |
실시예 5Example 5 | 2.22.2 | 58005800 | 코팅액 (B1)Coating liquid (B1) | 코팅액 (C2)Coating liquid (C2) |
비교예 1Comparative Example 1 | 1.81.8 | 35003500 | 코팅액 (B3)Coating liquid (B3) | 코팅액 (C1)Coating liquid (C1) |
비교예 2Comparative Example 2 | 1.61.6 | 30003000 | 코팅액 (B2)Coating liquid (B2) | 코팅액 (C1)Coating liquid (C1) |
비교예 3Comparative Example 3 | 1.31.3 | 32003200 | 코팅액 (B2)Coating liquid (B2) | 코팅액 (C1)Coating liquid (C1) |
비교예 4Comparative Example 4 | 1.81.8 | 15001500 | 코팅액 (B1)Coating liquid (B1) | 코팅액 (C2)Coating liquid (C2) |
*인장강도 비율: 광투과성 기재에서, 보다 작은 값을 갖는 일 방향의 인장강도에 대한, 보다 큰 값을 갖는 상기 일 방향과 수직하는 방향의 인장강도의 비율. 인장강도의 측정방법은, JIS C-2318에 준거하여 광투과성 기재의 인장강도를 측정한다.*Tensile strength ratio: In a light-transmitting substrate, the ratio of the tensile strength in a direction perpendicular to the one direction having a larger value to the tensile strength in one direction having a smaller value. The tensile strength measurement method is based on JIS C-2318, and the tensile strength of the light-transmitting substrate is measured.
평가evaluation
1. 반사 모드의 X-선 회절(XRD) 평가1. X-ray diffraction (XRD) evaluation of reflection mode
실시예 및 비교예에서 얻어진 반사 방지 필름에 대하여 2cm*2cm(가로*세로) 크기로 샘플을 준비한 후, 1.54 Å의 파장의 Cu-Kα선을 조사하여 반사 모드의 X-선 회절(XRD) 패턴을 측정하였다. For the antireflection film obtained in Examples and Comparative Examples, after preparing a sample in a size of 2 cm * 2 cm (horizontal * vertical), an X-ray diffraction (XRD) pattern in reflection mode was irradiated with Cu-Kα rays having a wavelength of 1.54 Å. Was measured.
구체적으로, 로우 백그라운드 규소 홀더(low background Si holder, Bruker 사) 위에 뜨지 않게 샘플을 고정하여 준비하고, 측정 장비는 Bruker AXS D4 Endeavor XRD를 이용하였다. 사용 전압 및 전류는 각각 40 kV 및 40 mA이며, 사용한 옵틱스(optics) 및 검출기(detector) 등의 장치 및 조건은 다음과 같다.Specifically, a sample was prepared by fixing it so that it does not float on a low background Si holder (Bruker, Inc.), and a Bruker AXS D4 Endeavor XRD was used as a measurement equipment. The voltage and current used are 40 kV and 40 mA, respectively, and the devices and conditions such as optics and detector used are as follows.
-Primary (incident beam) optics: motorized divergence slit, soller slit 2.3°-Primary (incident beam) optics: motorized divergence slit, soller slit 2.3°
-Secondary (diffracted beam) optics: soller slit 2.3°-Secondary (diffracted beam) optics: soller slit 2.3°
- Receiving slit: 0.1deg-Receiving slit: 0.1deg
-LynxEye detector (1D detector)-LynxEye detector (1D detector)
측정 모드는 coupled 2θ/θ 모드이며, FDS (Fixed Divergence Slit) 0.3°를 이용, 2θ값이 6°부터 70°까지인 영역을, 매 0.04°마다 175 초씩 측정하였다.The measurement mode is a coupled 2θ/θ mode, and using FDS (Fixed Divergence Slit) 0.3°, an area with a 2θ value of 6° to 70° was measured for 175 seconds every 0.04°.
또한, X-선 회절(XRD) 패턴에서 22 내지 24°의 2θ 값 사이에서 나타나는 피크의 반치전폭은, Bruker사의 TOPAS 프로그램을 사용하여 측정하였다. 구체적으로, TOPAS 프로그램에서 측정 범위(피팅 영역)을 10 내지 40°로 지정하고, PV (pseudo-Voigt) 함수를 이용해, 대략 17°, 19°, 23°, 26° 부근의 피크를 입력하여 반치전폭을 구하였다. 이후, 22 내지 24°의 2θ 값 사이에서 나타나는 피크의 2θ 값과, 상기 피크의 반치전폭을 하기 표 3에 기재하였다.In addition, the full width at half maximum of the peak appearing between 2θ values of 22 to 24° in the X-ray diffraction (XRD) pattern was measured using the Bruker's TOPAS program. Specifically, specify the measurement range (fitting area) from 10 to 40° in the TOPAS program, and use the PV (pseudo-Voigt) function to input peaks around 17°, 19°, 23°, and 26° to be half-valued. I found the full width. Thereafter, the 2θ value of the peak appearing between the 2θ value of 22 to 24° and the full width at half maximum of the peak are shown in Table 3 below.
한편, 도 1 은 실시예 1의 반사 방지 필름에 대한 X-선 회절(XRD) 패턴이고, 도 2는 비교예 3의 반사 방지 필름에 대한 X-선 회절(XRD) 패턴이다.Meanwhile, FIG. 1 is an X-ray diffraction (XRD) pattern for the antireflection film of Example 1, and FIG. 2 is an X-ray diffraction (XRD) pattern for the antireflection film of Comparative Example 3.
2. 평균 반사율 평가2. Average reflectance evaluation
실시예 및 비교예에서 얻어진 반사 방지 필름의 뒷면(하드코팅층이 형성되지 않은 광투과성 기재의 일면)을 암색 처리한 이후에, Solidspec 3700(SHIMADZU) 장비의 반사율(Reflectance) 모드를 이용하여 380 내지 780㎚ 파장 영역에서 평균 반사율을 측정하고, 그 결과를 하기 표3에 기재하였다. After dark color treatment of the back side of the antireflection film obtained in Examples and Comparative Examples (one side of the light-transmitting substrate on which the hard coating layer was not formed), 380 to 780 using the Reflectance mode of the Solidspec 3700 (SHIMADZU) equipment. The average reflectance was measured in the nm wavelength region, and the results are shown in Table 3 below.
3. 평균 반사율의 편차 평가3. Evaluation of deviation of average reflectance
실시예 및 비교예에서 얻어진 반사 방지 필름에 대해 임의의 포인트를 20 개를 선정하고, 각각의 포인트에 대해 상기 ‘2. 평균 반사율 평가 방법’으로 평균 반사율을 측정하였다. 이후, 측정된 20개의 포인트의 평균 반사율의 산술 평균값을 구하였다. 이후, 각 포인트에서 평균 반사율과 상기 산술 평균값 간의 차이(절대값)를 평균 반사율 편차로 정의하고, 각20개 포인트에서 각각 평균 반사율 편차를 계산하였다. 20개의 평균 반사율 편차 중 가장 큰 값을 갖는 평균 반사율 편차를 하기 표 3에 기재하였다.For the antireflection film obtained in Examples and Comparative Examples, 20 arbitrary points were selected, and for each point in '2. Average reflectance was measured by'average reflectance evaluation method'. Then, the arithmetic average value of the average reflectance of the measured 20 points was calculated. Thereafter, the difference (absolute value) between the average reflectance at each point and the arithmetic mean value was defined as the average reflectance deviation, and the average reflectance deviation was calculated at each of the 20 points. The average reflectance deviation having the largest value among 20 average reflectance deviations is shown in Table 3 below.
4. 투광율 편차 평가4. Transmittance deviation evaluation
실시예 및 비교예에서 얻어진 반사 방지 필름에 대해 임의의 포인트를 20 개 선정하고, 각각의 포인트에 대해 투광율을 측정하였다. Twenty arbitrary points were selected for the antireflection films obtained in Examples and Comparative Examples, and the transmittance was measured for each point.
구체적으로, 상기 반사 방지 필름을 Solidspec 3700(SHIMADZU) 장비의 투과율 (Transmittance) 모드를 이용하여 380 내지 780 ㎚ 파장 영역에서 평균 투광율을 측정하였다.Specifically, the anti-reflection film was measured for average transmittance in a wavelength range of 380 to 780 nm using the Transmittance mode of the Solidspec 3700 (SHIMADZU) equipment.
이후, 측정된 20개의 포인트의 투광율의 산술 평균값을 구하였다. 이후, 각 포인트에서 투광율과 상기 산술 평균값 간의 차이(절대값)을 투광율 편차로 정의하고, 각20개 포인트에서 투광율 편차를 계산하였다. 20개의 투광율 편차 중 가장 큰 값을 갖는 투광율 편차를 하기 표 3에 기재하였다.Then, the arithmetic average value of the measured transmittance of the 20 points was calculated. Thereafter, the difference (absolute value) between the transmittance and the arithmetic mean value at each point was defined as the transmittance deviation, and the transmittance deviation was calculated at each of the 20 points. The light transmittance deviation, which has the largest value among the twenty light transmittance deviations, is shown in Table 3 below.
5. 투습률 평가5. Evaluation of moisture permeability
실시예 및 비교예에서 얻어진 반사 방지 필름의 투습률은 38℃의 온도 및 100% 상대습도 하에서 MOCON test 장비 (PERMATRAN-W, MODEL 3/61)를 이용하여 측정하였다.The moisture permeability of the antireflection film obtained in Examples and Comparative Examples was measured using a MOCON test equipment (PERMATRAN-W, MODEL 3/61) under a temperature of 38°C and 100% relative humidity.
피크 (°)Peak (°) | 반치전폭 (°)Full width at half height (°) | 평균 반사율 (%)Average reflectance (%) | 평균 반사율 편차 (%p)Average reflectance deviation (%p) | 투광율 편차(%p)Transmittance deviation (%p) | 투습률 (g/m 2·day)Moisture permeability (g/m 2 ·day) | |
실시예 1Example 1 | 22.922.9 | 1.341.34 | 1.131.13 | 0.040.04 | 0.010.01 | 11.1311.13 |
실시예 2Example 2 | 22.922.9 | 1.401.40 | 1.271.27 | 0.110.11 | 0.080.08 | 10.2810.28 |
실시예 3Example 3 | 23.023.0 | 1.451.45 | 1.111.11 | 0.070.07 | 0.030.03 | 12.3112.31 |
실시예 4Example 4 | 22.922.9 | 1.381.38 | 1.031.03 | 0.160.16 | 0.040.04 | 11.5111.51 |
실시예 5Example 5 | 22.922.9 | 1.351.35 | 1.581.58 | 0.050.05 | 0.070.07 | 10.9510.95 |
비교예 1Comparative Example 1 | 23.023.0 | 1.731.73 | 1.151.15 | 0.310.31 | 0.290.29 | 11.3311.33 |
비교예 2Comparative Example 2 | 22.822.8 | 1.591.59 | 1.221.22 | 0.250.25 | 0.280.28 | 10.8210.82 |
비교예 3Comparative Example 3 | 23.223.2 | 1.811.81 | 1.01.0 | 0.280.28 | 0.30.3 | 11.1811.18 |
비교예 4Comparative Example 4 | 23.023.0 | 1.511.51 | 1.541.54 | 0.300.30 | 0.310.31 | 12.3612.36 |
상기 표 3에 따르면, 실시예 1 내지 5의 반사 방지 필름은 평균 반사율 편차가 0.16%p 이하이고, 투광율 편차가 0.08%p 이하로, 반사 방지 필름 전반에 평균 반사율과 투광율의 차이가 거의 없음을 확인했다. 그러나, 비교예 1 내지 4의 반사 방지 필름은, 실시예 1 내지 5의 반사 방지 필름과는 달리, 평균 반사율 편차 및 투광율 편차가 현저히 높음을 확인했다.According to Table 3, the antireflection films of Examples 1 to 5 had an average reflectance deviation of 0.16%p or less, and a transmittance deviation of 0.08%p or less, and that there was little difference between the average reflectance and transmittance throughout the antireflection film. Confirmed. However, it was confirmed that the antireflection films of Comparative Examples 1 to 4, unlike the antireflection films of Examples 1 to 5, had a remarkably high deviation in average reflectance and deviation in transmittance.
제조예3: 제2하드 코팅층이 일면에 형성된 편광자 제조Preparation Example 3: Preparation of a polarizer with a second hard coating layer formed on one surface
(1) 제2하드코팅층 형성용 코팅액 (A)의 제조(1) Preparation of coating solution (A) for forming the second hard coating layer
트리메틸로일프로판 트리아크릴레이트 28g, KBE-403 2g, 개시제 KIP-100f, 0.1g, 레벨링제(Tego wet 270) 0.06g을 균일하게 혼합하여 제2하드코팅층 형성용 코팅액 (A)를 제조하였다.Trimethylloylpropane triacrylate 28g, KBE-403 2g, initiator KIP-100f, 0.1g, leveling agent (Tego wet 270) 0.06g was uniformly mixed to prepare a coating solution (A) for forming a second hard coating layer.
(2) 제2하드 코팅층이 일면에 형성된 편광자 제조(2) Manufacturing of a polarizer with a second hard coating layer formed on one side
편광자인 폴리비닐알콜 편광자(두께: 25um, 제조사: 엘지화학)의 일면에 상기 제2하드코팅층 형성용 코팅액(A)을 7um의 두께로 도포하고, 질소 퍼징하에서 건조된 코팅물에 500 mJ/㎠의 자외선을 조사하여, 제2하드 코팅층이 일면에 형성된 편광자를 제조하였다.The coating solution (A) for forming the second hard coating layer was applied to one side of a polarizer, a polyvinyl alcohol polarizer (thickness: 25 um, manufacturer: LG Chem), with a thickness of 7 um, and 500 mJ/mJ/ By irradiating ultraviolet rays of cm 2, a polarizer having a second hard coating layer formed on one surface thereof was manufactured.
실시예Example
6 내지 10 및 6 to 10 and
비교예Comparative example
5 내지 8: 편광판 제조 5 to 8: polarizing plate manufacturing
하기 표 4에 기재된 바와 같이, 상기 실시예 1내지 5 및 비교예 1 내지 4에서 각각 얻어진 반사 방지 필름의 광투과성 기재 상에 상기 제조예 3에서 얻어진 제2하드코팅층이 일면에 형성된 편광자를 UV접착제로 접착하여 편광판을 제조하였다. 구체적으로, 상기 반사 방지 필름의 광투과성 기재와 상기 편광자가 직접적으로 접하도록 하여 편광판을 제조하였으며, 제조된 편광판은 저굴절층, 하드코팅층, 광투과성 기재, 편광자 및 제2하드코팅층이 순차적으로 적층되어 있다.As shown in Table 4 below, a polarizer in which the second hard coating layer obtained in Preparation Example 3 is formed on one surface of the light-transmitting substrate of the antireflection film obtained in Examples 1 to 5 and Comparative Examples 1 to 4, respectively, is formed on one surface with a UV adhesive. To prepare a polarizing plate. Specifically, a polarizing plate was manufactured by making the light-transmitting substrate of the anti-reflection film in direct contact with the polarizer, and the prepared polarizing plate includes a low refractive index layer, a hard coating layer, a light-transmitting substrate, a polarizer, and a second hard coating layer sequentially stacked. Has been.
반사방지필름Anti-reflection film | 제2하드코팅층이 형성된 편광자Polarizer with a second hard coating layer formed | |
실시예 6Example 6 | 실시예 1Example 1 | 제조예3Manufacturing Example 3 |
실시예 7Example 7 | 실시예 2Example 2 | 제조예3Manufacturing Example 3 |
실시예 8Example 8 | 실시예 3Example 3 | 제조예3Manufacturing Example 3 |
실시예 9Example 9 | 실시예 4Example 4 | 제조예3Manufacturing Example 3 |
실시예 10Example 10 | 실시예 5Example 5 | 제조예3Manufacturing Example 3 |
비교예 5Comparative Example 5 | 비교예1Comparative Example 1 | 제조예3Manufacturing Example 3 |
비교예 6Comparative Example 6 | 비교예2Comparative Example 2 | 제조예3Manufacturing Example 3 |
비교예 7Comparative Example 7 | 비교예3Comparative Example 3 | 제조예3Manufacturing Example 3 |
비교예 8Comparative Example 8 | 비교예4Comparative Example 4 | 제조예3Manufacturing Example 3 |
평가evaluation
1. 평균 반사율 편차 및 투광율 편차 평가1. Average reflectance deviation and light transmittance deviation evaluation
상기 실시예 6 내지 10 및 비교예 5 내지 8에 대해, 앞서 서술한 바와 같은 동일한 방법으로 평균 반사율 편차 및 투광율 편차를 측정하여 하기 표 5에 나타내었다.For Examples 6 to 10 and Comparative Examples 5 to 8, the average reflectance deviation and the transmittance deviation were measured in the same manner as described above, and are shown in Table 5 below.
2. 크랙 특성2. Crack characteristics
상기 실시예 6 내지 10 및 비교예 5 내지 8에 대해 한 변의 길이가 10cm인 정사각형으로 재단하고 TV용 유리(가로 12cm, 세로12cm, 두께 0.7mm)의 일면에 접합하여 열충격 평가용 샘플을 제조하였다. 이때, 편광자의 MD방향이 정사각형의 한변과 평행하도록 편광판을 재단하였다. 재단한 샘플을 열충격 챔버에 수직으로 세워 놓고, 상온에서 80℃로 승온하여 30분 방치하고, 이후 온도를 -30℃로 낮추어 30분 방치 뒤 상온으로 온도 조절하는 것을 1 Cycle로 하여 총 100 Cycle을 반복하였다. 이후 평가용 샘플의 편광자 사이에 발생한 Crack과 편광자 사이에 틈이 생긴 것을 육안으로 확인하여 길이 1 cm이상의 크랙의 개수를 확인하고, 그 결과를 하기 표 5에 기재하였다. For Examples 6 to 10 and Comparative Examples 5 to 8, a sample for thermal shock evaluation was prepared by cutting a square with a side of 10 cm and bonding to one side of a TV glass (12 cm wide, 12 cm long, and 0.7 mm thick). . At this time, the polarizing plate was cut so that the MD direction of the polarizer was parallel to one side of the square. Place the cut sample vertically in the thermal shock chamber, raise the temperature from room temperature to 80℃ and leave for 30 minutes, then lower the temperature to -30℃ and leave it for 30 minutes, then adjust the temperature to room temperature as 1 cycle. Repeated. After that, the cracks generated between the polarizers of the sample for evaluation and the gaps between the polarizers were visually checked to confirm the number of cracks having a length of 1 cm or more, and the results are shown in Table 5 below.
평균 반사율 편차 (%p)Average reflectance deviation (%p) | 투광율 편차 (%p)Transmittance deviation (%p) | 크랙crack | |
실시예 6Example 6 | 0.050.05 | 0.030.03 | 00 |
실시예 7Example 7 | 0.120.12 | 0.050.05 | 00 |
실시예 8Example 8 | 0.050.05 | 0.040.04 | 00 |
실시예 9Example 9 | 0.130.13 | 0.060.06 | 00 |
실시예 10Example 10 | 0.040.04 | 0.050.05 | 00 |
비교예 5Comparative Example 5 | 0.270.27 | 0.30.3 | 22 |
비교예 6Comparative Example 6 | 0.300.30 | 0.290.29 | 33 |
비교예 7Comparative Example 7 | 0.290.29 | 0.350.35 | 33 |
비교예 8Comparative Example 8 | 0.350.35 | 0.330.33 | 44 |
하기 표 5에 따르면, 실시예 6 내지 10의 평광판은 평균 반사율 편차가 0.13%p 이하이고, 투광율 편차가 0.06%p 이하로, 평광판 전반에 평균 반사율과 투광율의 차이가 거의 없어, 시인성의 부위별 편차가 없음을 확인했다. 그러나, 비교예 5 내지 8의 편광판은, 실시예 6 내지 8의 편광판과는 달리, 평균 반사율 편차 및 투광율 편차가 현저히 높아, 부위별 시인성 편차가 크게 나타날 것임을 예측할 수 있다. According to Table 5 below, the polarizing plates of Examples 6 to 10 had an average reflectance deviation of 0.13%p or less, and a light transmittance deviation of 0.06%p or less, and there was little difference between the average reflectance and light transmittance throughout the polarizing plate, and It was confirmed that there was no variation by site. However, the polarizing plates of Comparative Examples 5 to 8, unlike the polarizing plates of Examples 6 to 8, have remarkably high deviations in average reflectance and light transmittance, and thus, it can be predicted that a large deviation in visibility for each region will appear.
또한, 평균 반사율 및 투광율 편차가 낮은 실시예 6 내지 10은, 100Cycle 반복된 크랙 시험에서 크랙이 전혀 발생하지 않음을 확인했다. 반면, 비교예 5 내지 8의 편광판은 크랙이 발생함을 확인했다.In addition, in Examples 6 to 10 having low deviations in average reflectance and transmittance, it was confirmed that no cracks occurred at all in a crack test repeated 100Cycle. On the other hand, it was confirmed that cracks occurred in the polarizing plates of Comparative Examples 5 to 8.
Claims (16)
- 광투과성 기재; 하드코팅층; 및 저굴절층을 포함하고,Light-transmitting substrate; Hard coating layer; And a low refractive index layer,반사(Reflection) 모드의 X-선 회절(XRD) 패턴에서, 22 내지 24°의 2θ 값에서 나타나는 피크의 반치전폭(FWHM)이 1.5° 이하인, 반사 방지 필름.In the X-ray diffraction (XRD) pattern in the reflection mode, the full half width (FWHM) of the peak appearing at the 2θ value of 22 to 24° is 1.5° or less.
- 제1항에 있어서,The method of claim 1,상기 광투과성 기재는 30 내지 40℃의 온도 및 90 내지 100% 상대습도의 조건에서 투습률이 50 g/m 2·day 이하인, 반사 방지 필름.The light-transmitting substrate has a moisture permeability of 50 g/m 2 ·day or less under the conditions of a temperature of 30 to 40°C and a relative humidity of 90 to 100%, an antireflection film.
- 제1항에 있어서,The method of claim 1,상기 저굴절층은 바인더 수지, 및 상기 바인더 수지에 분산된 무기 미립자를 포함하는, 반사 방지 필름.The low refractive layer includes a binder resin and inorganic fine particles dispersed in the binder resin.
- 제3항에 있어서,The method of claim 3,상기 바인더 수지는 광중합성 화합물 및 광반응성 작용기를 포함한 함불소 화합물 간의 가교 중합체를 포함하는, 반사 방지 필름.The binder resin comprises a crosslinked polymer between a photopolymerizable compound and a fluorinated compound containing a photoreactive functional group, an antireflection film.
- 제3항에 있어서, The method of claim 3,상기 무기 미립자는 0.5 내지 100㎚의 직경을 갖는 솔리드형 무기 나노 입자 및 1 내지 200㎚의 직경을 갖는 중공형 무기 나노 입자로 이루어진 군에서 선택된 1종 이상을 포함하는, 반사 방지 필름.The inorganic fine particles include at least one selected from the group consisting of solid inorganic nanoparticles having a diameter of 0.5 to 100 ㎚ and hollow inorganic nanoparticles having a diameter of 1 to 200 ㎚, antireflection film.
- 제1항에 있어서, The method of claim 1,상기 하드코팅층은 광경화성 수지를 포함하는 바인더 수지, 및 상기 바인더 수지에 분산된 유기 또는 무기 미립자를 포함하는, 반사 방지 필름.The hard coating layer includes a binder resin including a photocurable resin, and organic or inorganic fine particles dispersed in the binder resin.
- 제6항에 있어서,The method of claim 6,상기 하드코팅층의 바인더 수지는 수평균분자량 10,000 이상의 고분자량 (공)중합체를 더 포함하는, 반사 방지 필름.The binder resin of the hard coating layer further comprises a high molecular weight (co)polymer having a number average molecular weight of 10,000 or more.
- 제1항에 있어서,The method of claim 1,상기 광투과성 기재는, The light-transmitting substrate,파장 400㎚ 내지 800㎚에서 측정되는 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 이상이고,The retardation (Rth) in the thickness direction measured at a wavelength of 400 nm to 800 nm is 5,000 nm or more,일 방향의 인장강도에 대한, 상기 일 방향과 수직한 방향의 인장강도의 비율은 2 이상인, 반사 방지 필름.The ratio of the tensile strength in a direction perpendicular to the one direction to the tensile strength in one direction is 2 or more.
- 제1항에 있어서,The method of claim 1,상기 광투과성 기재는 폴리에틸렌 테레프탈레이트 필름인, 반사 방지 필름.The light-transmitting substrate is a polyethylene terephthalate film, an anti-reflection film.
- 제1항에 있어서,The method of claim 1,상기 반사 방지 필름은 380㎚ 내지 780㎚의 파장대 영역에서 평균 반사율이 2.0% 이하인, 반사 방지 필름.The anti-reflective film has an average reflectance of 2.0% or less in a wavelength range of 380 nm to 780 nm.
- 제1항에 있어서,The method of claim 1,상기 반사 방지 필름은, The anti-reflection film,평균 반사율 편차가 0.2%p 이하이고,Average reflectance deviation is less than 0.2%p,투광율 편차가 0.2%p 이하인, 반사 방지 필름.An antireflection film having a light transmittance deviation of 0.2%p or less.
- 제1항에 따른 반사 방지 필름 및 편광자를 포함하는 편광판. A polarizing plate comprising the anti-reflection film and polarizer according to claim 1.
- 편광자와, With polarizer,상기 편광자를 중심으로 대향하도록 위치하는 10㎛ 이하의 두께를 갖는 제2하드 코팅층 및 제1항에 따른 반사 방지 필름을 포함하는, 편광판.A polarizing plate comprising a second hard coating layer having a thickness of 10 μm or less positioned to face the polarizer as a center and the antireflection film according to claim 1.
- 제13항에 있어서, The method of claim 13,상기 편광자; 상기 제2하드 코팅층; 및 상기 반사 방지 필름;를 합한 총 두께가 200㎛ 이하인, 편광판.The polarizer; The second hard coating layer; And the anti-reflection film; a total thickness of 200 μm or less.
- 제13항에 있어서, The method of claim 13,상기 편광자의 일면에는 상기 10㎛ 이하의 두께를 갖는 제2하드 코팅층이 위치하고, 다른 일면에는 상기 반사 방지 필름의 광투과성 기재가 위치하며,A second hard coating layer having a thickness of 10 μm or less is positioned on one side of the polarizer, and a light-transmitting substrate of the antireflection film is positioned on the other side,상기 광투과성 기재는, The light-transmitting substrate,파장 400㎚ 내지 800㎚에서 측정되는 두께 방향의 리타데이션(Rth)이 5,000 ㎚ 이상이고,The retardation (Rth) in the thickness direction measured at a wavelength of 400 nm to 800 nm is 5,000 nm or more,일 방향의 인장강도에 대한, 상기 일 방향과 수직한 방향의 인장강도의 비율은 2 이상이고,The ratio of the tensile strength in a direction perpendicular to the one direction to the tensile strength in one direction is 2 or more,상기 일 방향의 인장강도는 상기 일 방향과 수직한 방향의 인장강도 보다 작은 값을 갖는, 편광판.The tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction.
- 제1항에 따른 반사 방지 필름을 포함하는 디스플레이 장치.A display device comprising the anti-reflection film according to claim 1.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/275,494 US20220120952A1 (en) | 2019-05-28 | 2020-05-20 | Anti-reflective film, polarizing plate, and display apparatus |
JP2021509911A JP7102038B2 (en) | 2019-05-28 | 2020-05-20 | Anti-reflection film, polarizing plate and display device |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2019-0062633 | 2019-05-28 | ||
KR20190062633 | 2019-05-28 | ||
KR10-2020-0054680 | 2020-05-07 | ||
KR1020200054680A KR102581428B1 (en) | 2019-05-28 | 2020-05-07 | Anti-reflective film, polarizing plate, and display apparatus |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020242117A1 true WO2020242117A1 (en) | 2020-12-03 |
Family
ID=73552004
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2020/006581 WO2020242117A1 (en) | 2019-05-28 | 2020-05-20 | Anti-reflective film, polarizing plate, and display device |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2020242117A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005014584A (en) * | 2003-06-04 | 2005-01-20 | Fuji Photo Film Co Ltd | Cellulose acylate dope, cellulose acylate film and its manufacturing process |
KR20140031103A (en) * | 2012-09-03 | 2014-03-12 | 주식회사 엘지화학 | Polarizing plate comprising hard coating film |
KR20150003709A (en) * | 2012-05-31 | 2015-01-09 | 다이니폰 인사츠 가부시키가이샤 | Optical layered body, polarizing plate, polarizing plate fabrication method, image display device, image display device manufacturing method, and image display device visual recognizability improvement method |
KR20170106923A (en) * | 2016-03-14 | 2017-09-22 | 주식회사 엘지화학 | Anti-reflective film |
JP2017219861A (en) * | 2014-12-12 | 2017-12-14 | 住友化学株式会社 | Polarizing film and polarizing plate |
-
2020
- 2020-05-20 WO PCT/KR2020/006581 patent/WO2020242117A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005014584A (en) * | 2003-06-04 | 2005-01-20 | Fuji Photo Film Co Ltd | Cellulose acylate dope, cellulose acylate film and its manufacturing process |
KR20150003709A (en) * | 2012-05-31 | 2015-01-09 | 다이니폰 인사츠 가부시키가이샤 | Optical layered body, polarizing plate, polarizing plate fabrication method, image display device, image display device manufacturing method, and image display device visual recognizability improvement method |
KR20140031103A (en) * | 2012-09-03 | 2014-03-12 | 주식회사 엘지화학 | Polarizing plate comprising hard coating film |
JP2017219861A (en) * | 2014-12-12 | 2017-12-14 | 住友化学株式会社 | Polarizing film and polarizing plate |
KR20170106923A (en) * | 2016-03-14 | 2017-09-22 | 주식회사 엘지화학 | Anti-reflective film |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102371580B1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
KR102016710B1 (en) | Anti-reflective film | |
JP7486878B2 (en) | Anti-reflection film, polarizing plate and display device | |
WO2017048077A1 (en) | Polarizer protective film, polarizing plate comprising same, and liquid crystal display device comprising polarizing plate | |
WO2014204205A1 (en) | Polarizing plate and image display apparatus comprising same | |
WO2021187859A1 (en) | Anti-reflective film | |
WO2020080757A1 (en) | Polarizing plate, liquid crystal panel, and display device | |
WO2020242117A1 (en) | Anti-reflective film, polarizing plate, and display device | |
WO2020242210A1 (en) | Anti-reflective film, polarizing plate, and display device | |
WO2020080858A1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
KR102581428B1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
WO2020091552A1 (en) | Circular polarizing plate | |
KR102281759B1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
WO2020184865A1 (en) | Anti-reflective film, polarizing plate, and display device | |
WO2024144104A1 (en) | Anti-reflection polarizing plate and image display device comprising same | |
KR102363875B1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
WO2022182114A1 (en) | Polarizing plate and image display device comprising same | |
WO2022019610A1 (en) | Anti-glare film, polarizing plate, and display apparatus | |
WO2024144105A1 (en) | Polarizing plate for preventing reflection and image display device comprising same | |
KR102235481B1 (en) | Anti-reflective film, polarizing plate, and display apparatus | |
WO2021049903A1 (en) | Optical laminate | |
WO2020005041A1 (en) | Polarizing plate, liquid crystal panel, and display device | |
WO2021177689A1 (en) | Anti-glare film, polarizing plate and display apparatus |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20812832 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021509911 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: 20812832 Country of ref document: EP Kind code of ref document: A1 |