JP2011503658A - Antireflection coating composition, antireflection film and method for producing the same - Google Patents

Abstract

【Task】
The present invention includes a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2, and the surfaces of the low refractive material and the high refractive material. Provided are an antireflection coating composition having an energy difference of 5 mN / m or more, an antireflection film produced using the same, and a production method thereof. According to the present invention, an anti-reflection film having excellent wear resistance and anti-reflection function can be manufactured by a single coating process using a single composition, so that the manufacturing cost can be reduced. .
[Selection] Figure 1

Description

  The present invention relates to an antireflection coating composition, an antireflection film produced using the same, and a method for producing the same. More specifically, even when a single coating composition including resins having different refractive indexes is used to form a single coating layer by a single coating process, phase separation is performed within the single coating layer. It is related with the antireflection coating composition which can provide an antireflection function and abrasion resistance simultaneously, antireflection film manufactured using the same, and its manufacturing method.

  This application was filed with the 10-2007-0115348 and 10-2007-0115329 filed with the Korean Patent Office on November 13, 2007, and the 10-th filed with the Korean Patent Office on November 14, 2007. Claims the benefit of the filing date of 2007-0115967 and 10-2008-0035891 filed April 18, 2008, the entire contents of which are included herein.

  The purpose of applying a surface treatment to the surface of the display device is to improve the wear resistance of the display, reduce the reflection of the external light source, and improve the image contrast. The reduction in the amount of reflection of external light can be largely realized by two methods. The first is the induction of diffuse reflection through the surface irregularities, and the second is the method of inducing annihilation interference by multilayer coating design.

  Existing anti-glare coatings with surface irregularities were mainly applied. However, when the uneven surface shape is used, the high resolution display has a problem that the resolution is lowered and a problem that the sharpness of the image is lowered due to irregular reflection on the surface. In order to solve such a problem, in Japanese Patent Publication No. 11-138712 (Patent Document 1), an organic filler having a refractive index difference with a binder is used, and a light diffusion film in which light diffuses inside the film is used. Manufactured. However, when a light diffusing film is used, there is a problem that luminance and contrast are lowered, so that improvement is still necessary.

  Japanese Laid-Open Patent Publication No. 02-234101 (Patent Document 2) and Japanese Laid-Open Patent Publication No. 06-18704 (Patent Document 3) disclose a method of causing reflected light to annihilate and interfere by multilayer coating design. This method can perform an antireflection function without phase distortion. At this time, in order to cause the reflected light to annihilate, there should be a phase difference between the light reflected from each layer, and the waveform between the reflected lights can be minimized so that the reflectance can be minimized during annihilation interference. The amplitude must match. For example, when the incident angle is 0 degree with respect to the single-layer antireflection coating layer provided on the substrate, the following mathematical formula can be obtained.

[Mathematical Formula 1]
n _o n _s = n ₁ ²
2n ₁ d ₁ = (m + 1/2) λ (m = 0, 1, 2, 3,...)
(N _o : refractive index of air, n _s : refractive index of substrate, n ₁ : refractive index of film, d ₁ : film thickness, λ: wavelength of incident light)
Normally, the lower the refractive index of the antireflection coating layer is, the greater the antireflection effect is. However, considering the wear resistance of the coating layer, the refractive index of the antireflection coating layer is less than the refractive index of the substrate. The refractive index is preferably about 1.3 to 1.5 times. At this time, the reflectance is less than 3%. However, when the antireflection coating layer is formed on the plastic film, the abrasion resistance of the display cannot be satisfied, and therefore, a hard coating layer having a thickness of several microns is required below the antireflection coating layer. That is, in the case of an antireflection coating layer using annihilation interference, a hard coating layer for reinforcing wear resistance and one or more antireflection coating layers are formed thereon. Therefore, although the multilayer coating method has an antireflection function without phase distortion, a problem of increasing manufacturing cost due to the multilayer coating still occurs.

  Recently, a method has been proposed for annihilating and interfering reflected light with a single layer coating design. For example, in Japanese Laid-Open Patent Publication No. 07-168006 (Patent Document 4), an ultrafine particle dispersion is applied to a base material so that the spherical shape of the fine particles is exposed on the surface, and air and particles that are interfaces A method for providing an antireflection effect by causing a gradual difference in refractive index between the two is disclosed. However, such a method is difficult to realize by a general coating process because the shape and size of the ultrafine particles must be constant and the particles must be uniformly distributed on the substrate. Moreover, since a spherical shape cannot be obtained on the surface unless the binder is contained in a certain amount or less, there is a very weak disadvantage in wear resistance. Also, since the coating thickness should be smaller than the diameter of the fine particles, it is very difficult to achieve wear resistance by the single layer coating method as described above.

JP-A-11-138712 JP 02-234101 A Japanese Patent Laid-Open No. 06-18704 JP 07-168006 A

  In order to solve the conventional problems as described above, the present invention is able to form a coating layer by a single coating process using a single coating composition. An antireflection coating composition capable of providing an antireflection function and at the same time providing excellent wear resistance, thereby improving process efficiency and reducing manufacturing costs, and an antireflection film produced using the antireflection coating composition An object is to provide a manufacturing method.

  In order to achieve the above object, the present invention includes a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2. Provided is an antireflection coating composition in which a refractive energy has a surface energy difference of 5 mN / m or more.

The present invention also provides:
a) a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2, the surface energy difference between the low refractive material and the high refractive material being 5 mN / m Providing an antireflective coating composition as described above;
b) applying the coating composition onto a substrate to form a coating layer;
c) drying the coating layer so that the low refractive material and the high refractive material are phase separated; and d) curing the dried coating layer.

  The anti-reflective coating composition may further include a fluorine compound or a nano-particle dispersion to promote phase separation between the low refractive material and the high refractive material.

  The present invention also includes a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2, and a difference in surface energy between the low refractive material and the high refractive material. Is an antireflective film including a single coating layer in which the low refractive material and the high refractive material have a concentration gradient in the thickness direction.

  The present invention also provides a polarizing plate comprising a) a polarizing film and b) an antireflection film according to the present invention provided on at least one surface of the polarizing film.

  In addition, the present invention provides a display device including the antireflection film or the polarizing plate.

  In the present invention, by using the antireflection coating composition and the method for producing an antireflection film described above, an antireflection layer including an antireflection layer having excellent antireflection function and wear resistance while being a single coating layer. A film can be provided. The antireflection film according to the present invention has excellent wear resistance and low reflection function, and can be manufactured by a single coating process. Therefore, it has an effect of improving process efficiency and reducing manufacturing cost.

It is the photograph which observed the cross section of the antireflection film by Example 1 with the transmission electron microscope.

  Hereinafter, the present invention will be described in detail as follows.

  The antireflective coating composition according to the present invention includes a low refractive material having a refractive index of 1.2 to 1.45 and a high refractive resin having a refractive index of 1.46 to 2, the low refractive material and the high refractive index. The surface energy difference of the substance is 5 mN / m or more. By using the anti-reflective coating composition, the low refractive material and the high refractive material can be phase-separated in the process of applying, drying and curing due to the difference in surface energy. Thereby, the antireflection function and abrasion resistance which were excellent also by the single coating process by a single composition can be provided simultaneously.

  In the present invention, the surface energy means surface energy measured with a cured product generated when the corresponding material is cured.

  The low-refractive material gradually moves to the upper part of the coating layer due to the surface energy difference from the high-refractive material after coating, and the high-refractive material is relatively located at the lower part of the coating layer. In order to make maximum use of such phase separation and to fix the phase-separated position in the drying and curing steps to some extent, the low refractive material has fluidity at room temperature and gradually cures according to temperature. It is preferable to be a thermosetting type. Further, the low refractive material preferably has a surface energy of 25 mN / m or less, more preferably 5 mN / m or more and 25 mN / m or less.

  In the present invention, the low refractive material is preferably contained in an amount of 5 to 80 parts by weight and the high refractive material is preferably contained in an amount of 10 to 90 parts by weight with respect to 100 parts by weight of the total coating composition.

  The thermosetting low refractive material is a thermosetting material having a refractive index of 1.2 to 1.45, for example, an alkoxysilane reactant, a urethane reactive group compound, a urea reaction capable of sol-gel reaction. There are basic compounds, esterification reaction products, and the like.

  The alkoxysilane reactant refers to a reactive oligomer produced by subjecting alkoxysilane, fluorine-based alkoxysilane, silane-based organic substituent, or the like to hydrolysis and condensation reaction by sol-gel reaction under water and catalytic conditions. . For the sol-gel reaction, a method usually used in the technical field to which the present invention belongs can be used. The sol-gel reaction is allowed to proceed by reacting a composition component containing alkoxysilane, fluorine-based alkoxysilane, silane-based organic substituent, catalyst, water and organic solvent at a reaction temperature of 0 to 150 ° C. for 1 to 70 hours. it can. At this time, the average molecular weight of the alkoxysilane reactant, which is the reactive oligomer, is preferably 1,000 to 200,000 when measured using GPC (Gel Permeation Chromatography) and polystyrene as a standard substance. After the coating, the alkoxysilane reactant produced in this manner undergoes a condensation reaction under a temperature condition of room temperature or higher to form a network of a crosslinked structure.

  The alkoxysilane can provide a certain level of strength to the outermost coating thin film. Specifically, as the alkoxysilane component, tetraalkoxysilane or trialkoxysilane can be used, and tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, It is preferable to use one or more substances selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and the like, but is not limited to these examples. .

  The content of alkoxysilane as a basic monomer in the alkoxysilane reactant is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane reactant. When the amount is less than 5 parts by weight, the abrasion resistance is not sufficiently excellent, and when it exceeds 50 parts by weight, it is difficult to realize low refraction of the alkoxysilane reactant and phase separation from the high refraction material.

  The fluorine-based alkoxysilane can lower the refractive index and surface tension of the coating thin film and facilitate phase separation from a highly refractive material. As the fluorine-based alkoxysilane, it is preferable to use a low refractive material having a low refractive index of 1.3 to 1.4 and a low surface tension of 10 to 15 mN / m. Examples of the fluorine-based alkoxysilane include one or more substances selected from the group consisting of tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriisopropoxysilane, and the like. Although it is preferable to use it, it is not limited only to these examples.

  In order to easily induce phase separation from a highly refractive material while the alkoxysilane reactant has a refractive index of 1.2 to 1.45, the content of fluorine-based alkoxysilane is 100 parts by weight of the alkoxysilane reactant. It is preferably 10 to 70 parts by weight. If it is less than 10 parts by weight, it is difficult to realize low refraction and phase separation from a highly refractive material, and if it exceeds 70 parts by weight, it is difficult to ensure the liquid phase stability and scratch resistance of the composition.

  The silane-based organic substitute can chemically bond with alkoxysilane, reacts with a high-refractive substance to form a double bond, promotes compatibility between the low-refractive material and the high-refractive material, and after phase separation Plays a role in improving adhesion at the interface between the alkoxysilane and the highly refractive material. Therefore, any compound that fulfills such a role can be used without particular limitation. Examples of the silane-based organic substituent include vinyltrimethoxysilane, vinyltri (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-n-pentoxysilane, vinylmethyldimethoxysilane, diphenylethoxy. Vinylsilane, vinyltriisopropoxysilane, divinyldi (β-methoxyethoxy) silane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi (isopropoxy) silane, divinyldi-n-pentoxysilane, 3- Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldiethoxy Although it is preferable to use one or more substances selected from the group consisting of a run, but is not limited to these examples.

  In order for the alkoxysilane reactant to maintain compatibility and stability in the coating liquid state, the content of the silane-based organic substituent is 0 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane reactant. Is preferred. When the amount exceeds 50 parts by weight, it is difficult to realize low refraction, and phase separation from a highly refractive material is difficult. In addition, when the silane-based organic substitute is not added, the compatibility of the low refractive material with the high refractive material is insufficient, and the coating liquid may not be mixed uniformly.

  The catalyst used in the sol-gel reaction is a necessary component for controlling the sol-gel reaction time. The catalyst is preferably an acid such as nitric acid, hydrochloric acid, and acetic acid, and more preferably in the form of hydrochloride, nitrate, sulfate, and acetate together with a salt such as zirconium or indium. However, it is not necessarily limited to these. At this time, the content of the catalyst is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the alkoxysilane reactant.

  Water used for the sol-gel reaction is a necessary component for the hydrolysis reaction and the condensation reaction. The water content is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane reactant.

  The organic solvent used for the sol-gel reaction is a component for appropriately adjusting the molecular weight of the hydrolyzate. The organic solvent is preferably alcohols, cellosolves, ketones, or a mixed solvent of two or more selected from these. At this time, the content of the organic solvent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the alkoxysilane reactant.

  Meanwhile, the urethane reactive group compound can be produced by reacting an alcohol and an isocyanate compound under a metal catalyst. If a composition in which a polyfunctional alcohol containing two or more functional groups is mixed with a polyfunctional isocyanate and a metal catalyst is placed at a temperature equal to or higher than normal temperature, a network structure having urethane reactive groups can be formed. At this time, a fluorine group can be introduced into alcohol or isocyanate in order to realize low refractive characteristics and induce phase separation from a highly refractive material.

  Examples of the polyfunctional alcohol containing fluorine are 1H, 1H, 4H, 4H-perfluoro-1,4-butanediol, 1H, 1H, 5H, 5H-perfluoro-1,5-pentanediol, 1H, 1H, 6H. , 6H-perfluoro-1,6-hexanediol, 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol, 1H, 1H, 9H, 9H-perfluoro-1,9-nonanediol, 1H, 1H, Examples include 10H, 10H-perfluoro-1,10-decanediol, 1H, 1H, 12H, 12H-perfluoro-1,12-dodecanediol, fluorinated triethylene glycol, and fluorinated tetraethylene glycol. However, it is not necessarily limited to these.

  As the isocyanate component used in the production of the urethane reactive group compound, aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate, heterocyclic isocyanate and the like are preferably used. Specifically, diisocyanates such as hexamethylene diisocyanate, 1,3,3-trimethylhexamethylene diisocyanate, isophorone diisocyanate, toluene-2,6-diisocyanate, 4,4′-dicyclohexane diisocyanate, or trifunctional or higher functional isocyanates. For example, it is preferable to use DN950, DN980, etc. of brand name DIC.

  In the present invention, a catalyst can be used when producing the urethane reactive group compound, and a Lewis acid or a Lewis base can be used as the catalyst. Specific examples of the catalyst include, but are not limited to, tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin dimaleate, dimethyltin hydroxide and triethylamine.

  The content of isocyanate and polyfunctional alcohol used when producing the urethane reactive group compound is preferably such that the molar ratio of NCO group to OH group (NCO / OH) is 0.5 to 2, More preferably, it is .75 to 1.1. If the molar ratio of the functional groups is less than 0.5 or exceeds 2, there may be a problem that unreacted functional groups increase and the strength of the film decreases.

  The urea reactive group compound can be produced by a reaction between amines and isocyanates. As the isocyanate, the same component as that which can be used in the production of the urethane reaction product can be used, and as the amine, a perfluoro-functional bifunctional or higher amine substance can be used. In the present invention, a catalyst can be used if necessary, and a Lewis acid or a Lewis base can be used as the catalyst. Specific examples of the catalyst include, but are not limited to, tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin dimaleate, dimethyltin hydroxide and triethylamine.

  The esterification reaction product is produced through a dehydration and condensation reaction of an acid and an alcohol. If the esterification reaction product is also blended in the coating composition, a film having a crosslinked structure can be formed. As the acid, it is preferable to use a bifunctional or higher acid containing fluorine. Examples thereof include perfluorosuccinic acid, perfluoroglutaric acid, perfluoroadipic acid, and perfluorosuberic acid ( perfluorosuberic acid, perfluoroazelaic acid, perfluorosebacic acid, perfluorolauric acid, and the like. The alcohol is preferably a polyfunctional alcohol. Examples of the polyfunctional alcohol include 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1, Examples include, but are not limited to, 4-cyclohexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,4-heptanediol, pentaerythritol, and trimethylolpropane. For the esterification reaction, an acid catalyst such as sulfuric acid or an alkoxytitanium such as tetrabutoxytitanium can be used. However, it is not necessarily limited to these.

  The high refractive material is a resin having a refractive index of 1.45 to 2, has a relatively high refractive index as compared with the low refractive material, and the surface energy of the cured product at the time of curing is a low refractive material. It is characterized by a difference of 5 mN / m or more from the surface energy at the time of curing, and preferably 5 mN / m or more larger than the surface energy at the time of curing of the low refractive material.

  It is preferable to use a high refractive UV curable resin as the high refractive material. The material of the high refractive UV curable resin may include an acrylate resin, a photoinitiator and a solvent, and a surfactant if necessary.

  Examples of the acrylate resins include acrylate monomers, urethane acrylate oligomers, epoxy acrylate oligomers, and ester acrylate oligomers. In order to obtain a high refractive index, they may contain substituents such as sulfur, chlorine, metal, and aromatics. it can. Examples thereof include dipentaerythritol hexaacrylate, pentaerythritol tri / tetraacrylate, trimethylenepropane triacrylate, ethylene glycol diacrylate, 9,9-bis (4- (2-acryloxyethoxyphenyl) fluorene (refractive index 1. 62), bis (4-methacryloxythiophenyl) sulfide (refractive index 1.589), bis (4-vinylthiophenyl) sulfide (refractive index 1.695), and the like. It can be used by mixing.

  The content of the acrylate resin is preferably 10 to 80 parts by weight with respect to 100 parts by weight of the highly refractive material. When this content is less than 10 parts by weight, there is a problem that the scratch resistance and abrasion resistance of the coating film are lowered, and the viscosity of the coating solution becomes excessively low so as not to be transferred to the coating machine and the substrate. When the amount exceeds 80 parts by weight, there are problems that the viscosity of the coating liquid becomes high and phase separation from a low refractive material is difficult, and the flatness and coating properties of the coating film are deteriorated.

  As the photoinitiator, a compound decomposable into ultraviolet rays is preferably used. Examples thereof include 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. And benzoin butyl ether.

  The content of the photoinitiator is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the highly refractive material. When this content is less than 1 part by weight, uncured can occur, and when it exceeds 20 parts by weight, the scratch resistance and wear resistance of the coating film can be reduced.

  As the solvent, alcohols, acetates, ketones, or aromatic solvents can be used. Specifically, methanol, ethanol, isopropyl alcohol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-isopropoxyethanol, methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexane, cyclohexanone, toluene, xylene, benzene, or the like can be used, but is not limited thereto.

  The content of the solvent is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the high refractive material. When this content is less than 10 parts by weight, there is a problem that the viscosity of the coating liquid is high, phase separation from a low refractive material is difficult, and the flatness of the coating film is deteriorated. When exceeding, there is a problem that the scratch resistance and abrasion resistance of the coating film are lowered, and the viscosity of the coating liquid becomes excessively low so as not to be transferred to the coating machine and the substrate.

  The high refractive UV curable resin may include a surfactant. As the surfactant, a leveling agent, a wetting agent, or the like can be used. In particular, a fluorine-based or polysiloxane-based compound is preferably used, but is not limited thereto.

  The content of the surfactant is preferably 5 parts by weight at the maximum with respect to 100 parts by weight of the highly refractive material. When this content exceeds 5 parts by weight, there is a problem that the phase separation efficiency with the low refractive material is lowered, and the adhesion to the substrate, the scratch resistance and the wear resistance of the coating film are lowered. The surfactant is preferably added in an amount of 0.05 or more with respect to 100 parts by weight of the high refractive material in order to sufficiently exhibit the effect of this addition.

  The aforementioned low refractive material and high refractive material preferably have a refractive index difference of 0.01 or more after drying and curing between them. In this case, a single coating layer is functionally composed of two or more GRIN ( An antireflection effect can be obtained by forming a gradient refractive index) structure. At this time, the surface energy during curing of the low refractive material is 25 mN / m or less, and the phase separation is not effectively performed unless the surface energy difference between the low refractive material and the high refractive material is 5 mN / m or more. .

  The antireflection coating composition according to the present invention may further include at least one of a fluorine-based compound and a nanoparticle dispersion. These can promote phase separation between the low refractive resin and the high refractive resin.

  The fluorine-based compound preferably has a refractive index of 1.5 or less, a molecular weight smaller than that of the low refractive material, and a surface energy between the surface energy of the high refractive material and the low refractive material. The fluorine-based compound is preferably included in an amount of 0.05 to 72 parts by weight with respect to 100 parts by weight of the entire coating composition.

Examples of the fluorine compounds include fluorine-based alkoxysilanes, fluorine-based alcohols, fluorine-based isocyanates, fluorine-based amines, and fluorine-containing compounds exemplified as the low refractive thermosetting resin such as fluorine-containing bifunctional or higher acid. , is represented by the following chemical formula 1-5, containing one or more fluorine-based acrylates, fluorine component may further include a straight or branched chain hydrocarbon radical of C ₁ -C ₆ as a substituent One or more selected from the group consisting of various fluorine-based additives such as leveling agents, dispersants, surface modifiers, wetting agents, defoaming agents, compatibilizers, and fluorine-based solvents Substances are preferably used.

In Formula 1, R ₁ is —H or a C ₁ -C ₆ hydrocarbon group, a is an integer of 0 to 4, and b is an integer of 1 to 3. It is preferred hydrocarbon groups of the C ₁ -C ₆ is a methyl group (-CH _3).

In Chemical Formula 2, c is an integer of 1-10.

In Chemical Formula 3, d is an integer of 1-9.

In Formula 4, e is an integer of 1 to 5.

In Formula 5, f is an integer of 4 to 10.

  The fluorine-based compound is preferably used within a range that maintains the low reflection characteristics of the coating film, the strength of the coating film, and the adhesion to the display substrate, and specifically, with respect to 100 parts by weight of the low refractive material. It is preferable to use at a content of 1 to 90 parts by weight.

  The nanoparticulate dispersion is a nanoparticulate having an average particle size of 1,000 nm or less, preferably 1 to 200 nm, more preferably 2 to 100 nm or less in order to obtain a transparent film without scattering and diffusion of visible light. It is preferable to contain. The nanoparticle dispersion preferably has a refractive index of 1.45 or less. The nanoparticle dispersion may further include a dispersibility enhancing chelating agent, a fluorine-based acrylate, a solvent, and the like. The nano fine particle dispersion is preferably included in an amount of 2 to 27 parts by weight with respect to 100 parts by weight of the entire coating composition.

Examples of the nano fine particles include metal fluoride, other hollow hollow and porous fine particles. Specifically, the metal fluoride is a fine particle having an average particle size of 10 to 100 nm and is NaF, LiF, AlF ₃ , Na ₅ Al ₃ F ₁₄ , Na ₃ AlF ₆ , MgF ₂ , NaMgF ₃ and YF. One or more substances selected from the group consisting of _{3 and the} like can be used.

  The nanoparticles are preferably used within a range that maintains the low reflection characteristics of the coating film, the strength of the coating film, and the adhesion to the display substrate. The nano-particle content is preferably 5 to 70 parts by weight with respect to 100 parts by weight of the dispersion.

The dispersibility-enhancing chelating agent imparts compatibility between the high-refractive substance and the low-refractive substance and the nanoparticulate to prevent the nanoparticulate from easily solidifying during the formation of the coating film. It is a component used to solve the problem of stagnation, preferably in a liquid phase, and can be added as necessary. Examples of the dispersibility enhancing chelating agent include Mg (CF ₃ COO) ₂ , Na (CF ₃ COO), K (CF ₃ COO), Ca (CF ₃ COO) ₂ , Mg (CF ₂ COCHCOCF ₃ ) ₂ , Na It is preferable to use one or more substances selected from the group consisting of (CF ₂ COCHCOCF ₃ ), Zr (AcAc), Zn (AcAc), Ti (AcAc), and Al (AcAc). Here, AcAc is acetylacetone.

  Moreover, as a solvent, it is preferable to use DAA, AcAc, cellosolve, etc., However, It is not limited only to these.

  The dispersibility enhancing chelating agent is preferably used within a range that maintains the dispersibility of the nanoparticles, the strength of the coating film, and the adhesion to the display substrate. Specifically, it is preferable to use 10 to 80 parts by weight with respect to 100 parts by weight of the nano fine particle dispersion.

The fluorine-based acrylate is used to impart film strength through the compatibility and chemical bonds between the high refractive material and a low refractive material is represented by Formula 1 to 5, C ₁ - as a substituent One or more substances selected from the group consisting of compounds that may further have a C ₆ hydrocarbon group are used. The content of the fluorinated acrylate is preferably 80 parts by weight or less with respect to 100 parts by weight of the nanoparticulate dispersion.

  Alcohols, acetates, ketones, or aromatic solvents can be used as the solvent of the nanoparticle dispersion liquid. Specifically, methanol, ethanol, isopropyl alcohol, butanol, 2-methoxyethanol, 2-methoxyethanol, Ethoxyethanol, 2-butoxyethanol, 2-isopropoxyethanol, methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone, toluene, xylene, benzene, or the like can be used. The content of the solvent is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the nanoparticle dispersion.

  The present invention provides an antireflection film manufactured using the above-described antireflection coating composition and a method for manufacturing the same.

  The method for producing an antireflection film according to the present invention comprises: a) preparing the above-described antireflection coating composition; b) applying the coating composition on a substrate to form a coating layer; c) Drying the coating layer to phase separate the low refractive material and the high refractive material; and d) curing the dried coating layer.

  As the base material in the step b), glass, plastic sheet and film can be used, and the thickness is not limited. Examples of the plastic film include triacetate cellulose film, norbornene-based cycloolefin polymer, polyester film, polymethacrylate film, polycarbonate film, and the like, but are not limited to these examples.

  The coating method of the coating composition in the step b) is mainly selected from various methods such as bar coating, 2-roll or 3-roll reverse coating, gravure coating, die coating, micro gravure coating, and comma coating. This can be freely selected according to the type of substrate and the liquid phase and rheological properties of the coating liquid.

  The coating thickness is not particularly limited, and is preferably 0.5 to 30 μm. After coating, a drying process for solvent drying is performed. When the dry thickness of the coating is less than 0.5 μm, the abrasion resistance is not sufficient, and when it exceeds 30 μm, the phase separation between the low refractive material and the high refractive material is not smooth. It is not possible to obtain a reflectivity result sufficient to satisfy

  The drying in the step c) is performed at 40 to 150 ° C. for 0.1 to 30 minutes so that the organic solvent in the coating composition is volatilized and the low refractive material is gradually cured by being positioned on the coating layer. Is called. When the drying temperature is less than 40 ° C., the organic solvent may be insufficiently vaporized and the degree of curing during UV curing may decrease. When the drying temperature exceeds 150 ° C., a low-refractive material is formed on the coating layer. There is a concern that curing will occur before it is positioned.

  Curing in the step d) can be performed by ultraviolet rays or heat depending on the type of resin used. When all of the thermosetting resin and the ultraviolet curable resin are used, it is preferable that the ultraviolet curing is performed first and the thermal curing is performed later.

The ultraviolet curing can be performed by irradiating ultraviolet rays for 1 to 600 seconds at an ultraviolet irradiation amount of 0.01 to ² J / cm ² . Thereby, the coating layer may have sufficient abrasion resistance. When the amount of UV irradiation does not reach the above range, the uncured resin remains in the coating layer and the surface is sticky and wear resistance is not good. The degree of cure is too high and may hinder the curing of the thermosetting resin in the subsequent thermosetting step.

  The thermosetting can be performed at a temperature of 20 to 200 ° C. for 1 to 72 hours. When the curing temperature is less than 20 ° C, the thermal curing rate is slow and the heat curing time becomes excessively long. When the curing temperature exceeds 200 ° C, the stability of the coating substrate is dangerous. . The curing time is 1 to 72 hours depending on the temperature, but it is preferable that the thermosetting resin is sufficiently cured in order to maximize the scratch resistance of the coating layer.

  The antireflection film according to the present invention manufactured using the antireflection coating composition described above includes a low refractive resin having a refractive index of 1.2 to 1.45 and a high refractive material having a refractive index of 1.46 to 2. Preferably, it further includes at least one of a fluorine-based compound and a nano-particle dispersion liquid, and a surface energy difference between the low refractive material and the high refractive material is 5 mN / m or more, The refractive material includes a single coating layer having a concentration gradient in the thickness direction. The antireflection film may further include a substrate provided on one surface of the coating layer.

  In the antireflection film, the low refractive material contained in the region corresponding to 50% in the thickness direction from the surface of the coating layer in contact with air is preferably 70% or more, and 85% or more with respect to the total weight of the low refractive material. Is more preferable, and 95% or more is more preferable. The antireflection film according to the present invention exhibits an excellent antireflection effect when the reflectance is less than 3%.

  Moreover, this invention provides the polarizing plate containing the antireflection film which concerns on this invention mentioned above. Specifically, the polarizing plate according to the present invention includes a) a polarizing film, and b) an antireflection film according to the present invention provided on at least one surface of the polarizing film. A protective film may be provided between the polarizing film and the antireflection film. Moreover, the said protective film WHEREIN: The base material for forming a single coating layer may be used as it is at the time of manufacture of the said antireflection film. The polarizing film and the antireflection film can be bonded together with an adhesive. As the polarizing film, those known in the art can be used.

  The present invention provides a display device including the antireflection film or the polarizing plate. The display device may be a liquid crystal display device or a plasma display device. The display device according to the present invention may have a structure known in the art except that the antireflection film according to the present invention is provided. For example, in the display device according to the present invention, the antireflection film may be provided on the outermost surface on the observer side or the backlight side of the display panel. The display device according to the present invention may include a display panel, a polarizing film provided on at least one surface of the panel, and an antireflection film provided on an opposite side surface in contact with the panel of the polarizing film.

  Hereinafter, preferred examples are presented to help understanding of the present invention, but the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

Production Example <Preparation of Thermosetting Low Refractive Material (Material A)>
15.3 parts by weight of DN980 having a mean number of isocyanate functional groups of 3 (trade name of DIC), 1H, 1H, 12H, 12H-perfluoro-1,12-dodecanediol 14 as a bifunctional alcohol containing fluorine Part by weight, 0.7 parts by weight of dibutyltin dilaurate as a metal catalyst, and 35 parts by weight of diacetone alcohol (DAA) and methyl ethyl ketone (MEK) as a solvent were uniformly mixed to prepare a low refractive material as a solution phase.

<Preparation of Thermosetting Low Refractive Material (Material B)>
10 parts by weight of tetraethoxysilane, 30 parts by weight of heptadecafluorodecyltrimethoxysilane, 20 parts by weight of methacryltrimethoxysilane, 10 parts by weight of water, 0.5 part by weight of hydrochloric acid, 40 parts by weight of ethanol, 40 parts by weight of 2-butanol The mixture was subjected to a sol-gel reaction at room temperature for 12 hours to prepare a thermosetting low refractive material as a solution phase.

<Preparation of Thermosetting Low Refractive Material (Material C)>
25 parts by weight of fluoroalkylmethoxysilane, 20 parts by weight of tetraethoxysilane, 7 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.5 parts by weight of water, 0.5 parts by weight of nitric acid, 20 parts by weight of methanol and 2-butyl alcohol 20 parts by weight of the mixture was subjected to a sol-gel reaction at room temperature for 24 hours to form a solution of a low refractive thermosetting material.

<Preparation of Thermosetting Low Refractive Material (Material D)>
15 parts by weight of fluoroalkylmethoxysilane, 25 parts by weight of tetraethoxysilane, 12 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.5 parts by weight of water, 0.5 parts by weight of nitric acid, 20 parts by weight of methanol and 2-butyl alcohol 20 parts by weight of the mixture was subjected to a sol-gel reaction at room temperature for 24 hours to form a solution of a low refractive thermosetting material.

<Preparation of UV-curable high refractive material (Substance E)>
28 parts by weight of dipentaerythritol hexaacrylate (DPHA) as a polyfunctional acrylate imparting film strength of the coating film, 2 parts by weight of Darocur 1173 as an ultraviolet initiator, and diacetone alcohol (DAA) and methyl ethyl ketone (MEK) as solvents 35 parts by weight were uniformly mixed to prepare a UV-curable high refractive material as a solution phase.

<Preparation of UV-curable high refractive material (Substance F)>
30 parts by weight of dipentaerythritol hexaacrylate (DPHA) as a polyfunctional acrylate imparting film strength of the coating film, 1 part by weight of Darocur 1173 as an ultraviolet initiator, 20 parts by weight of ethanol as a solvent, 29 parts by weight of n-butyl alcohol And 20 parts by weight of acetylacetone (AcAc) were uniformly mixed to form a solution of a high refractive UV curable material.

<Preparation of Thermosetting Low Refractive Material (Material G)>
A mixture of 5 parts by weight of fluoroalkylethoxysilane, 37 parts by weight of tetramethoxysilane, 10 parts by weight of vinyltrimethoxysilane, 7.5 parts by weight of water, 0.5 parts by weight of nitric acid, and 40 parts by weight of methanol is dissolved at room temperature for 24 hours. A gel reaction was performed to form a solution of a low refractive thermosetting material.

<Preparation of UV curable high refractive material (Material H)>
As polyfunctional acrylate for imparting film strength of the coating film, 20 parts by weight of pentaerythritol tri / tetraacrylate, 10 parts by weight of trimethylenepropane triacrylate, 1 part by weight of Darocur 1173 which is an ultraviolet initiator, and BYK 333 which is a surfactant. 5 parts by weight, 4 parts by weight of BYK371, 20 parts by weight of ethanol as a solvent, 20 parts by weight of n-butyl alcohol and 20 parts by weight of methyl ethyl ketone (MEK) are uniformly mixed to form a solution of a high refractive UV curable material. did.

  An anti-reflective coating composition was prepared by uniformly mixing 30 parts by weight of substance A, which is a thermosetting low-refractive substance, and 70 parts by weight of substance E, which is an ultraviolet-curable high-refractive substance.

The prepared composition was coated on a triacetate cellulose film having a thickness of 80 μm with a wire bar (No. 5). This was dried in a 60 ° C. oven for 2 minutes, UV cured with 1 J / cm ² of UV energy, and then left in a 120 ° C. oven for 1 day for final heat curing. The thickness of the final coating layer is about 1 μm, and a photograph of the cross section observed with a transmission electron microscope is shown in FIG.

  Referring to FIG. 1, it can be confirmed that the high refractive material layer and the low refractive material layer are clearly separated on the substrate and have a layered structure. If such materials having different refractive indexes are formed in a layered structure, a more effective reflectivity can be realized as compared with the case of a single layer.

  The same method as in Example 1 was performed except that the material B was used instead of the material A as the thermosetting low refractive material.

  25 parts by weight of the substance C as a thermosetting low-refractive substance and 75 parts by weight of the substance F as an ultraviolet curable high-refractive substance were uniformly mixed to form a compatible mixed solution to prepare a coating composition.

The prepared coating solution was coated on a 80 μm thick triacetate cellulose film with a wire bar (No. 5). This was dried in a 120 ° C. oven for 2 minutes, UV cured with UV energy of 200 mJ / cm ² , and then left in a 120 ° C. oven for 1 day for final heat curing. The thickness of the coating film is about 1 μm.

  A compatible coating composition was prepared by uniformly mixing 30 parts by weight of the substance A as a thermosetting low refractive material and 70 parts by weight of the substance F as an ultraviolet curable high refractive substance. Using this composition, a coating film was produced in the same manner as in Example 3.

  Anti-reflective coating that is compatible by uniformly mixing 20 parts by weight of substance C as a thermosetting low-refractive substance, 75 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 5 parts by weight of trifluoroethyl acrylate as a fluorine compound. A composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

  Antireflective coating that is compatible by uniformly mixing 25 parts by weight of substance A as a thermosetting low-refractive substance, 70 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 5 parts by weight of trifluoroethyl acrylate as a fluorine compound. A composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

  Antireflective coating that is compatible by uniformly mixing 25 parts by weight of substance D as a thermosetting low-refractive substance, 70 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 5 parts by weight of trifluoroethyl acrylate as a fluorine compound A composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

  22 parts by weight of substance C as a thermosetting low-refractive substance, 70 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 8 parts by weight of tridecafluorooctyltriethoxysilane as a fluorine-based compound are uniformly mixed to be compatible. An antireflective coating composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

  26 parts by weight of substance C as a thermosetting low-refractive substance, 70 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 4 parts by weight of Fluorad FC4430 (3M company) as a fluorine-based compound are uniformly mixed to make a compatible reflection A preventive coating composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

A metal fluoride dispersion was prepared by uniformly mixing 50 parts by weight of 10% MgF ₂ dispersion, 30 parts by weight of magnesium trifluoroacetate, and 20 parts by weight of methyl ethyl ketone (MEK).

  8 parts by weight of substance C as a thermosetting low-refractive substance, 75 parts by weight of substance F as an ultraviolet curable high-refractive substance, and 17 parts by weight of the above-mentioned metal fluoride dispersion are uniformly mixed to provide a compatible antireflection coating composition. Prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

  A coating solution and a coating film were manufactured in the same manner as in Example 10 except that the material A was used instead of the material C as the thermosetting low refractive material.

  25 parts by weight of substance D as a thermosetting low-refractive substance, 70 parts by weight of substance F as an ultraviolet-curable high-refractive substance, and 5 parts by weight of the metal fluoride dispersion prepared in Example 10 are mixed uniformly to be compatible. An antireflective coating composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

A metal fluoride dispersion was prepared by uniformly mixing 10 parts by weight of NaMgF ₃ having an average particle size of 30 to 40 nm and 90 parts by weight of isopropyl alcohol (IPA). A coating solution and a coating film were produced in the same manner as in Example 10 except that this metal fluoride dispersion was used.

  10 parts by weight of Meso-porous Silica having an average particle size of 20 nm and a porosity of 20% and 90 parts by weight of methanol were uniformly mixed to form a nanoparticle dispersion. A coating solution and a coating film were produced in the same manner as in Example 10 except that this nanoparticle dispersion was used.

[Comparative Example 1]
Only the substance E which is an ultraviolet curable high refractive substance was used as a material for forming a coating layer, and this was coated on a triacetate cellulose film having a thickness of 80 μm with a wire bar (No. 5). This was dried in a 60 ° C. oven for 2 minutes, and UV-cured with UV energy of 1 J / cm ² to produce a coating film. The thickness of the coating film is about 1 μm.

[Comparative Example 2]
Only substance A, which is a thermosetting low-refractive substance, was used as a material for forming a coating layer, and this was coated on a triacetate cellulose film having a thickness of 80 μm with a wire bar (No. 5). This was left to stand in a 120 ° C. oven for 1 day to thermally cure to produce a coating film. The thickness of the coating film is about 1 μm.

[Comparative Example 3]
Only material B, which is a thermosetting low-refractive material, was used as a material for forming a coating layer, and this was coated on a triacetate cellulose film having a thickness of 80 μm with a wire bar (No. 5). This was left to stand in a 120 ° C. oven for 1 day to thermally cure to produce a coating film. The thickness of the coating film is about 1 μm.

[Comparative Example 4]
Only the substance F, which is an ultraviolet curable high-refractive substance, was used as a material for forming a coating layer, and this was coated on a triacetate cellulose film having a thickness of 80 μm with a wire bar (No. 5). This was dried in a 120 ° C. oven for 2 minutes, UV-cured with UV energy of 200 mJ / cm ² and then left in a 120 ° C. oven for 1 day. The thickness of the coating film is about 1 μm.

[Comparative Example 5]
Antireflective coating that is compatible by uniformly mixing 25 parts by weight of substance G as a thermosetting low-refractive substance, 70 parts by weight of substance H as an ultraviolet-curable high-refractive substance, and 5 parts by weight of trifluoroethyl acrylate as a fluorine compound. A composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

[Comparative Example 6]
25 parts by weight of the substance G as a thermosetting low-refractive substance, 70 parts by weight of the substance H as an ultraviolet curable high-refractive substance, and 5 parts by weight of the metal fluoride dispersion prepared in Example 10 are mixed uniformly to be compatible. An antireflective coating composition was prepared. Using this composition, a coating film was produced in the same manner as in Example 3.

Experimental Example Table 1 shows the refractive index and surface energy of the cured product using the low refractive and high refractive materials manufactured in the manufacturing example. The manufacturing method of the hardened | cured material of each material is as follows. The thermosetting low refractive material is coated on a 80 μm thick triacetate cellulose film with a wire bar (No. 5) and left in an oven at 120 ° C. for 1 day. The ultraviolet curable high refractive material is the same as the low refractive material. It was coated by the method, but this was dried in a 60 ° C. oven for 2 minutes and UV cured with 200 mJ / cm ² of UV energy. The refractive index was measured using a prism coupler manufactured by Sairon Technology, and the surface energy was measured using DSA100, a drop shape analysis product manufactured by KRUSS, based on water and diiodomethane (CH ₂ I ₂ ).

The thickness of the coating film produced by the methods of Examples and Comparative Examples was 1 μm. Reflectance, transmittance, and haze were evaluated as follows as wear resistance and optical properties of the antireflection films produced in Examples and Comparative Examples.

1) Evaluation of scratch resistance Each coating film sample prepared above was evaluated for the degree of occurrence of scratches after 10 reciprocations with steel wool (steel wool # 0000) under a 1 kg load.

2) Evaluation of reflectance After the black color was applied to the back surface of the coating film, Shimadzu's Solid Spec. The reflectance was measured with a 3700 spectrophotometer, and the low reflectance characteristics were evaluated with the minimum reflectance value.

3) Evaluation of transmittance and haze The transmittance and haze of the coating film were evaluated using HR-100 from Murakami of Japan.

  The evaluation results of reflectance, transmittance, and haze are shown in Tables 2 and 3.

As can be seen from Tables 2 and 3, in the case of Examples 1 to 14, scratch resistance is well evaluated and not only excellent in abrasion resistance, but also has excellent light characteristics in reflectance, transmittance and haze. Show. On the other hand, in the case of Comparative Examples 1 and 4 to 6, the optical properties related to transmittance and haze are lower than those of the Examples. In the case of Comparative Examples 2 and 3, the scratch resistance is weak, and there is a disadvantage that the process efficiency is lowered in that a separate hard coating is required to protect this.

  Through the examples and comparative examples, the antireflection film according to the present invention is manufactured by a single coating process, so that the process efficiency is excellent and the manufacturing cost is reduced, as well as antireflection performance and wear resistance. Can be confirmed.

  The preferred embodiment of the present invention described above has been disclosed. Certain terminology has been used herein for the purpose of describing the invention to those skilled in the art in detail, and is intended to be limited in meaning and claimed. It is not used to limit the scope of the invention.

Claims (22)

  A low refractive material having a refractive index of 1.2 to 1.45 and a high refractive material having a refractive index of 1.46 to 2, and a difference in surface energy between the low refractive material and the high refractive material is 5 mN / m or more. An antireflective coating composition.   The antireflective coating composition of claim 1, wherein the low refractive material has a surface energy of 25 mN / m or less.   The antireflection coating composition according to claim 1, wherein the low refractive material is a thermosetting resin, and the high refractive material is an ultraviolet curable resin.   The low-refractive material includes one or more selected from the group consisting of an alkoxysilane reactant, a urethane reactive group compound, a urea reactive group compound, and an esterification reactant capable of sol-gel reaction. Anti-reflective coating composition.   The antireflective coating composition according to claim 3, wherein the highly refractive material includes an acrylate resin, a photoinitiator, and a solvent.   The anti-reflective coating composition according to claim 1, wherein the content of the high refractive material is 10 to 90 parts by weight and the content of the low refractive material is 5 to 80 parts by weight with respect to 100 parts by weight of the total coating composition. object.   The antireflection coating composition according to claim 1, wherein a difference in refractive index after curing between the high refractive material and the low refractive material is 0.01 or more.   The antireflection coating composition according to claim 1, wherein the antireflection coating composition further comprises at least one of a fluorine-based compound and a nanoparticulate dispersion.   9. The fluorine compound according to claim 8, wherein the fluorine compound has a refractive index of 1.5 or less, a molecular weight is smaller than a molecular weight of the low refractive material, and a surface energy is between the surface energy of the high refractive material and the low refractive material. Anti-reflective coating composition.   The antireflection coating composition according to claim 8, wherein the nanoparticle dispersion includes nanoparticles having an average particle size of 1,000 nm or less.   The antireflection coating composition according to claim 8, wherein the nanoparticle dispersion has a refractive index of 1.45 or less.   The antireflection coating composition according to claim 10, wherein the nanoparticulate dispersion further comprises a dispersibility enhancing chelating agent, a fluorine-based acrylate and a solvent.   The antireflection coating composition according to claim 10, wherein the nanoparticle is a metal fluoride or an organic or inorganic hollow or porous particle. a) providing an antireflective coating composition according to any one of claims 1 to 13;
b) applying the coating composition onto a substrate to form a coating layer;
c) drying the coating layer so that the low refractive material and the high refractive material are phase separated; and d) curing the dried coating layer.   The method for producing an antireflection film according to claim 14, wherein the coating thickness in the step b) is 1 to 30 μm. The low-refractive material is a thermosetting resin, the high-refractive material is an ultraviolet curable resin, and the d) step includes d1) converting the high-refractive ultraviolet curable resin to an ultraviolet irradiation amount of 0.1 to 2 J / cm. ^The antireflective film according to claim 14, comprising a step of curing by irradiating ultraviolet rays for 1 to 600 seconds at ² , and d2) curing the low refractive thermosetting resin at 20 to 200 ° C. for 1 to 72 hours. Production method.   An antireflection film comprising the single coating layer formed using the antireflection coating composition according to any one of claims 1 to 13, wherein the low refractive material and the high refractive material have a concentration gradient in the thickness direction. .   The antireflection film includes a) a low refractive resin having a refractive index of 1.2 to 1.45 and a high refractive material having a refractive index of 1.46 to 2, and the surfaces of the low refractive material and the high refractive material. Providing an anti-reflective coating composition having an energy difference of 5 mN / m or more; b) applying the coating composition onto a substrate to form a coating layer; c) drying the coating layer 18. The antireflective film of claim 17, wherein the antireflective film is made by a method comprising: causing a refractive material and a high refractive material to phase separate; and d) curing the dried coating layer.   The low-refractive material included in a region corresponding to 50% in the thickness direction from the surface of the single coating layer in contact with air is 70% or more based on the total weight of the low-refractive material. Antireflection film.   The antireflection film according to claim 17, wherein the reflectance is less than 3%.   A polarizing plate comprising: a) a polarizing film; and b) the antireflection film according to claim 17.   A display device comprising an antireflection film according to claim 17.