KR100624308B1 - Composition for coating High refractive layer of Anti-reflection film - Google Patents

Abstract

The present invention relates to a composition for coating a high refractive index layer of an antireflection film, and more particularly, to a resin 1 containing a hydroxyl group based on 100 parts by weight of two or more kinds of inorganic oxide particles having different average particle diameters, and 100 parts by weight of the inorganic oxide particles. ˜100 parts by weight, 0.5-20 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group with respect to the resin containing the hydroxyl group, and an organic solvent 500 with respect to the total solids (resin + curing agent comprising an inorganic oxide particle + hydroxyl group) The present invention relates to a composition for coating a high refractive index layer for manufacturing an antireflection film including ˜4000 parts by weight, and may provide an antireflection film including a high refractive index layer having a high refractive index only by a simple physical operation in forming a coating composition.

Anti-reflection film, high refractive layer, low refractive layer, inorganic oxide, refractive index

Description

Composition for coating High refractive layer of Anti-reflection film             

FIG. 1 shows the prediction of porosity in a composition using particles of different sizes,

FIG. 2 is a prediction of the porosity in the composition using only particles of the same size,

Figure 3 illustrates the configuration of an antireflective film according to an embodiment of the present invention,

Figure 4 illustrates an embodiment of a multi-layered antireflection film to which the present invention is applicable,

5 is a prediction of the distribution of inorganic oxide particles in the composition for coating a high refractive index layer of the present invention,

6 is a TEM image of a composition for coating a high refractive index layer formed in an embodiment of the present invention.

(Explanation of symbols for each part of drawing)

1. Base film 2. Hard coat layer

3. High refractive layer 4. Low refractive layer

5. High refractive layer 6. Low refractive layer

The present invention relates to a composition for coating a high refractive index layer of an antireflection film, and more particularly, to a resin 1 containing a hydroxyl group based on 100 parts by weight of two or more kinds of inorganic oxide particles having different average particle diameters, and 100 parts by weight of the inorganic oxide particles. ˜100 parts by weight, 0.5-20 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group with respect to the resin containing the hydroxyl group, and an organic solvent 500 with respect to the total solids (resin + curing agent comprising an inorganic oxide particle + hydroxyl group) It relates to a composition for coating a high refractive index layer for the production of an anti-reflection film comprising ~ 4000 parts by weight.

Cathode ray tube (CRT), liquid crystal display (LCD), plasma display panel (PDP), field emission display The present invention relates to a multilayer antireflection film used in FED) and the like, and to developing and manufacturing a high refractive index coating liquid in a multilayer antireflection film.

Cathode ray tube (CRT), liquid crystal display (LCD), plasma display panel (PDP), field emission display (FED), etc. The screen display device is mostly used in an environment where external light is incident, regardless of indoor / outdoor, and thus an image is inevitably formed on the screen display device by external light. Due to this phase condensation, problems such as deterioration of visibility are caused in the screen display device, and various anti-reflection films have been proposed to solve this phenomenon and are widely used.

In the production of the antireflection film, characteristics of light that can reduce reflectance are used, and the characteristics of the antireflection film are induction of diffuse reflection of light on the surface of the display device and offset interference by diffraction of light. The most typical method of inducing diffuse reflection is to provide unevenness to the surface of an image display device. This method is characterized by low cost of manufacturing and is still widely used for manufacturing solar cells and other optical components. However, when the antireflection film using the unevenness is applied to the image labeling device, a problem occurs in the image display depending on the size, height, and shape of the unevenness. In other words, problems with resolution, sharpness, and visibility due to irregularities may occur.

Therefore, the method currently widely used as the method of providing the anti-reflective property of the screen display device uses a destructive interference by diffraction of light, and a film of a multi-layer type is required. Vacuum deposition, sputtering, chemical vapor deposition (CVD), wet coating, etc. are used to manufacture the multilayer antireflection film, and a plurality of materials having different refractive indices are used. Background Art [0002] Film design and fabrication have been carried out to prepare multilayer laminated films of thin films and to reduce reflectance in the visible region. However, dry manufacturing methods, such as vacuum deposition, sputtering, and chemical vapor deposition (CVD), have significantly higher equipment and manufacturing costs (vacuum equipment, target materials). Therefore, in recent years, the production of an antireflection film using a wet coating in terms of cost has been prevalent.

In general, an antireflection film manufactured by a dry method or a wet coating has a structure in which a hard coat layer, a high refractive layer, and a low refractive layer are sequentially stacked on a transparent substrate such as glass, plastic film, or sheet. Have Conventional multilayer anti-radiation films include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), zinc sulfide (ZnS), antimony oxide (Sb ₂ O ₃ ), zinc oxide (Zinc oxide) : ZnO ₂ ), Indium oxide doped Tin (ITO), Antimony-tin composite oxide (ATO), Titanium-antimony-tin composite oxide (TiO ₂ , Sb doped SnO ₂ ), Oxidation Various inorganic metal oxides and sulfide particles having a refractive index of 1.9 or more, such as cerium (CeO) selenium oxide (SeO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), and antimony-zinc composite oxide (AZO) A high refractive index layer with a refractive index of 1.6 or more is normally laminated using In the case of the low refractive layer, a layer having a refractive index of 1.3 to 1.5 is laminated on the high refractive layer by using silica (SiO ₂ ), magnesium fluoride (MgF ₂ ), fluororesin, or the like. As such, the refractive index of the high refractive index layer and the refractive index of the low refractive layer are limited, respectively, and are stacked in various forms and various combinations according to the antireflection required.

As described above, there are two important factors in the design of the antireflection film in the production of the antireflection film of the multilayer structure, that is, the refractive index of the layer and the thickness of the layer. This is because the multilayer antireflection film is manufactured according to the optical design while controlling the refractive index and thickness of each layer. However, in the manufacture of a multilayer anti-reflection film using a solution coating method, although the layer thickness control technology is at a considerably high level due to the development of various coating techniques, there is a limit in controlling the refractive index itself.

In the manufacture of a multilayer antireflection film, it is known that the greater the difference in refractive index between the high refractive index layer and the low refractive index layer, the better the antireflection performance. That is, the higher the refractive index of the high refractive index layer is preferable, for this purpose, inorganic particles having a high refractive index are currently used in the production of the antireflection film. However, in such a high refractive layer, the refractive index is lower than the refractive index of the inorganic particles used because of the distribution shape of the inorganic particles and the resin used for coating.

Therefore, the present inventors are to provide a composition for coating a high refractive index layer having a high refractive index when forming a high refractive index layer using various kinds of inorganic particles of various particle sizes.

It is an object of the present invention to provide a composition for coating a high refractive index layer of an antireflection film having a high refractive index when forming a refractive layer by mixing inorganic oxide particles having different particle diameters.

Another object of the present invention is to provide an antireflection film using the high refractive index coating composition.

Still another object of the present invention is to provide an image display apparatus using the antireflection film.

One aspect of the present invention for achieving the above object is 1 to 100 parts by weight of a resin containing a hydroxyl group with respect to 100 parts by weight of two or more inorganic oxide particles having a different average particle diameter, 100 parts by weight of the inorganic oxide particles, the hydroxyl group Antireflection comprising 0.5 to 20 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group relative to the resin to be included, and 500 to 4000 parts by weight of an organic solvent with respect to the total solids (resin + hardener comprising an inorganic oxide particle + hydroxyl group) It relates to a composition for coating a high refractive index layer for producing a film.

Another aspect of the present invention for achieving the above object relates to an antireflection film in which a high refractive index layer formed of a hard coating layer, a low refractive index layer, and a composition for coating the high refractive index layer is sequentially laminated on a substrate.

Another aspect of the present invention for achieving the above object is a cathode ray tube (CRT), liquid crystal display (LCD), plasma display (plasma display) of a television or computer monitor using the anti-reflection film panel: PDP) and OLED (Organic Light Emmitting Display) relates to a screen display device formed the outermost layer.

Hereinafter, the present invention will be described in more detail.

The composition for coating a high refractive index layer of the antireflection film of the present invention includes two or more inorganic oxides having different average particle diameters, a resin containing a hydroxyl group, a curing agent having a functional group capable of reacting with a hydroxyl group, and an organic solvent.

Specific examples of the inorganic oxide included in the composition of the present invention include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), zinc sulfide (ZnS), and antimony oxide (Sb ₂ O ₃ ). Zinc oxide (ZnO ₂ ), indium tin oxide (ITO), antimony-tin composite oxide (ATO), titanium-antimony-tin composite oxide (TiO ₂ , Sb doped SnO ₂ ), cerium oxide (CeO), selenium oxide (SeO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), antimony-zinc composite oxide (AZO), and the like. One or more kinds of inorganic oxides are selected and two or more kinds having different average particle diameters are mixed and used. Although these inorganic oxide particles can adjust the refractive index after hardening to 1.5 or more by comparatively small amount addition, it is more preferable to use the conductive metal oxide particle whose refractive index is 1.9 or more in order to provide antireflective function and antistatic function simultaneously. Specifically, it is preferable to use zirconium oxide, tin oxide, antimony-tin composite oxide, titanium oxide, zinc oxide, indium-tin composite oxide, and the like.

The amount of the inorganic oxide particles is preferably added in an amount of 10 to 90% by weight, and more preferably in a content of 5 to 30% by weight.

The average size of the inorganic oxide particles for easily achieving the object of the present invention is in the range of 10 to 100nm, more preferably 15 to 70nm. In particular, when the particle size range exceeds 100 nm, it becomes difficult to uniformly disperse the particles of the inorganic oxide in the laminate of the antireflection film, and there is a fear that the inorganic oxide particles are precipitated in the high refractive index coating liquid composition, resulting in a lack of storage stability. This is because the transparency of the resin may decrease or the haze may increase.

In the composition for coating a high refractive index layer of the present invention, the average particle diameter of two or more inorganic oxide particles different from each other is most preferably 10 to 45 nm. As such, when inorganic oxide particles having different particle diameters are used, as shown in FIG. 1, the particles are denser and uniformly higher in filling rate than in the case of using inorganic oxide particles having the same particle size, and thus they can be distributed in the high refractive layer. This is to be achieved.

In general, the porosity is defined as the ratio of the volume of the pore portion in the rock to the total volume of the rock including the pore. As shown in FIG. 2, the porosity has the same porosity when filled with particles of the same size regardless of the particle size. do. In this regard, the porosity in the composition for coating the high refractive index layer may be defined as the volume ratio of the void portion in the total high refractive index layer-resin and the inorganic particles- and the resin, inorganic particle-volume ratio of the entire high refractive layer including the voids. In other words, how much inorganic particles with relatively high refractive index are filled without voids is important in terms of refractive index. The aggregation of particles of different sizes in the same volume is briefly shown in FIG. 1, which makes it easy to understand that when different sizes of particles are mixed, they can take up more space in the same volume. . That is, it means that the high refractive index layer formed by using the composition for coating the high refractive index layer prepared by mixing inorganic oxide particles of different sizes may have a higher inorganic particle filling rate and thus exhibit a higher refractive index.

When preparing the composition for coating a high refractive index layer of the present invention, the ratio of mixing the inorganic oxide particles having different average particle diameters is not particularly limited, and those skilled in the art can be adjusted in any range as necessary. For example, among the inorganic oxide particles exemplified above, particles having an average particle diameter of 15 nm, 25 nm, and 45 nm may be mixed in a ratio of 1: 1: 1 to form a composition for coating a high refractive layer.

In the present invention, the resin used in the composition for coating the high refractive index layer of the antireflection film may be used as long as it is a thermosetting and photocurable resin containing a hydroxyl group, and specifically, polyvinyl acetal resin, polyvinyl alcohol resin, and polyacrylic resin. Resin, polyepoxy acrylic resin, polyurethane acrylic resin, polymethyl methacryl resin, polyphenol resin, phenoxy resin, polyterephthalate resin, urethane polyol resin, acryl polyol resin, etc. Can be used in combination. The amount of resin added in the composition for coating the high refractive index is added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the inorganic oxide particles in consideration of the adhesion of the high refractive layer to the hard coat layer. Since the amount of particles relative to each other decreases, it causes a decrease in refractive index, and at the same time, control of the high refractive index becomes difficult.

The curing agent used in the composition for coating the high refractive index layer of the antireflection film of the present invention is divided into a thermosetting type and a photosetting type curing agent according to the curing method of the coating layer, and is determined by the curing method of the resin. However, the curing method is not particularly limited. The thermosetting curing agent may be selected from at least one of isocyanate, melamine formaldehyde, urea formaldehyde, polyaziridine, titanate, zirconium composite, and epoxy curing agent. Moreover, as a photocurable hardening | curing agent, a benzene, a benzene ether compound, a benzyl ketal compound, the (alpha)-hydroxyalkyl phenone compound, the (alpha), (alpha)-dialkoxy acetophenone derivative compound, the (alpha)-hydroxy alkyl phenone compound, the (alpha)-aminoalkyl phenone derivative compound , α-hydroxyalkyl phenone polymer compound, acryl phosphine pin oxide compound, halogen compound, phenylglyxoxolate compound, banjophenone derivative compound, thioxanthone derivative compound, 1,2-diketone compound, water-soluble aromatic ketone compound, air Copolymer high molecular compounds, amine coagulants, or tinanocene compounds are used, and photocurable cationic photocuring agents include diazonium salts, iodonim salts, and sulfonium salts. , Metal complexes, arylsilanol-aluminum complexes, or pyridinium salts can be used. The amount of the curing agent used is preferably in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the curable resin, and addition of a curing agent other than this range causes problems in hardness of the coating layer due to the difference in degree of curing. As a hardening | curing agent used for the composition for high refractive index coating of the antireflection film of this invention, it is more preferable to use a photocurable hardening | curing agent.

Specific examples of the organic solvent used in the high refractive index coating composition of the antireflection film of the present invention include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propanol, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and methyl acetate Esters such as ethyl acetate, aromatic compounds such as toluene, xylene, benzene, and ethers such as diethyl ether, and the like. By using two or more kinds of mixed solvents in the solvent, it is easy to handle the high refractive layer curable composition and excellent anti-reflection performance or transparency can be obtained. The amount of the organic solvent added in the composition for coating the high refractive index layer is preferably 50 to 20000 parts by weight based on 100 parts by weight of the inorganic oxide particles, because when it is out of this range, it is difficult to adjust the viscosity of the coating liquid, which causes many problems in the process.

The antireflection film prepared by using the composition for coating a high refractive index layer of the present invention has a structure in which a hard coat layer is laminated on a transparent substrate and a high refractive index layer and a low refractive layer are laminated thereon, as shown in FIG. As shown in FIG. 4, a high refractive index layer and a low refractive index layer may be further laminated to prepare an antireflection film having a structure of three or more layers. In addition, Figure 4 conceptually illustrates the case of applying the composition for coating the high refractive index layer of the present invention.

Hereinafter, each layer of the antireflective film of the present invention will be described in more detail.

[Transparent]

The transparent substrate used in the production of the antireflection film of the present invention includes, but is not limited to, glass, plastic film, sheet, and the like. Substrates having a light transmittance of at least 80%, preferably at least 85% are effective, and a substrate having a haze of 3% or less, more preferably a substrate having a haze of 1.0% or less. Furthermore, the refractive index of a base material has a value between 1.4-1.7, and it is suitable as a base material of the antireflection film for display devices. Although the thickness of a transparent base material is not restrict | limited, Preferably the film of thickness 30-150 micrometers, More preferably, 70-120 micrometers is preferable.

Suitable polymers for plastic transparent materials include cellulose esters (e.g. cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and nitro cellulose), polyimides, polycarbonates, polyesters (e.g. polyethylene Terephthalate, polyethylene naphthalate, polyyl-1,4-cyclohexanedimethylene terephthalate, polyethylen 1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate), polystyrene (E.g. syndiotactic polystyrene), polyolefins (e.g. polypropylene, polyethylene, and polymethylpentene), polysulfones, polyether sulfones, polyarylates, polyether-imides, polymethyl methacrylates, And polyether ketones, polyvinyl alcohol, polyvinyl chloride and the like. In addition, when the antireflective film is applied to a liquid crystal display (LCD), OLED (Organic Light Emitting Display), cellulose triacetate (TAC) is preferable as a transparent substrate of the antireflective film, and a cathode ray tube of a completely flat computer monitor or a television When applied to cathode ray tube (CRT), liquid crystal display (LCD), plasma display panel (PDP), and the like, polyethylene terephthalate (PET) is preferable.

In some cases, a pressure-sensitive adhesive layer may be introduced on the back surface of the substrate, and as the material used as the pressure-sensitive adhesive layer, an acrylic pressure sensitive adhesive, an ultraviolet curable pressure sensitive adhesive, a heat curable pressure sensitive adhesive, or the like may be used. It may also optionally contain a sunscreen, a pigment for improving color contrast, or carbon black in the adhesive layer introduced on the back of the substrate. In addition, in order to protect the adhesive layer, a release film and a sheet (release film) may be laminated.

[Hard Coat Layer]

It is preferable to place a hard coat layer below the high refractive layer so as to increase the film strength and fix the high refractive layer more strongly. Although there is no restriction | limiting in particular in the structural material of a hard-coat layer, Generally, a siloxane resin, an acrylic resin, a melamine resin, an epoxy resin, etc. are used individually or in combination of 2 or more types. Among them, a thermosetting or ultraviolet curable resin in which reactive silica particles obtained by reacting alkyl alkoxysilane and colloidal silica in a hydrophilic solvent can be used as a material capable of further improving scratch resistance. Examples thereof include an ultraviolet curable hard coating material containing urethane acrylate and a polyfunctional acrylate as a main component.

In general, the hard coat layer may be a resin composed of a compound having two or more functional groups as a heat and radiation curable resin. As resin which can be used, the thing which has unsaturated double bond like (meth) acrylate, and reactive substituents, such as an epoxy group and a silanol group, are mentioned. In particular, the case where a group having an unsaturated double bond is included is preferable because it can be cured by irradiation of an activating energy ray. Specific examples include ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Polyol poly (meth) acrylate, di (meth) acrylate of bisphenol A- diglycidyl ether, polyester (meth) acrylate obtained by esterifying polyhydric alcohol, polyhydric carboxylic acid, and its anhydride and acrylic acid , Polysiloxane polyacrylate, urethane (meth) acrylate, pentaerythritol tetra methacrylate, glycerin tri methacrylate and the like. Or a fluorine-containing epoxy acrylate containing fluorine, a fluorine-containing alkoxysilane, or the like. For example, 2- (perfluorodecyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxy propyl acrylate, 3- (perfluoro-9-methyldecyl) -1, 2-epoxy Propane, (meth) acrylic acid-2,2,2-trifluoroethyl, (meth) acrylic acid-2,2,2-trifluoromethyl, 3,3,3, -trifluoropropyl, and the like. These compounds can be used 1 type or in mixture of 2 or more types.

In the present invention, the curing agent used in forming the hard coat layer may be a benzene, a benzene ether compound, a benzyl ketal compound, an α-hydroxyalkylphenone compound, an α, α-alkoxyacetophenone derivative compound, an α-hydroxyalkylphenone compound. , α-aminoalkylphenone derivative compound, α-hydroxyalkylphenone high molecular compound, acrylposipine oxide compound, halogen compound, phenylglyxolate compound, banjophenone derivative compound, thioxanthone derivative compound, 1,2-diketone Thermal and photopolymerization curing agents such as compounds, water-soluble aromatic ketone compounds, copolymer high molecular compounds, amine co-curing agents, tinanocene compounds, cationic photocuring agents, acid anhydrides and peroxides and the like can be used. The amount of the curing agent used is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the curable resin.

The solvent is not particularly limited, but alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propanol and isopropanol, ketones such as methyl isobutyl ketone and MEK, esters such as methyl acetate and ethyl acetate, toluene, xylene and benzene Aromatic compounds, such as these, Ether, such as diethyl ether, etc. are mentioned. The content is about 50-10000 with respect to the total solid. More preferably, it is 500-4000 weight part. Less than 50 parts by weight is difficult to apply for thin film coating uniformly due to the high viscosity, more than 10000 parts by weight causes pinholes after application, drying.

[Low refractive layer]

In the case of a normal antireflection film, the refractive index of a low refractive index layer has the preferable value within the range of 1.33-1.50, and its range of 1.34-1.45 is more preferable. If the refractive index is less than 1.33, the kind of available materials may be excessively limited, and if the refractive index is 1.50 or more, the antireflection effect may be lowered in combination with the high refractive index layer. Is preferably set to a value of 0.05 or more because the antireflection performance is significantly lowered when the difference is less than 0.05. The film thickness of the low refractive layer depends on the optical phenomenon which is a destructive interference phenomenon in accordance with the high refractive layer, but the film thickness of the general low refractive layer is preferably in the range of 50 to 1000 nm, and most preferably in the range of 50 to 300 nm.

In general, the low refractive index layer is a fluorine resin containing a hydroxyl group, a fluorine vinyl resin, a fluorine olefin compound, a fluorine acrylic resin and various thermosetting and photocurable resins are used. 100 parts by weight of a fluorine-containing copolymer having a fluorine content of 60 to 70% by weight, 30 to 150 parts by weight of a polymer having an ethylenically unsaturated group, and 0.5 to 15 parts by weight of a curing agent when the total thereof is 100 parts by weight, In some cases, inorganic particles may be added. The fluorine-containing copolymer can be obtained by copolymerizing a monomer containing a fluorine atom and a monomer containing a hydroxyl group or an epoxy group, and is prepared by adding an ethylenically unsaturated monomer as necessary, but is not limited thereto. Examples of the monomer containing a fluorine atom for use in the low refractive layer include tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, alkylvinyl fluoride, alkoxy fluorinated alkyl vinyl ether and perfluoro Bovine-containing alkyl vinyl ethers, perfluorine-containing alkoxy vinyl ethers, fluorine-containing (meth) acrylic acid esters, and the like, which are used alone or in combination. As the monomer containing a hydroxyl group or an epoxy group, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyethyl aryl ether, hydroxybutylaryl Ether, glycerol monoallyl ether, allyl alcohol, hydroxy meta (ethyl) acrylate ester, etc. are used individually or in combination of 2 or more types.

As the curing agent used in forming the low refractive layer, thermosetting and photocuring curing agents are used, and various curing methods are used. If necessary, silica-based inorganic particles or magnesium-based inorganic particles having a low refractive index may be added.

The organic solvent of the composition for coating the low refractive index layer is the same kind as the hard coat layer coating solvent, and there is no particular limitation. Specifically, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propanol and isopropanol, ketones such as methyl isobutyl ketone and MEK, esters such as methyl acetate and ethyl acetate, aromatics such as toluene, xylene and benzene Ethers, such as a compound and diethyl ether, etc. are mentioned. However, when using a fluorine resin, a fluorine solvent can be used. Examples of fluorine-based solvents include perfluoro carbons such as perfluoro pentane, perfluoro hexane, and perfluoro octane, methyl fluoroisobutyl ether, Perfluoro ethers such as methyl perfluorobutyl ether, chlorotrifluorocyclobutane (1-chloro-1,2,2-trifluorocyclobutane), chlorotrifluorobenzene (1-chloro-2 And chloro fluorocarbons such as 3,4-trifluorobenzne), chlorofluorobenzene, dichlorofluorobenzene, and the like. The solvent may be used alone or in combination of two or more, and the content thereof is 500 to 20,000 parts by weight based on the total coating liquid in consideration of the desired viscosity and thickness with respect to the entire low refractive index coating liquid composition, preferably 500 to 1000 parts by weight. The content of the solvent is determined by adjusting the ease of coating, such as viscosity, and the ease of adjusting the thickness of the coating layer, economy.

[High refractive layer]

In general, the layer thickness of the high refractive index layer coated on the antireflection film for display devices is determined to be paired with the low refractive index layer, but is preferably between 50 and 30000 nm, and is generally suitable between 50 and 1000 nm and the thickness of about 100 nm is best. .

The composition for coating a high refractive index layer for forming the high refractive layer of the present invention is configured as described above. Other additives may be added in addition to the inorganic oxide particles having a high refractive index, a resin containing a hydroxyl group, a curing agent, and a solvent. For example, a coupling agent (organic alkoxysilane compound having an unsaturated double bond, epoxy group or mercaptan group in the molecule; or alkoxytitanium or alkoxyzirconium and inorganic alkoxide) is added to induce the bonding of the inorganic oxide particles in the high refractive layer. Sometimes.

In addition, a photosensitizer, a polymerization inhibitor, a polymerization curing aid, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, an antifoaming agent, and the like can be optionally added. .

The antireflective film prepared as described above can be used in various image display devices such as cathode ray tubes (CRTs), liquid crystal displays (LCDs), plasma displays of televisions or computer monitors. panel: PDP), OLED (Organic Light Emmitting Display) can be applied to the outermost layer.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are provided for the purpose of description and are not intended to limit the present invention.

Example 1 Composition for Coating Hard Coat Layer

Methyl ethyl ketone, ethanol, isopropyl alcohol, diacetone alcohol and trace amounts of toluene and ethyl acetate are mixed thoroughly as a solvent, and based on the solid content of the photocurable acrylic resin (Aekyung Chemical; a mixture of oligomers and monomers) in the mixed solution. Added to complete dissolution. Thereafter, 5 to 20 parts by weight of silica (Gamatech Co., Ltd.) having a particle size of 15 nm was added to the resin and dispersed. 2 to 15 parts by weight was added to the dispersed coating solution in consideration of the degree of curing of the light curing agent (Igacure 184-based Igacure 907: Ciba-geigy) to the total resin to prepare a coating solution of 45% by weight of the total solid content.

Example 2. Composition for Coating Low Refractive Layer

Methyl ethyl ketone, ethanol, butyl acetate and diacetone alcohol were mixed as solvents, and three kinds of photocurable fluorine resins (Kyoeisha) containing hydroxyl groups were added and mixed based on the solid content. Accordingly, 0.5 to 5 parts by weight of silica nanoparticles was added to the fluorine resin powder as needed. As a photocuring agent, Igacure 184-based Igacure 907 (Ciba-geigy) was added in an amount of 5 to 10 parts by weight based on the degree of curing with respect to the resin. In addition, during the coating and curing process, a leveling agent (3M: fluorine-based surfactant) and an ultraviolet absorber were added as necessary. Finally, a coating solution having a total solid content of 7 wt% was prepared.

Example 3 High Refractive Coating Liquid Composition

Nanoparticles of antimony-tin composite oxide (Antimony Tin oxide: ATO) were stirred at the particle diameters and ratios shown in Table 1, and methanol, isopropyl alcohol, diacetone alcohol, ethyl acetate, and toluene were used as a solvent. After the sol was mixed, epoxy acrylate (Aekyung Chemical: UV Curing Resin) was added and completely dissolved. In consideration of the stability of the sol, urethane acrylate (Aekyung Chemical: UV curable resin) was also used as the binder. A light curing agent (Igacure 184 Igacure 907: Ciba-geigy) was added to the completely mixed coating solution. A coating solution having a total solids content of 7% by weight was prepared.

Example 4. Preparation of Antireflective Film

As shown in Table 1, a composition for coating a high refractive index layer prepared by combining inorganic oxide particles, a composition for coating a hard coat layer prepared in Example 1, and a composition for coating a low refractive layer prepared in Example 2, respectively It was laminated to the structure shown in FIG. The base material used PET film (A4100: Toyobo). In the case of the hard coat layer was fixed to 3 ㎛. The high refractive index layer and the low refractive layer positioned on the hard coat layer were laminated by performing spin coating and bar coating using the coating solution prepared according to the above embodiment. In the case of spin coating, the rotation speed (rpm) was adjusted to observe the change in the position of the wavelength at which the lowest reflectance was caused by the thickness of the high and low refractive layers. The wavelength at which the lowest reflectivity of the antireflective film currently desired to be produced is in the region of 580-610 nm. The thickness of the high refractive index layer and the low refractive layer at this time was measured using a TEM. That is, the layer thicknesses of the high and low refractive layers were determined using the measured reflectance results. Based on the results obtained through spin coating, the number of bar coating bars and solids were adjusted to control the thickness of the high and low refractive layers. The thickness of each layer was measured by TEM.

The hard coat layer, the high refractive index layer, and the low refractive layer were dried and independently hardened after lamination. The drying was performed in consideration of the boiling point of the main solvent of the coating solution. Drying temperature was carried out within 80 minutes at 80 ℃. After drying, UV cured for 30 seconds using a mercury lamp of 80 ~ 160 W / cm2.

Each was measured using a haze and a transmittance meter (Nippon Denshoku Kogyo Co.), and reflectance was measured in a UV-vis spectrophotometer (perkin elmer), and the results are shown in Table 1 below.

Films 1 to 7 were prepared on the PET (Toyobo) substrate in the same manner as in Example 1 to prepare a hard coat layer coating liquid and using the bar coating method of Example 4 (solid content: 45 wt%, layer thickness: 3 ㎛) After coating the hard coat layer formed by mixing and dispersing the different ATO nanoparticles as shown in Table 1 above (solid content: 7 wt%, nanoparticles / resin: 5/1, layer thickness: ˜120 nm) and a low refractive index coating liquid (solid content: 7 wt%, layer thickness: 110 nm) are antireflective films prepared by laminating by a bar coating method.

 It is an antireflection film manufactured in the structure shown in FIG. 5 by using the composition for coating the high refractive index layer used in the manufacture of the films 1 to 7. The TEM photograph (film 1 is (a), film 2 is (b), film 4 is (c), film 10 is (d)) of the composition for high refractive index coating manufactured in FIG. The TEM image shows that the small particles and the large particles are evenly mixed, which means that the porosity change occurred in the lamination of the particles compared to the case of using inorganic oxide particles having the same particle size. The films 8 to 11 are each laminated using a high refractive index layer using a composition for coating a high refractive index layer prepared using only one type of inorganic oxide particles having the particle size shown in Table 1 above, except that the conditions of the films 8 to 11 are different. The same as in the preparation of 7 was maintained. As shown in Table 1, it was confirmed that there is a difference in reflectance compared to the films 1 to 7.

High refractive index coating composition of the antireflection film of the present invention by using a mixture of inorganic oxide particles of different particle diameters, it is possible to achieve a high filling rate of inorganic particles when forming a high refractive layer, as a result high refractive index compared to the conventional high refractive index coating liquid It can provide excellent antireflection performance.

Claims (7)

100 parts by weight of two or more different inorganic oxide particles having an average particle diameter in the range of 10 to 100 nm and having an average particle diameter difference of 10 to 45 nm, and an acrylate-based or methacrylate-based resin 1 based on 100 parts by weight of the inorganic oxide particles. ~ 100 parts by weight, hardening agent 0.5-15 parts by weight, and the high refractive layer of the antireflection film containing 500 to 4000 parts by weight of an organic solvent relative to the total solids (inorganic oxide particles + acrylate-based or methacrylate-based resin + curing agent) Coating composition. delete The composition of claim 1, wherein the two or more inorganic oxide particles having different average particle diameters have an average particle diameter of 15 nm to 70 nm. The method of claim 1, wherein the inorganic oxide particles have an average particle diameter of 15nm, 25nm, and 45nm of the inorganic oxide particles selected from the group consisting of two or more inorganic oxide particles having different average particle diameters mixed and dispersed. High refractive index coating composition. The method of claim 1, wherein the inorganic oxide particles are zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), zinc sulfide (ZnS), antimony oxide (Sb ₂ O ₃ ), oxidation Zinc oxide (ZnO ₂ ), indium oxide doped tin (ITO), antimony-tin composite oxide (ATO), titanium-antimony-tin composite oxide (TiO ₂ , Sb doped SnO ₂ ), cerium oxide (CeO) selenium oxide (SeO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), and antimony-zinc complex oxide (AZO) The composition for coating a high refractive index layer of the antireflective film, characterized in that above. An antireflection film in which a base material, a hard coating layer, a low refractive layer, and a high refractive layer formed of the high refractive layer coating composition of claim 1 are sequentially stacked. Cathode ray tube (CRT), liquid crystal display (LCD), plasma display panel (PDP), OLED (Organic Light Emmitting) of a television or computer monitor using the antireflective film of claim 6 Screen display device that forms the outermost layer of Display.

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