WO2013032120A1 - Anti-glare film - Google Patents

Abstract

The present invention relates to an anti-glare film. Each layer in the anti-glare film has enhanced surface adhesion force and abrasion resistance, and the anti-glare film can be manufactured by a simplified process.

Description

 【Specification】

 [Name of invention]

 Antireflection film

 Technical Field

 The present invention relates to an antireflection film.

 [Technique to become background of invention]

 In general, display devices such as PDPs, CRTs, and LCDs are equipped with anti-reflection films (or anti-glare films) for minimizing reflection of light incident on the screen from the outside.

 In the conventional antireflection film, an antireflection layer is mainly formed on a light transmissive substrate. At this time, the antireflection layer is most widely used in a three-layer structure in which a hard coat layer, a high refractive index layer and a low refractive index layer sequentially stacked from the light transmissive substrate side. Recently, in order to simplify the manufacturing process, a two-layer structure in which the hard coat layer or the high refractive index layer is omitted from the antireflection layer is also commercialized. In addition, in order to have both anti-glare and scratch resistance, an anti-reflection film provided with an anti-glare hard coat layer is also used.

 On the other hand, the antireflection film is generally produced by a dry method or a wet method. Among them, the dry method is a method of laminating a plurality of thin film layers by vapor deposition, sputtering, and the like, but the interfacial adhesion between layers is strong, but the manufacturing cost is high and it is not widely used commercially.

 On the other hand, the wet method is a method of coating a composition including a binder, a solvent, and the like on a substrate, and drying and curing the wet method, which has a lower manufacturing cost than the dry method and is widely used commercially. However, the wet method generally produces a composition required for forming each layer, such as a hard coat layer, a high refractive index layer, and a low refractive index layer, and uses the same to form each layer sequentially, thus making the manufacturing process complicated and interlayer interface. Adhesion has a weak disadvantage.

Thus, studies on the composition for anti-reflective coating that can form a structure of two or more layers with a single wet coating are being actively conducted, but the phase separation is not performed smoothly during the application of the composition during the manufacturing process, and thus the function as each layer is reduced. Many problems still exist, including falling. In addition, the hard coat layer or the high refractive index layer is usually formed of a pure binder on the substrate, or formed of a separate layer including a binder and inorganic fine particles on the substrate, and a low refractive index layer in which hollow particles and the like are dispersed thereon. . However, there is still a problem that the antireflection film of the structure as described above has a weak interfacial adhesion and poor durability.

 [Content of invention]

 [Achievement to be solved]

 The present invention provides an antireflection film that can be formed in a simplified process while exhibiting improved interlayer interfacial adhesion and scratch resistance.

 [Solution of problem]

 According to one embodiment of the invention, a first layer comprising a first (meth) acrylate-based binder, inorganic fine particles in the first (meth) acrylate-based binder, eroded in the substrate; And a second layer comprising a second (meth) acrylate-based binder and hollow particles in the second (meth) acrylate-based binder and covering the first layer, wherein any cross section of the second layer is included. An antireflection film is provided, wherein the ratio of the cross-sectional area of the hollow particles to the area is 70 to 95%.

 In such an antireflection film, the first (meth) acrylate-based binder may comprise a crosslinked polymer of a (meth) acrylate-based compound having a molecular weight of less than 600, and the second (meth) acrylate-based binder may have a molecular weight of less than 600 It may include a crosslinked copolymer of a (meth) acrylate-based compound and a (meth) acrylate-based compound having a molecular weight of 600 to 100,000.

In addition to the region in which the crosslinked polymer is located, the first layer further includes a region in which a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000 is located. It may include. In this case, the region in which the crosslinked copolymer is positioned may be positioned to a depth of about 5 to 50% of the first charge based on the interface between the first layer and the second layer. In addition, the crosslinked copolymer may be included to increase the distribution gradient in the direction of the second layer. And, in the antireflection film of one embodiment, the second layer may further include inorganic fine particles.

 In addition, the (meth) acrylate-based compound having a molecular weight of less than 600 may be tri (meth) acrylate for pentaerythri, tetra (meth) acrylate for pentaerythri, nucleus (meth) acrylate for dipentaerythr, tri Methylenepropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 9,9-bis (4- (2-acryloxyephenyl) fluorene, bis (4-methacryloxythiophenyl) sulfide And at least one compound selected from the group consisting of bis (4-vinylthiophenyl) sulfide.

 And the second (meth) acrylate-based binder has a molecular weight of less than 600

In addition to the (meth) acrylate compound and the (meth) acrylate compound having a molecular weight of 600 to 100,000, a crosslinked copolymer in which a fluorine (meth) acrylate compound is further copolymerized may be included.

 In addition, the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 may include a compound having a structure in which two or more molecules of the (meth) acrylate-based compound having a molecular weight of less than 600 are connected by a linker, and the linker may include a urethane bond, Thioether bonds, ether bonds or ester bonds. In addition, the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 may have a substituent and at least one selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group, a thil group, an aromatic or aliphatic hydrocarbon group having 6 or more carbon atoms, and an isocyanate group.

 And, in the anti-reflection film of one embodiment, the inorganic fine particles may have a number average particle diameter of 5 to 50nm, for example, may be silica fine particles. In addition, the hollow particles may be one having a number average particle diameter of 5 to 80 nm, for example, hollow silica particles.

 【Effects of the Invention]

The antireflective film according to the present invention can be formed by a single coating, so that it can be formed in a simpler process, while maintaining improved interfacial adhesion and scratch resistance between layers. Also, the above The antireflection film can exhibit an excellent antireflection effect and can be preferably applied to an antireflection film such as a display device.

 [Brief Description of Drawings]

 1 is a cross-sectional view schematically showing the structure of an anti-reflection film according to an embodiment of the present invention.

 2 is a flow chart schematically showing a method of manufacturing an anti-reflection film according to an embodiment of the present invention.

 3 to 6 are enlarged observation photographs of cross-sections of the antireflection films according to Examples 1, 2, 4, and Comparative Example 1, respectively.

 [Specific contents to carry out invention]

 Hereinafter, with reference to the accompanying drawings, it will be described with respect to the anti-reflection film and its manufacturing method according to an embodiment of the invention.

 Prior to this, some terms used in the present specification are defined as follows unless explicitly stated throughout the present specification.

 First, the term "inorganic fine particles" refers to particles derived from various inorganic materials, and may collectively refer to particles having a number average particle diameter on the nanometer scale, for example, a number average particle diameter of 100 nm or less. Such 'inorganic particulates' may be amorphous particles having substantially no empty space inside the particles. For example, the “silica fine particles” may be particles derived from a silicon compound or an organosilicon compound, and may refer to silicon compound or organosilicon compound particles having a number average particle diameter of 100 nm or less and no empty space inside the particles.

 In addition, the term “hollow particles” may refer to particles in the form of empty spaces present on and / or inside the organic or inorganic particles. For example, the term “hollow silica particles” refers to silica particles derived from a silicon compound or an organosilicon compound, and may refer to particles having a void space on the surface and / or inside of the silica particles.

In addition, the term "(meth) acrylate" is defined as collectively referred to as acrylate (meth) or methacrylate (methacrylate). In addition, such '(meth) acrylates' can be defined as having no bloso-containing substituents. In addition, the compound having a fluorine-containing substituent may be referred to as a fluorine-based (meth) acrylate compound.

 In addition, the term "coating layer" means a composition layer formed by applying (coating) a composition for antireflection coating described below on a predetermined base film.

 In addition, the term "phase separation" means that a difference is formed in the distribution of specific components included in the composition due to differences in density, surface tension, or other physical properties of the components. Here, when the coating layer is phase-separated, it may be divided into at least two layers based on whether a specific component is distributed, for example, the distribution of hollow particles.

 In addition, 'eroding into the substrate' means that a component (for example, a (meth) acrylate-based compound and an inorganic fine particle, etc., for forming a binder of the layer) for forming a certain layer of the antireflection film It may be referred to as penetrating into the substrate to form the layer in question. For example, a component that has penetrated into the substrate can be dried and cured while penetrating into a region within the substrate to form a constant layer within the substrate of that region. In contrast, the formation of a layer 'on the substrate' means that the components for forming the layer are not substantially eroded within the substrate, and are dried and cured at an interface with the substrate, thereby ensuring that there is no overlapping area with the substrate. It may refer to forming a layer.

And that one layer (e.g., the second layer of one embodiment described below) 'covers' another layer (e.g., the first layer of one embodiment, described below), distinguishing them from these two layers. It can be said that no other layer is substantially present. For example, in the antireflection film of one embodiment described below, the second layer containing hollow particles' covers the first layer eroded in the substrate, and the first layer is an erosion layer in the substrate, and the hollow particles are contained. It may mean that there is no separate layer between the second layers, for example, no erosion into the substrate and no hollow particles. As an example, in the above embodiment, only a binder (for example, a crosslinked polymer formed from a (meth) acrylate-based compound) and / or inorganic fine particles is formed between the first layer, which is an erosion layer, and the second layer containing the hollow particles. It may mean that there is no separate layer that is included and not eroded into the substrate. On the other hand, the inventors of the present invention, in the course of repeated studies on the anti-reflection film, by using a predetermined composition described below to induce spontaneous phase separation to form an anti-reflection film, the interfacial adhesion between the layers and the scratch resistance is excellent It was confirmed that it was possible to provide an antireflection film showing an antireflection effect, and completed the invention. The excellent characteristic of such an antireflection film is that the first layer serving as the hard coat layer is formed in the form of erosion in the substrate, and the second layer serving as the low refractive index layer is formed to cover the first layer. It seems to be due to structural characteristics. In contrast, between the substrate and the low refractive index layer, a separate hard coat layer substantially free of hollow particles (eg, substantially free of hollow particles, containing only a binder, or containing only a binder and inorganic fine particles). In the case of the anti-reflection film having a structure formed with a separate hard coat layer or a high refractive index layer), a separate coating or curing process is required to form each layer, and the process is complicated or the interface adhesion between the layers is reduced. There is this.

 However, the antireflection film of one embodiment in which the first layer (hard coat layer) eroded in the substrate covers the second charge (low refractive index layer) can be formed in a simplified manner through a unified coating and curing process, Excellent interfacial adhesion between layers can be exhibited.

One such embodiment includes the anti-reflection film has been eroded in the base material inorganic fine particles in the first (meth) acrylate-based binder and wherein the first (meth) acrylate-based binder ^Peer first layer; And a second layer including a second (meth) acrylate binder and hollow particles in the second (meth) acrylate binder and covering the first layer. Further, in such antireflection film, the ratio of the cross-sectional area of the hollow particles to any cross-sectional area of the second layer is about 70 to 95%, or about 75 to 93%, black about 80 to 90%, or about 85 to 92%.

In such an antireflection film, the first layer eroded in the substrate may act as a high refractive index layer exhibiting a refractive index of about 1.5 or more, while acting as a hard coat layer of the antireflection film. Such hard coat layer into the substrate An eroded first (meth) acrylate-based binder is included, and the first (meth) acrylate-based binder may include a crosslinked polymer of a (meth) acrylate-based compound having a molecular weight of less than 600. In addition, the hard coat layer may include inorganic fine particles in the first (meth) acrylate-based binder.

Further, the substrate I 1 2 charged in my eroded layer of the covering them in contact with the first layer is the whole of the hollow particles, or most (e.g., about 97 parts by weight _^0/0 above, black is about 99 weight _^0/0 above) This may be substantially distributed to act as a low refractive index layer of the antireflection film. Such a low refractive index layer may exhibit a low refractive index of about 1.45 or less, thereby exhibiting an appropriate antireflection effect. The low refractive index includes a second (meth) acrylate-based binder, which is a (meth) acrylate-based compound having a molecular weight of less than 600 and a (meth) acrylate having a molecular weight of 600 to 100,000. It may include a crosslinked copolymer of the compound. In addition, the low refractive index layer may include vaporized particles in the second (meth) acrylate-based binder.

 In such an antireflection film, the agent of the first layer serving as a hard coat insect

The 1 (meth) acrylate binder may further include a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000. In addition, the second layer serving as the low refractive index layer may further contain inorganic fine particles.

A schematic schematic diagram of an example of such an antireflection film is shown in FIG. 1. Referring to FIG. 1, in such an antireflection film, a first layer 2 serving as a hard coat layer is formed in a hardened state by erosion in the substrate 1, and a second layer 3 serving as a low refractive index layer. The erosion layer can be formed on the substrate on which the erosion layer is formed while in contact with and covering the first layer 2 which is the erosion layer. At this time, no separate layer is distinguished between the first layer 2 eroded into the substrate and the second layer 3 over the substrate. The absence of such a separate layer means that, for example, only the binder and / or the inorganic fine particles are included between the first layer, which is an erosion layer, and the second layer, in which the hollow particles are substantially distributed, and the hollow particles are substantially not. It may be referred to that it does not include a separate filling that does not include the erosion into the substrate. As such, the first layer 2 serving as the hard coat layer remains eroded into the substrate 1, and as the second layer 3 serving as the low refractive index layer is formed on the substrate to contact them. , Anti-reflection film of another embodiment is excellent in the interfacial adhesion of the substrate, the hard coat layer and the low refractive index layer can minimize the peeling phenomenon in the use process.

 In addition, the ratio of the cross-sectional area of the hollow particles to any cross-sectional area of the second layer may be about 70 to 95%, black about 75 to 93%, or about 80 to 90%, or about 85 to 92%. To the extent, hollow particles may be densely distributed in the second layer serving as a low refractive index insect. Thus, the antireflection film of one embodiment may exhibit excellent low refractive index characteristics and antireflection effects.

 Hereinafter, each layer that may be included in the antireflection film of one embodiment will be described in more detail.

 First, the antireflective film comprises a substrate. As shown in FIG. 1, the base material 1 is a normal transparent thin film, and if the 1st (meth) acrylate type binder and inorganic microparticles | fine-particles of a 1st layer are of the material which can be corroded, the kind in particular will not be restrict | limited. For example, as a base material, what originated in materials, such as polyester resin, polycarbonate resin, acrylic resin, and acetate cellulose resin, can be used. In one example, in order to improve the transparency and the antireflection effect, a triacetate cell may be used as a base material of Rhodes (TAC) resin.

Moreover, the antireflection film contains the crosslinked polymer of the (meth) acrylate type compound of molecular weight less than 600 as a 1st (meth) acrylate type binder, and contains the inorganic fine particles in this 1st (meth) acrylate type binder. The first layer 2 can be included as a hard coat layer. Such hardcoat worms can be layers eroded into the substrate. The first layer 2 may be one in which the first (meth) acrylate-based binder and the inorganic fine particles are eroded into the substrate to be cured integrally with the substrate. Although the first pack 2 is shown as eroded to the entire surface of the substrate 1 in FIG. 1, in another example, the first layer 2 may be constructed by eroding a portion of the substrate 1. The second layer 3 acting as a low refractive index layer may be formed to contact and cover the first erosion 2 eroded in the substrate 1 and be a layer comprising hollow particles. More specifically, between the first layer 2 and the second layer 3, there is no separate layer containing only binders and / or inorganic particulates and not eroding into the crawfish. If there is a separate filling consisting of a binder only between the hard coat layer and the low refractive index layer, as in the previously known film, there may be a disadvantage that the adhesion between each layer and the substrate is reduced, the anti-reflection film of one embodiment is a low refractive index layer The acting second layer (3) is formed directly over and in contact with the substrate (1) and the first layer (2) acting as a hard coat layer, which can result in improved interlayer adhesion, scratch resistance and antireflection effect. .

 Here, the second (meth) acrylate binder of the second packing (3) may include a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000. Can be. In another example, the second (meth) acrylate-based binder is a cross-linked air of a (meth) acrylate compound having a molecular weight of less than 600, a (meth) acrylate compound having a molecular weight of 600 to 100,000 and a fluorine (meth) acrylate compound It may also include coalescence. As the crosslinked copolymer further copolymerized with such a fluorine-based (meth) acrylate compound is included in the second (meth) acrylate-based binder, the lower refractive index of the second layer 3 serving as the low refractive index layer and excellent Anti-reflection effect can be realized. Moreover, the scratch resistance of the 2nd layer 3 can be improved more.

 In addition, the crab second layer 3 may further include inorganic particulates in the second (meth) acrylate-based binder, through which the scratch resistance and the antireflection effect of the second layer 3 may be further improved. .

 On the other hand, the first (meth) acrylate-based binder of the first charge (2) is a (meth) acrylate-based compound and a molecular weight of less than 600 in addition to the crosslinked polymer of the (meth) acrylate-based compound having a molecular weight of less than 600 described above It may further comprise a crosslinking copolymer of 600 to 100,000 (meth) acrylate-based compound.

At this time, the crosslinked copolymer contained in the first (meth) acrylate-based binder of the first layer (2) is the first layer (2) and the first layer (based on the light interface of the second layer (3) 2) It may be included in a certain area, for example up to about 5-50% deep, or up to about 5-45% deep, or up to about 5-40% deep of the first layer 2. Then, the cross-linked copolymer contained in the binder of the first layer ⁽²⁾ may be included to increase the gradient distribution in the second layer (3) direction.

 As such, the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 is crosslinked and copolymerized with the (meth) acrylate-based compound having a molecular weight of less than 600 with a distribution gradient to a certain depth of the first layer (2). As a result of crosslinking copolymerization in the entirety of the second layer 3, the interfacial adhesion between the first layer 2 and the second layer 3 can be further improved, and the hollow contained in the second layer 3 can be improved. Particles can be densely distributed.

 In the above-described antireflection film, the first layer 2 is a layer having a higher refractive index than the second layer 3 serving as the low refractive index layer, and has a refractive index of about 1.5 to 1.58, black to about 1.5 to 1.57, Black may be about 1.51 to 1.56. In addition, the second layer 3 may have a refractive index of about 1.1 to 1.45, or about 1.15 to 1.43, or about 1.2 to 1.42.

 In addition, the anti-reflective film of another embodiment described above exhibits excellent anti-reflective properties such that the reflectance is about 0.5 to 4%, black is about 0.8 to 3%, or about 1 to 2%, and various PDP, CRT or LCD It can be suitably applied as an antireflection film in display devices.

 Hereinafter, a composition for antireflective coating and a method for manufacturing an antireflective film using the same to form an antireflective film according to one embodiment will be described.

 Such antireflective coating compositions include (meth) acrylate compounds having a molecular weight of less than 600; (Meth) acrylate-based compounds having a molecular weight of 600 to 100,000; Inorganic particulates; And hollow particles. Each composition of such a composition is demonstrated as follows.

 (Methyl V-Glyacrylate Compounds of Less Than 600 Molecular Weight)

First, the antireflective coating composition may include a (meth) acrylate-based compound having a molecular weight of less than 600. Of these low molecular weights The (meth) acrylate-based compound may be at least partially eroded into the substrate when the composition is applied to any substrate.

 The low molecular weight (meth) acrylate-based compound eroded into the substrate as described above is a first-layer binder copolymerized with homopolymerization or a high molecular weight (meth) acrylate-based compound having a molecular weight of 600 to 100,000, which will be described later. Can be formed.

 And, the remainder of the low molecular weight (meth) acrylate compound may remain on the substrate without being eroded. The remaining compound may be copolymerized with a high molecular weight (meth) acrylate compound to be described later to form a binder of a second layer covering the first layer of the erosion region. ·

 In order to enable the low molecular weight (meth) acrylate compound to be eroded into the substrate to form a binder and a first layer which acts as a hard coat layer of the antireflection film, the low molecular weight (meth) acrylate compound is For example, it may have a molecular weight of less than about 600, or less than about 500, or less than about 400, and in another example, may have a molecular weight of about 50 or more, or about 100 or more.

 In one example, the low molecular weight (meth) acrylate-based compound is formed so that a first layer (eg, a hard coat layer and / or a high refractive index layer) exhibiting higher refractive index can be formed in the substrate. Substituents and aromatic substituents such as sulfur, chlorine or metal may be used.

 These low molecular weight (meth) acrylate compounds include pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythroxy nucleated (meth) acrylate, trimethylenepropane tri ( Meth) acrylate, ethylene glycol di (meth) acrylate, 9,9-bis (4- (2-acryloxyephenyl) fluorene (refractories 1.62), bis (4-methacryloxythiophenyl) sulfide (Refractive index 1.689), and bis (4-vinylthiophenyl) sulfide (refractive index 1.695) may be included, and may include two or more kinds of combinations selected for these symptoms.

(Meth) acrylate compounds having a molecular weight of 600 to 100,000 Meanwhile, the antireflective coating composition may include a high molecular weight (meth) acrylate compound having a molecular weight of 600 to 100,000. Such high molecular weight (meth) acrylate-based compounds, when the composition is applied to any substrate due to the large molecular weight and the bulky chemical structure thereof, and the like, compared with the above-described low molecular weight compound, the relatively small amount of the substrate May be eroded into, and the remaining substantial amount may remain on the substrate.

 Accordingly, the high molecular weight (meth) acrylate compound is not eroded to the same depth as the low molecular weight (meth) acrylate compound described above. As a result, the erosion region in the substrate can be divided into the following two regions. First, a region in which only the low molecular weight (meth) acrylate-based compound is eroded is a region at a depth that can be eroded, where a binder which is a crosslinked polymer of the low molecular weight (meth) acrylate-based compound may exist. have. In the region where the high molecular weight (meth) acrylate compound is eroded as the remaining area of the erosion region, a binder in which a high molecular weight (meth) acrylate compound and a low molecular weight (meth) acrylate compound are crosslinked and copolymerized may be present. Can be.

 The second layer (eg, a low refractive index layer of the antireflection film) which is copolymerized with the above-described low molecular weight compound to cover the erosion layer, with the remainder of the high molecular weight (meth) acrylate compound not eroded to the substrate. The second (meth) acrylate binder can be formed. This improves the interfacial adhesion between the first layer that can act as a hard coat layer of the antireflection film and the second layer (low refractive index layer) covering the same, and at the same time improves the scratch resistance of the low refractive index layer, The hollow particles included in the low refractive index layer can be more densely distributed.

Such a high molecular weight (meth) acrylate-based compound is a compound having a relatively large molecular weight and bulky structure compared to the low molecular weight compound described above, for example, about 400 or more, or about 500 or more, or about It may have a molecular weight of 600 or more, and as another example may have a molecular weight of about 100,000 or less, or about 80,000 or less, black is about 50,000 or less. For such a large molecular weight and bulky structure, the high molecular weight (meth) acrylate-based compound may include a compound having a structure in which two or more molecules of the aforementioned low molecular weight (meth) acrylate-based compound are linked by a linker. In this case, the linker may be a bivalent or more radical including an arbitrary chemical bond known to be capable of connecting a (meth) acrylate-based compound, for example, a urethane bond, a thioether bond, an ether bond or an ester bond. . In addition, the high molecular weight (meth) acrylate-based compound is preferably one or more substituents selected from the group consisting of an epoxy group, a hydroxyl group, a carboxy group, a thi group, an aromatic or aliphatic hydrocarbon group having 6 or more carbon atoms, and an isocyanate group for a bulkier structure. Can be.

 As such a high molecular weight (meth) acrylate-based compound, a commercial article satisfying the above conditions may be used or may be directly synthesized. Examples of such commodities include UA-306T, UA-306I, UA-306H, UA-510T, UA-510I, UA-510H (above, manufactured by KYOEISHA); BPZA-66, BPZA-100 (above, manufactured by KYOEISHA Corporation); EB9260, EB9970 (above, manufactured by BAEYER); Examples include Miramer SP1107 and Miramer SP1114 (manufactured by MIWON).

High molecular weight (meth) acrylate type mentioned above ^. The compound may be included in the antireflective coating composition at about 5 to 30 parts by weight, or about 5 to 25 parts by weight, and about 5 to 20 parts by weight of black, based on 100 parts by weight of the low molecular weight compound. The content ratio of the high molecular weight (meth) acrylate compound is configured at the time of excessive addition while ensuring the minimum effect of the mixed use of the compound for forming a binder including a high molecular weight and a low molecular weight (meth) acrylate compound It may be set in consideration of optimization of physical properties of the layer or change in distribution tendency of hollow particles.

 Fluorine (meth) acrylate compound

Meanwhile, the above-described antireflective coating composition may further include a fluorine-based (meth) acrylate compound in which at least one fluorine is substituted as a compound for forming a binder. Such fluorine-based (meth) acrylate compounds are not eroded into the substrate when the composition is applied to the substrate due to the presence of a fluorine-containing substituent. For this reason, the fluorine-based (meth) acrylate compound has a low molecular weight and Together with the high molecular weight (meth) acrylate compound, a second (meth) acrylate-based binder of the second layer serving as the low refractive index layer of the antireflection film can be formed. Since the fluorine-based (meth) acrylate compound exhibits a lower refractive index, the refractive index of the low refractive index layer can be lowered. The fluorine-based (meth) acrylate compound has excellent compatibility with the hollow particles to be described later as it contains a polar functional group. It can help improve scratch resistance.

 These fluorine-based (meth) acrylate compounds may be

The (meth) acrylate compound may have a structure in which one or more fluorine-containing substituents are bonded thereto. Examples of such a fluorine-based (meth) acrylate compound include 1 selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 5 Species or more compounds may be mentioned:

 [Formula 1]

_Wherein R ¹ is a hydrogen group or an alkyl group of 1 to 6 carbon atoms _: a is an integer of 0 to 7 and b is an integer of 1 to 3;

 In Formula 2, c is an integer of 1 to 10;

 [Formula 3]

In Formula 3, d is an integer of 1 to 11; [Formula 4]

상기 화학식 4에서， e는 1 내지 5의 정수이고;

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

 [Formula 5]

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

On the other hand, the bloso-based (meth) acrylate compound is about 5 to 20 parts by weight, black is about ₅ to 1 ₈ parts by weight, and black is about 10 to about 100 parts by weight of the low molecular weight (meth) acrylate compound described above. 16 parts by weight may be included in the antireflective coating composition.

 As the fluorine-based (meth) acrylate compound, a commercial article satisfying the above conditions may be used. Examples of such commercial articles include OPTOOL AR110 (manufacturer: DAI IN), LINC-3A, and LINC-102A (manufacturer: KYOEISHA). , PFOA (manufacturer: Exfluor), OP-38Z (manufacturer: DIC), and the like.

 Inorganic fine particles

On the other hand, the anti-reflective coating composition may include inorganic fine particles. When the composition is applied to any substrate, the inorganic fine particles may be included in a state in which a portion thereof is eroded and dispersed in the substrate together with the above-described two or more compounds for forming a binder. In addition, the remainder not eroded into the substrate is included in the state dispersed in the second layer acting as the low refractive index layer, and may contribute to the improvement of scratch resistance and antireflection. In one embodiment, the inorganic fine particles are particles derived from various inorganic materials, and may have a number average particle diameter of nanometer scale.

 Such inorganic particles may have a number average particle size, for example, about 100 nm or less, or about 5 to 50 nm, or about 5 to 20 nm. In order to control the transparency, refractive index and scratch resistance of the coating layer, the particle size of the inorganic fine particles may be adjusted to be in the above-described range.

 In addition, in order to secure improved transparency of the coating layer on the substrate, silica particles derived from a silicon compound or an organosilicon compound may be used as the inorganic particles.

 Inorganic fine particles are, for example, about 5 to 30 parts by weight, black to about 5 to 25 parts by weight, and black to about 5 to 20 parts by weight with respect to 100 parts by weight of the above-described low molecular weight (meth) acrylate-based compound. It may be included in the composition for anti-coat. Inorganic particles can be minimized by considering the amount of inorganic particles that can be eroded depending on the type of substrate, and the reduction of the anti-reflective effect due to the increase of reflectance when added in excess. The content of sweets can be adjusted in the above range.

On the other hand, the inorganic fine particles are dispersed in a predetermined dispersion medium, may be included in the form of a sol (solid) content of about 5 to 40 increase ⁰ /. Herein, organic solvents that can be used as the dispersion medium include alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, butanol (tmtanol); Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Aromatic carbon hydrogens such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide, and N-methyl pyrrolidone; esters such as ethyl acetate, butyl acetate, and γ-butyrolactone; ); Ethers such as tetrahydroforan and 1,4-dioxane; Or combinations thereof.

 According to one embodiment, commercially available silica sol may be used as the inorganic particles. For example, MEK-ST, MIBK-ST, MIBK-SD, MIBK-SD-L, MEK-AC, DMAC- ST, EG-ST; Or Purisol from Gaematech.

 Hollow particles

 On the other hand, the anti-reflective coating composition may further include hollow particles. Such hollow particles mean particles in the form of empty spaces on the surface and / or inside of the particles, and are components for achieving low low refractive index and antireflection effect.

 These hollow particles are not substantially distributed in the first layer, which acts as a hard coat layer of the antireflective film when the composition is applied to the substrate, and acts as a layer on the substrate covering this erosion layer, ie a low refractive index layer. To be distributed in the second layer. Here, the hollow particles are not substantially distributed (included) in the first layer, meaning that the content ratio of the hollow particles present in the first layer, which is an eroding layer in the substrate, is less than about 5% by weight based on the total hollow particles, Or less than about 3% by weight, black may mean less than about 1% by weight.

 On the other hand, the composition of one embodiment, as a predetermined solvent is included with the above-described binder-forming compound, etc., spontaneous phase separation may occur to form an anti-reflection film. In this case, the hollow particles may not be substantially distributed in the first layer, which is an erosion layer during phase separation, due to density differences or surface energy differences with other constituents, and may be densely distributed in the second layer serving as a low refractive index layer. As a result, it is possible to form an antireflection film exhibiting improved film strength, scratch resistance and antireflection properties.

 The hollow particles are not particularly limited as long as the hollow particles are particles in the form of empty spaces on and / or inside the particles, but in one embodiment, the silicon compound or organic material is used to secure transparency and / or low refractive index of the low refractive index layer. Hollow silica particles derived from silicon compounds can be used.

In this case, the particle diameter of the hollow particles may be determined in a range capable of maintaining the transparency of the film while showing an antireflection effect. According to one example, The hollow particles may have a number average particle diameter, for example, of about 5 to 80 nm, or about 10 to 75 nm, or about 20 to 70 nm.

 The hollow particles may be, for example, about 1 to 30 parts by weight, or about 1 to 25 parts by weight, or about 5 to 20 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound described above. It may be included in the composition. The content of the hollow particles can be adjusted in the above-described range so that the minimum distribution by the hollow particles can be exhibited, so that a desirable distribution according to phase separation can be formed.

 In addition, the hollow particles may be included in a colloidal phase having a solid content of about 5 to 40% by weight in a form dispersed in a dispersion medium (water or an organic solvent). Here, the organic solvent that can be used as a dispersion medium includes alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol and butanol; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIB); Aromatic carbon hydrogens such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Ethers such as tetrahydrofliran and 1,4-dioxane; Or combinations thereof.

 menstruum

 The above-described antireflective coating composition may further include a solvent. The solvent serves to control the viscosity of the composition to an appropriate range, to control the erosion of the binder-forming compounds in the substrate, and to facilitate the smooth phase separation and distribution of the hollow particles.

In order for the above effects to be fully expressed, a solvent having a dielectric constant (25 ^° C.) of about 20 to 30 and a dipole moment of about 1.7 to 2.8 may be used. Examples of the solvent capable of satisfying such physical properties include methyl ethyl ketone, ethyl acetate, acetyl acetone, and the like, and other solvents that satisfy the above physical properties may be used. Moreover, according to an example, the other solvent is mixed together with the solvent which stirs the above-mentioned physical property, Can also be used. Examples of such a mixed solvent that can be used include isobutyl ketone, methanol, ethanol, π-butanol, i-butanol, t-butane, and the like. However, it is appropriate that the solvent satisfying the dielectric constant and the dipole moment range is included in an amount of about 60 wt% or more based on the total weight of the solvent included in the composition.

 In the antireflective coating composition, the solvent is, for example, about 100 to 500 parts by weight, or about 100 to 450 parts by weight, or about 100 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound. To 400 parts by weight. If the flowability of the composition is not good when the coating may cause defects such as streaks in the coating layer, in order to impart the minimum flowability required for the composition, the solvent may be included in a certain amount or more. In addition, when the solvent is added in an excessive amount, the solid content may be too low to cause defects during drying and curing, the distribution tendency of the hollow particles may be out of the preferred range.

 Polymerization initiator

 On the other hand, the above-described anti-reflective coating composition may further include a polymerization initiator. The polymerization initiator is a compound that can be activated by energy rays such as ultraviolet rays to induce a polymerization reaction of the compound for forming a binder, and a compound conventional in the art can be used.

 Examples of such polymerization initiators include 1-hydroxy cyclonuxylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin butyl ether, and the like. And various photopolymerization initiators may be used.

In this case, the content of the polymerization initiator may be, for example, about 5 to 25 parts by weight, or about 5 to 20 parts by weight, and black about 5 to 15 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound. have. In order for the polymerization reaction of the compound for forming a binder to be sufficiently made, the content of the polymerization initiation agent may be higher than a predetermined level. In addition, when an excessive amount of the polymerization initiator is added, mechanical properties such as scratch resistance or abrasion resistance of each layer forming the antireflection film may be lowered, which is not appropriate. Next, the manufacturing method of the anti-reflection film using the composition for anti-reflective coating mentioned above is demonstrated. Figure 2 schematically shows a method of manufacturing an antireflective film of one embodiment using the above-described antireflective coating composition as a flow chart.

 Referring to Figure 2, the manufacturing method of such an anti-reflection film comprises the steps of preparing the composition for the anti-reflective coating described above; Applying the anti-reflective coating composition to at least one side of the substrate; Eroding a portion of the compound for forming a binder and the inorganic fine particles onto the substrate while drying the applied composition; And curing the eroded and dried composition to form a first layer corresponding to the eroded region of the substrate and a second layer comprising the vaporizing particles and covering the first layer. .

 Through this method, a solvent having a predetermined physical property in the composition may first dissolve a part of the substrate, and thus, a part of the compound for forming a binder (eg, a (meth) acrylate-based compound having a low molecular weight and a high molecular weight). A portion of the compound) and at least a portion of the inorganic fine particles can be eroded into the substrate. At this time, some of the non-eroded compound for binder formation, the inorganic fine particles, and the hollow particles may form a coating layer (eg, a second layer) on the substrate. In particular, such a coating layer may remain in a thin thickness on the substrate where the above components are eroded, and hollow particles may be densely present in the coating layer.

 Subsequently, when the curing is performed, the first and second layers of the first layer and the second layer

While the (meth) acrylate-based binder is formed, a first layer, which is an erosion layer in the substrate serving as a hard coat layer, and a second layer including the hollow particles and covering the first layer may be formed. As a result, an antireflection film of one embodiment can be formed.

As such, the antireflective film of one embodiment may be formed in a simplified process by erosion and phase separation of the substrate in some components, even if a single coating and curing process using a single composition is applied. In particular, since the first layer acting as a hard coat layer is eroded in the substrate and formed in contact with the second layer, the reflective antiskid film may exhibit excellent interfacial adhesion and mechanical properties. Furthermore, such an antireflection film has a first layer and a second layer Hollow particles may be densely present in the second layer without a separate layer in between, and thus may exhibit better refractive index and excellent antireflection properties. This is because the anti-reflective coating composition described above includes at least two compounds for forming a binder, a solvent having a predetermined physical property, and the like, so that erosion and phase separation in the substrate may be optimized.

 In the above-described method for producing an anti-reflection film, the method of applying the composition to at least one side of the substrate may be performed using conventional coating apparatuses and methods in the art such as wire bars.

In addition, the drying step may be performed for about 0.1 to 60 minutes at a temperature of about 5 to 150 ^° C, or about 0.1 to 20 at a temperature of about 20 to 120 ^° C, to promote phase separation of the composition and erosion into the substrate. For minutes, or for about 1 to 10 minutes at a temperature of about 30 to 110 ^° C.

In addition, in the curing step, the polymerization reaction may be initiated by adding energy to the dried composition by irradiation with light or the like, and through this, the erosion and dried composition may be cured. This curing step takes about 1 to 600 seconds with an ultraviolet dose of about αΐ to 2 J / ofl ² or about 2 to 200 seconds with an ultraviolet dose of about 0.1 to 1.5 J / crf to induce a sufficient curing reaction. The silver may be performed for about 3 to 100 seconds at an ultraviolet dose of about 0.2 to l J / ctf.

Through the above method, the antireflection film of the above-described embodiment can be obtained, and in this antireflection film, the cross-sectional area ratio of the hollow particles to any cross-sectional area of the second layer serving as the low refractive index layer. It is about 70 to 95%, or about 75 to 93%, to such an extent that a black is about 80 to 90%, the black is about 85 to 92%, can be hollow particles ppaek distributed ppaek ^'in the low refractive index layer.

In addition to the above-described steps, the method of manufacturing the above-described anti-reflection film may be performed by further including steps that may be commonly performed in the art before or after each step. Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only intended to illustrate the invention, and the invention is not limited thereto. Example 1

 (Production of antireflective coating composition)

 100 parts by weight of a (meth) acrylate-based compound containing 11.33 parts by weight of penta erythritol acrylate (molecular weight 298.3) and acrylate having a urethane functional group (manufacturer: KYOEISHA, product name: UA-306T, molecular weight 1000) On wealth;

 Silica sol in which silica fine particles are dispersed (dispersion medium: methyl isobutyl ketone and methyl alcohol, solid content 40 wt%, number average particle diameter of silica fine particles: 10 rim, manufactured by Gaematech, product name: Purisol) about 15.87 parts by weight;

 Colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20% by weight, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight;

 About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.11 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And

 About 251.85 parts by weight of solvent (specifically, about 179.63 parts by weight of methyl ketone (MEK), about 24.07 parts by weight of ethane, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone) were mixed. A composition for preparation was prepared.

 (Manufacture of antireflection film)

The anti-reflective coating composition was coated on a triacetate cell (Rose 80) using a wire bar (No. 9). After drying for 1 min at 90 ^° C. Aubon, the composition was cured by irradiating with UV energy of 200 mJ / cuf for 5 seconds.

 Through this, an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.

And the cross-sectional photograph of the said antireflection film was shown to FIG. 3 (a), and the photograph which expanded and observed the part is shown to FIG. 3 (b). Notice through Figure 3 As can be seen, the antireflection film according to Example 1 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 (about 3.9) in which inorganic particles are dispersed in the binder; And a low refractive index layer 3 (about 0.15) in which the hollow particles 4 are dispersed in the binder, and a binder cured on the hard coat layer 2.

 In addition, no separate layer was observed between the hard coat layer 2 and the low refractive index layer 3, and the ratio of the cross-sectional area of the hollow particles 4 to the arbitrary cross-sectional area of the low refractive index layer 3 was increased. It became about 90% and it was confirmed that the hollow particles 4 were very densely distributed in the low refractive index layer 3. Example 2

 (Production of antireflective coating composition)

Penta in discrete little hex acrylate (molecular weight 298.3), 100 parts by weight of a fluorinated acrylate, a (trade name:: OPTOOL AR110, Manufacturer DAIKIN, solid content 15 wt. _^0/0, and methyl isobutyl ketone solvent) 11.33 parts by weight, and a urethane functional group To 100 weight part of (meth) acrylate type compounds containing 11.33 weight part of acrylate (manufacturer: KYOEISHA, product name: UA-306T, molecular weight 1000) which has;

 Silica sol in which silica fine particles are dispersed (dispersion medium: methyl isobutyl ketone and methyl alcohol, solid content 40 wt%, number average particle diameter of silica fine particles: 10 nm, manufacturer: Gaematech, product name: Purisol) about 15.87 parts by weight;

 Colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20% by weight, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight;

 About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.11 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And

About 251.85 parts by weight of solvent (specifically, about 179.63 parts by weight of methyl ketone (MEK), about 24.07 parts by weight of ethane, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone) A coating composition was prepared. (Preparation of antireflection film)

 Except for using the anti-reflective coating composition, an anti-reflection film was prepared under the same conditions and methods as in Example 1.

 A cross-sectional photograph of the anti-reflection film is shown in Fig. 4A, and a photograph of an enlarged observation of a portion thereof is shown in Fig. 4B. The antireflection film according to Example 2 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 (about 2.8 m) in which inorganic fine particles are dispersed in the binder; And a binder cured on the hard coat layer 2, and a low refractive index layer 3 (about 0.145) in which the hollow particles 4 are dispersed in the binder.

In addition, no separate layer was observed between the hard coat layer 2 and the low refractive index layer 3, and the ratio of the cross-sectional area of the hollow particles 4 to any cross-sectional area of the low refractive index layer 3 was reduced. It became about 90 ⁰ /. It was confirmed that the hollow particles 4 were very densely distributed in the low refractive index layer 3.

 In particular, the anti-reflection film according to Example 2 was confirmed that as the fluorine-based acrylate is included in the low refractive index layer, phase separation of the composition may occur more smoothly and scratch resistance is improved. Example 3

 (Preparation of Anti-reflective Coating Composition)

Pentaerythritol with respect to 100 parts by weight of a (meth) acrylate compound containing 100 parts by weight of nucleated acrylate (molecular weight 298.3) and 11.33 parts by weight of acrylate having a urethane functional group (manufacturer: KYOEISHA, product name: 510H, molecular weight 2000) ; Fine particles of silica are dispersed silica sol (dispersion medium: methyl isobutyl ketone and methyl alkoeul, solid content 40 wt. _^0/0, the number average particle diameter of the silica fine particles: 10 nm, Manufacturer: Gaematech, product name: Purisol) about 15.87 parts by weight;

Colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20 wt%, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight; About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.1 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And

 About 251.85 parts by weight of solvent (specifically, about 179.63 parts by weight of methyl ethyl ketone (MEK), about 24.07 parts by weight of ethanol, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone) Was prepared.

 (Manufacture of antireflection film)

The anti-reflective coating composition was coated with a triacetate cell on a rose film (thickness: 80 kPa) using a wire bar (9). After drying for 1 minute in a 90 ^° C oven, the composition was cured by irradiating UV energy of 200 mJ / ciif for 5 seconds.

 Through this, an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.

 The cross-sectional photograph of the said antireflection film was confirmed by SEM. As a result, the anti-reflection film according to Example 3 includes a binder hardened by erosion by a substrate and a hard coat layer (about 3.1 ^ m) in which inorganic particles are dispersed in the binder; And it was confirmed that it comprises a binder cured on the hard coat layer, and a low refractive index layer (about 0.16 // m) in which hollow particles are dispersed in the binder.

 In addition, no separate layer was observed between the hard coat layer and the low refractive index layer, and the ratio of the cross-sectional area of the hollow particles to the arbitrary cross-sectional area of the low refractive index layer was about 90%, so that the hollow particles in the low refractive index layer. Were found to be very tightly distributed. Example 4

 (Production of antireflective coating composition)

Pentae Ritri is 100 parts by weight of nucleacrylate (molecular weight 298.3) and an acrylate having an ester functional group (manufacturer: SK Cytec, product name: DPHA, Molecular weight 524) to 100 parts by weight of a (meth) acrylate compound including 11.33 parts by weight;

Silica particulate self sol dispersed silica (dispersion medium: methyl isobutyl ketone and methyl alcohol, the solid content of 40 wt. _^0/0, the silica particulate number average particle diameter's: 10 nm, Manufacturer: Gaematech, product name: Purisol) about 15.87 wt. part;

The colloid solution dispersed the hollow silica (dispersion medium: methyl isobutyl ketone, solids content 20 wt. _^0/0, the number average particle diameter of the hollow silica: 50 nm, Manufacturer: Catalyst Chemical Industry, Product name: MIBK-sol) about 1 L33 weight part;

 About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.11 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And

About 251.85 parts by weight of solvent (specifically, about 179.63 parts by weight of methyl ethyl ketone (MEK), about 24.07 parts by weight of ethanol, about 24.07 parts by weight of _n -butyl alcohol and about 24.07 parts by weight of acetylacetone) Was prepared.

 (Manufacture of antireflection film)

The antireflective coating composition was coated on a triacetate cell (Rose 80) using a wire bar (No. 9). After drying for 1 minute in a 90 ^° C oven, the composition was cured by irradiating UV energy of 200 mJ / oif for 5 seconds.

 Through this, an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.

And the cross-sectional photograph of the said antireflection film was shown to FIG. 5 (a), and the photograph which expanded and observed the part is shown to FIG. 5 (b). As can be seen from FIG. 5, the antireflection film according to Example 4 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 having inorganic particles dispersed therein (about). 2.78 ^ 1); And a low refractive index layer (3) (about 0.18 tm) in which the hollow particles 4 are dispersed in the binder, and the binder cured on the hard coat layer 2. Further, no separate layer was observed between the hard coat layer 2 and the ^' low refractive index layer 3 ^' , and the cross-sectional area ratio of the hollow particles 4 to any cross-sectional area of the low refractive index layer 3 was observed. This was about 90% and it was confirmed that the hollow particles 4 were very densely distributed in the low refractive index layer 3. Comparative Example 1

 (Production of antireflective coating composition)

 Pentaerytris based on 100 parts by weight of nucleated acrylate (PETA);

Silica particulate sol self-dispersed silica (dispersion medium: methyl isobutyl ketone and methyl alcohol, and solids content of 40 wt. _^0/0, the number average particle diameter: 10 nm, Manufacturer: Gaematech, product name: Purisol) 15.87 parts by weight

The colloid solution dispersed the hollow silica (dispersion medium: methyl isobutyl ketone, solids content 20 wt. _^0/0, the number average particle diameter of the hollow silica: 50 nm, Manufacturer: Catalyst Chemical Industry, Product name: MIBK-sol) about 11.33 increase unit

 About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.11 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And

 About 251.85 parts by weight of solvent (specifically, about 125.91 parts by weight of methyl isobutyl ketone, about 41.98 parts by weight of ethanol, about 41.98 parts by weight of n-butyl alcohol and about 41.98 parts by weight of acetylacetone) was prepared to prepare an antireflective coating composition. It was.

 (Manufacture of antireflection film)

 Except for using the anti-reflective coating composition, an anti-reflection film was prepared under the same conditions and methods as in Example 1. And the cross-sectional photograph of the said antireflection film was shown to FIG. 6 (a), and the photograph which expanded and observed the part is shown to FIG. 6 (b).

As can be seen from FIG. 6, the antireflective film according to Comparative Example 1 did not properly undergo phase separation of the composition (see the circle portion of FIG. 6 (a)), and in particular, the hollow particles 4 in the low refractive index layer were excessive. As it spreads out (see the circled portion of Figure 6 (b)), the appearance of the film was opaque, and the scratch resistance and The antireflection effect was also found to be inferior (see Experimental Example). In this anti-reflection film of Comparative Example 1, it was confirmed that the ratio of the cross-sectional area of the hollow particles to the arbitrary cross-sectional area in the total area where the hollow particles were distributed was about 30 to 60%. Experimental Example

 The following items were evaluated for the antireflection films prepared through the Examples and Comparative Examples, and the results are shown in Table 1 below.

 1) Reflectance Measurement: After the reverse side of the antireflection film was subjected to the darkening treatment, the low reflection characteristic was evaluated at the minimum reflectance value. At this time, the measuring equipment

Shimadzu's Solid Spec. 3700 spectrophotometer was used.

 2) Transmittance and Haze Measurement: The transmittance and Haze were evaluated using HR-100 of Murakami, Japan.

 3) Scratch resistance evaluation: After reciprocating 10 times of steel wool (loading 500 g / cuf) to the antireflection film at a speed of 24 m / min, the number of wounds of 1 cm or more in length was examined on the surface. At this time, if there are no scratches on the surface of the film, it is very good (©), the number of wounds of 1 cm or more in length is 1 or more and less than 5 is excellent (O). It evaluated as bad (X).

 4) Magnification of cross section of the film: The cross section of each film was magnified through the fabrication of specimens by microtome using Transmission Electron Microscope (Model: H-7650, manufacturer: HITACHI).

 5) Evaluation of adhesion force: The adhesion force to each film was evaluated through a cross cut test (ASTM D-3359) using Nichiban tape.

 Table 1

상기 표 1을 통해 알 수 있는 바와 같이， 실시 예들에 따른 반사 방지 필름은 비교예들의 필름에 비하여 반사율은 더 낮으면서도, 투과율은 더 높았으며， 내스크래치성 및 부착력 이 우수하였다.

As can be seen from Table 1, the anti-reflection film according to the embodiments was lower than the film of the comparative examples, while the transmittance was higher, scratch resistance and adhesion was excellent.

[Explanation of code]

 1:

 2: first layer (hard coat layer),

 3: second layer (low refractive index layer)

 4: hollow particles

Claims

[Patent Claims] [Claim 1]  A first layer comprising a first (meth) acrylate-based binder and inorganic particulates in the first (meth) acrylate-based binder and eroded in the substrate; And a second layer comprising a second (meth) acrylate-based binder and vaporized particles in the second (meth) acrylate-based binder, covering the first layer,  The antireflection film having a cross-sectional area ratio of the hollow particles to any cross-sectional area of the second layer is 70 to 95%. [Claim 2]  The antireflection film according to claim 1, wherein the first (meth) acrylate binder comprises a crosslinked polymer of a (meth) acryllate compound having a molecular weight of less than 600. . [Claim 3]  The antireflection film according to claim 1, wherein the second (meth) acrylate binder comprises a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000. . [Claim 4]  According to claim 2, wherein the first layer is a cross-linked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000 in addition to the region where the crosslinked polymer is located An antireflection film further comprising an area to be located. [Claim 5] The antireflective film of claim 1, wherein the second layer further comprises inorganic particulates. [Claim 6]  The antireflection film according to claim 4, wherein the area where the crosslinked copolymer is located is about 5 to 50% of the depth of the first layer, based on the light interface of the first layer and the second layer. [Claim 7]  The antireflection film according to claim 3 or 4, wherein the crosslinked copolymer is included to increase the distribution gradient in the direction of the second layer. [Claim 8]  The method of claim 2, wherein the (meth) acrylate-based compound having a molecular weight of less than 600 is pentaerythritri tri (meth) acrylate, pentaerythrith tetra (meth) acrylate, dipentaerythri nucleus (Meth) acrylate, trimethylene propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 9, At least one selected from the group consisting of 9-bis (4- (2-acryloxyethoxyphenyl) fluorene, bis (4-methacryloxythiophenyl) sulfide, and bis (4-vinylthiophenyl) sulfide Antireflection film, which is a compound.  The method of claim 1, wherein the second (meth) acrylate-based binder is a (meth) acrylate-based compound having a molecular weight of less than 600, a crosslinking of a (meth) acrylate-based compound having a molecular weight of 600 to 100,000 and a fluorine-based (meth) acrylate compound Anti-reflection film comprising a copolymer. [Claim 10]  The antireflection film according to claim 9, wherein the fluorine-based (meth) acrylate compound comprises at least one compound selected from the group consisting of compounds represented by Formulas 1 to 5: [Formula 1]

In Formula 1, R ¹ is an alkyl group or hydrogen group having 1 to 6 carbon _atoms: an integer of 1 to 7, b is an integer from 1 to 3; [Formula ² ]

In Formula 2, c is an integer of 1 to 10; [Formula 3]

In Formula 3, d is an integer of 1 to 11; [Formula 4]

In Chemical Formula 4, e is an integer of 1 to 5; [Formula 5]

 In Formula 5, f is an integer of 4 to 10. [Claim 11]  The antireflection film according to claim 3, wherein the (meth) acrylate compound having a molecular weight of 600 to 100,000 comprises a compound having a structure in which at least two molecules of the (meth) acrylate compound having a molecular weight of less than 600 are connected by a linker. [Claim 12]  The compound according to claim 3, wherein the (meth) acrylate compound having a molecular weight of 600 to 100,000 has one or more substituents selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group, a thil group, an aromatic or aliphatic hydrocarbon group having 6 or more carbon atoms, and an isocyanate group. Anti-reflection film comprising a. [Claim 13]  The antireflection film according to claim 11, wherein the linker comprises a urethane bond, a thioether bond, an ether bond or an ester bond. [Claim 14] The antireflection film according to claim 1, wherein the inorganic fine particles have a number average particle diameter of 5 to 50 nm. [Claim 15]  The antireflection film according to claim 1, wherein the inorganic fine particles are silica fine particles. [Claim 16] The antireflection film according to claim 1, wherein the hollow particles have a number average particle diameter of ⁵ to 80 nm. [Claim 17]  The antireflection film according to claim 1, wherein the hollow particles are hollow silica particles.