KR20160141694A - Method for preparing film - Google Patents

Abstract

The present application relates to a method for manufacturing a film, a film manufactured thereby, a polarizing plate having the same, and a liquid crystal display. According to the present application, a method for manufacturing a film can provide a film of which a reflection rate is minimized through a simple process by transferring a self-assembly nanostructure-shaped pattern on a substrate through an etching process by using a film having a self-assembly nanostructure of a block copolymer on a substrate as a mask for a conical nanostructure to be easily arranged. Moreover, the film can be usefully applied to a reflection prevention film.

Description

[0001] METHOD FOR PREPARING FILM [0002]

The present invention relates to a film, a method for producing the film, a polarizing plate including the film, and a liquid crystal display.

2. Description of the Related Art Generally, a display device such as a plasma display panel (PDP), a cathode ray tube (CRT), and a liquid crystal display (LCD) An anti-reflection film is used.

The antireflection film is one of the essential components of the optical filter together with the selective absorption layer for improving the color of the display device and the electromagnetic wave shielding layer for shielding the electromagnetic wave. The optical filters used in the display devices are arranged with a spacing of several millimeters, and the filters use glass or transparent plastic substrates as transparent substrates for attaching the respective films.

On the other hand, in the production of the antireflection film, Patent Documents 1 and 2 propose a technique of depositing an inorganic substance generally used or a technique of laminating a polymer film having a different refractive index in multiple layers.

However, this technique has a complicated process because it is subjected to a multi-step process, and since it uses a high-vacuum evaporator or a fluoropolymer as a component, expensive equipment or materials must be used.

Patent Document 1: Korean Patent Publication No. 2012-0114975 Patent Document 2: Korean Patent Publication No. 2005-0025087

The present application provides a film, a method for producing the film, a polarizing plate including the film, and a liquid crystal display.

The present application relates to films. The film may be, for example, an anti-reflection film applied to a display device to minimize reflection of light incident on the screen.

In one example, the film may comprise a substrate having self-assembled nanostructures arranged on at least one side.

For example, a glass substrate, an indium tin oxide (ITO) substrate, a plastic substrate, or the like may be used, and a plastic substrate may be suitably used.

Examples of the plastic substrate include a polyester resin such as a polyethylene terephthalate (PET) resin, a polyethylene naphthalate (PEN) resin, a polybutylene terephthalate (PBT) resin, (Meth) acrylate resin, a polyvinyl chloride resin, a polystyrene resin, a polyvinyl alcohol resin, a polyamide resin, a polyimide resin, a polyimide resin, Based resin, a polyarylate-based resin, and a polyphenylene sulfide-based resin, but the present invention is not limited thereto. The substrate may be a single layer, or may be a multilayer of two or more layers of the same type or different types.

It is preferable to use a substrate having a refractive index range capable of destructive interference of light for preventing reflection of light. For example, the substrate may have a refractive index of 1.45 to 1.8, but the present invention is not limited thereto.

In one example, the self-assembled nanostructures arranged in the substrate can satisfy the following general formula (1).

[Formula 1]

Y < X < P

Wherein X represents the average diameter of the open upper end of the self-assembled nanostructure, Y represents the average diameter of the closed bottom end of the self-assembled nanostructure, and P represents the distance between the center of the self- .

As used herein, the term " open top " means the surface of the self-assembled nanostructure where the surface of the substrate is in contact with the outside, and the term " closed bottom & . Further, in this specification, the term " pitch " can mean a gap between self-assembled nanostructures. FIG. 1 is a graph showing the relationship between the average diameter (X) of the open upper end of the self-assembled nanostructure and the average diameter (Y) of the closed bottom end of the self- Fig. 2 is a view showing a substrate usable in the plasma display panel. When the average diameter of the open upper end portion of the self-assembled nanostructure is larger than the average diameter of the closed bottom end portion and the average diameter of the open upper end portion of the self-assembled nanostructure is smaller than or equal to the distance between the center portions of the self- The nanostructure may have a conical shape, and when the self-assembled nanostructure is arranged on a substrate, the nanostructure resembles a moth-eye shape, The amount of reflection can be minimized.

For example, X may be formed within a range of 20 nm to 300 nm, 30 nm to 290 nm, or 40 nm to 280 nm, although the average diameter X of the open upper end of the nano pores is larger than the average diameter Y of the lower end of the opening. And Y may be formed at 20 nm to 100 nm, 30 nm to 90 nm, or 40 nm to 80 nm.

The nano structure of the conical shape is realized by adjusting the average diameter of the open upper end of the self-assembled nanostructure and the average diameter of the lower end of the closed end to satisfy the general formula 1, Due to the moth-eye structure formed, the reflectance of incident light can be effectively lowered.

The shape of the self-assembled nanostructure is not particularly limited as long as it is the above-mentioned conical shape, but can be expressed by, for example, a pitch P and a height H.

The pitch P of the self-assembled nanostructure refers to the distance between the self-assembled nanostructures arranged on the substrate, and may be about 50 nm to 300 nm, about 60 nm to 290 nm, or about 70 nm to 280 nm. The height H of the self-assembled nanostructure refers to a linear distance from the center of the open upper end of the self-assembled nanostructure to the center of the closed bottom end, and is about 50 nm to 400 nm, about 100 nm to 300 nm, To 250 nm, but is not limited thereto.

The ratio (H / P) of the height H to the pitch P of the self-assembled nanostructure may be 0.1 to 4, 0.2 to 3.5 or 0.3 to 3. By adjusting the ratio (H / P) of the height to the pitch of the self-assembled nanostructure to the above-mentioned range, it is possible to more efficiently realize the conical shape with high reflectance.

In one example, the film has a reflectance of 5% or less, 4.9% or less, 4.8% or less, 4.7% or less, 4.6% or less, 4.5% or less, 4.4% or less, 4.3% or less Or 4.2%, and the lower limit is not particularly limited, but may be, for example, 0.5%, 1.0%, 1.5%, or 2.0%.

The reflectance can be measured in a conventional manner, and can be measured through the methods described in the following examples and comparative examples. For example, after the sheet is joined to the back surface of the film and the reflected light is removed, 5 °, and the reflectance for the light having the reflected wavelength of 350 nm to 800 nm can be measured using a UV / VIS / NIR spectrometer (solidspec-3700, manufactured by Shimadzu).

The present application also relates to a method for producing a film.

In one example, the method of manufacturing the film is a step of etching (hereinafter also referred to as " etching ") the substrate using a block copolymer film formed on the substrate and having a self-assembled structure as a mask . ≪ / RTI >

In one example, the self-assembled structure of the block copolymer film may be a vertically oriented cylinder structure, but is not limited thereto.

Further, in one example, the method for producing the film may include a method for producing a film having a self-assembled nanostructure satisfying the following general formula (1).

[Formula 1]

Y < X < P

Wherein X represents the average diameter of the open upper end of the self-assembled nanostructure, Y represents the average diameter of the closed bottom end of the self-assembled nanostructure, and P represents the distance between the center of the self- .

The above terms, that is, the description of "open upper end", "closed lower end" and "pitch" may have the same meaning as described above. In addition, in this specification, the term " block copolymer " may refer to a copolymer comprising blocks of different polymerized monomers that are different from each other. The block copolymer may be formed in various shapes including a first block and a second block, and may also include a third block other than the first block and the second block, if necessary. In one example, the block copolymer may include a di-block copolymer including the first block and the second block in sequence, or a di-block copolymer including the first block, the second block, A tri-block copolymer or a mixture of the diblock copolymer and the triblock copolymer may be used. In addition, the block copolymer may include a linear block copolymer or a graft block copolymer. The term " self-assembled structure " used herein means a structure formed by coating a block copolymer on a substrate in the form of a film, followed by phase separation of the block copolymer. Or a triangle or the like.

The block copolymer is a kind of polymer material, and may have a form in which two or more kinds of polymers are connected to each other through covalent bonds. The two block copolymers are connected to each other to form a polymer, and the two polymers connected to each other have the same or different properties, resulting in a phase separation phenomenon. By using the self-assembly properties that follow, a wide variety of nanostructures can be demonstrated.

The block copolymer may be used without any particular restriction on the component or the shape as long as it has properties of phase separation and self-assembling property. For example, the block copolymer may include a polymer including polystyrene.

The polystyrene capable of forming at least one block of the block copolymer generally means a polymer which is one kind of vinyl polymer and also forms a basis of a styrene resin. The polystyrene may have a structure in which a phenyl group is bonded to carbon in a long hydrocarbon chain.

The polystyrene may be prepared by free radical polymerization of a styrene monomer as shown in FIG.

Examples of the block copolymer include a polystyrene-co-polymethyl methacrylate ("polystyrene-block-poly (methylmethacrylate)") block copolymer, a polystyrene- , Polystyrene-co-poly vinyl pyridine block copolymer, polystyrene-co-poly-isoprene block copolymer, polystyrene-co-polybutadiene ) Block copolymers, polyisoprene-block-poly (tert-methyl silyl styrene) block copolymers, polystyrene-co-poly-t-butyldimethylsilyloxystyrene block copolymer, polystyrene-polystyrene-block-poly (tert-butyl dimethyl silyl oxystyrene) block copolymer and polystyrene-co-polydimethylsiloxane block copolymer. The.

In one example, the number average molecular weight of the block copolymer can range from 50,000 to 200,000, from 70,000 to 160,000, or from 90,000 to 120,000. The term " number average molecular weight " in the present specification can be measured using, for example, GPC (Gel Permeation Chromatograph), but the present invention is not limited thereto. For example, measurement using a property such as boiling point, freezing point, can do. By controlling the number average molecular weight of the block copolymer within the range described above, it is possible to achieve an effect of excellent adhesive property when applied to a film, and it is possible to secure more efficient workability in the case of coating a block copolymer .

The method for producing the block copolymer is not particularly limited and can be produced in a usual manner. The block copolymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. For example, the block copolymer may be prepared by using an organic rare earth metal complex as a polymerization initiator or by using an organic alkali metal compound as a polymerization initiator to form an alkali metal or alkaline earth metal , An anion polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an anion polymerization method using an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Atomic Transfer Radical Polymerization (ATRP), and ICAR (Atomization Transfer), which perform polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator. Initiators for continuous activator regeneration) Atom transfer radical polymerization (ATRP ), A polymerization method (RAFT) using a reversible addition-cleavage chain transfer agent using an inorganic reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied .

The method of manufacturing a film according to the present application includes etching the substrate, and etching the substrate may be performed by performing an etching process on the substrate.

The etching process is not particularly limited, and for example, a chemical etching process, an electrochemical etching process, an electric discharge process, or an electrolytic process may be used, but a chemical etching process can be preferably used. The chemical etching may be performed, for example, by a reactive ion etching method, a plasma etching method, or an ozone processing method, and preferably, a reactive ion etching method may be used.

The reactive ion etching method may use a chemically reactive plasma. As a device for using the reactive ion etching method, a chamber and a vacuum system for carrying out the process while maintaining a constant pressure, a chuck capable of maintaining a constant temperature during the process, A gas supply system for supplying a reactive gas for performing a process, a plasma source system for generating a plasma used in the process, an RF system for supplying energy to a chuck of the plasma generator, And an end point detector (EPD) capable of detecting the end of the signal. The frequency of the RF system capable of generating the plasma is typically 13.56 MHz, but is not limited thereto.

The kind of the gas may be variously selected depending on the etching process to be performed. For example, a halogen gas, an oxygen gas or a nitrogen gas may be used, and preferably a halogen gas or an oxygen gas may be used.

The etching process may also be performed using a mask having a desired pattern formed thereon. In one example, a film having a self-assembled nanostructure of a block copolymer formed on the substrate with the mask can be used.

The block copolymer film may be formed by a method comprising coating a block copolymer on a substrate and inducing phase separation of the block copolymer to form a self-assembled nanostructure.

The step of coating the block copolymer on the substrate may be performed in various ways, but it is preferable that the block copolymer is dissolved in a solvent and coated on the substrate so that a phase separation phenomenon may occur between the same or different polymers. The coating method is not particularly limited as long as a phase separation phenomenon can occur between the polymers, but the coating method may be performed by, for example, spin-coating, bar-coating or roll- And preferably can be performed by spin coating.

The method of manufacturing a film according to the present application may further include removing at least one block of the block copolymer after the step of forming the self-assembled structure. Although not particularly limited, the step of removing at least one of the block copolymers may be carried out, for example, by ozone, ultraviolet rays or chemical treatment, preferably by ultraviolet treatment or chemical treatment .

In one example, the step of removing at least one of the block copolymers may be performed by decomposing at least one block of the block copolymer by ultraviolet ray or chemical treatment, then crosslinking remaining blocks, Lt; RTI ID = 0.0 > solvent < / RTI >

The method of removing at least one of the block copolymers may be selected according to the decomposition characteristics. For example, the polystyrene-co-polymethyl methacrylate block copolymer may be decomposed by ultraviolet treatment in a vacuum In the case of a polystyrene-co-polyisoprene block copolymer, the decomposition can be carried out by ozone treatment. In the case of a polystyrene-co-polyethylene oxide block copolymer, it can be decomposed by chemical acid treatment.

The method for removing at least one block of the block copolymer is not particularly limited. For example, in the case of the polystyrene-co-polymethyl methacrylate block copolymer, after treatment with ultraviolet rays, Only the methacrylate can be selectively removed.

The self-assembled nanostructure can be formed by the volume of any one of the blocks removed from the block copolymer to form a film having the self-assembled nanostructure of the present application.

In one example, the volume of the block to be removed in the block copolymer may be 0.1 to 0.45, 0.15 to 0.4 or 0.2 to 0.35 when the volume of the entire block copolymer is 1. When the volume of the block to be removed in the above-mentioned block copolymer is, for example, the volume of the whole block copolymer is 1, the ratio of 0.1 to 0.45 means that 10% to 45% of the entire block copolymer It may mean that the block removed at a rate occupies a volume.

By adjusting the volume of the block to be removed in the block copolymer within the above-mentioned range, it is possible to more effectively form the self-assembled nanostructure on the substrate, thereby minimizing the reflectance of light incident upon application of the film.

The thickness of the film having the self-assembled nanostructure can be appropriately adjusted according to the wavelength of incident light for the reflection preventing ability, and may be, for example, 100 nm to 250 nm although it is not particularly limited.

In the case of the self-assembled nanostructure formed on the substrate after the etching process, as shown in FIG. 3, a portion directly below the film having the self-assembled nanostructure (substrate surface portion) used as an etching mask during the etching process, The cone-shaped nanostructure can be realized because the degree of etching is larger than the inside of the substrate, and thus the regularly arranged nanoporous structure forms a moth-eye structure as a whole to minimize the reflectance .

In one example, the method of manufacturing a film of the present application may further include removing the block copolymer present on the substrate after the step of etching the substrate in addition to the step. The block copolymer present on the substrate may be a polystyrene block, and the removal method is not particularly limited as long as it does not affect the spot-assembled nanostructure formed on the substrate.

The present application also relates to a polarizing plate comprising the film.

The type of the polarizer included in the polarizing plate is not particularly limited, and for example, general types known in the art such as a polyvinyl alcohol polarizer and the like can be employed without limitation.

A polarizer is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions. Such a polarizer may be, for example, a form in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin constituting the polarizer can be obtained by, for example, gelling a polyvinyl acetate-based resin. In this case, the polyvinyl acetate-based resin that can be used may include not only homopolymers of vinyl acetate but also copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of the monomer copolymerizable with vinyl acetate include monomers such as unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group, or a mixture of two or more thereof. no. The degree of gelation of the polyvinyl alcohol-based resin may be generally from 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000 or about 1,500 to 5,000.

The polarizer is formed by a process of stretching a polyvinyl alcohol-based resin film as described above (e.g., uniaxial stretching), dyeing a polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, A process of treating a polyvinyl alcohol resin film with a boric acid aqueous solution and a process of washing with a boric acid aqueous solution after washing. As the dichroic dye, iodine or dichroic organic dyes may be used.

The polarizing plate may further include a protective film attached to one side or both sides of the polarizer. In this case, the protective film may be used as the antireflection film.

The polarizing plate may further include at least one functional layer selected from the group consisting of a retardation film, a wide viewing angle compensation film, and a brightness enhancement film.

The present application is also directed to a display device, for example, an LCD device. Exemplary LCD devices may include the film or the polarizer. When the display device is an LCD, the device may include the liquid crystal panel and the polarizing plate or the film in a form attached to one or both sides of the liquid crystal panel. The polarizing plate or film may be attached to the liquid crystal panel. Examples of the liquid crystal panel to be applied to the LCD include passive matrix type panels such as TN (twisted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) type; An active matrix type panel such as a two terminal or a three terminal type; A known panel such as an in-plane switching (IPS) panel and a vertical alignment (VA) panel may be used.

Other configurations of the display device, for example, types of upper and lower substrates such as a color filter substrate or an array substrate in an LCD are not particularly limited, and configurations known in this field can be employed without limitation.

A method of manufacturing a film according to the present application is a method of manufacturing a film by transferring a pattern of a self-assembled nanostructured pattern onto a substrate through an etching process using a film having a self-assembled nanostructure of a block copolymer on the substrate, It is possible to provide a film having a minimal reflectance through a simple process, and the film can be usefully applied as an anti-reflection film.

Brief Description of the Drawings Fig. 1 is a diagram schematically showing an average diameter of an open top end of a self-assembled nanostructure formed on a substrate, an average diameter of a bottom end of a closed end, and a space between the self-assembled nanostructures.
2 is a diagram showing a mechanism for producing polystyrene by free radical polymerization of styrene monomer.
FIG. 3 is a diagram schematically showing conical nano pores formed according to the portion immediately below the film having the self-assembled nanostructure before and after the etching process (the surface portion of the substrate) and the degree of etching inside the substrate.
4 is a view showing an image obtained by measuring the surface structure of the film of Example 1 with an atomic force microscope.
5 is an image showing the surface structure of the film of Example 2 of the present invention measured by an atomic force microscope.
6 is a view showing an image obtained by measuring the surface structure of the film of Example 3 with an atomic force microscope.
7 is an image showing the surface structure of the film of Comparative Example 1 of the present invention measured by an atomic force microscope.
8 is an image showing the surface structure of the film of Comparative Example 2 of the present invention measured by an atomic force microscope.
9 is a graph showing reflectance measurement results of the films of Examples 1 to 3 and Comparative Examples 1 and 2 according to wavelengths (in FIG. 9, the horizontal axis represents the wavelength and the vertical axis represents the reflectance).

Hereinafter, the method for producing the film and the film produced therefrom will be described in detail with reference to Examples and Comparative Examples. However, the method of manufacturing the film and the range of the film produced thereby are not limited by the following embodiments.

Hereinafter, the physical properties of the examples and comparative examples were analyzed and measured in the following manner.

Surface structure analysis

In order to analyze the structures of the surfaces of each of the films produced in Examples and Comparative Examples, the surface area of each of the films was measured with an atomic force microscope (Digital Instruments, Veeco) using a measuring area of 1 탆 1 탆 The film surface structure was measured with an image and is shown in Figs. 4 to 8, respectively.

Reflectance measurement

The reflectance of the films prepared in Examples and Comparative Examples was measured using a UV / VIS / NIR spectrometer (solidspec-3700, Shimadzu). A modern sheet "# 7080 " was laminated on the back surface of the produced film to remove reflected light. The reflectance was measured according to the wavelength (wavelength of 350 nm to 800 nm) of specular light among the reflected light after the light was transmitted at an incident angle of 5 °. The reflectance values are shown in Table 1, The graph is shown in Fig.

Example 1

A block copolymer prepared by adjusting the volume ratio of the polystyrene block having a number average molecular weight of 65,000 g / mol to the polymethyl methacrylate having a number average molecular weight of 35,000 g / mol as 0.7: 0.3 was coated on the PET substrate to a thickness of about 50 nm Spin coating. The block copolymer coated with the solvent annealing was then phase-separated to form a vertically aligned polymethyl methacrylate cylinder structure. Thereafter, the polymethylmethacrylate was decomposed by UV treatment at a wavelength of 245 nm, the remaining polystyrene block was crosslinked, and the polymethylmethacrylate block was removed with acetic acid. A film (A) having a nanostructure pattern of 50 nm in depth transferred onto a PET substrate was prepared by controlling the time differently by the oxygen reactive ion etching method.

Example 2

A film (B) was prepared in the same manner as in Production Example 1, except that a film (B) having a nanostructured pattern of 100 nm in depth, which was transferred onto a PET substrate, was prepared by an oxygen reactive ion etching method .

Example 3

A film (C) was prepared in the same manner as in Production Example 1, except that a film (C) having a nanostructure pattern of 200 nm in depth transferred onto a PET substrate was prepared by varying the time by an oxygen reactive ion etching method .

Comparative Example 1

A film (D) was prepared in the same manner as in Example 1, except that the block copolymer was not treated on the PET substrate.

Comparative Example 2

Except that the block copolymer coated on the substrate was subjected to ultraviolet treatment to form a nanostructured film on the substrate except that the nanostructured pattern was formed by controlling the time differently by the oxygen reactive ion etching method directly on the substrate, (E) having a depth of 50 nm.

The results of the surface structure analysis image and reflectance measured for each of the above Examples and Comparative Examples are shown in Table 1 below.

division Example Comparative Example One 2 3 One 2 Target film A B C D E Surface structure analysis 4 5 6 7 8 reflectivity(%) 4 to 4.2% 2.9 to 3.2% 2.2 to 2.6% 5.2 ~ 5.7% 5.1 ~ 5.6%

As can be seen from the above Table 1, in the case of the film produced by the method for producing a film according to the present application, the surface structure of the film becomes more conical when the etching process is performed, and when the film is regularly arranged, It is possible to minimize the reflectance to incident light through the formation of a moth-eye structure and thus to be usefully applied as an antireflection film.

101: substrate
102: Self-assembled nanostructure
103: Mask

Claims (10)

Forming a nanostructure formed on a substrate and satisfying the following general formula 1 by etching the substrate using a block copolymer film having a self-assembled structure as a mask, wherein the block copolymer Wherein the film has one block removed from the block copolymer after forming the self-assembled structure.
[Formula 1]
Y < X < P
X represents the average diameter of the open upper end of the formed nanostructure, Y represents the average diameter of the closed lower end of the formed nanostructure, and P (pitch) represents the distance between the center portions of the formed nanostructure . The method according to claim 1, wherein the self-assembled structure of the block copolymer film is a vertically aligned cylinder structure. The block copolymer of claim 1, wherein the block copolymer is selected from the group consisting of polystyrene-co-polymethyl methacrylate) block copolymer, polystyrene-co-polyethylene oxide block copolymer Block copolymers, polystyrene-co-polyvinyl pyridine block copolymers, polystyrene-co-polyisoprene block copolymers, polystyrene-block- polybutadiene block copolymer, polyisoprene-block-poly (tert-methyl silyl styrene) block copolymer, polystyrene-co-poly-t-butyldimethylsilyloxystyrene a polystyrene-block-poly (tert-butyl dimethyl silyl oxystyrene) block copolymer and a polystyrene-co-polydimethylsiloxane block copolymer. (2). The method for producing an antireflection film according to claim 1, wherein the number average molecular weight of the block copolymer is in the range of 50,000 to 200,000. The method of claim 1, wherein etching the substrate is performed by reactive ion etching, plasma etching, or ozone treatment. The method of claim 1, wherein the block copolymer film comprises: coating a block copolymer on a substrate; Forming a self-assembled nanostructure by inducing phase separation of the block copolymer; and removing at least one block of the block copolymer after forming the self-assembled nanostructure. ≪ / RTI > [7] The method of claim 6, wherein the step of coating the block copolymer on the substrate comprises the steps of: preparing an antireflection film by spin coating, bar coating or roll coating; . 7. The method according to claim 6, wherein the step of removing at least one block of the block copolymer is performed by ozone, ultraviolet rays or chemical treatment. The method for producing an antireflection film according to claim 6, wherein the volume of the block to be removed in the block copolymer is 0.1 to 0.45 when the volume of the whole block copolymer is 1. The method of claim 1, further comprising, after the step of etching the substrate, removing the block copolymer present on the substrate.

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