KR101014277B1 - Manufacturing method for anti-reflective surface and super water-repellent surface - Google Patents

Abstract

According to the present invention, (a) a bead arrangement step of arranging a plurality of beads having a sphere shape in a single layer on one side of the substrate; Etching a plurality of beads to form an etching mask having a predetermined interval spaced between the beads; A substrate etching step of etching one side of the substrate by using the plurality of beads as an etching mask; A bead removing step of removing a plurality of beads from one side of the etched substrate; A fluorine compound coating step of coating a fluorine compound on one side of the substrate on which fine iron is formed after the plurality of beads are removed; (f) converting the substrate surface to invert the processed surface of the substrate; (g) a secondary bead arranging step of arranging a plurality of beads having a spherical shape in a single layer on the other unprocessed side of the substrate; (h) a second bead etching step of etching a plurality of beads to form an etching mask having a predetermined interval spaced from each bead; (i) a secondary substrate etching step of etching the other side of the substrate A by using the plurality of beads as an etching mask; (j) a secondary bead removing step of removing a plurality of beads from the other side of the etched substrate (A); And (k) a second fluorine compound coating step of coating a fluorine compound on the other side of the substrate on which fine concavities and convexities are formed after a plurality of beads are removed.

Antireflection, beads, etching,

Description

Manufacturing method for anti-reflective surface and super water-repellent surface

 The present invention relates to a method of manufacturing an antireflective surface and a super water-repellent surface, and more particularly, by forming fine irregularities on the surface of the substrate, to significantly improve the transmittance of the substrate and at the same time have a super water-repellent chemical property. A method for producing an antireflective surface and a super water-repellent surface.

Recently, research is being actively conducted to use engineering inspired by natural nanostructures. Representative examples are lotus leaf showing super water repellency and moth eyes showing antireflection.

First, when looking at the super water repellency, water repellency generally refers to properties that are difficult to get wet. Super water-repellent surface technology is a field of surface modification technology to control the surface wetting phenomenon. The surface angle of the solid is physically or chemically modified so that the contact angle is changed when the liquid comes into contact with the surface of the solid. Refers to a technology that makes it over 150 °.

The representative model of the super water-repellent surface is lotus leaf. In the case of lotus leaf, there are numerous micro to nano sized ciliary protrusions on the surface and coated with wax component. And due to the wax coating is formed on the surface of the lotus leaf super water-repellent surface is characterized by not being wet with water.

In recent years, researches attempting to manufacture super water-repellent surfaces having improved water repellency by simulating micro / nano layer structures existing in nature beyond the manufacture of micro structures or nano structures have attracted much attention.

Such research on super water repellency is attracting attention not only in academic surface science but also in various industrial fields such as building materials, cosmetics, textile processing, and electronic and electronic component materials.

Generally, the surface of automobile glass or building window glass has a low contact angle with water as low as 20-40 ° so that water flows in the form of an uneven water film during rainy weather.

This heterogeneous water film causes light scattering in the case of automobile glass, thereby obstructing the driver's view, especially in rainy weather or at night driving, and easily contaminates the surface with dust, yellow sand, etc. in the case of building glass windows.

If the surface energy of the glass surface can be significantly lowered, it is possible to round the adhesion form of the water droplets, and the water droplets can be rolled down into a spherical shape, which makes it difficult to wet the water in most glass.

The glass that can prevent the wetness of water is called super water-repellent glass. Applying super water-repellent glass to a car prevents the distortion of the field of view coming from a heterogeneous water film, thereby securing a clear field of view. Can be.

In addition, in high-rise and large-area buildings that are difficult to clean, even if foreign matters are attached, glass with self-cleaning function can be easily removed as water droplets fall into a spherical shape due to low surface energy. This is possible and has significant advantages in terms of building maintenance.

The contact angle of water droplets formed on a solid surface is an index of water repellency. Generally, a contact angle of 90 ° or more is referred to as a water repellent (hydrophobic) surface, and a water repellency surface of 110 ° to 150 ° is referred to as a high water repellency surface. It is called.

The development of existing water repellent technology has focused on the research and development of materials with low surface energy, which are surface properties according to the chemical composition of the material surface from the 1950s. However, from the 1980s, it was found that not only the chemical properties of the surface but also the geometric spatial structure of the surface was a very important factor in determining superhydrophobicity.

The water-repellent film coated with various fluorine-based materials is an example using a material having a low surface energy. Since the contact angle of 150 ° or more cannot be obtained only by low surface energy, it is necessary to control the surface microstructure to obtain a super water-repellent material of 150 ° or more.

Currently, an example of producing a surface having a contact angle of water of 132 ° to 170 ° through dry etching using nanosphere lithography and oxygen plasma has been reported (Peilin Chen et al. Chem. Mater., vol. 16, no. 4, 561, 2004).

However, the above research results are only examples of increasing the contact angle of water by arranging polystyrene nanospheres in a single layer or a double layer on a gold film and changing the size and shape of the polystyrene nanospheres using oxygen plasma. Since the surface itself was not etched to form an uneven structure, there was a problem in that the water repellency was low.

In addition, in the method for producing water-repellent glass and the product of Korean Patent Laid-Open Publication No. 1997-007696, a raw material solution containing a silicon alkoxide compound and an organic solvent is hydrolyzed to form a silica film and to coat a water repellent layer. There was a problem in that the glass was produced, but the contact angle of water was not around 100 °, indicating that the water repellency was not shown.

In addition, the Republic of Korea Patent Laid-Open Publication No. 1999-0001695 'silica film having excellent durability and water-repellent glass using the same' is to provide a water-repellent glass that can effectively contain a water-repellent liquid by coating a water repellent on the surface of the silica film having irregularities In addition, since colloidal silica, which is a result of hydrolysis and condensation polymerization of the silane compound, is coated on the surface to provide an uneven structure, it is impossible to provide a regular uneven structure of a desired size.

In addition, surfaces containing nanostructures exhibiting super water-repellent properties also have an anti-reflective effect. In terms of anti-reflection, anti-reflection is generally a concept of anti-reflection, and the anti-reflection surface technology is caused by a sudden change in refractive index on the surface of an optical device. It is a technology to increase the amount of light transmitted by reducing the reflection of light.

Moth's eye is a representative model of anti-reflection. Moth's eye is composed of well-ordered nanostructures, so the reflection of light is very small, so you can protect yourself from predators like birds. It is easy to secure activities.

Anti-reflective surface using such nanostructure is applied to monitor including OLED / LCD, lighting including LED, advertisement, solar cell, glass for industrial / home appliance including automobile instrument panel, optical lens such as camera, etc. It can reduce glare and reduce the amount of light from the inside, providing clear and bright image quality.

In general, an antireflective surface uses a method of coating a thin film with a chemical material having an index of refraction between air and a substrate by using an electron beam deposition or an ion assisted deposition method. In addition, if you want to prevent reflection at different wavelengths, you need to deposit different layers of different materials with different refractive indices.

However, the antireflective surface using the nanostructure has the advantage of showing the effect of antireflection in a wide angle of incidence and wavelength range compared to the conventional technology using a coating thin film.

Antireflective surfaces using nanostructures have been approached by various nanoprocessing methods. Recently, nanostructures were fabricated on the silicon surface by nanosphere lithography and dry etching using SF ₄ plasma to report the antireflection effect (Peng Jiang et al. APL, vol. 92, 061112, 2008).

However, the above research results have a problem in that the uneven structure is formed on the silicon surface by using a plasma after the silica nanospheres are arranged in a single layer on silicon, which is not transparent.

In addition, in the same research group, a mold using silica nanoparticles was made and then replicated with PDMS (polydimethylsiloxane) to synthesize a structure of PETPTA (polyethoxylated trimethylolpropane triacrylate) on glass by UV polymerization. (Peng Jiang et al. APL, vol. 91, 101108, 2007).

However, this is difficult to control the shape of the structure and there is a problem that the durability is weak.

The present invention was devised to solve the above-mentioned problems, and forms a fine concavo-convex structure on the surface of the substrate and is coated with a fluorine compound to have excellent super water repellency, and at the same time reduce the reflectance of the surface of the glass or plastic substrate, It is an object of the present invention to provide a manufacturing method capable of easily producing an antireflective surface and a super water-repellent surface having characteristics.

The present invention for achieving the above object, in the method of manufacturing the surface of the substrate (A) formed of a glass material to produce a non-reflective surface and a super water-repellent surface, (a) a plurality of spheres (sphere) A bead arrangement step of arranging the beads in a single layer on one side of the substrate (A); (b) etching the plurality of beads to form an etching mask having a predetermined interval spaced between the beads; (c) a substrate etching step of etching one side of the substrate A by using the plurality of beads as an etching mask; (d) a bead removing step of removing the plurality of beads from one side of the etched substrate (A); (e) a fluorine compound coating step of coating a fluorine compound on one side of the substrate (A) on which fine irregularities are formed after the plurality of beads are removed; (f) a substrate surface conversion step of inverting the processed surface of the substrate (A); (g) a secondary bead arrangement step of arranging a plurality of beads having a spherical shape in a single layer on the other unprocessed side of the substrate A; (h) etching a plurality of beads to form a second bead etching step of forming an etching mask having a predetermined interval spaced between the beads; (i) a secondary substrate etching step of etching the other side of the substrate A by using the plurality of beads as an etching mask; (j) a secondary bead removing step of removing the plurality of beads from the other side of the etched substrate (A); And (k) a secondary fluorine compound coating step of coating the fluorine compound on the other side of the substrate (A) on which fine irregularities are formed after the plurality of beads are removed.

In addition, the method of manufacturing the anti-reflective surface and the super water-repellent surface of the present invention, in the method of manufacturing the non-reflective surface and the super water-repellent surface by processing the surface of the substrate (B) formed of a transparent plastic material, (l) sphere A bead arrangement step of arranging a plurality of beads having a shape in a single layer on one side of the substrate (B); (m) a bead etching step of etching the plurality of beads to form an etching mask having a predetermined distance from each bead; (n) a bead removing step of removing the plurality of beads from one side of the etched substrate (B); (o) a substrate surface conversion step of inverting the processed surface of the substrate (B); (p) a secondary bead arrangement step of arranging a plurality of beads having a spherical shape in a single layer on the other unprocessed side of the substrate B; (q) a secondary bead etching step of etching the plurality of beads to form an etching mask having a predetermined interval spaced from each bead; (r) a secondary substrate etching step of etching the other side of the substrate (B) by using the plurality of beads as an etching mask; And (s) a secondary bead removing step of removing the plurality of beads from the other side of the etched substrate (B).

Here, the plurality of beads, spin-coating, dip-coating, lifting up, electrophoretic deposition, chemical or electrochemical deposition ) And electrospray, which may be arranged on the surface of the substrates A and B.

Moreover, it is preferable that the said some beads have the magnitude | size of the diameter which each bead is 200 nm or less.

In addition, the etching can use dry etching by etching gas.

In addition, when the substrate A is a glass material and the bead is a plastic material, the etching gas may use any one or more selected from O ₂ , CF ₄ , and Ar in the bead etching step, and in the substrate etching step, The bead and the substrate are etched using at least one selected from CF ₄ , SF ₆ , and HF. When the substrate B is a plastic material and the bead is a glass material, CF ₄ , SF ₆ may be used in the bead etching step. , At least one selected from HF, and in the substrate etching step, the bead and the substrate may be etched using at least one selected from O ₂ , CF ₄ , and Ar.

In addition, the etching gas may be a mixture of H ₂ gas.

The surface of the substrate (A) coated with the fluorine compound is (CF _3- ), (-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) _m ) n-,-((CF ₂ ) _m O) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-(C (CF ₃ ) FCF ₂ O) n- may be characterized in that at least one. 1 or more and 25 or less, and said n is 1 or more and 100 or less.

In addition, the fluorine compound coating step and the secondary fluorine compound coating step, dip coating, spin coating, self-assembled monolayer treatment method of the fluorine silane compound, atom transfer radical polymerization of the fluorine monomer Surface polymerization method using Atom transfer radical polymerization method, grafting-from surface polymerization method of fluorine monomer, grafting-to surface polymerization method of fluorine compound, fluorine compound using plasma One or more methods of surface polymerization of and fluorine compound surface modification using plasma can be used.

On the other hand, using the manufacturing method of the non-reflective surface and the super water-repellent surface of the present invention, it is possible to duplicate the shape of the fine irregularities formed on the surface of the substrate (A, B) to form a mask for imprinting.

According to the manufacturing method of the non-reflective surface and the super water-repellent surface of the present invention, there is an advantage that can easily form fine irregularities on the surface of the substrate and surface treatment with a fluorine compound, to give a super water-repellent performance.

In addition, since the size of the fine irregularities is formed to 200nm or less, since the reflectance of the substrate is reduced, it is possible to provide a surface state with transparent and antireflective properties.

In addition, since self-sleaning is possible due to the super water-repellent effect, there is an advantage that a clean surface state can be maintained from external contaminants such as dust.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the present specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

1 is a flow chart illustrating a method of manufacturing an antireflective surface and a super water-repellent surface according to an embodiment of the present invention, Figure 2 is a perspective view showing a state in which beads are arranged on one side of the substrate, Figure 3a is a bead of Figure 2 3B is an enlarged view showing 'A' of FIG. 3A in an enlarged state, FIG. 4 is a perspective view showing a state in which the substrate of FIG. 3A is etched, and FIG. 5 is a side view of the substrate in FIG. 6 is a perspective view illustrating a state in which beads are removed, and FIG. 6 is a perspective view illustrating one side of the substrate of FIG. 5 coated with a fluorine compound.

7 is a perspective view showing a state in which the base of FIG. 6 is reversed, FIG. 8 is a perspective view illustrating a state in which beads are arranged on the other side of the base of FIG. 7, and FIG. 9 is a perspective view illustrating a state in which the beads of FIG. 8 are etched. FIG. 10 is a perspective view illustrating a state in which the substrate of FIG. 9 is etched, and FIG. 11 is a perspective view illustrating a state in which beads are removed from the other side of the substrate of FIG. 10.

12 is a perspective view showing a state in which the other side of the substrate of FIG. 10 is coated with a fluorine compound, and FIG. 13 is an electron micrograph of the surface of the substrate on which fine irregularities are formed through the method of manufacturing an anti-reflective surface and a super water-repellent surface of the present invention. FIG. 14 is a photograph showing the aggregated state of water droplets dropped on the surface of the substrate of FIG. 12 and the degree of transmission of the alphabet through the substrate, and FIG. 15 compares the transmittance of the substrate of FIG. The graph shown.

As shown in FIG. 1, the method of manufacturing an anti-reflective surface and a super water-repellent surface according to an embodiment of the present invention includes, bead arrangement step S10, bead etching step S20, substrate etching step S30, and bead removal. Step (S40), fluorine compound coating step (S50), substrate surface conversion step (S60), secondary bead arrangement step (S70), secondary bead etching step (S80), secondary substrate etching step (S90), secondary Bead removal step (S100) and the secondary fluorine compound coating step (S110).

First, Figure 2 is a perspective view showing the bead arrangement step (S10). Referring to FIG. 2, the bead arrangement step (S10) is a step of arranging a plurality of beads 200 having a spherical shape in a single layer on one side of the substrate 100.

Here, the substrate 100 may be a substrate (A) formed of a glass material, a substrate (B) formed of a material of a polymer plastic may be used.

In addition, when the glass substrate (A) is used, the bead 200 is formed of a polymer-based plastic material, and when the plastic substrate (B) is used, the bead 200 is a glass material It can be formed as.

On the other hand, it is preferable to clean the base material 100 before arranging the beads 200, the method of cleaning is as follows.

After dissolving 1% of the surfactant in a 5% KOH solution and then heated to 60 ℃ immersed the substrate 100 in the prepared solution and sonicated or stirred for 10 minutes and washed five times with distilled water. The cleaned substrate 100 is dried and treated in a UVO cleaner for about 3 minutes.

The beads 200 are arranged on one side of the substrate 100 cleaned as described above, wherein the beads 200 are arranged by spin-coating so that the beads 200 may be evenly arranged on the surface of the substrate 100. It is preferable to be.

At this time, the bead 200 is preferably a polymer of polystyrene (Polystyrene) material, but is not limited thereto, and materials such as polymers and inorganic materials may be used.

On the other hand, the specific method of the spin coating, first, the bead 200 is diluted using a methanol containing 0.25% of the surfactant in a solution dispersed at a concentration of 2.5%, 1 at a rotational speed of 3000rpm It is preferable to perform spin coating for a minute.

Here, the method of arranging the beads 200 is not limited to the spin coating, but may be dip-coating, lifting up, electrophoretic deposition, chemical or electrochemical coating ( chemical or electrochemical deposition) may optionally be used.

3A is a perspective view illustrating a bead etching step S20, and FIG. 3B is an enlarged view illustrating 'A' of FIG. 3A in an enlarged manner. Here, the circular dotted line having a shape surrounding each bead 200 in Figure 3b represents the diameter of the beads arranged in the substrate 100 through the bead arrangement step (S10), the circle located inside the circular dotted line Solid line represents the diameter of the bead 200 is reduced in size through the bead etching step (S20).

Referring to FIGS. 3A and 3B, the bead etching step S20 may be performed by etching the plurality of beads 200 to form an etching mask having a predetermined interval R spaced from each bead.

Here, as shown in FIG. 3B, when the predetermined random bead among the plurality of beads 200 is referred to as the reference bead S, the reference bead S and the reference bead ( A spaced distance from the peripheral beads arranged adjacent to the periphery of S).

In addition, the reason for forming the predetermined interval (R), the etching gas for etching the substrate 100 in the substrate etching step (S30) to be described later penetrates at intervals between the beads 200 to the surface of the substrate 100 To space the gap between each bead 200 to be easily reached. That is, the predetermined interval R is a spaced interval between the beads 200 etched by the etching gas to reduce the size of the diameter by applying a dry etching process.

4 is a perspective view showing a substrate etching step (S30). Referring to FIG. 4, in the substrate etching step S30, one side of the substrate 100 is etched using the plurality of etched beads 200 as an etching mask.

That is, the substrate etching step (S30) is a step of etching the substrate 100 so that the array shape of the beads 200 is transferred by applying a dry etching process to the substrate 100 on which the beads 200 are arranged. will be.

Here, in the dry etching process applied to the bead etching step (S20) and the substrate etching step (S30), etching using a high etching selectivity (Etching Selectivity) for the bead 200 and the substrate 100 is etched It is preferable to

In more detail, the etching gas is selected according to the type of the substrate 100 and the bead 200, and in some cases, an etching gas having a high or low etch selectivity of the substrate 100 and the bead 200 may be selected. Can be used as

That is, the etching gas, when the substrate 100 is a glass material and the bead 200 is a plastic material, at least one selected from O ₂ , CF ₄ , Ar in the bead etching step (S20). In the substrate etching step S30, the bead 200 and the substrate 100 may be etched using any one or more selected from CF ₄ , SF ₆ , and HF.

In addition, when the substrate 100 is a plastic material and the bead 200 is a glass material, in the bead etching step (S20), any one or more selected from CF ₄ , SF ₆ , and HF is used, and the substrate etching step is performed. In S30, the bead 200 and the substrate 100 may be etched using any one or more selected from O ₂ , CF ₄ , and Ar.

In addition, CHF ₃ , C ₂ F ₆ , C ₃ F ₆ , C ₃ F ₈ , C ₄ F ₁₀ , HF, according to the type and the form of the material forming the substrate 100 and the bead 200 Of course, etching gases such as HBr, SF ₆ , NF ₃ , SiCl ₄ , SiF ₄ , BCl ₃ , CCl ₄ , CClF ₃ , CCl ₂ F ₂ , and C ₂ ClF ₅ may be selectively used.

In addition, H ₂ gas may be mixed with the etching gas to further increase the etching selectivity.

By the substrate etching step (S30) as described above, the concave-convex 110 is formed on the surface of the substrate 100. As such, it is possible to easily form the fine concave-convex structure on the surface of the substrate 100 by etching using a dry etching process.

5 is a perspective view showing the bead removal step (S30). Referring to FIG. 5, only the irregularities 110 remain on the surface of the substrate 100 from which the beads 200 are removed.

As a method of removing the beads 200, an ashing process widely used in a semiconductor process may be applied.

More specifically, an O ₂ plasma ashing process may be applied, and methods such as a Piranha solution, an organic solvent, a dilute HF solution and steam, and ultrasonic cleaning may be used.

On the other hand, as described above, in one embodiment of the present invention, the substrate 100 may be formed of a material of glass or transparent plastic, even if the substrate 100 is a transparent material of the irregularities formed on the surface of the substrate 100 When the size is 400 nm or more, the substrate 100 becomes opaque.

This is because the wavelength of visible light that can be detected by the human eye is 400 nm to 800 nm. In particular, when the transparent anti-reflective surface is to be formed on the substrate 100, the size of the beads 200 is 200 nm or less. It is preferable.

Therefore, when the substrate 100 is formed of a plastic material (B), the bead arrangement step (S10), the bead etching step (S20), the substrate etching step (S30) and the bead removal step (S40) as described above By forming the fine concavo-convex 110 of 200 nm or less on one side of the substrate 100, the substrate 100 having both antireflective surface properties and super water-repellent surface properties can be manufactured as shown in FIGS. 13 to 15. It is.

Figure 6 is a perspective view showing a fluorine compound coating step (S50). Here, when the base material 100 used in the present invention is formed of the material (B) of the polymer-based plastic, water repellency appears due to the fine unevenness 100, but the base material 100 is made of glass (A). In the case of being formed with, due to the inherent properties of the glass material, even if the fine concave convex (110) is formed on the surface will show a hydrophilic property that is easily combined with water molecules.

Therefore, in the present invention, by coating the surface of the substrate 100 formed of a glass material with a fluorine compound, it is provided to implement a super water-repellent surface.

Referring to FIG. 6, when the substrate 100 is made of glass, a fluorine compound may be formed on one side of the substrate 100 on which the fine concave-convex 110 is formed after the plurality of beads 200 are removed. By performing the fluorine compound coating step (S50) to coat the (300), it can exhibit water repellency on the surface of the substrate (100).

Here, the fluorine compound 300 has a property of being coated on an object to lower the surface energy to exhibit water repellency, and the surface of the substrate 100 coated with the fluorine compound 300 is (CF _3- ), ( -(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) _m ) n-,-((CF ₂ ) _m O) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-( At least one of C (CF ₃ ) FCF ₂ O) n− is preferable, wherein m is 1 or more and 25 or less and n is 1 or more and 100 or less.

In addition, the method for coating the fluorine compound 300 on the surface of the substrate 100 is (CF ₃ -),-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) _m ) n-,- Prepare a fluorine compound 300 containing at least one of ((CF ₂ ) _m O) n-,-(OC (CF ₃ ) FCF ₂ ) n- and-(C (CF ₃ ) FCF ₂ O) n- After dipping the substrate 100 in a solution in which the fluorine compound 300 is dissolved, dip coating or taking out the solution at a speed of 10 mm / min, or dropping the solution on the substrate 100, the substrate 100 at 3000 rpm. A method such as spin coating that rotates for 1 minute at a rotational speed may be used.

In addition, a method of treating a self-assembled monolayer using fluoroalkyl silane may be mentioned. Preferably, the surface of the substrate 100 may be treated with tridecafluoro-1,1,2. , 2-tetrahydrooctyl) trichlorosilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) and a method of coating the fluorine compound 300 by treating with trimethoxysilane and (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane.

In addition, the fluorine compound 300 may be coated on the surface of the substrate 100 by applying the Atom transfer radical polymerization surface polymerization method. Perfluoroalkyl acrylate is used as the fluorine monomer, and more preferably, perfluorohexylethyl acrylate may be used.

Meanwhile, the fluorine compound 300 may be coated on the surface of the substrate 100 by applying a grafting-from surface polymerization method. In this case, an azo compound using heat and a photoinitiator using light may be used as an initiator. The fluoromonomer may be a perfluoroalkyl acrylate, more preferably perfluorohexylethyl acrylate.

In addition, the fluorine compound 300 is applied to the surface of the substrate 100 by applying a grafting-to surface polymerization method to the fluorine-based compound having a functional group capable of covalently bonded to the chemical functional group exposed to the substrate 100. Can be coated.

Furthermore, (CF ₃ -),-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) _m ) n-,-((CF ₂ ) _m O) n-,-(OC (CF ₃ ) FCF ₂₎ n-, and _{- (C (CF 3) FCF} 2 O) vaporizing the fluorine compound (300) comprising at least one of n- to create a plasma state in a plasma chamber, formed in the fluorine compound (300) surface The free radicals may be coated by graft polymerization on the substrate 100 exposed to the plasma.

Therefore, when the material of the substrate 100 is formed of a glass material (A), bead arrangement step (S10), bead etching step (S20), substrate etching step (S30), bead removal step (S40) and fluorine compound Through the coating step (S50), by coating the fluorine compound 300 as described above on the surface of the substrate 100, the fine concavo-convex 100 having a size of 200nm or less, as shown in Figures 13 to 15 As described above, the substrate 100 having the anti-reflective surface properties and the super water-repellent surface properties can be manufactured at the same time.

On the other hand, the method of manufacturing the anti-reflective surface and super water-repellent surface according to an embodiment of the present invention, as described above, by forming the uneven surface 110 on one side of the substrate 100, the object of the present invention can be achieved, More preferably, by forming the unevenness 110 ′ on the other side of the substrate 100, the transmittance of the substrate 100 may be maximized.

Therefore, hereinafter, the method of forming the unevenness 110 ′ on the other side of the base 100 in which the unevenness 110 is not formed and coating the fluorine compound 300 ′ will be described.

7 is a perspective view showing the substrate surface conversion step (S60). Referring to Figure 7, the substrate surface conversion step (S60), through the bead arrangement step (S10) to bead removal step (S40) or the bead arrangement step (S10) to fluorine compound coating step (S50), irregularities ( In order to form the same concave-convex 100 'as the concave-convex 100 on the opposite side of the surface of the substrate 100 on which the 110 is formed, it means a preparation step of inverting the substrate 100 by 180 °.

On the other hand, Figure 8 is a secondary bead array step (S70), through the same method as the bead arrangement step (S10), a plurality of beads having a spherical shape on the other unprocessed side surface of the substrate 100 (200 ') is arranged in a single layer.

Here, it is preferable to clean the substrate 100 before arranging the beads 200 ′, and when the substrate 100 is cleaned before arranging the beads 200 in the bead arranging step S10, It is preferable that the other side of the substrate 100 is also washed together.

In addition, since a specific method of arranging the beads 200 ′ in the secondary bead arranging step S70 is the same as the bead arranging step S10, a detailed description thereof will be omitted.

Next, Figure 9 is a perspective view showing a secondary bead etching step (S80). Referring to FIG. 9, in the secondary bead etching step S80, the etching of the plurality of beads 200 ′ may be performed to form an etching mask having a predetermined interval R spaced between the beads 200 ′. Since the specific implementation method is the same as the bead etching step S20, a detailed description thereof will be omitted.

10 is a perspective view illustrating a secondary substrate etching step S90. Referring to FIG. 10, the secondary substrate etching step S90 may be performed by etching the other side of the substrate 100 using the plurality of beads 200 ′ as an etching mask, and a specific implementation method may include Since the same as the substrate etching step (S30), a detailed description thereof will be omitted.

11 is a perspective view showing the secondary bead removal step (S100). Referring to FIG. 11, the secondary bead removing step (S100) is a step of removing the plurality of beads 200 ′ from the other side of the etched substrate 100.

The specific method of removing the beads 200 ′ is the same as in the bead removing step S4, and thus a detailed description thereof will be omitted.

Next, Figure 12 is a perspective view showing a secondary fluorine compound coating step (S110). Here, as described in the above-described fluorine compound coating step (S50), the water-repellent property of the polymer-based plastic material is formed on the surface on which the fine irregularities 110 'of the substrate 100 formed of the polymer-based plastic material (B) are formed. Although this appears, on the surface of the micro-concave convex (110 ′) of the substrate 100 formed of the glass material (A), due to the inherent properties of the glass material, the surface shows a hydrophilicity that is easily combined with water molecules.

Therefore, it is preferable to coat the other side on which the unevenness 110 'of the substrate 100 is formed with the fluorine compound 300' by the same method as the fluorine compound coating step S50.

Since the method of coating the fluorine compound 300 ′ on the substrate 100 is the same as in the fluorine compound coating step S50, a detailed description thereof will be omitted.

On the other hand, it is possible to form an imprinting mask used in the imprinting apparatus through the method of manufacturing the anti-reflective surface and super water-repellent surface according to an embodiment of the present invention, which is the bead arrangement step (S10) to the secondary fluorine compound coating The imprinting mask may be easily formed by duplicating the shape of the fine irregularities 100 and 100 'of the surfaces of the substrates A and B formed through the step S110.

As described above, although the present invention has been described by way of limited embodiments and drawings, the present invention is not limited thereto and is intended by those skilled in the art to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equivalents of the claims to be described.

1 is a flow chart showing a method of manufacturing a non-reflective surface and super water-repellent surface according to an embodiment of the present invention,

 2 is a perspective view showing a state in which beads are arranged on one side of the substrate;

3A is a perspective view illustrating a state in which the beads of FIG. 2 are etched;

3B is an enlarged view illustrating an enlarged view 'A' of FIG. 3A;

4 is a perspective view illustrating a state in which the substrate of FIG. 3A is etched;

5 is a perspective view illustrating a state in which beads are removed from one side of the substrate of FIG. 4;

6 is a perspective view showing a state in which one side of the substrate of FIG. 5 is coated with a fluorine compound;

7 is a perspective view showing a state in which the substrate of FIG. 6 is reversed;

8 is a perspective view showing a state in which beads are arranged on the other side of the substrate of FIG.

9 is a perspective view illustrating a state in which the beads of FIG. 8 are etched;

FIG. 10 is a perspective view illustrating a state in which the substrate of FIG. 9 is etched.

11 is a perspective view showing a state in which beads are removed from the other side of the substrate of FIG.

12 is a perspective view illustrating a state in which the other side of the substrate of FIG. 11 is coated with a fluorine compound;

13 is an electron micrograph of the surface of the substrate on which fine irregularities are formed through the method of manufacturing the anti-reflective surface and the super water-repellent surface of the present invention;

FIG. 14 is a photograph showing the aggregated state of water droplets dropped on the surface of the substrate of FIG. 13 and the extent to which English letters are transmitted through the substrate.

FIG. 15 is a graph illustrating the transmittance of the substrate of FIG. 13 and the transmittance of general glass.

<Explanation of symbols for the main parts of the drawings>

100 ... Based on 110, 110 '...

200, 200 '... bead 300, 300' ... fluorine compound

Claims (10)

In the method of processing the surface of the substrate (A) formed of a glass material to produce an antireflective surface and a super water-repellent surface, (a) a bead arrangement step of arranging a plurality of beads having a spherical shape in a single layer on one side of the substrate A; (b) etching the plurality of beads to form an etching mask having a predetermined interval spaced between the beads; (c) a substrate etching step of etching one side of the substrate A by using the plurality of beads as an etching mask; (d) a bead removing step of removing the plurality of beads from one side of the etched substrate (A); (e) a fluorine compound coating step of coating a fluorine compound on one side of the substrate (A) on which fine irregularities are formed after the plurality of beads are removed; (f) a substrate surface conversion step of inverting the processed surface of the substrate (A); (g) a secondary bead arrangement step of arranging a plurality of beads having a spherical shape in a single layer on the other unprocessed side of the substrate A; (h) etching the plurality of beads to form an etching mask having a predetermined interval spaced apart from each other; (i) a secondary substrate etching step of etching the other side of the substrate A by using the plurality of beads as an etching mask; (j) a secondary bead removing step of removing the plurality of beads from the other side of the etched substrate (A); And (k) a second fluorine compound coating step of coating a fluorine compound on the other side of the base (A) on which fine irregularities are formed after the plurality of beads are removed; The plurality of beads, Each bead has a diameter of 200 nm or less and is spin-coated, dip-coated, lifting up, electrophoretic deposition, chemical or electrochemical coating. arranged on the surface of the substrate A by at least one method selected from (chemical or electrochemical deposition) and electrospray, The etching is, Using dry etching by etching gas, The etching gas, When H ₂ gas is mixed, the substrate A is made of glass, and the beads are made of plastic, at least one selected from O ₂ , CF ₄ , and Ar may be used in the bead etching step. The beads and the substrate are etched using at least one selected from CF ₄ , SF ₆ , HF, The surface of the substrate (A) coated with the fluorine compound, (CF _3- ), (-(CF ₂ -CF ₂ ) n-,-(O (CF ₂ ) _m ) n-,-((CF ₂ ) _m O) n-,-(OC (CF ₃ ) FCF ₂ ) at least one of n- and-(C (CF ₃ ) FCF ₂ O) n- (wherein m is 1 or more and 25 or less, and n is 1 or more and 100 or less), The fluorine compound coating step and the secondary fluorine compound coating step, Deep coating, spin coating, self-assembled monolayer treatment of fluorine silane compounds, surface polymerization using atom transfer radical polymerization of fluorinated monomers, fluorinated monomers Any one of grafting-from surface polymerization, grafting-to surface polymerization of fluorine compounds, surface polymerization of fluorine compounds using plasma, and surface modification of fluorine compounds using plasma The manufacturing method of the anti-reflective surface and a super water-repellent surface characterized by using the above method. delete delete delete delete delete delete delete delete delete

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