KR20180134561A - Method of Glass surface treatment to have low reflectivity and anti-fingerprint and Surface treated glass by the same - Google Patents

Abstract

The present invention relates to a method for treating a surface of glass to ensure low reflectivity and anti-fingerprint characteristics, comprising a step of forming an aluminum film on a surface of the glass; a step of forming an anodic oxidation coating layer and porous aluminum by treating the aluminum film with anodic oxidation; a step of removing the anodic oxidation coating layer; a step of etching the surface of the glass by using the porous aluminum as a mask; and a step of removing the porous aluminum. In the etching step, the surface of the glass is wet etched to form a nanostructure on the surface of the glass.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass surface treatment method and a glass surface treatment method using the same,

The present invention relates to a glass surface treatment method having low reflectivity and high transparency. More particularly, the present invention relates to a surface treatment method for forming a nanostructure on a glass to have an antireflection function and forming an inner fingerprint coating layer thereon.

In recent years, it has become possible to improve the visibility or the efficiency of the device by reducing the reflection of light in the cover glass of a mobile phone, a tablet PC, their camera lens, a TV, a computer monitor, a solar cell cover window, There is a high demand for anti-reflection (AR) technology that can enhance the display quality. In general, the degree of reflection of light is determined by the reflectance which varies depending on the difference in refractive index between the two media, the incident angle and the reflection angle. When the mobile phone is used outdoors, the visibility is very low even with a small reflectance. In addition, in the case of a cover window of a solar cell, it is necessary to reduce reflection because the efficiency of the solar cell is increased by increasing the transmittance by reducing the reflectance of the sunlight. In the case of exterior glass or automobile glass of a building, if glare due to reflection occurs, safety of pedestrians and driver may be affected, and reflection prevention is needed.

In order to reduce the reflection of light on the surface of the substrate, a technique of coating a material having a refractive index between the air and the refractive index of the substrate to a thickness of? / 4 with respect to the wavelength? Of the incident light is coated on the surface of the substrate.

However, this technique can suppress the reflection only for a specific wavelength λ, and therefore, it is necessary to coat the multilayer thin film because an antireflection layer for various wavelengths is required in order to realize reflection prevention over the entire visible light range. As a result, peeling due to the weak adhesion to the substrate, resulting in color unevenness due to surface unevenness, and thickness control depending on the multilayer thin film, arise. For this reason, the antireflection technique using a multilayer thin film coating has a limitation that it is difficult to apply to a surface with frequent contact such as a touch panel.

Therefore, anti-reflection technology using a moth-eye effect is emerging. A nano-protrusion having a diameter smaller than that of the visible light wavelength band is formed on the surface of the substrate so that the visible light does not recognize the presence of the nano-protrusion when the nano-structured surface passes through the surface, and the refractive index of the substrate surface gradually increases The effect of the multilayer thin film coating can be obtained and the reflection of light can be reduced.

[0003] In addition, in relation to the emotional state, a touch panel type electronic product that operates with a finger is widely used. In the case of a smartphone with a high frequency of use, since fingerprints need to be removed on the front of the display, it is necessary to perform fingerprint processing (anti-fingerprint, AF coating) Based fingerprint material only on the surface of the fingerprint. In addition, it is an invisible fingerprint (IF coating) that prevents the fingerprints from being visible even when the back side of the electronic product is subjected to special treatment. IF coating is also required to improve the technique and performance by simply attaching a hydrophilic lipophilic substance to the surface.

In addition, a photolithography process is generally used as a method of manufacturing a nano-sized fine structure. There is a problem in that the production speed is very slow and the manufacturing cost is high because a pattern is made by exposure and development using ultraviolet rays after applying a photoresist, and then a nano structure is manufactured using reactive etching.

Therefore, development of a technique to replace the photolithography process and development of a maskless process have been carried out by various mask forming methods, but the process is complicated and the control of the pattern is not easy, and a special etching device is used in the subsequent etching There is a problem that it is difficult to use a typical low-cost and simple wet etching method, and a technique for improving this is required.

The present invention provides a method of surface treatment of glass for low reflectivity and high transparency to form a simple and easily etch-resistant mask and to form well-aligned nanostructures using the formed mask, So that the glass surface can be economically manufactured.

According to an embodiment of the present invention, there is provided a method of treating a glass surface having low reflectivity and smoothness, comprising the steps of: forming an aluminum film on a surface of a glass; anodizing the aluminum film for a certain period of time to form an anodized coating layer and porous aluminum Etching the glass surface using the porous aluminum as a mask; and removing the porous aluminum, wherein the step of etching comprises the steps of: wet etching the glass surface; And a nano structure is formed on the glass surface.

In one embodiment, the nanostructure is one of a porous form and a horn form.

In one embodiment, the method further comprises forming an inner fingerprint coating layer on the glass surface from which the porous aluminum is removed.

In one embodiment, the inner fingerprint coating layer is a self-assembled layer of fluorine-based silane.

In one embodiment, the inner fingerprint coating layer is a self-assembled layer of a hydrophilic lipophilic silane oligomer, wherein the silane oligomer has the structural formula 1,

,

,

In the above-mentioned structural formula 1, the group R < ₁ > is preferably a methoxyethoxy undecyl group, a methoxy triglycoleoxy group, a 3-methoxyethoxy-4-acetoxy cyclohexyl ethyl group, ethoxy) hexahydro to comprise a derivative thereof which comprises at least one or more of the group, R ₂ group is 3-cyclopentadienyl-propyl group, di-cyclo-pentyl group, cyclopentyl group, cyclohexyl group, cyclo octyl group at least one of And m and n are integers selected from 1 to 10. The term " m "

In one embodiment, the step of forming a silicon dioxide layer is formed to a thickness of 5 nm to 10 nm before the step of forming the inner fingerprint coating layer.

In one embodiment, the visible light transmittance of the glass surface treated with the nanostructure is higher than the visible light transmittance of the non-surface treated glass.

In one embodiment, the step of etching the glass surface is performed using any one of hydrofluoric acid, a mixture of hydrofluoric acid and ammonium fluoride (Buffered HF).

According to the present invention, it is possible to form a nanostructure on a glass surface in an inexpensive and simple manner without using a high-cost photolithography process, and to form an inner fingerprint coating layer on a nanostructure to form a glass surface .

1A and 1B are cross-sectional and top views of an aluminum film formed on the surface of a glass according to an embodiment of the present invention.
2A and 2B are cross-sectional and top views of an anodized glass surface according to an embodiment of the present invention.
3A and 3B are cross-sectional and top views of a glass surface on which porous aluminum is formed according to an embodiment of the present invention.
4A and 4B are cross-sectional and top views of a wet etched glass surface according to an embodiment of the present invention.
5A and 5B are cross-sectional and top views of a glass surface on which porous aluminum is removed according to an embodiment of the present invention.
6A and 6B are cross-sectional and top views of a glass surface on which porous aluminum is removed according to another embodiment of the present invention.
7 is a flowchart schematically showing a procedure of a glass surface treatment method according to an embodiment of the present invention.
8A is a graph showing changes in current with time of an anodic oxidation process in which an aluminum film is formed on a nonconductor according to an embodiment of the present invention.
8B, 8C, and 8D are cross-sectional views illustrating an anodization treatment of an aluminum film formed on a nonconductor, a conductor, and a valve metal according to an embodiment of the present invention.
9A and 9B are cross-sectional and top views of a glass surface on which porous aluminum is formed according to an embodiment of the present invention.
10A and 10B are cross-sectional and top views of a glass surface on which porous aluminum is formed according to another embodiment of the present invention.
11A and 11B are cross-sectional and top views of a glass surface in which porous aluminum is formed in an island shape according to another embodiment of the present invention.
12 is an SEM photograph of a glass surface on which a horn-shaped nanostructure is formed according to an embodiment of the present invention.
13A is a photograph showing a fingerprint formed on a non-surface-treated glass according to an embodiment of the present invention.
FIG. 13B is a photograph showing a fingerprint formed on a glass in which an inner fingerprint layer is formed according to an embodiment of the present invention.
13C is a photograph showing a fingerprint formed on a glass in which a fingerprint layer is formed, according to an exemplary embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to clarify the technical idea of the present invention. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a block diagram of a computer system according to an embodiment of the present invention; Fig. For convenience of explanation, the apparatus and method are described together when necessary.

The surface treatment of the substrate is performed for various purposes. The nanostructure is formed on the surface of the substrate, and the surface of the substrate is treated to control the water repellency, hydrophilicity, and light reflectivity of the substrate.

Water repellency refers to the property that water does not penetrate. Water repellency is evaluated by the contact angle θ of the water droplet placed on the surface. Generally, when θ exceeds 90 °, water repellency, 120 ° to 150 ° high water repellency, Is defined.

For example, there are numerous micro- to nano-sized ciliary protrusions on the surface of the lotus leaf, and at the same time, the wax component is coated so that it is super-water-repellent and does not get wet. Since water droplets easily roll on the surface where the water repellent film is formed, it has been attracting attention in various application fields such as construction materials, cosmetics electronic parts, etc. Especially, it is widely used in the front cover glass of a mobile phone have. However, the conventional water-repellent film prepared by coating various fluorine-based materials is an example of forming a coating layer using a hydrolysis condensation reaction using a material having a low surface energy. The low surface energy shows a contact angle of about 115 ° -120 °, It needs to be higher.

In view of this point, the present invention intends to produce a glass having low reflectivity and smoothness by forming a nanostructure on the surface of the glass.

FIG. 7 is a flowchart schematically showing a procedure of a glass surface treatment method according to an embodiment of the present invention, and FIGS. 1 to 6 are diagrams showing a cross section and an upper surface of the glass surface according to a glass surface treatment procedure. 1 to 7, an aluminum film 20 is formed on the surface of the glass 10 (S710). The aluminum film 20 may be formed using PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition). According to the embodiment, as shown in FIGS. 1A and 1B, an aluminum film 20 having a thickness of several tens to several hundreds of nm can be formed on a glass surface by using a sputtering deposition method.

The aluminum film 20 is subjected to anodic oxidation treatment for a certain period of time to form an anodized film layer 21 and porous aluminum (S720). The mask used to etch the glass is fabricated using aluminum anodization technology instead of the photoresist used in conventional photolithography.

Anodizing is one of the electrochemical film formation methods. It uses sulfuric acid, anhydrous acid, chromic acid, or a mixed solution thereof as an electrolyte and polarizes the electrolyte in a certain electrolytic solution using aluminum as a positive electrode to form a porous film having excellent mechanical, electrical and chemical properties Aluminum oxide coating layer. The coating layer formed by such anodizing treatment is extremely hard, has high corrosion resistance, and can be dyed in various colors.

In one embodiment, the aluminum film 20 may be anodized twice under different conditions, such as temperature, voltage, electrolyte ratio, etc., and the anodized coating layer 21 with well-aligned pores may be formed .

Referring to FIG. 2A, the anodic oxide coating layer 21 contacts the surface of the glass 10 according to the anodizing time, and the porous aluminum may be formed under the anodized coating layer 21 according to the anodization time.

Referring to FIG. 2B, in the aluminum anodization, the distance between the pores and pores of the anodized film layer 21 is proportional to the voltage at a rate of 2.5 nm / V. In addition, the pores of the anodic oxide coating layer 21 are proportional to the voltage at a ratio of 1.29 nm / V. As mentioned above, since aluminum is anodized to form porous aluminum, the relative positions of the pores are regulated and it is impossible to produce various forms such as photolithography. Therefore, the pores generated in the aluminum are in the form of a porous hexagonal honeycomb conforming to the rule that the distance between the pores and the pores is 2.5 nm / V ratio, just like the shape of the anodic oxide coating layer 21 thereon.

The anodized film layer 21 is removed using an etching solution for etching only the anodized film layer 21 without affecting the aluminum (S730). In one embodiment, the etchant may be a mixture of phosphoric acid and chromic acid. When the anodized oxide film layer 21 is removed, aluminum remaining under the anodized oxide film layer 21 may be formed into a horn shape as shown in FIG. 3A, and may be formed on the glass 10 in a porous form as shown in FIG. 3B .

The surface of the glass 10 is etched using the porous aluminum as a mask (S740). The etching is divided into isotropic etching and anisotropic etching. When reactive ion etching is used as the anisotropic etching method, if the pores or island shape of aluminum are formed during the anodization of aluminum, the substrate is etched in the same pattern as the mask. Therefore, it is possible to make various nanostructures by adjusting the etching depth only by the etching time. However, reactive ion etching is expensive compared with wet etching, which is isotropic etching, and is not suitable for mass production. Therefore, wet etching using low cost and mass production is used.

In the case of wet etching, since it is isotropic etching, the pore size is small and the space distance is large, which is easy to form the nanostructure. Whether the nanostructure is porous or horn-shaped, the depth of the pore or the height of the horn is about 50% of the distance between the largest pore and the pore, and the nanostructure is stable to external force and high in durability.

4A and 4B are cross-sectional views of a wet-etched glass surface according to an embodiment of the present invention. Referring to FIG. 4A, the pores 11 are formed as follows using wet etching, During the etching, the porous aluminum can retain its shape. If the etching rate is too high, it is preferable to etch the glass at an appropriate etching rate by diluting the glass etching solution since the nanostructure is easily collapsed by the excessive etching.

In one embodiment, if the substrate is glass, wet etching may be performed by diluting a mixture of hydrofluoric acid or hydrofluoric acid with ammonium fluoride (Buffered HF) with water. According to the embodiment, the etching of 1 volume of hydrofluoric acid and 6 volumes of 40% ammonium fluoride in BHF with 7 times water can etch the glass at an etching rate of 80 nm / min. If the amount to be etched is not large, etching can be performed with an etching solution diluted with a volume ratio of 1:50 of hydrofluoric acid and water, and the etching rate of the glass is about 7 nm / min. The two etchants described above can be used as a mask of porous aluminum until the etch rate of the porous aluminum is less than 1% of the etch rate of the glass until the etching is terminated.

When formation of the nanostructure is completed, the porous aluminum is removed (S750). In one embodiment, the porous aluminum can be removed using sodium hydroxide or potassium hydroxide as an etchant. When the porous aluminum is removed, only the glass in which the nanostructures of the porous and horn-shaped structures are formed remains as shown in FIGS. 5A and 6A, and the glass 10 on which the nanostructures are formed has a higher transmittance than the non-surface treated glass.

The shape of the nanostructure can be determined according to the wet etching time in addition to the distance between the pores 11 and the pores 11 of the anodized film layer 21. Since the wet etching is performed not only in the depth direction but also in the lateral direction of the lower portion of the mask, the mask is dropped from the substrate when the entire lower portion of the mask is etched. Therefore, the etching is performed in a direction to flatten the surface, not the formation of the nanostructure. Therefore, the shape of the nanostructure can be formed into a porous or horn shape by controlling the time of the wet etching.

FIG. 8A is a graph showing a change in electric current with an elapse of time for forming an aluminum film on a nonconductor according to an embodiment of the present invention and performing an anodizing treatment, and FIGS. 8B, 8C, Conductor, an aluminum film formed on the valve metal, and Fig. 8A and 8D, when an aluminum film is formed on the non-conductive base material to have a thickness of several tens to several hundreds of nm and anodic oxidation is carried out, a barrier layer is formed in a region where the current rapidly decreases initially as shown in FIG. After that, the current rises, then maintains a constant value, then rapidly decreases again, and eventually it hardly flows. The period where the current rapidly decreases at the initial stage is a period in which the barrier layer is formed. In the region where the current is rapidly reduced and the region in which the current hardly flows, most of the aluminum that can be oxidized in the anodizing process is oxidized and the current is rapidly reduced and does not flow. However, as shown in FIG. 8B, aluminum exists in the form of islands or nanoparticles at the center of three pores. In the section where the current increases, pores start to form in the anodic oxide coating layer 21, and the section where the constant value is maintained is a section where the depth of the pores deepens. When the barrier layer of the anodized film layer 21 reaches the non-conductive surface, the aluminum between the anodized film layer 21 and the anodized film layer 21 is continuously oxidized. However, since aluminum is not sufficiently left, . When the anodic oxidation is stopped when the current begins to decrease rapidly, the anodization can be stopped with the remaining aluminum having small pores. FIGS. 8C and 8D illustrate that there is no aluminum remaining between the pores and the pores after the valve metal is deposited on the conductor and the conductor, respectively, and then subjected to the anodic oxidation treatment.

9 to 11 are cross-sectional and top views of a glass surface on which porous aluminum is formed according to various embodiments of the present invention. Referring to Figs. 9 to 11, the shape of the aluminum film remaining depends on the anodizing time. When the anodic oxidation treatment is performed until the current does not flow, only the nanoparticle-type aluminum remains as shown in FIG. Thus, the desired nanostructure size can be adjusted by adjusting the anodizing time.

In one embodiment, the inner fingerprint coating layer can be formed on the glass surface from which the porous aluminum is removed. The fingerprint coating layer causes the fingerprint to be formed, and the fingerprint does not prevent the fingerprint from being stuck on the fingerprint.

There are AG coating (Anti glare) and IF (Invisible fingerprint) coating as a method of forming the inner fingerprint coating layer. IF coating is a method in which the contact angle to the fingerprint component is coated on the surface as opposed to the AF coating. When a fingerprint component containing water and a diiodomethane component adheres to a large contact angle surface with respect to these components, irregular reflection occurs when the light is irradiated and becomes conspicuous. The IF coating has a contact angle to water of 60 ° to 80 ° and a contact angle to diiodomethane of 45 ° or less, and a hydrophilic lipophilic cationic methoxyethoxydoundosilyl silane compound and a cyclooctyl silane A silane oligomer prepared by mixing a compound with water is formed on the surface, and water or diiodomethane as a fingerprint component is spread over the surface. After IF coating, light is irradiated and most of the light is transmitted through the substrate without being reflected. Therefore, even if a fingerprint containing a water diiodomethane component is deposited on the IF coating layer, the fingerprint spreads thinly on the surface, so that it is not conspicuous and does not appear dirty.

The AG coating is a method of preventing diffuse reflection using a concave-convex structure. The film is used in a form in which unevenness of 10 to 2000 nm is generated by dispersing an embossing roll or fine particles on the surface of a substrate to prevent irregular reflection of light and is mainly applied to a film and adhered with an adhesive.

When the contact angle of the plane exceeds 90 °, if the irregularity of the appropriate shape and size is formed on the surface, the contact angle increases and the super water repellency is exhibited. On the contrary, when the contact angle of the plane is smaller than 90 °, it is known that when the unevenness of the proper shape and size is formed on the surface, the contact angle is further reduced and sometimes the superhydrophilic property is shown.

Therefore, if the nano structure of the substrate surface has a hydrophilic lipophilic property, it is possible to produce a super-water repellent surface having a contact angle of 150 DEG or more by forming the unevenness of the nano structure on the substrate surface and forming the AF coating layer. Moonlight can be improved.

In one embodiment, the inner fingerprint coating layer may be a self-assembled layer of a fluorine-based silane, or a self-assembled layer of a hydrophilic lipophilic silane oligomer. Silane is a designation of a family of silicon hydrides and can be represented by the formula Si _n H _{2n + 2} . The silane compound represents a compound in which at least one hydrogen in Si _n H _{2n + 2} is substituted with another reactor, and a compound having various properties can be obtained depending on the substituted reactor. When a reactor bonded to Si is substituted with a hydroxyl group (-OH), the siloxane bonds with the substrate surface to increase durability.

According to the embodiment, the silane oligomer may have the following structural formula (1).

[Structural formula 1]

In one embodiment, the group R < ₁ > is selected from the group consisting of a methoxyethoxy undecyl group, a methoxy triglycoloxy group, a 3-methoxyethoxy-4-acetoxy cyclohexyl ethyl group, a 16- (2-methoxy- And a hexadecyl group, and the R ₂ group includes at least one of a 3-cyclopentadienyl propyl group, a dicyclopentyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group And m and n are integers between 1 and 10, inclusive.

In one embodiment, the silicon dioxide layer may be formed to a thickness of 5 nm to 10 nm before forming the inner fingerprint coating layer. What is important in the surface layer bonded to the self-assembled layer is the OH group concentration on the surface, which is siloxane bonded by the hydrolysis condensation reaction. Silicon dioxide is relatively often used as the final surface layer because of its relatively high OH group concentration in other oxides. However, if the OH group concentration on the surface is increased by a plasma treatment or the like, a silicon dioxide layer may not necessarily be required. For example, AF coating with wet spray does not form a silicon dioxide layer, and the surface is subjected to atmospheric plasma treatment to generate OH groups on the surface, so that the inner fingerprint coating layer formed thereafter has no problem in practical use. However, in the case of performing AF coating in vacuum, it is common that the silicon dioxide layer is deposited and the inner fingerprint coating layer is formed continuously, so that the silicon dioxide layer having a relatively high OH group concentration is formed.

Hereinafter, embodiments of the glass surface treatment method of the present invention will be described.

[Example 1]

Clean the glass surface with organic solvent. The surface is cleaned by a plasma treatment in the inside with a sputter coating, so that the adhesion between the aluminum thin film and the glass surface is improved. An aluminum thin film of 400 nm is formed on the glass and polycarbonate surface by sputtering. Anodic oxidation is carried out in two steps in order to produce a well-polished anodized film layer.

The primary anodization is carried out in 0.3M oxalic acid solution for 200 seconds at 0 ° C and 80V. As a result of the primary anodization, an aluminum film is present between the glass surface and the anodic oxide layer and is opaque. The surface of the anodic oxidation coating layer is removed with a mixture of 6 wt% phosphoric acid and 1.8 wt% chromic acid. The specimens were subjected to secondary anodization again and the conditions were 0 ° C and 80V in 0.3M oxalic acid solution, and samples were prepared according to the anodization time. As the barrier layer is initially formed, the current rapidly decreases, the current increases again, the current keeps a constant value, and the current decreases rapidly, so that the current value approaches zero. When the anodic oxidation is stopped at the initial stage of the anodic oxidation and the barrier layer does not reach the glass, the aluminum film under the anodized film layer covers the entire surface of the substrate without pores and can not be used as a mask in glass etching.

When the anodization is stopped immediately before the step of increasing the current through the step of maintaining the constant value and then reducing again, aluminum is present in a porous form in the lower part of the anodic oxide coating layer. As the anodization time increases, the specimen changes from opaque to clear. The distance between the pores and pores of the anodized film layer is 200 nm.

The surface of the specimen was removed with a mixture of 6 wt% phosphoric acid and 1.8 wt% chromic acid to remove the anodic oxide layer on the surface, and a porous aluminum type film or aluminum in the form of aluminum or nanoparticle is present on the substrate. The transmittance was measured with only aluminum remaining on the glass surface, and the results are shown in Table 1.

Psalter

One
2
3
4
5
6
7
8
Anodization Time Seconds

30
60
120
150
180
210
240
270
Transmittance
550 nm

29
45
50
57
65
70
75
78

It can be seen that the size of the aluminum pore changes with the anodization time and the transmittance is changed.

The glass is etched by wet etching. If wet etching is used, the bottom of the mask is also etched at the same time because it is an isotropic etching type, and when the etching is continued, the mask is eventually separated from the substrate.

The specimens were prepared for each glass etching time using specimen 2 of 60 seconds anodizing condition.

In the wet etching method, the substrate was etched with an etching solution diluted with 50: 1 of hydrofluoric acid in water, and the etching rate was 7 nm / min with respect to the glass.

The glass was etched and the mask aluminum was removed from the sodium hydroxide solution and the specimens were washed with ultrapure water. Subsequently, the substrate is placed in a 95% ethanol solution and held for 1 hour. After 1 hour, the substrate is taken out of the ethanol solution and dried using a nitrogen gas.

A fingerprint layer is formed on each of the specimens by spraying the wet fluorine AF material of MMT. The transmittance of each sample and the contact angle to water were measured. The results are shown in Table 2.

Wet etching time min

0
5
10
15
20
25
Transmittance
550 nm

92
93
95
95
94
92
Contact angle

115
140
155
160
152
115

The samples without glass etching showed the same transmittance and contact angle as glass.

The samples with the glass etched for 5 minutes to 20 minutes increased the transmittance and the contact angle, and improved the light transmittance and transparency.

FIG. 12 is a SEM photograph of a nano structure. Referring to FIG. 12, a 15-minute etched sample forms a horn-shaped nanostructure. The samples that were etched for 25 minutes showed the same results as the samples without the nanostructures.

[Example 2]

A self-assembled inner fingerprint layer of a silane oligomer is formed by spraying an IF material of MMT, which shows hydrophilicity and lipophilicity as an inner fingerprint layer, on a wet-etched sample of the glass sample of Example 1 for 15 minutes.

13A to 13C, it can be seen that the same fingerprint layer is formed on plain glass and plain glass, and the degree of visibility of the fingerprint is visually observed. FIG. 13A shows the fingerprint clearly with plain glass, and FIG. 13B shows that the fingerprint layer is formed on the plain glass, which is slightly less pronounced. Fig. 13C shows that the fingerprint is hardly seen as a result of the second embodiment, and the mobility is improved.

The present invention has been described in detail with reference to the preferred embodiments shown in the drawings. These embodiments are to be considered as illustrative rather than limiting, and should be considered in an illustrative rather than a restrictive sense. The true scope of protection of the present invention should be determined by the technical idea of the appended claims rather than the above description. Although specific terms are used herein, they are used for the purpose of describing the concept of the present invention only and are not used to limit the scope of the present invention described in the claims or the claims. Each step of the present invention need not necessarily be performed in the order described, but may be performed in parallel, selectively, or individually. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is to be understood that the equivalents include all components that are invented in order to perform the same function irrespective of the currently known equivalents as well as the equivalents to be developed in the future.

10: Glass
11: Groundwork
20: Aluminum film
21: Anodic oxidation coating layer

Claims (9)

Forming an aluminum film on the surface of the glass;
Anodizing the aluminum film for a certain period of time to form an anodized coating layer and porous aluminum;
Removing the anodized coating layer;
Etching the glass surface using the porous aluminum as a mask; And
Removing the porous aluminum,
Wherein the etching step comprises wet etching the glass surface to form a nanostructure on the glass surface. The method according to claim 1,
Wherein the nanostructure is one of a porous type and a horn type. The method according to claim 1,
Further comprising the step of forming an inner fingerprint coating layer on the glass surface from which the porous aluminum is removed. 5. The method of claim 4,
Wherein the inner fingerprint coating layer is a self-assembled layer of fluorine-based silane. 5. The method of claim 4,
Wherein the inner fingerprint coating layer is a self-assembled layer of a hydrophilic lipophilic silane oligomer,
The silane oligomer has the structural formula 1,

In the above-mentioned structural formula 1, the group R < ₁ > is preferably a methoxyethoxy undecyl group, a methoxy triglycoleoxy group, a 3-methoxyethoxy-4-acetoxy cyclohexyl ethyl group, Ethoxy) -hexadecyl group and a hexadecyl group,
The R ₂ group is composed of a derivative containing at least one of a 3-cyclopentadienylpropyl group, a dicyclopentyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group,
Wherein m and n are integers selected from 1 to 10. < RTI ID = 0.0 > 11. < / RTI > 5. The method of claim 4,
And forming a silicon dioxide layer to a thickness of 5 nm to 10 nm prior to the step of forming the inner fingerprint coating layer. The method according to claim 1,
Wherein the visible light transmittance of the glass surface treated with the nanostructure is higher than the visible light transmittance of the non-surface treated glass. The method according to claim 1,
Wherein etching the glass surface comprises:
Wherein the etching is performed using one of hydrofluoric acid, a mixture of hydrofluoric acid and ammonium fluoride (Buffered HF). A glass surface-treated by the method according to any one of claims 1 to 8.

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