KR102181607B1 - surface treatment method for glass and surface-treated glass - Google Patents

Abstract

The present invention comprises the steps of forming an aluminum layer on the surface of the glass; And forming a plurality of holes in the aluminum layer so that the surface of the glass is exposed. It relates to a method for surface treatment of glass comprising a.

Description

Surface treatment method for glass and surface-treated glass

The present invention relates to a glass surface treatment method and a surface-treated glass, and more particularly, to a surface treatment method of a glass used in a portable communication device and a surface-treated glass used in a portable communication device.

As various materials are applied to the exterior of a portable communication device, various methods of securing texture and color while securing durability have been proposed.

In the case of plastic materials, metal texture and non-conductivity can be realized by depositing tin and indium after undercoating using a transparent paint on the injection surface. At this time, tin and indium may be deposited and then colored paints may be applied to achieve color, and a transparent top coat may be additionally applied. However, this method is not preferred for surface treatment of materials used in smartphones due to durability issues.

As a method of implementing metallic texture and non-conductivity in glass material, a method of implementing non-conductive and color by combining multi-deposition and color printing is used, but it is a problem that various colors to be applied to portable communication devices cannot be realized. There is. In addition, in the case of conventional multi-deposition, there is a problem in that the light transmission properties of the glass material cannot be sufficiently utilized.

Further, when a metal is coated on the front or rear cover glass of the portable communication device, the performance of the antenna is degraded due to electromagnetic wave shielding and communication problems are caused. Therefore, an optical coating made of a non-conductive multilayer thin film has been applied to the cover glass of the existing portable communication device to avoid electromagnetic wave shielding, and the optical coating made of such a non-conductive multilayer thin film is difficult to realize the actual metal texture and There are disadvantages such as a change in color and a rainbow color phenomenon.

Although multi-evaporation is used as a method of implementing metal texture, non-conductivity and color in ceramic materials, there is a problem in that various colors to be applied to portable communication devices cannot be implemented.

An object of the present invention is to provide a glass surface treatment method capable of improving the above-described problems and a surface-treated glass manufactured according to the method.

In addition, the present invention is to provide a glass surface treatment method capable of providing a glass suitable for use in a portable communication device and a surface-treated glass manufactured according to the method.

In addition, the present invention is to provide a glass surface treatment method and a surface-treated glass that can have sufficient light transmittance to be used in a portable communication device, and can implement beautiful and various colors while securing durability.

As a result of intensive study, the present inventors formed an aluminum layer on the surface of the glass, and then subjected to a surface treatment such that the aluminum layer became a porous layer having a plurality of holes reaching the surface of the glass. It found out that the problem could be solved, and came to complete the present invention.

That is, the present invention is as follows.

[1] forming an aluminum layer on the surface of the glass; And forming a plurality of holes in the aluminum layer so that the surface of the glass is exposed. Glass surface treatment method comprising a.

[2] The method for surface treatment of glass according to [1], wherein the porous layer is formed by anodizing the aluminum layer.

[3] The glass surface treatment method according to [1], wherein the plurality of holes are formed at uniform intervals.

[4] The method for surface treatment of a glass according to [1], wherein the aluminum layer has a thickness of 20 µm to 50 µm.

[5] The step of forming the porous layer may include: a) primary anodizing the aluminum layer; And b) secondary anodizing the first anodized aluminum layer. The surface treatment method of the glass according to [1], including.

[6] The method for surface treatment of a glass according to [5], wherein the secondary anodization is performed at a higher voltage than that of the primary anodization.

[7] The method for surface treatment of a glass according to [5], wherein the first anodization is performed at 13V to 17V, and the secondary anodization is performed at 18V to 22V.

[8] After the first anodizing step and before the second anodizing step, c) the method for surface treatment of a glass according to [5], comprising an etching step of removing irregularly arranged holes generated in the aluminum layer. .

[9] The method for surface treatment of a glass according to [1], wherein the aluminum layer is formed on the glass surface by a magnetron sputtering method.

[10] The glass surface treatment method according to [1], further comprising a post-treatment step after the porous layer forming step.

[11] The post-treatment step is to perform at least one of electrolytic coloring, sealing treatment, and electrodeposition coating on the porous layer, wherein the method for surface treatment of a glass according to [10].

[12] glass; And a porous layer formed on the glass and having a plurality of holes reaching the surface of the glass. Including, wherein the porous layer is a surface-treated glass containing aluminum oxide.

[13] The surface-treated glass according to [12], wherein the porous layer is formed by anodizing an aluminum layer.

[14] The surface-treated glass according to [12], wherein the plurality of holes have uniform intervals.

[15] The surface-treated glass according to [12], wherein the porous layer has a thickness of 20 µm to 50 µm.

[16] The surface-treated glass according to [12], wherein the surface-treated glass is used for a portable communication device.

Advantageous Effects of Invention According to the present invention, it is possible to provide a method of surface-treating glass and surface-treated glass so as to be suitable for use in portable communication devices.

In addition, according to the present invention, it is possible to provide a surface-treated glass that can be applied to a fingerprint recognition module, a back cover, and a volume key of a smartphone.

In addition, the surface-treated glass of the present invention can have sufficient light transmittance, has excellent durability and corrosion resistance, and can realize a uniform color while implementing a variety of beautiful colors, thereby improving the quality of a portable communication device exterior material. .

1A is a cross-sectional view showing that an aluminum layer is formed on the surface of a glass.
1B is a cross-sectional view showing that a porous layer is formed on the surface of a glass.
2 is a cross-sectional view sequentially showing a method of forming a porous layer in a method for surface treatment of a glass according to an embodiment of the present invention.
3 is a cross-sectional view showing that a dye colored layer is formed on a porous layer.
4 is a cross-sectional view showing that a dye colored layer and a surface layer are formed on a porous layer.

The embodiments of the present invention are described in detail below, but the description of the constitutional requirements described below is an example of the embodiments of the present invention, and the present invention is not limited to the following contents as long as the gist is not exceeded. In addition, embodiments of the present invention are provided in order to more completely explain the present invention to those having average knowledge in the art. Accordingly, the shapes and sizes of elements in the drawings may be exaggerated for clearer explanation, and elements indicated by the same reference numerals in the drawings are the same elements.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the drawings, portions irrelevant to the description are omitted in order to clearly describe the present invention, and the thickness is enlarged to clearly express various layers and regions, and similar reference numerals are attached to similar portions throughout the specification. Let's do it.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

The present invention is a surface of a glass comprising the step of forming an aluminum layer on the surface of the glass, and forming a porous layer such that the aluminum layer becomes a porous layer having a plurality of holes reaching the surface of the glass. It relates to the treatment method.

1A is a cross-sectional view showing that an aluminum layer 11 is formed on the surface of the glass 10.

The glass 10 is not particularly limited, and all commonly used glass materials may be used, and may be prepared in various shapes according to the intended purpose.

The aluminum layer 11 is formed on the glass 10. The thickness of the aluminum layer 11 is not particularly limited, but is preferably formed to a thickness of 20 μm to 50 μm. If the thickness of the aluminum layer 11 is too thin, it is difficult to implement various colors during anodization treatment, and if it is too thick, there is a problem that the cost increases.

At this time, the method of forming the aluminum layer may be a PVD (physical vapor deposition) method, of which magnetron sputtering is more preferable. When the aluminum layer is formed by magnetron sputtering, the microstructure film formation rate of the aluminum layer is constant and high productivity can be obtained. In addition, when the aluminum layer is formed by magnetron sputtering, the formed aluminum layer has a high deposition adhesion strength and a high-density uniform structure, so that the film uniformity is large. In addition, the microstructure of the aluminum layer formed by magnetron sputtering shows a smooth surface and a fine microstructure.

1B is a cross-sectional view showing that the porous layer 12 is formed on the surface of the glass 10.

The porous layer 12 may be formed by anodizing the aluminum layer 11. In particular, it is possible to use a pore-type anodic oxidation method to form a porous type oxide film. When performing the pore-type anodization, while the aluminum layer is oxidized, the aluminum layer may be changed into a porous layer in which a plurality of holes are formed. As a result, a plurality of holes may be formed in the porous layer 12. At this time, the anodic oxidation of the aluminum layer 11 may be performed using an acid.

The plurality of holes h may be formed at uniform intervals. By forming the holes at uniform intervals, durability of the glass surface structure can be improved and uniform light transmittance can be secured.

The hole h may have a size (diameter) of a nano or micro level, and a gap between the plurality of holes may be formed at a nano or micro level. The size and spacing of the formed holes can be adjusted by changing the anodization conditions, for example, an anodization voltage, the type, concentration, and temperature of the acid solution.

Although not limited thereto, the average diameter of the plurality of holes is preferably 5 to 50 nm. The average diameter of the holes can be obtained by calculating the number average of the diameters of 100 adjacent holes.

Although not limited thereto, the distance between the plurality of holes is preferably 10 to 100 nm.

In this case, the hole h may be formed to reach the surface of the glass 10, which is a non-conductive material, so that the surface of the glass 10 is exposed. When the aluminum layer is anodized so that the plurality of holes h formed in the porous layer 12 reach the surface of the glass, all remaining portions of the aluminum layer (parts constituting the porous layer) are all oxidized to aluminum oxide. Can be. That is, the porous layer 12 includes aluminum oxide, and preferably, the porous layer 12 may be formed of aluminum oxide.

In addition, when a hole is formed so that the surface of the glass 10 is exposed, the surface-treated glass can secure sufficient light transmittance that can be used in a portable communication device.

2 is a cross-sectional view showing a method of forming a porous layer in a method for surface treatment of a glass according to an embodiment of the present invention.

First, as shown in FIG. 2A, masking is performed to form a mask 15 on the aluminum layer 11. Using the mask, the size and diameter of the holes to be formed in the porous layer can be adjusted and the alignment of the holes can be adjusted. Since the mask 15 is used to protect a part of the surface in the process of anodizing the aluminum layer, the material is not particularly limited, and a dry film or the like may be used.

Next, the aluminum layer on which the mask 15 is formed is first anodized to form a plurality of holes. 2B is a cross-sectional view schematically showing a hole formed after the first anodization. Holes formed after the first anodization do not reach the surface of the glass, and holes having an irregular arrangement may be included. In this case, the aluminum layer 11 ′ may be partially oxidized to include both a portion made of aluminum and a portion made of aluminum oxide.

The first anodized aluminum layer is etched to remove the irregularly arranged holes generated after the first anodization, and the holes formed in the aluminum layer 11" are uniformly aligned as shown in Fig. 2(c). can do.

Next, as shown in (d) of Figure 2, until the hole (h) reaches the surface of the glass 10, that is, until the surface of the glass 10 is exposed by the hole, the aluminum layer is a secondary anode. The porous layer 12 may be formed by oxidation.

The first and second anodic oxidation may be performed using an acid, and for example, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, and the like may be used.

Meanwhile, the first anodization and the second anodization may be performed under different conditions. The secondary anodization may be performed under a higher voltage than the primary anodization.

Preferably, the first anodization may be performed at a voltage of 13V to 17V, and the second anodization may be performed at a voltage of 18V to 22V.

Although not limited thereto, the first anodization may be performed for 15 to 30 minutes, and the second anodization may be performed for 60 to 210 minutes.

For example, unaligned holes are formed by primary anodization. In this case, when the first anodization time is increased, the depth of the unaligned holes becomes deep, making it difficult to remove the irregularly arranged holes, and then affecting the shape of the secondary anodized surface. Accordingly, by performing the first anodization and the second anodization under the above conditions, the position of the hole can be adjusted by the first anodization and the depth of the oxidation by the secondary anodization can be controlled. In addition, by setting the conditions for performing the first anodization and the second anodization as described above, a more uniform arrangement of holes can be obtained.

The method for surface treatment of the glass according to the present invention may further include a post-treatment step after forming the porous layer. The post-treatment step may be performing at least one of electric coloring, sealing, and electric deposition on the porous layer.

As shown in FIG. 3, by electrolytic coloring the porous layer 12, the dye colored layer 13 in which the dye is colored in the holes of the porous layer 12 may be formed. Electrolytic coloring can be carried out by plating or electrochemical deposition of oxides or chemicals by electrolysis.

In addition, as shown in FIG. 4, the surface layer 14 can be formed on the porous layer 12 and the dye colored layer 13 by performing sealing treatment or electrodeposition coating after electrolytic coloring. The surface layer 14 may be a sealing layer or an electrodeposition coating layer.

The sealing treatment may use a method such as hydration sealing, metallic sealing, organic sealing, low temperature sealing. The porous layer formed by anodization is very active at the beginning of its formation, and when left as it is, it adsorbs gases in the air and becomes inert (contaminated state). Therefore, sealing treatment can be performed to obtain a stable surface. Through this, it is possible to improve the corrosion resistance of the formed porous layer and extend the life.

The electrodeposition coating may be performed by electrically depositing a uniform coating film on the object to be coated by passing a current between the object to be coated and the counter electrode in a tank filled with a water-soluble paint of a certain concentration.

As described above, by performing electrolytic coloring on the holes formed in the porous layer, sealing treatment or electrodeposition coating treatment, beautiful and various colors are made, and weather resistance, durability, and corrosion resistance of the porous layer can be improved.

According to the present invention, it is possible to overcome the technical problems of the multi-coating, printing, and painting methods used as a surface treatment method of a glass material, and it is possible to implement a beautiful and various metallic texture colors excellent in corrosion resistance and durability to the glass material.

Referring to FIG. 1B, another embodiment of the present invention includes a glass 10 and a porous layer 12 formed on the glass and having a plurality of holes reaching the surface of the glass, The porous layer 12 provides a surface-treated glass containing aluminum oxide. The porous layer may be formed by anodizing the aluminum layer.

Preferably, the entire aluminum layer remaining as the porous layer is oxidized so that the porous layer 12 may be made of aluminum oxide.

The plurality of holes formed in the porous layer may be arranged at uniform intervals.

The thickness of the porous layer is not limited thereto, but may be 20 µm to 50 µm.

The surface-treated glass may be used in a portable communication device, and examples of the portable communication device may include a mobile phone, a smart phone, and a tablet PC. The surface-treated glass of the present invention can be used, for example, in a case of a portable communication device, a fingerprint recognition module, a back cover, and a volume key.

In addition, the surface-treated glass according to the present invention can be used as a front and rear cover glass of a portable communication device, and in this case, the design problem can be solved by not absorbing electromagnetic waves while maintaining the texture and color of metal in the glass cover. have.

The surface-treated glass may be manufactured according to the above-described surface treatment method of the glass, and a description of a configuration overlapping with that described in the above-described surface treatment method of the glass will be omitted.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as long as the gist is not exceeded.

Example

The surface of the glass (brand name: Gorilla 4) is cleaned using an organic solvent and an ultrasonic cleaning device. After installing the cleaned glass on the Magnetron Sputtering System, plasma treatment is performed by introducing argon (Ar) gas and oxygen (O2) gas, and applying a pulsed DC voltage. Argon (Ar) gas was injected into the magnetron sputtering system and a direct current (DC) voltage of 450V was applied to the sputter cathode to deposit an Al thin film of 50 μm.

Prior to anodization to form holes in the aluminum layer deposited on the glass, it was immersed in an acetone solution to remove organic matter and impurities from the surface of the aluminum layer and washed with ultrasonic waves for 10 minutes, and also realized the uniform surface roughness of the aluminum layer. In order to remove the oxide layer, electrolytic polishing was performed for 3 minutes under a constant current of 150 mA/cm² in a solution of perchloric acid and ethyl alcohol.

The primary anodic oxidation was performed using 1.8M sulfuric acid as an electrolyte, and applied at 15V for 30 minutes at 1°C. Next, holes having irregular arrangements generated after the first anodization were removed by immersing them in a solution containing 1.8 wt% chromic acid and 6 wt% phosphoric acid for 1 hour (etching step). Thereafter, the secondary anodic oxidation was carried out at 1° C. for 3 hours and 30 minutes by using 0.1M phosphoric acid as an electrolyte, and applying a voltage of 20V.

After completion of the anodization, residual aluminum that was not oxidized was removed using 0.1 M copper chloride and 20 vol% hydrochloric acid solution. In order to make the hole size uniform, pore widening was performed by immersing in 5 wt% phosphoric acid solution for 20 minutes.

Table 1 below shows the diameter of pores and the spacing between the holes formed when the first anodization and the second anodization are performed under the same conditions as described above.

Electrolyte Applied voltage Running time Pore diameter Spacing between holes 1st anodization 1.8M sulfuric acid 15V 30 minutes 14nm 15nm Secondary anodization 0.1M phosphoric acid 20V 210 minutes 19nm 45nm

evaluation

For the glass surface-treated according to the method of the above example, evaluation of light transmission, durability, acid resistance, and color realization was performed by the following method.

Transmittance was evaluated by measuring the transmittance of light to the specimen of the glass (brand name: Gorilla 4) before surface treatment, and the transmittance was measured with a Hitachi U-4100 spectrophotometer.

Durability evaluation and color realization evaluation were carried out after additionally performing electrolytic coloring and sealing treatment for each specimen surface-treated according to the method of Examples.

To evaluate the durability, X-Cut (which forms scratches on the surface in the form of a grid) on the surface of the surface-treated glass was performed 3 times with an OPP tape, and a 5 wt% aqueous solution of sodium chloride (Nacl) was applied. After continuous spraying at 35° C. for 72 hours, it was immersed in a pH 4.6 solution for 48 hours to check whether or not reliability failure occurred.

In preparing the aqueous sodium chloride solution, sodium chloride was dissolved in deionized water and the salt concentration was adjusted to 5±0.5% by weight. As for the adjustment result, the specific gravity was measured using a hydrometer, and it was confirmed that it was in the range of 1.0259 to 1.0329 at 35°C. In this case, it was manufactured again when it exceeded the specified specific gravity range.

Color realization was conducted by visual evaluation.

The surface-treated glass formed according to the embodiment has excellent transmittance of 92% or more, did not cause any reliability defects in durability evaluation, and the target color was accurately and uniformly implemented.

The present invention is not limited by the above-described embodiments and the accompanying drawings, but is intended to be limited by the appended claims. Therefore, various types of substitutions, modifications and changes will be possible by those of ordinary skill in the art within the scope not departing from the technical spirit of the present invention described in the claims, and this also belongs to the scope of the present invention something to do.

10: glass
11: aluminum layer
12: porous layer
h: hall
13: dye coloring layer
14: surface layer
15: mask

Claims (16)

Forming an aluminum layer on the surface of the glass; And
A porous layer forming step of forming a plurality of holes in the aluminum layer so that the surface of the glass is exposed;
As a method for surface treatment of a glass comprising,
The step of forming the porous layer,
a) primary anodizing the aluminum layer; And
b) secondary anodizing the first anodized aluminum layer; Including,
The secondary anodization is performed at a higher voltage than the primary anodization. delete The method of claim 1,
The method for surface treatment of glass in which the plurality of holes are formed at uniform intervals. The method of claim 1,
The thickness of the aluminum layer is 20 ㎛ to 50 ㎛ of the glass surface treatment method. delete delete The method of claim 1,
The first anodization is performed at 13V to 17V, the secondary anodization is performed at 18V to 22V. The method of claim 1,
After the first anodizing step and before the second anodizing step, c) an etching step of removing irregularly arranged holes generated in the aluminum layer. The method of claim 1,
The aluminum layer is a method of surface treatment of glass formed on the surface of the glass by a magnetron sputtering method. The method of claim 1,
After the step of forming the porous layer, a method for treating a surface of a glass further comprising a post-treatment step. The method of claim 10,
The post-treatment step is to perform at least one of electrolytic coloring, sealing treatment, and electrodeposition coating on the porous layer. Glass; And
A porous layer formed on the glass and having a plurality of holes reaching the surface of the glass; Including,
The porous layer is a surface-treated glass containing aluminum oxide,
The porous layer is formed by primary anodizing the aluminum layer and secondary anodizing the aluminum layer, wherein the secondary anodization is performed at a higher voltage than the primary anodization. . delete The method of claim 12,
The plurality of holes are surface-treated glass having uniform spacing. The method of claim 12,
The thickness of the porous layer is a surface-treated glass of 20 ㎛ to 50 ㎛. The method of claim 12,
The surface-treated glass is used for a case of a portable communication device.

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