KR20200048733A - surface treatment method for glass and surface-treated glass - Google Patents

Abstract

The present invention relates to a surface treatment method of a glass, capable of providing a glass suitable for use in portable communication devices and, more specifically, to a surface treatment method of a glass, comprising the steps of: forming an aluminum layer on a surface of the glass; and forming a porous layer which forms a plurality of holes in the aluminum layer so that the surface of the glass is exposed.

Description

Surface treatment method for glass and surface-treated glass

The present invention relates to a surface treatment method of glass and a surface treated glass, and more particularly, to a surface treatment method of 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 for securing texture and color while securing durability have been proposed.

In the case of a plastic material, metal texture and non-conductivity can be realized by depositing tin and indium after coating undercoat using a transparent coating on the injection surface. In this case, after depositing tin and indium, a colored paint may be applied to implement a color, and additionally, a transparent top coat may be coated. However, this method is not preferred as a surface treatment of materials used in smartphones due to durability issues.

As a method of realizing metallic texture and non-conductivity in glass materials, a method of implementing non-conductivity and color in combination with multi-deposition and color printing methods is used, but various colors to be applied to portable communication devices cannot be realized. There is. In addition, in the case of conventionally used multi-evaporation, there is a problem that the transparency of the glass material cannot be sufficiently utilized.

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

As a method of implementing metal texture, non-conductivity, and color on ceramic materials, multi-deposition is used, but there is a problem that various colors to be applied to portable communication devices cannot be realized.

The present invention is to provide a surface treatment method and a surface-treated glass prepared accordingly, which can improve the above problems.

In addition, the present invention is to provide a surface treatment method of the glass and a surface-treated glass prepared accordingly, which can provide a glass suitable for use in a portable communication device.

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

As a result of earnestly examining the present inventors, after forming an aluminum layer on the surface of the glass, the aluminum layer is subjected to a surface treatment to form a porous layer having a plurality of holes reaching to the surface of the glass. It has been found that a problem can be solved, and the present invention has been completed.

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. The surface treatment method of the glass containing.

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

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

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

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

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

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

[8] The method for surface treatment of the glass according to [5], comprising an etching step of removing irregular array holes formed in the aluminum layer after the first anodizing step and before the second anodizing step. .

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

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

[11] The post-treatment step is to perform at least one of electrolytic coloring, sealing treatment and electrodeposition coating on the porous layer, the surface treatment method of the 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. Included, the porous layer is a surface treatment 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 treatment glass according to [12], wherein the plurality of holes have uniform spacing.

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

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

According to the present invention, it is possible to provide a method of surface-treating glass and a surface-treated glass to be suitable for use in a portable communication device.

Further, 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, a volume key, etc. of a smartphone.

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

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

The embodiments of the present invention will be 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 unless the gist is exceeded. In addition, embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Accordingly, the shape and size of elements in the drawings may be exaggerated for a clearer description, 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, this means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and thicknesses are enlarged to clearly express various layers and regions, and like reference numerals are attached to similar parts throughout the specification. To do.

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

The present invention, the surface of the glass comprising a step of forming an aluminum layer on the surface of the glass, and the step of forming the aluminum layer, a porous layer having a plurality of holes (holes) reaching to the surface of the glass It relates to a processing method.

1A is a cross-sectional view showing that the 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 purpose to be used.

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. When the thickness of the aluminum layer 11 is too thin, it is difficult to implement various colors during anodizing, and if it is too thick, there is a problem in that the cost increases.

At this time, the method of forming the aluminum layer may be a PVD (physical vapor deposition) method, of which a magnetron sputtering (magnetron sputtering) method is more preferable. When the aluminum layer is formed by magnetron sputtering, the microstructure deposition 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 an advantage in that the deposition adhesion strength is high and a high-density uniform structure, resulting in a large film uniformity. In addition, the microstructure of the aluminum layer formed by magnetron sputtering shows a smooth surface and a dense 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, the pore-type anodization method for forming a porous type oxide film can be used. When the pore-type anodization is performed, as the aluminum layer is oxidized, the aluminum layer may be changed to 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, anodization 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, it is possible to improve the durability of the glass surface structure and ensure uniform light transmission properties.

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

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 adjacent 100 holes.

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

At this time, 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 a plurality of holes (h) formed in the porous layer 12 reach the surface of the glass, all of the remaining portions (parts constituting the porous layer) of the aluminum layer are oxidized to aluminum oxide. Can be. That is, the porous layer 12 includes aluminum oxide, and preferably, the porous layer 12 may be made 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 glass according to an embodiment of the present invention.

First, as shown in (a) of FIG. 2, masking to form a mask 15 on the aluminum layer 11 is performed. The size and diameter of holes to be formed in the porous layer can be adjusted and alignment of holes can be controlled using the mask. Since the mask 15 is used to protect some surfaces in the process of anodizing the aluminum layer, the material is not particularly limited, and a dry film or the like can 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 holes formed after primary anodization. The hole formed after the primary anodization does not reach the surface of the glass, and a hole having an irregular arrangement may be included. At this time, the aluminum layer 11 'may be partially oxidized to include both a portion made of aluminum and a portion made of aluminum oxide.

The primary anodized aluminum layer is etched to remove holes having an irregular arrangement created after the primary anodization, so that 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 FIG. 2, the aluminum layer is a secondary anode 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 porous layer 12 can be formed by oxidation.

The primary and secondary anodization may be performed using an acid, for example, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, and the like.

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

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

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

For example, the primary anodization furnace leads to unaligned holes. At this time, when the primary anodization time is prolonged, the depth of the unaligned holes becomes deep, which makes it difficult to remove irregularly arranged holes, and then affects the shape of the secondary anodized surface. Thus, by performing the primary anodization and the secondary anodization under the above conditions, it is possible to control the position of the hole by primary anodization and the depth to be oxidized by secondary anodization. In addition, by performing the conditions for performing the primary anodization and the secondary anodization as described above, holes in a more uniform arrangement can be obtained.

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

As illustrated in FIG. 3, the dye coloring layer 13 in which the dye is colored may be formed in the holes of the porous layer 12 by electrolytic coloring on the porous layer 12. The electrolytic coloring may be performed by electrochemical method of depositing oxides or chemicals by plating or electrolysis.

In addition, as illustrated in FIG. 4, after electrolytic coloring, sealing treatment or electrodeposition coating may be performed to form the surface layer 14 on the porous layer 12 and the dye coloring layer 13. The surface layer 14 may be a sealing layer or an electrodeposition coating layer.

For the sealing treatment, methods such as hydration sealing, metallic sealing, organic sealing, and low temperature sealing may be used. The porous layer formed by anodization is very active at the beginning of formation, and if left unattended, it adsorbs gas and the like in air and becomes inactive (contaminated). Therefore, a 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 an electric current between the object to be coated and the counter electrode in a tank filled with a water-soluble coating of a certain concentration.

As described above, by performing electrolytic coloring on the hole formed in the porous layer and sealing or electrodeposition coating treatment, beautiful and various colors are produced, and weathering resistance, durability of coloring, 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 coating methods used as a surface treatment method for glass materials, and it is possible to implement beautiful and various metal texture colors excellent in corrosion resistance and durability in glass materials.

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 include a mobile phone, a smart phone, and a tablet PC. The surface treatment 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, a volume key, and the like.

In addition, the surface treatment glass according to the present invention can be used as the 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 preserving the texture and color of the metal on the glass cover. have.

The surface-treated glass may be manufactured according to the surface treatment method of the above-described glass, and descriptions of the components overlapping with those described in the surface treatment method of the glass will be omitted.

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by the following examples unless the gist is exceeded.

Example

The surface of the glass (trade name: Gorilla 4) is cleaned using an organic solvent and an ultrasonic cleaning device. After the cleaned glass is mounted on a magnetron sputtering system, argon (Ar) gas and oxygen (O2) gas are added, and pulsed DC voltage is applied to perform plasma treatment. Argon (Ar) gas was injected into the magnetron sputtering system, and a 50 µm Al film was deposited by applying a direct current (DC) voltage of 450 V to the sputter cathode.

Prior to anodization to form holes in the aluminum layer deposited on the glass, it was immersed in acetone solution to remove organic substances and impurities on the surface of the aluminum layer, and ultrasonically washed for 10 minutes, and also realized a 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.

As the primary anodization, 1.8M sulfuric acid was used as the electrolyte, and a voltage of 15 V was applied to perform it for 30 minutes at 1 ° C. Next, holes having an irregular arrangement formed after the primary anodization were removed by immersion in a solution containing 1.8 wt% chromic acid and 6 wt% phosphoric acid for 1 hour (etching step). Subsequently, the secondary anodization was performed using 0.1 M phosphoric acid as the electrolyte, and a voltage of 20 V was applied for 3 hours and 30 minutes at 1 ° C.

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

Table 1 below shows the gap between the diameter of the pores and the holes formed when the primary anodization and the secondary anodization were performed under the same conditions as described above.

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

evaluation

Evaluation of light transmittance, durability, acid resistance, and color implementability was performed on the glass surface-treated according to the method of the above example by the following method.

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

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

For durability evaluation, X-Cut (which forms a flaw on the surface in a grid) at 1 mm intervals on the surface of the treated glass is subjected to desorption with OPP tape three times, and a 5 wt% aqueous solution of sodium chloride (Nacl) is used. After continuously spraying at 35 ° C. for 72 hours, it was immersed in a pH 4.6 solution for 48 hours to perform a method to determine whether reliability was poor.

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 a result of the adjustment, 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, when it was outside the specified specific gravity range, it was manufactured again.

Color realization was performed by visual evaluation.

The surface-treated glass formed according to the embodiment had excellent light transmittance of 92% or more, no reliability defects in durability evaluation, and a 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. Accordingly, various forms of substitution, modification, and modification will be possible by those skilled in the art without departing from the technical spirit of the present invention as set forth 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: hole
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;
The surface treatment method of the glass containing. According to claim 1,
The porous layer is a surface treatment method of glass that is formed by anodizing the aluminum layer. According to claim 1,
The plurality of holes are formed at uniform intervals, the surface treatment method of the glass. According to claim 1,
The aluminum layer has a thickness of 20 μm to 50 μm. According to claim 1,
The step of forming the porous layer,
a) primary anodizing the aluminum layer; And
b) secondary anodizing the primary anodized aluminum layer; The surface treatment method of the glass containing. The method of claim 5,
The secondary anodization is a surface treatment method of the glass is performed at a higher voltage than the primary anodization. The method of claim 5,
The primary anodization is performed at 13V to 17V, and the secondary anodization is performed at 18V to 22V. The method of claim 5,
And after the first anodizing step and before the second anodizing step, c) an etching step of removing holes in irregular arrangements formed in the aluminum layer. According to claim 1,
The aluminum layer is a method of treating a surface of glass formed on a surface of a glass by a magnetron sputtering method. According to claim 1,
After the porous layer forming step, the surface treatment method of the glass further comprising a post-treatment step. The method of claim 10,
The post-treatment step is to perform one or more 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 to the surface of the glass; Including,
The porous layer is a surface treatment glass containing aluminum oxide. The method of claim 12,
The porous layer is a surface treatment glass formed by anodizing the aluminum layer. The method of claim 12,
The plurality of holes are surface-treated glass having uniform spacing. The method of claim 12,
The porous layer has a thickness of 20 μm to 50 μm. The method of claim 12,
The surface-treated glass is used for a case of a portable communication device.

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