KR102565854B1 - Coating glass for preventing stain - Google Patents

Abstract

The present invention relates to an anti-stain glass capable of maintaining transparency even in a high temperature and high humidity environment for a long time by improving durability against acidic or basic products by coating a dielectric layer and an anti-stain layer on a glass plate to minimize moisture reaction.

Description

Coating glass for preventing stain}

The present invention relates to anti-stain coated glass having improved moisture resistance and chemical resistance.

Glass is one of the products used for many useful purposes at home or industrial sites, and due to its nature, stains, clouding, and whitening occur on the surface of the glass when exposed to high temperature and high humidity environments, such as bathrooms and shower rooms, for a long time. There is a problem with

Specifically, when a glass product used in a bathroom environment, such as a washbasin, bathtub, or shower booth, is exposed to products such as soap, detergent, shampoo, etc. in addition to water, organic matter or soap residue from the product adheres to the surface and becomes contaminated. In addition, when glass products such as shower booths are exposed to a high temperature and high humidity environment for a long time, stains and whitening occur on the glass surface. Therefore, a method of minimizing contact with contaminants or moisture was used by treating the surface of the product to be water-repellent using wax, fluorine-containing material, or the like. In addition, a method of applying a surface active agent or an absorbent material composed of organic matter such as a hydrophilic polymer to the surface of the product was used to prevent contamination or fogging of the product.

However, the above method has a problem in that performance deteriorates over time. Water-repellent treatment using conventional water-repellent wax does not have sufficient waterproof effect, or even if sufficient water-repellent treatment is performed, water repellency is only given temporarily or for a short period of time, and it is difficult to expect the persistence of the water-repellent effect. In addition, it is difficult to uniformize the water film, and there are problems in commercialization of the product, such as distorted perspective images or reflected images on the glass surface.

In addition, Japanese Patent Application No. 2005-176390 discloses a technique of utilizing titanium dioxide to manufacture glassware suitable for use in a high-temperature and high-humidity bathroom environment. However, there is a limitation that ultraviolet rays must be irradiated in order for titanium dioxide to function, and such glass products have difficulty in demonstrating their function in an actual bathroom environment. In addition, a long post-processing process may be required in order for titanium dioxide to have crystallinity.

Therefore, there is still a need for a coated glass that can secure excellent moisture resistance and chemical resistance without a separate post-treatment process, and is suitable for use in a high temperature and high humidity environment.

The present invention provides anti-stain glass.

The anti-stain glass of the present invention is a glass comprising a glass substrate and an anti-stain layer formed on the glass substrate, wherein the anti-stain layer is any one selected from the group consisting of Al, Ti, Si, Zr and alloys thereof. It includes an oxide film, and the glass has a haze of 0.1 to 4.0% after being maintained at 60° C. and 95% relative humidity for 1,000 hours.

The anti-stain glass of the present invention can secure excellent moisture resistance and chemical resistance without a separate post-processing process, and is suitable for use in a high temperature and high humidity environment.

1 schematically shows the glass of the present invention comprising an anti-stain layer 11 and a glass substrate 10 .
Figure 2 shows the presence or absence of cracks in the glass of Examples 1 and 4 and Comparative Example 7.
Figure 3 shows the results of evaluation of abrasion resistance and moisture resistance and chemical resistance and moisture resistance of Example 1 and Comparative Example 1.
Figure 4 shows the results of evaluation of abrasion resistance and moisture resistance and chemical resistance and moisture resistance of Comparative Examples.

Hereinafter, the present invention will be described in more detail.

The anti-stain glass of the present invention is a glass comprising a glass substrate and an anti-stain layer formed on the glass substrate, wherein the anti-stain layer is any one selected from the group consisting of Al, Ti, Si, Zr and alloys thereof. It includes an oxide film, and the glass has a haze of 0.1 to 4.0% after being maintained at 60° C. and 95% relative humidity for 1,000 hours.

In the anti-stain glass of the present invention, since the anti-stain layer, which is a metal oxide film, is formed on the glass substrate, direct contact between the glass and moisture can be minimized, so that the transparency of the glass can be maintained and moisture resistance and chemical resistance can be secured. .

The glass substrate included in the anti-stain glass of the present invention is not particularly limited, but, for example, architectural soda lime glass having a thickness of 1 to 20 mm may be used.

The anti-stain layer is formed on a glass substrate through deposition and serves to protect the glass from high temperature and high humidity environments and acidic and basic solutions. The anti-stain layer may be any one oxide film selected from the group consisting of Al, Ti, Si, Zr, and alloys thereof, and may be, for example, an oxide film of Zr.

The anti-stain layer may have a thickness of 1 to 10 nm, such as 2 to 9 nm, such as 4 to 8 nm. If it exceeds 10 nm, cracks in the anti-stain layer may occur during heat treatment, and if the glass is exposed to a high temperature and high humidity bathroom environment for a long time, stains may occur and transparency may decrease. Transparency may be lost.

In addition, the anti-stain layer may be formed on both sides of the glass substrate, for example, on both sides of the glass substrate, on a surface in contact with air during a glass manufacturing process. In general, a glass substrate is manufactured by a float method in which a glass material is poured over a molten metal bath and solidified. At this time, a molten metal bath in which Sn is dissolved is used. In this process, it can be divided into a surface in contact with air when the glass water flows (Air surface) and a surface in contact with the molten metal tank as the opposite surface (Tin (Sn) surface). The tin surface has a different property from the air surface due to the reaction (substitution) of Sn and glass dissolved in the molten metal bath. In general, since stain occurs on the air surface, a stain prevention layer is formed on the air surface, that is, the surface in contact with air. can do. In this specification, the “surface in contact with air” or the “air surface” of the glass substrate means the surface in which the glass substrate is in contact with air during the manufacturing process of the glass substrate as described above.

In addition, the glass may further include a dielectric layer positioned between the glass substrate and the anti-stain layer, and the dielectric layer may include any one oxide film selected from the group consisting of Al, Ti, Si, and alloys thereof.

The dielectric layer is a metal oxide formed on a glass substrate and serves to prevent cracks and haze in the anti-stain layer during heat treatment. Although not particularly limited, the dielectric layer may be any one oxide film selected from the group consisting of Al, Ti, Si, and alloys thereof, and may be, for example, an oxide film of Si.

The thickness of the dielectric layer may be 1 to 20 nm, such as 2 to 18 nm or 4 to 15 nm. If the thickness exceeds 20 nm, productivity of the product may decrease due to the characteristics of the metal oxide film having a low deposition rate, and if the thickness is less than 1 nm, cracks and haze may occur.

The anti-stain glass of the present invention shows a low haze value even in a high-temperature and high-humidity environment, and although not particularly limited, the haze value after maintaining for 1,000 hours at 60 ° C and 95% relative humidity is 0.1 to 4.0%, for example, 0.1 to 1.0%. can

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Example]

Using a magnetron sputtering method, an anti-stain coated glass having a coating film having the composition and thickness shown below was formed on a 4 mm soda lime transparent glass substrate was prepared.

Each sample was produced using the PVD method (sputtering), and as detailed process conditions, the process pressure was 4 mTorr, the power was 2KW, and the Ar:O ₂ ratio = 80%:20%.

Example 1

As an anti-stain layer, ZrO ₂ was coated on the air side of a 4 mm thick transparent glass to a thickness of 5 nm under an oxygen/argon atmosphere. [Film Structure: Glass/ZrO ₂ ]

Example 2

ZrO ₂ as an anti-stain layer was coated on the air surface of a 4 mm thick transparent glass to a thickness of 8 nm under an oxygen/argon atmosphere. [Film Structure: Glass/ZrO ₂ ]

Example 3

As an anti-stain layer, ZrO ₂ was coated on the air side of a 4 mm thick transparent glass to a thickness of 10 nm under an oxygen/argon atmosphere. [Film Structure: Glass/ZrO ₂ ]

Example 4

SiO ₂ as a dielectric layer was coated on the air surface of 4 mm thick transparent glass in an oxygen/argon atmosphere to a thickness of 5 nm. Subsequently, as an anti-stain layer, ZrO ₂ was coated to a thickness of 5 nm under an oxygen/argon atmosphere. [Film Structure: Glass/SiO ₂ /ZrO ₂ ]

Example 5

SiO ₂ as a dielectric layer was coated on the Air side of a transparent glass having a thickness of 4 mm to a thickness of 10 nm under an oxygen/argon atmosphere. Subsequently, as an anti-stain layer, ZrO ₂ was coated to a thickness of 10 nm under an oxygen/argon atmosphere. [Film Structure: Glass/SiO ₂ /ZrO ₂ ]

Comparative Example 1

A transparent glass with a thickness of 4 mm without a separate coating was used.

Comparative Example 2

A dielectric film AlN layer was coated on transparent glass having a thickness of 4 mm to a thickness of 5 nm under a nitrogen/argon atmosphere. [Film Structure: Glass/AlN]

Comparative Example 3

A dielectric layer of AlO ₃ was coated on transparent glass having a thickness of 4 mm to a thickness of 5 nm in an oxygen/argon atmosphere. [Membrane Structure: Glass/AlO ₃ ]

Comparative Example 4

A 5 nm thick dielectric TiON layer was coated on a 4 mm thick transparent glass under a nitrogen/argon atmosphere. [Membrane Structure: Glass/TiON]

Comparative Example 5

A dielectric TiO ₂ layer was coated on transparent glass having a thickness of 4 mm to a thickness of 5 nm under an oxygen/argon atmosphere. [Membrane Structure: Glass/TiO ₂ ]

Comparative Example 6

A 5 nm thick dielectric ZrN layer was coated on transparent glass having a thickness of 4 mm under a nitrogen/argon atmosphere. [Film Structure: Glass/ZrN]

Comparative Example 7

A dielectric film layer of ZrO ₂ was coated on transparent glass having a thickness of 4 mm in an oxygen/argon atmosphere to a thickness of 30 nm. [Film Structure: Glass/ZrO ₂ ]

Comparative Example 8

A dielectric film ZrO ₂ was coated on transparent glass (Tin surface) having a thickness of 4 mm to a thickness of 5 nm under an oxygen/argon atmosphere. [Film Structure: Glass/ZrO ₂ ]

The prepared glass samples of Examples and Comparative Examples were heat-treated by the following method. In a general electric furnace, heat treatment was performed by slowly cooling at room temperature after heat treatment for about 14 minutes while maintaining the set temperature at a temperature of about 700 to 720 ° C. This heat-treated sample was evaluated for moisture resistance by maintaining it for 1,000 hr at an internal temperature of 60 ° C and a relative humidity of 95% using JISICO's J-RHC-2CH constant temperature and humidity chamber. After conducting the Taber test 10 times with a load of 500g on the CS-10F abrasion wheel using a mock tester, the moisture resistance test was conducted for 1,000hr. In addition, the chemical resistance evaluation was conducted by immersing the glass samples in 1N HCl solution and 1N NaOH solution for 24 hours, respectively, and then subjected to moisture resistance evaluation for 1,000 hours. After the evaluation of moisture resistance and abrasion resistance + moisture resistance, chemical resistance + moisture resistance, the haze of the evaluation sample was measured using a BYK hazemeter to determine the moisture resistance, abrasion resistance, and chemical resistance of the coated glass. The evaluation results are shown in Table 1 and Table 2 below. In addition, the glass of each Example and Comparative Example prepared is shown in FIGS. 2 to 4 .

As can be seen from Tables 1 and 2, when the uncoated general glass as in Comparative Example 1 is exposed to a high temperature and high humidity environment for a long time, as can be seen in FIG. 3, high haze value due to whitening of the glass this was measured As such, in order to prevent staining of the glass, the glass surface was coated with an oxide film or a nitride film using Al, Ti, and Zr as materials as in Comparative Examples 2 to 8 to evaluate moisture resistance, abrasion resistance, and chemical resistance, but in FIG. As can be seen, when exposed to a high-temperature and high-humidity environment for a long time, no sample having a coating film excellent in moisture resistance, abrasion resistance, and chemical resistance was identified.

In Comparative Example 7, when a 30 nm Zr oxide film was coated, surface cracks occurred as shown in FIG. 2, and it was confirmed that the crack generation level increased as the thickness increased. When such surface cracks occur, durability of the coating film may become a problem when the glass is exposed to a high temperature and high humidity environment for a long time.

Examples 1 to 5 of the anti-stain glass of the present invention are cases in which a Zr oxide film is coated on a glass substrate in order to solve this problem, or a Si-based oxide film is additionally coated between the glass and the Zr oxide film. As can be seen from, surface cracks did not occur, and as shown in Table 1, it was confirmed that excellent results were obtained in moisture resistance, abrasion resistance, and chemical resistance.

10: transparent glass
11: zirconium oxide film

Claims (6)

A glass comprising a glass substrate and a stain prevention layer formed on the glass substrate,
The anti-stain layer includes a Zr oxide film containing ZrO ₂ ,
The glass has a haze of 0.1 to 4.0% after maintaining for 1,000 hours at 60 ° C. and 95% relative humidity,
The anti-stain layer has a thickness of 1 to 10 nm, glass. The method of claim 1, wherein the glass further comprises a dielectric layer positioned between the glass substrate and the anti-stain layer, wherein the dielectric layer comprises any one oxide film selected from the group consisting of Al, Ti, Si, and alloys thereof. Inclusive, glass. The glass according to claim 1, wherein the glass substrate is soda lime glass having a thickness of 1 to 20 mm. delete 3. The anti-stain glass of claim 2, wherein the dielectric layer has a thickness of 1 to 20 nm. The glass according to claim 1, wherein the anti-stain layer is formed on a surface in contact with air among both surfaces of the glass substrate.