KR102633186B1 - A functional building material for windows - Google Patents

Abstract

The present invention relates to a transparent substrate; A low-emissivity coating comprising one or more layers located on top of the transparent substrate; and a top protective layer located on top of the low-emissivity coating, wherein the top protective layer includes a first top protective layer including metal zirconium and zirconium oxide; It relates to a functional building material for windows and doors including a second top protective layer located on the first top protective layer and containing carbon.

Description

Functional building material for windows {A FUNCTIONAL BUILDING MATERIAL FOR WINDOWS}

The present invention relates to a functional building material for windows and doors including a top protective layer.

Low-emissivity glass refers to glass in which a low-emissivity layer containing a metal with a high reflectivity in the infrared region, such as silver (Ag), is deposited as a thin film. This low-emission glass is a functional material that reflects radiation in the infrared range, blocking outdoor solar radiation in the summer and preserving indoor heating radiation in the winter, resulting in energy savings in buildings.

Since silver (Ag), which is generally used as a low-emissivity layer, is oxidized when exposed to air, a low-emissivity coating in which a metal and/or dielectric layer is deposited as an oxidation prevention film on the top and bottom of the low-emission layer is deposited on the glass. . This dielectric layer also serves to increase visible light transmittance.

However, when low-emissivity coatings come into contact with corrosive agents such as oxygen, chloride, sulfide, and sulfur dioxide in the atmosphere in a high temperature and humidity environment, the silver (Ag) layer is corroded and damaged. In addition, low-emissivity coatings are vulnerable to external shocks, so damage to the coating due to scratches frequently occurs during transportation or handling. In particular, in the case of construction materials with heavy loads, such as glass, scratches occur more frequently during transportation and handling due to the heavy load.

In order to solve problems such as damage, low-emission protection has been achieved by coating a top protective layer (3) containing a metal, etc. on top of the conventional transparent substrate (1) and low-emission coating (2) as shown in FIG. 1(a). Primary protection has been provided for the coating.

However, in the case where scratches occur on the top protective layer 3 in the prior art due to external force (Figure 1(a)), scratches generated on the top protective layer 3 as shown in Figure 1(b) during heat strengthening There is a problem that it further expands and damages the lower low-emissivity coating (2).

The object of the present invention is to provide a functional building material for windows and doors with excellent durability against physical and chemical attacks from the outside.

In addition, the present invention aims to provide a functional building material for windows that can be easily removed during the subsequent heat strengthening process and at the same time, scratches can be easily removed.

In addition, the present invention aims to provide a functional building material for windows that can minimize natural oxidation of the lower metal layer.

In addition, the present invention aims to provide a functional building material for windows and doors that is easy to handle and can dramatically reduce the defect rate by easily removing scratches.

In addition, the present invention aims to provide a functional building material for windows and doors that can reduce scratches due to friction due to surface characteristics having excellent smoothness.

In addition, the present invention aims to provide a functional building material for windows and doors having a surface layer with excellent chemical durability.

As a means to solve the above-described problem, the functional building material for windows and doors of the present invention includes a first uppermost protective layer containing metal zirconium and zirconium oxide; a second uppermost protective layer located on the first uppermost protective layer and containing carbon; It is characterized as a functional building material for windows and doors including a top protective layer.

More specifically, the functional building material for windows and doors according to an embodiment of the present invention includes a transparent base material; A low-emissivity coating comprising one or more layers located on top of the transparent substrate; and a top protective layer located on top of the low-emissivity coating, wherein the top protective layer includes a first top protective layer including metal zirconium and zirconium oxide; It is characterized as a functional building material for windows and doors including a second uppermost protective layer located on the first uppermost protective layer and containing carbon.

In addition, the functional building material for windows is characterized in that the hybridization ratio of sp ³ orbitals out of the total hybridization ratio of carbon hybrid orbitals is 40% or more.

In addition, the functional building material for windows is characterized in that the total ratio of -O (oxygen) bonding groups of carbon is 15% or less compared to the total bonding ratio of carbon.

In addition, in the functional building material for windows, the RMS surface roughness of the second top protective layer is 0.5 nm or less.

In addition, the functional building material for windows is characterized in that it does not include the second uppermost protective layer.

In addition, the functional building material for windows is characterized in that the maximum diameter of the surface pinhole is 20㎛ or less after an accelerated long-term storage performance test in which the material is left at a temperature of 50°C and a humidity of 90%RH for 3 weeks.

In addition, it is characterized in that it includes a dielectric layer located between the first uppermost protective layer and the second uppermost protective layer.

In addition, the thickness of the zirconium is 1 to 2 nm, and the thickness of the zirconium oxide film is 2 to 3 nm.

In addition, after exposure to an acidic solution of pH 2 for 5 minutes, the color change (△E) of the functional building material for windows is 1, with the transmission color change (color (T)) and the glass surface reflection color change (color (S)) being 1. It is characterized in that the coating surface reflection color change (color R) is less than 2.

In addition, the low-emissivity coating is characterized in that it includes at least one selected from a barrier layer, a blocking layer, and a dielectric layer.

When applied to building materials for windows and doors, the top protective layer of the present invention does not affect the optical performance of functional building materials for windows and doors after final processing, and therefore can be directly applied to the top protective layer of existing building materials for windows and doors. It works.

In particular, the unique Zr metal/Zr oxide layered structure of the present invention is very effective in securing not only physical and chemical durability, but also resistance to discoloration under harsh acidic or basic conditions.

In addition, even if scratches occur on a portion of the uppermost protective layer due to external impact during transportation or construction, the second uppermost protective layer reacts first during heat strengthening, thereby reducing natural oxidation of the first uppermost protective layer. This has the effect of improving the long-term storage performance of functional building materials for windows and preventing the expansion of scratches during heat strengthening.

In particular, the second top protective layer unique to the present invention has a low ratio of oxygen bonding groups and a high sp ³ hybrid bonding ratio, so it can have excellent physical durability as well as chemical durability.

Furthermore, the functional building material for windows and doors including the top protective layer of the present invention has the effect of reducing the frequency of scratches and defective rates and making it easy to transport and handle.

Figure 1 is a cross-sectional view showing (a) a scratch formed on the top protective layer of low-emissivity glass coated with a conventional top protective layer and (b) a case where the scratch on the top protective layer extends to the low-emissivity coating layer after heat strengthening. .
Figure 2 is a cross-sectional view of a functional building material for windows and doors according to an embodiment of the present invention.
Figure 3 is a cross-sectional view showing one embodiment of the top protective layer of the present invention.
Figure 4 is a cross-sectional view showing another embodiment of the top protective layer of the present invention.
Figure 5 shows (a) a case where a scratch is formed on the second top protective layer of the functional building material for windows and doors including the top protective layer of the present invention, and (b) the scratch is removed by removing the second top protective layer after heat strengthening. This is a cross-sectional view showing the case.
Figure 6 is a diagram showing the results of the long-term storage performance accelerated test of Example 1.
Figure 7 is a diagram showing the results of an accelerated long-term storage performance test of Comparative Example 1.
Figure 8 is a diagram showing the change in scratches before and after heat strengthening when scratches were reproduced on the second top protective layer of Example 1.
Figure 9 is a diagram showing the change in scratches before and after heat strengthening when scratches were reproduced on the uppermost protective layer of Comparative Example 1.
Figure 10 is a diagram showing the change in scratches before and after heat strengthening when scratches were reproduced on the first and second uppermost protective layers of Example 1.
Figure 11 is a diagram showing the change in scratches before and after heat strengthening when scratches were reproduced on the uppermost protective layer of Comparative Example 1.
Figure 12 (a) (left) is a graph of the Raman analysis results of sp hybridized orbitals and bonding groups of the second top protective layer of the conventional example, and (b) (right) is a graph of the second top protective layer of Example 1. This is a graph of the Raman analysis results analyzing the sp hybrid orbitals and bonding groups of the protective layer.
Figure 13 shows the results of measuring the surface roughness of the multilayer structure of Example 1 and Comparative Example 1 using an atomic force microscope (AFM).
Figure 14 shows the surface of the functional building material for windows and doors having a multi-layer structure of Example 2 observed after passing through the brush of a glass washer, which is a transparent transparent substrate.
Figure 15 shows the surface of the functional building material for windows and doors having a multilayer structure of Comparative Example 2 observed after passing through the brush of a glass washer, which is a transparent transparent substrate.
Figure 16 shows the surface of the functional building material for windows and doors having a multilayer structure of Example 2 observed after being exposed to 40°C and 90% RH (humidity) for 3 to 7 days.
Figure 17 shows the surface of the functional building material for windows and doors having a multilayer structure of Comparative Example 2 observed after being exposed to 40°C and 90% RH (humidity) for 3 to 7 days.
Figure 18 shows the color change (ΔE) measured after the functional building materials for windows and doors having a multilayer structure of Example 2 and Comparative Example 2 were each exposed to an acidic solution of pH 2 for 5 minutes.
Figure 19 shows the color change (ΔE) measured after the functional building materials for windows and doors having a multilayer structure of Example 2 and Comparative Example 2 were exposed to a basic solution of pH 12 for 5 minutes.

The above-mentioned objects, features, and advantages will be described in detail later with reference to the attached drawings, so that those skilled in the art will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the attached drawings. In the drawings, identical reference numerals are used to indicate identical or similar components.

Hereinafter, the “top (or bottom)” of a component or the arrangement of any component on the “top (or bottom)” of a component means that any component is placed in contact with the top (or bottom) of the component. Additionally, it may mean that other components may be interposed between the component and any component disposed on (or under) the component.

Additionally, when a component is described as being “connected,” “coupled,” or “connected” to another component, the components may be directly connected or connected to each other, but the other component is “interposed” between each component. It should be understood that “or, each component may be “connected,” “combined,” or “connected” through other components.

Hereinafter, the functional building material for windows and doors of the present invention will be described in detail with reference to the drawings.

Referring to FIG. 2, the functional building material for windows and doors according to an embodiment of the present invention includes a transparent substrate 10, a low-emissivity coating 20 including one or more layers on top of the transparent substrate 10, and the low-emission coating 20. An uppermost protective layer 100 may be included on top of the radiation coating 20.

As shown in FIG. 3, in one embodiment of the present invention, the top protective layer 100 may sequentially include a first top protective layer 30 and a second top protective layer 40.

The first uppermost protective layer 30 may include zirconium, a metal.

In another embodiment of the present invention, the first top protective layer 30 may further include zirconium oxide. The zirconium oxide is formed on top of the zirconium.

At this time, the zirconium oxide may be produced through a separate additional process, or may be formed by oxidation of the zirconium in a natural state. In particular, since zirconium is a metal, natural oxidation may occur due to exposure to air. When the zirconium is oxidized to form zirconium oxide on top of the zirconium, the uppermost protective layer 200 forms a structure in which the first uppermost protective layer 30 is divided into a layer containing zirconium and a layer containing zirconium oxide. do. At this time, the second uppermost protective layer 40 has a structure stacked on top of a layer containing zirconium oxide. Hereinafter, the layer containing zirconium will be referred to as 'metal protective layer 31', and the layer containing zirconium oxide will be referred to as 'ceramic protective layer 32'. This is the same as Figure 4.

The metal protective layer 31 containing zirconium, a metal, plays a role in improving the chemical durability of the lower low-emission coating layer and functional building materials for windows and doors due to the excellent moisture permeability and moisture-resistant properties of the metal zirconium. do. Accordingly, the metal protective layer 31 can improve the durability and long-term storage performance of functional building materials for windows and doors.

Since the chemical durability of the uppermost protective layer can be improved only when the metal zirconium, which is a component of the metal protective layer 31, is not completely oxidized and remains in a metallic state, it is preferable that the metal zirconium is not completely (or completely) oxidized in the thickness direction. do. At this time, the thickness of the metal protective layer 31 may be about 1 to 2 nm.

Meanwhile, the ceramic protective layer 32 located on the metal protective layer 31 is a layer that can be formed by natural oxidation of zirconium due to exposure of the metal protective layer 31 to air, and has a thickness of about 2 to 3 nm. is formed The ceramic protective layer 32 formed by the oxidation of zirconium is not only the uppermost protective layer but also the lower part due to the high resistance to plastic deformation inherent in the ceramic, high hardness, and an increase in thickness when forming ceramic zirconium oxide from metal zirconium. It can improve the physical durability of the laminated structure and thereby improve scratch resistance.

At this time, the first uppermost protective layer 30 preferably has a thickness of about 3 to 5 nm. If the thickness of the first uppermost protective layer is less than 3 nm, a thin film cannot be formed, so the improvement in physical or chemical durability may be small, and if it is more than 5 nm, the absorption rate increases, thereby increasing the transmittance of the final product, a functional building material for windows. Managing reflectance or color can become difficult.

The second top protective layer 40 may include carbon. The carbon can be obtained through a physical vapor deposition process such as sputtering using a graphite material as a target.

At this time, the deposited carbon may have a mixed form of sp ² and sp ³ hybrid orbitals. In general, carbon is known to be a thermodynamically stable phase of graphite, which has a two-dimensional structure with sp ² hybrid orbitals. Meanwhile, diamond with a three-dimensional structure having sp ³ hybrid orbitals is not a thermodynamically stable phase compared to graphite. Unlike the above thermodynamic stability, diamond has higher hardness than graphite, so diamond has better mechanical properties than graphite.

Therefore, controlling the hybridization ratio of carbon, which is a component of the second uppermost protective layer 40, is important in controlling the properties of the second uppermost protective layer 40. In particular, it is very important to increase the ratio of sp ³ hybrid orbitals of carbon in the second uppermost protective layer 40. At this time, the hybridization ratio can be characterized or quantified by Raman analysis.

The second top protective layer 40 is located on the top of the first top protective layer 30, so it not only has the function of improving the scratch resistance of the functional building material for windows and doors, but also reduces the subsequent heat performed during construction of the functional building material for windows and doors. During hardening, it serves to reduce excessive natural oxidation, especially thermal oxidation, of zirconium included in the first upper protective layer, especially the metal protective layer 31. In particular, when the ceramic protective layer 32 is formed on the first uppermost protective layer 30, physical durability increases, but excessive formation of the ceramic protective layer 32 causes excessive loss of the metal protective layer 31 located below it. As chemical durability decreases, the second top protective layer 40 can reduce the decrease in chemical durability of the first top protective layer 30.

The second top protective layer 40 in the functional building material for windows and doors of the present invention can strengthen the multi-layer low-emissivity coating coated on the transparent substrate through heat treatment.

When an impact from an external force is applied to a functional building material for windows, the second uppermost protective layer 40 is located at the outermost layer of the uppermost protective layer 100, so scratches caused by the external force mainly occur on the second uppermost protective layer. It occurs at (40) (Figure 5(a)). However, scratches formed on the second top protective layer 40 can be removed during heat strengthening.

Specifically, if a scratch occurs on the second uppermost protective layer 40, which is the surface of the uppermost protective layer 100 of the present invention, the second uppermost protective layer is protected in the heat strengthening step of the post-treatment process of the functional building material for windows. Since the layer 40 is mainly composed of carbon, it can be removed by heat in the heat strengthening step. In other words, the second top protective layer 40 of the functional building material for windows is completely burned after heat strengthening. As a result, the scratches contained in the second uppermost protective layer 40 are removed simultaneously with the second uppermost protective layer 40, so that only the scratch-free first upper protective layer 30 is ultimately exposed on the outermost layer. It will happen.

Even if a scratch occurs beyond the thickness of the second top protective layer 40 and extends to the first top protective layer 30, the degree of expansion due to oxidation of the scratch after heat strengthening due to the presence of the second top protective layer 40 has the effect of improving.

If a scratch passes through the second top protective layer 40 due to a strong external force, a scratch may also occur in the first top protective layer 30.

In this case, if heat strengthening is not performed, scratches generated on the first uppermost protective layer 30 remain as is. However, when thermal strengthening is performed, as oxidation progresses around the scratched portion of the first uppermost protective layer 30, the scratch expands to the side to the extent that it can be easily observed with the naked eye.

However, if a second top protective layer 40 is present on the first top protective layer 30, during the thermal strengthening process, the carbon in the second top protective layer is oxidized to CO2 and vaporized while the first top protective layer 40 is present on the first top protective layer 30. Oxidation of the layer 30 is relatively suppressed. As a result, oxidation of scratches occurring on the first uppermost protective layer 30 is reduced, and ultimately, the expansion of scratches present on the first uppermost protective layer 30 can be suppressed.

On the other hand, if the second top protective layer 40 is not present on the first top protective layer 30, oxidation of the first top protective layer 30 cannot be suppressed during the heat strengthening process. As a result, expansion of scratches occurring on the first uppermost protective layer 30 becomes unavoidable.

The thickness of the second top protective layer is 1 to 5 nm.

If the thickness of the second top protective layer is thicker than 5 nm, light absorption by the second top protective layer may cause a change in transmittance of the functional building material for windows, which is not desirable.

On the other hand, when the thickness of the second top protective layer is thinner than 1 nm, there is a problem in that the thickness of the second top protective layer is too thin and is not effective in protecting the lower first top protective layer.

Meanwhile, the second top protective layer can be completely removed after the subsequent heat strengthening process, so it does not affect the optical properties of the low-emissivity coating layered structure.

According to another embodiment of the present invention, a dielectric layer may be additionally positioned between the first top protective layer 30 and the second top protective layer 40. Si ₃ N ₄ :Al may be used as a non-limiting and specific example of the dielectric layer.

However, it is not desirable for the dielectric layer to be located directly on the low-emissivity coating 20, which will be described later, without the first top protective layer 30. This is because the dielectric layer may also be included in the stacked structure of the low-emission coating 20, so not only is it substantially the same as simply overlapping the same dielectric layer, but also the arrangement of the dielectric layer alone is not effective in protecting the lower layer or lower structure. . However, when the dielectric layer is located on the first top protective layer 30, the dielectric layer acts synergistically with the physical and chemical resistance of the underlying first top protective layer 30 to resist external substances such as acids and/or bases. It can be very effective in protecting the lower low-emissivity coating 20 structure from contamination.

In the functional building material for windows and doors of the present invention, the transparent substrate 10 may be a transparent substrate with high visible light transmittance. As a non-limiting and specific example, the transparent substrate 10 may be a glass or transparent plastic substrate having a visible light transmittance of about 80% to about 100%. More preferably, it may be glass. The glass may be any glass used for construction without limitation, for example, may have a thickness of about 2 mm to about 12 mm, and may vary depending on the purpose and function of use, but is not limited thereto.

The functional building material for windows and doors of the present invention has a low-emissivity coating (20) coated on the top of the transparent substrate (10), and the top protective layer (100) is deposited on the top of the low-emission coating (20) to play a protective role. do.

The low-emissivity coating 20 may have a multilayer thin film structure. The low-emissivity coating 20 may be any suitable optical laminated structure and is not particularly limited. The low-emissivity coating 20 preferably comprises at least one silver layer, at least one barrier layer to protect the silver layer, optionally at least one barrier layer to protect the silver layer from oxidation during heat treatment, a dielectric layer, etc. It may include one or more of the selected items. The layers within the structure of the low-emissivity coating 20 may be arranged or changed in various ways to improve or modify optical properties.

The low-emissivity coating structure may be repeated one or more times on the transparent substrate. Other layers may also be provided above or below the aforementioned layers. Meanwhile, other layers may be provided in between. Other layers may be added in another embodiment, and certain layers may be removed in another embodiment without departing from the purpose of the present invention.

Preferably, the low-emissivity coating 20 may include one or more layers of NiCr, Ag, ZnOx, TiOx, and SiAlNx.

The top protective layer 100 does not affect changes in reflectance and transmittance of functional building materials for windows and doors, and protects the low-emissivity coated transparent substrate without seriously affecting optical properties such as transmission or reflection, and prevents scratches. It acts as a protective layer that substantially reduces.

The present invention is explained in more detail by examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

Example 1

A multi-layer low-emissivity coating is formed on a transparent glass substrate using a magnetron sputtering evaporator. A first uppermost protective layer is formed by depositing 3 to 5 nm of zirconium on top of the low-emissivity coating. The zirconium is partially oxidized in the air to form a first uppermost protective layer together with zirconium. Sp hybrid orbital carbon is deposited on the first top protective layer to form a second top protective layer with a thickness of 1 to 5 nm. At this time, the second uppermost protective layer uses graphite as a target, and the ratio of various bonds of carbon and oxygen is controlled through process control such as vacuum degree, substrate temperature, pressure, power including acceleration voltage, and gas purity. The ratio of sp ³ hybridized orbitals within sp hybridized orbitals was controlled.

Comparative Example 1

A multi-layer low-emissivity coating is formed on a transparent glass substrate using a magnetron sputtering evaporator. 3 to 5 nm of zirconium is deposited on top of the low-emissivity coating. The zirconium is partially oxidized in the air and forms an uppermost protective layer together with zirconium.

Experiment example

(1) Accelerated long-term storage performance test

Figures 6 and 7 show the multilayer structures of Example 1 (when the second top protective layer is present) and Comparative Example 1 (when the second top protective layer is not present), respectively, at a temperature of 50°C and a humidity of 90%RH. After being left for 3 weeks, the pinhole (corrosion) tendency of the surface was observed using an optical microscope.

Example 1 was confirmed to be a fine pinhole that cannot be observed with the naked eye as shown in Figure 6, that is, the size of the pinhole was not observed with the naked eye (maximum diameter of 20㎛ or less), and chemical durability was improved. You can check it.

On the other hand, in Comparative Example 1, as shown in FIG. 7, a very large pinhole was observed with the naked eye, that is, it was confirmed to be a coarse pinhole (corrosion) clearly visible to the naked eye, and the chemical durability was low and the possibility of defects was high. You can check it.

(2) Scratch expansion test by heat strengthening (shallow scratch)

Figure 8 shows scratches only on the second top protective layer of Example 1, and Figure 9 shows scratches on the top protective layer (corresponding to the first top protective layer) of Comparative Example 1, respectively. Scratch changes were observed after heat strengthening at ℃ or higher.

As shown in Figure 8, in Example 1, it was observed that scratches formed on the second uppermost protective layer disappeared after heat strengthening.

On the other hand, as shown in FIG. 9, in Comparative Example 1, it was observed that the scratches formed on the uppermost protective layer increased in width after heat strengthening and expanded to the point where they were visible to the naked eye.

(3) Scratch expansion test by heat strengthening (deep scratch)

Figure 10 shows the scratch changes in the first and second top protective layers of Example 1 with forces of 1.0 N and 3.0 N, respectively, and observed after heat strengthening at about 650° C. or higher.

On the other hand, Figure 11 shows scratch changes on the top protective layer (first top protective layer) of Comparative Example 1 with forces of 1.0N and 3.0N, respectively, and then observing changes in the scratch after heat strengthening at about 650°C or higher.

In Example 1, as shown in FIG. 10, it was observed that the degree of expansion of scratches formed across the first top protective layer and the second top protective layer was improved compared to Comparative Example 1 after heat strengthening. This is because, as described above, the expansion of scratches formed on the first top protective layer due to oxidation is suppressed due to the presence of the second top protective layer.

On the other hand, in Comparative Example 1, as shown in FIG. 11, it was observed that the scratches formed on the uppermost protective layer increased in width after heat strengthening and expanded to the point where they were visible to the naked eye.

(4) Hybridization orbital ratio measurement test

The hybridization ratio of carbon hybrid orbitals included in the second top protective layer of Example 1 was measured using Raman analysis. Meanwhile, the bonding of carbon contained in the second uppermost protective layer obtained through process control such as vacuum degree, substrate temperature, pressure, power including acceleration voltage, and gas purity is shown in Table 1 and Figure 12 below. Meanwhile, the experimental example indicated as a conventional example in Table 1 and FIG. 12(a) (left) is the measurement result of carbon bonding manufactured through commonly known process conditions.

[Table 1]

Through the above analysis, it can be confirmed that the carbon in the second uppermost protective layer of the present invention is a mixture of sp2 and sp3 orbitals and has a high sp2 orbital ratio. It can be seen from Table 1 above that in Example 1, compared to the conventional example, the hybridization ratio of sp3 orbitals is relatively high, and further, the ratio of -O (oxygen) bonding groups is relatively low.

First, a low ratio of -O (oxygen) bonding groups may mean that the carbon in the second top protective layer is chemically durable. Furthermore, the higher the hybridization ratio of sp3 orbitals, the higher the proportion of physically stable diamond bonds. In particular, in the case of Example 1, the hybridization ratio of sp3 orbitals is more than 90% compared to the hybridization ratio of sp2 orbitals, and the hybridization ratio of sp3 orbitals among the total hybridization ratios of carbon orbitals is as high as 40% or more. This means that the physical durability is very excellent. In addition, in Example 1 of the present invention, the total ratio of -O (oxygen) bonding groups, which means bonding with relatively highly active oxygen, was measured to be 13% or less compared to the total bonding ratio of carbon. This means that the chemical durability is also very excellent.

As a result, the Raman spectrum analysis results in Table 1 and Figure 12 mean that the carbon in the second top protective layer of Example 1 has very excellent physical and chemical durability.

(5) Surface roughness measurement test

Table 2 and Figure 13 below show the results of measuring the surface roughness of the multilayer structure of Example 1 and Comparative Example 1 using an atomic force microscope (AFM).

[Table 2]

The average surface roughness value of Example 1 compared to Comparative Example 1 of the present invention was improved by about 18%. The improved surface roughness as described above can contribute to improving not only the scratch resistance but also the dent resistance against external impact of the functional building material for windows and doors of the present invention.

Meanwhile, in order to evaluate the chemical and physical durability of the first top protective layer 30 of the present invention, the following Example 2 and Comparative Example 2 were manufactured and then evaluated.

Example 2

A multi-layer low-emissivity coating is first formed on a transparent glass substrate through a reactive sputtering evaporator or chemical vapor deposition. A dielectric layer of SiAlNx composition is formed on top of the multi-layer low-emissivity coating. A first uppermost protective layer is formed by depositing 3 to 5 nm of zirconium on top of the dielectric layer. The zirconium is partially oxidized in the air to form a first uppermost protective layer together with zirconium.

Comparative Example 2

A multi-layer low-emissivity coating is formed on a transparent glass substrate using a magnetron sputtering evaporator. A dielectric layer of Si ₃ N ₄ :Al composition is formed on top of the multi-layer low-emissivity coating.

Experiment example

(6) Physical/chemical durability evaluation

Figures 14 and 15 show the surfaces of the functional building materials for windows and doors having a multi-layer structure of Example 2 and Comparative Example 2, respectively, after passing through the brush of a glass washer, which is a transparent transparent substrate.

As clearly shown in FIGS. 14 and 15, a relatively small number of scratches were observed on the surface of Example 2, where the top layer had a Zr/ZrO structure, while Comparative Example 2, where the top layer had a dielectric layer, had scratches on the surface. A relatively large number of scratches were observed.

Figures 16 and 17 show the surfaces of the functional building materials for windows and doors having the multilayer structure of Example 2 and Comparative Example 2, respectively, after exposure to 40°C and 90% RH (humidity) for 3 to 7 days.

As clearly shown in FIG. 16, Example 2, in which the uppermost layer has a Zr/ZrO structure, showed a tendency for the number of corrosion points on the surface to increase as the exposure time increased, but showed corrosion for 3 days. Upon exposure, it had good chemical durability at approximately 20, and showed excellent durability at less than 60 even after long-term exposure for 7 days.

On the other hand, in Comparative Example 2, where the uppermost layer has a dielectric layer, more than 200 corrosion points were observed even after exposure for 3 days, which is a relatively short exposure time, as clearly shown in FIG. 17, and after long-term exposure for 7 days, the corrosion points created Growth was also observed with the naked eye.

The experimental results of FIGS. 14 to 17 directly demonstrate that Example 2, in which the uppermost layer has a Zr/ZrO structure, has excellent physical and chemical durability, and at the same time, the Zr/ZrO laminated structure demonstrates the durability of functional building materials for windows and doors. This can be said to directly prove that it is a very effective layered structure for improvement.

(7) Acid/base resistance evaluation

Figures 18 and 19 measure the color change (ΔE) after the functional building materials for windows and doors having the multilayer structure of Example 2 and Comparative Example 2 were exposed to acidic and basic solutions of pH 2 and pH 12 for 5 minutes, respectively. This is one result. In particular, the △E value is the degree of change in the L, a, and b values in the color coordinate system and is a representative indicator of the degree of discoloration.

In particular, as shown in FIG. 18, Comparative Example 2, in which the uppermost layer has a dielectric layer, has a transmission color change (color (T)) and a glass surface reflection color change (color (S)) of 1 or more, and a coating surface reflection color change (color). R) had a discoloration of 2 or more, while Example 2, in which the uppermost layer had a Zr/ZrO structure, had a transmission color change (color (T)) and a glass surface reflection color change (color (S)) of less than 1, and a coating surface reflection. It was confirmed that the color change (color R) had very excellent discoloration characteristics of less than 2.

1, 10: Transparent substrate
2, 20: low-emissivity coating
3: Top protective layer
30: first top protective layer
31: Metal protective layer
32: Ceramic protective layer
40: second top protective layer
100, 200: Top protective layer

Claims (11)

transparent substrate;
A low-emissivity coating comprising one or more layers located on top of the transparent substrate; and
It includes a top protective layer located on top of the low-emissivity coating,
The top protective layer includes a first top protective layer including metal zirconium and zirconium oxide;
A second top protective layer located on the first top protective layer and containing carbon,
It includes a dielectric layer located between the first top protective layer and the second top protective layer,
The second top protective layer is a functional building material for windows and doors that is burned in the heat strengthening step.
According to claim 1,
A functional building material for windows and doors in which the hybridization ratio of sp ³ orbitals is 40% or more among the total hybridization ratio of carbon hybridization orbitals.
According to claim 1,
A functional building material for windows and doors in which the total ratio of -O (oxygen) bonding groups to carbon is 15% or less compared to the total bonding ratio of carbon.
According to claim 1,
A functional building material for windows wherein the second top protective layer has an RMS surface roughness of 0.5 nm or less.
delete According to claim 1,
The functional building material for windows has a maximum surface pinhole diameter of 20㎛ or less after an accelerated long-term storage performance test in which the functional building material for windows is left at a temperature of 50℃ and a humidity of 90%RH for 3 weeks.
delete According to claim 1,
A functional building material for windows wherein the second top protective layer has a thickness of 1 to 5 nm.
According to claim 1,
A functional building material for windows wherein the zirconium has a thickness of 1 to 2 nm, and the zirconium oxide film has a thickness of 2 to 3 nm.
According to claim 1,
After exposure to an acidic solution of pH 2 for 5 minutes, the color change (△E) of the functional building material for windows is less than 1, with the transmission color change (color (T)) and the glass surface reflection color change (color (S)) being less than 1, A functional building material for windows with a coating surface reflection color change (color R) of less than 2.
According to claim 1,
The low-emission coating is a functional building material for windows and doors including at least one selected from a barrier layer, a blocking layer, and a dielectric layer.

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