KR20210077639A - A functional building material for windows - Google Patents

Abstract

The present invention relates to a functional building material for windows, comprising: a transparent substrate; a low-emissivity coating comprising one or more layers positioned on top of the transparent substrate; and an uppermost protective layer positioned on the low-emissivity coating. The uppermost protective layer includes: a first uppermost protective layer comprising metal zirconium and zirconium oxide; and a second uppermost protective layer disposed on the first uppermost protective layer and comprising carbon. The functional building material for windows according to the present invention has excellent durability against physical and chemical attacks from the outside.

Description

Functional building materials for windows and doors {A FUNCTIONAL BUILDING MATERIAL FOR WINDOWS}

The present invention relates to a functional building material for windows and doors comprising an uppermost protective layer.

Low-emissivity glass refers to a glass in which a low-emissivity layer including a metal having 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 region to block outdoor solar radiation in summer and preserves indoor heating radiation in winter to save energy in buildings.

Silver (Ag), which is generally used as a low-emission layer, is oxidized when exposed to air, so a low-emissivity coating in which a metal and/or dielectric layer is deposited as an anti-oxidation film on the upper and lower portions of the low-emissivity layer is deposited on the glass. . Such a dielectric layer also serves to increase visible light transmittance.

However, when the low-emissivity coating comes into contact with corrosive agents such as oxygen, chloride, sulfide, sulfur dioxide, etc. in the atmosphere in a high temperature and high humidity environment, corrosion of the silver (Ag) layer occurs and is damaged. In addition, the low-emission coating is vulnerable to external impact, and damage to the coating due to scratching occurs frequently even during transportation or handling. In particular, in the case of a building material with a heavy load such as glass, scratches occur more frequently during transportation and handling due to the heavy load.

In order to solve the problem of such damage, in the prior art, low-emission by coating the uppermost protective layer 3 comprising a metal, etc. on the conventional transparent substrate 1 and the low-emission coating 2 as shown in Fig. 1 (a). The primary protection against the coating has been provided.

However, in the case of a scratch caused by an external force on the uppermost protective layer 3 in the prior art (FIG. 1(a)), scratches generated on the uppermost protective layer 3 as shown in FIG. 1(b) when performing thermal strengthening is further expanded and there is a problem of damaging the low-emissivity coating (2) part of the lower part.

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

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

Another object of the present invention is to provide a functional building material for windows and doors that can minimize the natural oxidation of the lower metal layer.

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

Another object of the present invention is to provide a functional building material for windows and doors that can reduce scratches due to friction due to surface properties having excellent smoothness.

Another object of the present invention is to provide a functional building material for windows and doors having a surface layer having excellent chemical durability.

As a means for solving the above problems, the functional building material for windows and doors of the present invention includes a first uppermost protective layer comprising metal zirconium and zirconium oxide; a second uppermost protective layer positioned on the first uppermost protective layer and comprising carbon It is characterized in that it is a functional building material for windows and doors including; the uppermost protective layer.

More specifically, a functional building material for windows and doors according to an embodiment of the present invention includes a transparent substrate; a low-emissivity coating comprising one or more layers positioned on top of the transparent substrate; and an uppermost protective layer positioned on the low-emissivity coating, wherein the uppermost protective layer includes: a first uppermost protective layer comprising metal zirconium and zirconium oxide; It is characterized in that it is 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, in the functional building material for windows and doors, the hybridization ratio of sp ³ orbitals among the total hybridization ratio of hybrid orbitals of carbon is 40% or more.

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

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

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

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

Further, it is characterized by comprising a dielectric layer positioned between the first uppermost protective layer and the second uppermost protective layer.

In addition, the thickness of the zirconium is 1 to 2 nm, it is characterized in that the thickness of the zirconium oxide film is 2 to 3 nm.

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

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

The uppermost protective layer of the present invention does not affect the optical performance of functional building materials for windows and doors after final processing when applied to building materials for windows and doors, and thus can be directly applied to the uppermost 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 physical and chemical durability as well as resistance to discoloration in severe acidic or basic conditions.

In addition, even if a part of the uppermost protective layer is scratched due to an external impact during transport or construction, the second uppermost protective layer reacts first during thermal strengthening, thereby reducing the natural oxidation of the first uppermost protective layer. Accordingly, it is possible to improve the long-term storage performance of functional building materials for windows and doors, and to prevent scratches from expanding when heat is strengthened.

In particular, the second uppermost protective layer unique to the present invention has a low ratio of oxygen bonding groups and a high sp ³ hybrid bonding ratio at the same time, so that not only physical durability but also chemical durability can be very excellent.

Furthermore, the functional building material for windows and doors including the uppermost protective layer of the present invention has the effect of reducing the frequency of occurrence of scratches and the defect rate, and facilitating transport and handling.

1 is a cross-sectional view showing (a) a case in which a scratch is formed on the uppermost protective layer of a conventional low-emissivity glass coated with the uppermost protective layer and (b) a case in which the scratch of the uppermost protective layer is extended to the low-emissivity coating layer after thermal strengthening. .
2 is a cross-sectional view of a functional building material for windows and doors according to an embodiment of the present invention.
3 is a cross-sectional view showing an embodiment of the uppermost protective layer of the present invention.
4 is a cross-sectional view showing another embodiment of the uppermost protective layer of the present invention.
Figure 5 shows (a) when scratches are formed on the second uppermost protective layer of the functional building material for windows and doors including the uppermost protective layer of the present invention and (b) scratches are removed by removing the second uppermost protective layer after heat strengthening; A cross-sectional view showing the case.
6 is a view showing the results of performing the long-term storage performance acceleration test of Example 1.
7 is a view showing the results of performing a long-term storage performance acceleration test of Comparative Example 1.
8 is a view showing a change in the scratch before and after thermal strengthening when the scratch on the second uppermost protective layer of Example 1 is reproduced.
9 is a view showing a change in the scratch before and after thermal strengthening when the scratch on the uppermost protective layer of Comparative Example 1 is reproduced.
10 is a view showing a change in scratches before and after thermal strengthening when the scratches on the first and second uppermost protective layers of Example 1 are reproduced.
11 is a view showing a change in the scratch before and after thermal strengthening when the scratch on the uppermost protective layer of Comparative Example 1 is reproduced.
12 (a) (left) is a graph of the Raman analysis result of analyzing sp hybrid orbitals and bonding groups of the second uppermost protective layer of the prior art, (b) (right) is the second uppermost part of Example 1 It is a graph of the Raman analysis result of analyzing the sp hybrid orbital and bonding group of the protective layer.
13 is a result of measuring the surface roughness of the multilayer structures of Example 1 and Comparative Example 1 using an atomic force microscope (AFM).
14 is a surface observed after the functional building material for windows having a multi-layer structure of Example 2 passes through the brush of a glass cleaner, which is a transparent transparent substrate.
15 is a surface observed after the functional building material for windows having a multi-layer structure of Comparative Example 2 passes through the brush of a glass cleaner, which is a transparent transparent substrate.
16 is a surface observed after exposure of the functional building material for windows and doors having a multilayer structure of Example 2 at 40° C. and 90% RH (humidity) for 3 to 7 days.
17 is a surface observed after exposure of the functional building material for windows and doors having a multilayer structure of Comparative Example 2 at 40° C. and 90% RH (humidity) for 3 to 7 days.
18 shows the color change (ΔE) measured after exposure of the functional building materials for windows and doors having a multilayer structure of Example 2 and Comparative Example 2 to an acidic solution of pH 2 for 5 minutes, respectively.
19 shows the color change (ΔE) measured after exposure of the functional building materials for windows and doors having a multilayer structure of Example 2 and Comparative Example 2 to a basic solution of pH 12 for 5 minutes, respectively.

The above-described objects, features and advantages will be described below in detail with reference to the accompanying drawings, and accordingly, those of ordinary skill in the art to which the present invention pertains 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 a known technology 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 accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

In the following, that an arbitrary component is disposed on the "upper (or lower)" of a component or "upper (or below)" of a component means that any component is disposed in contact with the upper surface (or lower surface) of the component. Furthermore, it may mean that other components may be interposed between the component and any component disposed on (or under) the component.

Also, when it is described that a component is "connected", "coupled" or "connected" to another component, the components may be directly connected or connected to each other, but other components are "interposed" between each component. It is to be understood that “or, each component may be “connected,” “coupled,” or “connected” through another component.

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

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

3 , in an embodiment of the present invention, the uppermost protective layer 100 may include a first uppermost protective layer 30 and a second uppermost protective layer 40 sequentially.

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

In another embodiment of the present invention, the first uppermost 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 generated by a separate additional process, or may be formed by oxidizing the zirconium in a natural state. In particular, since the 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 zirconium, the uppermost protective layer 200 forms a structure in which the first uppermost protective layer 30 is separated 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 the layer including zirconium oxide. Hereinafter, the layer including zirconium will be referred to as a 'metal protective layer 31', and the layer including zirconium oxide will be referred to as a 'ceramic protective layer 32'. This is the same as in FIG. 4 .

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

In the metal protective layer 31, since the metal zirconium, which is a component, is not completely oxidized and remains in a metallic state, the chemical durability of the uppermost protective layer can be improved, so it is preferable that the metal zirconium is not completely (or completely) oxidized in the thickness direction. Do. In this case, the thickness of the metal protective layer 31 may be about 1 to 2 nm.

Meanwhile, the ceramic protective layer 32 positioned on the metal protective layer 31 is a layer that can be formed by natural oxidation of zirconium due to air exposure of the metal protective layer 31, and has a thickness of about 2 to 3 nm. is formed The ceramic protective layer 32 formed due to the oxidation of zirconium has a high resistance to plastic deformation inherent in the ceramic, high hardness, and an increase in thickness when forming a ceramic zirconium oxide from metal zirconium. It is possible to improve the physical durability of the laminated structure, thereby improving the scratch resistance.

At this time, it is preferable that the first uppermost protective layer 30 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 may not be formed, so the improvement of physical or chemical durability may be small, and if it exceeds 5 nm, the transmittance of the functional building material for windows and doors as a final product due to an increase in absorption. Management of reflectivity or color can be difficult.

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

In this case, the deposited carbon may have a mixed form ^{of sp 2} and sp ^{3 hybrid orbital.} In general, carbon is known as a thermodynamically stable phase of two-dimensional graphite ^{having a sp 2 hybrid orbital (graphite).} Meanwhile ^{, diamond having a three-dimensional structure having sp 3} hybrid orbitals is not a thermodynamically stable phase compared to graphite. Unlike the thermodynamic stability described above, since diamond has a higher hardness than graphite, diamond has superior mechanical properties than graphite.

Therefore, control of the hybridization ratio of carbon, which is a component constituting 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 sp 3} hybrid orbital ratio of carbon in the second uppermost protective layer 40 . In this case, the hybridization ratio may be characterized or quantified by Raman analysis.

The second uppermost protective layer 40 is located on top of the first uppermost protective layer 30, so that not only the function of improving the scratch resistance of the functional building material for windows and doors, but also the subsequent heat performed during the construction of the functional building material for windows and doors It serves to reduce excessive natural oxidation, particularly thermal oxidation, of zirconium included in the first uppermost protective layer, in particular, the metal protective layer 31 during the curing process. In particular, when the ceramic protective layer 32 is formed on the first uppermost protective layer 30 , physical durability is increased, but excessive formation of the ceramic protective layer 32 is caused by excessive loss of the metal protective layer 31 located thereunder. Since the chemical durability is lowered, the second uppermost protective layer 40 may reduce the deterioration of the chemical durability of the first uppermost protective layer 30 .

The second uppermost protective layer 40 in the functional building material for windows and doors of the present invention may strengthen the low-emission coating of the multilayer structure coated on the transparent substrate through heat treatment.

When an impact by an external force is applied to the functional building material for windows and doors, the second uppermost protective layer 40 is located at the outermost portion of the uppermost protective layer 100 , so the scratch by the external force is mainly caused by the second uppermost protective layer (40) (Fig. 5(a)). However, scratches formed on the second uppermost protective layer 40 may be removed during thermal 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 protection in the thermal strengthening step, which is the post-treatment process of the functional building material for windows and doors Since the layer 40 is mainly made of carbon, it can be removed by heat in the thermal strengthening step. In other words, in the functional building material for windows and doors, the second uppermost protective layer 40 is completely burned after heat strengthening. As a result, scratches included in the second uppermost protective layer 40 are also removed together with the second uppermost protective layer 40, so that only the first uppermost protective layer 30 without scratches is finally exposed to the outermost layer. will become

Even if a scratch occurs to the first uppermost protective layer 30 beyond the thickness of the second uppermost protective layer 40, the degree of expansion due to oxidation of the scratch after thermal strengthening due to the presence of the second uppermost protective layer 40 has an improvement effect.

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

In this case, if thermal strengthening is not performed, scratches generated on the first uppermost protective layer 30 remain as they are. However, when thermal strengthening is performed, as oxidation proceeds around the scratch portion generated in the first uppermost protective layer 30, the scratch is laterally expanded to the extent that it can be easily observed with the naked eye.

However, if the second uppermost protective layer 40 is present on the first uppermost protective layer 30, the first uppermost protective layer is vaporized while carbon of the second uppermost protective layer is oxidized to CO2 during the thermal strengthening process. Oxidation of the layer 30 is relatively suppressed. As a result, oxidation of the scratch generated in the first uppermost protective layer 30 is reduced, and thus the expansion of the scratch existing in the first uppermost protective layer 30 may be finally suppressed.

On the other hand, when the second uppermost protective layer 40 does not exist on the first uppermost protective layer 30 , oxidation of the first uppermost protective layer 30 cannot be suppressed during the thermal strengthening process. As a result, the expansion of the scratch generated on the first uppermost protective layer 30 is unavoidable.

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

When the thickness of the second uppermost protective layer is thicker than 5 nm, it is not preferable because the light absorption of the second uppermost protective layer may cause a change in transmittance of the functional building material for windows and doors.

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

Meanwhile, since the second uppermost protective layer may be all removed after a subsequent thermal strengthening process, the optical properties of the low-emission coating laminate structure are not affected.

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

However, without the first uppermost protective layer 30 , in other words, it is not preferable that the dielectric layer be located directly on the low-emission coating 20 , which will be described later. This is because, in the laminated structure of the low-emissivity coating 20, the dielectric layer may also be included, so that the same dielectric layer is substantially the same as simply overlapping, and disposition of the dielectric layer alone is not effective in protecting the underlying layer or the underlying structure. . However, when the dielectric layer is positioned on the first uppermost protective layer 30 , the dielectric layer synergizes with the physical and chemical resistance of the lower first uppermost protective layer 30 to cause external such as acid and/or base. It can be very effective in protecting the structure of the lower low-emission coating 20 from contamination of the.

In the functional building material for windows and doors of the present invention, the transparent substrate 10 may be a transparent substrate having 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. As the glass, glass used for construction may be used 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 is coated with a low-emission coating 20 on the upper portion of the transparent substrate 10, and the uppermost protective layer 100 is deposited on top of the low-emission coating 20 to play a protective role do.

The low-emissivity coating 20 may have a multi-layered thin film structure. The low-emissivity coating 20 may be of any suitable optical laminate structure and is not particularly limited. The low-emissivity coating 20 is preferably 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 thermal treatment, a dielectric layer, etc. It may include any one or more selected. The layers in the structure of the low-emission coating 20 may be variously arranged or modified 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. In another embodiment, other layers may be added, and in another embodiment, certain layers may be removed 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 uppermost protective layer 100 protects the low-emission coated transparent substrate without affecting the reflectance and transmittance change of the functional building material for windows and doors, and without seriously affecting the optical properties such as transmission or reflection, and scratch Acts as a protective layer that substantially reduces the

The present invention will be described in more detail by way of examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited by the following examples.

Example 1

A low-emission coating of a multi-layer structure 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 the low-emission coating. The zirconium is partially oxidized in air to form a first uppermost protective layer together with the zirconium. A second uppermost passivation layer having a thickness of 1 to 5 nm is formed by depositing sp hybrid orbital carbon on the first uppermost passivation layer. At this time, the second uppermost protective layer uses graphite as a target, and the ratio of various bonds of carbon and oxygen through process control such as vacuum degree, substrate temperature, pressure, power including accelerating voltage, and purity of gas. ^{The ratio of sp 3} hybrid orbitals in sp hybrid orbitals was controlled.

Comparative Example 1

A low-emission coating of a multi-layer structure 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-emission coating. The zirconium is partially oxidized in air to form an uppermost protective layer together with the zirconium.

Experimental example

(1) Long-term storage performance accelerated test

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

Example 1 is a fine pinhole as shown in FIG. 6, which is at a level that cannot be observed with the naked eye, that is, it was confirmed as a fine pinhole whose size was not observed with the naked eye (maximum diameter of 20 μm or less), and chemical durability was improved. can be checked

On the other hand, Comparative Example 1 was confirmed as a level observed with the naked eye due to the occurrence of a very large pinhole as shown in FIG. can be checked

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

8 is after the scratch is reproduced only on the second uppermost protective layer of Example 1, FIG. 9 is after the scratch is reproduced on the uppermost protective layer (corresponding to the first uppermost protective layer) of Comparative Example 1, each about 650 Scratch changes were observed after thermal strengthening at ℃ or higher.

As shown in FIG. 8, in Example 1, it was observed that scratches formed on the second uppermost protective layer disappeared after thermal 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 thermal strengthening, and thus expanded enough to be visually distinguished.

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

FIG. 10 is an observation of a scratch change after thermal strengthening at about 650° C. or higher after replaying the scratch reaching the first uppermost protective layer and the second uppermost protective layer of Example 1 with a force of 1.0N and 3.0N, respectively.

On the other hand, FIG. 11 shows that after replaying the scratch on the uppermost protective layer (first uppermost protective layer) of Comparative Example 1 with a force of 1.0N and 3.0N, respectively, a scratch change was observed after thermal 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 over the first uppermost protective layer and the second uppermost protective layer was improved compared to Comparative Example 1 after thermal strengthening. This is because, as described above, the expansion due to oxidation of the scratch formed on the first uppermost protective layer was suppressed due to the presence of the second uppermost protective layer.

On the other hand, in Comparative Example 1, as shown in FIG. 11 , it was observed that the scratch formed on the uppermost protective layer increased in width after thermal strengthening and expanded to the extent that it was visually distinguished.

(4) hybrid orbital ratio measurement test

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

[Table 1]

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

First, a low ratio of -O (oxygen) bonding groups may mean that carbon in the second uppermost protective layer is chemically durable. Furthermore, the higher the sp3 orbital hybridization ratio, the higher the ratio of physically stable diamond bonds. In particular, in the case of Example 1, the hybridization ratio of sp3 orbitals is 90% or more compared to the hybridization ratio of sp2 orbitals, and the hybridization ratio of sp3 orbitals among the total hybridization ratio of carbon hybrid orbitals is 40% or more. It means that the physical durability is very good. 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 in Example 1 of the present invention. Chemical durability is also very good.

As a result, the results of Raman spectrum analysis in Table 1 and FIG. 12 indicate that the carbon in the second uppermost protective layer of Example 1 has very good physical and chemical durability.

(5) surface roughness measurement test

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

[Table 2]

Compared to Comparative Example 1 of the present invention, the average surface roughness value of Example 1 was improved by about 18%. The improved surface roughness as described above can contribute to the improvement of the scratch resistance as well as the scratch resistance to the external impact of the functional building material for windows and doors of the present invention.

On the other hand, to evaluate the chemical and physical durability of the first uppermost protective layer 30 of the present invention, Example 2 and Comparative Example 2 were prepared and then evaluated.

Example 2

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

Comparative Example 2

A low-emission coating of a multi-layer structure 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 the low-emission coating of the multilayer structure.

Experimental example

(6) Physical/chemical durability evaluation

14 and 15 are observations of the surface of the functional building material for windows and doors having the multilayer structure of Example 2 and Comparative Example 2, respectively, after passing through the brush of a glass cleaner, which is a transparent transparent substrate.

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

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

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

In contrast, in Comparative Example 2, in which the uppermost layer had 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 corrosion points generated after long-term exposure for 7 days growth was also observed with the naked eye.

The experimental results of FIGS. 14 to 17 directly prove 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 laminate structure is the durability of functional building materials for windows and doors. It can be said to directly prove that the laminate structure is very effective for improvement.

(7) Acid/base resistance evaluation

18 and 19 show the color change (ΔE) of the functional building materials for windows and doors having the multilayer structure of Example 2 and Comparative Example 2, respectively, after being exposed to acidic and basic solutions of pH 2 and pH 12 for 5 minutes, respectively. is a result In particular, the ΔE value is a value for the change of L, a, and b values in the color coordinate system, and is a representative index indicating 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) is 2 or more discoloration occurred, whereas Example 2 in which the uppermost layer has a Zr/ZrO structure has a transmission color change (color (T)) and a glass surface reflection color change (color (S)) of less than 1, the coating surface reflection It was confirmed that the color change (color R) had a very good color change property of less than 2.

1, 10: transparent substrate
2, 20: low-emission coating
3: Top protective layer
30: first uppermost protective layer
31: metal protective layer
32: ceramic protective layer
40: second uppermost protective layer
100, 200: the uppermost protective layer

Claims (11)

transparent substrate;
a low-emissivity coating comprising one or more layers positioned on top of the transparent substrate; and
Including; the uppermost protective layer located on top of the low-emission coating,
The uppermost protective layer includes: a first uppermost protective layer comprising metal zirconium and zirconium oxide;
A functional building material for windows and doors comprising a; a second uppermost protective layer positioned on the first uppermost protective layer and comprising carbon.
The method of claim 1,
A functional building material for windows and doors in which the ^{hybridization ratio of sp 3} orbitals among the total hybridization ratio of the carbon hybrid orbitals is 40% or more.
The method of claim 1,
A functional building material for windows and doors in which the total ratio of carbon -O (oxygen) bonding groups is 15% or less of the total carbon bonding ratio.
The method of claim 1,
The RMS surface roughness of the second uppermost protective layer is 0.5 nm or less.
The method of claim 1,
The functional building material for windows and doors does not include the second uppermost protective layer.
The method of claim 1,
The functional building material for windows and doors is a functional building material for windows and doors in which the maximum diameter of the surface pinhole is 20㎛ or less after an accelerated long-term storage performance test left for 3 weeks at a temperature of 50℃ and a humidity of 90%RH.
The method of claim 1,
A functional building material for windows and doors comprising a dielectric layer positioned between the first uppermost protective layer and the second uppermost protective layer.
The method of claim 1,
The second uppermost protective layer has a thickness of 1 to 5 nm, a functional building material for windows and doors.
The method of claim 1,
The thickness of the zirconium is 1 to 2 nm, the thickness of the zirconium oxide film is 2 to 3 nm of functional building materials for windows and doors.
6. The method of claim 5,
After exposure to an acidic solution of pH 2 for 5 minutes, the color change (ΔE) of the functional building material for windows and doors is less than 1, the transmission color change (color (T)) and the glass surface reflection color change (color (S)) are less than 1, A functional building material for windows and doors whose coating surface reflection color change (color R) is less than 2.
The method of claim 1,
The low-emissivity coating is a functional building material for windows and doors comprising at least one selected from a barrier layer, a blocking layer, and a dielectric layer.

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