Patent Application
20100255294
The present invention relates to a heat reflecting glass having at least a chromium nitride film formed on a glass substrate. Particularly, it relates to a heat reflecting glass having a thin film formed on the surface of a glass substrate for the main purpose of blocking solar radiation heat, and a process for producing such a heat reflecting glass.
At present, a heat reflecting glass having a thin film formed on the surface of a glass substrate for the main purpose of blocking solar radiation heat, is used for e.g. a window of architectural structures such as buildings, or as a rear glass for vehicles. From a viewpoint of a light transmitting property of such a heat reflecting glass, a demand for a heat reflecting glass having a low transmittance is also increasing. In a case where a glass is used for a window of architectural structures such as buildings, depending upon the site where the glass is to be installed, strengthening treatment is required, or it is preferred to install a strengthened glass. Whereas, a rear glass for vehicles is not a plate form having a flat surface, but is a plate form having a curved surface, and a heat reflecting glass subjected to bending treatment is employed.
In order to obtain a heat reflecting glass subjected to strengthening treatment or bending treatment, a method may be mentioned wherein a thin film having a heat reflection property is formed on a glass substrate subjected to strengthening treatment or bending treatment. However, it is difficult to form a heat reflecting thin film with good precision on e.g. the surface of a glass substrate subjected to bending treatment i.e. on the glass substrate surface having a curvature, so that the film thickness and the in-plane distribution of the composition become good. In order to form a heat reflecting thin film on a glass substrate surface having a curvature so that the film thickness and the in-plane distribution of the composition become good, it is necessary to adjust e.g. the thin film-forming step or the thin film-forming conditions to meet the curvature of the glass substrate surface, and thus an extra cost will be required.
On the other hand, in order to carry out bending treatment of a glass substrate having a heat reflecting thin film preliminarily formed, it is necessary e.g. to heat the glass substrate to a high temperature at a level of from 500 to 700° C. A conventional heat reflecting glass has had a problem that at such a high temperature, the heat reflecting thin film may for example be oxidized, and the heat reflecting performance may change between before and after the heating. Therefore, with such a conventional heat reflecting glass, it has been difficult for the glass processing dealer who purchased the glass having a heat reflecting thin film preliminarily formed, to carry out the bending. For example, in a case where the glass processing dealer carries out the bending by himself, in order to prevent a change in the heat reflecting performance between before and after the heating, the glass processing dealer himself is required to carry out the bending while maintaining the atmosphere during the bending to be a non-oxidizing atmosphere to prevent oxidation of the film to be protected. In such a case, a special apparatus or time and efforts will be required, and the resulting cost will be substantial. Therefore, a demand for a flat plate-form heat reflecting glass is substantial whereby strengthening treatment or bending treatment can be carried out by the glass processing dealer himself without requiring an extra time and efforts or a special apparatus having a function to keep the atmosphere during the bending to be a non-oxidizing atmosphere.
Whereas, the following Patent Document 1 discloses a process for producing a heat-treated heat reflecting glass (heat reflecting glass). In the process disclosed in Patent Document 1, a heat ray-blocking film or an electroconductive film is formed on a glass substrate, and then, a first protective film transparent in a visible light region is formed to obtain a heat reflecting glass having a multilayer film composed of at least two layers, and then, heat treatment is applied to such a heat reflecting glass. This process for producing a heat reflecting glass is characterized in that the first protective film is made of a film containing, as its main component, a nitride of silicon or boron, or nitrides of at least two types selected from silicon, boron, aluminum, zirconium and tin. The Patent Document 1 discloses that in the heat reflecting glass disclosed in Patent Document 1, the first protective film serves as an oxygen barrier by sufficiently absorbing oxygen entering from the atmosphere during the heat treatment, whereby the heat ray-blocking film undergoes no substantial change. That is, the Patent Document 1 discloses that with the heat reflecting glass prepared by the process for producing a heat reflecting glass disclosed in Patent Document 1, there is no substantial change in e.g. the optical properties of the coating layer to be protected, even if bending treatment or strengthening treatment is carried out by a simple method commonly employed (in the atmosphere without controlling the atmosphere).
Patent Document 1: Japanese Patent No. 2,518,129
A heat reflecting glass to be used for architectural structures such as buildings is required not only to be of a low price but also to have a proper balance of the optical properties and the thermal properties. In the present invention, the optical properties and the thermal properties will be together referred to as optical properties. The optical properties may, for example, be a nature relating to glare felt by a person in a room in e.g. a building, or a privacy nature such as inside not being seen from outside, and a nature relating to the degree of transmittance of a wavelength component mainly in a visible light region. Such a nature may be represented by a visible light transmittance defined in JIS R-3106 (1998). Whereas, the thermal properties is a nature relating to the amount of heat entering into a room in e.g. a building by sunlight, and a nature relating to the degree of transmittance of a wavelength component mainly in a near infrared region of sunlight. Such a nature may be represented by a solar transmittance defined in JIS R-3106 (1998).
Particularly, a heat reflecting glass which has a visible light transmittance Tv of at most 35% and a solar transmittance Te/visible light transmittance Tv ratio of less than 1.0 with respect to the visible light transmittance and solar transmittance as defined above and of which the optical properties undergo no substantial change even when heat treatment is applied for strengthening or bending, is practically excellent and is demanded also by the market.
It has been confirmed by the present inventors that by Examples disclosed in Patent Document 1, the ratio of the solar transmittance to the visible light transmittance cannot be made sufficiently low as compared with heretofore. The heat reflecting glass prepared by the process disclosed in Patent Document 1 cannot satisfy all of the demands by the market in recent years. Particularly, in Southeast Asian areas or areas right on the equator where insolation is intense and day time sunlight is dazzling, one having a low solar transmittance in a state of a low visible light transmittance is especially desired.
The present invention has an object to solve such problems. That is, it is an object of the present invention to provide a heat reflecting glass which has a visible light transmittance Tv of at most 35% and a solar transmittance Te/visible light transmittance Tv ratio of less than 1.0 and of which the optical properties undergo no substantial change even if a heat treatment is applied for strengthening or bending.
In order to accomplish the above object, the present invention provides a heat reflecting glass comprising a glass substrate, and an oxygen-blocking undercoat film, a chromium nitride film and an oxygen-blocking protective film formed in this order on the glass substrate, wherein in the chromium nitride film, the ratio in the number of atoms of nitrogen to chromium (i.e. the number of nitrogen atoms/the number of chromium atoms) is from 20% to 60%.
Here, each of the oxygen-blocking undercoat film and the oxygen-blocking protective film, is preferably a film containing, as its main component, a nitride of silicon or boron, or a film containing, as its main components, nitrides of at least two elements selected from the group consisting of silicon, boron, aluminum, zirconium and tin.
Further, it is preferred that the visible light transmittance is at most 35% as defined in JIS R-3106 (1998) and the ratio of its solar transmittance as defined in JIS R-3106 (1998) to the visible light transmittance (i.e. the solar transmittance/the visible light transmittance) is less than 1.0. At that time, it is preferred that the heat reflecting glass has been subjected to heat treatment at a temperature of at least 500° C.
Further, the film thickness of the oxygen-blocking undercoat film is preferably from 5 to 20 nm, and the thickness of the oxygen-blocking protective film is preferably from 10 to 30 nm.
Further, the heat reflecting glass preferably has an impurity-blocking undercoat film to prevent migration of impurities contained in the glass substrate, between the glass substrate and the oxygen-blocking undercoat film.
Further, the present invention provides a process for producing a heat reflecting glass comprising a glass substrate, and an oxygen-blocking undercoat film, a chromium nitride film and an oxygen-blocking protective film formed in this order on the glass substrate, which comprises:
a step of introducing a glass substrate into a film deposition chamber, and sputtering a chromium target in a nitrogen-containing atmosphere in the chamber to form a chromium nitride film on the glass substrate, and
a step of supplying not only nitrogen gas but also an inert gas other than the nitrogen gas into the chamber during the sputtering, and adjusting the ratio of the amount of the inert gas supplied to be within a range of (the inert gas:the nitrogen gas)=(70:30) to (90:10).
Further, the process preferably has:
a step of forming, prior to the sputtering, an oxygen-blocking undercoat film being a film containing, as its main component, a nitride of silicon or boron, or a film containing, as its main components, nitrides of at least two elements selected from the group consisting of silicon, boron, aluminum, zirconium and tin, on the glass substrate, and
a step of forming, after the sputtering, an oxygen-blocking protective film being a film containing, as its main component, a nitride of silicon or boron, or a film containing, as its main components, nitrides of at least two elements selected from the group consisting of silicon, boron, aluminum, zirconium and tin, on the surface of the chromium nitride film.
Further, the process preferably includes heat treatment at a temperature of at least 500° C. after forming the oxygen-blocking undercoat film, the chromium nitride film and the oxygen-blocking protective film.
According to the present invention, it is possible to provide, for example, a heat reflecting glass which has a visible light transmittance Tv of at most 35% and a solar transmittance Te/visible light transmittance Tv ratio of less than 1.0 and of which the optical properties undergo substantially no change even if heat treatment is applied for strengthening or bending.
In other words, it is possible to provide a heat reflecting glass which can be heat-treated and of which the visible light transmittance Tv is sufficiently low to prevent glare felt by a person in a room in e.g. a building and to provide a privacy nature such that the inside is not seen from outside, and the solar transmittance Te/visible light transmittance Tv ratio is as low as less than 1.0 thereby to satisfy a performance to prevent heat from entering into the room.
a) and 1(b) are schematic cross-sectional views illustrating different embodiments of the heat reflecting glass of the present invention.
Now, the heat reflecting glass of the present invention and the process for producing the heat reflecting glass will be described in detail with reference to the preferred embodiments shown in the attached drawings.
Firstly, with reference to
Firstly, the embodiment shown in
In the heat reflecting glass 10 shown in
In the heat reflecting glass 10, the oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18 are formed primarily to prevent penetration of oxygen into the chromium nitride film 14 for heat reflection. For example, in a case where a chromium nitride film 14 is formed directly on the surface of a glass substrate 12 without the oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18, if heat treatment (such as heat treatment at a temperature of from 500° C. to 700° C.) is applied for strengthening or bending without maintaining the atmosphere during the bending to be a non-oxidizing atmosphere, the balance of the optical properties and the thermal properties of the chromium nitride film 14 for heat reflection is likely to collapse (the transmittance tends to increase over the entire wavelength region of sunlight). That is, in a state where the oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18 are not present, especially when heat treatment is applied, oxygen penetrates into the chromium nitride (CrNx) film 14 for heat reflection. The oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18 are capable of preventing penetration of oxygen in the atmosphere into the chromium nitride film 14 for heat reflection thereby to prevent oxidation of the chromium nitride film 14 by the penetrated oxygen and to prevent collapse of the balance of the optical properties and the thermal properties, even when heat treatment is applied without keeping the atmosphere to be a non-oxidizing atmosphere during strengthening or bending.
In a case where the oxygen-blocking undercoat film 16 is made of silicon nitride (SiNx), such an oxygen-blocking undercoat film 16 may be formed on the surface of a glass substrate 12, for example, by disposing a glass substrate 12 having a clean surface in a vacuum chamber of a sputtering apparatus and carrying out sputtering by using a polycrystalline Si target as a sputtering target. At the time of forming the oxygen-blocking undercoat film 16, the interior of the vacuum chamber is firstly evacuated to e.g. 1.3×10−3 Pa, and nitrogen gas is supplied into the vacuum chamber e.g. at a gas flow rate of 100 sccm to bring the pressure in the vacuum chamber to be e.g. 6.0×10−1 Pa. In such a state, reactive sputtering is carried out by applying an electric power of 2.00 kW by means of a DC pulse power source to form a film on the glass substrate.
In a case where the oxygen-blocking protective film 18 is made of silicon nitride (SiNx), also such an oxygen-blocking protective film 18 may be formed, for example, by disposing the glass substrate 12 in a state provided with the oxygen-blocking undercoat film 16 and the after-described chromium nitride film 14, in a vacuum chamber of a sputtering apparatus, and carrying out reactive sputtering under the same conditions as for the oxygen-blocking undercoat film 16. In the present invention, the method for forming the oxygen-blocking undercoat film or the oxygen-blocking protective film is not particularly limited, and depending upon the optical performance or oxygen-blocking performance required for the oxygen-blocking undercoat film or the oxygen-blocking protective film, various conditions in the sputtering may optionally be set. Further, the method for forming a thin film in order to form the oxygen-blocking undercoat film or the oxygen-blocking protective film is not particularly limited to the reactive sputtering, and various conventional methods such as a CVD (chemical vapor deposition) method may be employed.
The oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18 may be set to have a film thickness whereby it is possible to sufficiently prevent penetration of oxygen into the chromium nitride (CrNx) film 14 when heat treatment is applied. For example, the thickness of the oxygen-blocking undercoat film 16 is preferably from 5 to 20 nm, particularly preferably from 7 to 15 nm. The thickness of the oxygen-blocking protective film 18 is preferably from 10 to 30 nm, particularly preferably from 15 to 25 nm. SiNx has a relatively high refractive index as compared with the glass substrate, and if the oxygen-blocking undercoat film 16 or oxygen-blocking protective film 18 made of SiNx is thicker than necessary, it presents a substantial influence over the appearance of the heat reflecting glass 10. With respect to the oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18, it can be said that the film thickness should better be thick in order to block oxygen, and the film thickness should better be thin from the viewpoint of the appearance.
In this embodiment, the oxygen-blocking undercoat film and the oxygen-blocking protective film are described as films made of SiNx. However, in the present invention, the oxygen-blocking undercoat film and the oxygen-blocking protective film are, respectively, not limited to SiNx. In the present invention, the oxygen-blocking undercoat film and the oxygen-blocking protective film are required to be non-oxide films or films not completely oxidized and even if oxidized, they must be transparent films in a visible light region. The oxygen-blocking undercoat film and the oxygen-blocking protective film are film which prevent penetration of oxygen into the chromium nitride film when heated at the time of heat treatment and which will not discharge oxygen to the chromium nitride film even if the oxygen-blocking undercoat film itself or the oxygen-blocking protective film itself contains oxygen. Such oxygen-blocking undercoat film and oxygen-blocking protective film, even if oxidized, will remain transparent without absorption, with a mere change in the refractive index. Accordingly, they are preferably made of a material which presents no substantial influence over the optical properties after the heat treatment.
As examples of the oxygen-blocking undercoat film and the oxygen-blocking protective film, films containing, as the main component, at least one member selected from a nitride, a boronitride, a carbonitride and a silicon nitride may be mentioned as preferred examples. Particularly preferred may, for example, be a film containing, as its main component, a nitride of silicon or boron; or a film containing, as its main components, nitrides of at least two members selected from the group consisting of silicon, boron, aluminum, zirconium and tin (typical examples being a zirconium silicon nitride film, a tin silicon nitride film, etc.). Otherwise, it may be a film containing, as its main component, a partial oxide of the above-mentioned nitride, boronitride, carbonitride or silicon nitride. Among the forgoing, a film containing, as its main component, silicon nitride or zirconium silicon nitride is particularly good in the oxygen barrier performance and thus is most preferred. Here, “oxygen barrier performance” is a performance to prevent oxygen from penetrating into the chromium nitride film by passing through the oxygen-blocking undercoat film from the substrate side or through the oxygen-blocking protective film from the atmosphere side.
With respect to e.g. nitride films as the above-mentioned oxygen-blocking undercoat film and oxygen-blocking protective film, silicon nitride is represented by SiNx, where x represents a number. This means that the nitride may not necessarily be bonded in a stoichiometrically most common ratio, so long as it is transparent in a visible light region. For example, in the case of silicon nitride, Si3N4 is common, but in order to be transparent in a visible light region, the ratio of N to Si (corresponding to the above x) is preferably at least 1.25, particularly preferably at least 1.28.
The chromium nitride (CrNx, where x is a numerical value of 0<x<1) film 14 for heat reflection is characterized in that in the chromium nitride film, the ratio of the number of nitrogen atoms to the number of chromium atoms is from 20% to 60%, more preferably from 40% to 60%. Here, the ratio of the number of nitrogen atoms to the number of chromium atoms means (number of nitrogen atoms/number of chromium atoms)×100%, and by using (number of nitrogen atoms/number of chromium atoms)=x, the ratio of the number of nitrogen atoms to the number of chromium atoms may be represented by x×100%. In the heat reflecting glass 10 of this embodiment, with respect to the chromium nitride (CrNx) film 14 for heat reflection, by adjusting the ratio of the number of nitrogen atoms to the number of chromium atoms in the film to be from 20% to 60%, a heat reflecting glass is realized which has a visible light transmittance of at most 35% and a ratio of the solar transmittance to the visible light transmittance of less than 1.0.
Here, the visible light transmittance is a value defined in JIS R-3106 (1998). Further, the solar transmittance is a value defined in JIS R-3106 (1998). Specifically, the visible light transmittance can be obtained by multiplying the value of spectral transmittance of the object by weighting coefficients (coefficients set over the wavelength range of from 380 nm to 780 nm) obtained from the wavelength distribution of the CIE light-adapted relative luminocity and the CIE daylight D65 spectrum, followed by obtaining a weighted average. Further, the solar transmittance can be obtained by multiplying the measured values of spectral transmittance of the object by weighting coefficients (coefficients set over the wavelength range of from 300 nm to 2,100 nm) representing a standard spectral distribution of sunlight, followed by obtaining a weighted average. Here, the weighting coefficients representing a standard spectral distribution of sunlight to be used for the calculation of the solar transmittance, are set to be particularly large values within the wavelength range of from about 1,000 nm to 1,300 nm as compared with other wavelength ranges. The solar transmittance may be said to well represent the degree of transmittance of heat rays particularly in a wavelength range of from 1,000 to 1,300 nm i.e. a near infrared region, of the sunlight.
The chromium nitride (CrNx) film 14 for heat reflection in the heat reflecting glass 10 of this embodiment, can be prepared by the following method. For example, a glass substrate 12 provided with an oxygen-blocking undercoat film 16 is disposed in a vacuum chamber of a sputtering apparatus, and the interior of the vacuum chamber is firstly evacuated to e.g. 1.3×10−3 Pa. Then, while supplying nitrogen gas (hereinafter nitrogen may be represented by N2) at a flow rate of e.g. 20 sccm and argon gas (hereinafter argon may be represented by Ar) at a gas flow rate of e.g. 80 sccm into the vacuum chamber, the pressure in the vacuum chamber is controlled to be e.g. 6.0×10−1 Pa. Under such a controlled state, using a DC pulse power source, an electric power of e.g. 2.00 kW is applied to form plasma in the reactor, and reactive sputtering is carried out by using a chromium target as the sputtering target, to form the film 14.
Here, Ar gas is taken as an example of the inert gas, but the inert gas may be other than Ar gas or may be a combination of a plurality of inert gases.
The flow rates (flow rates per unit time) of N2 gas and Ar gas are, respectively, adjusted by mass flow controllers provided on the respective gas supply tubes connected to the chamber. The flow rate of each gas is represented by a volume stipulated for each gas (a volume stipulated under 1 atm (atmospheric pressure of 1,013 hPa) at 0° C.) and may, for example, be represented by using a sccm (standard cc/min) unit. The Ar gas flow rate/N2 gas flow rate corresponds to the Ar gas partial pressure/N2 gas partial pressure in the chamber and thus corresponds to the number of atoms of Ar gas/the number of molecules of N2 gas in the chamber. In this specification, the gas ratio will be represented by the Ar gas flow rate/N2 gas flow rate or by (Ar gas:N2 gas).
Heretofore, at the time of forming a chromium nitride film by reactive sputtering, it has been common to carry out reactive sputtering by using a chromium target in N2 gas being 100%. The reason is such that with chromium nitride, it is desired to stabilize the optical constants (refractive index and extinction coefficient) of the film, but even if the N2 gas ratio (such as the ratio of N2 gas at the time of mixing Ar gas and N2 gas) is the same, the nitriding degree (value x) of chromium nitride may change depending upon the influences of the apparatus (such as the position of the exhaust gas pump, and the position for introduction of the mixed gas), the electric power to be applied during sputtering, etc., and it was necessary to adjust it. In order to avoid such adjustment, it was common to carry out sputtering with a gas which consists of 100% of N2.
In this embodiment, the ratio in the flow rate (the supply rate per unit time) of N2 gas to Ar gas supplied into the reactor (vacuum chamber) at the time of preparing a chromium nitride (CrNx) film 14 by reactive sputtering, is adjusted to be (Ar gas: N2 gas)=(70:30) to (90:10), so that the ratio of the number of nitrogen atoms to the number of chromium atoms in the chromium nitride (CrNx) film 14 will be from 20% to 60%. The ratio in the flow rate of Ar gas to N2 gas is more preferably adjusted to be (Ar gas:N2 gas)=(70:30) to (80:20). The ratio of the number of nitrogen atoms to the number of chromium atoms in the film at that time will be from about 40% to about. 60%.
As described above, the oxygen-blocking undercoat film 16 and the oxygen-blocking protective film 18 are set to have a film thickness whereby it is capable of sufficiently preventing oxygen from penetrating into the chromium nitride (CrNx) film 14 during the heat treatment. Accordingly, the heat reflecting glass 10 undergoes no substantial change in the optical properties even if the heat reflecting glass 10 is subjected to common heat treatment (e.g. heat treatment at a temperature of from 500° C. to 700° C.) for glass strengthening treatment or bending treatment. Further, the heat reflecting glass constructed by using a chromium nitride film 14 as a heat reflecting film also has good appearance. The heat reflecting glass 10 shown in
The heat reflecting glass 20 shown in
The glass substrate 12 being a float plate glass contains, as its main component, silicon dioxide (SiO2) but also contains various impurities in a relatively large amount. Impurities contained in the glass substrate 12 substantially migrate particularly when heat treatment is applied. However, in the heat reflecting glass 20 shown in
In order to prevent impurities in the glass substrate 12 from reaching the chromium nitride film 14 without impairing the appearance of the heat reflecting glass more than necessary, it is preferred to construct the heat reflecting glass in the form as shown in
Now, a heat reflecting glass as an example of the heat reflecting glass of the present invention will be described with reference to Examples and Test Examples.
As Example 1, a heat reflecting glass corresponding to the first embodiment shown in
The conditions at the time of forming the oxygen-blocking undercoat film and the oxygen-blocking protective film made of silicon nitride (SiNx), were as follows.
Here, SiNx is usually Si3N4 and may include also a material having a composition wherein the ratio of N to Si is slightly different.
Further, the conditions at the time of forming the chromium nitride film were as follows.
With respect to the heat reflecting glass in Example 1, at the time of preparing the chromium nitride film by reactive sputtering, the above-mentioned Ar gas flow rate/N2 gas flow rate, supplied into the reactor (vacuum chamber) was adjusted to be 4.0. In the chromium nitride film 14 formed under such condition, the ratio (N/Cr) of the number of nitrogen atoms to the number of chromium atoms was about 41%.
Here, the ratio (N/Cr) of nitrogen atoms to chromium atoms was obtained by subjecting the formed chromium nitride film to XPS (X-ray photoelectron spectroscopy). In Example 1, as the XPS apparatus, Quantera SXM apparatus, manufactured by PHI (Physical Electronics Inc.) was used. By using this apparatus, the ratio (N/Cr) of nitrogen atoms to chromium atoms was measured under the following measuring conditions.
X-ray source: Al monochromated, Kα, 1486. 7 (eV), 25 W
Detect angle: 45 (deg)
Pass energy: 224.0 (eV)
eV/step: 0.4 (eV)
Sputtering condition: Ar gas 2 (kV), 3×3 (mm2), 3 (min)
Here, the above sputtering condition is to remove a contaminated layer on the surface.
The ratio (N/Cr) of nitrogen atoms to chromium atoms in Example 1 is a value obtained by determining the ratio (N/Cr) of nitrogen atoms to chromium atoms from an emitted photoelectron spectrum obtained by such measurement by using a software attached to the XPS apparatus. Specifically, N/Cr was calculated on such a basis that the spectral amount within a range of from 565 to 600 (eV) corresponding to the 2 p peak of Cr atoms corresponds to the Cr amount, and the spectral amount within a range of from 392 to 407 (eV) corresponding to the 1 s peak of nitrogen atoms corresponds to the N amount.
Here, at the time of the calculation by the software attached to the XPS apparatus, as relative sensitivity coefficients, coefficients of the 2 p peak of Cr atoms: 0.860 and the 1 s peak of nitrogen atoms: 0.499, were used, and the amounts of chromium atoms and nitrogen atoms were obtained from the values measured by the XPS apparatus.
Further, in Example 1, the thickness of the chromium nitride film was 21 nm, and the oxygen-blocking undercoat film was 10 nm and the oxygen-blocking protective film was 20 nm. For the thickness of each layer, a film deposition rate is preliminarily obtained from the film deposition time and the film thickness by means of a stylus film thickness meter, and the film thickness of each layer is a value estimated from such a film deposition rate and film deposition time. The film thickness (21 nm) of the chromium nitride film is a film thickness which is preliminarily set so that the visible light transmittance Tv will be about 14.0% in such a state that the oxygen-blocking undercoat film is 10 nm and the oxygen-blocking protective film is 20 nm.
Table 1 is a table which summarizes the values of the solar transmittance Te and the visible light transmittance Tv measured under the measuring conditions stipulated in the above-identified JIS, and the solar transmittance Te/visible light transmittance Tv ratio. Table 1 also shows the measured values of the visible light transmittance Tv′ and the solar transmittance Te′ in a state after the heat treatment was applied to the heat reflecting glass in Example 1, and the solar transmittance Te′/visible light transmittance Tv′ value. Here, the conditions for the heat treatment were 650° C. (the atmosphere temperature in the furnace) and 15 minutes in accordance with common heating conditions (500° C. to 700° C.) employed in glass strengthening treatment or bending treatment.
As shown in Table 1, the heat reflecting glass in Example 1 underwent no substantial change in the optical properties even when heat treatment was applied for strengthening or bending. Both before the heat treatment and after the heat treatment, the heat reflecting glass in Example 1 satisfies the properties required for a heat reflecting glass for which the demand is increasing in recent years, for example, such properties as a visible light transmittance Tv of at most 35%, and a solar transmittance Te/visible light transmittance Tv ratio of less than 1.0.
Firstly, the optical performance of a single chromium nitride (CrNx) film was examined as a Reference Example.
Each of chromium nitride (CrNx) single film samples A1 to A5 is a sample prepared in such a manner that a glass plate is disposed in a reactor (vacuum chamber) and sputtering is carried out by using a chromium (Cr) target as a sputtering target while the interior of the vacuum chamber is controlled to be a N2 gas-containing atmosphere, to form a chromium nitride film for heat reflection on the surface of the glass substrate. The respective samples A1 to A5 are ones wherein the ratio Ar/N2 of the flow rate of Ar gas to the flow rate of N2 gas supplied to the vacuum chamber during the reactive sputtering is changed. Not only in
In the preparation of the plurality of samples A1 to A5, the conditions for forming the chromium nitride films other than the ratio of the flow rate of Ar gas to the flow rate of N2 gas, were as follows.
Further, the film thickness of the chromium nitride film of each of samples A1 to A5 was set so that by the film deposition rate and the film deposition time preliminarily obtained, the thickness of the chromium nitride film of each of samples A1 to A5 became about 20 nm.
At the time of forming each of samples A1 to A5, the Ar gas flow rate/N2 gas flow rate ratio was adjusted to be one identified in the graph shown in
Table 2 is a table summarizing the gas ratio and the ratio (N/Cr) in the number of nitrogen atoms to chromium atoms, at the time of forming a chromium nitride film, corresponding to each of samples A1 to A5. Further, in Table 2 and in
As shown in
Then, as an Example, a construction having the above chromium nitride film sandwiched by silicon nitride (SiNx) was formed. That is, by reactive sputtering, an oxygen-blocking undercoat film (10 nm) made of silicon nitride (SiNx) was formed on a glass substrate (FL6), and as laminated on the surface of the oxygen-blocking undercoat film, a chromium nitride film (20 nm) was formed by reactive sputtering by changing the Ar gas flow rate/N2 gas flow rate ratio in the sputtering gas. Further, as laminated on the surface of the chromium nitride film, an oxygen-blocking protective film (20 nm) made of silicon nitride was formed.
The conditions at the time of forming the oxygen-blocking undercoat film and the oxygen-blocking protective film made of silicon nitride (SiNx) were as follows.
In the case of samples B1 and B2 as Comparative Examples, as compared with the spectral transmittance in the visible light region, the spectral transmittance on the longer wavelength side than the visible light region is large as a whole. As compared with samples B1 and B2, in the case of samples B3 to B5 of the present invention, the spectral transmittance in the visible light region and the spectral transmittance on the longer wavelength side than the visible light region are substantially equal as a whole. However, when attention is drawn to the near infrared region (the wavelength range of from about 1,000 nm to 1,300 nm) in the wavelength region on a longer wavelength side, particularly in the case of samples B3 and B4, the spectral transmittance in the near infrared region is remarkably low as compared with the spectral transmittance in the visible light region. In the case of B6 as a Comparative Example, the transmittance in a visible light region is lower than in the near infrared region.
With respect to these samples B3 to B5, the optical properties after heat treatment are not confirmed. However, sample B4 is substantially equal to the sample in Example 1, and it is considered that the optical properties after heat treatment of B3 to B5 are free from a change in the optical property (Te/Tv) like in Example 1.
As mentioned above, it can be said that the visible light transmittance Tv defined in the above JIS well reflects the degree of the spectral transmittance in the visible light region (wavelength range of from 380 nm to 780 mm), and the solar transmittance as defined in the same JIS well reflects the degree of the spectral transmittance in the near infrared region (wavelength range of from 1,000 nm to 1,300 nm). When the solar transmittance Te/visible light transmittance Tv ratio is obtained, as compared with samples B1 and B2 as Comparative Examples, samples B3 to B5 show relatively small values of the solar transmittance Te/visible light transmittance ratio, and particularly in the case of samples B3 and B4, such a ratio becomes less than 0.9.
Calculated values by a simulation are shown in Table 4 wherein the solar transmittance Te/visible light transmittance Tv ratio is obtained under such a condition that the visible light transmittance Tv becomes constant (14%). In order to adjust the visible light transmittance Tv to be constant (14%), the thickness of the chromium nitride film was changed, and the thicknesses of the oxygen-blocking undercoat film (10 nm) made of silicon nitride and the oxygen-blocking protective film (20 nm) made of silicon nitride were fixed.
Each of samples C1 to C6 shown in Table 4 is assumed to be a heat reflecting glass having the same construction as the heat reflecting glass 10 shown in
The results in Tables 3 and 4 are shown in
Further, in
From these results, it was found that when the ratio (N/Cr) of the number of nitrogen atoms to the number of chromium atoms is adjusted to be from 20% to 60%, or reactive sputtering is carried out to form a chromium nitride film at a ratio of (Ar:N2)=(70:30) to (90:10), it is possible to obtain a heat reflecting glass having such a performance that the visible light transmittance Tv is at most 35% and the transmittance Te/visible light transmittance Tv ratio is less than 1.0 and it is possible to reduce fluctuation in the solar transmittance Te/visible light transmittance ratio against fluctuation in the conditions for film deposition of the chromium nitride film.
Further,
As shown in
Table 5 shows the physical property values obtained from the spectral transmittance values shown in Table 6. The solar transmittance Te/visible light transmittance Tv ratio is the same even when the film thickness of the chromium nitride film changes. Samples D1 to D5 have a visible light transmittance Tv within a range of from about 10% to about 20%, which is sufficient to prevent glare felt by a person in a room in e.g. a building or sufficient for a privacy nature not being seen from outside, and the solar transmittance Te/visible light transmittance Tv ratio is as low as 0.87, which is effective to prevent heat from entering into the room.
In the heat reflecting glass of the present invention, the construction of layers formed on the glass substrate is not limited to the embodiments in the above Examples. For example, in order to prevent, with higher precision, oxygen from entering into the chromium nitride film for heat reflection, a second protective film may further be provided as an upper layer of the oxygen-blocking protective film as the topmost layer in the embodiment shown in
In the foregoing, the heat reflecting glass of the present invention and the process for producing such a heat reflecting glass have been described in detail. However, it should be understood that the present invention is by no means restricted to the above embodiments or examples and may include various modifications and changes within a range not departing from the concept of the present invention.
The heat reflecting glass of the present invention is excellent in the solar heat-blocking performance and undergoes no substantial change in the optical performance even when subjected to strengthening treatment or bending treatment, and thus, it is useful for a glass window for buildings or vehicles and is widely useful also for mobile means other than vehicles, such as aircraft or trains.
The entire disclosure of Japanese Patent Application No. 2007-336133 filed on Dec. 27, 2007 including specification, claims, drawings and summary is incorporated herein by reference in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-336133 | Dec 2007 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP08/73013 | Dec 2008 | US |
| Child | 12820295 | US |
