JP3057785B2 - Heat shielding glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat shielding glass.
Particularly, the present invention relates to a heat-shielding glass having abrasion resistance that can be used in a single plate state and suitable for a window glass for automobiles and buildings.

[0002]

2. Description of the Related Art In recent years, heat-shielding glass coated with a heat-shielding film has been used for window glass of vehicles and buildings for the purpose of reducing sunlight energy flowing into the inside. Examples of such a heat ray shielding glass include Cu,
Utilizing the heat ray shielding properties of metal films such as A1 and Ag, metal nitride films such as titanium nitride and zirconium nitride, or alternately laminating high-refractive-index material films and low-refractive-index material films There is known a glass in which heat rays are reflected by an optical interference effect. Among these, Cu, A1,
In order to overcome the problems of chemical durability, that is, corrosion due to an atmosphere containing an acid or an alkali, and mechanical durability, that is, damage to a film due to scratches, a material using a metal film such as Ag is used. It is used as a laminated glass so that the coating is not exposed to the external environment. Also,
Even a film using a metal nitride film, which is said to have excellent durability as a heat ray shielding film, does not have sufficient durability to be used as a single glass sheet. Therefore, in order to improve the durability of the heat-shielding glass, studies on covering the uppermost layer with a protective film having excellent durability have been actively conducted. For example, JP-A-1-314163 discloses a heat-shielding glass in which a zirconium boride (ZrB ₂ ) target is reactively sputtered in a reduced-pressure oxygen atmosphere and coated with a zirconium-boron oxide film as a protective film. Have been.

[0003]

When used in a state of being directly exposed to an external atmosphere, such as glass for vehicles and buildings, the coating is required to have mechanical and chemical durability. It is important that the wear resistance is strong. However, in the prior art, a protective film having excellent mechanical durability such as abrasion resistance against scratches while maintaining excellent chemical durability against acids and alkalis has not been obtained. In the case where the above-mentioned oxide film of zirconium and boron was used as the protective film, the acid resistance was slightly inferior, and it could not be said that it had sufficient durability for practical use. In addition, when a large-area glass plate is coated with a protective film by a reactive sputtering method, which is the most excellent method for uniformly coating a large-area substrate with a film, a target or a substance formed on the target is required. However, since the electrical conductivity of the coating is not large, arcing is likely to occur and the coating process becomes unstable. The above-described arc discharge not only makes the coating process unstable, but also causes a problem that the particles of the target material adhere to the protective film, and the adhered matter causes defects such as film peeling. The present invention has been made in order to solve the above-mentioned problems of the prior art, without the adhesion of particles,
An object of the present invention is to provide a heat ray shielding glass in which a protective film having excellent chemical durability and mechanical durability is provided on the uppermost layer.

[0004]

According to the present invention, a transparent glass plate is coated with at least one heat-shielding film, and silicon, tantalum, carbon and nitrogen are coated on the heat-shielding film. This is a heat-shielding glass coated with a protective film that is transparent in the wavelength region of visible light composed of oxygen. The protective film of the uppermost layer of the heat ray shielding glass of the present invention, the thin film composed of silicon, carbon, nitrogen and oxygen is extremely excellent in wear resistance, and has a low refractive index, and tantalum, carbon and nitrogen This is achieved by finding that a thin film composed of oxygen has a property of extremely excellent chemical durability.

[0005] The protective film of the present invention is made of SiTajCkNmO.
n, where j, k, m, and n represent the atomic fraction, and the size and relative relationship of j, k, m, and n are the durability and transparency of the required protective film. And heat ray shielding properties. That is, when importance is placed on transparency over all wavelengths in the visible region, m is set to a small value and n
Is a relatively large value. In order for the protective film to have both high wear resistance and high chemical durability and to have a low refractive index, the value of j is preferably set in the range of 0.2 to 0.6. When the value of j is smaller than 0.2, the chemical durability is undesirably reduced. On the other hand, if the value of j is larger than 0.6, the refractive index of the film becomes larger than 2.0, and light is more likely to be absorbed. Set the value of k to 0.
A protective film having a composition of 8 or less, m of 1.0 or less, and n of 1.5 or more is more preferable because it is a transparent film that does not cause optical absorption in the visible region. Further, when the value of j is within the above range and the value of j is 0.5 or less, the refractive index of the film becomes 1.7 or less, so that the film has high transmittance, low reflectivity and durability in the visible region. It can be used as an excellent heat-shielding glass protective film. Although it is difficult to strictly determine the lower limits of the values of k and m related to the wear resistance of the protective film, in practice, in order to obtain a protective film having sufficient wear resistance, The value of k is preferably 0.3 or more, and the value of m is preferably 0.2 or more. By doing so, the smoothness of the surface of the protective film is increased, and the wear resistance is improved.

The thickness of the protective film according to the present invention is 5n
m or more. If the thickness is less than 5 nm, it becomes difficult to obtain practically necessary wear resistance. On the other hand, even if the coating is made thicker than 100 nm, the wear resistance is not significantly improved, and a long time is required for coating, and the film is easily peeled off, which is not preferable. For these reasons, it is more preferable to set the thickness in the range of 20 to 50 nm in consideration of the economics of coating and the optical properties of the obtained glass. The heat-shielding film coated on the transparent glass plate is not particularly limited as long as it transmits part of visible light and reflects part of solar radiation energy. A film of at least one metal nitride selected from the group consisting of zirconium, hafnium nitride and chromium nitride is preferably used. At this time, the thickness of the metal nitride film is preferably thin in order to increase the visible light transmittance, and thicker in order to increase the shielding property of heat rays. 2 to 7 n to obtain a glass with high visible light transmittance
The range of m is preferred. Further, the heat ray shielding film,
A configuration of a multilayer film in which films of a low refractive index material and films of a high refractive index material are alternately laminated. Assuming that the wavelength of the heat ray to be shielded is λ, the thickness of these films is determined to be about λ / 4 by the optical film thickness. Here, as the coating of the high refractive index material, TiO ₂ , SnO ₂ , In ₂ O ₃ , ITO, Z
Examples of the film include rO ₂ , Ta ₂ O _{5, and the} like. Examples of the film of the low refractive index material include SiO ₂ , AI ₂ O ₃ , ZnO, and Sn.
O ₂ and the protective film according to the present invention can be exemplified.

[0007] As a method for coating a protective film comprising silicon, tantalum, carbon, nitrogen and oxygen according to the present invention, a sputtering method, an arc evaporation method or a vacuum evaporation method performed in a reduced-pressure atmosphere can be used. Among them, the sputtering method is preferable for stably coating a film on a substrate having a large area. When coating the protective film of the present invention by a sputtering method, using a target consisting of a sintered body of a mixture containing silicon carbide and at least one of tantalum carbide or tantalum nitride, the pressure was reduced to at least nitrogen and oxygen A reactive sputtering method performed in an atmosphere is preferably used.

[0008] By mixing tantalum carbide or tantalum nitride in the target, the chemical durability of the obtained protective film is improved, and at the same time, the electric resistance of the target is reduced, and the target is formed on the target surface during sputtering. By reducing the electrical resistance of such materials, the stability of the coating process can be significantly improved.
The mixing ratio of silicon carbide and tantalum carbide or tantalum nitride is expressed as a volume ratio of tantalum carbide or tantalum nitride, and is 10 to 50% by volume, or 25 to 50% by volume.
50% by volume is preferred. If the content is less than 25% by volume, tantalum carbide or tantalum nitride in the target is difficult to form a continuous structure, and the electric resistance does not decrease. On the other hand, when the content is more than 50% by volume, the refractive index of the obtained protective film is increased, and light is easily absorbed in the visible region, which is not preferable. The ratio of the components of the target corresponds to the value j representing the ratio of silicon and tantalum in the obtained protective film. The composition of the protective film can be adjusted by changing the gas composition of the atmosphere when the protective film is coated by reactive sputtering. The gas in the atmosphere may include an amount of an inert gas such as argon or neon, and the amount is determined so as not to be too large. It is preferable to adjust the composition of the atmosphere so that nitrogen has a partial pressure of at least 0.2 Pa or more and occupies 40% or more of the total pressure in order to obtain a protective film having good durability. Thus, the absorption of the obtained protective film can be reduced, and the stability of reactive sputtering can be increased. Further, in order to form a protective film having a small refractive index, substantially no light absorption, and excellent wear resistance and chemical durability, the partial pressure of oxygen in the atmosphere during sputtering is 10% of the total pressure. It is preferable to make the above.

The protective film according to the present invention has a high visible light transmittance due to a small light absorption and a small surface reflectance due to a small refractive index.
By appropriately selecting the thickness of the heat ray shielding film and the thickness of the protective film, a heat ray shielding window glass having a visible light transmittance of 70% or more particularly suitable for a window glass of an automobile can be obtained. As the transparent glass plate of the present invention, a colorless transparent float glass or a colored transparent float glass such as bronze, gray, and blue can be used.

[0010]

The protective film comprising silicon, tantalum, carbon, nitrogen and oxygen as the uppermost layer of the heat-shielding glass of the present invention is transparent in the visible region and has high chemical durability and abrasion strength. This protects the heat-shielding film coated on the substrate from chemical corrosion from the surrounding environment, external forces such as abrasion and scratches, and hardly causes defects such as scratches. Further, by adjusting the thickness and the refractive index of the protective film, the visible light reflectance of the heat ray shielding glass can be suppressed low. Furthermore, tantalum carbide or tantalum nitride in the target used when coating the protective film of the present invention by the reactive sputtering method stabilizes glow discharge when coating the protective film by lowering the electrical resistance of the target during sputtering. This serves to prevent abnormal discharge from occurring, and suppresses the occurrence of film defects caused by particles adhering to the protective film.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. FIG. 1 is a partial cross-sectional view of the heat ray shielding glass of the present invention, 1 is a glass plate, 2 is a heat ray shielding film, and 3 is a protective film made of silicon, tantalum, carbon, nitrogen and oxygen.

Example 1 A protective film made of silicon, tantalum, carbon, nitrogen and oxygen was coated by using a target obtained by sintering silicon carbide and tantalum carbide or tantalum nitride with a slight amount of a sintering aid. This was performed by reactive sputtering in an atmosphere consisting of oxygen. In order to find the optimal coating conditions for the protective film, a single-layer protective film was coated and the obtained film was evaluated. 65% by volume (32% by weight) of S as a target
A mixture composed of iC, 30% by volume (66% by weight) of TaC, and a sintering aid was used (the remainder consists of a sintering aid). The cleaned float glass plate having a thickness of 2.1 mm was put in a sputtering apparatus, and a vacuum chamber in which a target was installed was set to about 5 × 10
^-4 Pa, and then the total flow rate of nitrogen and oxygen is 10
A gas of 0 sccm was introduced into the sputtering apparatus, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. Then, power was supplied to the target from a DC power supply to start discharge, and a film having a current value of 4 A and a film thickness of about 75 nm was formed on the glass substrate.
By changing the ratio of the nitrogen and oxygen gas flow rates introduced into the vacuum chamber,
The same procedure was repeated to prepare seven types of preliminary samples 1 to 7. Tables 1 and 2 show the wear resistance, alkali resistance, acid resistance, refractive index, and chemical composition of the obtained preliminary sample.

[0013]

[Table 1]

[0014]

[Table 2]

The abrasion resistance was measured by applying a load of 500 g to each of the two wear wheels No. and CS10F using a commercially available Taber abrasion tester and applying abrasion to the coating at 1000 rpm at a rotation speed of 60 rpm. The rate change and the haze rate were evaluated.
Alkali resistance and acid resistance are each 0.1N NaO
The sample was immersed in H, H ₂ SO ₄ solution for 240 hours, and evaluated before and after the change in transmittance and reflectance. The refractive index was measured using an ellipsometer, and the refractive index n at a wavelength of 632.8 nm was used.
And the extinction coefficient k were measured. Chemical composition was measured using ESCA.

From the above preliminary experiments, it was found that at least 10% or more of oxygen is required to form a protective film that is transparent without light absorption in the visible light region and excellent in all of abrasion resistance, alkali resistance and acid resistance. It has been found that it is preferable to perform sputtering in an atmosphere including the above. Next, in order to know the optimal conditions of the composition of the target used for sputtering, sintered bodies having different compositions were prepared, and the electric resistance was measured. As a result, by changing the volume fraction of tantalum carbide mixed in the matrix of silicon carbide from 20% to 30%, the electrical resistance of the sintered body is changed from 2 × 10 ⁻¹ Ω · cm to 1 × 10 ⁻³ Ω.・ C
m. In fact, by using a target obtained by sintering 30% by volume of tantalum carbide and a trace amount of a sintering aid in silicon carbide, even when the atmosphere during DC sputtering is 100% oxygen, discharge is stable. It has been confirmed that the DC sputtering can be performed without causing harmful abnormal arc discharge for at least several hours. On the other hand, when a target having a tantalum carbide content of 20% by volume is used, when the sputtering is performed under the condition that the oxygen in the atmosphere is about 30% or less, the discharge is stable for several hours or more. It was found that an abnormal arc discharge gradually occurred as the value was increased, and the discharge stability was reduced. Next, when the tantalum compound to be mixed into silicon carbide is changed from tantalum carbide to tantalum nitride, the electric resistance of the sintered body is 8 × 10 ⁻² Ω even if the content is the same of 30% by volume.・
cm, which was inferior to tantalum carbide in terms of discharge stability. Next, in order to know the upper limit of the amount of the tantalum compound to be mixed, 80% of nitrogen and 20% of oxygen were mixed in the same manner as described above using a target containing 50% by volume of silicon carbide and 50% by volume of tantalum nitride. When a film was formed by direct current sputtering in an atmosphere containing, the resulting film was colored brown to the extent that light absorption was clearly observed, and when the abrasion resistance was evaluated,
The change rate of the visible light transmittance and the haze rate showed large values, indicating that the wear resistance was slightly inferior.

Example 2 A direct current magnetron sputtering apparatus equipped with two cathodes contains metallic titanium as a first cathode and about 30% by volume of tantalum carbide and a trace amount of a sintering aid in a second cathode. Each of the silicon carbide sintered bodies was set as a target. The cleaned 4 mm-thick bronze-colored transparent float glass was placed in a vacuum chamber of a sputtering apparatus, and the vacuum pump was evacuated to 5.3 × 10 ⁻⁴ Pa using a vacuum pump. afterwards,
The pressure in the vacuum chamber was adjusted to 0.4 Pa at a flow rate of 100 sccm of nitrogen gas. Then, power was supplied from a DC power supply to the metal titanium target to start sputter discharge. After the current value was set at 5 A, a titanium nitride film of about 5 nm was formed on the glass substrate by passing through the glass substrate at a predetermined speed over the cathode.
The application of electric power to the cathode was stopped, the introduction of gas was stopped, and the gas was again evacuated to 5.3 × 10 ⁻⁴ Pa by a vacuum pump.
It was introduced into the vacuum chamber at a flow rate of m and the pressure was adjusted to 0.4 Pa. Then, power was applied from the DC power supply to the second cathode, and sputter discharge was started at a current value of 4 A. Then, a glass substrate was again passed through the cathode at a predetermined speed to form a film of silicon, tantalum, carbon, nitrogen and oxygen having a thickness of about 20 nm on the titanium nitride film. . Sample 1 thus obtained has a heat-ray shielding glass exhibiting a performance of a visible light transmittance of 72.7%, a solar light transmittance of 64.3%, and a visible light reflectance from a glass surface of 8.6%. Met. Table 3 shows the results of evaluating abrasion resistance, alkali resistance, and acid resistance of Sample 1 by the same method as that performed on the preliminary sample described above.

[0018]

[Table 3]

Example 3 Next, the composition of the gas when forming the protective film by sputtering was as follows:
A titanium nitride film and a protective film made of silicon, tantalum, carbon, nitrogen and oxygen are coated on a 4 mm thick bronze-colored transparent float glass substrate by exactly the same procedure except that nitrogen gas is 80 sccm and oxygen gas is 20 sccm. Sample 2 was obtained. Sample 2 was a heat-shielding glass exhibiting performance of a visible light transmittance of 73.4%, a solar light transmittance of 65.2%, and a visible light reflectance from a glass surface of 8.8%. Table 3 shows the results of evaluating the durability in the same manner as in Sample 1. Both samples 1 and 2 were found to be heat-shielding glasses exhibiting excellent wear resistance, alkali resistance and acid resistance.

EXAMPLE 4 In a sputtering apparatus having three magnetron cathodes, a metal tin target was used as a first cathode, a metal titanium target was used as a second cathode, and about 30% by volume of tantalum carbide was used as a third cathode. And a target of a silicon carbide sintered body containing a trace amount of a sintering aid. The cleaned bronze-colored float glass having a thickness of 4 mm was put in a vacuum chamber of a sputtering apparatus, and the inside of the vacuum chamber was evacuated by a vacuum pump to 7 × 10 4.
^It was evacuated to ^-4 Pa. 20 sccm argon, 80 oxygen
A mixed gas of sccm was introduced into the vacuum chamber, and the pressure was set to 0.3.
It was adjusted to 3 Pa. A current of 5 A was applied to the cathode of the tin target, and sputtering was performed for a predetermined time to coat a 65-nm SnO ₂ film on the substrate glass. Next, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of 40 sccm of argon and 60 sccm of oxygen, the pressure was adjusted to 0.4 Pa, and a current of 8 A was applied to the cathode of the titanium target to perform sputtering for a predetermined time. 5 on the SnO ₂ film
A 0 nm TiO ₂ film was coated. Next, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of argon 20 sccm and oxygen 80 sccm, and the pressure was adjusted to 0.4 Pa. A current of 5 A is applied to the cathode of the tin target, and sputtering is performed for a predetermined time, and 40 nm of S is deposited on the TiO ₂ film.
The nO ₂ film was coated. Finally, the atmosphere in the vacuum chamber was changed to nitrogen 8
It was almost completely replaced with a mixed gas of 0 sccm and 20 sccm of oxygen and adjusted to 0.4 Pa. A current of 4 A is applied to a cathode of a target of a sintered body of tantalum carbide and silicon carbide, and sputtering is performed for a predetermined time, so that 1 μm is formed on the SnO ₂ film.
A 5-nm thick film made of silicon, tantalum, carbon, nitrogen, and oxygen was formed. Sample 3 obtained in this manner has a visible light transmittance of 75.3%, a solar light transmittance of 60.8%, and a visible light reflectance from the glass surface side of 8.5%. It turned out to be a shielding glass. Table 3 shows the results of evaluating the wear resistance, alkali resistance and acid resistance of Sample 3 in the same manner as described above. Sample 3 was also found to exhibit excellent durability.

Example 5 A film composed of silicon, tantalum, carbon, nitrogen and oxygen was formed on a titanium nitride film by the same method using the same apparatus as in Examples 1 and 2. However, when forming a film composed of silicon, tantalum, carbon, nitrogen and oxygen, a silicon carbide sintered body containing 40% by volume of tantalum nitride and a small amount of a sintering aid was used as a target. 4 cleaned
A transparent bronze colored float glass having a thickness of mm was put in a vacuum chamber of a sputtering apparatus, and the vacuum pump was evacuated to 5.3 × 10 ⁻⁴ Pa using a vacuum pump. Then, nitrogen gas is supplied at 100 sccm.
The pressure in the vacuum chamber was adjusted to 0.4 Pa at a flow rate of. Then, power was supplied from a DC power supply to the metal titanium target to start sputter discharge. After the current value was set at 5 A, a titanium nitride film of about 5 nm was formed on the glass substrate by passing through the glass substrate at a predetermined speed over the cathode. The application of electric power to the cathode was stopped, the introduction of gas was stopped, and the vacuum pump was again evacuated to 5.3 × 10 ⁻⁴ Pa.
m and oxygen gas were introduced into the vacuum chamber at a flow rate of 20 sccm, and the pressure was adjusted to 0.4 Pa. Then, power was applied from the DC power supply to the second cathode, and sputter discharge was started at a current value of 4 A. Then, a glass substrate was again passed through the cathode at a predetermined speed to form a film of silicon, tantalum, carbon, nitrogen and oxygen having a thickness of about 20 nm on the titanium nitride film. . The sample 4 obtained in this manner has a heat-shielding glass exhibiting a performance of a visible light transmittance of 70.7%, a sunlight transmittance of 62.3%, and a visible light reflectance from a glass surface of 8.9%. Met. Table 3 shows the results of evaluating abrasion resistance, alkali resistance and acid resistance of Sample 4 in the same manner. Sample 4 was also found to be a heat-shielding glass exhibiting excellent durability.

COMPARATIVE EXAMPLE 1 Similar to Examples 1 and 2, a DC magnetron sputtering apparatus having two cathodes was provided, one of which had metallic titanium and the other had about 18% by weight of free silicon. A silicon carbide sintered body containing no tantalum was set as a target. The cleaned 4 mm-thick bronze-colored float glass plate is placed in a vacuum chamber of a sputtering apparatus, and 5.3 × 10 ^-4 P is applied by a vacuum pump.
Evacuated to a. Then, 100 sc of nitrogen gas
The pressure was adjusted to 0.4 Pa by introducing into the vacuum chamber at a flow rate of cm. Then, power was supplied from a DC power supply to the metal titanium target to start sputter discharge. After the current value was set at 5 A, a titanium nitride film having a thickness of 5 nm was formed by passing the glass substrate above the target at a predetermined speed. The application of electric power to the target was stopped, the gas introduction was stopped, and the gas was again evacuated to 5.3 × 10 ^-4 Pa by a vacuum pump, and then nitrogen gas was discharged at 95 scc.
m, oxygen gas was introduced into a 5 sccm vacuum chamber, and the pressure was adjusted to 0.4 Pa. Then, power was applied from a DC power supply to the silicon carbide target, and sputter discharge was started at a current value of 2 A. Thereafter, a protective film made of silicon, carbon, nitrogen and oxygen was formed with a thickness of 20 nm by passing the glass substrate over the target at a predetermined speed. Comparative sample 1 thus obtained has optical characteristics such that the visible light transmittance is 73.5%, the sunlight transmittance is 65.5%, and the visible light reflectance from the glass surface side is 7.6%. It was a heat ray shielding glass. This comparative sample 1
Table 3 shows the evaluation results of the abrasion resistance by the Taber abrasion test and the evaluation of the alkali resistance and the acid resistance in the same manner as in the examples. It shows excellent abrasion resistance, but poor alkali resistance.

COMPARATIVE EXAMPLE 2 As an example in which the protective film according to the present invention was not formed on the uppermost layer in exactly the same manner as in Example 3, an SnO ₂ film having a thickness of 65 nm was formed on a 4 m-thick bronze-colored float glass plate. 5
0 nm thick TiO ₂ film and 50 nm thick SnO
_Two films were formed in this order. Comparative sample 2 obtained
Has a visible light transmittance of 75.2% and a solar light transmittance of 6
1.4%, the visible light reflectance from the glass surface side is 8.9%
It was a heat ray shielding glass exhibiting such optical characteristics. Table 3 shows the results of the same evaluation of abrasion resistance, alkali resistance and acid resistance for Comparative Sample 2. It shows that it has relatively excellent chemical resistance, but is slightly inferior in wear resistance.

[0024]

The outermost layer of the heat ray shielding glass of the present invention, which is in contact with air, has a protective film made of silicon, tantalum, carbon, nitrogen and oxygen and having excellent chemical durability and wear resistance. It does not corrode or scratch due to scratches or the like even when used in the state of touching. Therefore, it can be used in the form of a single plate without being made into a multi-layer glass or a laminated glass as an automobile window glass or a building window glass. Moreover, since the heat ray shielding glass of the present invention can be stably coated by the direct current sputtering method, it can be stably coated on a glass plate having a large area.

[0025]

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a heat ray shielding glass of the present invention.

[0026]

[Explanation of symbols]

1 Glass plate, 2 Heat ray shielding film, 3 Protective film made of silicon, tantalum, carbon, nitrogen and oxygen.

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Atsushi Kawaguchi 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka Nippon Sheet Glass Co., Ltd. (56) References JP-A-2-263738 (JP, A) JP-A-2-307844 (JP, A) JP-A-3-173763 (JP, A) JP-A-4-42837 (JP, A) JP-A-4-270142 (JP, A) JP-A-4-280957 (JP JP, A) Special table Hei 3-504120 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 15/00-23/00 C23C 14/06 CA (STN) REGISTRY (STN )

Claims (7)

(57) [Claims] 1. A transparent glass plate is coated with at least one heat-ray shielding film, and a visible light beam comprising silicon, tantalum, carbon, nitrogen and oxygen is coated on the heat-ray shielding film. Heat shielding glass coated with a protective film that is transparent in the wavelength range. 2. The composition of the protective film is SiTa _j C _k N _m.
O _n when (j, k, m, n are atomic fraction) was expressed by comprising formula, 0.2 ≦ j ≦ 0.6, k ≦ 0.8, m ≦ 1.0,
The heat ray shielding glass according to claim 1, wherein n ≧ 1.5. 3. The heat ray-shielding film is made of titanium nitride,
The heat ray shielding glass according to claim 1 or 2, wherein the heat ray shielding glass is at least one selected from the group consisting of zirconium nitride, hafnium nitride, and chromium nitride. 4. The heat ray shielding film according to claim 1, wherein the film made of a low-refractive-index material and the film made of a high-refractive-index material are alternately laminated. Heat ray shielding glass. 5. The method according to claim 1, wherein the thickness of the protective film is 5 nm or more and 100 or more.
The heat-shielding glass according to any one of claims 1 to 4, wherein the thickness is not more than nm. 6. The heat-shielding glass according to claim 1, wherein the visible light transmittance is 70% or more. 7. A DC reactive sputtering method in which the protective film is made of a target made of a mixture containing silicon carbide and at least one of tantalum carbide and tantalum nitride in a reduced-pressure atmosphere containing at least oxygen and nitrogen. 7. A coating according to claim 1, wherein
The heat ray shielding glass according to any one of the above items.