JP3200637B2 - 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, a heat-shielding glass coated with a heat-shielding film has been used for a window glass of a vehicle or a building in order to reduce sunlight energy flowing into the inside. Examples of such heat ray shielding glass include C
Utilizing the heat ray shielding properties of metal films such as u, Al, Ag, and 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 device in which a heat ray is reflected by an optical interference effect. Among these, Cu, A
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, those using a metal film such as Ag. Glass and laminated glass are used so that the coating is not exposed to the external environment. Further, 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 sheet glass. Therefore, in order to improve the durability of the heat ray shielding glass, research on covering the uppermost layer with a protective film having excellent durability has been actively conducted. For example, JP-A-1-314163 discloses a highly durable hot wire in which a zirconium boride (ZrB2) target is reactively sputtered in a reduced-pressure oxygen atmosphere and a coated zirconium-boron oxide film is used as a protective film. A shielding glass is disclosed.

[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, with the above-mentioned conventional technology, while maintaining excellent chemical durability against acids and alkalis,
A film excellent in mechanical durability such as abrasion resistance to scratch was not obtained. When the protective film is made of an oxide film of zirconium and boron as described above, it has excellent durability in general, but has a problem that it is slightly inferior in acid resistance. In addition, when the protective film is formed by reactive sputtering, which is the best method for forming a film on a large-sized glass plate, the electric conductivity of the target is not sufficiently low, and furthermore, the film formed on the target However, since the electric conductivity is not low, an arc discharge is easily generated during the sputtering, and the film forming process becomes unstable. This arc discharge not only made the process unstable, but also caused particles of the target material to adhere to the film, which caused defects such as film peeling.

The present invention has been made to solve these problems of the prior art, and a protective film having no chemical adhesion and excellent chemical durability and mechanical durability is formed on the uppermost layer. It is intended to provide a provided heat ray shielding glass.

[0005]

Means for Solving the Problems] This onset Ming, heat ray shielding property of the film at least composed of one on a transparent glass plate is coated, on the heat ray shielding property of the coating, silicon, zirconium, and carbon Oxygen protective film or silicon
Protective film consisting of oxygen, zirconium, carbon, oxygen and nitrogen
In the coated heat-shielding glass, the composition of the protective film
Of the _{SiZr j C k N m O n} (j, k, m, n are atomic fractions)
When represented by the following chemical formula, 0.2 ≦ j ≦ 0.6, 0 <k ≦
0.8, 0 ≦ m ≦ 1.0, n ≧ 1.2
Is a heat ray shielding glass.

[0006] It is an object of the present invention to provide silicon, carbon, and oxygen.
Is extremely excellent in abrasion resistance as a protective film
And have a low refractive index
And a thin film consisting of zirconium, carbon and oxygen
See that the chemical durability of the protective film is extremely excellent.
This makes it possible to simultaneously improve chemical durability and mechanical strength.
To provide a heat shielding glass coated with a protective film having
And

In the present invention, the shadow constituting the protective film is used.
Ion contains nitrogen in addition to oxygen
Is also good. that's all

[0008] protective layer of the present _{invention, SiZr j C k N m O} n becomes can be represented by the formula, j, k, m, the size and relative relationship of n is Ya durability and transparency require It is determined in consideration of heat ray shielding properties. That is, when importance is placed on transparency over all wavelengths in the visible region, m is a small value and n is a relatively large value. In order to simultaneously satisfy high wear resistance, high chemical durability and low refractive index, it is preferable to control the value of j in the range of 0.2 to 0.6. If the value of j is smaller than 0.6, a film having sufficient chemical durability cannot be obtained. If the value of j is larger than 0.6, the refractive index becomes larger than 2.0 and the absorption tends to occur. The protective film in which the value of k is 0.8 or less, the value of m is 1.0 or less, and the value of n is 1.2 or more is a transparent film that does not substantially cause optical absorption in the visible region. It becomes a film. In this case, when the value of j is 0.5 or less, the refractive index becomes a small value of 1.7 or less, so that the heat ray shielding glass has high transmittance, low reflectivity, and excellent durability in the visible region. Is a protective film. The lower limit of the values of k and m is hard to be strictly limited, but it is a value related to wear resistance,
In order to obtain a 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. However, even if the value of m is 0, excellent wear resistance is obtained. have. j, k,
By setting the values of m and n within the above ranges, the smoothness of the surface of the protective film is increased and the wear resistance is improved.

The coating having a heat ray shielding property coated on the transparent glass plate is not particularly limited, but at least one kind of nitride film or oxynitride film selected from the group consisting of titanium, zirconium, hafnium and chromium is used. Used favorably. At this time, the thickness of the metal nitride film or the oxynitride film is preferably thin in order to increase the visible light transmittance, and is preferably thick in order to increase the heat ray shielding property. In order to obtain a glass having a high visible light transmittance required as a window glass, 2 to 10 nm
Is preferable. Further, the heat ray shielding film may have a multilayer film structure in which a film of a low refractive index material and a film 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, Zr
Examples of the film include O ₂ and Ta ₂ O _5. Examples of the low refractive index material film include SiO ₂ , Al ₂ O ₃ , ZnO, SnO ₂ , and S
_{iZr j C k N m O n} (0.2 ≦ j ≦ 0.6,0 <k ≦ 0.
8, 0 ≦ m ≦ 1.0, n ≧ 1.2).

The protective film according to the present invention has a thickness of 5n.
m or more. If the thickness is smaller than this, it will be difficult to obtain practically necessary wear resistance. On the other hand, if the coating is thicker than 100 nm, the abrasion resistance is not further improved, and it takes a long time to coat the protective film, and the protective film may peel off, which is not preferable. For these reasons, the thickness of the protective film is more preferably set in the range of 20 to 50 nm in consideration of the economics of coating and the optical properties of the obtained glass.

As a method for coating the protective film containing at least silicon, zirconium, carbon 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. However, the sputtering method is preferable for stably coating a film on a substrate having a large area. When coating the protective film according to the present invention by a sputtering method, silicon carbide, using a target consisting of a sintered body of a mixture containing at least one of zirconium carbide or zirconium nitride, a reduced pressure atmosphere containing oxygen or oxygen It is preferable to use a reactive sputtering method performed in a reduced-pressure atmosphere containing nitrogen. The purpose of mixing zirconium carbide or zirconium nitride in the target is to increase the chemical durability as described above in terms of film properties, but also at the same time in securing the stability of the film forming process. By reducing the electric resistance of the target and the electric resistance of the film formed on the target, the stability of the process can be greatly improved. The mixing ratio of silicon carbide and zirconium carbide or zirconium nitride is preferably 10 to 80% by volume, more preferably 25 to 50% by volume, expressed as a volume ratio of zirconium carbide or zirconium nitride. 25% by volume
If the amount is smaller, it is difficult for zirconium carbide or zirconium nitride to have a continuous structure in the target, and the electric resistance of the target does not become lower than a value required to secure a stable film forming process, which is not preferable. 50% by volume
If the amount is larger, the refractive index of the obtained film becomes higher, and light is easily absorbed in the visible region, which is not preferable. The value of the mixing ratio of these targets respectively corresponds to the value of j in the film described above.

The composition of the protective film can be adjusted by changing the gas composition of the atmosphere during the reactive sputtering. When reactive sputtering is performed in an atmosphere containing at least oxygen, an inert gas such as argon or neon may be contained, but it is not preferable to contain too much. Reactive sputtering may be performed by adding nitrogen together with oxygen. The amounts of the inert gas and nitrogen are selected so that by adjusting the composition of the atmosphere, the absorption of the resulting film is reduced and the stability of the reactive sputtering is increased. The most important factor is the proportion of oxygen gas in the atmosphere. In order to obtain a film having a small refractive index, no absorption, and excellent abrasion resistance and chemical durability, the partial pressure of oxygen is 20% 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 glass having a visible light transmittance of 70% or more, which is particularly suitable for a window glass of an automobile, can be obtained.

As the transparent glass plate used in the present invention, a colorless transparent float glass or a colored transparent float glass such as bronze, gray, and blue can be used.

[0015]

The protective film containing at least silicon, zirconium, carbon and oxygen and the protective film containing at least silicon, zirconium, carbon, oxygen and nitrogen formed on the uppermost layer of the heat ray shielding glass of the present invention are visible. Protects the heat-shielding film coated on the transparent substrate from chemical corrosion, abrasion, and external forces such as abrasion and scratches from the surrounding environment. Disadvantages are less likely to occur. 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, when a protective film having such excellent durability is formed by a reactive sputtering method with high productivity, zirconium carbide or zirconium nitride in the target reduces the electric resistance of the target, thereby stabilizing the process. In addition, it is possible to suppress the disadvantage that particles adhere due to the increase in the property and the occurrence of abnormal discharge.

[0016]

The present invention will be described in detail with reference to the following examples. FIG. 1 is a partial cross-sectional view of the heat ray shielding glass of the present invention. The heat ray shielding glass 1 is provided with a heat ray shielding film 3 coated on a glass plate 2 and protected on the heat ray shielding film 3. The membrane 4 is covered. Example 1 A protective film made of silicon, zirconium, carbon and oxygen was formed by sintering silicon carbide and zirconium carbide or zirconium nitride using a trace amount of a sintering agent in an atmosphere containing at least oxygen. It was formed by reactive sputtering in a gas. Before forming a protective film on the heat ray shielding film, a single layer of the protective film was formed and evaluated in order to find the optimum film forming conditions for the protective film. 65% by volume silicon carbide (SiC) as target
And 30% by volume of zirconium carbide (ZrC) (the remainder consists of a sintering aid). The 2.1mm thick float glass plate was cleaned placed in a sputtering apparatus, evacuating the vacuum chamber was installed target to about 5 × 10 ^{over 4} Pa, ^100scc in total flow rate of subsequent nitrogen and oxygen
m gas was introduced into the sputtering apparatus, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. Then, power is supplied to the target from the DC power supply to start discharging, and a current of 4 A
A film having a thickness of nm was formed on a glass substrate. The same procedure was repeated while changing the ratio of the gas flow rates of nitrogen and oxygen to be introduced into the vacuum chamber, thereby preparing seven types of samples. Abrasion resistance, alkali resistance, acid resistance, refractive index,
The chemical composition is shown in Tables 1 and 2.

Abrasion resistance was measured by applying a load of 500 g to two wear wheels of No. CS10F using a commercially available Taber abrasion tester and applying abrasion to the coating at 1,000 revolutions at a rotation speed of 60 rpm. It was evaluated by the change of change of (ΔY _a) and haze (ΔH _a). Alkali resistance and acid resistance are each 240 Hr in 0.1 N NaOH and H ₂ SO ₄ solution.
It was evaluated by the change in transmittance (ΔY _A ) and the change in reflectance (ΔR _A ) before and after immersion. The refractive index measured the refractive index n and the extinction coefficient k at the wavelength of 632.8 nm using an ellipsometer. Chemical composition was measured using ESCA.

[0018]

[Table 1]

[0019]

[Table 2]

From the above preliminary experiments, it is 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 important to form a film 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 manufactured, and the electric resistances thereof were measured. As a result, by changing the volume fraction of zirconium carbide mixed in the silicon carbide matrix from 20% to 30%,
The electric resistance of the sintered body is from 2 × ^10-1 Ω · cm to 1 × ^10-3
It was found that the value rapidly decreased to Ω · cm. actually,
By using a target obtained by mixing 30% by volume of zirconium carbide and a small amount of a sintering aid in silicon carbide and sintering the same, it is possible to reduce the amount of oxygen to 10
It was confirmed that the discharge stability was significantly improved even in an atmosphere of 0%, and that DC sputtering could be performed without causing harmful abnormal arc discharge for at least several hours. on the other hand,
When a target having a zirconium carbide content of 20% by volume is used, when the oxygen in the atmosphere is sputtered under the condition of about 30% or less, the discharge is stable for several hours or more, while the oxygen is further increased. It was found that abnormal arc discharge gradually started to occur, and the discharge stability decreased. Next, when the zirconium compound to be mixed into silicon carbide is changed from zirconium carbide to zirconium nitride, the electric resistance of the sintered body is 8 × 10 ⁻² Ω · cm even if the content is the same of 30% by volume. It was found to be inferior to zirconium carbide in terms of discharge stability.
Next, in order to know the upper limit of the amount of the zirconium compound to be mixed, an atmosphere containing 80% of nitrogen and 20% of oxygen was produced in the same manner as above using a target containing 20% by volume of silicon carbide and 80% by volume of zirconium nitride. When the film was formed by direct current sputtering in a room, the obtained film was colored brown to the extent that light absorption was clearly observed, and the abrasion resistance was evaluated. And the haze ratio was large, indicating that the abrasion resistance was slightly inferior. Example 2 In a direct current magnetron sputtering apparatus having two cathodes, a first cathode was made of titanium metal, and a second cathode was made of silicon carbide containing about 30% by volume of zirconium carbide and a small amount of a sintering aid. Each sintered body 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. Thereafter, nitrogen gas was introduced at a flow rate of 100 sccm, and the pressure in the vacuum chamber was adjusted to 0.4 Pa. 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 power to the cathode was stopped, the introduction of gas was stopped, and 5.3 × 10 ^-4 Pa was again applied by the vacuum pump.
After exhausting to 85 sccm of nitrogen gas and 15
It is introduced into the vacuum chamber at a flow rate of sccm and the pressure is set to 0.4 Pa
Was adjusted. 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, zirconium, carbon, nitrogen and oxygen having a thickness of about 20 nm on the titanium nitride film. The glass sample 1 thus obtained had a visible light transmittance of 72.7.
%, The solar light transmittance was 64.3%, and the visible light reflectance from the glass surface was 8.6%. Table 3 shows the results of evaluating the abrasion resistance, alkali resistance, and acid resistance of this sample by the same method as that performed on the single-layer film described above. Example 3 Next, the composition of the gas when forming the protective film by sputtering was
A titanium nitride film, silicon, zirconium, carbon, nitrogen and oxygen were formed on a 4 mm-thick bronze-colored transparent float glass substrate by the same procedure as in Example 2 except that the nitrogen gas was 80 sccm and the oxygen gas was 20 sccm. A glass sample 2 on which a coating was formed was obtained. This sample has 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 zirconium carbide and a trace amount were used as a third cathode. A target of a silicon carbide sintered body containing a sintering aid was set. The cleaned bronze-colored float glass of 4 mm thickness is put in a vacuum chamber of a sputtering apparatus, and the vacuum chamber is evacuated to 7 × by a vacuum pump.
Evacuation was performed to 10 ^-4 Pa. A mixed gas of 20 sccm of argon and 80 sccm of oxygen was introduced into the vacuum chamber, and the pressure was adjusted to 0.33 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 changed to argon 40 sccm and oxygen 60 sccc.
m, and the pressure was adjusted to 0.4 Pa, a current of 8 A was applied to the cathode of the titanium target, and sputtering was performed for a predetermined time, and a 50 nm TiO ₂ film was formed on the SnO ₂ film. 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, sputtering is performed for a predetermined time, and 40 n is formed on the TiO ₂ film.
m of SnO ₂ film. Finally, the atmosphere in the vacuum chamber was almost completely replaced with a mixed gas of 80 sccm of nitrogen and 20 sccm of oxygen, and adjusted to 0.4 Pa. 4A for cathode of target of sintered body of zirconium carbide and silicon carbide
Is applied and sputtering is performed for a predetermined time to obtain SnO.
_{On the two} films, a film of silicon, zirconium, carbon, nitrogen and oxygen having a thickness of 15 nm was formed. The glass sample 3 thus obtained has the characteristics that the visible light transmittance is 75.3%, the sunlight transmittance is 60.8%, and the visible light reflectance from the glass surface side is 8.5%. It turned out to be heat ray shielding glass. Table 3 shows the results of evaluating abrasion 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 made of silicon, zirconium, carbon, nitrogen and oxygen was formed on a titanium nitride film by the same method using the same apparatus as in Example 2. However, when forming a film made of silicon, zirconium, carbon, nitrogen and oxygen, a silicon carbide sintered body containing 40% by volume of zirconium nitride and a trace amount of a sintering aid was used as a target. The cleaned 4 mm-thick bronze-colored transparent float glass was put in a vacuum chamber of a sputtering apparatus, and 5.3 × 1 with a vacuum pump.
The chamber was evacuated to 0 ^-4 Pa. After that, nitrogen gas
The pressure in the vacuum chamber was adjusted to 0.4 Pa at a flow rate of 0 sccm. Then, power was supplied from a DC power supply to the metal titanium target to start sputter discharge. After setting the current value to 5 A, the glass substrate is passed over the cathode at a predetermined speed at a predetermined speed, so that about 5 n
m of titanium nitride was formed. 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.
0 sccm 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, the glass substrate was again passed through the cathode at a predetermined speed to form a film of silicon, zirconium, carbon, nitrogen and oxygen having a thickness of about 20 nm on the titanium nitride film. . Glass sample 4 thus obtained
Has a visible light transmittance of 70.7% and a solar light transmittance of 6
The heat ray shielding glass exhibited a performance of 2.3% and a visible light reflectance from the glass surface of 8.9%. Table 3 shows the results of evaluating the abrasion resistance, alkali resistance, and acid resistance of this sample in the same manner as described above. Sample 4 was also found to be a heat-shielding glass exhibiting excellent durability.

[0021]

[Table 3]

COMPARATIVE EXAMPLE 1 As in Example 2, a DC magnetron sputtering apparatus provided with two cathodes has one cathode containing metallic titanium and the other cathode containing about 18% by weight of free silicon. A silicon sintered body (containing no zirconium) 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 had a visible light transmittance of 73.5%, a solar light transmittance of 65.5%,
The heat ray shielding glass exhibited optical characteristics such that the visible light reflectance from the glass surface side was 7.6%. Table 3 shows the results of evaluation of the wear resistance of this comparative sample 1 by the Taber abrasion test and the evaluation of alkali resistance and acid resistance in the same manner as in the example. It shows excellent abrasion resistance, but poor alkali resistance. Comparative Example 2 In exactly the same manner as in Example 4, as an example in which the protective film according to the present invention was not formed on the uppermost layer, a SnO ₂ film having a thickness of 55 nm was formed on a 4 mm-thick bronze-colored float glass plate,
60 nm thick TiO ₂ film and 55 nm thick Sn
O ₂ 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. From Table 3,
It can be seen that Comparative Sample 2 was inferior in abrasion resistance, and was not excellent in both chemical durability and abrasion characteristics.

As can be seen from the above examples, the heat ray shielding glass of the present invention has been improved so that both chemical durability and wear resistance are enhanced.

[0024]

The outermost layer of the heat ray shielding glass of the present invention, which is in contact with air, is made of silicon, zirconium, carbon and oxygen or silicon, zirconium, carbon, oxygen and nitrogen and has excellent chemical durability and wear resistance. Since it is a protective film, it does not corrode or be damaged by scratches or the like even when it is used in direct contact with the outside air. 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. Further, since the protective film of the present invention can be stably coated by the DC sputtering method, it can be stably coated on a large substrate.

[Brief description of the drawings]

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

[Explanation of symbols]

1 ... heat ray shielding glass, 2 ... glass plate, 3 ...
Heat shielding film, 4 ... Protective film

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-833 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 15/00-23/00 C23C 14 / 00-14/58

Claims (6)

(57) [Claims] A transparent glass plate is coated with at least one heat ray shielding film, and a protective film made of silicon, zirconium, carbon and oxygen, or silicon, is formed on the heat ray shielding film . Zirconium, carbon, oxygen
Heat shielding glass covered with a protective film made of
There are, SiZr the composition of the protective layer _{j C k N m O n (} j,
k, m, and n are represented by a chemical formula:
2 ≦ j ≦ 0.6, 0 <k ≦ 0.8, 0 ≦ m ≦ 1.0, n
A heat ray shielding glass characterized by ≧ 1.2 . Wherein said heat ray shielding property of the coating is titanium, zirconium, hafnium, heat ray shielding according to claim 1, characterized in that at least one of the nitride or oxynitride films selected from the group consisting of chromium Glass. 3. A heat-shielding film according to claim 1, wherein said heat-shielding film is a multilayer film in which films made of a low-refractive-index material and films made of a high-refractive-index material are alternately laminated. 3. The heat ray shielding glass according to item 2 . 4. The thickness of the protective film is 5 nm or more and 100 n.
The heat ray shielding glass according to any one of claims 1 to 3 , which is not more than m. 5. A solar control glass of any one of claims 1 to 4, wherein the visible light transmittance of 70% or more. 6. The protective film is coated by DC reactive sputtering in a reduced pressure atmosphere containing at least oxygen using a target comprising a mixture containing silicon carbide and at least one of zirconium carbide and zirconium nitride. The heat shielding glass according to any one of claims 1 to 5 , characterized in that: