JPH03187736A - Heat rays barrier glass - Google Patents

Abstract

PURPOSE:To obtain a heat rays barrier glass with excellent durability and chem. stability by preparing the heat rays barrier glass wherein three layers consisting of a heat rays barrier film, a low refractive index oxide film and a protective film are laminated on a transparent substrate 1 and the refractive index of the low refractive index oxide film is at most a specified value and the protective layer consists of an amorphous film wherein a specified oxide is a main ingredient. CONSTITUTION:As a transparent substrate 1, various glass plates and plastics are used. A heat rays barrier film 2 is formed on the transparent substrate 1 and a low refractive index oxide film 3 is formed thereon. Then, a protective film 4 with excellent durability is formed thereon. As a film material of the low refractive index oxide film 3, an oxide with a refractive index of 2.0 or smaller contg. at least one of boron and silicon and at least one among zirconium, titanium, tantalum, hafnium, indium and tin is used. A film material of the heat rays barrier film 2 is selected from a metal, a carbide, an oxide or a composite film thereof. As the protective film 4, an oxide film consisting of at least one among titanium, zirconium, hafnium, tin, tantalum and indium and at least one of boron and silicon is pref.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to heat-shielding glass.

[Prior Art] Heat ray blocking glass has traditionally been used to block solar energy from flowing into the interior of a building through window glass, suppress the rise in indoor temperature, and reduce the cooling load. Conventional heat-shielding glass is known in which several hundred thin films of oxides such as titanium oxide, tin oxide, etc. are formed on glass by spraying, CVD, or dipping. Recently, sputtering has been used to produce not only oxides but also
Thin films of metals, nitrides, etc. can now be formed freely over large areas. For this reason, single-layer film systems of transition metals such as chromium or titanium, metal/oxide films, two-layer film systems of nitride films/oxide films, oxide films/nitride films/oxide films, or Heat-shielding glass having a three-layer structure of oxide film/metal/oxide film, or a multilayer structure of more than that, has also come to be used.

Unlike a single-layer film, a heat-shielding glass having a multi-layer structure of three or more layers allows the reflectance and reflection color tone to be selected quite freely by utilizing interference. For this reason, demand is increasing for architectural applications where design is important.

In addition, heat-reflecting glass called Low-E glass (low-emissivity glass) is also known, which prevents the indoor temperature from dropping by reflecting heat rays from the room and reduces the heating load. .

This is oxide film/A g/oxide film or oxide film/A
It has a laminated film with a structure of g/oxide film/Ag/oxide film and is mainly used in cold regions. However, since it uses an Ag film, it is inferior in durability.

For this reason, laminated glass or double-glazed glass is used to prevent the laminated film from being exposed to the outside. This Low-
Since E-glass also has the effect of blocking heat rays from sunlight, it is also used in some automobile glasses for this purpose.

Heat-shielding glass, in which a film of oxides such as titanium oxide or tin oxide is formed on glass using conventional spraying, CVD, or dipping methods, can be manufactured at low cost and with high productivity; Compared to metal or alloy-based single-layer or multi-layer heat-shielding glass, tin oxide has a slightly inferior heat-shielding performance, and tin oxide is susceptible to acids and lacks sufficient chemical stability. Ta.

In addition, single-layer heat-shielding glass made of transition metals such as chromium and titanium generally has a high visible light reflectance Rv of 10 to 50%, and the reflective colors include bronze, blue, green, gray, gold, and silver due to design considerations. It is colored. Moreover, the visible light transmittance Tv is also as low as 10 to 60%. Therefore, natural colors, i.e. neutral colors and low reflectance,
In addition, it was unsuitable for application to window glasses for automobiles or general households, which require a visible light transmittance of 70% or more. In addition, such single-layer metal films do not have sufficient durability such as scratch resistance and chemical stability (for example, for automobiles, etc.).
It was impossible to use a single plate in applications where the operating environment was harsh.

In addition, the aforementioned type of Low-E glass has a relatively neutral reflective color and a visible light transmittance of 70% or more, but since it uses an Ag film, it has insufficient scratch resistance. The drawback was that it could not be used as a single sheet and had to be laminated or double-glazed.

In addition, conventional two-layer heat-shielding glasses such as metal/oxide film or nitride film/oxide film have not been able to provide neutral color tone, durability, high transmittance, and low reflectance. There wasn't.

In addition, heat ray blocking glass with a three-layer structure in which a film made of metals such as titanium, zirconium, chromium, or nitrides of these metals is sandwiched between high refractive index oxide films also has sufficiently good heat ray blocking performance. It is possible to adjust the thickness of the oxide film and use light interference to suppress the reflectance of visible light and increase the visible light transmittance to 70% or more, and the outermost layer is an oxide film. Although it is suitable as a single-pane heat-shielding glass because of its excellent durability, it can also cause blue color due to light interference.
The problem is that it takes on a pink or yellow color, making it difficult to obtain a natural, neutral appearance.

In this way, it has high durability that can be used as a veneer,
It has not been possible to obtain a heat-shielding glass that has a high visible light transmittance, particularly 70% or more so that it can be used as a window glass for automobiles, and is neutral in both transmittance and reflective color.

Therefore, the present inventor has proposed a heat ray blocking glass in which at least two layers, a heat ray absorbing film and an oxide film, are sequentially laminated on a transparent substrate, the oxide film being the outermost layer on the air side, and having a film density of 2.0 or less. A heat-shielding glass has already been provided which is characterized by having a refractive index of . (Patent Application No. 63-144827) However, when silicon oxide, aluminum oxide, tin oxide, etc. are used as a low refractive index film with a refractive index of 2.0 or less, long-term chemical durability such as alkali resistance and acid resistance is insufficient. It was inferior.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a heat ray shielding glass with excellent durability, especially chemical stability. be.

[Means for Solving the Problems] That is, the present invention consists of at least three layers laminated in sequence, a heat ray blocking film, a low refractive index oxide film, and a protective film on a transparent substrate, and the low refractive index oxide film A heat ray blocking glass having a refractive index of 2.0 or less, the protective layer of which is an oxide containing at least one of boron and silicon and at least one of zirconium, titanium, hafnium, tin, tantalum, and indium. Heat-shielding glass characterized by being composed of an amorphous film whose main component is solids.

It provides:

FIG. 1 is a cross-sectional view of an example of the heat ray blocking glass of the present invention, in which 1 is a transparent substrate, 2 is a heat ray blocking film, 3 is a low refractive index oxide film, and 4 is a protective film.

As the transparent substrate 1, various glass plates such as a soda lime glass plate and a heat ray absorbing glass plate, plastics, etc. can be used, and the transparent substrate 1 is not particularly limited.

Next, a heat ray blocking film 2 is formed as a first layer on the transparent substrate. On top of this, an oxide film (second layer) 3 with a low refractive index is formed to lower the reflectance and make the color caused by interference less noticeable.Prior to this, an oxide film (second layer) 3 with a low refractive index is formed to prevent the heat ray blocking layer from being oxidized. Forming a thin barrier layer makes it easier to control transmittance, reflectance, color tone, etc.

Next, a protective film (third layer) 4 having excellent durability and especially chemical stability is formed.

The film material of the low refractive index oxide film 3 has a refractive index of 2.0.
If it is below, it is easy to obtain a heat-shielding glass with a visible light transmittance of 70% or more, so there is no particular limitation, but at least one of boron or silicon and at least one of zirconium, titanium, tantalum, hafnium, indium, and tin Suitable examples include oxides containing these, tin oxide, and silicon oxide.

Since the oxide film containing at least one of boron or silicon and at least one of zirconium, titanium, tantalum, hafnium, indium, and tin is amorphous,
It has very good wear resistance and is especially suitable for applications that require high durability. The content ratio of boron and silicon to zirconium, titanium, etc. is not particularly limited, but if the content ratio of boron or silicon is too low, the refractive index will exceed 2.0, and the heat-shielding glass has a visible light transmittance of 70% or more. It becomes difficult to obtain boron, silicon, or the total of them in an atomic ratio of 30 or more per 100 parts of zirconium.
In particular, it is desirable to contain 80 parts or more.

As described above, as the low refractive index oxide film 3 of the heat ray blocking glass of the present invention, an oxide film containing at least one kind of boron or silicon and at least one kind of zirconium, titanium, etc.
Although the tin oxide film and the silicon oxide film are mentioned, the invention is not limited to these, and these oxide films can improve durability, adjust optical constants, stabilize film formation, or speed up film formation. In order to improve the refractive index, the low refractive index oxide film 3 may contain other components, and the low refractive index oxide film 3 of the present invention does not necessarily have to be completely transparent. or may contain a portion of nitrogen or carbon.

The thickness of the low refractive index oxide film layer 3 is not limited, but if it is too thin, sufficient durability cannot be obtained, so depending on the application,
It is desirable that the thickness be 508 Å or more, preferably 100 Å or more, particularly 150 Å or more. On the other hand, if it becomes too thick, interference effects will occur and the reflected color will become stronger, although it depends on the refractive index. Therefore, the thickness is preferably 1000 Å or less, preferably 700 Å or less, and particularly 500 Å or less.

The film material of the heat ray blocking film 2 is not particularly limited, and may be metal, carbide, oxide, or
Or selected from these composite membranes. Specifically, a film containing one of titanium, chromium, zirconium, tantalum, hafnium, titanium nitride, chromium nitride, zirconium nitride, tantalum nitride, and hafnium nitride as a main component is preferable because it has good heat ray blocking performance.

The thickness of the heat ray blocking film 2 is determined depending on the type of the substrate 1, the visible light transmittance decreases if it becomes too thick, and so on.
Although it depends on the refractive index and film thickness of the low refractive index oxide film 3, it is 100
A thickness of 0 Å or less, preferably 800 Å or less is desired. 800
If the thickness exceeds that of a person, the internal stress becomes large, especially in the case of a nitride film, and the film is likely to peel off. Moreover, if it is too thin, sufficient heat ray blocking performance cannot be obtained, so it is preferable that the thickness is 20 Å or more, preferably 20 to 100, although it depends on the film material and the thickness and type of the substrate glass.

The protective film 3 is preferably an oxide film made of at least one member selected from the group consisting of titanium, zirconium, hafnium, tin, tantalum, and indium, and at least one member selected from the group consisting of boron and silicon.

The composition of the protective film 3 is not particularly limited, but in order to make the film amorphous and improve scratch resistance and reliability, oxide films of titanium, zirconium, hafnium, tin, tantalum, indium, boron, and silicon are recommended. are Ti0g, ZrOs, and HfO*, respectively.
, Sn0m, Ta1Os, InaOi, Ba0a.

Stow, Ties, ZrOs, H
fO*, Snow, TatO++.

and In10m, the total molar ratio of oxides selected from B*Os and SIO□ is 5 parts or more, preferably 10 parts or more, especially 20 parts or more. In the case of B, 03, if there are too many, the reliability will decrease, so depending on the application, Ties,
ZrOs, HfO*, Snow, TazOs, and In, 0. 200 parts or less, preferably 100 parts or less, particularly 5
0 parts or less is better.In the case of Sin, if too much is used, the durability against alkali will decrease, so TiO, Zr
O□.

Hf0z, SnO*+ 19 molar ratio to 100 parts in total of oxides selected from TazOs and InaOi
00 parts or less, preferably 900 parts or less, especially 400 parts or less.

Table 1 specifically shows the properties of various amorphous oxide films most suitable for the protective film of the present invention.

Films were formed by reactive sputtering using targets with the compositions listed in the table. Crystallinity is
Observation was made by thin film X-ray diffraction. In addition, the scratch resistance is the result of a rubbing test using a sand eraser, where ○ indicates that there were almost no scratches, and × indicates that scratches occurred easily.

As for wear resistance, as a result of a taper test (wearing wheel C5-10F, weighted sooo g, too rotation), those with a haze of 4% or less were rated as ○, and those with a haze of more than 4% were rated as poor. Acid resistance was immersed in 0.1N HISO for 240 hours.
If the rate of change in Tv (visible light transmittance) and Rv (visible light reflectance) is within 1% compared to before immersion, O, 1 to 4%.
Those in which the film was dissolved and disappeared were marked as ×. Alkali resistance is 0. As a result of immersion in 1N NaOH for 240 hours, the rate of change in TV and Rv from before immersion was rated ◯ if it was within 1%, Δ if it was within 2%, and × if the film had dissolved. The boiling test is under 1 atm.
After immersion in 100°C water for 2 hours, Tv.

○, when the rate of change of R from before immersion is within 1%;
When it exceeded 1%, it was marked as ×.

Regarding the ZrBxOy film, as is clear from Table 1,
It can be seen that when the amount of B in the film is small, a crystalline film tends to be formed, and when the amount of B is large, an amorphous film tends to be formed. It can be seen that the crystalline film has poor scratch resistance and abrasion resistance, whereas the amorphous film has excellent scratch resistance and abrasion resistance. This is an amorphous film,
This is thought to be due to the smooth surface. Therefore, Zr
BxOv film (atomic ratio X of B to Zr in the film is 0.1
A film with 0<x) has excellent scratch resistance and abrasion resistance. B2
0. Since the film is hygroscopic and absorbs moisture in the air and dissolves, it is preferable that x<4 for the ZrBxOy film.

The atomic ratio of ZrB, tO, and 0 (oxygen) to Zr in the film is not particularly limited, but if it is too high, the film structure will become rough and uneven, and if it is too low, the film will become metallic. Zr0i and B20 tend to decrease in transmittance and abrasion resistance of the film.
．． It is preferable that the amount is such that a composite system of . That is,
If the composite oxide is expressed as ZrO□+xBO+,s, then Z
When X is included in the atomic ratio to r, y=2+1.5z
It is preferable that the degree of

Furthermore, Table 1 shows that as the amount of B in the peritoneum of ZrB and Oy increases, the refractive index of the film tends to decrease. The relationship between the composition of the film and the refractive index n is shown in FIG. 2(a). By increasing the amount of B in the film, the refractive index n decreases from about 2.0 to about 1.5.

Therefore, the ZrBxOy film with 0.10<x<4.2<y<8 has good scratch resistance and abrasion resistance, and is suitable for the purpose of the present invention since the refractive index can be freely selected depending on the amount of B. It is an amorphous oxide film.

Furthermore, as shown in Table 1, as the content of B in the film increases, the acid resistance and alkali resistance tend to deteriorate. When X≧2.3, the acid resistance deteriorates, and when x>4, the alkali resistance decreases and deterioration occurs in the boiling test. Therefore, Zr
A protective film of B, 0° (x<2.3, y<5.45) is preferred.

As mentioned above, by adding boron oxide B30. to the z"0. film, the film becomes amorphous and the surface becomes smooth, which is thought to contribute to improved wear resistance and scratch resistance. In addition, the refractive index can be adjusted by adjusting the amount of %B, and furthermore,
Compared to a ZrOs film, it has a smaller internal stress, so it is advantageous in terms of adhesion with adjacent films. This is especially advantageous when forming thick films.

Next, regarding the Zr5ixOy film, it is also amorphous, and a film with high scratch resistance and abrasion resistance can be obtained.

Regarding the refractive index, ZrO, (n = 2.14) and 5
ins (n = 1.46) depending on the composition ratio (see Figure 2 (b)).
In the r5LOy film, it is preferable that 0.05≦2 (atomic ratio of St to Zr in the film)<19.

If z<0.05, the film will not become amorphous and sufficient physical durability will not be obtained, and if 2≧19, alkali resistance will deteriorate. In addition, y (the atomic ratio of 0 to Zr in the Zr51m0y film) is approximately y = 2 + 2z when the atomic ratio of SL to Zr is 2 for the same reason as described for the ZrBxOy film. is preferable, that is, 0.05≦2≦19.2.1≦y<40.

Further, a ZrBmSi,O, film is also a film suitable for the purpose of the present invention. If the atomic ratio x of B to Zr, the atomic ratio z of Si, and the atomic ratio y of O to Zr in such a film are This is preferable because it results in a high film thickness.

In addition, if x+z<19, the alkali resistance is also good, so in the ZrBgSxxOy film, 0.05≦x+
Preferably, z<19. However, as mentioned above,
Since B803 is hygroscopic and dissolves by absorbing moisture in the air, it is better not to contain too much in the ZrBxSi*Oy film.
Zr<25 for the sum of Zr, B, and Sl other than
If B is included to the extent that the remainder is B when atomic % and St<25 atomic %, the chemical durability will be insufficient. That is, Z
Zr:B:Si (atomic ratio) in the rBmSimOy film is 1
:x:z.

1/ (1+x+z)<0.25 and Z/(1+x+Z
)<0.25, i.e. x+z-3>0 and x-32+1
>0 composition has unfavorable chemical durability, y is Zr
For the same reason as stated in the case of BxOy, considering this film as a composite system of ZrOs + B*Os + 5ift, y is preferably about 2+1.5 x+ 2z, so approximately 2<, y< It is preferable that it is about 40, and the higher the content of B+Sl, the more ZrB+gSimOy
The refractive index of the film decreases* An example of a ZrB+Si+tOy film is shown in FIG. 2(c).

Metals other than Zr, i.e. T 1 e Hf * S n
The oxide containing e Ta e I n and at least one of B and SL similarly becomes amorphous, and sufficient scratch resistance and abrasion resistance are obtained e Tl51m0y
The membrane is shown as sample 28 in Table 1 by way of example.

Above, ZrBxO, system%Zr5nxOy system, ZrBI
In a film such as IS1mOy, the amount of B or SL added may be adjusted so as to have a desired refractive index depending on the film design.

The thickness of this protective layer 4 is not particularly limited, but if it is too thin, it will not form a continuous film, so it is preferably 30 Å or more, preferably 50 Å or more, although it depends on the film forming method. Further, if the thickness is thick, the color due to interference becomes noticeable, so if a neutral appearance is required, the thickness should be 500 Å or less, preferably 200 Å or less.

As the low refractive index oxide layer 3 in the present invention, Zr, Ti
, Hf, Ta, Sn, and In;
An oxide containing at least one of Si and B can also be used. In this case, an oxide containing zirconium and boron ZrBxOyt an oxide containing zirconium and silicon Z
r5izOy - In a film made of ZrB, 51m0y, an oxide containing zirconium, boron, and silicon, its optimum composition is B (boron).

Letting the atomic ratio of SL (silicon) and 0 (oxygen) to Zr (zirconium) in each film to be X+Z+y, the range is as follows.

As is clear from Table 1, 1.0 for ZrBxOy
It is preferable that ≦X. If x<1.0, the refractive index of the film will exceed 2.0, making it difficult to obtain a heat-shielding glass with a visible light transmittance of 70% or more. On the other hand, as the refractive index of the film decreases as X increases (see Figure 2 (a)), the upper limit of x is not particularly limited.
≧2.3 Acid resistance decreases, and when X≧4, alkali resistance decreases and deterioration occurs in the boiling test. It is preferable that ≦x<2.3. Although y is not particularly limited, Zr0g and B, 0. If we consider it as a composite system and express it as Zr0g+xBO+, then y=2+1
．． It is preferable that it is about 5z, that is, 2.5≦y<s, 4s.

Regarding the Zr5iiO, film, as with the ZrBxOy film, the refractive index decreases as 2 increases (see Figure 2 (b)), but since SL contributes more to the refractive index decrease than B, B With a smaller amount, n=2.0 or less, so 0.
It is preferable that 28≦2. There is no particular upper limit, but Z2! :19, the alkali resistance of the film becomes insufficient and the advantage of containing Zr is hardly recognized, so it is preferable that 0.28≦z<19. y
Similarly, considering a composite system of ZrO* and 5ift, it is preferable that y=2+2Z, that is, 2.56≦y<40.

Regarding the ZrBxSizO film, similarly, from the viewpoint of refractive index, it is preferable that 0.28≦X+Z. Similarly, there is no particular upper limit limit, but if x+z<19, the alkali resistance is also good, so in the ZrBwSLxOsp film, it is preferable that 0.28≦x+z<19. However, the above-mentioned As B2O, is hygroscopic and absorbs moisture in the air and dissolves, ZrBxSixO,
It is better not to contain too much in the film. in particular,
As mentioned above about the protective film, in the film,
If Zr<25 at% and SL<25 at% and B is included as the remainder, the chemical durability will be insufficient. That is, ZrBmSi, 0. Zr:B:St in the film
If (atomic ratio) is 1:x:z, then 1/(10x +
z ) <0.25, and Z/ (1+x+z)<0.
25, that is, a composition in which x+z-3>O and x-3z+1>0 has unfavorable chemical durability.

For the same reason as mentioned in the case of ZrB++Oy, considering this film as a composite system of ZrO + B*Om + SiO snow, y is preferably about 2 + 1.5 x + 2z, so it is approximately 2.5. It is preferable that ≦y<40, and the higher the content of B and Si, the more ZrBmSix
O, the refractive index of the film decreases (see FIG. 2(c)).

From the above, as the low refractive index oxide film 3 of the present invention, the oxide film containing at least one of boron and silicon and zirconium is selected from ZrB, 0.0. Membrane (1,0≦x<2.3
．． 2.5≦y<5.45), Zr5ixOy film (0
,28≦z<19.2.56≦y<40, Zr
BxStxO,.

Particularly preferred are membranes (0,28≦x+z<19.2.5≦y<40, excluding the portions where x + z −3>O and x−3z+l>O).

For these films, X≧0.1O1 for ZrBxOy films.
ZrS1! For OF film, 2≧0.05, ZrB+t
For the SixO film, if x+z≧0.05, the film becomes amorphous and has excellent wear resistance.

An oxide containing at least one of Ti, B, and SL can also be used as the low refractive index oxide 3 of the present invention.

In this case, from FIG. 2(d), the refractive index of the Ti5ixOy film is 2 or less when Z≧0.56.

Also, a heat ray blocking film 2, a low refractive index oxide layer 3, and a protective film 4
The film forming method is not particularly limited either (vacuum evaporation method, ion blating method, sputtering method, etc. are possible, but if large area coating is required, reactive sputtering method with excellent uniformity is recommended). preferable.

"Function" The first layer is a layer that reflects and absorbs heat rays, and the second layer has the function of lowering the reflectance and making colors caused by interference of reflection less noticeable. The third layer plays the role of a protective film consisting of a film with excellent scratch resistance and chemical stability. The boron and silicon contained in the third layer improve the scratch resistance that is lacking in films made of zirconium oxide, etc. It works to make things happen. It is thought that boron changes the zirconium oxide film from crystalline to amorphous, making the surface friction as smooth as glass, reducing frictional resistance and improving scratch resistance. In addition, the internal stress is also low accordingly, which improves adhesion with the underlying layer.On the other hand, as the boron content increases, the acid resistance gradually decreases, and when the boron content increases further, the alkali resistance and water resistance also decrease. Therefore, it is preferable to control the amount of boron or silicon contained in zirconium oxide or the like within the above-mentioned range.

[Example] Example 1 A glass substrate was set in a vacuum chamber of a sputtering device.
It was evacuated to X 10-' Torr. A 4 mm thick blue plate was used as the glass substrate. Similar glass substrates were used in Example 2 and subsequent examples. After introducing a mixed gas of argon and nitrogen to set the pressure to 2×10-” Torr, titanium was reactively sputtered to form about 20 pieces of titanium nitride as the heat ray shielding film 2. The titanium nitride was then oxidized. A ZrBx film was formed by sputtering a ZrB1 target in Ar gas as a barrier layer. Next, the mixture gas of argon and oxygen was switched to a pressure of 2 x 10-"T.
orr, a ZrB* target is reactively sputtered to form an oxide film consisting of zirconium and boron (ZrBxOy, x=2.y=5) as the low refractive index oxide film 3.
A Zf'tBs target with a refractive index n: 1.80) was reactively sputtered in a zero-order mixed gas of argon and oxygen to form a protective film 4 of ZrBx'Oy.
'(X' !10, 43.y' = 2.6) The film is approximately 1
00 people were formed to produce the heat ray blocking glass of the present invention.

Visible light transmittance TV of the heat ray blocking glass thus obtained
, sunlight transmittance TE% coated surface visible light reflectance r,
The glass surface visible light reflectance RV) is 72 and 57, respectively.
It was 10.8 (%).

Furthermore, the transmitted and reflected colors were so neutral that they were almost indistinguishable from the original glass.

To test the durability of the membrane, it was immersed in 0.1N sulfuric acid and sodium hydroxide for 200 hours, or in boiling water for 2 hours, but the change in transmittance was within 1%, and almost no change in optical performance was observed. I couldn't.

Even in a rubbing test with a sand eraser, there were almost no scratches and extremely excellent scratch resistance was exhibited.

Example 2 Instead of the titanium nitride film as the first layer in Example 1, a Cr target was reactively sputtered in a mixed gas of argon, nitrogen, and oxygen to form a heat ray blocking film 2 of CrNx0y.
A heat ray blocking glass was manufactured in the same manner as in Example 1, except that about 20 layers were formed, and the optical performance and durability were the same as in Example 1.

Comparative Example 1 After forming a TiN film (20 films) as the heat ray blocking film 2 and a 15 film oxidation barrier film in the same manner as in Example 1, a Zr5By target was formed as a low refractive index oxide film in a mixed gas of argon and oxygen. ZrBxOy film (x=2.3.y=5.5.refractive index n=1.76) by reactive sputtering
200 layers were formed, and no protective film was formed thereon. What are Tv, Tt, Rvr, and RVQ, respectively?
1.56.13.12 (%), the scratch resistance was similar to Example 1.2, but the acid resistance test in Example 1 (200 hours immersion in 0.1N H,SO,) On TV
It showed a change of 1% or more.

Example 3 About 20 titanium nitride films were formed on glass in the same manner as in Example 1, and then about 60 films of tin oxide (n=2.0) were formed, and Zr5izOy (z=1) was further formed as a protective layer. .y=4
．． n=1.74) films were formed by about 80 people to form the heat ray blocking glass of the present invention. The optical performance of this heat ray blocking glass is as follows: T v , T z , RVF% RVO are each 7.
2.58.10.8 (%), and the appearance was almost neutral. Durability was similar to Example 1.

Comparative Example 2 In Example 3, no protective film was formed and glass/TiN
(20 people)/Snow (60 people) (n=2.0) heat ray blocking glass was formed. Its optical performance is T
V, Tt, RVF, and RVO are 72 and 5, respectively.
Regarding durability, the scratch resistance was the same as in Example 1.2.3, but the acid resistance test (
0,1 N HgSO4 for 200 hours), the Tv increased by about 3%.

[Effect of the invention] The heat ray blocking glass of the present invention has a heat ray blocking film on a transparent substrate,
It has a structure consisting of a low refractive index oxide film with a refractive index of 2.0 or less and a protective film layered on top of it, so it has a natural, neutral color tone, high visible light transmittance, and high durability. It has a sexual nature. Therefore, even as a veneer, it can be used satisfactorily in applications with severe operating environments, such as in construction and automobiles.

The chromium oxide/nitride film used as a heat ray shielding film has a higher resistance (more than 1M07) than that using titanium nitride, so it is suitable for automobiles without reducing the function of the printed antenna when used in the rear glass of an automobile. Advantages also arise, such as the ability to provide glass windows.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing an example of the heat ray blocking glass of the present invention. FIG. 2(a) shows ZrB, 0. A diagram showing the relationship between the content of B in the film and the refractive index n of the film, Figure 2 (b) is ZrS, 1
The relationship between the Si content and n in the xOy film is shown in Figure 2 (C
) is a diagram showing the relationship between the St content and n in the ZrB+5iaOy film, and FIG. 2(d) is a diagram showing the relationship between the St content and n in the ZrB+5iaOy film. FIG. 3 is a relationship diagram between the Si content in the Oy film and n. 1: Transparent substrate, 2: Heat ray blocking film, 3: Low refractive index oxide film, 4: Protective film (Figure 2Cb) lrBxOBp(Ktfey)-11-p=Sshim-
(:e, le /,)'i! roz+BxOs Fig. 2 (a) "lr f5+ S; 101!71% f ノjOx HrOLsu5jOz (MoIshiγ・) Fig. (C)

Claims (5)

[Claims] (1) A heat ray shield consisting of at least three layers laminated in sequence: a heat ray shielding film, a low refractive index oxide film, and a protective film on a transparent substrate, and the refractive index of the low refractive index oxide film is 2.0 or less. The protective layer is made of glass, and the protective layer is composed of an amorphous film mainly composed of an oxide containing at least one of boron and silicon and at least one of zirconium, titanium, hafnium, tin, tantalum, and indium. Heat ray blocking glass characterized by: (2) The heat-shielding glass according to claim 1, wherein the protective film is composed of a film whose main component is an oxide containing at least one of boron and silicon and zirconium atoms. (3) The heat ray shielding glass according to claim 1 or 2, wherein the low refractive index oxide film is composed of a film whose main components are zirconium and an oxide containing at least one of boron and silicon. (4) The heat ray blocking film is made of titanium, chromium, zirconium,
Claims 1 to 3 are characterized in that they consist of an oxide whose main component is at least one of tantalum, nitrides of these metals, oxynitrides of these metals, or absorbent oxides of these.
The heat ray blocking glass according to any one of the items. (5) The heat ray blocking glass according to any one of claims 1 to 4, wherein the heat ray blocking film is made of titanium nitride or chromium oxynitride.