JPH03187737A - Solar control product - Google Patents

Abstract

PURPOSE:To obtain a solar control product with excellent durability by forming a solar control film wherein at least one of a metal, a metal oxide and a metal oxide nitride is formed in this order on a substrate from the substrate side and an amorphous oxide film wherein a specified oxide is a main ingredient as an outer layer. CONSTITUTION:A solar control product is prepd. by forming at least two layers consisting of a solar control film 2 wherein at least one of a metal, a metal oxide and a metal oxide nitride is a main ingredient and an amorphous oxide film 3 wherein an oxide contg. at least one selected from titanium, zirconium, hafnium, tin, tantalum and indium and at least one of boron and silicon is a main ingredient. The refractive index of the oxide film 3 can be controlled by changing the content ratio of boron and silicon to enlarge the freedom of film design and a solar control product with various color tones and high durability can be obtd. by changing the quality and the thickness of the solar control film 2 and the refractive index and the thickness of the amorphous oxide layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly durable solar control article having a function of blocking solar energy.

[Conventional technology] Mirrors, heat-reflecting glass, solar control glass, low-emission glass, interference filters, camera lenses, and glasses have traditionally been made by forming thin films on transparent substrates such as glass or plastic to add optical functions. There are anti-reflection coatings for lenses.

Heat-reflective glass has been formed using titanium oxide, tin oxide, or the like by a spray method, a CVD method, or a dipping method. Recently, metal films and nitride films.

Glass plates made of tin-doped indium oxide (ITO) formed by sputtering are now being used as heat-reflecting glasses. The sputtering method allows for easy film thickness control and the ability to form multiple films in succession, and in combination with a transparent oxide film, it is possible to design transmittance, reflectance, color tone, etc. For this reason, demand is increasing for applications such as architectural and automobile window glass, where design is important.

Also, among heat-reflecting glasses, those with a film that has low transmittance in the visible spectrum band are called solar control glasses, and because they block most of the sunlight spectrum, high visible light transmittance is not necessary. However, they are used in applications where it is desired to block solar energy, such as car sunroofs and rear side windows.

[Problems to be Solved by the Invention] Surface mirrors, single-panel heat-reflecting glass, solar control glass, anti-reflection coatings for lenses, etc. are used with the coated film exposed to the air. For this reason, it must have excellent chemical stability and abrasion resistance, but even low-emission glass can be defective due to scratches during transportation or handling before it is made into double-glazed or laminated glass. For this reason, there is a demand for an optical thin film that is stable and has excellent wear resistance and also serves as a protective film.

To improve durability, a chemically stable and transparent oxide film is usually provided on the air side. These oxide films include titanium oxide, tin oxide, tantalum oxide, zirconium oxide,
Silicon oxide and other materials have been selected and used depending on the required performance.

However, although titanium oxide and zirconium oxide have excellent chemical stability, they tend to form crystalline films with large irregularities on the surface, which increases friction when rubbed and has poor wear resistance. .

On the other hand, tin oxide and silicon oxide are weak to acids and alkalis, respectively, and cannot withstand long-term immersion.Among these, tantalum oxide has both wear resistance and chemical stability, but it is still wear resistant. I can't say enough about it.

Furthermore, titanium oxide, tin oxide, tantalum oxide, and zirconium oxide have a relatively high refractive index, whereas silicon oxide has a relatively low refractive index, which limits the degree of freedom in optical design when providing various optical functions. be.

As described above, there is no known thin film that has both high durability and a wide degree of freedom in optical design.

[Means for Solving the Problems J] The present invention has been made to solve the above-mentioned problems.At least one of metals, metal oxides, and metal oxynitrides is deposited on a substrate in order from the substrate side. The solar control membrane is mainly composed of seeds, and the outermost layer on the air side is made of titanium,
Formation of at least two layers of an amorphous oxide film whose main component is an oxide containing at least one member selected from the group consisting of zirconium, hafnium, tin, tantalum, and indium, and at least one member selected from boron and silicon. The present invention provides a solar control article characterized by:

FIG. 1 shows a cross-sectional view of an example of a solar control article according to the present invention, in which 1 is a substrate or film made of transparent or colored glass or plastic, and 2 is a first layer that is a solar control film. , 3 indicates an amorphous oxide film serving as the outermost layer on the air side, particularly a second layer made of an oxide containing at least zirconium, boron, and/or silicon.

As described above, the present invention has at least a two-layer structure, but in some cases, the substrate 1 and the first layer 2 shown in FIG.
One layer or a plurality of layers may be formed between the second layer 3 and the second layer 3 to improve adhesion, adjust optical properties, or have various other functions.The most important feature of the present invention is that By forming an amorphous oxide film on the outermost layer on the air side, it is possible to create a solar control article with excellent wear resistance and chemical stability.

The amorphous oxide film of the second layer 3 in FIG. A composite oxide film containing at least one selected from the group of tin, tantalum, and indium and at least one of boron or silicon is preferable, and among these, especially zirconium and at least one of boron and silicon. The composite oxide film containing seeds has excellent scratch resistance and abrasion resistance.
It is preferred because it has sufficient chemical stability.

In this way, the second layer 3 or the third layer 13 is made of an oxide containing zirconium, boron, and/or silicon (ZrBNO,...
ZrSi! The content ratio of boron or silicon when using ZrBxSi toy) is not particularly limited. As the content ratio of boron or silicon increases, the refractive index of this film increases from 2.15 to 1.8 or less. (see FIGS. 2(a) to 2(c)). Therefore, the content of boron or silicon may be selected based on the optically required refractive index.

Table 1 shows the properties of various amorphous oxide films suitable for the outermost layer on the air side of the present invention. Films were formed by reactive sputtering using targets with the compositions listed in the table. Crystallinity was observed by thin film X-ray diffraction.

In addition, the scratch resistance is the result of a scratch test using a sand eraser.
O indicates that there were almost no scratches, and × indicates that scratches were easily generated.

As for wear resistance, as a result of a taper test (wearing wheel C5-10F, load 500 g, 1000 rotations), those with haze within 4% were rated O, and those with haze exceeding 4% were rated x. Fly resistance is O,
As a result of immersion in 1N HISO4 for 240 hours, the TV
(Visible light transmittance), Rv (Visible light reflectance) changes within 1% from before immersion are Q, 1 to 4% are Δ, and those where the film has dissolved and disappeared. I set it as X. Alkali resistance is determined by immersion in O, IN Na0)1 for 240 hours, and the rate of change in Tv and Rv from before immersion is within 1%, 012% is △, and the membrane has dissolved. × The boiling test is 100 at 1 atm.
After being immersed in water at a temperature of 0.degree. C. for 2 hours, the rate of change in Tv and Rv relative to before immersion was rated 0% if it was within 1%, and × if it exceeded 1%.

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
BxOy film (atomic ratio X of B to Zr in the film is 0, 1
0 < x) has excellent scratch resistance and abrasion resistance.
Since the BO film is hygroscopic and dissolves by absorbing moisture in the air, it is preferable that x<4 for the ZrBmOy film.

The atomic ratio of O (oxygen) to Zr in the ZrBmOy 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 and the transmittance will decrease. ZrO□, B, 0.
It is preferable that the amount is such that a composite system of Zr0g+XBO+,s is obtained.
When X is included in the atomic ratio to Zr, y=2+1.
It is preferable that it is about 5z.

Furthermore, from Table 1, it can be seen that as the amount of B in the ZrBxOy film increases, there is a tendency for the refractive index of the film 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, for applications where the film is exposed in the air, an amorphous oxide film of ZrB++0y (x<2.3) is preferable;
The film of ≧2.3) can be used as a low refractive index film in other applications.

As mentioned above, * By adding boron oxide B, 08 to the ZrO snow film, the film becomes amorphous and the surface becomes smooth, which is thought to contribute to the improvement of wear resistance and scratch resistance. . In addition, the refractive index can be adjusted by adjusting the amount of B, and since the internal stress is smaller than that of the Zr0t film, it is advantageous in terms of adhesion with adjacent films. This is especially advantageous when forming thick films.

Next, ZrSi, 0. As for the film, it is still amorphous, and a film with high scratch resistance and abrasion resistance can be obtained.

The refractive index varies depending on the composition ratio between ZrO* (n = 2.14) and 5ill (n = 1.46) (see Figure 2 (b)).More specifically, in the zrSigOy film, 0.05≦2 (Z in the film
The atomic ratio of Si to r) is preferably 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. Also, y (the atomic ratio of O to Zr in the ZrSi*Oy film) is approximately y=2+2z when the atomic ratio of St to Zr is 2 for the same reason as described for the ZrBxOy film. It is preferable that there be.

Therefore, for applications where it is used exposed in the air, 0
．． Zr51m0y where 05≦z<19.2.1≦y<40
Films are preferred, ZrSi with 19<z, 0. The film can be used as a low refractive index film in other applications.

Further, ZrB and 5liOy films are also suitable for the purpose of the present invention. In such a film, if the atomic ratio x of B to Zr, the atomic ratio z of Si, and the atomic ratio y of 0 are X+Z≧0.05, the film becomes amorphous and has high scratch resistance and wear resistance. This is preferable.

In addition, if X+Z<19, the alkali resistance is also good, so in ZrBxSimO, 0,05≦x+
Preferably, z<t9, provided that, as mentioned above,
Since Ba5s is hygroscopic and dissolves by absorbing moisture in the air, it is better not to contain too much in the %ZrBxSigOy film. Specifically, in the film, 0 (oxygen)
If B is included to the extent that Zr<25 atomic % and Sl<25 atomic % and the remainder is B with respect to the total of B, SL, and Zr other than that, the chemical durability will be insufficient. That is, ZrB
, Zr:B:Si (atomic ratio) in the 51m0y film is l:
If x:z, then 1/(1+x+z) <0.25 and Z/(1-1-x+z)<0.25, that is, x+z-
A composition in which 3>O and x-3z+1>0 has unfavorable chemical durability.

Considering this film as a composite system of ZrO* + B*Os + SlO* for the same reason as stated in the case of ZrBxOy, y is preferably about 2 + 1.5 x + 2z, so approximately It is preferable that 2<y<40, and the higher the content of B and SL, the more ZrBxSi
The refractive index of the xOy film decreases* An example of a ZrB+Sl*Oy film is shown in FIG. 2(c).

Metals other than Zr, i.e. T 11 Hf * S n
, Ta + I n , and an oxide containing a small amount (both of one kind) of B and SL similarly becomes amorphous, and sufficient scratch resistance and abrasion resistance can be obtained. Sample 28 is shown as an example.

The amorphous oxide film of the outermost layer on the air side of the present invention is made of Zr, TL
, Hf, Sn, Ta, In, B, SL, and elements other than O may be contained in trace amounts.

The amorphous oxide film of the outermost layer on the air side of the present invention does not necessarily have to be transparent, and an absorbent film in an oxygen-deficient state or a partially nitrogen-containing film is equally effective.

The thickness of the second layer 3, which is the outermost layer, is not particularly limited and may be determined depending on the application, taking into account the transmitted color and reflected color, but if it is too thin, sufficient durability will not be obtained. Therefore, it is desirable that the thickness be 50 Å or more, preferably 100 Å or more, particularly 200 Å or more.

The film forming method for the second layer 3 is also not particularly limited, such as vacuum evaporation method,
Both the ion blasting method and the sputtering method are possible, but when a large area coating is required for automobiles, architecture, etc., the reactive sputtering method is preferable because it has excellent uniformity.

The film material of the first layer 2 is not particularly limited, and is selected from metals, nitrides, carbides, borides, oxides, silicides, or composites thereof depending on the application or required specifications.

The first layer 2 as the solar control film of the present invention is made of metal such as Ti, Cr, Zr, Hf, Ta, Sn, etc.

Alternatively, absorbent oxides, nitrides, nitrides, etc. of these metals are mainly selected.

Nitride can vary in color tone depending on the degree of oxidation. Specifically, when a film is formed by reactive sputtering in a mixed atmosphere of nitrogen and oxygen, films exhibiting various color tones can be produced by changing the oxygen content ratio of the atmosphere.

The thickness of the solar control film of the first layer 2 depends on the desired transmittance, but it is preferably 50 Å or more because solar energy blocking performance can be obtained, and 1000 Å or less, preferably 500 Å or less. As the film thickness increases, the solar energy blocking performance improves, but when the number of people exceeds 1000, the absorption of the film increases (too much and the visible light transmittance Tv becomes 0).
%, and peeling is likely to occur due to internal stress. The outermost layer of the second layer 3 is an oxide film containing zirconium, boron, and/or silicon. If the first layer 2 and the second layer 3
A metal, metal oxide, or metal oxynitride containing boron or silicon is used as the first layer 2 in order to improve the adhesion between the layers and reduce the internal stress of the first layer 2.

It is particularly effective to use zirconium boride or zirconium silicide.

The solar control film article of the present invention preferably has a visible light transmittance Tv of 70% or less, although it varies depending on the application, in order to lower the solar energy σ transmittance T, and when used for a sunroof. is less than 10%, and
It is preferably 25% or more and 50% or less for rear side glass, and 50% or more and 70% or less for window glass of buses and the like.

[Function] The amorphous oxide film which is the outermost layer on the air side of the optical body in the present invention, that is, the second layer 3 in FIG.

The optical body of the present invention is made amorphous by containing glass constituent elements such as boron and silicon, which increases the smoothness of the surface and reduces frictional resistance, resulting in high durability. It has the role of a protective layer to improve abrasion resistance and chemical resistance, and by adjusting its refractive index, film thickness, etc., it can adjust optical functions, i.e., transmittance, reflectance, color tone, etc. Has a function.

When B and/or St are added to oxides of Zr, Ti, Hf, Ta, In, and Sn, B and/or Si
is believed to destroy the lattice of such oxides, hinder the growth of crystal grains of such oxides, and make the film more amorphous.

It is thought that an amorphous film has fewer irregularities on the film surface than a film that is an aggregation of microcrystals, and as a result, the amorphous film of the present invention is thought to have a reduced coefficient of friction. For this reason, the amorphous film of the present invention has excellent lubricity and is less likely to get caught, so it is unlikely to be scratched by friction (it is thought that high scratch resistance and high wear resistance can be obtained).

In particular, when the outermost layer is an oxide film containing zirconium and boron and/or silicon, the film can be formed by adding boron to zirconium oxide, which has strong chemical stability against acids and alkalis. This contributes to the realization of a highly durable film that is amorphous and satisfies both abrasion resistance and chemical stability.

Further, boron and silicon also contribute to adjusting the refractive index of the film. That is, the refractive index can be lowered by increasing the content of boron or silicon.

Further, in the solar control article of the present invention, the solar control film has a solar energy blocking function by blocking a portion of light in the infrared region and visible region.

[Example] (Example 1) Bronze-colored glass substrate (41all thickness, visible light transmittance 79.3%, solar ray transmittance 69.4%, visible light reflectance 7.8%, solar ray reflectance 6) .8%) is sputtered! It was set in a vacuum chamber and evacuated to I X 10-" Torr. Argon was introduced to increase the pressure to 2 X 10-"
After setting the temperature to Torr, chromium was sputtered to form about 200 chromium (first layer).

Next, switch to a mixed gas of argon and oxygen and increase the pressure to 2
An amorphous oxide film consisting of zirconium and boron is formed by reactive sputtering using a zirconium/boron target (atomic ratio 60/40) at 10-” Torr.
Approximately 120 people formed xOy (second layer).

Visible light transmittance TV of the solar control glass obtained in this way, solar light transmittance T1, coated surface visible light reflectance RVF%, coated surface solar light reflectance RtF + glass surface visible light reflectance RVO, glass surface solar light reflectance Rta are respectively 25.7°26.4.29.2.25.3.
It was 11.5.8.5 (%).

The color tone was almost a neutral color with a slight purplish tinge. To test the durability of the membrane, it was immersed in 1N hydrochloric acid or sodium hydroxide for 6 hours, or in boiling water for 2 hours.
In both cases, the change in transmittance and reflectance was within 1%.

Also, taper test (wear theory CS-I, weight 500g).

Change in visible light transmittance before and after rotation (100 rotations) ΔTv2.
0 (%), indicating excellent abrasion resistance.

(Example 2) Chromium (
After forming about 200 people (first layer), switch to a mixed gas of argon and oxygen and increase the pressure to 2 x 10-”Torr, then use a zirconium/silicon target (atomic ratio 33/67).
An amorphous oxide film Zr5ixO (second layer) consisting of zirconium and silicon is formed by reactive sputtering.
A was formed.

Optical performance TV of the obtained solar control glass,
Tg, Rv□Rtr, and RVO5Rto are each 2
5.0.25.7.30.3.26.6.12.9.9
．． The 0 color tone, which was 3 (%), was the same as in Example 1.

A durability test similar to that in Example 1 was conducted, and similarly excellent performance was shown. Further, the ΔTv measured by the same taper test as in Example 1 was l, 9 (%), indicating similarly excellent wear resistance.

(Example 3) A glass substrate similar to that in Example 1 was set in a vacuum chamber of a sputtering apparatus, and the vacuum chamber was evacuated to I x 10-' Torr. Mixed gas of argon and oxygen (Ar:0s=85:1
5) was introduced to bring the pressure to 2×10-” Torr, and then chromium was reactively sputtered to form about 400 absorbable chromium oxides (first layer).

Next, zirconium/silicon target (atomic ratio 33/
67) was formed by about 120 people (an amorphous oxide film ZrSi-O1 second layer by reactive sputtering).

Optical performance Tv of the obtained solar control glass
%Tt, RVF%RKF, RVII, RIO are 4.6.5.3.60.4.51S, 1.3g, 4, respectively.
．． The color tone 0, which was 29.1 (%), was a slightly darker purple than that of Example 1. A durability test similar to that in Example 1 was conducted, and similarly excellent performance was shown. Further, ΔTv in the same taper test as in Example 1 was 1.8 (%), indicating similarly excellent wear resistance.

(Example 4) A transparent glass substrate was set in a vacuum chamber of a sputtering apparatus, and the vacuum chamber was evacuated to I.times.10-' Torr.

Mixed gas of argon, nitrogen and oxygen (Ar:Nt:0z=
20 near 5: 5) to increase the pressure to 2 x 10-
After reducing the temperature to Torr, chromium was reactively sputtered to form about 200 chromium oxynitride (first layer).Next, a zirconium/silicon target (atomic ratio 33/67) was formed.
) was also reactively sputtered to form an amorphous oxide film Z.
r5lzOy 2nd layer) was formed by approximately 100 people.

Optical performance T v of the obtained solar control glass
s Tt h Rve%Rzrt Rva and Rta are respectively 27.2.30.5.32.5.29.2.
Tone 0, which was 20.5.15.9 (%), had a bronze transparent color. A durability test similar to that in Example 1 was conducted, and similarly excellent performance was shown. Further, ΔTv in the same taper test as in Example 1 was 1.5 (%), indicating similarly excellent wear resistance.

(Example 5) A transparent glass substrate was set in a vacuum chamber of a sputtering device, and the vacuum chamber was evacuated to 1×10-” Torr.

Mixed gas of argon and nitrogen (Ar:Nt:=70:3
0) to bring the pressure to 2 × 10-” Torr, and then reactively sputter titanium to form titanium nitride (
Approximately 200 people formed the first layer. Continue with zirconium/
A silicon target (atomic ratio: 33767) was similarly subjected to reactive sputtering to form an amorphous oxide film (Zr5izOy second layer) of about 10 OA.

Optical performance Tv of the obtained solar control glass
, Tt, Rvr-REF, Rva, and Rta are 31.6.21.4.11.6.21.4.20., respectively.
For the 0 color tone, which was 7.17.2 (%), the transmitted color was almost neutral, and the reflected color was slightly yellowish. A durability test similar to that in Example 1 was conducted, and similarly excellent performance was shown. Further, the 8Tv in the same taper test as in Example 1 was 1.0 (%), indicating similarly excellent wear resistance.

(Comparative Example 1) In order to see the effects of Examples 1 and 2, only about 200 people formed a chromium film (first layer) on the same glass substrate as in Example 1.

Optical properties of the sample thus obtained Tv, T't, R□,
Ro, Ro, and Rta are each 26.0°26.7.
When the same durability test as in Example 1 was conducted, the result was 28.8.27.5.11.0.8.3 (%).
Although the chemical durability was good, when subjected to the same taper test as in Example 1, the chromium film peeled off.

[Effects of the Invention] The present invention uses an amorphous oxide film as the outermost layer when viewed from the substrate, that is, the outermost layer on the air side, thereby improving chemical stability and wear resistance as shown in Examples. Moreover, it is possible to obtain an optical body having excellent scratch resistance. This allows the solar control article of the present invention to be used in severe applications that were not previously possible.

For example, it is ideal for solar control glass for buildings and vehicles.

In particular, the ZrB-Oy of the present invention (0,10<x<2
．． 3.

2 < 3. <5.5) Film, Zr5xxOy (0,
05≦z<19゜2.1≦y<40) film, ZrB
XSilO, (0,05≦X+z<19 (where x+z
-3>0 and x-3z+1>0 compositions are excluded <), 2<y
<40 membrane has not only scratch resistance and abrasion resistance, but also extremely excellent chemical durability, so it is suitable for applications in harsh environments, such as construction and vehicle applications where it is used as a veneer. It can be used in solar control glass, etc.

In addition, when using an amorphous oxide film containing boron or silicon, the refractive index of the oxide film can be adjusted by changing the content of boron or silicon, making it possible to improve the optical film. This also has the effect of increasing the degree of freedom in needle setting.

Therefore, by changing the material and thickness of the solar control film, and the refractive index and thickness of the amorphous oxide layer, highly durable solar control articles with various color tones can be provided.

[Brief explanation of drawings]

FIG. 1 shows a partial cross-sectional view of an example of an optical body according to the present invention. FIG. 2(a) is a diagram showing the relationship between the content of B in the ZrB/O2 film and the refractive index n of the film. Figure 2(b) shows Zr
Figure 2(c) shows the relationship between the content of Si, O, and SL in the film and n. Figure 2(c) shows the relationship between the content of Si in the ZrB+5isOy film and n. Figure 2(d) shows the relationship between n and the content of Si, O, and SL in the film. T i S i *
FIG. 3 is a relationship diagram between the content of SL in the Oy film and n. Substrate 2: Solar control (first layer) 3: Amorphous oxide film (second layer) Figure 1 Figure 2 (a, > Figure (c) Figure Cb) Figure (cl)

Claims (6)

[Claims] (1) On the substrate, in order from the substrate side, a solar control film mainly composed of at least one of metals, metal oxides, and metal oxynitrides, and titanium, zirconium, and hafnium as the outermost layer on the air side. , tin, tantalum, and indium, and at least one of boron and silicon. A solar control article featuring: (2) The solar control article according to claim 1, wherein the solar control film contains chromium or chromium oxide as a main component. (3) The amorphous oxide film consists of Zr (zirconium) and B(
The main component is an oxide (ZrB_xO_y) containing boron), and the atomic ratio x of boron to zirconium in the film is 0.1.
Claim 1 or 2, characterized in that 0<x<4, and the atomic ratio y of oxygen to zirconium is 2<y<8.
Solar control articles listed. (4) The amorphous oxide film consists of Zr (zirconium) and B(
The main component is an oxide (ZrB_xO_y) containing boron), and the atomic ratio x of boron to zirconium in the film is 0.1.
3. The solar control article according to claim 1, wherein 0<x<2.3, and the atomic ratio y of oxygen to zirconium is 2<y<5.5. (5) The amorphous oxide film is composed of Zr (zirconium) and Si
(silicon), the atomic ratio z of boron to zirconium in the film is 0.05≦z<19, and the atomic ratio y of O to Zr is 0.05≦z<19.
The solar control article according to claim 1 or 2, wherein 2.1≦y<40. (6) The amorphous oxide film is composed of Zr (zirconium) and Si.
(Silicon) (ZrB_xSi_zO_y)
When the atomic ratio of boron to zirconium in the film is x, the atomic ratio of Si to zirconium is z, and the atomic ratio of oxygen to Zr is y, 0.05≦x+
z<19 (however, x+z-3>0 and x-3z+1>
3. The solar control article according to claim 1, wherein the solar control article has a composition of 2<y<40.