JPH08104547A - Heat insulating glass - Google Patents

Abstract

PURPOSE: To keep natural appearance without showing chromatic color or transmitting color in appearance by forming films of a 1st to 6th layer, which have respectively a specific component and thickness, successively on a glass plate. CONSTITUTION: In a sputtering device, two cathodes using respectively metallic Sn and metallic Ag as a target are installed in a sputtering chamber, a glass substrate 10 of a colorless 'and transparent float glass is transported to the sputtering chamber after evacuation and the pressure of the sputtering chamber is controlled to 0.3Pa by introducing Ar gas and O2 gas. A tin oxide film 11 having 36.2nm film thickness is formed as the 1st layer by supplying electric powder to the cathode of the Sn target to discharge and passing the glass substrate 10 on the target, the 2nd layer of a Ag film 12 having 8.0nm film thickness is formed by discharging to the Ag target and passing thereon, the 3rd layer of a tin oxide film 13 having 73.3nm film thickness on the Sn target, the 4th layer of a Ag film 14 having 73.3nm film thickness on the Ag target, the 5th layer of a tin oxide film 15 on the Sn target and if necessary, a protective film as the 6th layer are formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a function of transmitting visible rays and reflecting infrared rays when it is used as a window glass of a building or a vehicle, and prevents inflow of solar heat in the summer to prevent inflow of solar heat. Relates to a heat insulating glass coated with an infrared reflecting film for preventing heat from flowing out from the room. More specifically, the present invention relates to such an insulating glass, which is covered with an infrared reflection film and does not exhibit a chromatic reflection color or a transmission color in appearance and maintains a natural appearance.

[0002]

2. Description of the Related Art Heretofore, as this type of glass, there has been known a heat-insulating glass coated with an infrared reflecting film formed by forming three layers of a metal oxide film, an Ag film and a metal oxide film in this order on a glass substrate. ing. In such a glass, the heat insulating function is based on the infrared reflection property of the Ag film. That is, by using the Ag film in a predetermined thickness range,
It is sufficiently transparent in the visible light range, and while maintaining the essential properties as a window glass, it can highly reflect infrared rays and ensure heat insulation. In such a conventional insulating glass, the metal oxide film used together with the Ag film shields the Ag film from the outside air environment to prevent the Ag film from corroding, and at the same time, prevents the Ag film from being exposed to the outside air (usually air). Alternatively, it serves to suppress the reflection of visible light between the Ag film and the glass substrate and increase the transmittance. Then, by appropriately adjusting the thickness of the Ag film and the refractive index and the thickness of the metal oxide film, the visible light transmittance can be maintained at a high value of 70% or more and sufficient transparency can be secured. It was.

In recent years, from the viewpoint of energy saving,
There is a growing demand for window glass with improved heat insulation. For this, it is effective to use a divided two-layer Ag film as disclosed in JP-A-54-133507 and JP-A-63-134232. By using the Ag film divided into two layers, it is possible to increase the reflectance of infrared rays while maintaining a high transmittance of visible light. As an additional effect, in JP-A-63-134232, a metal oxide film, Ag is used.
In the infrared reflection glass consisting of a five-layer coating of a film, a metal oxide film, an Ag film, and a metal oxide film, it is possible to suppress the red or blue reflection color as compared with the infrared reflection glass consisting of a three-layer coating. ing.

[0004]

Problems to be Solved by the Invention JP-A-54-1335
As disclosed in Japanese Laid-Open Patent Publication No. 07-134232 and Japanese Laid-Open Patent Publication No. 63-134232, the Ag film is divided into two layers to form a five-layer structure of alternating lamination with a transparent metal oxide, whereby It is possible to increase infrared reflectance while maintaining high transmittance. However, in such a conventional technique, although the infrared reflectance is significantly increased as compared with a three-layer infrared reflective film in which a single Ag film is sandwiched by transparent metal oxide films, the infrared reflectance is increased at the same time. Since it is not possible to sufficiently suppress the reflectance of visible light in the near wavelength range, the reflection color when viewed from the side where the infrared reflective film is formed becomes purple or red, which impairs the appearance. There was a flaw. In Japanese Patent Laid-Open No. 63-134232, an attempt is made to improve such a defect, but in order to cancel the reflected colors of red and blue, the means is to reflect the reflected color of green which is an intermediate region of visible light. Is to overlap,
The effect was not sufficient. That is, JP-A-63-
As described in Japanese Patent No. 134232, even if the reflected colors of red and blue are suppressed, the reflected color of green becomes dominant and the reflected colors of green, yellow and orange are exhibited. As a result, complete neutralization of the reflection color tone has not been achieved. The present invention has been made to solve the above-mentioned problems of the prior art.

[0005]

In order to solve the above-mentioned conventional problems, the present invention provides, on a glass plate, a metal oxide film as a first layer and a silver (Ag) as a second layer in order. The film containing the main component is a metal oxide film as the third layer, the film containing silver (Ag) as the fourth layer is the fourth layer, the metal oxide film is the fifth layer, and if necessary, the sixth layer. In the heat-insulating glass having the protective film formed thereon, the metal oxide film is mainly composed of one or both of tin oxide and zinc oxide as the entire layer of the first layer, the third layer or the fifth layer. 1 or 2 or more layers, and the thickness of the third layer is 65 nm
Or more and 80 nm or less, the thickness of the second layer is 7 nm or more and less than 11 nm, and the thickness of the fourth layer is 11 n.
The present invention provides a heat-insulating glass having a thickness of more than m (greater than 11 nm) and 14 nm or less.

In the present invention, in order to adjust the reflection color tone to an achromatic color, the metal oxide film used together with the film containing Ag as a main component contains one or both of tin oxide and zinc oxide as a main component. It is limited to those having two or more layers. Then, the thickness of the metal oxide film of the third layer, which is used by being sandwiched between the two layers containing Ag as a main component, is limited to 65 nm or more and 80 nm or less. Further, in addition to these limitations, the thickness of the Ag film of the second layer, which is close to the substrate, of the Ag films divided into two and used is 7 nm or more.
and the thickness of the Ag film of the other fourth layer is 11 nm or less.
It exceeds 14 nm and is 14 nm or less.

In the present invention, the material of the metal oxide film is
The limitation as described above is essential. Tin oxide and zinc oxide are used as the whole layer as a metal oxide film to effectively increase the infrared reflectance and adjust the transmitted color and the reflected color to an achromatic color while maintaining a high visible light transmittance. It was impossible except using one or more layers containing one or both of the above as the main components. For example, when titanium oxide having a high refractive index is used as the metal oxide film, the infrared reflectance is reduced by about 10% as compared with the present invention. When trying to increase infrared reflectance,
The reflection color mainly when viewed from the side where the infrared reflection film is formed deviates from the achromatic color, and the reflection color of yellow comes to appear. On the other hand, when silicon oxide having a low refractive index is used as the metal oxide film, it becomes more difficult to maintain an achromatic color tone, the transmitted color is blue green, and the reflected color is a remarkable orange color. I will begin to present.

Next, regarding the thickness of the metal oxide film, 2
It is important to adjust the thickness of the third layer sandwiched between the Ag films that are divided into two parts, and in order to keep both the transmitted color and the reflected color achromatic, the thickness should be 65 nm or more and 85 nm or less. Required. If the thickness of the metal oxide film of the third layer deviates from this range and becomes thicker, it will exhibit a chromatic reflection color such as green, blue-green, or purple. On the other hand, if the thickness deviates from the above range and becomes thin, the reflected color from red to purple becomes extremely remarkable. Thus, in order to keep both the transmitted color and the reflected color achromatic, it is essential that the thickness of the third layer be 65 nm or more and 85 nm or less. However, as a result of further detailed study, it was found that the reflection color could not always be adjusted to an achromatic color even if the thickness of the third layer was 65 nm or more and 85 nm or less. Japanese Unexamined Patent Publication No. 54-133507 describes that the film thickness of the Ag film to be divided and used is in the range of 11 nm or more and 25 nm or less, but when the film thickness of the Ag film is limited to such a range. Although it is possible to easily increase the reflectance of infrared rays, it is unavoidable that the transmittance of visible rays decreases, and the transmitted and reflected colors are achromatic while maintaining high transmittance of visible rays. Even if I tried to adjust it, it was impossible. As a result of our research, when trying to adjust the transmitted color and the reflected color to an achromatic color, the film thickness of the Ag layer must be infinitely close to 11 nm, and even in such a case, the infrared reflective film is formed. It was found that the reflected color on the open side exhibited a noticeable blue color. Next, in JP-A-63-134232, the thickness of the Ag layer is set to 6 nm.
It is described that it is adjusted to 11 nm or less. High visible light transmittance can be easily achieved by limiting the content to such a range, but in order to fully exert the effect of increasing the infrared reflectance by adopting the five-layer structure, each film thickness of the five layers is required. Must be properly adjusted.
However, according to our research, it has been found that the transmission color and the reflection color cannot be adjusted to an achromatic color by limiting the film thickness of the two Ag layers to 6 nm or more and 11 nm or less. Even when the transmitted color and the reflected color are adjusted to the most achromatic color, the reflected color on the side where the infrared reflecting film is formed is blue or green. Furthermore, when trying to adjust the color tone to an achromatic color, the infrared reflectance is 10
There was also a drawback that the percentage decreased. On the contrary, even if the transmitted color and the reflected color are kept achromatic while keeping the infrared reflectance high, the result is that the reflected color blue or green on the side on which the infrared reflective film is formed is increased.

In the present invention, in order to solve the above problems, the second layer film formed on the side closer to the substrate among the layers containing Ag as a main component divided into two. The thickness is adjusted to 6 nm or more and less than 11 nm, and the film thickness of the other fourth layer is adjusted to more than 11 nm and 17 nm or less. Only when the film thicknesses of the two Ag layers are adjusted in this way, it becomes possible to make the transmitted color and the reflected color achromatic while maintaining the high visible light transmittance and infrared reflectance.

In the present invention, regarding the film thickness of the two Ag layers,
The thickness of the side closer to the substrate and the thickness of the other side are adjusted to differ by 11 nm.
It is relatively thin with less than m, and the other exceeds 11 nm and is 1
It is relatively thick as 4 nm or less. This relationship is essential to the present invention, and if this relative relationship is reversed, the transmitted color and the reflected color cannot be adjusted to achromatic color.

As described above, according to the present invention, the transparent metal oxide film material and its film thickness and the film thickness of the two Ag films of the five-layer film constituting the infrared reflective film are properly adjusted. Therefore, while maintaining high visible light transmittance and infrared reflectance, transmitted color, reflected color on the side where the infrared reflective film is formed,
It acts to keep any of the reflection colors on the side where the infrared reflection film is not formed achromatic.

Incidentally, hereinafter, a state in which the degree of achromatic color such as transparent color is kept to some extent at -4 <a ^* <4 and -4 <b ^* <4 in Hunter chromaticity coordinates is called "neutral". Sometimes.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming each layer of the heat insulating glass according to the present invention is not particularly limited, but a sputtering method is generally used as shown in Examples described later.

The metal oxide film contains 1 or 2 containing tin oxide and / or zinc oxide as a main component.
It is sufficient that the metal oxide film is composed of the above-mentioned layers, and that the metal oxide film as a whole has tin oxide, zinc oxide, or tin oxide and zinc oxide as main components. That is, metal oxides other than tin oxide and zinc oxide, metal nitrides, metal oxynitrides, etc. are added to the first layer, the third layer or the fifth layer to the extent that the effects of the present invention are not impaired, or these A layer forming a part of the layer may be formed.

The metal oxide layer is preferably a tin oxide film, a zinc oxide film, a tin oxide film doped with one or both of Sb and F, and an oxidized film doped with one or both of Al and Ga. It is a zinc film or a film in which two or more layers of these films are laminated.

The film containing Ag as the main component is not limited to the Ag film, and Pd, Au, In, Zn, Sn, and A may be appropriately added to Ag.
Other metals such as l and Cu may be added.

As described above, the multi-layer coating for infrared reflection according to the present invention may be a multi-layer metal oxide film, and in a strict sense, it does not have to be five layers. In addition, in the present invention, a protective layer may be provided as a sixth layer on the fifth layer, if necessary. As this protective layer,
Titanium oxide, silicon nitride or the like can be used. Furthermore, in the present invention, if necessary, an additional layer having a thickness of 1 to 10 nm may be provided so as to be in contact with the second layer or the fourth layer. As the additional layer, a metal or a metal oxide, specifically, titanium, zinc, a zinc / tin alloy, or an oxide thereof can be used. This additional layer has the effect of improving the heat resistance of the coating, etc., and when it is provided in contact with the second layer or the fourth layer, it prevents oxidation of the Ag forming these layers in the film forming process. It also has the effect of

In the present invention, in order to improve the durability of the heat insulating glass and further improve the heat insulating property, 2
It may be used as a double glazing configured to hold a layer of dry air between the sheets of glass via a spacer. In this case, it is preferable that the infrared reflective film is configured to face the dry air side. That is, by using a double-layer glass having the infrared reflecting film on the dry air side of the outdoor transparent glass plate or the dry air side of the indoor transparent glass plate, it is a highly durable insulating glass, and from the outdoor side It is possible to provide a multilayer insulating glass in which the reflection color when viewed, the reflection color when viewed from the indoor side, and the transmission color when viewed from the indoor side to the outside are kept achromatic.
Further, it may be a double glazing using three or more glass plates as needed.

The thickness of each of the first layer and the fifth layer of the present invention is preferably within the range of 25 to 50 nm.

[0020]

1 is a schematic sectional view of an embodiment of the present invention, in which a transparent metal oxide film 11, 13, 1 is formed on a glass substrate 10.
5 and Ag films 12 and 14 are coated. FIG. 2 is a schematic cross-sectional view of another embodiment of the present invention, in which the glass substrate 20 and the glass substrate 30 covered with the transparent metal oxide films 21, 23, 25 and the Ag films 22, 24 are spacers. 40 and butyl rubber 50 are bonded on their four circumferences, and the inside 6
0 is filled with dry air.

Example 1 An infrared reflective film was formed by using an in-line type sputtering apparatus consisting of a preliminary exhaust chamber and a sputtering chamber. Two cathodes are prepared in the sputtering chamber. Metal Sn was set as a target for one cathode, and metal Ag was set as a target for the other cathode. The sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa or less with a rotary pump and a cryopump. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. A in the sputter chamber
Introducing r gas 50SCCM and oxygen gas 50SCCM,
The pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3 A (voltage was about 490 V). 497m glass substrate over this target
36.2n by passing at a speed of m / min
A tin oxide film having a thickness of m was formed as the first layer. Then
The sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, then Ar
A gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1 A (voltage was about 475 V). A glass substrate was passed over this target at a speed of 3125 mm / min to form an Ag film having a thickness of 8.0 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After evacuating to Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode equipped with the Sn target to cause discharge, and the current was adjusted to 0.7 A (voltage was about 363).
V). Put a glass substrate on this target 9
It was passed at a speed of 750 mm / min to form a metal tin film with a thickness of 1 nm (this very thin metal tin film prevents the surface of the Ag film from being oxidized when the tin oxide film is subsequently formed. It is formed to prevent this, and it is known that this very thin metal Sn film itself is oxidized and changes to tin oxide when the tin oxide film is formed next time). Next, after exhausting the sputtering chamber to 5 × 10 ⁻⁴ Pa again,
Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a rate of 245 mm / min to form a tin oxide film having a thickness of 73.3 nm as a third layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After evacuating to Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 2120 mm / min to form an Ag film having a thickness of 11.8 nm as a fourth layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After evacuating to Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 0.7A. A glass substrate was passed over the target at a speed of 9750 mm / min to form a metal tin film having a thickness of 1 nm (this very thin metal tin film was also used when a tin oxide film was formed next time). A
It is formed in order to prevent the surface of the g film from being oxidized, and when the tin oxide film is formed, it is similarly oxidized and changes to a tin oxide film). Next, again set the sputtering chamber to 5 × 10.
After evacuating to ^-4 Pa, 50 SCCM of Ar gas and 50 SCCM of oxygen gas were introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate 584 mm /
A tin oxide film having a thickness of 30.8 nm was formed as a fifth layer by passing the tin oxide film at a speed of min.

The constitution of the heat insulating glass thus obtained is shown in Table 1. Table 2 shows the results of measuring various optical characteristics of this heat insulating glass using a spectrophotometer. In the standard C light source, the visible light transmittance is 81.2%, which is a very high value, but the solar light transmittance is 48.4.
It showed a very low value such as%, and the infrared rays were effectively blocked. Transparent color is L ^* a ^* b ^* color system, and a ^* value is -2.1,
The b ^* value was -1.7, which was colorless and transparent. The visible light reflectance on the side on which the infrared reflective film was formed was a low value of only 4.8%, and there was no glare. The solar light reflectance reached 35.0%, indicating that infrared rays were reflected very effectively. Reflected color is L ^* a ^* b ^* color system, a ^*
It was completely colorless with a value of 0.3 and a b ^* value of 0.2. The visible light reflectance on the side where the infrared reflection film is not formed,
It was a low value of only 4.9%, and there was no glare. The solar reflectance was as high as 24.0%. Reflected color is L ^* a ^* b ^* color system, a ^* value is -1.1, b ^* value is 0.4.
After all it was completely colorless. Thus, it was possible to obtain an adiabatic glass in which the transmitted color and the reflected color were achromatically adjusted to neutral while maintaining the high visible light transmittance and infrared reflectance.

[0023]

[Table 1]

[0024]

[Table 2]

Example 2 An infrared reflecting film was formed by using the same in-line type sputtering apparatus as in Example 1. Three cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
Target metal Zn was set on the second cathode, and metal Ag was set on the third cathode. The sputter chamber uses a rotary pump and cryopump at 5 × 10 ^-4 P
Exhausted to a or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50SCCM and oxygen gas 50SCCM in sputter chamber
Was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 510 mm / min to form a tin oxide film having a thickness of 35.3 nm as a first layer. Then re-sputter the chamber 5x
After exhausting to 10 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 3086 mm / min to form an Ag film having a thickness of 8.1 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10.
After evacuating to ^-4 Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6 A (voltage was about 483).
V). Place a glass substrate on top of this target.
It was passed at a speed of 500 mm / min to form a metal zinc film having a thickness of 1 nm (this very thin metal zinc film prevents the surface of the Ag film from being oxidized when the tin oxide film is subsequently formed. It is formed to prevent it, and it is known that when the tin oxide film is formed next time, it is oxidized and converted to zinc oxide). Next, again set the sputtering chamber to 5 × 1.
After exhausting to 0 ⁻⁴ Pa, Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced to adjust the pressure to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate 248 mm /
A tin oxide film having a thickness of 72.6 nm was formed as a third layer by passing it at a speed of min (however, 1 nm was used).
Is formed between the Ag film and the tin oxide film). Then, the sputtering chamber is again set to 5 × 10 ⁻⁴ Pa.
After exhausting up to 100 Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 2083 mm / min to form an Ag film having a thickness of 12.0 nm as a fourth layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to form a metal zinc film having a thickness of 1 nm (this very thin metal zinc film was also formed when a tin oxide film was formed next time). A
It is formed in order to prevent the surface of the g film from being oxidized, and when the tin oxide film is formed, it is also oxidized to a zinc oxide film). Next, re-sputter the sputtering chamber 5 ×
After exhausting to 10 ⁻⁴ Pa, Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced to adjust the pressure to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. 583 mm glass substrate over this target
30.9 nm by passing at a speed of / min
A tin oxide film having a thickness of 1 nm was formed as a fifth layer (however, 1n
A zinc oxide film having a thickness of m is formed between the Ag film and the tin oxide film. ).

Table 1 shows the constitution of the heat insulating glass thus obtained. Table 2 shows the results of measuring various optical characteristics of this heat insulating glass using a spectrophotometer. In the standard C light source, the visible light transmittance is 81.3%, which is a very high value, but the solar light transmittance is 48.2.
It showed a very low value such as%, and the infrared rays were effectively blocked. Transparent color is L ^* a ^* b ^* color system, a ^* value is -2.6, b ^*
The value was -1.9, which was colorless and transparent. The visible light reflectance on the side on which the infrared reflective film was formed was as low as 4.6%, and there was no glare. Solar reflectance is 3
It was as high as 5.1%, and it was found that infrared rays were reflected very effectively. The reflected color was in the L ^* a ^* b ^* color system and was neutral with a ^* value of 0.2 and b ^* value of 1.5. The visible light reflectance on the side on which the infrared reflective film was not formed was only 4.8%, which was a low value, and there was no glare. The solar reflectance was as high as 24.1%. Reflected color is L ^* a ^* b ^* color system, a ^* value is -0.7, b ^* value is 0.6.
After all it was completely colorless. Thus, it was possible to obtain a heat insulating glass in which the transmitted color and the reflected color were adjusted to be completely colorless while maintaining high visible light transmittance and infrared reflectance. In the present embodiment, a part (about 1 nm) of tin oxide in the third layer and the fifth layer is replaced with zinc oxide, but the optical properties of tin oxide and zinc oxide are similar to each other. Therefore, it did not affect the characteristics of the heat ray reflective film.

Example 3 An infrared reflective film was formed by using the same in-line type sputtering apparatus as in Example 1. Two cathodes are prepared in the sputtering chamber. Metal Zn for one cathode
On the other cathode, metal Ag was set as a target. The sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa or less with a rotary pump and a cryopump. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50SCC in sputter chamber
M and oxygen gas of 50SCCM are introduced, and the pressure is 0.3 Pa.
Adjusted to. On the cathode equipped with a Zn target,
Electric power is supplied from the DC power supply to cause discharge and current is 3A
(Voltage was about 410V). A glass substrate was passed over this target at a speed of 364 mm / min to form a tin oxide film having a thickness of 33.8 nm as a first layer. Then, the sputter chamber is again set to 5
After exhausting to × 10 ^-4 Pa, Ar gas 100 SCCM
Was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 3125 mm / min to form an Ag film having a thickness of 8.0 nm as a second layer. Then, the sputter chamber is again 5 × 1
After exhausting to 0 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to form a metal zinc film having a thickness of 1 nm. Next, after exhausting the sputtering chamber to 5 × 10 ⁻⁴ Pa again,
Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 134 mm / min to form a zinc oxide film having a thickness of 73.3 nm as a third layer. Then, the sputtering chamber is again set to 5 × 10.
After evacuating to ^-4 Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 2100 mm / min to form an Ag film having a thickness of 11.9 nm as a fourth layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After evacuating to Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to form a metal zinc film having a thickness of 1 nm (this very thin metal zinc film was also formed when a zinc oxide film was formed next It is formed in order to prevent the surface of the Ag film from being oxidized, and when the zinc oxide film is formed, it is similarly oxidized and changes to a zinc oxide film). Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas was 50 SC.
Introduced CM and oxygen gas 50SCCM, pressure 0.3P
Adjusted to a. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 3A. By passing a glass substrate over this target at a speed of 378 mm / min, 3
A zinc oxide film having a thickness of 2.6 nm was formed as the fifth layer.

Table 1 shows the constitution of the heat insulating glass thus obtained. Table 2 shows the results of measuring various optical characteristics of this heat insulating glass using a spectrophotometer. In the standard C light source, the visible light transmittance is as high as 77.6%, but the solar light transmittance is 46.0.
It showed a very low value such as%, and the infrared rays were effectively blocked. The transparent color is the L ^* a ^* b ^* color system, and the a ^* value is -2.6,
The b ^* value was -1.3, which was neutral. The visible light reflectance on the side where the infrared reflective film is formed is only 4.1%.
It was a low value and there was no glare. The solar reflectance was as high as 34.5%, indicating that infrared rays were reflected very effectively. The reflection color is L ^* a ^* b ^* color system.
It was completely colorless with an a ^* value of -0.2 and a b ^* value of 1.5. The visible light reflectance on the side where the infrared reflecting film was not formed was only 4.7%, which was a low value, and there was no glare. The solar reflectance was as high as 23.7%.
The reflection color was L ^* a ^* b ^* color system, and the a ^* value was -0.9 and the b ^* value was 0.0, which was also neutral and completely achromatic.
Thus, it was possible to obtain a heat insulating glass in which the transmitted color and the reflected color were adjusted to a completely achromatic color while maintaining the high visible light transmittance and infrared reflectance.

Example 4 to Example 9 In the same manner as in Example 2, the insulating glass films obtained when the film thicknesses of the second to fourth layers were changed within the range limited by the present invention The constitution and optical characteristics are summarized in Table 1 and Table 2, respectively. All of the insulating glasses were able to effectively shield infrared rays while maintaining high transmittance of visible light, and neutrally adjust both transmission color and reflection color.

Example 10-Example 12 The insulating glass obtained in Example 1-Example 3 was used as one glass and another transparent glass plate (combined with a commercially available float having a thickness of 5 mm to obtain a multi-layered glass). Insulating glass was used.Specifically, aluminum spacers were set around two sheets of glass and overlapped at a distance of 6 mm. Dry the adhesive around the spacer (butyl rubber)
Was filled and firmly adhered. In any of the examples, the surface on the side where the infrared reflection film was formed was set to be the spacer side. With the structure of the multilayer insulating glass obtained in these examples,
The optical characteristic results are shown in Table 3 and Table 4, respectively.

[0031]

[Table 3]

[0032]

[Table 4]

Example 10 is an example of a multi-layer heat insulating glass using the heat insulating glass described in Example 1 as the glass on the indoor side. The side on which the infrared reflective film is formed faces the 6 mm-thick air layer surrounded by the spacer. It can be seen that while maintaining a high visible light transmittance, the solar light transmittance is suppressed to be low, and all of the transmitted color, the outdoor reflection color and the indoor reflection color are kept in a very neutral achromatic color. Example 11 is an example of a multi-layer heat insulating glass using the heat insulating glass described in Example 2 as a glass on the indoor side.
The side on which the infrared reflective film was formed was surrounded by a spacer 6
It faces the mm-thick air layer. As in Example 10, while maintaining a high visible light transmittance, the solar light transmittance is kept low, and all of the transmitted color, the outdoor-side reflected color, and the indoor-side reflected color are kept neutral. I understand.
Example 12 is an example of a multi-layer heat insulating glass using the heat insulating glass described in Example 3 as the glass on the outdoor side. The side where the infrared reflective film is formed is surrounded by a spacer 6mm
Facing a thick air layer. Similar to Examples 10 and 11, while maintaining a high visible light transmittance, the solar light transmittance was kept low, and all of the transmitted color, the outdoor reflection color and the indoor reflection color were extremely neutral achromatic colors. You can see that it is kept at.

Example 13 An infrared reflective film was formed by using the same in-line type sputtering apparatus as in Example 1. Three cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
For the second cathode, a sintered body (ZnO: Al ₂ O ₃ ) in which ₂ % by weight of Al ₂ O ₃ was added to ZnO was set, and for the third cathode, metal Ag was set as a target. The sputter chamber uses a rotary pump and a cryopump 5 ×
The gas was exhausted to 10 ⁻⁴ Pa or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 98SCCM and oxygen gas 2S in the sputter chamber
CCM was introduced and the pressure was adjusted to 0.3 Pa. Zn
Electric power was supplied from a DC power supply to the cathode provided with the O: Al ₂ O ₃ target to cause discharge, and the current was adjusted to 6 A (voltage is about 560 V). On this target,
A glass substrate was passed through at a speed of 1508 mm / min to form ZnO: Al ₂ O ₃ having a thickness of 31.6 nm as a first layer. Then re-sputter the chamber 5x
After exhausting to 10 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 3125 mm / min to form an Ag film having a thickness of 8.0 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10.
After exhausting to ⁻⁴ Pa, Ar gas 98 SCCM and O ₂ gas ₂ SCCM were introduced to adjust the pressure to 0.3 Pa.
A cathode provided with a ZnO: Al ₂ O ₃ target,
Electric power is supplied from the DC power source to cause discharge, and the current is reduced to 0.
Adjusted to 6 A (voltage was about 560 V). A glass substrate was passed over this target at a speed of 2383 mm / min to obtain ZnO: Al having a thickness of 20.0 nm.
_{A 2} O ₃ film was formed. Then, the sputtering chamber is again set to 5 × 10.
After evacuating to ^-4 Pa, 50 SCCM of Ar gas and 50 SCCM of oxygen gas were introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3 A (voltage was 490 V). A glass substrate was passed over this target at a speed of 521 mm / min to form a tin oxide film having a thickness of 34.5 nm as a third layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After exhausting to Pa, Ar gas 98SCCM and O ₂ gas 2SCCM were introduced to adjust the pressure to 0.3 Pa. Z
Electric power was supplied from a DC power supply to the cathode provided with the nO: Al ₂ O ₃ target to cause discharge, and the current was adjusted to 6 A (voltage was 560 V). A glass substrate was passed over this target at a speed of 2383 mm / min to obtain ZnO: A having a thickness of 20.0 nm.
An l ₂ O ₃ film was formed. Then, the sputter chamber is again 5 × 1
After exhausting to 0 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1 A (voltage was 475 V). 192 glass substrate on top of this target
The Ag film having a thickness of 13.0 nm was formed as the fourth layer by passing the Ag film at a speed of 3 mm / min. Next, after the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, Ar gas 98S was used.
CCM and O ₂ gas 2SCCM are introduced and the pressure is 0.3P.
Adjusted to a. Electric power was supplied from a DC power supply to the cathode provided with the ZnO: Al ₂ O ₃ target to cause discharge, and the current was adjusted to 6 A (voltage was 560 V). 2326m glass substrate over this target
20.5n by passing at a speed of m / min
A ZnO: Al ₂ O ₃ film with a thickness of m was formed as the fifth layer.

Table 5 shows the constitution of the heat insulating glass thus obtained. Table 6 shows the results of measurement of various optical properties of this heat insulating glass using a spectrophotometer. In the standard C light source, the visible light transmittance is 73.4%, which is a very high value, but the solar light transmittance is 39.4%.
It showed a very low value such as%, and the infrared rays were effectively blocked. Transparent color is L ^* a ^* b ^* color system, a ^* value is -3.8, b ^*
The value was -1.3, which was colorless and transparent. The visible light reflectance on the side where the infrared reflective film was formed was a low value of 11.8%, and there was no glare. The solar reflectance was as high as 45.1%, indicating that infrared rays were reflected very effectively. Reflected color is L ^* a ^* b ^* color system, a ^* value is 2.8, b ^*
The value was 3.6, which was neutral. The visible light reflectance on the side where the infrared reflecting film was not formed was a low value of 8.9%, and there was no glare. The solar reflectance was 30.1%. The reflected color was in the L ^* a ^* b ^* color system, and the a ^* value was -1.8 and the b ^* value was 0.1, which was also colorless. Thus, it was possible to obtain a heat insulating glass in which the transmitted color and the reflected color were completely neutralized and achromatic while maintaining high visible light transmittance and infrared reflectance.

[0036]

[Table 5]

[0037]

[Table 6]

Example 14 An infrared reflective film was formed by using the same in-line type sputtering apparatus as in Example 1. Three cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
Was set on the second cathode with metal Ti, and on the third cathode with metal Ag. The sputter chamber uses a rotary pump and a cryopump 5 × 1
The gas was evacuated to ^0-4 Pa or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50 SCCM and oxygen gas 50 in the sputter chamber
SCCM was introduced and the pressure was adjusted to 0.3 Pa. Sn
Electric power was supplied from a DC power supply to the cathode provided with the target to cause discharge, and the current was adjusted to 3 A (voltage was about 490 V). A glass substrate was passed over this target at a speed of 506 mm / min to form SnO ₂ having a thickness of 35.6 nm as a first layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode provided with the Ag target to cause discharge,
The current was adjusted to 1 A (voltage was 475V). A glass substrate of 2778 mm / mi is placed on this target.
An Ag film having a thickness of 9.0 nm was formed as a second layer by passing the Ag film at a speed of n. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 100S was used.
CCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Ti target to cause discharge, and the current was adjusted to 0.6 A (voltage was about 287 V). A glass substrate is passed over this target at a speed of 977 mm / min,
A 1.0 nm thick Ti film was formed (this very thin metallic titanium film was found to be oxidized to titanium oxide during subsequent tin oxide formation). Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then 50 SCCM of Ar gas and 50 SCCM of oxygen gas were introduced to adjust the pressure to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode provided with the Sn target to cause discharge,
The current was adjusted to 3A (voltage was 490V). 238 mm / min of glass substrate on this target
Then, a tin oxide film having a thickness of 75.6 nm was formed as a third layer. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 100 was added.
SCCM was introduced and the pressure was adjusted to 0.3 Pa. Ag
Electric power was supplied from the DC power supply to the cathode provided with the target to cause discharge, and the current was adjusted to 1 A (voltage was 475 V). A glass substrate was passed over this target at a speed of 1923 mm / min to form an Ag film having a thickness of 13.0 nm as a fourth layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode equipped with the Ti target to cause discharge,
The current was adjusted to 0.6 A (voltage was 287V). 977mm glass substrate over this target
/ Ti of 1.0 nm thickness
A film was formed (this very thin metallic titanium film was found to be oxidized to titanium oxide during the subsequent formation of tin oxide). Next, the sputtering chamber is again set to 5 × 10 ⁻⁴ P
After exhausting to a, Ar gas 50SCCM and O ₂ gas 5
0 SCCM was introduced and the pressure was adjusted to 0.3 Pa. S
Electric power was supplied from the DC power supply to the cathode provided with the n target to cause discharge, and the current was adjusted to 3 A (voltage was 490 V). A glass substrate was passed over this target at a speed of 659 mm / min to form a SnO ₂ film having a thickness of 27.3 nm as a fifth layer.

The constitution of the heat insulating glass thus obtained is shown in Table 5, and various optical characteristics of the heat insulating glass were measured by using a spectrophotometer.

Example 15 Using the same in-line sputtering apparatus as in Example 1, an infrared reflecting film was formed. Four cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
Metal Ti was set as the target for the second cathode, metal Ag was set as the third cathode, and metal Zn was set as the target for the fourth cathode. The sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa or less with a rotary pump and a cryopump. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. And
The glass substrate was transferred to the sputtering chamber. Argon gas 50SCCM and oxygen gas 50SCCM were introduced into the sputtering chamber, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3 A (voltage was about 490 V). On this target, place a glass substrate 500 mm
36.0 nm by passing at a speed of / min
The SnO ₂ of thickness was formed as the first layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1 A (voltage was 475 V). A glass substrate was passed over this target at a speed of 2500 mm / min to form an Ag film having a thickness of 10.0 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10 ^−4.
After evacuating to Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6 A (voltage was 483 V).
Met). Place a glass substrate on this target 75
A Zn film having a thickness of 1.0 nm was formed by passing the metal film at a speed of 00 mm / min.
Next, it is known that when tin oxide is formed, it is oxidized to zinc oxide. ). Then re-sputter the chamber 5x
After exhausting to 10 ⁻⁴ Pa, Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced to adjust the pressure to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the metal Sn target to cause discharge, and the current was adjusted to 3 A (voltage was 490 V). A glass substrate was passed over this target at a speed of 228 mm / min to form a tin oxide film having a thickness of 78.9 nm as a third layer. Then, the sputter chamber is again 5 × 1
After exhausting to 0 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1 A (voltage was 475 V). On this target, place a glass substrate 178
By passing it at a speed of 6 mm / min, 14.
An Ag film having a thickness of 0 nm was formed as the fourth layer. Then, after exhausting the sputtering chamber again to 5 × 10 ⁻⁴ Pa,
Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was reduced to 0.6.
Adjusted to A (voltage was 483V). A glass substrate was passed over this target at a speed of 7500 mm / min to form a Zn film with a thickness of 1.0 nm (this very thin metallic zinc film was oxidized during the subsequent formation of tin oxide). Is known to become zinc oxide).
Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then 50 SCCM of Ar gas and 50 SCCM of O ₂ gas were introduced to adjust the pressure to 0.3 Pa. Electric power was supplied from a DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3 A (voltage was 490 V). A glass substrate 101 is placed on the target.
By passing it at a speed of 1 mm / min, 17.
An SnO ₂ film having a thickness of 8 nm was formed as the fifth layer. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then 100 SCCM of O ₂ gas was introduced to adjust the pressure to 0.3 P.
Adjusted to a. Electric power was supplied from a DC power supply to the cathode provided with the metallic Ti target to cause discharge, and the current was adjusted to 8 A (voltage was 436 V). By passing a glass substrate over this target at a speed of 202 mm / min, TiO 2 having a thickness of 9.9 nm is obtained.
_Two films were formed.

The composition of the heat insulating glass thus obtained is shown in Table 5, and various optical characteristics of the heat insulating glass are shown in Table 6 as measured by a spectrophotometer.

Example 16 In the same manner as in Example 13, the thickness of each layer was changed within the range limited by the present invention to produce a heat insulating glass. The film constitution and the optical characteristics are also shown in Tables 5 and 6.

In the above embodiments, the degree of achromatic color of transmitted color and reflected color is -4 <a in Hunter chromaticity coordinates.
^* <4 and -4 <b ^* <4 were maintained to some extent, and a neutral appearance could be obtained. Also, -2 <a
It was possible to achromaticize to a certain extent as ^* <2 and -2 <b ^* <2.

Comparative Example 1 An infrared reflective film was formed using the same in-line sputtering apparatus as in Example 2. Three cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
Target metal Zn was set on the second cathode, and metal Ag was set on the third cathode. The sputter chamber uses a rotary pump and cryopump at 5 × 10 ^-4 P
Exhausted to a or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50SCCM and oxygen gas 50SCCM in sputter chamber
Was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 560 mm / min to form a tin oxide film having a thickness of 32.1 nm as a first layer. Then re-sputter the chamber 5x
After exhausting to 10 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 3125 mm / min to form an Ag film having a thickness of 8.0 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10.
After evacuating to ^-4 Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to form a metal zinc film having a thickness of 1 nm. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then 50 SCCM of Ar gas and 50 SCCM of oxygen gas were introduced to adjust the pressure to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode provided with the Sn target to cause discharge,
The current was adjusted to 3A. A glass substrate was passed over this target at a speed of 267 mm / min to form a tin oxide film having a thickness of 67.5 nm as a third layer (however, a zinc oxide film having a thickness of 1 nm was an Ag film). And is formed between the tin oxide film). Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 100S was used.
CCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. By passing a glass substrate over this target at a speed of 3125 mm / min, Ag having a thickness of 8.0 nm was obtained.
The film was formed as the fourth layer. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas of 100 SC
CM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is placed on this target at 7500 mm / min.
And a metal zinc film having a thickness of 1 nm was formed. Next, after the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, Ar gas 50 SCCM and oxygen gas 50 SCCM were used.
Was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 444 mm / min to form a tin oxide film having a thickness of 40.5 nm as a fifth layer (however, a zinc oxide film having a thickness of 1 nm was an Ag film. And is formed between the tin oxide film).

Table 7 shows the structure of the heat insulating glass thus obtained. This heat insulating glass is disclosed in JP-A-63-134.
This is a representative example of the preferred embodiment disclosed in Japanese Patent No. 2232, and the thicknesses of the Ag layers of the second layer and the fourth layer are both adjusted to 11 nm or less. Table 8 shows the results of measuring various optical properties of the heat insulating glass thus obtained using a spectrophotometer. In the standard C light source,
The visible light transmittance was 80.8%, which was a very high value, but the solar light transmittance was 54.7%, which was a high value as compared with the examples of the present invention, and the infrared ray blocking performance was poor. I understand. The transmission color is the L ^* a ^* b ^* color system, and the a ^* value is -2.
0, b ^* value was -0.6, which was colorless and transparent. The visible light reflectance on the side on which the infrared reflective film was formed was 7.5%, which was a higher value than that of the example. The solar reflectance is 26.7%,
It was found that this is also inferior to the example. The reflection color is the L ^* a ^* b ^* color system, where the a ^* value is -2.1 and the b ^* value is -4.
Although it was almost achromatic as 2, it was slightly bluish green in combination with a slightly high reflectance. The visible light reflectance on the side where the infrared reflective film was not formed was a slightly high value of 8.2%, and there was a slight glare. The solar reflectance was 20.9%, which was a slightly insufficient value. Reflected color is L ^* a ^* b ^* color system, a ^* value is 1.5, b ^* value is −
It was an achromatic color of 0.5. As described above,
In the heat insulating glass obtained based on Japanese Patent No. 34232,
If you try to keep the visible light transmittance high while keeping the transmission and reflection tones neutral, you will not be able to increase the infrared reflectance sufficiently, and the reflectance will also increase slightly, so the infrared reflection It was found that the reflected color on the side on which the film was formed became a slightly blue-green adiabatic glass.

[0046]

[Table 7]

[0047]

[Table 8]

Comparative Example 2 An infrared reflecting film was formed by using the same in-line type sputtering device as in Example 2. Three cathodes are prepared in the sputtering chamber. Metal Sn for the first cathode
Target metal Zn was set on the second cathode, and metal Ag was set on the third cathode. The sputter chamber uses a rotary pump and cryopump at 5 × 10 ^-4 P
Exhausted to a or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50SCCM and oxygen gas 50SCCM in sputter chamber
Was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 629 mm / min to form a tin oxide film having a thickness of 28.6 nm as a first layer. Then re-sputter the chamber 5x
After exhausting to 10 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 2840 mm / min to form an Ag film having a thickness of 8.8 nm as a second layer. Then, the sputtering chamber is again set to 5 × 10.
After evacuating to ^-4 Pa, 100 SCCM of Ar gas was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to form a metallic zinc film having a thickness of 1 nm. Next, after exhausting the sputtering chamber to 5 × 10 ⁻⁴ Pa again,
Ar gas of 50 SCCM and oxygen gas of 50 SCCM were introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Sn target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 304 mm / min to form a tin oxide film with a thickness of 59.3 nm as a third layer (however, a zinc oxide film with a thickness of 1 nm was
It is formed between the Ag film and the tin oxide film). Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. 2525mm glass substrate on this target
The Ag film having a thickness of 9.9 nm was formed as a fourth layer by passing the Ag film at a speed of / min. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 1
00SCCM was introduced and the pressure was adjusted to 0.3Pa.
Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is placed on the target for 7500 mm.
It was passed at a speed of / min to form a metal zinc film having a thickness of 1 nm. Next, the sputtering chamber is again set to 5 × 10 ⁻⁴ Pa.
After exhausting up to 50, Ar gas 50 SCCM and oxygen gas 50
SCCM was introduced and the pressure was adjusted to 0.3 Pa. Sn
Electric power was supplied from the DC power supply to the cathode provided with the target to cause discharge, and the current was adjusted to 3A. A glass substrate was passed over this target at a speed of 475 mm / min to form a tin oxide film having a thickness of 37.9 nm as a fifth layer (however, a zinc oxide film having a thickness of 1 nm was an Ag film). And is formed between the tin oxide film).

Table 7 shows the constitution of the heat insulating glass thus obtained. This heat insulating glass is also disclosed in JP-A-63-13.
This is a representative of the preferred embodiment described in Japanese Patent No. 4232, and the thicknesses of the Ag layers of the second layer and the fourth layer are both adjusted to 11 nm or less. Table 8 shows the results obtained by measuring various optical properties of the heat insulating glass thus obtained using a spectrophotometer. In the standard C light source,
The visible light transmittance was maintained at a very high value of 79.5%, while the solar light transmittance could be suppressed to a low value of 48.5%, and it was found that infrared rays were effectively blocked. . The transmitted color was the L ^* a ^* b ^* color system, and was colorless and transparent with an a ^* value of -2.5 and a b ^* value of -0.8. The visible light reflectance on the side where the infrared reflecting film is formed is 5.9%, which is a low value.
There was no glare. The solar reflectance was a high value of 33.8%. However, the reflected color was a L ^* a ^* b ^* color system and had a noticeable blue color with an a ^* value of -1.7 and a b ^* value of -7.9. The visible light reflectance on the side where the infrared reflective film was not formed was 7.8%, which was a slightly higher value than that of the example. The solar reflectance was 25.6%, effectively blocking infrared rays. The reflection color was the L ^* a ^* b ^* color system, which was completely colorless with a ^* value of 0.6 and b ^* value of -0.4. As described above, in the heat insulating glass obtained based on JP-A-63-134232, if the infrared reflectance is sufficiently increased while maintaining the high visible light transmittance at a high level, the infrared reflective film on the side where the infrared reflective film is formed is formed. It was found that the reflected color was noticeably blue.

Comparative Example 3 An infrared reflective film was formed by using the same in-line sputtering apparatus as in Example 2 and Comparative Examples 1 and 2. Finally, on the glass substrate, a tin oxide film having a thickness of 35.7 nm was formed as a first layer, and an Ag film having a thickness of 11.2 nm was formed as a second layer.
65.2 as a third layer (through a 1 nm zinc oxide film)
a tin oxide film with a thickness of nm as a fourth layer, an Ag film with a thickness of 11.1 nm, and a tin oxide film with a thickness of 33.7 nm as a fifth layer (via a zinc oxide film with a thickness of 1 nm), A heat-insulating glass having an infrared reflection film formed of a 5-layer coating was obtained. This heat insulating glass represents a preferred embodiment described in JP-A-54-133507, and the thicknesses of the Ag layer of the second layer and the fourth layer are both 11 nm.
It is adjusted above.

Various optical characteristics of the heat insulating glass thus obtained were measured with a spectrophotometer.
It was shown to. With standard C light source, visible light transmittance is 7
It was found that the solar radiation transmittance could be suppressed to a low value of 44.1% while maintaining a very high value of 8.0%, and that infrared rays could be effectively blocked. Transparent color is L ^* a ^*
In the b ^* color system, the a ^* value was -2.6 and the b ^* value was -1.8, which were colorless and transparent. The visible light reflectance on the side where the infrared reflecting film was formed was a low value of 5.4%, and there was no glare. The solar reflectance was a high value of 38.1%. However, the reflected color is the L ^* a ^* b ^* color system, and the a ^* value is -2.
9, b ^* value was -7.8, which was a noticeable blue color. The visible light reflectance on the side where the infrared reflection film is not formed,
The value was 7.4%, which was slightly higher than that of the example. The solar reflectance was 28.4%, which effectively blocked infrared rays. Reflected color is L ^* a ^* b ^* color system, a ^* value is -0.8, b ^*
The value was 1.5, which was completely achromatic. As described above, in the heat insulating glass obtained according to Japanese Patent Laid-Open No. 54-133507, when the infrared reflectance is sufficiently increased while maintaining a high visible light transmittance, the side on which the infrared reflecting film is formed is formed. It was found that the reflected color of the product turned into a noticeable blue color.

Comparative Example 4 An infrared reflecting film was formed by using the same in-line type sputtering device as in Example 3. Two cathodes are prepared in the sputtering chamber. Metal Zn for one cathode
On the other cathode, metal Ag was set as a target. The sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa or less with a rotary pump and a cryopump. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50SCC in sputter chamber
M and oxygen gas of 50SCCM are introduced, and the pressure is 0.3 Pa.
Adjusted to. On the cathode equipped with a Zn target,
Electric power is supplied from the DC power supply to cause discharge and current is 3A
Adjusted to. Put a glass substrate over this target 33
By passing at a speed of 9 mm / min, 36.
A zinc oxide film having a thickness of 3 nm was formed as the first layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, then 100 SCCM of Ar gas was introduced, and the pressure was 0.3 P.
Adjusted to a. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. By passing a glass substrate over this target at a speed of 2273 mm / min,
An Ag film having a thickness of 11.0 nm was formed as the second layer.
Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, then 100 SCCM of Ar gas was introduced, and the pressure was 0.3 P.
Adjusted to a. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is passed over this target at a speed of 7500 mm / min to obtain 1 nm.
A metal zinc film having a thickness of 1 was formed. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas was 50 SCC.
M and oxygen gas of 50SCCM are introduced, and the pressure is 0.3 Pa.
Adjusted to. On the cathode equipped with a Zn target,
Electric power is supplied from the DC power supply to cause discharge and current is 3A
Adjusted to. On top of this target, place a glass substrate 16
By passing it at a speed of 2 mm / min, 76.
A zinc oxide film having a thickness of 0 nm was formed as the third layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, then 100 SCCM of Ar gas was introduced, and the pressure was 0.3 P.
Adjusted to a. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. By passing a glass substrate over this target at a speed of 1866 mm / min,
An Ag film having a thickness of 13.4 nm was formed as the fourth layer.
Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, then 100 SCCM of Ar gas was introduced, and the pressure was 0.3 P.
Adjusted to a. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is passed over this target at a speed of 7500 mm / min to obtain 1 nm.
A metal zinc film having a thickness of 1 was formed. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas was 50 SCC.
M and oxygen gas of 50SCCM are introduced, and the pressure is 0.3 Pa.
Adjusted to. On the cathode equipped with a Zn target,
Electric power is supplied from the DC power supply to cause discharge and current is 3A
Adjusted to. Place a glass substrate over this target.
32. by passing it at a speed of 0 mm / min.
A zinc oxide film having a thickness of 4 nm was formed as the fifth layer.

Table 7 shows the constitution of the heat insulating glass thus obtained. Table 8 shows the results of measuring various optical characteristics of this heat insulating glass using a spectrophotometer. In the standard C light source, the visible light transmittance is 74.6%, which is a sufficiently high value, but the solar light transmittance is 40.3.
It showed a very low value such as%, and the infrared rays were effectively blocked. Transmission color is L ^* a ^* b ^* color system, a ^* value is -3.0, b ^*
The value was -2.3, which was almost colorless and transparent. The visible light reflectance on the side on which the infrared reflective film was formed was as low as 4.0%, and there was no glare. The solar reflectance was as high as 39.8%, indicating that infrared rays were reflected very effectively. The reflected color was in the L ^* a ^* b ^* color system and exhibited a green color with an a ^* value of -4.6 and a b ^* value of -1.2. The visible light reflectance on the side where the infrared reflection film is not formed,
The value was as low as 5.3%, and there was no glare. The solar reflectance was as high as 28.2%. Reflected color is L ^* a ^* b ^* color system, a ^* value is -1.5, b ^* value is 1.5.
After all it was completely achromatic. As described above,
Two Ag as described in JP-A-4-133507
When the thickness of each layer is 11 nm or more (the thickness of the second layer is the limit of 11.0 nm), the transmitted color can be adjusted to be almost achromatic while maintaining high visible light transmittance and infrared reflectance. It was found that the color reflected from the side on which the infrared reflection film was formed was green.

Comparative Example 5 The following shows the results when the metal oxide film material was changed from tin oxide or zinc oxide used in the present invention to titanium oxide having a high refractive index. An infrared reflective film was formed using the same in-line sputtering device as in Example 2. Three cathodes are prepared in the sputtering chamber. Metal Ti was set as the target for the first cathode, metal Zn was set as the second cathode, and metal Ag was set as the third cathode. The sputter chamber uses a rotary pump and a cryopump 5 ×
The gas was exhausted to 10 ⁻⁴ Pa or less. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. Ar gas 50 SCCM and oxygen gas 50 in the sputter chamber
SCCM was introduced and the pressure was adjusted to 0.3 Pa. Ti
Electric power was supplied from a DC power source to the cathode provided with the target to cause discharge, and the current was adjusted to 6 A (voltage was about 470 V). A glass substrate was passed over this target at a speed of 50 mm / min to form a titanium oxide film having a thickness of 35.5 nm as a first layer. Then, the sputtering chamber is again set to 5 × 10-4 Pa.
After exhausting up to 100 Pa, Ar gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate was passed over this target at a speed of 2600 mm / min to form an Ag film having a thickness of 9.6 nm as a second layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode provided with the Zn target to cause discharge,
The current was adjusted to 0.6A. A glass substrate is passed over this target at a speed of 7500 mm / min,
A metal zinc film having a thickness of 1 nm was formed. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 50
SCCM and 50 SCCM oxygen gas were introduced, and the pressure was adjusted to 0.
It was adjusted to 3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ti target to cause discharge, and the current was adjusted to 6A. By passing a glass substrate over this target at a speed of 23 mm / min,
A titanium oxide film having a thickness of 5.7 nm was formed as the third layer (however, a zinc oxide film having a thickness of 1 nm was formed between the Ag film and the titanium oxide film). Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas 100 was added.
SCCM was introduced and the pressure was adjusted to 0.3 Pa. Ag
Electric power was supplied from the DC power supply to the cathode provided with the target to cause discharge, and the current was adjusted to 1A. A glass substrate is placed over this target at 3086 mm / min.
At a rate of 8.1 nm,
A g-film was formed as the fourth layer. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas of 100 SC
CM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is placed on this target at 7500 mm / min.
And a metal zinc film having a thickness of 1 nm was formed. Next, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then 50 SCCM of Ar gas and 50 SCCM of oxygen gas were introduced to adjust the pressure to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ti target to cause discharge, and the current was adjusted to 6A. A glass substrate was passed over this target at a speed of 51 mm / min to form a titanium oxide film having a thickness of 34.0 nm as a fifth layer (however, a zinc oxide film having a thickness of 1 nm was an Ag film). And is formed between the titanium oxide film).
Table 5 shows the constitution of the heat insulating glass thus obtained. This heat insulating glass also represents a desirable embodiment described in JP-A-63-134232, and the thickness of the Ag layer of the second layer and the thickness of the fourth layer are both 11 nm.
It has been adjusted to:

Various optical characteristics of the heat insulating glass thus obtained were measured with a spectrophotometer and the results are shown in Table 8.
It was shown to. With standard C light source, visible light transmittance is 8
Although it was a very high value of 0.3%, the solar light transmittance was also 5
At a high value of 9.0%, it was found that the ability to block infrared rays was insufficient. The transmitted color was the L ^* a ^* b ^* color system, and the a ^* value was -1.3 and the b ^* value was -2.7, which were almost colorless and transparent. The visible light reflectance on the side where the infrared reflective film is formed is
The value was slightly high at 10.6%, and there was a slight glare. The solar light reflectance was 22.4%, which was a small value as compared with the examples. The reflection color is the L ^* a ^* b ^* color system, and the a ^* value is -1.
7, b ^* value was 5.1, which was slightly yellowish.
The visible light reflectance on the side where the infrared reflecting film was not formed was 9.1%, which was a slightly higher value than that of the example. The solar reflectance was 18.1%, and the ability to block infrared rays was insufficient. The reflected color is the L ^* a ^* b ^* color system, and the a ^* value is 1.
5, b ^* value was -1.5 and it was colorless. Thus, when a titanium oxide film is used as the metal oxide film, the heat insulating glass obtained based on JP-A-63-134232 has a sufficient infrared reflectance while maintaining a high visible light transmittance. It was not possible to increase the height, and it was also found that the reflection color on the side on which the infrared reflection film was formed was noticeably yellow. In this comparative example, the Ag of the fourth layer is
It was found that even if the film thickness is 11 nm or more, the infrared reflectance increases, but the reflection color on the side on which the infrared reflecting film is formed cannot be made neutral, and rather a more remarkable yellow color is exhibited. It was

Comparative Example 6 The results are shown when the metal oxide film material was changed from tin oxide or zinc oxide used in the present invention to silicon oxide having a low refractive index. An infrared reflective film was formed using the same in-line sputtering device as in Example 2. 3 in the sputter chamber
Two cathodes are prepared. The first cathode is a rotary magnetron type cathode, and cylindrical metal Si is set as a target, and the second cathode
Of metal Zn for the cathode and metal A for the third cathode
g was set as the target. The sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa or less with a rotary pump and a cryopump. The washed 5 mm thick colorless transparent float glass was put in a preliminary exhaust chamber and exhausted to 0.3 Pa or less. Then, the glass substrate was transferred to the sputtering chamber. 20 SCCM of Ar gas and 80 SCCM of oxygen gas were introduced into the sputtering chamber, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Si target to cause discharge, and the current was adjusted to 2 A (voltage was about 350 V). A glass substrate 95m above this target
35.5n by passing at a speed of m / min
A silicon oxide film having a thickness of m was formed as the first layer. Then, the sputtering chamber is evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar
A gas of 100 SCCM was introduced and the pressure was adjusted to 0.3 Pa. Electric power was supplied from the DC power supply to the cathode provided with the Ag target to cause discharge, and the current was adjusted to 1A. A glass substrate over this target is 2684m.
9.3 nm by passing at a speed of m / min
Was formed as the second layer. Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate is placed on this target for 7500
It was passed at a speed of mm / min to form a metal zinc film with a thickness of 1 nm. Next, the sputtering chamber is again set to 5 × 10 ^−4.
After exhausting to Pa, 20 SCCM of Ar gas and 80 SCCM of oxygen gas were introduced to adjust the pressure to 0.3 Pa.
Electric power was supplied from the DC power supply to the cathode provided with the Si target to cause discharge, and the current was adjusted to 2A.
A glass substrate was passed over this target at a speed of 44 mm / min to form a silicon oxide film having a thickness of 76.1 nm as a third layer (however, a zinc oxide film having a thickness of 1 nm is an Ag film). Formed between silicon oxide films). Then, the sputtering chamber was evacuated again to 5 × 10 ⁻⁴ Pa, Ar gas 100 SCCM was introduced, and the pressure was adjusted to 0.3 Pa. Electric power is supplied from the DC power supply to the cathode provided with the Ag target to cause discharge,
The current was adjusted to 1A. A glass substrate was passed over this target at a speed of 3125 mm / min to form an Ag film having a thickness of 8.0 nm as a fourth layer. Then, the sputtering chamber was again evacuated to 5 × 10 ⁻⁴ Pa, Ar gas of 100 SCCM was introduced, and the pressure was adjusted to 0.
It was adjusted to 3 Pa. Electric power was supplied from a DC power source to the cathode provided with the Zn target to cause discharge, and the current was adjusted to 0.6A. A glass substrate was passed over this target at a speed of 7500 mm / min to
A metallic zinc film having a thickness of m was formed. Then, the sputtering chamber was evacuated to 5 × 10 ⁻⁴ Pa again, and then Ar gas was 20 SCC.
Introduce M and oxygen gas 80SCCM, pressure 0.3Pa
Adjusted to. On the cathode equipped with Si target,
Electric power is supplied from the DC power supply to cause discharge and current is 2A
Adjusted to. On top of this target, place a glass substrate
34.6 by passing through at a speed of mm / min
A silicon oxide film having a thickness of nm was formed as the fifth layer (however, a zinc oxide film having a thickness of 1 nm was formed between the Ag film and the titanium oxide film).

Table 7 shows the constitution of the heat insulating glass thus obtained. This heat insulating glass is also disclosed in JP-A-63-13.
This is a representative of the preferred embodiment described in Japanese Patent No. 4232, and the thicknesses of the Ag layers of the second layer and the fourth layer are both adjusted to 11 nm or less. Table 8 shows the results of measuring various optical properties of the heat insulating glass thus obtained using a spectrophotometer. In the standard C light source, the visible light transmittance could not be maintained at a sufficiently high value of 64.4%. The solar light transmittance was as low as 36.6%, and it was found that the ability to block infrared rays was excellent. The transmitted color was in the L ^* a ^* b ^* color system and exhibited a noticeable bluish green color with an a ^* value of -8.4 and a b ^* value of -8.7. The visible light reflectance on the side on which the infrared reflecting film was formed was as high as 14.1%, and there was a feeling of glare. Solar reflectance is 48.0
It was a high value of%. The reflected color was in the L ^* a ^* b ^* color system, and had a very noticeable orange color with an a ^* value of 21.2 and a b ^* value of 21.1. The visible light reflectance on the side where the infrared reflection film was not formed was also a very high value of 17.3%. The solar reflectance was 37.1%, and the ability to block infrared rays was excellent. Reflected color is L ^* a ^* b ^* color system, and a ^* value is 1
4.7, and b ^* value was 19.7, which was also a remarkable orange color. As described above, when a silicon oxide film is used as the metal oxide film, the infrared ray reflectance of the heat insulating glass obtained based on JP-A-63-134232 can be sufficiently increased, but high visible light transmittance is obtained. It was found that it was difficult to maintain a high rate, and that the reflected color on the side on which the infrared reflective film was formed was noticeably orange. In addition, in this comparative example, even when the thickness of the fourth layer Ag film was set to 11 nm or more, the visible light transmittance was further reduced, and the reflectance on the side where the infrared reflecting film was formed and the side where the infrared reflecting film was not formed were measured. It was also found that the reflection color became extremely achromatic and the achromaticity of the reflected color could not be achieved.

Comparative Example 7-10 Compared with Example 1, the film thickness of the metal oxide film (tin oxide film) of the third layer, the film thickness of the Ag film of the second layer, and the film thickness of the Ag film of the fourth layer were compared. Table 8 shows the characteristics when the film thickness is out of the limited range of the present invention. Comparative Example 7 is an example in the case where the thickness of the third layer tin oxide film is less than 65 nm,
In that case, it can be seen that the reflected color on both the side where the infrared reflecting film is formed and the side where the infrared reflecting film is not formed becomes an extremely bright orange color. Comparative Example 8 is an example in which the thickness of the tin oxide film of the third layer is thicker than 80 nm, in which case the reflection color on the side where the infrared reflection film is not formed is slightly green. Like The reflection color on the side on which the infrared reflection film was formed was slightly yellow. Comparative Example 9 is an example in which the film thickness of the Ag film of the second layer is thinner than 7 nm, and in this case, the reflection colors on both the side where the infrared reflecting film is formed and the side where the infrared reflecting film is not formed are , It turns out that it becomes extremely bright yellow. Comparative Example 10
Is an example in which the film thickness of the Ag film of the fourth layer is thicker than 14 nm, in which case the reflected colors on both the side where the infrared reflecting film is formed and the side where the infrared reflecting film is not formed are extremely vivid. You can see that it turns orange.

Comparative Example 11 Comparative Example 11 is different from Example 1 in that the relationship of the film thicknesses of the Ag film of the second layer and the Ag film of the fourth layer was reversed, that is, the film of the Ag film of the second layer. The thickness is 11 nm or more and 14 nm or less,
This is an example of the case where the thickness of the fourth layer Ag film is set to 7 nm or more and 11 nm or less, and in this case, the reflection colors on both the side where the infrared reflection film is formed and the side where the infrared reflection film is not formed are extremely vivid yellow. You can see that

[0060]

According to the present invention, it is possible to adjust both the transmitted color and the reflected colors from both sides to an achromatic color while maintaining a sufficiently high visible ray transmittance and infrared ray reflectance. When used as a window glass of a building or a vehicle, it is possible to realize a heat insulating glass having an extremely natural appearance and excellent design. Since both the transmitted color and the reflected color are achromatic colors, an elegant and high-class appearance can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the present invention.

[Explanation of symbols]

10, 20, 30: Transparent glass substrate (float glass) 11, 21: First layer of transparent metal oxide film 13, 23: Second layer of transparent metal oxide film 15, 25: First of transparent metal oxide film Three layers 12, 14, 22:24: Ag film 40: Spacer, 50: Butyl rubber, 60: Dry air layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location E06B 3/66 5/00 B (72) Inventor Kokujo Terubo 3-5, Doshomachi, Chuo-ku, Osaka City No. 11 Japan Sheet Glass Co., Ltd. (72) Inventor Etsushi Ogino 3-5-11 Doshomachi, Chuo-ku, Osaka City Japan Sheet Glass Co., Ltd.

Claims (6)

[Claims] 1. A glass plate is provided with a metal oxide film as a first layer, a film containing Ag as a main component as a second layer, and a metal oxide film as a third layer in this order from the glass plate side. In a heat-insulating glass in which a film containing Ag as a main component as the fourth layer, a metal oxide film as the fifth layer, and a protective film as the sixth layer is formed as necessary, the metal oxide film is the first The layer, the third layer or the fifth layer as a whole is composed of one or more layers containing at least one of tin oxide and zinc oxide as a main component,
A heat insulating glass, wherein the thickness of the third layer is 65 nm or more and 80 nm or less, the thickness of the second layer is 7 nm or more and less than 11 nm, and the thickness of the fourth layer is more than 11 nm and 14 nm or less. 2. The metal oxide film is a tin oxide film, a zinc oxide film, a tin oxide film doped with one or both of Sb and F, and a zinc oxide doped with one or both of Al and Ga. The insulating glass according to claim 1, which is a film or a film in which two or more layers of these films are laminated. 3. The heat insulating glass according to claim 1, wherein the layer containing Ag as a main component is an Ag layer. 4. The heat insulating glass according to claim 1, wherein an additional layer having a thickness of 1 nm or more and 10 nm or less is provided so as to be in contact with the second layer or the fourth layer. 5. A plurality of glass plates are bonded together so as to maintain a dry air layer between the glass plates by hermetically sealing the periphery of these glass plates in a state where adjacent glass plates are separated from each other. A laminated glass, wherein at least one of the plurality of glass plates is the heat insulating glass according to any one of claims 1 to 4, and a film forming surface of the heat insulating glass is provided on the dry air side. A heat insulating double glazing characterized by being arranged so as to face. 6. A heat insulating double glazing window having the heat insulating double glazing according to claim 5 installed in an opening, the reflection color being viewed from the outside, the reflection color being viewed from the inside and the inside from the outside. The insulated double-glazing window is characterized in that the transmitted color when viewed is achromatic.