JPH10182192A - Heat insulating glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the moisture resistance by successively laminating a transparent oxide film layer, a noble metallic film layer and an Al-Zn film layer on the surface of a glass substrate and making the Al-Zn layer present so as to protect the noble metallic film layer. SOLUTION: This heat insulating glass is obtained by successively laminating a transparent oxide film layer, a noble metallic film layer and an Al-Zn film layer on the surface of a glass substrate and making the noble metallic film layer present so as to protect the Al-Zn film layer. The Al-Zn film layer acts as a sacrificing metal reactive with oxygen preferentially to the noble metallic film layer and manifests barrier properties to suppress the occurrence of white spots or opaque pinholes or cracking, etc., due to aggregation or peeling of the noble metallic such as Ag. As a result, the moisture resistance of the laminated film is remarkably improved. An Al-Zn film layer containing Al in an amount of >=3 and <=10wt.% based on the Zn added thereto is preferred as the Al-Zn film and the thickness thereof is preferably >=2 and <=10nm by taking functions and productivity as a barrier layer into consideration. A ZnOX film, etc., are preferred as the transparent oxide film layer in aspects of no deterioration in both film-forming rate and ultraviolet shielding. A noble metallic film layer consisting essentially of the Ag is preferably used as the noble metallic film layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating glass having excellent moisture resistance, and more particularly to a window glass for a vehicle as well as a building.
Further, the present invention provides an insulating glass which is useful as various glass articles such as window glasses for ships and aircraft.

[0002]

2. Description of the Related Art Conventionally, from a viewpoint of energy saving, a specific wavelength portion of sunlight radiated into a vehicle or a room through a window glass is cut off, a temperature rise in the vehicle or a room is reduced, and a load on a cooling device is reduced. There is a demand for window glasses having high heat insulating properties.

As a method of heat insulation, a so-called drude mirror is formed by forming a transparent conductive film typified by a mixed film of indium oxide and tin oxide (ITO film) or a zinc oxide film to which aluminum is added on a transparent substrate. Methods for blocking heat rays are known. This type of glass blocks heat rays but has a wavelength of 1.5 μm or more, and the heat ray blocking performance is not so good. It is also known that various kinds of metal films are laminated, and light of a specific wavelength is reflected or transmitted by combining a Drude mirror effect with an optical interference effect. For example, JP-B-47-6315 discloses a structure in which a silver film is sandwiched between transparent dielectric films, and JP-A-63-206333 discloses a structure in which a nitride is sandwiched between transparent dielectric films. A configuration is disclosed.

Japanese Patent Application Laid-Open No. Sho 62-41740 discloses a method for producing a heat ray reflective glass. The third layer is formed by direct current sputtering in a non-oxidizing atmosphere or an atmosphere having a low oxygen partial pressure with a ZnO target. A glass plate / ZnO-Ag-ZnO is obtained by forming, and a configuration of a glass plate / ZnO-Zn-Ag-ZnO is disclosed as a conventional technique.

Japanese Patent Application Laid-Open No. 62-235232 describes a curved and / or tempered silver-coated glass substrate and a method for producing the same. The silver substrate has a thickness of 5 to 30 nm;
l, an additional metal layer selected from Ti, Zn and Ta; and a glass substrate having a coating comprising an anti-reflective metal oxide layer on the additional metal layer, by bending and / or heating to a temperature above the softening point of the glass. Alternatively, it is disclosed to operate a tempering cycle, thereby imparting high light transmission to the coated glass during the bending and / or tempering cycle. It is also disclosed that the additional metal layer below the silver layer may be provided arbitrarily and the silver layer may be sandwiched between upper and lower additional metal layers.

Japanese Patent Publication No. 4-44721 discloses a transparent material for preventing transmission of ultraviolet light and infrared light. A zinc oxide thin film and an aluminum-containing zinc oxide containing 1-20 atom% of aluminum with respect to zinc atom. It discloses an ultraviolet and infrared blocking film formed by laminating a thin film on a transparent substrate.

[0007] Japanese Patent Publication No. 5-70580 discloses an infrared reflective article having a high transmittance. A first layer of a transparent oxide and a second layer of silver are sequentially formed on a transparent substrate from the substrate side. A five-layer infrared reflecting article comprising a third layer of a transparent oxide, a fourth layer of silver, and a fifth layer of a transparent oxide, wherein the thickness of the silver layer is 110 mm or less; One having a visible light transmittance of 70% or more is disclosed. Specifically, for example, substrate / ZnO [400 (200-600)] / Ag [100 (60
~ 110Å)] / ZnO [800Å (400-1200Å)] / Ag [100Å (60
-110110)] / ZnO [400Å (200-600Å)], and as a conventional example, substrate / ZnO (400Å) / Ag (100Å) / ZnO (400Å)
Are listed.

Japanese Patent Application Laid-Open No. 5-229052 describes a heat ray blocking film, and a (2n + 1) layer (n ≧ 2) in which an oxide film, a metal film, and an oxide film are alternately laminated on a substrate. In the heat ray blocking film of 1), the oxide film (B) formed on the opposite side of the metal film (A) farthest from the base when viewed from the base is Si, Ti, Cr, B, Mg, Sn. And at least one layer of zinc oxide in which at least one of Ga is doped with 1 to 10 atomic% with respect to the total amount of Zn.
Further, the metal film (A) is mainly composed of Ag, and the zinc oxide film has a hexagonal crystal system of zinc oxide, and is formed of hexagonal zinc oxide by an X-ray diffraction method using CuK α ray. (002) The value of the diffraction angle 2θ (center of gravity) of the diffraction line is 33.88.
It is described that the film is not less than 35.00 °.
Specifically, for example, a substrate / Si dope (3.0 atomic%) ZnO (45
0Å) / Ag (100Å) / Si dope Zn (20Å) is formed, then ZnO is deposited in an oxidizing atmosphere, and the final Si dope (3.0 at%) ZnO is formed.
(Total film thickness of 450 mm) is disclosed.

Furthermore, Japanese Patent Application Laid-Open No. 7-330381 describes a functional article, in which a transparent oxide layer and a metal layer are alternately laminated on a transparent substrate, and a transparent oxide layer is formed on the outermost layer. In the formed functional article, an article in which at least one transparent nitride layer is formed between the uppermost transparent oxide layer and the first metal layer counted from the outermost layer is described. It is described that the oxide layer contains, as a main component, an oxide of at least one metal selected from the group consisting of zinc, indium, tin, titanium, bismuth, tantalum, aluminum, and zirconium. Specifically, for example,
Glass plate / ZnO (40nm) / Ag (10nm) / Zn (2nm) / SiN (10n
m) / ZnO (40 nm) is disclosed.

Further, Japanese Patent Application Laid-Open No. Hei 4-357025 discloses a heat ray blocking film, and a (2n + 1) layer (AlN) is formed by alternately stacking an oxide film, a metal film, and an oxide film on a substrate. n ≧ 1), the oxide film (B) formed on the opposite side of the metal film (A) farthest from the base when viewed from the base is 1.1 × 10 ¹⁰ dyn / cm ² or less. Is described as having an internal stress of Specifically, for example, by DC sputtering method, Ar: O ₂ = 2: 8 6.5 on a glass substrate.
In an atmosphere of × 10 ^-3 Torr, Al is added to the total amount of Zn and Al
Al-doped ZnO as a target containing 3.0 atomic% of metal
A film was formed at a thickness of 450 ° C., and then an Ag film was formed at a thickness of 100 ° C. in an atmosphere of Ar alone at 6.5 × 10 ⁻³ Torr, using Ag as a target. Against the total amount
Using a metal containing 3.0 atomic% of Al as a target, a very thin Al-doped Zn film of about 20 ° is formed. Finally, Ar: O ₂ = 2: 8
In an atmosphere of 6.5 × 10 ⁻³ Torr of the above, a metal containing 3.0 atomic% of Al with respect to the total amount of Zn and Al as a target is used as a target.
An Al-doped ZnO film was formed on the film. During the formation of the Al-doped ZnO film, the Al-doped Zn film was oxidized in an oxidizing atmosphere to form an Al-doped ZnO film, so that the Al-doped ZnO film was formed on the Ag film.
The total thickness of the ZnO film was 450 °. The substrate temperature during film formation was room temperature, and the sputter power density was Al-doped ZnO film formation 2.
7W / cm ^2, it Ag film was deposited at 0.7 W / cm ² have been disclosed.

[0011]

Problems to be Solved by the Invention
In the method for manufacturing a heat ray reflective glass described in JP-A-62-41740, even if the Ag film layer is protected by the Zn film layer, the moisture resistance and heat resistance are poor, and the influence of the oxidation and the like on the Ag film layer is suppressed instead. This is a heat ray reflective glass in which an Ag film layer and a ZnO 2 film layer are directly laminated, but if the heat ray reflective glass is used for a long period of time, it is hard to say that the moisture resistance is particularly sufficient.

Further, according to the curved and / or tempered silver-coated glass substrate and the method of manufacturing the same described in JP-A-62-235232, an additional metal layer selected from Al, Ti, Zn and Ta provided on a silver layer is provided. Can be enhanced in light of the fact that they are oxidized in the curvature and / or reinforcement and migrate to the oxide layer, but the additional metal layer is oxidized in the curvature and / or reinforcement and the additional metal layer remains. It is hard to say that the additional metal layer in the product protects the silver layer and has sufficient moisture resistance.

Further, in the infrared reflective article having a high transmittance described in Japanese Patent Publication No. Hei 5-70580, a film structure in which, for example, a ZnO layer and a silver layer are alternately sandwiched between silver layers as a transparent oxide. Is merely durable from the conventional three layers to five layers, as long as the ZnO film is used as the outermost surface layer, the durability is as high as the conventional one, and particularly, the moisture resistance is inferior. That is no different.

Further, in the heat-ray shielding film described in Japanese Patent Application Laid-Open No. 5-229052, at least one of Si, Ti, Cr, B, Mg, Sn, and Ga is 1 to 10 atoms with respect to the total amount of Zn. In order to include at least one layer of a zinc oxide film which has been doped with at least one%, the internal stress of the zinc oxide film is reduced so that the film is hardly damaged and the deterioration due to moisture is suppressed. It does not change itself, and it is hard to say that the internal stress has been sufficiently eliminated, and it is hard to say that it has sufficiently excellent moisture resistance.

Further, in the functional article described in JP-A-7-330381, at least one transparent nitride is provided between the uppermost transparent oxide layer and the first metal layer counted from the outermost layer. Even if a layer is formed, the transparent nitride layer is merely a barrier layer of the metal layer, and is not an improvement in the moisture resistance due to the improvement of the uppermost transparent oxide layer, for example, the ZnO film itself. It is necessary to add at least one layer, and it is not always possible to say that the productivity is good.

Furthermore, in the heat ray blocking film described in JP-A-4-357025, at least one of Al, Si, B, Ti, Sn, Mg, and Cr is contained in a ZnO film with respect to the total amount of Zn. 10 by atomic ratio
% Or less, the internal stress can be reduced, the film is hardly damaged, and the deterioration due to moisture can be suppressed.
The doped Zn film is intended to be oxidized during the formation of the Al doped ZnO film to become an Al doped ZnO film, and even if the internal stress can be reduced, the Al doped ZnO film is reduced. The film does not remain, and it is hard to say that the product has sufficiently excellent moisture resistance.

In any case, the one described in each of the above-mentioned publications and the like can prevent Ag from aggregating and causing defects such as white spots and white turbidity during handling and storage in a single plate. Because it is easy to become difficult, special contrivance is required, and it is something that is not sufficiently improved or the productivity is deteriorated, and a product excellent in durability such as further moisture resistance is provided with good productivity. It was hoped that it would be.

Therefore, the inventors of the present invention have found that the deterioration of a heat insulating film with a noble metal film layer such as Ag due to moisture is caused by Zn in the transparent oxide film layer.
It is not limited to the case where a material having high orientation and high internal stress such as O is used, the spacing between the (002) planes of the ZnO film layer and the moisture resistance are not always correlated, and the noble metal film layer such as Ag In view of the fact that the thickness of the protective metal film layer between the transparent oxide film layers on the transparent oxide film layer has a strong influence on the moisture resistance, it was noted that the moisture resistance strongly depends on the oxygen concentration in the noble metal film layer such as Ag.

The protective metal film layer not only functions to prevent oxidation of the noble metal film layer such as Ag when forming the transparent oxide film layer thereon, but rather actively deoxidizes the noble metal film layer such as Ag. This has the effect of absorbing oxygen taken in as an impurity during the formation of a noble metal film layer such as Ag.In addition, when treated as a single-panel insulating glass, oxidizing molecules such as oxygen and water diffuse from the surface. It absorbs and prevents them from affecting the noble metal film layer such as Ag.

As described above, in order to improve the moisture resistance by protecting the noble metal film layer such as Ag with the protective metal film layer serving as at least a sacrificial metal film layer, 1) an appropriate sacrificial metal film layer must be used. Selection, 2) adjusting the thickness of the sacrificial metal film layer to a necessary and sufficient thickness, 3) improving the adhesion with the layer in contact with the sacrificial metal film layer, particularly with the transparent oxide film layer, etc. Was found.

[0021]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has at least a transparent oxide film layer, a noble metal film layer, and an Al-Zn film layer formed on a surface of a glass substrate. In the laminated film thus formed, the presence of the Al-Zn film layer in the laminated film so as to protect the noble metal film layer with the Al-Zn film layer allows the existing Al-Zn film layer without impairing the optical characteristics. The present invention provides useful heat-insulating glass, such as exhibiting barrier properties and adhesiveness, further improving the moisture resistance of the laminated film itself, and being durable.

That is, the present invention provides a laminated film in which at least a transparent oxide film layer, a noble metal film layer, and an Al—Zn film layer are combined and sequentially laminated on a surface of a glass substrate, wherein the noble metal film layer is formed of at least Al—Zn. An insulating glass characterized by having an Al-Zn film layer so as to be protected by a Zn film layer.

The heat insulating glass as described above, wherein the outermost layer of the laminated film is a transparent oxide film layer.
Further, the transparent oxide film layer is composed of ZnOx, SnOx, TiOx, ZnOx.
-The heat insulating glass described above, comprising a film of TiOx, a film containing these as a main component, or a film combining these components.

The thickness of the Al-Zn film layer at the time of film formation is as follows:
The above-mentioned insulating glass having a thickness of 2 nm or more.
The above-mentioned heat insulating glass, wherein the noble metal film layer is made of Ag or a noble metal film containing Ag as a main component.

The layer for protecting the metal film layer is made of Al.
-The above-mentioned heat-insulating glass, comprising a Zn film and another metal film. Further, the present invention provides the above-mentioned heat-insulating glass, wherein the layer for protecting the metal film layer comprises an Al—Zn film and a Zn film.

[0026]

DETAILED DESCRIPTION OF THE INVENTION As described above, a transparent oxide film layer, a noble metal film layer, an Al-Zn
A heat insulating glass having an Al-Zn film layer so as to protect at least the noble metal film layer with at least the Al-Zn film layer is obtained as follows.

As the transparent glass substrate, various glass plates such as soda lime glass and aluminosilicate glass (for example, float glass), colored glass such as bronze, gray, blue and green (for example, float colored glass), or polymethyl methacrylate (PMMA), polycarbonate (PC), and other transparent resin substrates, and various commercially available glasses, such as bent glass, reinforced glass, strength-up glass, glass with a base film layer, or glass with mesh, can be used. In some cases, translucent glass may be used.

As the transparent oxide film layer, ZnOx, Sn
Ox, TiOx, ZnOx-TiOx films, films containing these as main components, or films combining these components, preferably ZnOx films, or ZnOx films and TiOx films. In addition, the film forming rate is not reduced and / or the ultraviolet shielding property is not impaired. It is preferable that the transparent oxide film layer be the outermost surface layer of the laminated film. The thickness of the transparent oxide film layer is about
It is 70 nm or less, preferably about 50 nm or less and 30 nm or more.

As the noble metal film layer, Ag or Ag
Is a noble metal film containing Ag as a main component, and specific examples thereof include Au, Cu, Pt, Ir and the like in addition to Ag, and these are components in which Ag is a main component and these components are appropriately combined. Especially
It becomes a heat ray shielding film (heat insulating film) made of a Low-E (Low-Emissivity) film. The thickness of the noble metal film layer is about 20 nm or less, preferably about 15 nm to 5 nm.

The Al—Zn film layer is preferably a layer in which Al is added in an amount of 3 wt% or more and 10 wt% or less with respect to Zn. The film thickness at the time of film formation is 2 nm or more. In consideration of this, the thickness is preferably 2 nm or more and 10 nm or less. In any case, it is important that an Al-Zn film layer is present in the laminated film of the insulating glass so as to protect the noble metal film layer. Furthermore, when the Al-Zn film and another metal film are used in combination, the Zn film is preferable because oxygen can be easily taken in.
Ti, Zr, Cr, Al, SUS, Ta, NiCr, etc. can also be used in some cases.

Further, these transparent oxide films, noble metal films, Al
The heat insulating film made of a -Zn film or the like can be formed by a vacuum film forming method such as a sputtering method, an evaporation method, an ion plating method, a chemical vapor method (CVD method), or a sol-gel method. Among them, the sputtering method and the ion plating method are preferable from the viewpoint of increasing the area and productivity.

For the purpose of improving the optical properties of the heat insulating film, and further improving the abrasion resistance, chemical resistance, weather resistance, etc., various films other than the heat insulating film can be appropriately selected and formed depending on the purpose. Needless to say.

Further, preferably used heat insulating glass includes a glass substrate / a transparent oxide film layer / a noble metal film layer / Al-Z
n film layer / transparent oxide film layer, glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / transparent oxide film layer / transparent oxide film layer, and glass substrate / transparent oxide film Layer / Al-Zn
Film layer / noble metal film layer / Al-Zn film layer / transparent oxide film layer, and glass substrate / transparent oxide film layer / Al-Zn film layer / noble metal film layer / Al-Zn film layer / transparent oxide film layer / Transparent oxide film layer or glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / Zn film layer / transparent oxide film layer or glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / Zn film layer / transparent oxide film layer / transparent oxide film layer.

Glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / transparent oxide film layer / noble metal film layer / Al
-Zn film layer / transparent oxide film layer, glass substrate / transparent oxide film layer / Al-Zn film layer / noble metal film layer / Al-Zn film layer / transparent oxide film layer / Al-Zn film layer / noble metal Film layer / Al-Zn film layer / transparent oxide film layer, and glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / Zn film layer / transparent oxide film layer / noble metal film layer / Al -Zn film layer / Zn film layer / transparent oxide film layer, and glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / Zn film layer / transparent oxide film layer / noble metal film layer / Al -Zn film layer / Zn film layer / transparent oxide film layer.

Further, there is an AlZnO film having improved adhesion between the Al-Zn film layer and the transparent oxide film layer as a gradient film. For example, a glass substrate / transparent oxide film layer / noble metal film layer / Al-Z
n film layer / AlZnO film layer / transparent oxide film layer, glass substrate / transparent oxide film layer / Al-Zn film layer / noble metal film layer / Al-Zn film layer / AlZnO film layer / transparent oxide film layer, Glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / AlZnO film layer /
Transparent oxide film layer / noble metal film layer / Al-Zn film layer / AlZnO film layer / transparent oxide film layer.

Further, the heat insulating glass of the present invention is most preferably used as a double glazing, and is useful as a double glazing for architectural use. In some cases, it can be used as a double glazing for automobiles. It can also be used as a multi-layer window glass for ships and aircraft. It goes without saying that it is possible to use a laminated glass, a bent glass or the like as well as a single plate in some cases in addition to the double-glazed glass.

As described above, according to the heat insulating glass of the present invention, in the laminated film formed on the surface of the glass substrate, at least the Al-Zn film layer is provided so as to protect the noble metal film layer. As a result, the Al-Zn film layer, which acts as a so-called sacrificial metal that reacts with oxygen in preference to the noble metal film layer and has the same role in the electric protection method, becomes more excellent in barrier properties, and is caused by aggregation and peeling of Ag. Useful heat insulation that significantly improves the moisture resistance of the laminated film, which is a heat insulating film, and makes it possible to exhibit extremely excellent durability, such as the occurrence of defects such as white spots, cloudy binholes, and cracks. Glass can be provided with high productivity without lowering the film formation rate. Further, no special device is required for handling and storing in a single plate, and the handling is easy, and the storage is simple and longer.

[0038]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 Float glass having a size of about 300 mm × 300 mm and a thickness of about 3 mm was washed with a neutral detergent, water rinse, isopropyl alcohol and the like, and dried to obtain a glass substrate.

Next, a Zn target, a Zn (96 to 95) -Al (4 to 5) alloy target, and an Ag target which are set in a vacuum chamber of a DC magnetron sputtering apparatus are opposed to each other. The glass substrate was set so that it could reciprocate upward.

Next, the inside of the tank was vacuum pumped to about 5 × 10 ^−6.
After degassing to Torr, a mixed gas of Ar gas (30) and O ₂ gas (70) was introduced into the vacuum chamber to maintain the degree of vacuum at about 2 × 10 ^-3 Torr, Apply about 1.0 kW of power to the get,
By transporting the glass substrate at a speed of about 415 mm / min above the Zn target in the DC magnetron reaction sputtering by the mixed gas, the Zn having a thickness of about 35 nm is formed.
An O 2 thin film was formed as a first layer. After the completion of the film formation, the application to the Zn target was stopped.

Next, while the glass substrate was kept in the vacuum chamber, the inside of the chamber was evacuated to about 5 × 10 ⁻⁶ Torr by a vacuum pump, and Ar gas was introduced into the vacuum chamber to form a vacuum. The pressure is maintained at about 2 × 10 ⁻³ Torr, and the Ag target is
A power of kW is applied, and the glass substrate is transported at a speed of about 1259 mm / min above the Ag target in the DC magnetron reaction sputtering by the Ar gas, whereby a thickness of about 10 nm is formed on the ZnO thin film. Was formed as a second layer. After the film formation was completed, the application to the Ag target was stopped.

Subsequently, similarly, Ar gas was introduced into the vacuum chamber to maintain the degree of vacuum at about 2 × 10 ⁻³ Torr, and the Zn (96)
-Apply power of about 0.14kW to the Al (4) alloy target
In the DC magnetron reaction sputtering by Ar gas, the Z
By transporting the glass substrate above the n-Al alloy target at a speed of about 1259 mm / min, a Zn-Al alloy thin film having a thickness of about 2 nm was formed as a third layer on the Ag thin film.
After the completion of the film formation, the application to the Zn-Al alloy target was stopped.

Further, similarly to the first layer film, a mixed gas of Ar gas (30) and O ₂ gas (70) is introduced into the vacuum chamber to maintain the degree of vacuum at about 2 × 10 ^-3 Torr. Then, about 1.
A power of 0 kW was applied, and the glass substrate was conveyed at a speed of about 415 mm / min above the Zn target in the DC magnetron reaction sputtering by the mixed gas, so that the Zn-Al alloy thin film was formed on the Zn-Al alloy thin film. A 35 nm thick ZnO 2 thin film was formed as a fourth layer. After the completion of the film formation, the application to the Zn target was stopped.

With respect to the obtained glass substrate with a laminated film,
The following evaluation was performed. [Moisture resistance test] Stored in a constant temperature and humidity chamber at 30 ° C and 90% relative humidity for one month, and the number of spots with a size of about 0.2mmφ or more in the area of 100mm x 100mm of the above substrate Was evaluated by. The defect at that time was confirmed by irradiating the film surface with a light source of a fluorescent white plate and visually observing the difference in reflectance. [Optical characteristics] Apparatus: 340 type self-recording spectrophotometer (Hitachi, light source;
D ₆₅ 2 ° field of view).

Measurement: Visible light transmittance (Tv: 380 to 780 nm)
), Visible light reflectance (Rv: 380 to 780 nm) and solar transmittance (Ts: 340 to 1800 nm) and solar reflectance (Rs: 340 to 1800 nm)
And UV transmittance (Tuv: 300 to 380 nm), etc., and the transmittance and reflectance data for each predetermined wavelength and JI
Determined by SZ 8722 and JISR 3106, respectively.

As a result, in the moisture resistance test, the obtained glass substrate with a laminated film was about 0.2 mm in size within a 100 mm × 100 mm area.
Only about one cloudy spot-like defect of not less than mm φ occurred, and there was almost no cloudy spot-like defect of about 0.2 mm or less in size. It had moisture resistance.

Further, the glass substrate with a laminated film has a visible light transmittance Tv of about 76.7%, a visible light reflectance Rv (glass side) of about 14.1%, a solar transmittance Ts of about 64.5%, and an ultraviolet transmittance. Tuv
Was about 18.7%, the emissivity was about 0.09, and it had low-E performance, sufficiently excellent moisture resistance, and was the intended heat insulating glass.

Further, when the insulating glass having a space of about 6 mm and a double-layer glass made of ordinary float glass (3 mm) are used, the visible light transmittance Tv is 69.2% and the visible light reflectance Tv.
Is 15.8%, the solar transmittance Ts is about 51.6%, and the UV transmittance Tuv
Was about 16.3%.

Example 2 In the same manner as in Example 1, the first layer was mixed with the first layer of Example 1 in a mixed gas ratio of Ar gas (5) and O ₂ gas (95). Transfer speed to about 332mm / min and film thickness about 35nm
The second layer and the third layer of the ZnO thin film of
The same as the third and third layers, an Ag thin film having a thickness of about 10 nm and a Zn-Al alloy thin film having a thickness of about 2 nm.
The transfer speed is about 581 mm / mi with Ar gas (5) and O ₂ gas (95).
n, a ZnO thin film having a thickness of about 20 nm, and a fifth layer in the same mixed gas, at an applied power of 3 kW, and the transfer speed of about 160 mm /
A glass substrate with a laminated film in which a TiO 2 thin film having a thickness of about 15 nm was sequentially formed as a min was obtained.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, the moisture resistance test was the same as in Example 1, and had a greatly improved moisture resistance. The glass substrate with a laminated film has a visible light transmittance Tv of 77.7%, a visible light reflectance Rv (glass surface side) of about 13.8%, a solar transmittance Ts of 65.2%, and an ultraviolet transmittance Tuv of about 19.2%. , The emissivity is 0.09, it has Low-E performance,
In addition, it exhibited sufficiently excellent moisture resistance, and was a desired heat insulating glass.

Example 3 In the same manner as in Example 1, the first, second and third layers are the same as the first, second and third layers of Example 2. The ZnO thin film having a thickness of about 35 nm, the Ag thin film having a thickness of about 10 nm, and the Zn-Al alloy thin film having a thickness of about 2 nm. The thickness of the ZnO thin film is about 70 nm, the thickness of the fifth layer is the same as that of the second layer, the thickness of the Ag thin film is about 10 nm, and the thickness of the sixth layer is the same as the third layer.
A glass substrate with a laminated film was formed by sequentially forming a Zn-Al alloy thin film having a thickness of 35 nm and a ZnO thin film having the same thickness as the first layer of about 35 nm as the first layer.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, only about two white opaque spot-like defects having a size of about 0.2 mm φ were generated in an area of about 100 mm × 100 mm.
And had sufficiently improved moisture resistance. The glass substrate with the laminated film has a visible light transmittance.
Tv is 75.2%, visible light reflectance Rv (glass side) is about 6.0
%, Solar transmittance Ts is 41.2%, UV transmittance Tuv is about 9.7
%, Emissivity is 0.05, has excellent Low-E performance,
In addition, it exhibited sufficiently excellent moisture resistance, and was a desired heat insulating glass.

Further, when a double-glazed glass is used as in Example 1, the visible light transmittance Tv is 67.7% and the visible light reflectance Tv is
Is 11.3%, solar transmittance Ts is about 35.4%, UV transmittance Tuv
About 8.3%.

Fourth Embodiment In the same manner as in the first embodiment, the first layer is a ZnO thin film having the same thickness as that of the first layer of the first embodiment and has a thickness of about 35 nm, and the second layer is the second layer of the first embodiment. Only the eyes and applied power are changed to about 0.21 kW Ag with a film thickness of about 13 nm
Only the third layer of the thin film and the third layer of the first embodiment and the applied power
An Al-Zn alloy thin film with a thickness of about 7 nm, changed to 0.49 kW, and a laminated film in which a fourth layer is formed as a first layer and a ZnO thin film with a thickness of about 40 nm, which is changed only to the transfer speed of about 363 mm / min. To obtain a glass substrate.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, it was equal to or more than that of Example 1, and the moisture resistance was remarkably improved. The glass substrate with a laminated film has a visible light transmittance Tv of 71.2%, a visible light reflectance Rv (glass side) of about 19.6%, a solar transmittance Ts of 59.3%, and an ultraviolet transmittance Tuv of about 13.5%. It had an emissivity of 0.08, had low-E performance, exhibited remarkably excellent moisture resistance, and was the intended heat insulating glass.

Fifth Embodiment In the same manner as in the first embodiment, the target of the first layer in the first layer of the first embodiment is changed from Zn to Sn, and the transport speed is set to about 305 mm.
/ Min and a second layer of about 35 nm thick SnO thin film
An Ag thin film having the same thickness as the second layer of about 13 nm, an Al-Zn alloy thin film having a thickness of about 4 nm instead of the third layer of the first embodiment and the applied power of only about 0.28 kW. A glass substrate with a laminated film was obtained by sequentially forming a SnO thin film having a thickness of about 40 nm by changing the fourth layer to the first layer and the above-mentioned transfer speed only to about 267 mm / min.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, about two white opaque spot-like defects having a size of about 0.2 mm φ were generated in an area of about 100 mm × 100 mm.
As in the above, the moisture resistance was greatly improved.
The glass substrate with a laminated film has a visible light transmittance Tv of 7
4.3%, visible light reflectance Rv (glass side) is about 15.9%, solar transmittance Ts is 62.2%, ultraviolet transmittance Tuv is about 37.6%, and emissivity is 0.07. It was a shielding glass, exhibited sufficiently excellent moisture resistance, and was an intended heat ray shielding glass. Incidentally, the ultraviolet shielding property was not improved because of the SnO thin film.

Example 6 In the same manner as in Example 1, the first layer was a ZnO thin film having the same thickness as the first layer of Example 4 and about 35 nm thick, and the second layer was the second layer of Example 4. An Ag thin film having a thickness of about 13 nm, which is the same as the thickness of the third layer, and the third layer and the applied power of only about 0.21 kW in Example 1 were changed to a thickness of about 3 kW.
Al-Zn alloy thin film having a thickness of about 25 nm, and the fourth layer of Example 4 and the fourth layer having the thickness of about 25 nm were changed only to the transfer speed of about 581 mm / min.
The O thin film and the fifth layer are further mixed in a mixed gas of Ar gas (30) and O ₂ gas (70) at an applied power of 3 kW and the transfer speed is about 200 mm / mi.
A glass substrate with a laminated film was formed by sequentially forming a TiO 2 thin film having a thickness of about 15 nm as n.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, it was the same as in Example 1, and the moisture resistance was greatly improved. The glass substrate with a laminated film has a visible light transmittance Tv of 75.4%, a visible light transmittance Tv of 15.2%, and a solar transmittance.
Ts is 63.7%, UV transmittance Tuv is about 17.6%, and emissivity is 0.
The glass had a low-E performance and exhibited sufficiently excellent moisture resistance, and was a useful heat-insulating glass intended.

Example 7 In the same manner as in Example 1, the first layer was a ZnO thin film having the same thickness of about 35 nm as the first layer of Example 4, and the second layer was the same film as in Example 4. Ag thin film with a thickness of about 13 nm, the third layer
Al-Zn with a thickness of about 5 nm by changing only the layer and applied power to about 0.35 kW
The alloy thin film, the fourth layer was changed to only about 208 mm / min in the transport speed of the fourth layer of the fourth embodiment, and the ZnO thin film having a thickness of about 70 nm, and the fifth layer was the same film thickness as the second layer. 13nm Ag thin film,
The sixth layer is an Al-Zn alloy thin film having the same thickness of about 3 nm as the third layer, and the seventh layer is Zn having the same thickness of about 35 nm as the first layer.
A glass substrate with a laminated film, which was sequentially formed with an O thin film, was obtained.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, only about one cloudy spot-like defect having a size of about 0.2 mm φ or more occurred in an area of about 100 mm × 100 mm, and the moisture resistance was remarkably excellent. The glass substrate with a laminated thin film has a visible light transmittance Tv of 71.5%, a visible light transmittance Tv of 9.4%, a solar transmittance Ts of 36.9%, and an ultraviolet transmittance Tu.
The v was about 8.3%, the emissivity was 0.04, and it had low-E performance, showed remarkably excellent moisture resistance, and was a useful heat insulating glass aimed at.

Eighth Embodiment In the same manner as in the first embodiment, the first layer is a ZnO thin film having the same film thickness of about 35 nm as the first layer of the fourth embodiment, and the second layer is the second layer of the first embodiment. An Ag thin film having a thickness of about 10 nm, which is the same as that of the first layer, an Al-Zn alloy thin film having a thickness of about 2 nm, which is the same as the third layer of the first embodiment,
The fourth layer is inclined by changing the ratio of the mixed gas to the third layer of Example 1 by changing the ratio of the mixed gas to Ar gas (30) and O ₂ gas (70), the applied power to about 0.56 kW, and the transfer speed to about 1259 mm / min. About 5 nm thick as component layer
The fifth layer is a ZnO thin film having the same thickness of about 70 nm as the fourth layer of the seventh embodiment, and the sixth layer is the second layer of the fourth embodiment.
An Ag thin film having a thickness of about 12 nm, which is almost the same as the above, an Al-Zn alloy thin film having the same thickness of about 2 nm as the third layer, and an eighth layer having a thickness of about 4 nm.
An AlZnO thin film having the same thickness as that of the first layer and having a thickness of about 5 nm. A substrate was obtained.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, only about two cloudy spot-like defects having a size of about 0.2 mm φ or more occurred in an area of about 100 mm × 100 mm, and the moisture resistance was greatly improved. .

The glass substrate with a laminated film has a visible light transmittance Tv of 74.9%, a visible light transmittance Tv of 7.3%, a solar transmittance Ts of 40.5%, an ultraviolet transmittance Tuv of about 9.4%, and an emissivity. But
It was 0.05, which was an excellent low-E performance, exhibited sufficiently excellent moisture resistance, and was a useful heat insulating glass intended for the intended purpose.

[0066] In the same manner as in Comparative Example 1 Example 1, Zn0 thin and the thickness of the first layer and the second layer and the first layer of Example 2 the second layer of the same thickness of about 35nm An Ag thin film of about 10 nm, the third layer is a third layer of Example 1 and a target is Zn from an Al-Zn alloy, and the applied power is about
Changed to 0.11kW, Zn metal thin film of about 2nm thickness, 4th layer as 1st
A glass substrate with a laminated film was formed in which a Zn0 thin film having the same thickness as the layer and having a thickness of about 35 nm was sequentially formed.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, about 57 opaque spot-like defects having a size of about 0.2 mm φ or more were generated in an area of about 100 mm × 100 mm, which was not considered to be moisture resistant. Further, the glass substrate with a laminated film has a visible light transmittance Tv of 76.3% and a visible light transmittance Tv.
Is 14.7%, the solar transmittance Ts is 64.1%, the UV transmittance Tuv is about 17.8%, the emissivity is 0.09, and it is a heat ray shielding glass with Low-E performance, but the moisture resistance is poor, It wasn't the heat insulating glass we wanted.

When a double-glazed glass is formed in the same manner as in Example 1, the visible light transmittance Tv is 68.9% and the visible light reflectance Tv is
16.2%, solar transmittance Ts was about 51.2%, and UV transmittance Tuv was about 16.0%.

COMPARATIVE EXAMPLE 2 In the same manner as in Example 1, the first layer and the target of Comparative Example 1 were changed from Zn to the Al-Zn alloy, and the transport speed was changed to about 265 mm / min. An AlZnO 2 thin film having a thickness of about 35 nm, an Ag thin film having a thickness of about 10 nm and a Zn metal thin film having a thickness of about 2 nm which are the same as the second and third layers of Comparative Example 1 Then, a glass substrate with a laminated film was obtained in which the fourth layer was successively formed with the same AlZnO 3 thin film having a thickness of about 35 nm as the first layer.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, about 47 opaque spot-like defects having a size of about 0.2 mmφ or more were generated in an area of about 100 mm × 100 mm, which was hardly said to be moisture resistant. Further, the glass substrate with a laminated film has a visible light transmittance Tv of 76.7% and a visible light transmittance Tv.
Is 14.1%, the solar transmittance Ts is 65.2%, the UV transmittance Tuv is about 42.3%, and the emissivity is 0.09. It is a heat-shielding glass with low-E performance, but it is effective for Zn metal thin film and AlZnO thin film. And the moisture resistance was inferior, and the ultraviolet shielding property was deteriorated, and it was not the intended heat insulating glass.

Comparative Example 3 In the same manner as in Example 1, the first layer was a Zn0 thin film having the same thickness as the first layer of Example 1 and about 35 nm thick, and the second layer was the second layer of Example 4. An Ag thin film having the same film thickness as about 13 nm, and the third layer was changed to the third layer of Comparative Example 1 with an applied power of about 0.39 kW, and the film thickness was about 7 nm.
Zn metal thin film, the fourth layer has the same thickness of about 35 nm as the first layer
To obtain a glass substrate with a laminated film, which was sequentially formed with the above Zn0 thin film.

The obtained glass substrate with a laminated film was evaluated in the same manner as in Example 1. As a result, in the moisture resistance test, about 50 opaque spot-like defects having a size of about 0.2 mm φ or more were generated in an area of about 100 mm × 100 mm, which was not considered to be moisture resistant. The glass substrate with a laminated film has a visible light transmittance Tv of 70.4% and a visible light transmittance Tv.
Is 17.1%, the solar transmittance Ts is 59.1%, the UV transmittance Tuv is about 14.6%, the emissivity is 0.07, and it is a heat ray shielding glass with low-E performance, but the moisture resistance is poor, It wasn't the heat insulating glass we wanted.

COMPARATIVE EXAMPLE 4 In the same manner as in Example 1, the first layer was mixed with the first layer of Comparative Example 2 by a ratio of the mixed gas of Ar gas (30) and O ₂ gas (70), and AlZnO thin film with a thickness of about 35 nm changed to about 319 mm / min,
The second layer and the third layer are the same as the second layer and the third layer of Comparative Example 3, the same Ag thin film having a thickness of about 13 nm and the Zn metal thin film having the thickness of about 7 nm, and the fourth layer is the first layer. AlZn with the same thickness of about 35 nm as the layer
A glass substrate with a laminated film, which was sequentially formed with an O thin film, was obtained.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, about 50 opaque spot-like defects having a size of about 0.2 mm φ or more were generated in an area of about 100 mm × 100 mm, which was not considered to be moisture resistant. Further, the glass substrate with a laminated film has a visible light transmittance Tv of 70.9%, and a visible light transmittance Tv.
Is 16.6%, the solar transmittance Ts is 59.9%, the UV transmittance Tuv is about 40.1%, and the emissivity is 0.07. It is a heat-insulating glass with low-E performance, but it is effective for Zn metal thin film and AlZnO thin film. And the moisture resistance was inferior, and the ultraviolet shielding property was deteriorated, and it was not the intended heat insulating glass.

COMPARATIVE EXAMPLE 5 In the same manner as in Example 1, the first layer and the second layer were replaced with a Zn0 thin film having a thickness of about 35 nm, which was the same as the first layer and the second layer of Comparative Example 3, and An Ag thin film of about 13 nm, the third layer is the same as the third layer of Example 1, and the applied power is changed to about 0.07 kW.
A glass substrate with a laminated film was obtained in which the alloy thin film and the fourth layer were sequentially formed with a Zn0 thin film having the same thickness as the fourth layer of Example 4 and a thickness of about 40 nm.

The same evaluation as in Example 1 was performed on the obtained glass substrate with a laminated film. As a result, in the moisture resistance test, about 32 opaque spot-like defects having a size of about 0.2 mm φ or more were generated in an area of about 100 mm × 100 mm, which was hardly said to be moisture resistant. The glass substrate with a laminated film has a visible light transmittance Tv of 80.6% and a visible light transmittance Tv
Is 10.3%, solar transmittance Ts is 67.3%, ultraviolet transmittance Tuv is about 20.3%, emissivity is 0.09, and it is a heat insulating glass with low-E performance, but the Al-Zn alloy thin film is too thin It was inferior in moisture resistance and was not the intended heat insulating glass.

[0077]

According to the present invention, in the laminated film formed on the surface of the glass substrate, the noble metal thin film is protected by the Al-Zn alloy thin film, so that the moisture resistance is remarkably improved and the durability is further improved. Window glass for architectural use, which makes handling, storage, packaging, etc. easy and simple.
In particular, it is possible to economically provide a heat-insulating glass useful as a double-glazed glass with higher productivity.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI B60J 1/00 B60J 1/00 C23C 14/06 C23C 14/06 N 14/08 14/08 N G02B 1/10 G02B 1/10 Z

Claims (7)

[Claims] 1. A laminated film in which at least a transparent oxide film layer, a noble metal film layer, and an Al-Zn film layer are sequentially laminated on the surface of a glass substrate, and the noble metal film layer is formed of at least Al-Z.
A heat-insulating glass characterized in that an Al-Zn film layer is provided so as to be protected by the n-film layer. 2. The heat insulating glass according to claim 1, wherein the outermost surface layer of the laminated film is a transparent oxide film layer. 3. The method according to claim 1, wherein the transparent oxide film layer is made of ZnOx, SnOx, Zn.
3. The heat-insulating glass according to claim 1, wherein the heat-insulating glass is formed of a film of Ox-TiOx, a film containing these as a main component, or a film obtained by combining these components. 4. The film thickness of the Al—Zn film layer at the time of film formation is 2 nm.
The heat insulating glass according to claim 1, wherein: 5. The heat insulating glass according to claim 1, wherein the noble metal film layer is made of Ag or a noble metal film containing Ag as a main component. 6. The layer for protecting the noble metal film layer is made of Al-Zn.
The heat insulating glass according to any one of claims 1 to 5, comprising a film and another metal film. 7. The layer for protecting the noble metal film layer is made of Al-Zn.
7. The heat insulating glass according to claim 1, comprising a film and a Zn film.