JP3392000B2 - Insulated glass - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, from the viewpoint of energy saving, in order to reduce the temperature rise inside the vehicle or the room and to reduce the load on the cooling equipment by blocking a specific wavelength portion of the sunlight radiated into the vehicle or the room through the window glass. Window glass with high heat insulation is required.

As a heat insulating method, a so-called drude mirror is used to form 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. A method of shutting off heat rays is known. Although this type of glass blocks heat rays, it has a wavelength of 1.5 μm or more, which is not very good. It is also known that various metal films are laminated to combine a Dru-de-Mirror effect with an optical interference effect to reflect or transmit light of a specific wavelength. As this heat ray reflective film, for example, Japanese Patent Publication No. 47-6315 discloses a structure in which a silver film is sandwiched between transparent dielectric films, and Japanese Patent Laid-Open No. 63-206333 discloses a structure in which a nitride is sandwiched between transparent dielectric films. The configuration is disclosed.

Further, Japanese Patent Application Laid-Open No. 62-41740 describes a method for producing a heat ray reflective glass, in which a third layer is formed by direct current sputtering in a non-oxidizing atmosphere or a low oxygen partial pressure in a ZnO target. It is disclosed to obtain a glass plate / ZnO-Ag-ZnO by forming it, and as a conventional technique, a structure of glass plate / ZnO-Zn-Ag-ZnO.

Further, JP-A-62-235232 describes a curved and / or toughened silver-coated glass substrate and a method for producing the same. A silver layer having a thickness of 5 to 30 nm; A on the silver layer.
a glass substrate having a coating of an additional metal layer selected from l, Ti, Zn and Ta; and an antireflection metal oxide layer on the additional metal layer, and bending and / or heating to a temperature above the softening point of the glass. Alternatively, it is disclosed that a tempering cycle is applied, which imparts a 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 appropriately provided and the silver layer may be sandwiched between the upper and lower additional metal layers.

Further, Japanese Patent Publication No. 4-44721 discloses a transparent material for blocking transmission of ultraviolet rays and infrared rays, which is a zinc oxide thin film and an aluminum-containing zinc oxide containing 1-20 atomic% of aluminum with respect to zinc atoms. An ultraviolet and infrared ray blocking film formed by laminating a thin film is provided on a transparent substrate.

Further, Japanese Patent Publication No. 5-70580 describes an infrared reflecting article having a high transmittance, in which a transparent oxide first layer and a silver second layer are successively formed on a transparent substrate from the substrate side. In a infrared reflective article having a five-layer coating comprising a transparent oxide third layer, a silver fourth layer, and a transparent oxide fifth layer, the silver layer has a thickness of 110 Å or less, It is disclosed that the visible light transmittance is 70% or more. Specifically, for example, substrate / ZnO [400Å (200-600Å)] / Ag [100Å (60
~ 110 Å)] / ZnO [800 Å (400 ~ 1200 Å)] / Ag [100 Å (60
~ 110 Å)] / ZnO [400 Å (200 to 600 Å)], as a conventional example substrate / ZnO (400 Å) / Ag (100 Å) / ZnO (400 Å)
Are listed.

Further, Japanese Patent Application Laid-Open No. 5-229052 describes a heat ray blocking film, and a (2n + 1) layer (n ≧ 3) in which an oxide film, a metal film and an oxide film are alternately laminated on a substrate. In the heat ray-shielding film consisting of 1), the oxide film (B) formed on the opposite side of the metal film (A) farthest from the substrate is Si, Ti, Cr, B 2, Mg, Sn. , Ga containing at least one layer of zinc oxide film doped with at least one of Ga and Zn with respect to the total amount of Zn.
Further, the metal film (A) contains Ag as a main component, the zinc oxide film has a hexagonal crystal system of zinc oxide, and the hexagonal zinc oxide film is formed by an X-ray diffraction method using CuK α-rays. The value of the diffraction angle 2θ (centroid position) of the (002) diffraction line is 33.88.
It is described that the film has a temperature of not less than 0 ° and not more than 35.00 °.
Specifically, for example, substrate / Si doped (3.0 at.%) ZnO (45
After forming 0 Å) / Ag (100 Å) / Si dope Zn (20 Å), ZnO film is formed in an oxidizing atmosphere to form the final Si dope (3.0 at%) ZnO.
The composition of (total film thickness 450 Å) is disclosed.

Further, 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. The formed functional article is described 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. 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. 4-357025 describes a heat ray blocking film, and a (2n + 1) layer ((2n + 1) layers (oxide film, metal film, and oxide film) alternately laminated on a substrate ( In the heat ray-shielding film consisting of n ≧ 1), the oxide film (B) formed on the opposite side of the metal film (A) farthest from the substrate when viewed from the substrate is 1.1 × 10 ¹⁰ dyn / cm ² or less. It is described to have an internal stress of. Specifically, for example, by direct current sputtering method, on a glass substrate, Ar: O ₂ = 2: 8 6.5
In an atmosphere of × 10 ^-3 Torr, Al is added to Zn with respect to the total amount.
Al-doped ZnO with a metal content of 3.0 atom% as a target
A film is formed at 450 Å, then Ag film is formed at 100 Å using Ag as a target in an atmosphere of 6.5 × 10 ^-3 Torr containing only Ar, and then Al is mixed with Zn without changing the atmosphere. For the total amount
Using a metal containing 3.0 atomic% of Al as a target, a very thin Al-doped Zn film of about 20Å is formed, and finally Ar: O ₂ = 2: 8
In an atmosphere of 6.5 × 10 ^-3 Torr, a metal containing 3.0 atomic% of Al with respect to the total amount of Zn and Zn 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 become an Al-doped ZnO film, so the Al-doped ZnO film formed on the Ag film was formed.
The total thickness of the ZnO film was 450Å. The substrate temperature during film formation is room temperature, and the sputtering power density is during Al-doped ZnO film formation 2.
7W / cm ^2, it Ag film was deposited at 0.7 W / cm ² have been disclosed.

[0011]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the method for producing 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 in place of this, the influence of oxidation etc. on the Ag film layer is suppressed. It is a heat ray reflective glass in which an Ag film layer and a ZnO 2 film layer are directly laminated and formed. However, if the heat ray reflective glass is used for a long time, it is difficult to say that the moisture resistance is particularly sufficient.

Further, in the curved and / or strengthened silver-coated glass substrate and the manufacturing method thereof described in JP-A-62-235232, an additional metal layer selected from Al, Ti, Zn and Ta provided on the silver layer is used. However, it is possible to increase the light transmission in consideration of the fact that the additional metal layer is oxidized in the bending and / or strengthening and moves to the oxide layer, but the additional metal layer is oxidized in the bending and / or strengthening and the additional metal layer remains. It is difficult to say that the additional metal layer protects the silver layer in the product to provide sufficient moisture resistance.

Further, in the infrared reflective article having a high transmittance described in JP-B-5-70580, a film structure in which, for example, a ZnO layer and a silver layer are alternately sandwiched as a transparent oxide. Even if it is changed from the conventional 3 layers to 5 layers, the durability is the same as the conventional one as long as a ZnO film is used for the outermost surface layer, and especially the moisture resistance is inferior, and improvement of these is desired. It remains the same.

In the heat ray blocking film described in Japanese Patent Laid-Open No. 5-229052, 1 to 10 atoms of at least one of Si, Ti, Cr, B, Mg, Sn, and Ga relative to the total amount of Zn is contained. % At least one layer of doped zinc oxide film is included to lower the internal stress of the zinc oxide film, thereby making it difficult to damage the film and suppressing deterioration due to moisture. For example, C-axis orientation of ZnO film It is difficult to say that the internal stress is not completely eliminated, and that it has sufficiently excellent moisture resistance, without changing itself.

Further, in the functional article described in JP-A-7-330381, at least one layer of 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 merely serves as a barrier layer of the metal layer, and not the improvement of the moisture resistance due to the improvement of the uppermost transparent oxide layer such as the ZnO film itself. It is necessary to add at least one layer, and it cannot be said that productivity is necessarily high.

Further, in the heat ray blocking film described in Japanese Patent Application Laid-Open No. 4-357025, at least one of Al, Si, B, Ti, Sn, Mg and Cr is added to the ZnO film with respect to the total amount of Zn. 10 atomic ratio
% Or less, internal stress can be reduced, damage to the film is less likely to occur, and deterioration due to moisture can be suppressed.
It is intended that the doped Zn film be oxidized during the formation of the Al doped ZnO film to become the Al doped ZnO film, and even if the internal stress can be reduced, the Al doped Zn film can be reduced. It is difficult to say that the product does not have a film and has sufficiently excellent moisture resistance as a product.

In any case, in the materials described in the above-mentioned respective publications, Ag is aggregated and defects such as white spots and cloudiness are developed during handling and storage on a single plate. Therefore, special measures are required because it is easy to become, and it is such that it is not sufficient improvement or productivity is deteriorated, and further excellent durability such as moisture resistance is provided with good productivity. It was hoped that it would happen.

Therefore, the inventors of the present invention have found that the deterioration of the heat insulating film accompanied by the noble metal film layer such as Ag due to moisture is caused by the Zn in the transparent oxide film layer.
This is not limited to the case of using a highly oriented material with high internal stress such as O. Also, the (002) plane spacing of the ZnO film layer does not necessarily correlate with the moisture resistance, and it does not differ from 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 thereabove strongly influences the moisture resistance, etc., 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 positively deoxidizes the noble metal film layer such as Ag. Due to the effect, it has a function of absorbing oxygen taken in as an impurity during the formation of a noble metal film layer such as Ag, and when it is treated as a single-plate heat insulating glass, it does not absorb oxidizing molecules such as oxygen and water that diffuse from the surface. It has a function of absorbing and preventing them from affecting the noble metal film layer such as Ag.

As described above, in order to improve the moisture resistance by protecting the precious metal film layer such as Ag by using the protective metal film layer as at least the sacrificial metal film layer, 1) select a proper sacrificial metal film layer. It is important to select, 2) adjust the thickness of the sacrificial metal film layer to a necessary and sufficient thickness, and 3) improve the adhesion to the layer in contact with the sacrificial metal film layer, especially to the transparent oxide film layer. Found.

[0021]

The present invention has been made in view of the above-mentioned problems, and at least a transparent oxide film layer, a noble metal film layer, and an Al-Zn film layer are formed on the surface of a glass substrate. In the laminated film formed, by allowing the Al-Zn film layer to exist in the laminated film so as to protect the noble metal film layer with the Al-Zn film layer, the existing Al-Zn film layer is not impaired. Provides a useful heat-insulating glass, which exhibits barrier properties and adhesion, further enhances the moisture resistance of the laminated film itself, and becomes durable.

[0022] Namely, the present invention is, on the surface of the glass substrate, at least a transparent oxide film layer, a noble metal film layer, a laminated film obtained by sequentially laminating combines Al-Zn layer, a noble metal layer
Is composed of Ag or a noble metal film containing Ag as a main component, and the Al-Zn film layer is used to protect the noble metal film layer with at least the Al-Zn film layer.
A film layer is present, and the Al-Zn film layer contains 3 wt% of Al for Zn.
% Or more and 10 wt% or less is added to the insulating glass.

[0023]

The film thickness of the Al-Zn film layer at the time of film formation is
An insulating glass characterized by having a thickness of 2 nm or more and 10 nm or less.

The above-mentioned heat insulating glass, characterized in that the metal film layer is protected by an Al--Zn film and another metal film. Moreover, other metals of the its is intended to provide the above-described insulating glass, characterized by comprising at Zn film.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Here, as described above, the transparent oxide film layer, the noble metal film layer, and the Al-Zn layer are formed on the surface of the glass substrate.
A heat insulating glass in which at least Al-Zn film layers are present so as to protect the noble metal film layer with at least the Al-Zn film layer, which is a laminated film in which film layers are at least combined and sequentially laminated, 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, green (for example, float colored glass), or polymethylmethacrylate. (PMMA), Polycarbonate (PC), etc., selected from transparent resin substrates, and various commercially available glasses such as bent glass, tempered glass, strength-up glass, glass with underlying film layer or mesh glass, etc. can be adopted. In some cases, translucent glass may also be used.

As the transparent oxide film layer, ZnOx, Sn
Ox, TiOx, each film of ZnOx-TiOx, each film composed of these as the main component or a film combining these components, preferably a ZnOx film, or a ZnOx film and a TiOx film The film forming rate does not decrease and / or the ultraviolet shielding property is not impaired. Further, it is preferable that the transparent oxide film layer is the outermost surface layer of the laminated film. About the thickness of the transparent oxide film layer
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 used.
It is composed of a noble metal film containing as a main component, and specific examples thereof include Au, Cu, Pt, and Ir in addition to Ag. The main component is Ag, and these components are appropriately combined. Especially
It is 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.

As the Al-Zn film layer, it is preferable that Al is added in an amount of 3 wt% to 10 wt% with respect to Zn. The film thickness during film formation is 2 nm or more, and the function and productivity as a barrier layer. Considering the above, it is preferably 2 nm or more and 10 nm or less. In any case, it is important that the Al-Zn film layer is present in the laminated film of insulating glass so as to protect the precious metal film layer. Furthermore, when the Al-Zn film is used in combination with another metal film, the Zn film is preferable because it easily takes in oxygen, but if another metal film is used,
Ti, Zr, Cr, Al, SUS, Ta, NiCr, etc. can be used together depending on the case.

Further, these transparent oxide film, noble metal film, Al
The heat insulating film made of -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 deposition method (CVD method), or a sol-gel method. Among these, the sputtering method and the ion plating method are preferable from the viewpoints 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 above heat insulating film can be appropriately selected and formed according to the purpose. Needless to say.

Further, as the heat insulating glass which is preferably used, glass substrate / transparent oxide film layer / 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, or glass substrate / transparent oxide film Layer / Al-Zn
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 / Transparent oxide film layer, also glass substrate / 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 // transparent oxide film layer.

Further, 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, also 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, 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, 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.

Furthermore, there is an AlZnO 2 film having improved adhesion between the Al—Zn film layer and the transparent oxide film layer as a gradient film. For example, 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, In addition, glass substrate / transparent oxide film layer / noble metal film layer / Al-Zn film layer / AlZnO film layer /
Examples include 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 construction, but in some cases, it can be used as a double glazing for an automobile. In addition, it can be used as a multi-layered window glass for ships and aircrafts. It goes without saying that it is possible to use laminated glass, bent glass, and the like, in addition to the double-layer glass, as the case may be, even a single plate.

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 present so as to protect the noble metal film layer. As a result, the Al-Zn film layer, which functions as a so-called sacrificial metal that reacts with oxygen in preference to the noble metal film layer, and which has a similar role in the electric protection method, has a more excellent barrier property, and thus Ag aggregation and peeling may occur. Useful insulation that greatly improves the moisture resistance of the laminated film, which is a heat insulating film, and makes it possible to exhibit outstanding durability, such as the appearance of defects such as white spots, cloudy binholes, and cracks. Glass can be provided with good productivity without lowering the film formation rate. Furthermore, no special device is required for handling and storage on a single plate, and it is easy to handle and can be stored for a longer time.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.

Example 1 A 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, etc. and dried to obtain a glass substrate.

Next, the Zn target, the Zn (96 to 95) -Al (4 to 5) alloy target, and the Ag target, which are set in the vacuum chamber of the DC magnetron sputtering device, are opposed to each other. Then, the glass substrate was set so that it could be reciprocated above.

Next, the inside of the tank is vacuum pumped to about 5 × 10 ^-6.
After degassing up 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, and Apply about 1.0kW of power to the get,
By transporting the glass substrate in the DC magnetron reactive sputtering with the mixed gas above the Zn target at a speed of about 415 mm / min, a Zn film having a thickness of about 35 nm is formed.
An O 2 thin film was formed as the first layer. After the film formation was completed, the application to the Zn target was stopped.

Next, with the glass substrate kept in the vacuum chamber, the chamber was evacuated by a vacuum pump to about 5 × 10 ^-6 Torr, and then Ar gas was introduced into the vacuum chamber to obtain a vacuum. The degree is maintained at about 2 × 10 ^-3 Torr, and the Ag target is set at about 0.16.
Approximately 10 nm thick on the ZnO thin film by transporting the glass substrate at a speed of about 1259 mm / min above the Ag target in the DC magnetron reactive sputtering with Ar gas at a power of kW applied. Was deposited as a second layer. After the film formation was completed, the application to the Ag target was stopped.

Then, similarly, Ar gas was introduced into the vacuum chamber to maintain the vacuum degree at about 2 × 10 ^-3 Torr, and the Zn (96)
-Applying about 0.14 kW of power to the Al (4) alloy target,
In the DC magnetron reactive sputtering with 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 film formation was completed, 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) was introduced into the vacuum chamber to maintain the degree of vacuum at about 2 × 10 ^-3 Torr. Then, about 1 to the Zn target.
By applying a power of 0 kW and carrying the glass substrate in the DC magnetron reactive sputtering by the mixed gas above the Zn target at a speed of about 415 mm / min, the thin film on the Zn-Al alloy thin film can be transferred. A 35 nm thick ZnO thin film was deposited as the fourth layer. After the film formation was completed, the application to the Zn target was stopped.

Regarding the obtained glass substrate with a laminated film,
The following evaluations were made. [Moisture resistance test] Number of spots with a size of 0.2 mm φ or more generated within a 100 mm × 100 mm area of the above substrate, stored in an atmosphere of a constant temperature and humidity chamber at 30 ° C and 90% relative humidity for one month. Evaluated by In addition, the defect at that time was confirmed by irradiating the film surface with a light source of a fluorescent white plate and visually observing from the difference in reflectance. [Optical characteristics] Device: 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: 380-780nm) and solar radiation transmittance (Ts: 340-1800nm) and solar reflectance (Rs: 340-1800nm)
Also, the UV transmittance (Tuv: 300 to 380 nm) etc. was measured, and the transmittance and reflectance data and JI for each specified wavelength were measured.
Determined by SZ 8722 and JISR 3106, respectively.

As a result, the glass substrate provided with the laminated film thus obtained had a size of about 0.2 mm within a 100 mm × 100 mm area in the moisture resistance test.
Only one spotted opaque defect with a diameter of mm φ or more was generated, and there was almost no opaque spotted defect with a size of about 0.2 mmφ or less, and there was no cracking. It had moisture resistance.

The laminated film-coated glass substrate had a visible light transmittance Tv of about 76.7%, a visible light reflectance Rv (glass surface side) of about 14.1%, a solar radiation transmittance Ts of about 64.5%, and an ultraviolet transmittance. Tuv
Of about 18.7% and emissivity of about 0.09, having low-E performance and sufficiently excellent moisture resistance, it was the desired insulating glass.

Further, in the case of a double glazing composed of the heat insulating glass having a space of about 6 mm and ordinary float glass (3 mm), the visible light transmittance Tv is 69.2% and the visible light reflectance Tv is
Is 15.8%, solar radiation transmittance Ts is about 51.6%, UV transmittance Tuv
Was about 16.3%.

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

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, the moisture resistance test was the same as that of Example 1, and the moisture resistance was greatly improved. The laminated film-coated glass substrate has a visible light transmittance Tv of 77.7%, a visible light reflectance Rv (glass surface side) of about 13.8%, a solar radiation transmittance Ts of 65.2%, and an ultraviolet transmittance Tuv of about 19.2%. , Emissivity is 0.09, and has Low-E performance,
It also had sufficiently excellent moisture resistance and was the desired heat insulating glass.

Example 3 Similar to Example 1, the first layer, the second layer and the third layer are the same as the first layer, the second layer and the third layer of Example 2. ZnO thin film with a thickness of about 35 nm, Ag thin film with a thickness of about 10 nm, and Zn-Al alloy thin film with a thickness of about 2 nm. The fourth layer was the fourth layer of Example 2 and the transfer speed was about 166 mm / min. Altered film thickness is about 70nm ZnO thin film, 5th layer is the same thickness as the 2nd layer about 10nm Ag thin film, 6th layer is the same thickness as the 3rd layer About 2nm
A glass substrate with a laminated film was obtained by sequentially forming a Zn-Al alloy thin film having a thickness of nm and a ZnO thin film having a thickness of about 35 nm, which is the same as the first layer, for the seventh layer.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, only about two spots of opaque spots having a size of about 0.2 mmφ were generated within an area of about 100 mm × 100 mm, and the other Example 1 was used.
And had sufficiently improved moisture resistance. In addition, the glass substrate with the laminated film has a visible light transmittance.
Tv is 75.2%, visible light reflectance Rv (glass surface side) is about 6.0
%, Solar radiation transmittance Ts is 41.2%, UV transmittance Tuv is about 9.7
%, Emissivity is 0.05, and has excellent Low-E performance,
It also had sufficiently excellent moisture resistance and was the desired heat insulating glass.

Further, in the case of the double-layer glass as in Example 1, the visible light transmittance Tv is 67.7% and the visible light reflectance Tv is
Is 11.3%, solar radiation transmittance Ts is about 35.4%, UV transmittance Tuv
Was about 8.3%.

Example 4 In the same manner as in Example 1, the first layer was a ZnO thin film having the same thickness as the first layer in Example 1 and having a film thickness of about 35 nm, and the second layer was the second layer in Example 1. Only the eyes and applied power are changed to about 0.21kW
About the thin film and the third layer, only the third layer of Example 1 and the applied power are about
Al-Zn alloy thin film with a thickness of about 7 nm changed to 0.49 kW, a laminated film in which the fourth layer is a first layer and a ZnO thin film with a thickness of about 40 nm is sequentially changed to about 363 mm / min. The attached glass substrate was obtained.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, the moisture resistance test was equivalent to or higher than that of Example 1, and the moisture resistance was remarkably improved. The laminated film-coated glass substrate had a visible light transmittance Tv of 71.2%, a visible light reflectance Rv (glass surface side) of about 19.6%, a solar radiation transmittance Ts of 59.3%, and an ultraviolet transmittance Tuv of about 13.5%. The emissivity was 0.08, it had Low-E performance, and it showed outstanding moisture resistance, and it was the desired insulating glass.

Example 5 In the same manner as in Example 1, the target of the first layer of Example 1 was changed from Zn to Sn and the carrying speed was about 305 mm.
/ Min and the thickness of about 35 nm SnO 2 thin film, the second layer of Example 4
Of the same thickness as the second layer of about 13 nm, the third layer of Example 1 and the applied power is changed to about 0.28 kW, the Al-Zn alloy thin film of about 4 nm, A glass substrate with a laminated film was obtained in which the fourth layer was changed to the first layer and only the above-mentioned transport speed was changed to about 267 mm / min, and a SnO 2 thin film having a thickness of about 40 nm was sequentially formed.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the moisture resistance test, about 2 mm white spot-like defects having a size of about 0.2 mm φ were generated within an area of about 100 mm × 100 mm, and the other example 1 was used.
The moisture resistance was greatly improved.
Further, the glass substrate with the laminated film has a visible light transmittance Tv of 7
4.3%, visible light reflectance Rv (glass surface side) about 15.9%, solar radiation transmittance Ts 62.2%, ultraviolet ray transmittance Tuv about 37.6%, emissivity 0.07, low-E heat rays It was a shielding glass and showed sufficiently excellent moisture resistance, and was a desired heat ray shielding glass. The UV shielding property was not improved due to the SnO 2 thin film.

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

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, the moisture resistance test was similar to that of Example 1, and the moisture resistance was greatly improved. The laminated film-coated glass substrate had a visible light transmittance Tv of 75.4%, a visible light transmittance Tv of 15.2%, and a solar radiation transmittance.
Ts 63.7%, UV transmittance Tuv about 17.6%, emissivity 0.
It was 09, had low-E performance, showed sufficiently excellent moisture resistance, and was a useful heat-insulating glass for the intended purpose.

Example 7 In the same manner as in Example 1, the first layer was a ZnO thin film having the same film thickness as the first layer in Example 4 and having a film thickness of about 35 nm, and the second layer was the same film as in Example 4. The Ag thin film having a thickness of about 13 nm and the third layer are the third of the first embodiment.
Al-Zn with a film thickness of about 5 nm, 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 fourth layer of Example 4, and the ZnO thin film having a film thickness of about 70 nm was changed. The fifth layer had the same film thickness as the second layer. 13 nm Ag thin film,
The sixth layer is an Al-Zn alloy thin film with the same thickness as the third layer, about 5 nm, and the seventh layer is Zn with the same thickness as the first layer, about 35 nm.
A glass substrate with a laminated film was sequentially formed with an O 2 thin film.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, only one spot-like cloudy defect having a size of about 0.2 mmφ or more occurred within an area of about 100 mm × 100 mm, and the moisture resistance was remarkably excellent. Further, the glass substrate with the laminated thin film has a visible light transmittance Tv of 71.5%, a visible light transmittance Tv of 9.4%, a solar radiation transmittance Ts of 36.9%, and an ultraviolet transmittance Tu.
It had a v of about 8.3% and an emissivity of 0.04, had low-E performance, and showed outstanding moisture resistance, and was a useful insulating glass for the intended purpose.

Example 8 In the same manner as in Example 1, the first layer was a ZnO thin film having the same film thickness as the first layer in Example 4 and having a thickness of about 35 nm, and the second layer was the second layer in Example 1. An Ag thin film having a film thickness of about 10 nm, which is the same as the third layer, and a third layer, an Al-Zn alloy thin film having a film thickness of about 2 nm, which is the same as that of the third layer of Example 1,
The fourth layer is the third layer of the first embodiment, the ratio of the mixed gas is Ar gas (30) and O ₂ gas (70), the applied power is about 0.56 kW, and the transfer speed is about 1259 mm / min. Thickness of about 5 nm as a component layer
AlZnO thin film, the fifth layer is the same as the fourth layer of Example 7 and the ZnO thin film has a thickness of about 70 nm, and the sixth layer is the second layer and the fourth example.
The Ag thin film having a film thickness of approximately 12 nm, which is almost the same as the above, the seventh layer is an Al-Zn alloy thin film having a film thickness of approximately 2 nm which is the same as the third layer, and the eighth layer is a fourth film.
AlZnO thin film with the same thickness as the 5th layer, and glass with laminated film formed by sequentially depositing the 8th layer as the 1st layer and ZnO thin film with the thickness of about 30nm by changing only the transport speed to about 484mm / min. A substrate was obtained.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, there were only about two spot-like defects that were opaque and had a size of about 0.2 mm φ or more within an area of about 100 mm × 100 mm, and the moisture resistance was greatly improved. .

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

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

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, about 57 spots of cloudy spots having a size of about 0.2 mmφ or more were generated within an area of about 100 mm × 100 mm, and it could not be said that it has moisture resistance. Further, the glass substrate with the laminated film has a visible light transmittance Tv of 76.3% and a visible light transmittance Tv.
Is 14.7%, solar radiation transmittance Ts is 64.1%, UV transmittance Tuv is about 17.8%, and emissivity is 0.09.It is a heat ray shielding glass with Low-E performance, but it has poor moisture resistance and It was not the desired insulating glass.

In the case of using a double-layer glass as in Example 1, the visible light transmittance Tv is 68.9% and the visible light reflectance Tv is
16.2%, solar radiation 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 was changed to the first layer of Comparative Example 1 and the target was changed from Zn to the Al-Zn alloy, and the transfer speed was changed to about 265 mm / min. AlZnO thin film with a thickness of about 35 nm, the second and third layers are the same as the second and third layers of Comparative Example 1 Ag thin film with a thickness of about 10 nm and Zn metal thin film with a thickness of about 2 nm A glass substrate with a laminated film was obtained by sequentially forming the fourth layer and an AlZnO 3 thin film having the same thickness as the first layer and having a film thickness of about 35 nm.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, about 47 spots of cloudy spots having a size of about 0.2 mmφ or more were generated within an area of about 100 mm × 100 mm, and it was difficult to say that the sample had moisture resistance. Further, the glass substrate with the laminated film has a visible light transmittance Tv of 76.7% and a visible light transmittance Tv.
Is 14.1%, solar radiation transmittance Ts is 65.2%, UV transmittance Tuv is about 42.3%, and emissivity is 0.09.It is a heat ray shielding glass with low-E performance, but it is effective with Zn metal thin film and AlZnO thin film. However, it was not the desired heat insulating glass because of its low moisture resistance and poor ultraviolet resistance.

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

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, about 50 spots of cloudy spots having a size of about 0.2 mmφ or more occurred within an area of about 100 mm × 100 mm, and it cannot be said that the material has moisture resistance. Further, the glass substrate with the laminated film has a visible light transmittance Tv of 70.4% and a visible light transmittance Tv.
Is 17.1%, the solar radiation transmittance Ts is 59.1%, the UV transmittance Tuv is about 14.6%, and the emissivity is 0.07.It is a heat ray-shielding glass with Low-E performance, but it has poor moisture resistance. It was not the desired insulating glass.

Comparative Example 4 In the same manner as in Example 1, the ratio of the mixed gas of the first layer to that of the first layer of Comparative Example 2 was Ar gas (30) and O ₂ gas (70), and the transfer speed was the same. AlZnO thin film with a thickness of about 35 nm, changing 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 in that the Ag thin film has a thickness of about 13 nm, the Zn metal thin film has a thickness of about 7 nm, and the fourth layer is the first layer. AlZn with the same film thickness as the first layer, about 35 nm
A glass substrate with a laminated film was sequentially formed with an O 2 thin film.

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, about 50 spots of cloudy spots having a size of about 0.2 mmφ or more occurred within an area of about 100 mm × 100 mm, and it cannot be said that the material has moisture resistance. Further, the glass substrate with the laminated film has a visible light transmittance Tv of 70.9% and a visible light transmittance Tv.
Is 16.6%, solar radiation transmittance Ts is 59.9%, UV transmittance Tuv is about 40.1%, and emissivity is 0.07. It is a heat-insulating glass with low-E performance, but Zn metal thin film and AlZnO thin film are effective. However, it was not the desired heat insulating glass because of its low moisture resistance and poor ultraviolet resistance.

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

The glass substrate with a laminated film thus obtained was evaluated in the same manner as in Example 1. As a result, in the humidity resistance test, about 32 spot-like, cloudy, spot-like defects having a size of about 0.2 mmφ or more occurred within an area of about 100 mm × 100 mm, and it was hard to say that the sample had moisture resistance. Further, the glass substrate with the 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%, UV transmittance Tuv is about 20.3%, and emissivity is 0.09. It is a heat-insulating glass with Low-E performance, but the Al-Zn alloy thin film is too thin. Inferior in moisture resistance, it was not the desired 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, whereby the moisture resistance is remarkably improved and the durability is further improved. Window glass for construction, which can be easily and easily handled, stored, and packaged.
In particular, it is possible to economically provide a heat insulating glass that is useful as a double glazing with higher productivity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G02B 1/10 G02B 1/10 Z (56) References JP-A-5-221692 (JP, A) JP-A-9-314745 ( JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C03C 15/00-23/00 B32B 1/00-35/00 B60J 1/00 C23C 14/00-14/58

Claims (4)

(57) [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 combined and sequentially laminated on a surface of a glass substrate, and the noble metal layer is mainly composed of Ag or Ag.
Of the precious metal film, and the precious metal film layer is at least Al.
It is allowed to be present the Al-Zn film layer to protect at -Zn film layer, the Al
-In the Zn film layer, Al is added to Zn in an amount of 3 wt% or more and 10 wt% or less.
Insulated glass characterized by being 2. The heat insulating glass according to claim 1, wherein the film thickness of the Al—Zn film layer when formed is 2 nm or more and 10 nm or less . 3. A process according to claim 1 or 2 Neu, characterized in that to protect the noble metal film layer with Al-Zn film and the other metal film
Insulated glass described in the slip . 4. The heat insulating glass according to claim 3, wherein the other metal film is a Zn film.