JPH11157881A - Low radiation glass-laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated body excellent in chemical durability by interposing one or more silver layers on a glass substrate and making a zinc oxide layer form to be filmed just under the silver layers and a zinc or zinc-base protective metallic layer form to be filmed just on the layer of the silver layers. SOLUTION: A tin oxide layer and/or a titanium dioxide layer of 5-27 nm thickness is formed as a 1st layer on a glass substrate and then, a zinc oxide layer of 3-25 nm thickness is formed as a 2nd layer on the 1st layer in 15-30 nm total thickness of the 1st and 2nd layers. A silver or silver-base layer of 9-25 nm thickness is formed as a 3rd layer on the 2nd layer, then, a zinc or zinc-base protective metallic layer of 1-8 nm thickness contg. 2-10 atom.% aluminum is formed as a 4th layer on the 3rd layer and a tin oxide layer and/or a titanium dioxide layer of 35-55 nm thickness is further formed as a 5th layer on the 4th layer to obtain an objective laminated body preferably having <=37% solar UV transmissivity, 70-90% visible light transmissivity and 40-70% solar radiation transmissivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low radiation glass laminate useful as a window glass for vehicles such as houses and offices as well as for vehicles, and also as various glass articles such as window glasses for ships and aircraft. .

[0002]

2. Description of the Related Art Recently, for example, in offices and houses, low-radiation glass having excellent heat insulation, heat retention and heat shielding properties is used mainly in cold regions. This glass is a multi-layered glass composed of two pieces of glass with dry air sealed in between the glass and a so-called low-radiation film that transmits visible light but reflects infrared light on the side of the intermediate air layer. It is. The main component of these coatings is that Ag is used as the metal layer, and the upper and lower layers of the Ag layer are formed of Zn.
It is coated with O or nonmetal layer of SnO ₂ or the like are generally known.

For example, Japanese Patent No. 2598476 discloses a method in which a Ni alloy is interposed at the interface between the two oxide layers sandwiching the Ag layer. In this method, a visible light transmittance of 70% or more is obtained. There is a problem in obtaining a low-emission glass that has Japanese Patent Publication No. 6-62319 discloses a method in which an oxide film of both components is used for a low radiation glass laminate by reactive sputtering using an alloy composed of zinc and tin as a target. It is necessary to manufacture the alloy and then process it into a target, which inevitably increases the cost. Also, the obtained coating film has the disadvantages of adhesion to the Ag layer, which is a disadvantage of tin oxide, and chemical, which is a disadvantage of zinc oxide. There is a problem with durability. Further, JP-A-2-23913
No. 5 and JP-A-2-289449, a zinc oxide layer having a thickness of 15 nm or less is provided below or above an Ag layer,
A coated glass material in which an oxide layer such as tin oxide, aluminum oxide, or titanium oxide is provided as a lower or upper layer is described. In addition, metals in contact with an Ag layer include titanium, aluminum, stainless steel, bismuth, tin, and the like. Is used, but there is a problem in adhesion between zinc oxide and these metals.
Also, JP-A-4-357,025 and JP-A-5-426.
No. 24 describes that an oxide layer composed of a zinc oxide layer and a tin oxide layer is disposed outside the Ag layer farthest from the glass. The stress of the coating is relaxed by sandwiching tin oxide between 20 nm or less, and a low-emission glass laminate resistant to corrosion is obtained. For example, when tin oxide is disposed immediately above the protective metal layer, it is not necessarily It is presumed that a sufficiently durable coating cannot be obtained, and when zinc oxide is placed on the top layer,
It is considered that the durability of the weak acid and weak alkali is insufficient. Further, Japanese Patent Application Laid-Open No. 8-10447 describes that tin oxide and / or zinc oxide is used for the oxide layer, but the properties of zinc oxide and tin oxide are not described. No order or film thickness is mentioned.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has a zinc oxide layer immediately below a silver layer and zinc or zinc as a main component immediately above the silver layer. By forming a protective metal layer, a tin oxide layer and / or a titanium oxide layer on the glass directly above and on the top layer of the coating, the emissivity is small and the visible light transmittance is 70% or more;
It has been found that low radiation glass having excellent chemical durability can be obtained by improving the adhesion between the layers.

[0005] The present invention also provides a laminate comprising a glass substrate and at least one silver layer interposed therebetween and a multilayer film formed thereon, wherein a zinc oxide layer is formed immediately below the silver layer and a zinc oxide layer is formed immediately above the silver layer. The present invention relates to a low-emissivity glass laminate formed by depositing zinc or a protective metal layer containing zinc as a main component.

The lowermost layer of the laminate and / or the uppermost layer of the laminate are preferably formed by forming a tin oxide layer and / or a titanium oxide layer. The present invention also provides a first layer comprising a tin oxide layer and / or a titanium oxide layer on a glass substrate,
A second layer made of a zinc oxide layer, a third layer made of a silver layer, a fourth layer made of zinc or a protective metal layer containing zinc as a main component,
The present invention relates to a low-emissivity glass laminate in which a fifth layer having a tin oxide layer and / or a titanium oxide layer as an uppermost layer is laminated thereon.

It is preferable that the fifth layer be a layer in which a zinc oxide layer, a tin oxide layer and / or a titanium oxide layer are laminated. Further, regarding the thickness of each layer, the first layer has a thickness of 5 to 27 nm, the second layer has a thickness of 3 to 25 nm, and the total thickness of the first layer and the second layer is 15 to 30 nm. The third layer has a thickness of 9 to 25 nm, the fourth layer has a thickness of 1 to 8 nm, the fifth layer has a thickness of 35 to 55 nm, and one of the zinc oxide layers in the fifth layer has a thickness of 25 nm. The following is preferred.

[0008] The five-layer laminate has a solar ultraviolet transmittance of 37% or less and a visible light transmittance of 70 to 90%.
%, And the solar radiation transmittance is preferably 40 to 70%. Further, according to the present invention, on a glass substrate, a first layer composed of a tin oxide layer and / or a titanium oxide layer, a second layer composed of a zinc oxide layer, a third layer composed of a silver layer, and zinc or zinc as a main component. A fourth layer made of a protective metal layer, a fifth layer having a zinc oxide layer on the fourth layer, a sixth layer made of a silver layer, and a seventh layer made of a protective metal layer containing zinc or zinc as a main component.
The present invention relates to a low-emissivity glass laminate in which an eighth layer having a tin oxide layer and / or a titanium oxide layer as the uppermost layer is laminated thereon.

The fifth layer and the eighth layer are preferably composed of a layer in which a zinc oxide layer, a tin oxide layer and / or a titanium oxide layer are laminated. The first layer has a thickness of 5 to 37 nm, the second layer has a thickness of 3 to 35 nm, and the total thickness of the first and second layers is 25 to 40 nm. Film thickness of 9
The thickness of the fourth layer is 1 to 8 nm, the thickness of the fifth layer is 55 to 80 nm, the thickness of the uppermost layer of zinc oxide is 1 nm or more, and the thickness of the sixth layer is 9 ~ 13 nm,
The thickness of the seventh layer is 1 to 8 nm, and the thickness of the eighth layer is 25 to 45.
and the thickness of one of the zinc oxide layers in the eighth layer is preferably 25 nm or less.

[0010] The eight-layer laminate has a solar ultraviolet ray transmittance of 25% or less and a visible ray transmittance of 70 to 8%.
It is preferable that the solar radiation transmittance is 5% and the solar radiation transmittance is 40 to 50%.

Further, the zinc metal used for the protective metal layer is preferably an alloy containing zinc as a main component and containing 2 to 10 atomic% of aluminum.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The low radiation glass laminate of the present invention comprises:
Obtained as follows. As the glass substrate, there are ordinary plate glass and so-called float plate glass which are usually used for automotive and architectural glass, etc., and various colored glass such as clear, green, bronze, various functional glass, tempered glass and so on. Needless to say, it can be used as similar glass, laminated glass, double-glazed glass, and various flat glass products such as flat and bent plates. Further, the glass may be a laminate with a transparent plastic plate or the like. The composition of the glass is soda-lime glass, aluminosilicate glass or the like, but it goes without saying that the glass is not limited to these.

An amorphous film composed of a tin oxide layer and / or a titanium oxide layer is chemically and mechanically strong, and has a strong adhesion to glass due to its amorphous structure, and has an internal stress. Is also less likely to occur. Therefore, the first layer coating directly over the glass is preferably a tin oxide layer and / or a titanium oxide layer. The thickness of the tin oxide layer and / or titanium oxide layer of the first layer for increasing the adhesion to glass and cutting off the influence of alkali ions must be at least 5 nm. However, the tin oxide layer and / or the titanium oxide layer have poor adhesion to metals, particularly Ag, and are likely to peel off at the tin oxide layer, the titanium oxide layer / silver layer interface. In addition, as can be seen from the ionization tendency, tin oxide has a weak bond with oxygen and has a high chemical potential of oxygen in the film, so that oxygen easily diffuses into the Ag layer. For this reason, the electrical resistance of the Ag layer increases and it is difficult to achieve a low emissivity. From the above, it is preferable that the layer composed of the tin oxide layer and / or the titanium oxide layer is not brought into contact with the silver layer. Note that the tin oxide layer and / or the titanium oxide layer may contain an element as an amorphous coating component that improves chemical and mechanical properties and enhances adhesion to glass.

Zinc oxide has a high adhesion to the Ag layer and has a low oxygen potential in the layer due to a high bonding force with oxygen, so that oxygen hardly diffuses into the silver layer and a low emissivity is easily achieved. . Therefore, a layer immediately below the Ag layer is preferably a zinc oxide layer. Prevents diffusion of oxygen from the underlying tin oxide layer,
The thickness of the zinc oxide layer of the second layer for obtaining a strong adhesion to the g layer must be at least 3 nm. Note that the zinc oxide layer may contain a known element as a component of a film that does not decrease the adhesion to the silver layer and makes it difficult for oxygen to diffuse into the silver layer.

It is important to keep the chemical potential of oxygen in the oxide layer in contact with the Ag layer as low as possible, and it is desirable to add as much argon as possible together with oxygen to the atmosphere during the deposition of zinc oxide. The desirable argon addition rate varies depending on the equipment, but is generally about 10 to 30%.
This value is determined by gradually adding argon from an oxygen atmosphere, observing a sudden increase in the voltage applied to the target or a sudden decrease in the current, and then slightly reducing the argon.

The total film thickness of the first tin oxide layer and / or the titanium oxide layer and the second zinc oxide layer formed between the glass and the silver layer has a high visible light transmittance, especially 70% or more. In order to secure the visible light transmittance and keep the reflection color tone as neutral as possible, it is necessary to use glass / tin oxide layer and / or titanium oxide layer / zinc oxide layer / silver layer / protective metal layer / fifth layer. In the case of the configuration described above, the thickness is preferably 15 to 30 nm. In the case of glass / tin oxide layer and / or titanium oxide layer / zinc oxide layer / silver layer / protective metal layer / fifth layer / silver layer / protective metal layer / eighth layer, the thickness is preferably 25 to 45 nm. Above or below this range, the reflectance will be high and the transmittance will be low.

The thickness of the third silver layer affects the emissivity, the visible light transmittance and the reflection color tone, and at least 9 nm is required for low-emission glass having an emissivity of about 0.1 or less. Further, in order to ensure a high visible light transmittance, particularly 70% or more, and to avoid red reflected light, the thickness is preferably 25 nm or less. The silver layer may contain silver as a main component, and silver may contain a known element such as gold, copper, platinum, or iridium as a component of a normal coating.

The fourth protective metal layer formed immediately above the third silver layer is preferably zinc or an alloy layer containing zinc as a main component, which has high adhesion to both the silver layer and the oxide layer. . The protective metal layer referred to here is a metal layer having the entire thickness immediately after the fourth protective metal layer is formed immediately above the silver layer. When forming the eight oxide layers, since a film is formed in an oxidizing atmosphere (for example, oxygen 80%, argon 20%), part of the upper layer of the metal layer is converted to oxide. The upper metal layer is referred to as a protective metal layer including the oxidized oxide layer and the remaining metal layer. The function of the protective metal layer is to interpose the protective metal layer so that the oxidizing atmosphere does not affect the lower silver layer when the fifth or eighth oxide layer is formed. To protect the silver layer from being oxidized. As a protective metal layer, a zinc alloy containing 2 to 10 atomic% of aluminum is particularly preferable because it has a high bonding force with oxygen and most effectively traps oxygen and other corrosive ions diffused into the silver layer. . It goes without saying that the thicker the protective metal layer, the longer the strong effect lasts, but if too thick, the visible light transmittance is reduced. However, when the oxide is formed next, a part of the protective metal layer is oxidized. Therefore, if the thickness of the first metal layer before the oxidation is 8 nm or less, a high transmittance can be obtained.

When the silver layer is a single layered product, diffusion of oxygen from the uppermost tin oxide layer and / or titanium oxide layer is prevented,
In order to increase the adhesion with the tin oxide layer and / or the titanium oxide layer, a total of 0.5
It is preferable that the thickness be at least nm. The zinc oxide layer may be formed of zinc in the protective metal layer or may be a zinc oxide containing a metal element other than zinc. If the oxidation of the protective metal is insufficient, the zinc oxide layer in the fifth layer may be used. A zinc oxide layer may be provided as the lowermost layer. The upper limit of the thickness of the zinc oxide layer in the fifth layer is determined by an appropriate range of the thickness of the fifth layer for maintaining high transmittance and neutrality of the reflected color. However, as the thickness of the zinc oxide layer increases, the internal stress tends to increase.
It is preferable to provide a tin oxide layer and / or a titanium oxide layer thereon with a thickness of nm or less.

Here, the oxidized protective metal, especially oxidized zinc alloy, especially oxidized aluminum
One of the differences between a zinc alloy containing 10 atomic% (ZnAlO _x ) and zinc oxide (ZnO _x ) is that the latter strongly absorbs ultraviolet rays contained in sunlight, whereas the former weakly absorbs ultraviolet rays. . This is because the band gap of zinc oxide is widened by the addition of the impurity, and the absorption region shifts to the short wavelength side. Another difference is that the former film forming rate is reduced to about 70% compared to the latter. This is due to the former, especially aluminum being 2 to 10 atomic%.
The melting point of the containing zinc alloy is about 20 ° C compared to 420 ° C of zinc.
This is because the power required for film formation cannot be sufficiently supplied to the target because of its low power. Therefore, the zinc oxide layer contains at most 2 atomic% of the impurity metal element except for the portion caused by oxidation of the protective metal.
A pure zinc oxide layer containing no above is preferred.

The zinc oxide layer is dense and has an effect of preventing the diffusion of corrosive gas in the atmosphere, and has a function of absorbing ultraviolet rays contained in sunlight but has low chemical durability. Is preferably provided with a tin oxide layer and / or a titanium oxide layer which are amorphous oxides. The thickness of the tin oxide and / or titanium oxide layer is preferably 1 nm or more.

In order to keep the high visible light transmittance and the reflection color tone as neutral as possible, it is appropriate that the total thickness of the fifth layer in the case of a single silver layer is 35 to 55 nm. If the film thickness is too thin or too thick, the reflectance is high, and thus the transmittance is low. Therefore, in the case of the configuration of glass / tin oxide layer and / or titanium oxide layer / zinc oxide layer / silver layer / protective metal layer / fifth layer, oxidation of the oxide layer in the protective metal layer and the lowermost layer in the fifth layer The total thickness of the zinc layer and the zinc layer is 0.5 to 25 nm, and the tin oxide layer and / or the titanium oxide layer 10
４０40 nm, zinc oxide layer 5-25 nm, tin oxide layer and / or
Alternatively, it is more preferable to form a titanium oxide layer having a thickness of 1 to 39.5 nm.

Glass / tin oxide layer having two silver layers and / or
Alternatively, the fifth layer in the structure of titanium oxide layer / zinc oxide layer / silver layer / protective metal layer / fifth layer / silver layer / protective metal layer / eighth layer is the sixth layer which is an upper layer of the fifth layer. Since the layer is a silver layer, the layer immediately below the silver layer is preferably a zinc oxide layer as described above. However, since the potential of oxygen in the tin oxide layer and / or the titanium oxide layer is suppressed low by the presence of the protective metal layer under the fifth layer, the thickness of the zinc oxide layer is 1 nm or more. Good. In this case, since the diffusion of corrosive gas from the atmosphere is not a problem, the zinc oxide layer is not indispensable except for the contact portion with the protective metal layer and the silver layer, but it absorbs ultraviolet rays contained in sunlight. A zinc oxide layer may be provided for the purpose. If such a zinc oxide layer is provided, a tin oxide layer of 5 nm or more above and below the zinc oxide layer and / or
Alternatively, if the film is sandwiched between titanium oxide layers, the thickness is not affected by internal stress up to 40 nm. When the thickness is 40 nm or more, phenomena such as peeling easily occur in the fifth layer, which causes destruction of a layer thereabove, and pinhole defects easily occur.

The thickness of the fifth layer in the case of two silver layers is as follows:
The range of 55 to 80 nm is preferable in terms of preferable optical characteristics, and the fifth layer has a total thickness of the oxide layer in the protective metal and the zinc oxide layer in the fifth layer of 0.5 to 25 nm, and a tin oxide layer. And / or a titanium oxide layer of 15 to 78.5 nm, and further thereon a zinc oxide layer of 1 to 25 nm or a film thickness of an oxide layer in the protective metal layer and a zinc oxide layer in the fifth layer 0.5 to 25 nm, tin oxide layer and / or titanium oxide layer 5 nm or more, zinc oxide layer to 40 nm or less, tin oxide layer and / or titanium oxide layer 5 nm or more, zinc oxide layer 1 to
It is preferable to sequentially form a film with a thickness of 25 nm.

The concept of the sixth and seventh layers is the same as that of the third and fourth layers. The eighth layer is considered to be the same as the fourth to fifth layers in the case of the configuration of glass / tin oxide layer and / or titanium oxide layer / zinc oxide layer / silver layer / protective metal layer / fifth layer, and has a high visible light transmittance. In order to keep the reflection color tone as neutral as possible, it is appropriate that the total thickness of the eighth layer is in the range of 25 to 45 nm. Is reduced, the configuration of the seventh to eighth layers is such that the total thickness of the zinc oxide layer from the protective metal layer and the zinc oxide layer from the fifth layer is 0.5 to 25 nm, and Sequentially a tin oxide layer and / or a titanium oxide layer 10 to 40 nm, a zinc oxide layer 5
~ 25 nm, tin oxide layer and / or titanium oxide layer 1-2
It is preferable to form a film having a thickness of 9.5 nm.

[0026]

The present invention will be described below in detail with reference to examples. The film was formed by DC magnetron sputtering. However, the present invention is not limited to such an embodiment.

Example 1 A coating was formed on a float glass having a size of 1800 mm × 24000 mm × about 3 mm in the following order. The sputtering apparatus has Sn, Zn (three), Ag,
After attaching each metal target of ZnAl (Al content 4 atomic%), the inside of the vacuum chamber was sufficiently evacuated until the pressure before film formation reached 5 × 10 ⁻⁵ Torr. In this method, a transfer roll is installed below a target in a vacuum chamber, and when a glass plate reciprocates on the roll, a predetermined metal layer or metal oxide layer is applied to the glass plate from the target to which power is applied. A film is formed.

First, as the first pass, the atmosphere in the film forming chamber is kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and a SnO _x layer as a first layer is formed to a thickness of 10 nm by a Sn target. A ZnO _x layer as a second layer was formed to a thickness of 12 nm by using a Zn target under the same conditions as the first layer. Next, in a second pass, the atmosphere is maintained in a reducing atmosphere of Ar 100%, and an Ag layer serving as a third layer is formed to a thickness of 10 nm by using an Ag target.
A 4 nm thick ZnAl alloy layer (a so-called protective metal layer) was formed to a thickness of 2 nm using an Al target. At the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the fifth ZnAlO _x layer is 2 nm, the SnO _x layer is 10 nm, and the ZnO _x layer is 11 nm in order. A ZnO _x layer is formed as a fourth pass in the same atmosphere as in the third pass.
After forming a 1 nm and 10 nm SnO _x layer, the glass was discharged from the film forming chamber. When the ZnAlO _x layer was formed in an oxidizing atmosphere on the fourth ZnAl alloy layer (protective metal layer), some ZnAl alloy layers were oxidized.

The film thickness D of each film is adjusted by the transfer speed and the cathode power, and the value is adjusted by partially etching the film previously formed at a power E ₀ and the transfer speed V ₀ to a thickness of about 100 nm. The thickness D ₀ was determined by measuring the step with a stylus-type surface roughness meter, and D = D ₀ × E / E ₀ × V ₀ / V, where cathode power E and transfer speed were V in the examples. Was determined according to the following equation. The numbers in the column of the film composition in Table 1 indicate the film thickness (nm) of each film. The film thickness of the protective metal layer in the column of the film composition indicates the total thickness of the metal layer immediately after the formation of the metal layer. →) The fifth layer of Examples 1, 2, 3, and 6 in the film configuration of Table 1 is indicated by (), and the fifth and eighth layers of Examples 4 and 5 are indicated by (). The first and fifth layers of Example 7 are also shown in parentheses.

The transmittance and emissivity of the obtained low emission glass for ultraviolet light, visible light, and solar radiation were measured by a spectrophotometer. The moisture resistance was evaluated by evaluating the moisture resistance of the film after exposure for 2 weeks in an environmental tester at 30 ° C. and 90% RH.
Counting the number of 1 m ² per pinholes or more diameter 3 mm, × 20 or more, 10 to 20 pieces of △, 5 to 10 ○, was evaluated 4 or less as ◎.

The acid resistance was evaluated by immersing low-emission glass in an aqueous solution of adipic acid adjusted to pH 3 and changing the color within 10 seconds. A substance which changed color was evaluated as ○, and a substance which did not show discoloration in 10 minutes was evaluated as ◎.

As a result of evaluating the quality of the low-emission glass obtained in Example 1, excellent optical characteristics shown in Table 1 were obtained for the transmittance and emissivity of ultraviolet light, visible light, and solar radiation.
On the other hand, the pinholes are 2 to 2 in moisture resistance and acid resistance.
The number was as small as three, and the chemical durability was good.

Example 2 As in Example 1, Sn and Zn (3
), Ag and ZnAl. First, as the first pass, the atmosphere in the film forming chamber is kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the SnO _x layer as the first layer is 10 nm and the second layer is Zn
The O _x layer was deposited 12nm. Next, in the second pass, the atmosphere is kept in a reducing atmosphere of 100% Ar, the Ag layer as the third layer is 10 nm, and the ZnAl alloy layer as the fourth layer is 5 nm.
A film was formed. In the third pass, the atmosphere in the film formation chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the fifth layer SnO _x
A 16-nm layer and a 19-nm ZnO _x layer were sequentially formed. A fourth pass was formed to form a 4-nm ZnO _x layer and a 4-nm SnO _x layer in the same atmosphere as in the third pass, and then the glass was discharged from the deposition chamber. . As in the first embodiment, the fourth layer Zn
A part of the Al alloy layer 5 nm was oxidized. The evaluation result is
As shown in Table 1, good results were all obtained.

Example 3 In the same manner as in Example 1, Sn (three), Z
Each metal target of n, Ag, and ZnAl was attached.
First, as the first pass, the atmosphere in the film forming chamber is changed to an acidic atmosphere (O
₂ : Ar = 8: 2), and a SnO _x layer as the first layer was formed to 20 nm, and a ZnO _x layer as the second layer was formed to 3 nm in the same manner as in Example 1. Next, the atmosphere is Ar1 as the second pass.
While maintaining a reducing atmosphere of 00%, an Ag layer as a third layer was formed to a thickness of 20 nm, and a ZnAl alloy layer as a fourth layer was formed to a thickness of 2 nm. In the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and ZnAlO _{x of} the fifth layer is formed.
Layer 2 nm, SnO _x layer 19 nm, ZnO _x layer 2 nm
Were sequentially formed, and as a fourth pass, a ZnO _x layer was formed to a thickness of 2 nm and a SnO _x layer was formed to a thickness of 19 nm in the same atmosphere as in the third pass, and the glass was discharged from the deposition chamber. As in Example 1,
A part of the 4 nm ZnAl alloy layer was partially oxidized.
As shown in Table 1, good evaluation results were obtained.

Example 4 As in Example 1, Sn and Zn (3
), Ag and ZnAl. First, in the first pass, the atmosphere in the film forming chamber is kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the SnO _x layer as the first layer is 17 nm in the same manner as in the first embodiment, and the second layer is Zn
The O _x layer was deposited 19nm. Next, in the second pass, the atmosphere is kept in a reducing atmosphere of Ar 100%, the Ag layer as the third layer is 10 nm, and the ZnAl alloy layer as the fourth layer is 8 nm.
A film was formed. In the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and a SnO _x layer as a fifth layer is formed to 24 nm and a ZnO _x layer is formed to 28 nm in order. As the fourth pass, Zn in the same atmosphere as the third pass
An Ox layer is formed to a thickness of 4 nm and a SnO _x layer is formed to a thickness of 4 nm.
4n of SnO _x layer in the same atmosphere as the fourth pass as the pass
m, a ZnO _x layer was formed to a thickness of 4 nm. Next, as a sixth pass, the atmosphere was kept in a reducing atmosphere of 100% Ar, and an Ag layer as a sixth layer was formed to a thickness of 12 nm, and a seventh layer of a ZnAl alloy layer was formed to a thickness of 8 nm. Further, in the seventh pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and a SnO _x layer as an eighth layer and a ZnO _x layer are successively formed in a thickness of 14 nm and 16 nm, respectively. Then, as the eighth pass, the ZnO _x layer is 4 nm and the SnO _x layer is 4 nm in the same atmosphere as the seventh pass.
A film was formed. Next, the glass was discharged from the film forming chamber. The fourth ZnAl alloy layer 8 nm above the silver layer and the seventh
A part of the ZnAl alloy layer having a thickness of 8 nm was oxidized. As shown in Table 1, good evaluation results were obtained.

Example 5 As in Example 1, the cathode was previously provided with Sn (three), Z
Each metal target of n, Ag, and ZnAl was attached.
First, as the first pass, the atmosphere in the film forming chamber is changed to an acidic atmosphere (O
₂ : Ar = 8: 2), and a SnO _x layer as the first layer was formed to 32 nm and a ZnO _x layer as the second layer was formed to 4 nm in the same manner as in Example 1. Next, the atmosphere is Ar1 as the second pass.
While maintaining a reducing atmosphere of 00%, an Ag layer as a third layer was formed to a thickness of 10 nm, and a fourth ZnAl alloy layer was formed to a thickness of 2 nm. In the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and Zn as the fifth layer is formed.
An AlO _x layer of 3 nm, a SnO _x layer of 42 nm, and a ZnO _x layer of 5 nm are sequentially formed. Further, as the fourth pass, the ZnO _x layer is 1 nm and the SnO _x layer is 11 n in the same atmosphere as the third pass.
Then, as the fifth pass, a SnO _x layer was formed to have a thickness of 11 nm and a ZnO _x layer was formed to have a thickness of 1 nm in the same atmosphere as the fourth pass.
Next, as the sixth pass, the atmosphere was kept in a reducing atmosphere of 100% Ar, and an Ag layer as a sixth layer was formed to a thickness of 12 nm, and a seventh layer of a ZnAl alloy layer was formed to a thickness of 2 nm. Further, in the seventh pass, the atmosphere in the film forming chamber is again changed to an acidic atmosphere (O ₂ : A
r = 8: 2), a ZnAlO _x layer serving as an eighth layer was formed to a thickness of 2 nm, a SnO _x layer was formed to a thickness of 22 nm, and a ZnO _x layer was formed to a thickness of 3 nm. A ZnO _x layer was formed to a thickness of 1 nm, and a SnO _x layer was formed to a thickness of 11 nm. Next, the glass was discharged from the film forming chamber. . It should be noted that the fourth layer ZnAl alloy layer 2 nm above the silver layer and the Z layer
A part of the nAl alloy layer 2 nm was oxidized. As shown in Table 1, good evaluation results were obtained.

Embodiment 6 As in the case of Embodiment 1, Ti (three) and Z
Each metal target of n, Ag, and ZnAl was attached.
First, as the first pass, the atmosphere in the film forming chamber is changed to an acidic atmosphere (O
₂ : Ar = 8: 2), and a TiO _x layer as the first layer was formed to 8 nm and a ZnO _x layer as the second layer was formed to 14 nm in the same manner as in Example 1. Next, the atmosphere is Ar1 as the second pass.
While maintaining a reducing atmosphere of 00%, an Ag layer as a third layer was formed to a thickness of 10 nm, and a fourth ZnAl alloy layer was formed to a thickness of 2 nm. In the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and ZnAlO _{x of} the fifth layer is formed.
7nm layer, 7nm a TiO _x layer, the ZnO _x layer 12nm
Were sequentially formed, and as a fourth pass, a ZnO _x layer was formed to a thickness of 12 nm and a TiO _x layer was formed to a thickness of 7 nm in the same atmosphere as in the third pass, and the glass was discharged from the deposition chamber. As in Example 1,
A part of the 4 nm ZnAl alloy layer was partially oxidized.
As shown in Table 1, good evaluation results were obtained.

Example 7 As in Example 1, the cathode was previously made of Sn, Ti (2
), Zn, Ag and ZnAl. First, in the first pass, the atmosphere in the film forming chamber is kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the SnO _x layer as the first layer is formed to 14 nm and TiO _x by the same method as in the first embodiment.
A 2 nm thick ZnO _x layer and a 6 nm thick ZnO _x layer were formed. Next, as a second pass, the atmosphere was kept in a reducing atmosphere of 100% Ar, and an Ag layer as a third layer was formed to a thickness of 10 nm, and a fourth layer of a ZnAl alloy layer was formed to a thickness of 2 nm. At the third pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and the fifth ZnAlO _x layer is 3 nm, the SnO _x layer is 14 nm, the TiO _x layer is 2 nm, and the ZnO layer is 5 nm. _{An x} layer is sequentially formed to a thickness of 6 nm, and a fourth pass is performed, and a ZnO _x layer is formed to a thickness of 6 nm, a TiO _x layer is formed to a thickness of 2 nm, and a SnO _x layer is formed to a thickness of 14 nm in the same atmosphere as in the third pass. Discharged. As in the first embodiment, the ZnAl alloy layer of the fourth layer is 2 nm.
Some were oxidized. As shown in Table 1, good evaluation results were obtained.

Comparative Example 1 In the same manner as in Example 1, Sn (4 units), Z
Each metal target of n and Ag was attached. First one
In the next step, the atmosphere in the film forming chamber was changed to an acidic atmosphere (O _Two: Ar
= 8: 2) and SnO as the first layer_x23 layers
nm. Next, the atmosphere was Ar100 as the second pass.
% Reducing atmosphere, then the Ag layer is 10 nm,
A second Zn layer was formed to a thickness of 2 nm. Film formation as the third pass
The atmosphere of the room is changed to an acidic atmosphere (O_Two: Ar = 8: 2)
Hold, then SnO_xA 23 nm layer, and then
In the same atmosphere as the third pass, SnO_x15 layers
The glass was discharged from the film forming chamber. Note that Zn
A part of the metal layer 2 nm was oxidized. The evaluation results are shown in Table-
As shown in FIG. 1, the ultraviolet transmittance was as large as 40% or more.
Many pinholes (more than 20) in moisture resistance test
I was born. The thickness of the silver layer in Comparative Example 1 was the same as that in Example 1.
10 nm, but the emissivity is 0.1 compared to Example 1.
It has grown to two.

Comparative Example 2 As in Example 1, the cathode was previously made of Ag and ZnAl.
(5) Each metal target was attached. First, as a first pass, the atmosphere in the film formation chamber is changed to an acidic atmosphere (O ₂ : Ar =
8: 2), and the ZnAlOx layer as the first layer is 3
A 6 nm film was formed. Next, the atmosphere was Ar10 as the second pass.
0% reducing atmosphere and then Ag layer
m, a ZnAl alloy layer was formed to a thickness of 2 nm. In the third pass, the atmosphere in the film forming chamber is again changed to an acidic atmosphere (O ₂ : Ar = 8:
Held in 2), and 23nm deposited ZnAlO _x layer, ZnAlO _x As yet the fourth pass in the same atmosphere as the third pass
A layer was formed to a thickness of 23 nm, and a ZnAlO _x layer was formed to a thickness of 23 nm as the fifth pass in the same atmosphere as in the fourth pass. Next, in the sixth pass, the atmosphere was maintained in a reducing atmosphere of 100% Ar, the Ag layer was 12 nm, and the ZnAl alloy layer was 2 n.
m was formed. Further, as the seventh pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), and a ZnAlO _x layer as the uppermost layer is formed to a thickness of 20 nm.
As the pass, a ZnAlO _x layer was formed to a thickness of 20 nm in the same atmosphere as in the seventh pass, and then the glass was discharged from the deposition chamber. In addition, a part of each ZnAl alloy layer 2 nm above the silver layer was oxidized. As shown in the evaluation results, as shown in Table 1, in the acid resistance test, discoloration of the coating was observed within 10 seconds after immersion.

Comparative Example 3 In the same manner as in Example 1, Sn (4 units) and Z
Each metal target of n and Ag was attached. First one
In the next step, the atmosphere in the film forming chamber was changed to an acidic atmosphere (O _Two: Ar
= 8: 2), and the SnOx layer as the first layer is 37
nm. Next, the atmosphere was Ar100 as the second pass.
% Reducing atmosphere, the Ag layer is 10 nm, the Zn layer
Was deposited to a thickness of 2 nm. In the third pass, the atmosphere in the deposition chamber is
And acidic atmosphere (O_Two: Ar = 8: 2), and SnO_x
A layer is formed to a thickness of 23 nm, and a fourth pass is performed as a fourth pass.
In the same atmosphere, SnO_xA 23 nm layer is deposited and
In the same atmosphere as the fourth pass, SnO_xLayer 2
3 nm was formed. Next, the atmosphere is Ar as the sixth pass.
Keeping in 100% reducing atmosphere, Ag layer was 12 nm,
A second Zn layer was formed to a thickness of 2 nm. Film formation as the 7th pass
The atmosphere of the room is changed to an acidic atmosphere (O_Two: Ar = 8: 2)
Hold, SnO_xThe layer is formed to a thickness of 21 nm, and the eighth pass is performed.
In the same atmosphere as the 7th pass, SnO_x21 nm layer
After forming the film, the glass was discharged from the film forming chamber. Note that each Z
A part of the n-metal layer 2 nm was oxidized. The evaluation results are shown in the table.
High UV transmittance as shown in -1
Many pinholes (20 or more) occurred. What
The thickness of the silver layer of Comparative Example 3 was smaller than that of Examples 4 and 5.
Same 10 and 12 nm, but compared to Examples 4 and 5.
In comparison, the emissivity was increased to 0.08.

Comparative Example 4 In the same manner as in Example 1, Zn (5 units) and A
g of each metal target was attached. First, as a first pass, the atmosphere in the film forming chamber is changed to an acidic atmosphere (O ₂ : Ar = 8:
2), a 37 nm thick ZnO _x layer was formed as the first layer. Next, in the second pass, the atmosphere is maintained in a reducing atmosphere of Ar 100%, the Ag layer is 10 nm, and the fourth layer is Zn.
The layer was deposited to a thickness of 2 nm. In the third pass, the atmosphere in the film forming chamber was again maintained in an acidic atmosphere (O ₂ : Ar = 8: 2), and Zn
The O _x layer was 23nm deposited, at the same atmosphere as the third pass as the fourth pass, the ZnO _x layer was 23nm deposited, at the same atmosphere as the fourth pass as a fifth pass, 23nm formed a ZnO _x layer Filmed. Next, as a sixth pass, the atmosphere was maintained in a reducing atmosphere of Ar 100%, and the Ag layer was
m and Zn layers were formed to a thickness of 2 nm. As the seventh pass, the atmosphere in the film forming chamber is again kept in an acidic atmosphere (O ₂ : Ar = 8: 2), a ZnO _x layer is deposited to a thickness of 20 nm, and as the eighth pass, ZnO _x is deposited in the same atmosphere as the seventh pass. After forming the _x layer to a thickness of 20 nm, the glass was discharged from the film forming chamber. Note that a part of each Zn metal layer was oxidized at 2 nm. The evaluation results are shown in Table-
As shown in FIG. 1, many pinholes (20
And in the acid resistance test, the coating was discolored within 10 seconds after immersion.

As shown in Table 1, Examples 1 to 7 satisfy all of the optical characteristics, moisture resistance, acid resistance, and emissivity. On the other hand, Comparative Example 1 failed the UV transmittance and humidity resistance tests. Comparative Example 2 failed the acid resistance test. Comparative Example 3 failed in the UV transmittance and humidity resistance tests. Comparative Example 4
Failed the moisture and acid resistance tests.

[0044]

[Table 1]

[0045]

According to the present invention, the resistivity of the silver layer is reduced by forming a zinc oxide layer immediately below the silver layer and a protective metal layer containing zinc or zinc as a main component immediately above the silver layer. Is maintained, has a small emissivity, and each layer has a well-balanced film thickness to maintain a high visible light transmittance of 70% or more. The reflection color tone is a neutral color without irritation. It is possible to obtain an excellent low-emission glass having excellent chemical durability and the like by improving the adhesion between the layers by an appropriate configuration.

Continued on the front page (72) Inventor Hiroyuki Muraharu 1521-2 Oguchi-cho, Matsusaka-shi, Mie Central Matsusaka Factory

Claims (11)

[Claims] A laminate comprising a glass substrate and at least one silver layer interposed therebetween and a multilayer film formed thereon, wherein a zinc oxide layer is formed immediately below the silver layer and zinc or zinc is formed immediately above the silver layer. A low-emissivity glass laminate formed by forming a protective metal layer containing zinc as a main component. 2. The low emission glass according to claim 1, wherein the lowermost layer of the laminate and / or the uppermost layer of the laminate are formed by forming a tin oxide layer and / or a titanium oxide layer as an amorphous oxide. Laminate. 3. A first layer comprising a tin oxide layer and / or a titanium oxide layer, a second layer comprising a zinc oxide layer on a glass substrate,
A third layer composed of a silver layer, a fourth layer composed of zinc or a protective metal layer containing zinc as a main component, and a fifth layer having a tin oxide layer and / or a titanium oxide layer as an uppermost layer laminated thereon. Low radiation glass laminate. 4. The low-emission glass laminate according to claim 3, wherein the fifth layer comprises a layer in which zinc oxide, tin oxide and / or titanium oxide are laminated. 5. The first layer has a thickness of 5 to 27 nm, the second layer has a thickness of 3 to 25 nm, and the total thickness of the first layer and the second layer is 15 nm.
The third layer has a thickness of 9 to 25 nm, the fourth layer has a thickness of 1 to 8 nm, the fifth layer has a thickness of 35 to 55 nm, and one layer of the zinc oxide layer in the fifth layer. Film thickness is 25 nm
The low-emissivity glass laminate according to claim 3 or 4, wherein: 6. A solar ultraviolet ray transmittance of 37% or less, a visible ray transmittance of 70 to 90%, and a solar radiation transmittance of 40 to 70%.
The low-emission glass laminate according to claim 3, 4, or 5. 7. A first layer comprising a tin oxide layer and / or a titanium oxide layer, a second layer comprising a zinc oxide layer on a glass substrate,
A third layer composed of a silver layer, a fourth layer composed of zinc or a protective metal layer containing zinc as a main component, a fifth layer having an uppermost layer composed of a zinc oxide layer, a sixth layer composed of a silver layer, and zinc Alternatively, a low-emissivity glass laminate in which a seventh layer made of a protective metal layer containing zinc as a main component and an eighth layer having a tin oxide layer and / or a titanium oxide layer as the uppermost layer are laminated thereon. 8. The low-emissivity glass laminate according to claim 7, wherein the fifth layer and the eighth layer are formed by laminating zinc oxide, tin oxide and / or titanium oxide. 9. A third layer film wherein the first layer has a thickness of 5 to 37 nm, the second layer has a thickness of 3 to 35 nm, and the total thickness of the first layer and the second layer is 25 to 40 nm. A thickness of 9 to 13 nm, a thickness of the fourth layer of 1 to 8 nm, a thickness of the fifth layer of 55 to 80 nm, a thickness of zinc oxide in the fifth layer of 1 nm or more, and a thickness of the sixth layer. Has a thickness of 9 to 13 nm, and the seventh layer has a thickness of 1 to 13.
The low emissivity glass laminate according to claim 7 or 8, wherein the thickness of the eighth layer is 8 to 25 nm, and the thickness of one zinc oxide layer in the eighth layer is 25 nm or less. 10. A solar ultraviolet ray transmittance of 25% or less, a visible ray transmittance of 70 to 85%, and a solar radiation transmittance of 40 to 50.
%. The low emissivity glass laminate according to claim 7, 8 or 9. 11. The low radiation glass laminate according to claim 1, wherein the zinc metal used for the protective metal layer is an alloy containing zinc as a main component and containing 2 to 10 atomic% of aluminum.