JPH0985893A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate using Ag and having improved moisture resistance and scuff resistance. SOLUTION: An oxide layer 1 containing ZnO or made of ZnO containing one or more types of metal, a metal layer 2 made of Ag containing Pd and an oxide layer 4 made of SnO2 or ZnO containing one or more types of metal are sequentially formed on a transparent base 11.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a laminate.

[0002]

2. Description of the Related Art Conventionally, Low-E glass (Low E
Highly insulating glass called “missivity glass” is used for window glass of houses. This glass has a high transmittance in the visible region, near infrared light and 10μ
The reflectance for infrared light having a long wavelength of about m is high. Therefore, the use of this glass reduces the inflow of heat rays contained in sunlight into the room and the release of indoor heat to the outside while taking in the visible sunlight from the outside. Therefore, when this Low-E glass is used, dew condensation on the window glass is prevented in winter and the heating load is reduced. In addition, the cooling load is reduced in the summer.

One known as Low-E glass is a glass plate having a single layer of SnO ₂ , and the manufacturing method is an online spray method or a CVD method. The thermal insulation of the Low-E glass is evaluated by the emissivity, and the smaller this value is, the better, but the value of the type is about 0.2.

Another example is a glass plate formed by combining Ag and a transparent film. A sputtering method is known as a manufacturing method. This type has a low emissivity, and
It is around 1. Normally, Ag is sandwiched between transparent films, but this transparent film lowers the reflectance and increases the transmittance of the Ag film due to the interference effect, protects Ag, and improves the mechanical and chemical durability of the film system. do.

As the transparent film, ZnO, SnO ₂ , TiO
An oxide film such as ₂ or a nitride film such as SiN _x is used. Among them, because the material cost is low and the film formation speed is high, Z
nO is often used. The film structure is ZnO / Ag / Zn
3 layers of O or ZnO / Ag / ZnO / Ag / Zn
In the case of 5 layers of O, the latter has a smaller emissivity.

In order to stabilize Ag, a barrier layer is often inserted at the interface between Ag and ZnO. In particular, the barrier layer on the Ag layer is effective in preventing Ag from being oxidized by atmospheric oxygen when the oxide layer on the Ag layer is laminated by reactive sputtering in an atmosphere containing oxygen.

Chemical of Low-E glass using Ag,
Mechanical durability is inferior to ordinary heat ray-reflecting glass (so-called solar control glass). This is because the chemical and mechanical durability of Ag is significantly inferior to the films used in solar control glass, such as stainless steel, TiO ₂ , SnO ₂ , titanium nitride, and chromium nitride. Therefore, Low-E using Ag
The glass cannot be used as a single glass, but is used as a double-layer glass or a laminated glass so that the film surface is not exposed indoors or outdoors.

Low-E glass using Ag is particularly inferior in the moisture resistance of the film. If this film is left in the air while being exposed, deterioration in appearance such as white spots (speckled defects) and white turbidity will occur within a few days. Therefore, it has been necessary to form a multi-layer glass or a laminated glass immediately after the film formation.

In addition, the film of Low-E glass using Ag is easily scratched, and even if it is slightly touched with a hard material such as metal, or even with a resin powder scattered between the glasses to prevent adhesion of the glass. However, the film surface was sometimes scratched.

As described above, the Low-E glass using Ag requires great care in storage and handling until it is made into a double-glazing or laminated glass.

Conventional ZnO / Ag / barrier / ZnO system L
The following mechanism is considered to be the cause of the white turbidity and the white spot-like defects in the ow-E glass. That is, water vapor in the air reaches the Ag film through the pinholes of the ZnO film in the upper layer and reaches the Ag film, causing an increase in the crystal grain size due to the oxidation and aggregation of Ag. At the same time, the ZnO film is cracked. Since the ZnO film has a high internal stress, the adhesion to the underlying layer is poor, and Ag / ZnO or barrier / Zn
Peeling of the ZnO film occurs at the O film interface, and the peeled portion is observed as white turbidity or white spots due to light scattering.

It has been proposed that a second element be added to ZnO to reduce the internal stress of the ZnO film, improve the adhesion of the upper ZnO film to Ag, and prevent the ZnO film from peeling. (JP-A-4-357025)
However, even this method was not sufficient to satisfy the actually required moisture resistance performance.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminate using Ag, which has improved moisture resistance and scratch resistance.

[0014]

According to the present invention, a first oxide layer made of ZnO or ZnO containing at least one metal is provided on a transparent substrate from the side of the substrate, and A containing Pd.
Provided is a laminate in which a first metal layer composed of g and a _second oxide layer composed of SnO ₂ or ZnO containing at least one metal are sequentially formed (hereinafter referred to as Ag1 layer system laminate). To do. The Ag single-layer system laminate is configured by using only one metal layer made of Ag containing Pd.

The present invention also provides, on a transparent substrate, from the substrate side, a first oxide layer made of ZnO or ZnO containing at least one metal, and a first metal made of Ag containing Pd. Layer, a second oxide layer made of ZnO containing at least one metal, and a second oxide layer made of Ag containing Pd.
And a third oxide layer made of ZnO containing SnO ₂ or one or more kinds of metals are sequentially formed (hereinafter referred to as Ag2 layer-based laminate). Ag
In the two-layer system laminate, only two metal layers made of Ag containing Pd are used.

1 to 4 are cross-sectional views of an example of the laminated body of the present invention. 11 is a transparent substrate, 1 is an oxide layer made of ZnO or ZnO containing one or more metals, 2 is a metal layer made of Ag containing Pd, 3 is a metal thin film layer or a nitride film layer, and 4 is SnO. _An oxide layer made of ZnO containing ₂ or at least one metal, 5 is SnO ₂ containing Si
An oxide layer made of Zn, 6 is Zn containing at least one metal
An oxide layer of O.

Examples of ZnO containing one or more metals include Sn, Al, Cr, Ti, Si, B, Mg and G.
Preferred is ZnO containing at least one of a.

Z containing one or more metals on top of the Ag layer
When an oxide layer made of nO is used, the content ratio of the metal is preferably 1 to 10 at% with respect to the total amount of the metal and Zn. If it is less than 1 at%, the internal stress of the ZnO film is not sufficiently reduced, the adhesion between the ZnO film and the Ag layer is hardly improved, and as a result, the moisture resistance of the laminate is not improved. On the other hand, if it exceeds 10 at%, the moisture resistance is lowered again. It is considered that this is because the crystallinity of ZnO decreases and the compatibility with Ag decreases when the proportion of the contained metal increases. In consideration of obtaining a ZnO film with stable and good reproducibility and a low internal stress, and considering the crystallinity of ZnO, the metal content is 2 to
6 at% is preferable.

ZnO is used as the first oxide layer on the substrate.
An oxide layer containing as a main component is used. The use of pure ZnO stabilizes the Ag layer deposited thereon due to its high crystallinity.

When an oxide layer made of ZnO containing one or more kinds of metals is used as the first oxide layer on the substrate, the internal stress is lowered, the adhesion with the substrate is increased, and as a result, the laminate is obtained. The moisture resistance of is improved. However, if the content ratio of the metal is too large, the crystallinity of ZnO required for stabilizing Ag decreases, so the content ratio of the metal is preferably 1 to 10 at%, particularly preferably 2 to 6 at%.

The geometric film thickness (hereinafter, simply referred to as film thickness) of the Ag one-layer system laminate is 1 to 1 for the first oxide layer.
00 nm, the first metal layer has a thickness of 5 to 30 nm, and the second oxide layer has a range of 20 to 100 nm, and are appropriately adjusted to satisfy the required optical performance.

The thickness of the Ag two-layer laminate is 1 to 100 nm for the first oxide layer and 5 to 30 n for the first metal layer.
m, the second oxide layer is 40 to 100 nm, the second metal layer is 5 to 30 nm, and the second oxide layer is 20 to 100 nm. It

The content ratio of Pd in the metal layer made of Ag containing Pd (hereinafter referred to as Pd-Ag) is Pd.
Is preferably 0.3 to 10 at% with respect to the total amount of Ag and Ag.

If it is less than 0.3 at%, the stabilizing effect of Ag is lowered, and if it exceeds 10 at%, the stabilizing effect is lowered again. Moisture resistance improves as the amount of addition increases in the range up to 10%, but when the amount of Pd increases, the film formation rate decreases, the visible light transmittance decreases, and the emissivity increases. Therefore, from the above viewpoint, the amount of Pd added is 5.0 at.
% Or less is appropriate. Further, since the target cost increases remarkably when the amount of Pd added increases, it is in the range of about 0.5 to 2.0 at% when the normally required moisture resistance is taken into consideration.

In the Ag one-layer system laminate, a metal thin film layer or a nitride film layer is preferably provided between the first metal layer and the second oxide layer.

In the Ag two-layer system laminate, a metal thin film is provided between the first metal layer and the second oxide layer and / or between the second metal layer and the third oxide layer. A layer or nitride film layer is preferably provided.

The metal thin film layer or the nitride film layer functions as a barrier layer and prevents Ag from being oxidized. As the metal thin film or the nitride film, Ti, Zn, Ta, NiCr,
A film containing SiN _x as a main component is suitable. The film thickness is 1-5
nm is desirable. When the thickness is less than 1 nm, the function as a barrier layer is not sufficiently exhibited. If it is thicker than 5 nm, the transmittance of the film system is lowered. SiN _x is a transparent nitride film, in this case
There is no particular upper limit on the film thickness.

In the Ag one-layer system laminate, it is preferable that a SnO ₂ layer containing Si is formed further outside the second oxide layer. In the Ag two-layer system laminate,
SnO containing Si is further outside the third oxide layer.
Preferably _two layers are formed.

Sn and S in SnO ₂ containing Si
The content ratio of Si with respect to the total amount of i is preferably 5 to 95 at%. In particular, 30 to 90 at% is more preferable, and 40 to 90 at% is more preferable.

This layer improves the ability to prevent the ingress of water (water resistance) and improves the scratch resistance of the membrane system. SnO
_When Si is added to ₂ , the film changes from crystalline to amorphous structure and the film becomes dense. If the proportion of Si is too low, the water resistance of the film is reduced. In addition, the film approaches from amorphous to crystalline, and the smoothness of the film surface is lost, so that the scratch resistance of the film decreases. If the proportion of Si is high, arcing is likely to occur during film formation by the DC sputtering method, and productivity is reduced.

The thickness of the SnO ₂ layer containing Si is not particularly limited, but it is required to be about 5 nm or more in order to improve the moisture resistance and the scratch resistance. As the film thickness increases, the moisture resistance and scratch resistance improve. There is no particular upper limit on the film thickness, but if it is 20 nm, sufficient performance can be obtained.

The point of the invention is to combine these layers as described above. Even if other layers are combined, the moisture resistance and scratch resistance are not improved as much as the above combination. The inventor examined various layer combinations and as a result found the above combinations to be optimal.

As an oxide layer below the Ag layer, a layer containing ZnO as a main component is most suitable. ZnO has a hexagonal crystal structure, and when it is formed by sputtering on a glass substrate, it usually has C-axis orientation. This is because the Ag layer, which is a face-centered cubic lattice, has (111) orientation on the ZnO layer, and Ag is stabilized.

Use of the same material as the oxide layer above the Ag layer for the oxide layer below the Ag layer can save the number of targets when the film is formed by multi-pass using an in-line type sputtering apparatus. Is advantageous in that.

It is known that Pd is contained in the Ag layer to improve the chemical durability of the Ag layer (JP-A-59-13).
1449). The effect of containing Pd is immobilization of Ag atoms, that is, reduction of Ag migration. However, the use of this Pd-containing Ag does not immediately improve the moisture resistance of the Low-E, and it is important to select the type of oxide layer that comes above it.

As for the oxide layer on the Ag layer, a layer containing ZnO as a main component is suitable for improving the durability of the film system as described above. However, pure ZnO has large internal stress, insufficient adhesion at the Ag / ZnO interface, and poor moisture resistance. Furthermore, the scratch resistance is also poor. In this case, even if Pd-containing Ag is used, the durability of the film system is hardly improved.

On the other hand, even when pure Ag is used, Zn
It is known that moisture resistance is improved by using a film in which an element having an ionic radius smaller than Zn ²⁺ is added to O to reduce internal stress (Japanese Patent Laid-Open No. 4-35702).
5). The additive elements exhibiting the effect of reducing internal stress are Sn, A
1, Cr, Ti, Si, B, Mg, Ga and the like.

The inventor tried various combinations of ZnO and Pd-Ag to which various metals were added, and as a result, Al or S
It has been found that ZnO containing n is preferred. Al
Alternatively, an oxide layer made of ZnO containing Sn and Pd-
It has a good compatibility with the metal layer made of Ag, and by combining the two, the moisture resistance is remarkably improved.

In particular, Al is inexpensive and ZnO after it is contained.
The film formation speed is fast. Also, the Al-doped ZnO oxide layer is extremely compatible with the Pd-Ag metal layer.

It is considered that this is because Al has the same crystal structure as Ag or Pd. For this reason,
Even if Al precipitates at the grain boundary or interface of ZnO, Ag or P
It is considered that the interface at the atomic level with d is improved.

Also, Sn is relatively inexpensive and is a preferable material as described above. In particular, Sn-containing ZnO has a smaller change in the reflection color (hereinafter referred to as the film-surface reflection color) viewed from the film surface side when it is placed in a high-humidity atmosphere for a long time, as compared with Al-containing ZnO.

Even when Al or Sn-doped ZnO is used, the moisture resistance is not so improved when combined with pure Ag. This is because Ag is not sufficiently stabilized.

The effect of improving the moisture resistance by Pd-Ag is as follows.
Sn, Al, Cr, Ti, Si, B, M in the upper oxide layer
It is remarkably exhibited by using a ZnO layer containing g, Ga, etc. and having a low internal stress.

As described above, ZnO is formed as the oxide layer on the Ag layer.
Although the oxide layer of the system is described, SnO ₂ is also used as a layer other than the oxide layer of the ZnO system. SnO _{2 is} also relatively compatible with Ag, and the moisture resistance of the film system is significantly improved.
However, in this case, the scratch resistance is Z containing Sn or Al.
It is slightly weaker than when the nO layer is used.

On the other hand, even a film having a low internal stress, for example, Ti
Even if O ₂ is used, the moisture resistance is not so improved as compared with the case of using ZnO, and the scratch resistance is slightly lowered. In addition, Ta ₂
When O ₅ is used, the moisture resistance is improved as compared with the case where ZnO is used, but the scratch resistance is significantly reduced.

In order to compensate for the decrease in scratch resistance, it is possible to select, as the barrier layer, a material which is compatible with both the Ag layer and the oxide layer on the Ag layer. However, since the barrier layer usually has a thickness of several nm, it is difficult to significantly improve the scratch resistance.

S containing Si provided as the outermost layer
The nO ₂ layer has good compatibility with the layer containing ZnO as a main component or the SnO ₂ layer, and strong adhesion is obtained at the interface. Therefore, by overcoating the SnO ₂ layer containing Si, the invasion of water into the film system is reduced, so that the film surface reflection color due to the deterioration of the film when placed in a high humidity atmosphere for a long time The changes are significantly reduced.

With respect to the color tone of the laminate of the present invention viewed from the glass substrate side, the thickness of the first metal layer is 50 to 70% of the thickness of the second metal layer, especially the thickness of the second metal layer in the Ag2 layer-based laminate. 5
By controlling from 5 to 65%, a pale green reflection can be obtained. Moreover, the reflected color does not change significantly even when viewed from an angle.

FIG. 5 shows an Ag two-layer system laminate in which the film thickness of the first metal layer is 50 to 70% of the film thickness of the second metal layer when the incident angle is 0 degree (B in the figure). ) And the case of 60 degrees (A in the figure) are compared. As can be seen from FIG. 5, by changing the incident angle from 0 degree to 60 degrees, the rising position of reflection on the long wavelength side is shifted to the short wavelength side. As a result of this shift, the reflection in the long wavelength range becomes relatively high and the color tone appears to change (specifically, the color tone takes on a reddish tinge). If the rising of the reflection on the side is suppressed as low as possible, the change in color tone becomes small.

By setting the film thickness of the infrared-reflecting metal of the first layer to be about 50 to 80% of the film thickness of the infrared-reflecting metal of the second layer, the optical appearance of external reflection is substantially independent of the incident angle. It is known that it becomes constant (JP-A-7-16544).
2). However, the change in color tone with this incident angle is
Infrared reflection characteristics Used greatly depends on the type of metal.

The laminate of the present invention is characterized by containing Pd in Ag. As described above, the inclusion of Pd stabilizes Ag, but its resistance value is higher than that of pure Ag. The rise on the long wavelength side of the spectral reflection curve is related to this resistance value, and the higher the resistance value, the more likely the rise is.

That is, the layered product of the present invention is more pure Ag.
The rise on the long wavelength side of the spectral reflection curve becomes slower than in the case where is used, and this is advantageous for the change in color tone depending on the incident angle. That is, according to the present invention, the change in the reflection color tone depending on the incident angle can be suppressed to be lower than that in JP-A-7-165442.

In the Ag two-layer system laminate of the present invention, the layer structure for obtaining a light green reflection is such that the thickness of the first metal layer is 6.5 to 8 nm and the thickness of the second metal layer is 10.
The thickness is preferably 5 to 12.5 nm. In this case, the thickness of the first oxide layer is 30 to 37 nm, the thickness of the second oxide layer is 58.5 to 71.5 nm, and the thickness of the third oxide layer is 22.5 to 27. It is preferably set to 0.5 nm. The thicknesses of these metal layer and oxide layer are appropriately adjusted depending on the target degree of light green.

The method for forming these layers is not particularly limited,
A vapor deposition method, a CVD method or the like can be used. The DC sputtering method is effective for a large area substrate such as window glass.

As the substrate used in the present invention, in addition to glass, a transparent substrate such as a resin can be used. For example, it can be used as a wall sheet of a greenhouse.

[0056]

In the present invention, by using an oxide layer made of ZnO or ZnO containing at least one metal as the oxide layer below the Ag layer, the crystallinity of Ag is improved.
stabilize g.

By using an oxide layer made of SnO ₂ or ZnO containing at least one metal as the oxide layer on the Ag layer, the oxide layer is peeled off at the interface with Ag due to the low internal stress. It becomes difficult and improves the durability of the membrane system.

By using Pd-Ag, Ag itself is stabilized as compared with Ag containing no Pd.

The use of a SnO ₂ layer containing Si reduces the penetration of water into the film system. Further, since the surface of the oxide layer has a small friction coefficient, the scratch resistance of the film system is also improved.

[0060]

EXAMPLES In the following Examples (Examples 1 to 24) and Comparative Examples (Examples 25 to 32), a Low-E film was formed on a glass substrate under the film forming conditions shown in Table 1, and Low-E was formed. I got a glass.

In the table, 5Al-ZnO means
Zn containing 5 at% of the total amount of Al and Zn
O means 5Al-Zn means Zn containing 5 at% of Al with respect to the total amount of Al and Zn. Also,
1Pd-Ag means 1 for Pd relative to the total amount of Pd and Ag.
This means Ag containing at%. The same applies to the following. Further, SnSiO _x means a complex oxide having an atomic ratio of Sn and Si of 1: 1 and SnSi means an alloy having an atomic ratio of Sn and Si of 1: 1.

The humidity resistance of the obtained Low-E glass was 4
Stored in a thermo-hygrostat at 0 ° C. and 90% RH for 3 weeks, the number of white spot defects (10 cm
The number in 10 cn) was visually counted.

For the scratch resistance of the Low-E glass, the critical load for film peeling was measured with a CSR-02 type scratch tester manufactured by Reska. The test conditions are using a diamond needle (tip R = 50 μm), substrate tilt angle 4 °, substrate moving speed 1
5 μm / sec.

The change in the color reflected on the film surface of the Low-E glass is the change Δx, Δ in x, y on the CIE color coordinates before and after storage.
When y is measured, [(Δx) ² + (Δy) ² ] ^1/2 is 0.0
000 to 0.0100, ○, 0.0101 to 0.
When it was 0200, it was evaluated as Δ, and when it was 0.0201 or more, it was evaluated as x.

[Example 1] A washed float glass plate having a thickness of 2 mm was set in a sputtering apparatus, and 10 ^-6 To was added.
The air was exhausted to the rr level. Next, under the conditions of Table 1, 5Al-Zn
O (film thickness 40 nm) / 1Pd-Ag (10 nm) / 5A
1-Zn (barrier layer, 2 nm) / 5Al-ZnO (40
nm) to form a four-layer film.

Table 2 shows the test results of the moisture resistance and scratch resistance of this Low-E glass. In the table, G means a 2 mm float glass plate, the number in () is the film thickness, and the unit is nm. The same applies below.
This Low-E glass had a practically sufficient film strength.

[Examples 2 to 32] In the same manner as in Example 1, the thickness 2 was obtained.
Various Ls shown in Tables 2 and 3 on a float glass substrate of mm.
An ow-E film was formed to obtain various Low-E glasses. Tables 2 and 3 show the test results of the moisture resistance and scratch resistance of these Low-E glasses. All the obtained Low-E glasses had a practically sufficient film strength.

The color tone reflected from the glass substrate side of Example 21 is
In the L ^* a ^* b ^* coordinate form, a ^* = 4.5, b ^* =
At 1.3, it had a pale green reflection tone. Also, when viewed from an angle, it was only slightly bluer.

The reflection color tone from the glass substrate side of Example 22 is as follows:
In the L ^* a ^* b ^* coordinate form, a ^* = 3.0, b ^* = −
At 1.5, the color tone was more bluish than in Example 21.
However, even when viewed from an angle, the color tone hardly changed.

The Low-E glasses of Examples 25-28 were prepared according to Example 1
It was confirmed that the moisture resistance and the scratch resistance were inferior to those of the Low-E glass of No. 10 to 10. In addition, Low of Examples 29 to 32
It was confirmed that -E glass was inferior in both moisture resistance and scratch resistance to the Low-E glasses of Examples 11 to 20.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

EFFECTS OF THE INVENTION Since the laminate of the present invention has improved moisture resistance, the packaging can be simplified and the amount of the hygroscopic agent or the like can be reduced in storage and handling, and the cost can be reduced.
In addition, since scratch resistance is improved, scratches are less likely to occur, and the frequency of occurrence of scratches during handling can be reduced.
Suitable as ow-E glass.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of a laminate of the present invention.

FIG. 2 is a sectional view of another example of the laminated body of the invention.

FIG. 3 is a sectional view of another example of the laminated body of the invention.

FIG. 4 is a cross-sectional view of another example of the laminated body of the invention.

FIG. 5 is a spectral reflection curve (B) when the incident angle is 0 degree and a spectral reflection curve (A) when the incident angle is 60 degrees of the Ag2 layer-based laminate.

[Explanation of symbols]

1: oxide layer made of ZnO or ZnO containing one or more metals 2: metal layer made of Ag containing Pd 3: metal thin film layer or nitride film layer (barrier layer) 4: SnO ₂ or 1 type Oxide layer made of ZnO containing the above metals 5: Oxide layer made of SnO ₂ containing Si 6: 1 Oxide layer made of ZnO containing one or more kinds of metals 11: Transparent substrate

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasuo Hayashi 1150, Hazawa-cho, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Masashi Tada 25, Towada, Kamisu-cho, Kashima-gun, Ibaraki Asahi Glass Kashima Factory Co., Ltd.

Claims (12)

[Claims] 1. A first oxide layer made of ZnO or ZnO containing at least one metal, a first metal layer made of Ag containing Pd, and S on a transparent substrate from the side of the substrate.
A laminated body in which a second oxide layer made of nO ₂ or ZnO containing at least one metal is sequentially formed. 2. The first oxide layer contains ZnO containing Al.
The second oxide layer is SnO ₂
The laminated body according to claim 1, which is an oxide layer made of ZnO containing Sn and / or Al. 3. Between the first metal layer and the second oxide layer,
The laminate according to claim 1 or 2, wherein a metal thin film layer or a nitride film layer is provided. 4. The laminate according to claim 1, wherein a SnO ₂ layer containing Si is formed further outside the second oxide layer. 5. A first oxide layer made of ZnO or ZnO containing at least one metal, a first metal layer made of Ag containing Pd, and 1 from a substrate side on a transparent substrate.
A second oxide layer made of ZnO containing at least one metal, a second metal layer made of Ag containing Pd, and Sn.
A laminated body in which a third oxide layer made of ZnO containing O ₂ or at least one metal is sequentially formed. 6. The first oxide layer contains ZnO containing Al.
The second oxide layer is an oxide layer made of ZnO containing Al, and the third oxide layer is made of ZnO containing SnO ₂ or Sn and / or Al. The laminated body according to claim 5, which is an oxide layer of 7. Between the first metal layer and the second oxide layer and / or between the second metal layer and the third oxide layer,
The laminate according to claim 5 or 6, wherein a metal thin film layer or a nitride film layer is provided. 8. The laminate according to claim 5, wherein a SnO ₂ layer containing Si is formed on the outer side of the third oxide layer. 9. The geometric thickness of the first metal layer is 50 to 70% of the geometric thickness of the second metal layer.
6, 7 or 8 laminates. 10. The geometric thickness of the first metal layer is 6.5 to 5.
8 nm and the geometric thickness of the second metal layer is 10.5
It is -12.5 nm, The laminated body of any one of Claims 5-9. 11. The laminate according to claim 1, wherein the content ratio of the metal in ZnO containing one or more metals is 1 to 10 at% with respect to the total amount of the metal and Zn. . 12. The content ratio of Pd in Ag containing Pd is 0.3 to 10 at with respect to the total amount of Pd and Ag.
% Of the laminated body according to any one of claims 1 to 11.