JP7252713B2 - Glass laminate manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a glass laminate and a glass laminate.

In recent years, a large number of low-emissivity glass laminates having an infrared reflective function, called Low-E glass, have been developed. For example, Patent Document 1 discloses a glass laminate obtained by forming a silver layer on a substrate (glass plate) by sputtering, and further laminating an oxygen-containing ceramic on the silver layer. Note that the glass laminate is not a laminate of a plurality of glass plates, but a laminate in which a plurality of metal layers or the like are laminated on a glass plate.

Japanese Patent No. 4498615

However, the sputtering method using the oxygen-containing ceramic target has a problem of frequent occurrence of arcing in the chamber. Arcing is a phenomenon in which an abnormal discharge occurs at locally charged portions when a high voltage is applied to the surface of a sputtering target. In particular, it is known that arcing is more likely to occur when using a ceramic target than when using a metal target. This is because the ceramic target has lower conductivity than the metal target, so when a high voltage is applied to the target, electric charges tend to accumulate locally on the target surface. This is probably because the surface is easily charged. Frequent occurrence of such arcing may damage the formed layer or cause generation of particles. Therefore, there has been a demand for an improvement in the occurrence of arcing. The present invention has been made in order to solve this problem. The object is to provide a method for manufacturing a body.

Section 1. forming a first layer containing silver or a silver alloy on a glass plate by a sputtering method;
forming a second layer containing niobium oxide or niobium-doped oxide on the first layer by a sputtering method;
A method for manufacturing a glass laminate.

In item 1, the first layer includes both the case where it is formed directly on the glass plate and the case where it is formed via another layer. Similarly, the second layer also includes both the case where it is formed directly on the first layer and the case where it is formed via another layer.

Section 2. Item 2. The method for producing a glass laminate according to Item 1, wherein the oxygen concentration in the sputtering atmosphere during the formation of the first layer is 10% by volume or less.

Item 3. Item 2. The method for producing a glass laminate according to Item 1, wherein the oxygen concentration in the sputtering atmosphere during the formation of the first layer is 3% by volume or less.

Section 4. Item 4. The method for producing a glass laminate according to Item 2 or 3, wherein the oxygen concentration in the sputtering atmosphere during the formation of the first layer is 1% by volume or more.

Item 5. Item 5. The method for producing a glass laminate according to any one of Items 2 to 4, wherein the formation of the first layer and the second layer by the sputtering method is performed in the same chamber.

Item 6. 6. Any of paragraphs 1-5, further comprising forming a base layer containing a metal oxide, a niobium oxide, or a niobium-doped oxide on the glass sheet prior to forming the first layer. The manufacturing method of the glass laminated body as described in 1.

Item 7. Item 7. The method for producing a glass laminate according to Item 6, wherein the metal oxide is niobium oxide or niobium-doped oxide, and the metal nitride is niobium nitride or niobium-doped nitride.

Item 8. 7. Item 6, wherein the metal oxide is zinc oxide, tin oxide, or a metal oxide containing these as main components, and the metal nitride is silicon nitride or a metal nitride containing silicon nitride as a main component. A method for producing a glass laminate of.

Item 9. Item 9. The method for producing a glass laminate according to any one of Items 6 to 8, wherein the metal oxide or metal nitride and the first layer are adjacent to each other.

Item 10. Item 10. The method for producing a glass laminate according to any one of Items 1 to 9, further comprising the step of forming a protective layer containing a metal or metal oxide on the first layer.

Item 11. Item 11. The method for producing a glass laminate according to any one of Items 1 to 10, wherein the second layer contains a niobium oxide represented by NbOx (2.0≤x≤2.5).

Item 12. Item 12. The method for producing a glass laminate according to any one of Items 1 to 11, wherein the formation of the first layer and the second layer is repeated multiple times.

Item 13. a glass plate and
a first layer containing silver or a silver alloy formed on the glass plate by a sputtering method;
a second layer containing niobium oxide or niobium-doped oxide formed on the first layer by a sputtering method;
A glass laminate comprising:

Item 14. 14. The glass laminate of paragraph 13, further comprising a base layer containing a metal oxide, metal nitride, niobium oxide, or niobium-doped oxide between the glass sheet and the first layer.

Item 15. 15. The glass of item 14, wherein the metal oxide is zinc oxide, tin oxide, or a metal oxide containing these as a main component, and the metal nitride is silicon nitride or a metal nitride containing silicon nitride as a main component. laminate.

Item 16. Item 16. The glass laminate according to any one of Items 13 to 15, further comprising a protective layer containing a metal or metal oxide on the first layer.

Item 17. Item 17. The glass laminate according to any one of Items 13 to 16, wherein the second layer contains a niobium oxide represented by NbOx (2.0≤x≤2.5).

Item 18. Item 18. The glass laminate according to any one of Items 13 to 17, having a plurality of combinations of the first layer and the second layer.

Item 19. a glass plate and
a first layer containing silver or a silver alloy formed on the glass plate;
a second layer containing niobium oxide or niobium-doped oxide formed on the first layer;
A glass laminate comprising:

The first layer and the second layer of the glass laminate according to item 19 can also be formed by a film forming method other than the sputtering method as described in item 10 above. For example, CVD, vapor deposition, or the like can also be used.

According to the present invention, arcing can be prevented from occurring when film formation for Low-E glass is performed by sputtering.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the glass laminated body which concerns on this invention.

Hereinafter, the glass laminate according to the present invention will be described. The glass laminate according to the invention is a so-called Low-E glass and has at least a first layer comprising silver or a silver alloy and a second layer comprising niobium oxide or niobium-doped oxide on a glass plate. A base layer, which will be described later, may be formed between the glass plate and the first layer, or a protective layer or an intermediate layer may be separately provided. Furthermore, the first layer and the second layer can be formed repeatedly. Each layer will be described in detail below.

<1. Layer Constituting Glass Laminate>
<1-1. Glass plate>
The glass plate that serves as the substrate is not particularly limited, and a known glass plate can be used. For example, various glass plates such as heat-absorbing glass, clear glass, green glass, UV green glass, and soda-lime glass can be used. In particular, in the case of architectural glass, it is preferable to use inexpensive soda-lime glass. The thickness of the glass plate is not particularly limited, but can be, for example, 3 to 10 mm.

<1-2. First layer>
The first layer is a layer containing silver or a silver alloy as a main component. The thickness of the first layer is not particularly limited, but can be, for example, 5 to 20 nm. The silver or silver alloy contained in the first layer can reflect light with frequencies in the near-infrared region or infrared region to improve the emissivity.

<1-3. Second layer>
The second layer is a layer mainly composed of niobium oxide or niobium-doped oxide. Niobium oxide is an oxide represented by NbOx, preferably 2.0≦x≦2.5, more preferably 2.3≦x≦2.5. This is because when x is less than 2.3, the absorption amount in the visible light band increases and the transmittance of visible light decreases. On the other hand, if x is less than 2.0, the amount of absorption in the visible light band is further increased, and the transmittance of visible light is decreased. As a result, the function of the second layer as an antireflection film is impaired, which is not preferable.

On the other hand, examples of niobium-doped oxides include titanium oxide or the like doped with 0.5 to 5% by mass of niobium.
Here, doping means adding a small amount of impurities to change the physical properties of the crystal, that is, replacing part of the crystal lattice with a dopant. Niobium may also be added. That is, it may be a mixture of niobium. In addition, addition may mean a dope as well as a mixture.

The thickness of the second layer is not particularly limited, but can be, for example, 1 to 100 nm.

The second layer is used as or part of an antireflection layer for increasing the transmittance of visible light. That is, since the first layer containing silver alone also reflects visible light, it is used to reduce the reflection of this visible light. Further, as will be described later, when niobium oxide is used as a target for sputtering, it is preferable to use niobium oxide in an oxygen-deficient state in order to make the target conductive. However, depending on the film thickness, if the amount of oxygen deficiency in the niobium oxide is too large, the absorption of visible light may become too large. , it is preferable to form a niobium oxide layer with a small amount of oxygen deficiency or no oxygen deficiency.

Further, as will be described later, by including niobium in the sputtering target for forming the second layer, frequent occurrence of arcing in the sputtering target can be prevented.

<1-4. Base layer>
The base layer is a layer formed directly on the glass plate prior to the formation of the first layer on the glass plate, and is a layer based on a metal oxide, metal nitride, or the same material as the second layer. be. Examples of metal oxides different from the material of the second layer include substances containing tin oxide and zinc oxide as main components. Examples of metal nitrides include substances containing silicon nitride as a main component. The thickness of the base layer is not particularly limited, but can be, for example, 5 to 50 nm. By providing this base layer, it is possible to protect the first layer from components, such as alkaline components, that may enter through the glass plate and affect silver in the first layer. This base layer also has the function of reducing the reflection of visible light. In particular, when the base layer contains zinc and is in contact with the first layer, there is an advantage that the crystallinity of the silver in the first layer is improved.

<1-5. Additional layer>
The additional layer is a layer containing metal oxide or metal nitride as a main component. These are the same materials as described for the base layer above. The position where the additional layer is arranged is not particularly limited. second first layer). Alternatively, it can be arranged in the outermost layer farthest from the glass plate. The thickness of the additional layer is not particularly limited, but can be, for example, 5 to 100 nm. By arranging the additional layer on the outermost layer, for example, it is possible to cover the first layer and prevent the silver of the first layer from deteriorating under the influence of the atmosphere. Further, when an additional layer is provided in the middle, it can be an antireflection layer that plays a role of improving the visible light transmittance. Note that the additional layer can also have a structure of two or more layers in which different materials are laminated.

<1-6. Protective layer>
When the additional layer is formed on the first layer by sputtering, the target is made of metal such as Sn or Zn. In this case, since the atmosphere in the chamber has a high oxygen concentration, silver may be oxidized when an additional layer is formed after the formation of the first layer. Therefore, when laminating an additional layer after forming the first layer, a protective layer can be laminated prior to the additional layer, thereby protecting the silver of the first layer. The protective layer is thus arranged between the first layer and the additional layer. The protective layer can be formed of, for example, a metal containing zinc, titanium, or the like as a main component, or a material containing a metal oxide as a main component. The thickness of the protective layer is not particularly limited, but can be, for example, 1 to 100 nm. Also, the protective layer may have a structure of two or more layers in which different materials are laminated. In addition, since the material constituting the second layer also serves as a protective layer, when the second layer is arranged between the first layer and the additional layer, this serves as a protective layer. or a protective layer based on a metal oxide is not required. From this point of view, the second layer is sometimes called a protective layer.

<1-7. Aspect of Lamination>
An example of the combination of each layer described above is shown below. In the table below, the order from left to right is the order of the layers laminated to the glass sheet. Table 1 shows an embodiment having one first layer, and Table 2 shows an embodiment having two first layers. However, the present invention is not limited to the following combinations, having at least a first layer and a second layer, with one or more other first and second layers added thereto, or at least one base layer, Additional layers may be provided as appropriate. The numbers in parentheses in the table indicate sputtering atmospheres, which will be described later. Also, for example, pattern 1 in Table 1 has a structure as shown in FIG.

<2. Glass laminate manufacturing method>
Each layer of the glass laminate can be formed by, for example, a sputtering method. The sputtering atmosphere for performing the sputtering method can mainly be the following three types.

(1) First Atmosphere 20% oxygen in the case of forming a metal oxide film, and 20% nitrogen in the case of forming a metal nitride film.
~100% by volume. For example, the additional layer can be formed in this atmosphere. For example, when depositing ZnO, SnO ₂ , etc., if Zn and Sn are set as targets in a chamber, the Zn and Sn released from the targets are oxidized by the atmosphere with a high oxygen concentration, resulting in ZnO and SnO ₂ . is deposited.

(2) Second Atmosphere This is an atmosphere with a very small oxygen concentration. The oxygen content is preferably 10% by volume or less, preferably 5% by volume or less, and preferably 3% by volume or less. Although the lower limit of the oxygen concentration is not particularly limited, it can be, for example, 1% by volume or more. In this atmosphere, for example, the first layer and the second layer can be formed. As described above, by keeping the oxygen concentration low, it is possible to prevent oxidation of silver in the first layer. Oxidation of the silver in the first layer is not preferable because the reflection performance in the infrared region is lowered. In order to form a niobium oxide layer with a small amount of oxygen deficiency or no oxygen deficiency, the oxygen concentration does not have to be high, and may be 10% by volume or less as described above, or even 3% by volume or less. It's okay.

On the other hand, if the oxygen concentration is too low, the resulting niobium oxide film will have a large amount of oxygen deficiency, resulting in a large amount of visible light absorption and a low visible light transmittance. From this point of view, the oxygen concentration is preferably 1% by volume or more. In addition to oxygen, an inert gas such as argon can be contained.

(3) Third Atmosphere An inert gas such as argon is used. For example, the first layer, the second layer, and the protective layer can be formed in this atmosphere. In addition to argon, krypton can also be used, but argon is preferable in consideration of cost.

As described above, there are three kinds of atmospheres for the sputtering method, and different atmospheres require the sputtering method to be performed in different chambers. However, when films are formed in the same atmosphere, films can be formed continuously in the same chamber without changing the chamber. Therefore, a compact facility can be realized. In this case, a plurality of targets to be film-formed are attached in the chamber.

For example, pattern 1 in Table 1 is numbered (2), which means that all layers can be formed in the second atmosphere. Therefore, the number of chambers may be one. Also, in pattern 5 in Table 2, the first three layers are formed in the second atmosphere, the subsequent two layers are formed in the third atmosphere, and finally one layer is formed in the first atmosphere. Therefore, film formation is performed in a total of three chambers.

<3. Features>
As described above, according to the present invention, the following effects can be obtained.
(1) Since niobium oxide or niobium-doped oxide is used as the sputtering target for forming the second layer, the occurrence of arcing during sputtering can be reduced.

(2) Since the second layer of niobium oxide or niobium-doped oxide is provided on the first layer, for example, a necessary protective layer (metal target or ceramic target) when a metal oxide is used as an additional layer is provided. No need to set. Therefore, fewer chambers can be used. As a result, manufacturing equipment can be made compact.

(3) When niobium oxide in an oxygen-deficient state is used as a sputtering target like the second layer, sputtering can be performed in an atmosphere with a low oxygen concentration. Since silver is prevented from being oxidized in such a low oxygen concentration atmosphere, the first layer can be formed by a sputtering method. Therefore, since the first layer and the second layer can be formed in a chamber having the same atmosphere, a compact facility can be realized.

(4) The second layer of niobium oxide (NbOx) preferably has a large value of x, for example, 2.0≦x≦2.5. Thus, when x is 2.0 or more, the amount of absorption of visible light decreases and the transmittance increases.

Examples of the present invention will be described below. However, the present invention is not limited to the following examples.
<A. Examination of the second layer>
A suitable material for the second layer was examined when forming the second layer by a sputtering method. Below, four types of materials, that is, Examples 1 and 2 and Comparative Examples 1 and 2 were prepared as targets.

・Example 1
A material of TiO ₂ and Nb ₂ O ₅ doped with 1% by weight of Nb ₂ O ₅ was used.
・Example 2
NbOx (x=2.3)
・Comparative example 1
A material doped with ZnO and Al ₂ O ₃ in an amount of 2% by weight of Al ₂ O ₃ was used.
・Comparative example 2
A material of ZnO and SnO ₂ doped with SnO ₂ in an amount of 50% by weight was used.

Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated as follows.
(1) Basic Conditions A flat plate target of 127×508 mm was used as the target in the sputtering apparatus. Then, a predetermined gas was flowed into the chamber evacuated to 1×10 ⁻³ Pa or less so that the gas pressure was 1.3 Pa, and a DC power source was used at a power density of 5 W/cm ² for Examples 1 and 2. , the targets according to Comparative Examples 1 and 2 were discharged. The sputtering atmosphere was 100% argon gas.
(2) Occurrence of Arcing Each target was discharged under the above basic conditions, and the total amount of arcing generated during 8 hours of discharge was measured using an arc counter. Frequent occurrence of arcing may cause damage to formed layers or cause generation of particles. As for the evaluation, when arcing occurred 80 times or more in 8 hours, it was evaluated as B because there is a possibility that a defect may occur, and as less than 80 times, it was evaluated as no problem. Also, the actual number of occurrences of arcing is described.

(3) Amount of Particles Generated Each target was discharged under the above basic conditions, and it was confirmed whether or not particles (powder substances) were generated on the target after discharging for 8 hours. When the target is discharged for a long time, the material sputtered and scattered from the target may redeposit on the target surface, and this is thought to be the cause of particle generation. may become As for the evaluation, if no particles were generated on the target, there was no problem and it was evaluated as A, and if particles were generated, it was evaluated as B. In addition, the actual particle amount is also described.

(4) Cracking of target Each target was discharged under the basic conditions described above, and after 8 hours of discharge, it was confirmed whether or not chipping due to cracking of the target had occurred. If the target cracks, more discharge will occur at the cracked portion, and there is a risk that fragments will scatter on the substrate. As for the evaluation, if the target had no cracks, it was rated as A because there was no problem, and if cracks occurred, it was rated as B.

(5) Particles adhering to the target caused by pinhole arcing after film formation may scatter and adhere to the glass plate during film formation. As described above, since the layered film is not completely formed in the portion where the particles are attached, the appearance is different from the portion where the particles are not attached. Specifically, a film dropout defect, that is, a pinhole occurs at a location where particles adhere. Therefore, pinholes were evaluated here. The evaluation method is as follows. First, under the above basic conditions, each target is discharged, and after 8 hours of discharge, the same target is used to form a film on a float glass having a thickness of 6 mm and a size of 300 mm × 300 mm to produce 30 glass laminates. bottom. The structure of the deposited layers was glass (6 mm) / various oxide layers (25 nm) / silver layers (17 nm) / various oxide layers (67 nm) / silver layers (19 nm) / various oxide layers (26 nm). . The conditions for forming the oxide layer are as follows. In addition, the film thickness was adjusted by changing the transport speed.
・Oxygen gas ratio: 2.5%
・Gas thickness: 1.3 Pa
・Input power density: 5 W/cm ²
・Power supply: DC power supply

Then, immediately after the film formation, the glass laminates were placed under illumination of a fluorescent lamp through a diffusion plate, and the presence or absence of pinholes was observed in 30 glass laminates. A pinhole is defined as a point-like film missing defect of 100 μm or more, which is a visually recognizable size.

The results are as follows.

According to the above results, Examples 1 and 2 containing niobium had less arcing. On the other hand, Comparative Examples 1 and 2, which do not contain niobium, exhibited a large amount of arcing. In addition, since almost no particles were generated in the examples, almost no pinholes were generated in the glass laminates produced.

(6) Relationship Between Input Power, Arcing, and Particles The inventors have found that arcing and particles are affected when the power (input power density) applied to the NbOx target changes. Regarding this point, each target was discharged under the following conditions at four types of input power densities, and the total amount of arcing and the amount of particles generated during discharge for 8 hours were measured.
・Oxygen gas ratio: 2.5%
・Gas thickness: 1.3 Pa
・Input power density: 5 W/cm ²
・Power supply: DC power supply ・Target size: 127 x 508mm
・ Target: Example 2 (NbOx (x = 2.3)

The results are as follows.

According to this result, when the applied power density is higher than 5 W/cm ² , the number of occurrences of arcing and the amount of particles increase. Therefore, it was found that it is preferable to set the input power density to 5 W/cm ² or less.

<B. Examination of optical properties of glass laminate>
Next, in order to examine the optical properties of the glass laminate, Examples 3 to 16 and Reference Example were prepared under the following conditions.
(1) A film was formed on a soda-lime glass having a thickness of 6 mm using a magnetron sputtering method to produce glass laminates according to Examples 3 to 16 and Reference Example below.
(2) A predetermined gas was flowed to a gas pressure of 1.3 Pa in a chamber evacuated to 1×10 ⁻³ Pa or less, and a voltage was applied to the target to cause electric discharge. A DC power supply was used to supply power to each target.
(3) The layer structures of Examples 3 to 16 and Reference Examples shown in Tables 4 to 12 below indicate the order of lamination on the glass plate from top to bottom. The table also shows the thickness of each layer and which atmosphere among the first to third atmospheres shown in the above embodiment was used in the chamber. For chambers, layer configurations numbered with the same atmosphere indicate that successive layers were formed in the same chamber. For example, in Example 3, the first three layers (NbOx, Ag, NbOx) are all continuously formed in one chamber in the second atmosphere. As for the NbOx target, in Examples 3 to 11 and 16, x=2.3, and in Examples 12 to 15, x=1.9.

The following evaluations were performed on Examples 3 to 16 and Reference Example formed as described above.
(1) Number of chambers This is the number of chambers used to form all layers.
(2) Visible light transmittance (%)
The transmission spectrum was measured using a spectrophotometer and calculated according to JIS-R3106.
(3) Film surface visible light reflectance (%)
A reflection spectrum was measured using a spectrophotometer from the side where the film was formed, and calculated according to JIS-R3106.
(4) Glass surface visible light reflectance (%)
The transmission spectrum and reflection spectrum were measured using a spectrophotometer from the glass surface opposite to the surface on which the film was formed, and calculated according to JIS-R3106.
(5) Visible light absorption rate (%)
Using the above visible light transmittance T and film surface visible light reflectance Rf, it was calculated by (100-T-Rf).
(6) Emissivity Measured according to JIS JIS-R3106 using a Fourier transform infrared spectrometer.

The results are as follows.

According to Tables 13 and 14 above, NbOx and Ag can be formed in the same chamber in an atmosphere with a low oxygen concentration, so the number of chambers used can be reduced. Therefore, Examples 3 to 15 having such a layer structure have a smaller number of chambers than the Reference Example.

In Examples 9 and 15, the oxygen concentration during the deposition of the first layer of silver is slightly higher than in Examples 3 to 8, so it is considered that the silver is oxidized. Therefore, it is considered that the emissivity is low because the reflection performance of light in the infrared region is lowered. In addition, it is considered that the absorption rate of visible light by the silver of the first layer is also increased along with this.

In Example 11, since the oxygen concentration was considerably high when the film of silver as the first layer was formed, it is considered that the oxidation of silver proceeded greatly. Therefore, the emissivity is remarkably high.

In addition, in Examples 10 and 12, the oxygen concentration when forming the second layer of niobium oxide was lower than in Examples 3 to 8 (because it was zero), so the niobium oxide film was The amount of oxygen vacancies is too large, resulting in high absorption of visible light. As a result, the visible light transmittance is low. In particular, in Example 12, the amount of oxygen deficiency in NbOx, which is the second layer, is larger than in Example 10 (x=1.9), so the visible light transmittance is even lower than in Example 10.

Further, when comparing Example 7 and Example 13, which have the same conditions except for the amount of oxygen deficiency in NbOx in the second layer, Example 13 has a larger amount of oxygen deficiency than Example 7 (x=1. 9) The visible light absorptance is higher than that of Example 7, and the visible light transmittance is lower. This is the same for Examples 6 and 14, and Examples 9 and 15, which have the same conditions other than the amount of oxygen deficiency in NbOx. Thus, it was found that when the amount of oxygen deficiency in NbOx increased, the visible light absorptance in the second layer increased and the visible light transmittance decreased.

In Example 16, a metal (ZnAl) protective layer was used, and this was deposited in the same chamber and atmosphere as the first and second layers, but it was found that the optical properties were hardly affected.

Claims (9)

A method for manufacturing a glass laminate for light transmission, comprising:
forming a first layer containing silver or a silver alloy on a glass plate by a sputtering method;
forming a second layer containing niobium oxide on the first layer by a sputtering method;
with
The oxygen concentration in the sputtering atmosphere during the formation of the first layer is 1% by volume or more and 10% by volume or less,
A method for producing a glass laminate , wherein the second layer contains a niobium oxide represented by NbOx (2.3≦x≦2.5) . The method for producing a glass laminate according to claim 1, wherein the oxygen concentration in the sputtering atmosphere during formation of the first layer is 3% by volume or less. The manufacturing method of the glass laminated body of Claim 1 or 2 which performs formation of the said 1st layer and 2nd layer by the said sputtering method within the same chamber. 4. The method of any one of claims 1 to 3, further comprising forming a base layer containing a metal oxide or metal nitride on the glass plate prior to forming the first layer. A method for manufacturing a glass laminate. The method for producing a glass laminate according to claim 4, wherein the metal oxide is niobium oxide or niobium-doped oxide, and the metal nitride is niobium nitride or niobium-doped nitride. 5. The method according to claim 4, wherein the metal oxide is zinc oxide, tin oxide, or a metal oxide containing these as main components, and the metal nitride is silicon nitride or a metal nitride containing silicon nitride as a main component. A method for producing the described glass laminate. The method for producing a glass laminate according to any one of claims 4 to 6, wherein said metal oxide or metal nitride and said first layer are adjacent to each other. The method for manufacturing a glass laminate according to any one of claims 1 to 7, further comprising the step of forming a protective layer containing metal or metal oxide on said first layer. The manufacturing method of the glass laminated body in any one of Claim 1 to 8 which repeats formation of a said 1st layer and a 2nd layer in multiple times.

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