JP2011063500A - Heat ray shielding laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat ray shielding laminated film in which, in depositing a metallic film such as a ZnO film, the problem in the deposition of nodules and waste caused in a target is improved. <P>SOLUTION: The heat ray shielding laminated film is formed on a substrate through a vapor deposition process. The heat ray shielding laminated film is obtained, on a substrate, by successively depositing at least a transparent oxide film layer, a precious metal film layer and a precious metal protective film layer. The transparent oxide film layer includes a Zn<SB>x</SB>Sn<SB>y</SB>O<SB>z</SB>film (x, y and z are positive rational numbers). In the Zn<SB>x</SB>Sn<SB>y</SB>O<SB>z</SB>film, the value expressed by Sn/(Zn+Sn) in a relation between Sn and Zn included in the film is 5 to 20 wt.%, and the precious metal film layer is made of an Ag film or a film essentially composed of Ag. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a heat ray shielding laminated film mainly used for multilayer glass and laminated glass.

  A heat ray shielding laminated film (hereinafter sometimes referred to as a Low-E film) is a laminated film having a function of reflecting heat rays, and is used for window glass for vehicles, buildings, etc. A specific wavelength portion of sunlight irradiated inside the vehicle or the room is shielded to suppress a temperature rise in the vehicle or the room, thereby reducing the load on the cooling device. The glass on which the Low-E film is formed is called Low-E glass, and has a lower ultraviolet transmittance than a commonly used float glass window glass, and reduces sunburn of indoor furniture. Is effective.

  In general, as the Low-E film, a thin film laminate having a structure in which a dielectric film, a metal film, and a dielectric film are sequentially laminated on a substrate is widely used. As an excellent metal film of a heat ray shielding film, one using an Ag film is well known. For example, a thin film laminate in which a ZnO film and an Ag film are sequentially laminated on a substrate is widely used.

  As a method for forming a Low-E film on a substrate, a sputtering method is widely adopted from the viewpoint of productivity, and various studies have been made to improve the productivity of a metal oxide film such as a ZnO film. ing. For example, Patent Document 1 discloses a method for improving productivity by controlling generation of nodules and abnormal discharge on the target surface by periodically supplying indirect power to the target. Patent Document 2 discloses a thin film obtained by using a ZnO target having a relative density of 80% or more and adding a trivalent or higher positive element to the target in order to improve the film formation rate. Yes. Also in the present applicant, Patent Document 3 discloses a ZnO film in which the deposition rate is improved by using a mixed gas atmosphere in the vacuum chamber during film formation.

Japanese Patent Laid-Open No. 8-53761 JP 2009-62618 A JP-T-2004-323941

  When forming a metal film such as a ZnO film, black or brown microprojections (hereinafter sometimes referred to as nodules) are generated on the target surface, and stable discharge cannot be performed, or the non-erosion portion of the target In addition, there may be a problem that particles or flakes are deposited on the target adjacent portion. When the above problem occurs, a product defect is caused, resulting in a decrease in productivity.

  Further, when a specific dissimilar metal is added to the ZnO film, the ultraviolet transmittance may be rapidly increased.

  Therefore, an object of the present invention is to provide a heat ray shielding laminated film that improves the above-described problems and has a low ultraviolet transmittance.

  As a result of intensive studies to solve the above-mentioned problems, the present applicant uses the ZnO film to which a different metal is added as the transparent oxide film, thereby improving the aforementioned defects such as nodules and deposited debris. I found. Further, as a result of further studies, it has been shown that when Al is added to the ZnO film, the ultraviolet transmittance is rapidly increased. By using Sn as the dissimilar metal to be added, the above-mentioned problems can be solved, and ultraviolet transmission can be achieved. It was revealed that a heat ray shielding laminated film excellent in the moisture resistance of the Ag layer of the metal layer can be obtained without impairing the rate.

That is, the present invention is a heat ray shielding laminated film formed on a substrate through a vacuum film forming process, and the heat ray shielding laminated film comprises at least a transparent oxide film layer, a noble metal film layer, and a noble metal protective film on the substrate. The transparent oxide film layer has a Zn _x Sn _y O _z film (x, y, z are positive rational numbers), and the Zn _x Sn _y O _z film is formed on the film. The value represented by Sn / (Zn + Sn) of Sn and Zn contained is 5 to 20 wt%, and the noble metal film layer is composed of an Ag film or a film containing Ag as a main component. It is a membrane.

In the present invention, the above Zn _x Sn _y O _z film has a value represented by Sn / (Zn + Sn) of Sn and Zn contained in the film of 5 to 20 wt%, and less than 5 wt%. Defects such as nodules and deposited debris cannot be improved, and if it exceeds 20 wt%, the ultraviolet transmittance increases. In addition, it is good also as 10-18 wt% more preferably.

  Further, in the heat ray shielding laminated film of the present invention, the noble metal protective film layer has a Zn film to which Al is added, and from the viewpoint of improving moisture resistance, Al / Zn of Al and Zn contained in the film is included. The value represented by (Zn + Al) is 1 to 10 wt%.

In the heat ray shielding laminated film of the present invention, the SnO _x film is provided on the opposite side of the noble metal protective film layer farthest from the substrate to the substrate.

Further, when manufacturing the heat ray shielding laminated film of the present invention, characterized in that it comprises step manufacturing process, the forming a Zn _x Sn _y O _z layer with Zn-Sn alloy target containing Zn and Sn.

  In the Zn—Sn alloy sputtering target, the value represented by Sn / (Zn + Sn) of Sn and Zn contained in the target is 5 to 20 wt%, preferably 10 to 18 wt%. If the above value is less than 5 wt%, defects such as nodules and deposited debris cannot be improved, and if it exceeds 20 wt%, the ultraviolet ray transmittance of the formed heat ray shielding laminated film becomes high.

In the present invention, by using a Zn _x Sn _y O _z film as a transparent oxide film layer, it has become possible to improve generation of defects such as nodules and deposited debris during film formation. Moreover, the heat ray shielding laminated film of the present invention achieves both high visible light transmittance and low ultraviolet transmittance, and exhibits excellent heat shielding properties when used as a Low-E film or the like. Furthermore, it has been clarified that the heat ray shielding laminated film of the present invention is a film excellent in moisture resistance of the Ag layer.

It is the top view which showed the outline of the sputtering device. It is sectional drawing which shows the outline of a heat ray shielding laminated film.

  As the substrate, various plate glasses such as soda lime glass and aluminosilicate glass (for example, float plate glass), colored glass such as bronze, gray, blue and green (for example, float colored glass), or transparent such as polymethyl methacrylate and polycarbonate It can be selected from resin substrates, and it can be used for various types of glass such as bent glass, tempered glass, strength-enhanced glass, glass with a film such as a base film layer, or netted glass. Can be adopted.

  Further, as shown in FIG. 2, the present invention is a heat ray shielding laminated film in which at least a transparent oxide film layer, a noble metal film layer, and a noble metal protective film layer are sequentially laminated on a substrate. Further, two or more noble metal film layers such as a transparent oxide film layer, a noble metal film layer, a noble metal protective film layer, a transparent oxide film layer, a noble metal film layer, and a noble metal protective film layer are laminated on the substrate. Also good. In the heat ray shielding laminated film laminated as described above, a noble metal protective film layer may be interposed between the transparent oxide film layer and the noble metal film layer, and the heat ray shielding laminated film laminated as described above A transparent oxide film layer is preferably laminated on the outermost layer on the side opposite to the substrate. The “on the substrate” may be on the substrate, and another film is interposed between the substrate and the transparent oxide film layer as long as the characteristics of the heat ray shielding laminated film of the present invention are not impaired. It does not matter even if it does.

The transparent oxide film layer is a layer formed by laminating two or more layers of a Zn _x Sn _y O _z film alone or a Zn _x Sn _y O _z film and another metal film. The metal film includes, for example, a transparent oxide film such as ZnO _x , SnO _x , TiO _x , Zn _x Al _y O _z , Zn _x Ti _y O _z , a nitride film such as SiN _{x, and the} like as a main component. Preferably, a ZnO _x film, a SnO _x film, a Zn _x Al _y O _z film, a TiO _x film, or a SiN _x film may be used.

The film thickness of the transparent oxide film layer may be about 1200 mm or less, preferably about 150 mm or more and 1000 mm or less. Furthermore, in the heat ray shielding laminated film of the present invention, a SnO _x film is provided on the opposite side of the noble metal protective film layer farthest from the substrate, and the SnO _x film has a thickness of 10 mm or more. preferable.

  The noble metal film layer is composed of an Ag film or a noble metal film containing Ag as a main component, and the noble metal film includes, for example, a different metal such as Au, Cu, Pt, or Ir containing Ag as a main component. It may be a thing.

  The thickness of the noble metal film layer may be about 200 mm or less, preferably about 50 mm or more and 150 mm or less.

  The noble metal protective film layer is a film containing at least one selected from Zn, Ti, Ni—Cr, Zn—Al, Ni—Cr—O, Ti, Zr, Cr, Al, SUS, and Ta as a main component. In particular, it is preferable to use a Zn—Al film. The Zn—Al film is a film having Zn and Al, and the value represented by Al / (Zn + Al) of Zn and Al in the film is 1 to 10 wt%. Moreover, it is good also as 4-10 wt% preferably.

  Further, the film thickness of the noble metal layer protective film layer is preferably 10 mm or more, and preferably 13 mm or more and 100 mm or less in consideration of the function and productivity as a barrier layer for protecting the noble metal film layer. When the thickness of the noble metal protective film layer is increased, the visible light transmittance is lowered. Therefore, the thickness of the noble metal protective film layer is more preferably 15 to 30 mm.

  As the film forming apparatus, a magnetron sputtering apparatus as shown in FIG. 1 is preferably used. After holding the glass 3 on the substrate holder 2, the inside of the vacuum chamber 8 is evacuated by the vacuum pump 5, and the vacuum pump 5 is continuously operated during the film formation, and the atmosphere gas in the vacuum chamber is the gas introduction pipe 7. The gas flow rate is controlled and adjusted by a mass flow controller (not shown). Note that the base holder 2 is installed in front of the target 1. The pressure in the vacuum chamber during film formation is adjusted by controlling the opening degree of the valve 6 installed between the vacuum chamber and the vacuum pump and changing the gas flow rate. Using the target 1 with the magnet 4 arranged on the back side, the power is supplied to the target through the power cord 9.

When forming the Zn _x Sn _y O _z film, a Zn—Sn alloy target having Zn and Sn is used. At this time, the gas introduced into the vacuum chamber is preferably a reactive gas such as O ₂ , CO ₂ , CO, N ₂ , and the above gas contains Ar, A gas such as Xe, Ne, or Kr may be added to form a mixed gas.

  Further, when the noble metal film layer constituting the heat ray shielding laminated film is one layer, it is preferable that the ultraviolet transmittance of the thermal battle shielding laminated film is 40% or less, and the noble metal film layer is two layers. At this time, it is preferable that the thermal transmittance shielding laminated film has an ultraviolet transmittance of 25% or less.

  The heat ray-shielding laminated film of the present invention, particularly those using glass as the substrate, is most preferably used as a multi-layer glass as a low-E glass having a low-E film formed thereon, and is useful as a multi-layer window glass for construction. However, it can also be used as a double-glazed window glass for automobiles and laminated glass for automobiles, and can also be used as a double-glazed window glass for ships and aircrafts. In addition to double-layer glass, laminated glass, bent glass, etc. may be used as a single plate in some cases. The above-mentioned low radiation multi-layer glass is a window glass in which mainly two glasses are combined through a spacer, a dry air layer is formed between the glasses, and a Low-E film is formed on the glass surface in contact with the dry air layer. It is. The low-radiation double-glazed glass is a window glass that helps to save energy by reflecting solar heat flowing from the outdoor to the indoor in the summer through the window glass, and heating and cooling heat flowing from the indoor to the outdoor in the winter. Is preferably used.

Generally, when a heat ray shielding laminated film is used with the above-mentioned multilayer glass, laminated glass, single plate glass, etc., after the heat ray shielding laminated film was formed on the single plate glass, it passed through processes such as storage, transportation, and washing. Later, it is incorporated into each product. On the other hand, the Ag film widely used as the metal film of the heat ray shielding laminated film is likely to cause defects due to moisture, peeling of the film, etc., and is inferior in moisture resistance. During the process, film defects and peeling may occur. The heat ray reflective laminated film of the present invention uses Zn _x Sn _y O _z as a transparent oxide film layer, and is a film excellent in moisture resistance, so it is possible to suppress the occurrence of defects in the manufacturing process. Yes, it is suitably used as Low-E glass.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the embodiment.
1. Example 1 for evaluation of defects during formation of transparent oxide film
After setting a Zn—Sn target (Sn / (Zn + Sn) = 12 wt%) in the vacuum chamber and degassing the vacuum chamber of the DC magnetron sputtering apparatus to about 5 × 10 ⁻⁴ Pa with a vacuum pump The gas was introduced so that the volume of the mixed gas was Ar: O ₂ = 2: 8, and the pressure in the chamber was adjusted to 0.3 Pa. A clear soda lime glass substrate (thickness: 3 mm) was placed in the apparatus, and a Zn _x Sn _y O _z film was formed on the glass substrate.

Comparative Examples 1-7
The target to be installed in the vacuum chamber is a Zn—Sn target (Sn / (Zn + Sn) = 30 wt%: Comparative example 1, 2 wt%: Comparative example 4), Zn target (Comparative example 2), Sn target (Comparative example) 3), except that the Zn—Al target (Al / (Zn + Al) = 1 wt%: Comparative Example 5, 2 wt%: Comparative Example 6, 4 wt%: Comparative Example 7) was used. The Zn _x Sn _y O _z film (Comparative Examples 1 and 4), the ZnO _x film (Comparative Example 2), the SnO _x film (Comparative Example 3), the Zn _x Al _y O _z film ( Comparative examples 5 to 7) were formed.

[Evaluation of nodules and particle debris]
The output power of the DC power source was set to 2.2 kW / cm ^2, and energized for about 12 hours, and generated nodules and particle dust were observed. The results are shown in Table 1, where no nodules or particle debris was observed, and ◯ was observed.

  From Example 1 and Comparative Examples 1 to 7, the Zn target is more likely to produce nodules and particle debris than the Sn target, and the generation of nodules and particle debris is suppressed as Sn or Al is added to the Zn target. I found out that

2. Preparation of heat ray shielding laminated film Example 2
After degassing the vacuum chamber of the DC magnetron sputtering apparatus to about 5 × 10 ⁻⁴ Pa with a vacuum pump, the gas is introduced so that the volume of the mixed gas becomes Ar: O ₂ = 2: 8. Was adjusted to 0.3 Pa. Using a Zn—Sn target (Sn / (Zn + Sn) = 12 wt%), a first Zn _x Sn _y O _z film having a thickness of 170 mm is formed on a clear soda-lime glass substrate (thickness: 3 mm). Deposited as a layer. Next, the gas in the vacuum chamber is changed to Ar gas, the pressure in the chamber is adjusted to 0.3 Pa, an Ag target is used to form a 108 Å Ag film as the second layer, and then Zn—Al Using a target (Al / (Zn + Al) = 4 wt%), a 20-inch Zn _x Al _y layer was formed as a third layer. Next, the gas in the chamber is changed so that the volume of the mixed gas becomes Ar: O ₂ = 2: 8, the pressure in the chamber is adjusted to 0.3 Pa, and under the same conditions as in the first layer, 450 Ｚｎ Zn _{The x} Sn _y O _z layer was formed as a fourth layer. Next, a SnO _x layer having a thickness of 50 mm was formed as a fifth layer using a Sn target to obtain a heat ray shielding laminated film.

Example 3
Except that a Zn _x Sn _{y Oz} film having a thickness of 120 mm was formed on a clear soda-lime glass substrate and then a Zn-Al target (Al / (Zn + Al) = 4 wt%) was used. A 50-thick Zn _x Al _y O _z film was formed as the second layer under the same conditions as the first layer in Example 2, and then the third layer, the fourth layer, the fifth layer, and the sixth layer were respectively formed in the examples. Films were formed under the same conditions as those for the second layer, the third layer, the fourth layer, and the fifth layer of No. 2 to obtain a heat ray shielding laminated film.

Example 4
On the clear soda-lime glass substrate, the first layer, the second layer, the third layer, and the fourth layer are in the same conditions as the first layer, the second layer, the third layer, and the fourth layer of Example 3, respectively. Then, each film is formed with the same film thickness, and then the fifth layer is formed to be 50 mm under the same conditions as the second layer of Example 3, and then the sixth layer and the seventh layer are respectively formed. Under the same conditions as those of the fourth layer and the fifth layer in Example 2, films were formed so as to be 400 mm and 50 mm, respectively, and a heat ray shielding laminated film was obtained.

Example 5
On a clear soda-lime glass substrate, under the same conditions as the first layer, the second layer, the third layer, and the fourth layer of Example 2, the first layer is 290 mm, the second layer is 100 mm, the third layer The film was formed to a thickness of 16 mm as the fourth layer and 700 mm as the fourth layer, and then the fifth layer, the sixth layer, the seventh layer, and the eighth layer were respectively formed as the second layer and the third layer of Example 2. Under the same conditions as those of the fourth layer and the fifth layer, films were formed to have a thickness of 115 mm, 16 mm, 270 mm, and 50 mm, respectively, to obtain a heat ray shielding laminated film.

Example 6
On a clear soda-lime glass substrate, 240 Å as the first layer and as the second layer under the same conditions as the first layer, the second layer, the third layer, the fourth layer, and the fifth layer of Example 3 50 mm, 100 mm as the third layer, 16 mm as the fourth layer, 650 mm as the fifth layer, and then the sixth layer, the seventh layer, the eighth layer, the ninth layer, the tenth layer Are formed to be 50 mm, 115 mm, 16 mm, 270 mm, and 50 mm, respectively, under the same conditions as the second layer, third layer, fourth layer, fifth layer, and sixth layer of Example 3. As a result, a heat ray shielding laminate was obtained.

Comparative Example 8
Five layers were laminated on a clear soda lime glass substrate to obtain a heat ray shielding laminate. Under the same conditions as the first layer of Example 2, except that the first layer and the fourth layer were formed using a cathode provided with a Zn-Al target (Al / (Zn + Al) = 4 wt%). The films were formed to be 170 mm and 450 mm, respectively. The second layer, the third layer, and the fifth layer were respectively formed under the same conditions as the second layer, the third layer, and the fifth layer of Example 2, and the heat ray shielding laminate of Comparative Example 8 was formed. Obtained.

Comparative Example 9
Four layers were laminated on a clear soda lime glass substrate to obtain a heat ray shielding laminate. The first layer and the fourth layer were formed to have a thickness of 170 mm and 500 mm, respectively, under the same conditions as the fifth layer of Example 2. The second layer and the third layer were formed under the same conditions as the second layer and the third layer of Example 2, respectively, and a heat ray shielding laminate of Comparative Example 9 was obtained.

Comparative Example 10
Five layers were laminated on a clear soda lime glass substrate to obtain a heat ray shielding laminate. The first and fourth layers have the same conditions as those of the first layer of Example 2 except that the first layer and the fourth layer are formed using a cathode provided with a Zn—Sn target (Sn / (Zn + Sn) = 30 wt%). Thus, films were formed to be 170 mm and 450 mm, respectively. The second layer, the third layer, and the fifth layer were respectively formed under the same conditions as the second layer, the third layer, and the fifth layer of Example 2, and the heat ray shielding laminate of Comparative Example 10 was formed. Obtained.

Comparative Example 11
Eight layers were laminated | stacked on the clear soda-lime glass substrate, and the heat ray shielding laminated body was obtained. The first layer, the fourth layer, and the seventh layer are the first layer of Example 2 except that the first layer, the fourth layer, and the seventh layer are formed using a cathode provided with a Zn—Al target (Al / (Zn + Al) = 4 wt%). The film was formed to be 290 mm, 700 mm, and 270 mm respectively under the same conditions as those described above. The second layer, the third layer, the fifth layer, the sixth layer, and the eighth layer are respectively the same conditions as the second layer, the third layer, the fifth layer, the sixth layer, and the eighth layer of the fifth embodiment. Each was formed into a film to obtain a heat ray shielding laminate of Comparative Example 11.

Comparative Example 12
Eight layers were laminated | stacked on the clear soda-lime glass substrate, and the heat ray shielding laminated body was obtained. The first layer, the fourth layer, and the seventh layer are the first layer of Example 2 except that the first layer, the fourth layer, and the seventh layer were formed using a cathode provided with a Zn—Sn target (Sn / (Zn + Sn) = 30 wt%). The film was formed to be 290 mm, 700 mm, and 270 mm respectively under the same conditions as those described above. The second layer, the third layer, the fifth layer, the sixth layer, and the eighth layer are respectively the same conditions as the second layer, the third layer, the fifth layer, the sixth layer, and the eighth layer of the fifth embodiment. Each film was formed to obtain a heat ray shielding laminate of Comparative Example 12.

3. Evaluation of heat ray shielding laminate The following evaluation was performed on the heat ray shielding laminates obtained in Examples 2 to 6 and Comparative Examples 8 to 12, and Table 2 shows the results.

[Optical performance]
Using a spectrophotometer U-4100 (manufactured by Hitachi High-Technology Corporation), the transmittance in the wavelength range of 300 to 2500 nm was measured. Using the result, the visible light transmittance was calculated based on JIS R 3106, and the ultraviolet transmittance was calculated based on ISO9050.

[Moisture resistance test]
The heat ray shielding laminate formed on the glass was stored in an environmental tester at 30 ° C. and 90% Rh for 2 weeks, and the number of points of deterioration such as point defects (0.3 mmφ or more) was visually counted. As a result, the case where the number of generated defects was 10 or less per 1 m ² was evaluated as ◯, the case of 11 to 20 as Δ, and the case of 21 or more as x.

From Examples 2 to 6 and Comparative Examples 8 to 12, all visible light transmittances were excellent, and Zn _x Sn _y O _z having a Sn content of 20 wt% or less was used as the transparent oxide film layer. In this case, both ultraviolet light transmittance and moisture resistance were excellent. On the other hand, when Zn _x Al _y O _z is used instead of Zn _x Sn _y O _z , the moisture resistance is excellent, but the ultraviolet light transmittance is deteriorated. Further, when SnO _x is used instead of Zn _x Sn _y O _z , both the ultraviolet light transmittance and the moisture resistance deteriorate. Further, Sn content of the transparent oxide film layer is the use of 30 wt% of _Zn x _Sn y _{O z,} ultraviolet light transmittance, moisture resistance, and that both deteriorated.

From the above, by using Zn _x Sn _y O _z with a Sn content of 5 to 20 wt% as the transparent oxide film layer, heat ray shielding excellent in visible light transmittance, ultraviolet light transmittance, and moisture resistance is achieved. It became clear that it became possible to obtain a laminated body.

DESCRIPTION OF SYMBOLS 1 Target 2 Base material holder 3 Glass 4 Cathode magnet 5 Vacuum pump 6 On-off valve 7 Gas introduction pipe 8 Vacuum chamber 9 Power supply cord 10 DC power supply 11 Backing plate 12 Transport roll 13 Transparent oxide film layer 14 Precious metal film layer 15 Precious metal protective film layer

Claims (7)

A heat ray shielding laminated film formed through a vacuum film forming process on a substrate, and the heat ray shielding laminated film is obtained by sequentially laminating at least a transparent oxide film layer, a noble metal film layer, and a noble metal protective film layer on the substrate. The transparent oxide film layer has a Zn _x Sn _y O _z film (x, y, z are positive rational numbers), and the Zn _x Sn _y O _z film contains Sn and Zn contained in the film. The heat ray shielding laminated film is characterized in that the value represented by Sn / (Zn + Sn) is 5 to 20 wt%, and the noble metal film layer is composed of an Ag film or a film containing Ag as a main component. The noble metal protective film layer has a Zn film to which Al is added, and a value represented by Al / (Zn + Al) of Al and Zn contained in the film is 1 to 10 wt%. The heat ray shielding laminated film according to claim 1. 3. The heat ray shielding laminated film according to claim 1, further comprising a SnO _x film on the opposite side of the noble metal protective film layer farthest from the substrate to the substrate. 4. The ultraviolet ray transmittance of the thermal warpage shielding laminated film is 40% or less when the precious metal film layer constituting the heat ray shielding laminated film is one layer, according to any one of claims 1 to 3. The heat ray shielding laminated film as described. 5. The ultraviolet ray transmittance of the thermal battle shielding laminated film is 25% or less when the noble metal film layer constituting the heat ray shielding laminated film is two layers. The heat ray shielding laminated film as described. Method for manufacturing a heat ray shielding laminated film according to any one of claims 1 to 5, the step of forming a Zn _x Sn _y O _z layer with Zn-Sn alloy sputtering target containing Zn and Sn The manufacturing method of the heat ray shielding laminated film characterized by including these. The heat-shielding laminated film according to claim 6, wherein the Zn-Sn alloy sputtering target has a value represented by Sn / (Zn + Sn) of Sn and Zn contained in the target of 5 to 20 wt%. Manufacturing method.

Images