WO2014109369A1

WO2014109369A1 - Laminated body and multi-layered glass

Info

Publication number: WO2014109369A1
Application number: PCT/JP2014/050248
Authority: WO
Inventors: すすむ鈴木; 史栄坂本; 秀文小高
Original assignee: 旭硝子株式会社
Priority date: 2013-01-11
Filing date: 2014-01-09
Publication date: 2014-07-17

Abstract

A laminated body including a transparent substrate and a laminated film that is provided upon the transparent substrate. The laminated film includes, in order from the transparent substrate side, a first dielectric layer, a silver layer, a light-absorbing layer, and a second dielectric layer. The first dielectric layer has a refractive index of 1.9-2.1 and a geometrical thickness of 20-30nm. The silver layer includes silver as a main component and has a geometrical thickness of 11-18nm. The light-absorbing layer has a geometrical thickness of 1-6nm. The second dielectric layer has a refractive index of 1.9-2.1 and a geometrical thickness of 35-48nm.

Description

Laminate and double glazing

The present invention relates to a laminate and a multi-layer glass, and more particularly, to a multi-layer glass having one silver layer, good thermal insulation and obtaining specific optical characteristics, and a multi-layer glass using the same.

The silver layer has a neutral color (neutral color) in the visible and transmitted colors and a low resistivity. For example, when the thickness is about 10 nm, there is little absorption in the visible range, and the reflectance is several tens of percent. The reflectance increases as the wavelength becomes longer, and shows a high reflectance in the infrared region.

A silver multilayer film with a silver layer sandwiched between dielectric layers with low reflectivity in the visible range and high reflectivity in the infrared range shows the same appearance as general glass, and has low emissivity and high heat ray reflectivity. Show. Therefore, the silver-based multilayer film is used for highly heat-insulating Low-E glass and heat ray reflective glass having high transmittance in the visible light region. In recent years, with the growing awareness of energy saving, the demand for these glasses has increased.

A silver-based multilayer film having two silver layers is known (for example, see Patent Document 1). Moreover, what has two silver layers and a light absorption layer is known as a silver type multilayer film (for example, refer patent document 2, 3).

US Pat. No. 6,576,349 US Pat. No. 7,687,149 US Pat. No. 7,706,641

As described above, a silver multilayer film having two silver layers is known. Those having two silver layers have good heat shielding properties because the thickness of the silver layer is increased as a whole, but the productivity is not necessarily good because of the increased number of layers. On the other hand, those having one silver layer have good productivity because the number of laminated layers is small, but the heat shielding property is not necessarily good only with a thin silver layer.

Also, in application to window glass, not only has good heat shielding properties, but also has specific visible light transmittance and visible light reflectance from the viewpoint of use place, usage, design, etc., and transmitted light It is also required that the reflected light has a specific color tone.

The present invention has been made in order to solve the above-mentioned problems, and has one silver layer, has good heat shielding properties, and has a good appearance by obtaining specific optical characteristics. The purpose is to provide the body. Another object of the present invention is to provide a multi-layer glass using such a laminate.

The laminate of the present invention has a transparent substrate and a laminated film provided on the transparent substrate. The laminated film has a first dielectric layer, a silver layer, a light absorption layer, and a second dielectric layer in order from the transparent substrate side. The first dielectric layer has a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm. The silver layer is mainly composed of silver and has a geometric thickness of 11 to 18 nm. The light absorbing layer has a geometric thickness of 1 to 6 nm. The second dielectric layer has a refractive index of 1.9 to 2.1 and a geometric thickness of 35 to 48 nm.

The multilayer glass of the present invention has the above-described laminate of the present invention and a counter substrate disposed on the laminate film side of the laminate.

The laminated body of the present invention comprises, as a laminated film, a first dielectric layer having a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm in order from the transparent substrate side, and silver as a main component. A silver layer having a geometric thickness of 11-18 nm, a light-absorbing layer having a geometric thickness of 1-6 nm, and a refractive index of 1.9-2.1 and a geometric thickness of 35-48 nm A second dielectric layer having a thickness. Thereby, even if it has one silver layer, heat-shielding property can be made favorable, a specific optical characteristic can be acquired, and an external appearance can be made favorable.

Sectional drawing which shows one Embodiment of a laminated body. Sectional drawing which shows the 1st structural example of a laminated body. Sectional drawing which shows the 2nd structural example of a laminated body. Sectional drawing which shows the 3rd structural example of a laminated body. Sectional drawing which shows one Embodiment of multilayer glass. The figure which shows a ^* b ^* of the transmitted light of Example 1,2. The figure which shows a ^* b ^* of the reflected light (board | substrate side) of Example 1,2. The figure which shows a ^* b ^* of the reflected light (film | membrane side) of Example 1,2. The figure which shows a ^* b ^* of the transmitted light of Example 3. FIG. The figure which shows a ^* b ^* of the reflected light (board | substrate side) of Example 3. FIG. The figure which shows a ^* b ^* of the reflected light (film | membrane side) of Example 3. FIG.

Hereinafter, embodiments of the laminate of the present invention will be described.
FIG. 1 is a cross-sectional view showing an embodiment of a laminate.

The laminate 10 has a transparent substrate 11 and a laminate film 12 provided on the transparent substrate 11. The laminated film 12 includes a first dielectric layer 13, a silver layer 14, a light absorbing layer 15, and a second dielectric layer 16 in order from the transparent substrate 11 side.

The first dielectric layer 13 has a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm. The silver layer 14 is mainly composed of silver and has a geometric thickness of 11 to 18 nm. The light absorption layer 15 has a geometric thickness of 1 to 6 nm. The second dielectric layer 16 has a refractive index of 1.9 to 2.1 and a geometric thickness of 35 to 48 nm. In addition, the refractive index in this invention means the refractive index in wavelength 550nm.

The laminate 10 is roughly divided into a non-heat treated product and a heat treated product. Here, the non-heat-treated product is simply a laminated film 12 formed into a final product in the final form, and no heat treatment for strengthening or bending is performed after the film formation. The heat-treated product is subjected to a heat treatment for strengthening or bending after the formation of the laminated film 12 to be a final product in a final form. The laminate 10 may be either a non-heat treated product or a heat treated product.

The above geometric thicknesses are all in the finished product. In the case of a non-heat-treated product, the geometric thickness is after the formation of the laminated film 12, and in the case of a heat-treated product, after the formation of the laminated film 12. After heat treatment for strengthening or bending performed. Hereinafter, the thickness is assumed to be a geometric thickness unless otherwise specified.

The transparent substrate 11 is not particularly limited. For example, a glass plate having an inorganic transparency such as a window glass for buildings, a commonly used float glass, or a soda-lime glass manufactured by a roll-out method is used. Can be used. As the glass plate, colorless ones such as clear glass and high transmission glass and green ones such as heat ray absorbing glass can be used. In consideration of visible light transmittance, colorless glass such as clear glass and high transmittance glass is preferable among them. Various tempered glasses such as air-cooled tempered glass and chemically tempered glass can also be used. Furthermore, various glasses such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used. The thickness of the transparent substrate 11 is not necessarily limited, but is preferably 0.5 to 20 mm, for example.

The first dielectric layer 13 is provided in order to adjust the reflectance in the visible range and the like by the optical interference effect so that the optical characteristics of the laminate 10 become desired characteristics. The first dielectric layer 13 has a refractive index of 1.9 to 2.1. By setting it as such a refractive index, the reflectance etc. in a visible region are adjusted with a light interference effect, and the optical characteristic of the laminated body 10 can be made into a desired characteristic.

The first dielectric layer 13 has a thickness of 20 to 30 nm. By setting the thickness of the first dielectric layer 13 within the above range, the optical characteristics of the stacked body 10 can be adjusted to desired characteristics by adjusting the reflectance in the visible range by the optical interference effect. The thickness of the first dielectric layer 13 is preferably 21 nm or more, more preferably 22 nm or more, and further preferably 23 nm or more. The thickness of the first dielectric layer 13 is preferably 29 nm or less, more preferably 28 nm or less, and even more preferably 27 nm or less.

The constituent material of the first dielectric layer 13 is not particularly limited as long as it is a dielectric having the above refractive index, and includes various oxides and nitrides. Examples of the oxide include an oxide mainly composed of an oxide of at least one element selected from zinc, tin, niobium, and titanium. Examples of the nitride include those containing as a main component a nitride of at least one element selected from silicon and aluminum.

As the oxide, aluminum zinc oxide and tin zinc oxide are particularly preferable. The aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum. The tin zinc oxide is preferably one in which the ratio of tin to the total amount of zinc and tin is 10 to 80% by mass, and more preferably 20 to 80% by mass.

Note that the first dielectric layer 13 is not necessarily limited to a single-layer structure composed of one kind of dielectric layer, but may be a laminated structure in which two or more kinds of dielectric layers are laminated, although not shown. In the case of a laminated structure, the refractive indexes of the individual dielectric layers are not necessarily the same, and may be different as long as they are within the refractive index range of 1.9 to 2.1.

In the case of a single layer structure, aluminum zinc oxide is preferred. The aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum. By using aluminum zinc oxide, the crystallinity of the silver layer 14 can be improved when the silver layer 14 is formed thereon.

In the case of a laminated structure, the layer disposed at the position closest to the silver layer 14 is preferably aluminum zinc oxide. The aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum. By using aluminum zinc oxide as the layer disposed closest to the silver layer 14, the crystallinity of the silver layer 14 can be effectively improved when the silver layer 14 is formed thereon. In this case, the thickness of the aluminum zinc oxide is preferably 1 nm or more, and more preferably 3 nm or more.

Further, in the case of a laminated structure, the layers other than the layer disposed at the position closest to the silver layer 14 are not necessarily limited, but tin zinc oxide is preferable. The tin zinc oxide preferably has a tin ratio of 10 to 90% by mass and more preferably 20 to 80% by mass with respect to the total amount of zinc and tin.

The silver layer 14 only needs to be composed mainly of silver, and is made of, for example, silver alone or a silver alloy containing a metal such as palladium. In the case of a silver alloy, the ratio of the metal other than silver to the total amount of silver and a metal element other than silver is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass in terms of heat shielding properties and cost. The following is more preferable. It is preferable that the silver layer 14 consists essentially of silver.

The silver layer 14 has a thickness of 11 to 18 nm. By making the thickness of the silver layer 14 relatively large, 11 nm or more, the transmittance in the infrared region is lowered, and the heat shielding property can be improved. Moreover, the optical characteristic of the laminated body 10 can be made into a desired characteristic by the thickness of the silver layer 14 being 18 nm or less. The thickness of the silver layer 14 is preferably 12 nm or more, more preferably 13 nm or more, and further preferably 14 nm or more.

The light absorption layer 15 has absorption in the visible light region, reduces visible light transmittance by absorption of visible light, improves thermal insulation, and makes the optical characteristics of the laminate 10 desired characteristics. . The thickness of the light absorption layer 15 is 1 to 6 nm. By setting the thickness of the light absorption layer 15 to 1 nm or more, the visible light transmittance can be effectively reduced by absorbing visible light. Further, by setting the thickness of the light absorption layer 15 to 6 nm or less, excessive absorption of visible light can be suppressed, and the optical characteristics of the laminate 10 can be set to desired characteristics. The thickness of the light absorption layer 15 is preferably 5 nm or less.

The constituent material of the light absorption layer 15 is not particularly limited as long as it has absorption in the visible light region. Examples of the constituent material of the light absorption layer 15 include metals or nitrides having absorption in the visible light region.

Examples of the metal include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals. Examples of the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. Among these, an alloy mainly containing titanium is preferable, an alloy containing 90% by mass or more of titanium is preferable, and only titanium is more preferable.

Examples of the nitride include a nitride of at least one element selected from silicon, aluminum, and chromium. The nitride may be one closer to the metal side from stoichiometry, for example, silicon nitride (SiNx (x = 0.1 to 1.33)), aluminum nitride (AlNx (x = 0.1) To 1.0)), chromium nitride (CrNx (x = 0.1 to 1.0)) and the like.

In the case of a non-heat-treated product, the light absorption layer 15 preferably has a metal layer made of the above metal, and more preferably only a metal layer. On the other hand, in the case of a heat-treated product, the light absorption layer 15 preferably has a nitride layer made of the nitride. By having the nitride layer, the reaction between the silver layer 14 and the upper layer thereof during heat treatment or the like can be suppressed, the heat shielding property can be improved, and desired optical characteristics can be obtained. The light absorption layer 15 may have both a nitride layer and a metal layer. When it has a nitride layer and a metal layer, it is preferable to have a nitride layer and a metal layer in order from the silver layer 14 side. By adopting such an arrangement, the reaction between the silver layer 14 and the metal layer at the time of heat treatment or the like can be suppressed, the heat shielding property can be improved, and desired optical characteristics can be obtained.

The second dielectric layer 16 is provided in order to adjust the reflectance in the visible range by the optical interference effect and to make the optical characteristics of the laminate 10 desired characteristics. The second dielectric layer 16 has a refractive index of 1.9 to 2.1. By setting it as such a refractive index, the reflectance etc. in a visible region are adjusted with a light interference effect, and the optical characteristic of the laminated body 10 can be made into a desired characteristic.

The second dielectric layer 16 is mainly composed of a dielectric film formed from the beginning (dielectric layer from the beginning). The second dielectric layer 16 is not necessarily limited to the original dielectric layer. That is, the second dielectric layer 16 is a dielectric when it is finished, in addition to the original dielectric layer, and is continuous with the original dielectric layer. Is included.

Such a dielectric is, for example, a metal film functioning as a barrier film provided as a base layer positioned under the dielectric layer before the initial formation of the dielectric layer. Examples are those that are oxidized when the dielectric layer is formed into a dielectric, and have a refractive index of 1.9 to 2.1.

Further, for example, in order to improve the adhesiveness of the protective film formed on the outermost surface of the laminate 10, an adhesive film provided as a base layer located under the protective film, and when the protective film is subsequently formed An oxide that has been oxidized into a dielectric and has a refractive index of 1.9 to 2.1 can be used.

The film formed as a barrier film or an adhesive film as described above is also a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product, If it is continuously disposed as a dielectric relative to the layer, it is included in the second dielectric layer 16. That is, it is included in the thickness of the second dielectric layer 16.

The second dielectric layer 16 has a thickness of 35 to 48 nm. By setting the thickness of the second dielectric layer 16 within the above range, it is possible to adjust the reflectance in the visible range by the optical interference effect, and to make the optical characteristics of the stacked body 10 desired characteristics. The thickness of the second dielectric layer 16 is preferably 37 nm or more, more preferably 38 nm or more, and further preferably 39 nm or more. The thickness of the second dielectric layer 16 is preferably 47 nm or less.

The constituent material of the second dielectric layer 16 is not particularly limited as long as it is a dielectric having the above-described refractive index, and various oxides and nitrides can be used. Examples of the oxide include an oxide mainly composed of an oxide of at least one element selected from zinc, tin, niobium, and titanium. Examples of the nitride include those containing as a main component a nitride of at least one element selected from silicon and aluminum.

The constituent material of the second dielectric layer 16 that is a dielectric from the beginning is preferably an oxide, and particularly preferably aluminum zinc oxide or tin zinc oxide. The aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum. The tin zinc oxide preferably has a tin ratio of 10 to 90% by mass, more preferably 20 to 80% by mass with respect to the total amount of zinc and tin.

The portion that has been a dielectric material from the beginning is not necessarily limited to a single-layer structure composed of one kind of dielectric layer, but may be a laminated structure in which two or more kinds of dielectric layers are laminated, although not shown. . In the case of a laminated structure, the refractive indexes of the individual dielectric layers are not necessarily the same, and may be different as long as they are within the refractive index range of 1.9 to 2.1.

In the case of a single layer structure, aluminum zinc oxide or tin zinc oxide is preferable. The aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.

In the case of a laminated structure, it is preferable to use aluminum zinc oxide and tin zinc oxide in combination. In this case, the stacking order is not necessarily limited, and may be the order of aluminum zinc oxide and tin zinc oxide in order from the transparent substrate 11 side, or the order of tin zinc oxide and aluminum zinc oxide. Among these, the order of aluminum zinc oxide and tin zinc oxide is more preferable.

It is preferable that a metal oxide layer formed by oxidation of a metal film functioning as a barrier film is disposed on the light absorption layer 15 side of the second dielectric layer 16. Examples of the metal oxide include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals. Examples of the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. The thickness of the metal oxide layer is usually about 1 to 3 nm.

FIG. 2 shows a first configuration example of the laminate 10.
The first configuration example is a preferable configuration example of the non-heat treated product.

In the case of a non-heat treated product, the light absorption layer 15 preferably has a metal layer 151. The metal oxide layer 17 is formed by oxidation of a metal film that functions as a barrier film. If the refractive index is in the range of 1.9 to 2.1, the metal oxide layer 17 is included in the second dielectric layer 16. If the refractive index is outside the range of 1.9 to 2.1, it is not included in the second dielectric layer 16. The metal oxide layer 17 is preferably made of an oxide of the same metal as that contained in the metal layer 151.

The light absorbing layer 15 (metal layer 151), the metal oxide layer 17, and the second dielectric layer 16 are formed on the metal layer after a relatively thick metal film is formed on the silver layer 14. In addition, the second dielectric layer 16 can be formed. That is, when the second dielectric layer 16 is formed, a part of the metal film on the second dielectric layer 16 side can be oxidized to form the metal oxide layer 17, and the silver layer 14 of the metal film can be formed. The metal layer 151 can be formed by leaving the remaining portion on the side without being oxidized. In this case, the metal film is used for forming the metal layer 151 and also used as a barrier film for suppressing oxidation of the silver layer 14 when the second dielectric layer 16 is formed. With such a configuration, the light absorption layer 15 (metal layer 151) can be formed while suppressing the oxidation of the silver layer 14, and the productivity can be improved.

The thickness of the metal layer 151 is 1 to 6 nm. The thickness of the metal layer 151 is more preferably 5 nm or less, further preferably 4 nm or less, and particularly preferably 3 nm or less. Examples of the constituent material of the metal layer 151 include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals. Examples of the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. Among these, an alloy mainly containing titanium is preferable, an alloy containing 90% by mass or more of titanium is more preferable, and only titanium is more preferable.

The metal oxide layer 17 is preferably made of the same metal oxide as the metal contained in the metal layer 151. The metal oxide layer 17 is formed, for example, by oxidizing a part of the metal film that becomes the metal layer 151 when the second dielectric layer 16 is formed. The thickness of the metal oxide layer 17 is usually about 1 to 3 nm.

On the second dielectric layer 16, for example, an adhesive layer 18 and a protective layer 19 are provided in this order from the second dielectric layer 16 side as necessary.

The adhesive layer 18 is provided as necessary to improve the adhesiveness between the second dielectric layer 16 and the protective layer 19. The constituent material of the adhesive layer 18 is not particularly limited as long as the adhesion between the second dielectric layer 16 and the protective layer 19 can be improved, but a nitride or a dielectric having a refractive index of 1.9 to 2.5 is preferable. In particular, an oxide of titanium is preferable. For example, the adhesive layer 18 may be formed as a nitride film and then oxidized into an oxide film when the protective layer 19 is formed. The constituent material of the nitride film includes a material that is closer to the metal side from stoichiometry. An example of such a material is TiNx (x = 0.1 to 1.0).

When providing the adhesive layer 18, a thickness of 0.5 nm or more is preferable. By setting the thickness to 0.5 nm or more, the adhesion between the second dielectric layer 16 and the protective layer 19 can be effectively improved. The thickness of the adhesive layer 18 is usually sufficient if it is 5 nm.

The protective layer 19 is not particularly limited as long as it can improve the scratch resistance of the surface, but a dielectric having a refractive index of 1.9 to 2.4 is preferable. The constituent material of the protective layer 19 is preferably a zirconium titanium oxide film from the viewpoint of scratch resistance.

The thickness of the protective layer 19 is preferably 1 nm or more. By setting the thickness of the protective layer 19 to 1 nm or more, the scratch resistance can be effectively improved. The thickness of the protective layer 19 is more preferably 2 nm or more. Further, the thickness of the protective layer 19 is preferably 10 nm or less, more preferably 7 nm or less, and even more preferably 5 nm or less from the viewpoint of suppressing an excessive decrease in visible light transmittance.

The adhesive layer 18 is regarded as a part of the second dielectric layer 16 when it is a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product. Further, when the adhesive layer 18 is a dielectric having a refractive index of 1.9 to 2.1 and the protective layer 19 is a dielectric having a refractive index of 1.9 to 2.1, The protective layer 19 is also regarded as a part of the second dielectric layer 16.

FIG. 3 shows a second configuration example of the laminate 10.
The second configuration example is a preferable configuration example of the heat-treated product.

In the case of a heat-treated product, the light absorption layer 15 preferably has a nitride layer 152. Moreover, it is preferable to have the metal oxide layer 17 and the 2nd dielectric material layer 16 in order from the nitride layer 152 side. Here, the metal oxide layer 17 is formed by oxidation of a metal film that functions as a barrier film.

The light absorption layer 15 (nitride layer 152), the metal oxide layer 17 and the second dielectric layer 16 are formed by forming a nitride layer 152 on the silver layer 14 and forming the nitride layer 152 on the nitride layer 152. It can be formed by forming a metal film and forming the second dielectric layer 16 on the metal film. That is, when the second dielectric layer 16 is formed, the metal film can be oxidized to form the metal oxide layer 17. In this case, the metal film functions as a barrier film that suppresses oxidation of the silver layer 14 when the second dielectric layer 16 is formed. The nitride layer 152 has a function of suppressing the reaction between the silver layer 14 and the upper layer thereof during heat treatment or the like and maintaining absorption as an optical property. With such a configuration, the light absorption layer 15 (nitride layer 152) can be formed while suppressing the oxidation of the silver layer 14, and the productivity is improved.

The thickness of the nitride layer 152 is preferably 1 nm or more from the viewpoint of effectively reducing the visible light transmittance by assisting the absorption of visible light and suppressing deterioration of the silver layer 14, and 1.5 nm or more. Is more preferable.

Examples of the constituent material of the nitride layer 152 include a nitride of at least one element selected from silicon, aluminum, and chromium. The nitride may be one closer to the metal side from stoichiometry, for example, silicon nitride (SiNx (x = 0.1 to 1.33)), aluminum nitride (AlNx (x = 0.1) To 1.0)), chromium nitride (CrNx (x = 0.1 to 1.0)) and the like.

The metal oxide layer 17 is formed by oxidation of a metal film that functions as a barrier film when the second dielectric layer 16 is formed. The metal film is preferably made of a metal having absorption in the visible light region. Examples of the metal include metals such as titanium, zirconium, hafnium, niobium, nickel, chromium, and alloys containing at least one of these metals. Examples of the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. The thickness of the metal oxide layer 17 is usually about 1 to 3 nm.

On the second dielectric layer 16, for example, an adhesive layer 18 and a protective layer (not shown) are provided in this order from the second dielectric layer 16 side as necessary.

The adhesive layer 18 is provided as necessary in order to improve the adhesion between the second dielectric layer 16 and the protective layer. The constituent material of the adhesive layer 18 is not particularly limited as long as the adhesion between the second dielectric layer 16 and the protective layer can be improved, but a nitride or dielectric having a refractive index of 1.9 to 2.5 is preferable. In particular, an oxide of titanium is preferable. The adhesive layer 18 is formed as a nitride film, for example, and then oxidized when forming the protective layer to become an oxide film. The constituent material of the nitride film includes a material that is closer to the metal side from stoichiometry. An example of such a material is TiNx (x = 0.1 to 1.0).

When providing the adhesive layer 18, a thickness of 0.5 nm or more is preferable. By setting the thickness to 0.5 nm or more, the adhesiveness between the second dielectric layer 16 and the protective layer can be effectively improved. The thickness of the adhesive layer 18 is usually sufficient if it is 5 nm.

In the case of a heat-treated product, the protective layer may disappear when a heat treatment for strengthening or bending is performed, and may not exist in the finished product. An example of such a protective layer is a carbon film containing carbon as a main component. The thickness of the protective layer is preferably 1 nm or more. By setting the thickness of the protective layer to 1 nm or more, the scratch resistance can be effectively improved. The thickness of the protective layer is more preferably 2 nm or more. Further, the thickness of the protective layer is preferably 10 nm or less, more preferably 7 nm or less, and further preferably 5 nm or less. For the heat-treated product, a protective layer similar to that in the first configuration example can be provided.

The adhesive layer 18 is regarded as a part of the second dielectric layer 16 if it is a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product. When there is a protective layer, the adhesive layer 18 is a dielectric having a refractive index of 1.9 to 2.1, and the protective layer is a dielectric having a refractive index of 1.9 to 2.1. The protective layer is also considered part of the second dielectric layer 16.

FIG. 4 shows a third configuration example of the laminate 10.
The third configuration example is another preferable configuration example of the heat-treated product.

In the case of a heat-treated product, a metal layer 151 can be further provided as the light absorption layer 15 between the nitride layer 152 and the metal oxide layer 17 in the second configuration example. In this case, the metal oxide layer 17 is preferably made of an oxide of the same metal as that contained in the metal layer 151. The configurations of the second dielectric layer 16, the adhesive layer 18, and the protective layer can be basically the same as those of the second configuration example.

The light absorption layer 15 (the nitride layer 152 and the metal layer 151), the metal oxide layer 17, and the second dielectric layer 16 are formed by forming the nitride layer 152 on the silver layer 14, The metal layer can be formed on the nitride layer 152 so as to be thicker than that in the configuration example 2, and the second dielectric layer 16 can be formed on the metal film. That is, when the second dielectric layer 16 is formed, a part of the metal film on the second dielectric layer 16 side can be oxidized to form the metal oxide layer 17, and the silver layer 14 of the metal film can be formed. The metal layer 151 can be formed by leaving the remaining portion on the side without being oxidized. In this case, the metal film is used for forming the metal layer 151 as the light absorption layer 15 and also used as a barrier film for suppressing oxidation of the silver layer 14 when forming the second dielectric layer 16. The With such a configuration, the light absorption layer 15 (the metal layer 151 and the nitride layer 152) can be formed while suppressing the oxidation of the silver layer 14, and the productivity can be improved.

The thickness of the metal layer 151 is not particularly limited, and is preferably determined as appropriate according to the thickness of the nitride layer 152 so that the thickness of the light absorption layer 15 is 6 nm or less as a whole. The constituent material of the metal layer 151 can be the same constituent material as the constituent material of the metal layer 151 of the configuration example 1 or the constituent material of the metal film of the configuration example 2.

The laminate 10 preferably has the following optical characteristics. The optical characteristics of the present invention can be obtained by measuring with a “C light source 2 ° visual field” as a light source. Here, when the laminated body 10 is a heat-treated product, the post-heat-treated product preferably has the following optical characteristics.

The solar heat gain coefficient (SHGC) is preferably 0.37 to 0.43. Solar heat gain is a measure of how much heat from sunlight is blocked. That is, the solar heat gain rate (SHGC) is the ratio of the energy released to the indoor side with respect to the energy incident from the outdoor side in the multi-layer glass or single plate glass. The solar heat acquisition rate is represented by a numerical value between 0 and 1. The smaller the solar heat gain rate, the less solar heat is transmitted. In the laminated body 10 of the embodiment, even if the silver layer 14 is only one layer, the solar heat acquisition rate can be reduced by making the silver layer 14 relatively thick and providing the light absorption layer 15. Here, the solar heat gain rate (SHGC) is an index used by National Fenestration Rating Council.

In addition, a solar radiation acquisition rate (SHGC) is calculated | required about the multilayer glass which has a hollow layer between the laminated body 10 and an opposing board | substrate. The transparent substrate 11 and the counter substrate of the laminate 10 are preferably glass plates, and the hollow layer is preferably an air layer. Here, the laminated body 10 is disposed so as to be on the outdoor side, and the laminated film 12 is disposed on the hollow layer side. The thickness of the transparent substrate 11 and the counter substrate is preferably about 3 to 6 mm, and the thickness of the hollow layer is preferably about 6 to 18 mm.

The visible light transmittance (T _v ) is preferably 66 to 72%, and the visible light reflectance (R _v1 ) on the transparent substrate 11 side (hereinafter simply referred to as the substrate side) is preferably 20 to 25%, and the laminated film 12 side The visible light reflectance (R _v2 ) (hereinafter referred to simply as “film side”) is preferably 13 to 20%. The reflectance difference (R _v1 −R _v2 ) between the visible light reflectance (R _v1 ) on the substrate side and the visible light reflectance (R _v2 ) on the film side is preferably 3.5% or more, and is preferably 4.0% or more. Is more preferable. The visible light transmittance (T _v ) and the visible light reflectance (R _v ) are both defined in JIS R3106: 1998.

Furthermore, the transmitted light and reflected light of the laminate 10 preferably have the following color tone. That is, in the L ^* a ^* b ^* color system, the transmitted light preferably has a ^* of −4 to −1 and b ^* of 3 to 8. The reflected light on the substrate side preferably has a ^* of −4 to 1 and b ^* of −13 to −8. The reflected light on the film side preferably has a ^* of -1 to 7 and b ^* of -20 to -11.

A glass plate for a building is required to have a low solar heat acquisition rate from the viewpoint of cooling efficiency and the like, and the colors of transmitted light and reflected light are important from the viewpoint of design. Since the laminated body 10 of the embodiment has a low solar heat acquisition rate and has predetermined optical characteristics, it is preferably used for a glass plate for buildings, particularly a glass plate for high-rise buildings, specifically a window. It is suitably used for applications such as glass.

Hereinafter, the manufacturing method of the laminated body 10 is demonstrated.
In the case of the non-heat treated product shown in FIG. 2, a dielectric film that becomes the first dielectric layer 13, a silver film that becomes the silver layer 14, a metal film that becomes the metal layer 151 and the metal oxide layer 17 on the transparent substrate 11. In addition, a dielectric film to be the second dielectric layer 16, an adhesive film to be the adhesive layer 18, and a protective film to be the protective layer 19, if necessary, can be sequentially formed.

The film forming method is not particularly limited, but a sputtering method is preferably used. Sputtering methods include DC sputtering using a metal target, AC and RF sputtering using metal and non-metal targets. In all cases, magnetron sputtering can be used. Sputtering is performed in an inert gas or in a reactive gas as required. Each film is formed as follows, for example.

The dielectric film to be the first dielectric layer 13 is, for example, reactive sputtering in an oxidizing atmosphere containing argon and oxygen using a metal target made of metal contained in the dielectric film as a sputtering target. The film is formed by

The silver film to be the silver layer 14 is formed by sputtering in a non-oxidizing atmosphere consisting only of argon containing no oxygen, for example, using a silver target containing silver as a main component as a sputtering target.

For the metal film to be the metal layer 151 and the metal oxide layer 17, for example, a metal target made of metal contained in the metal film is used as a sputtering target, and sputtering is performed in a non-oxidizing atmosphere made only of argon not containing oxygen. The film is formed by

The metal film is partly oxidized to form the metal oxide layer 17 when the dielectric film to be the second dielectric layer 16 is formed, and the remaining part is not oxidized to the metal layer 151. Therefore, the metal film is preferably formed thicker than the metal layer 151. Usually, the thickness of the metal film oxidized to become the metal oxide layer 17 is about 1 to 3 nm. Therefore, the thickness of the metal film is preferably 1 nm or more thicker than the thickness of the metal layer 151.

The dielectric film to be the second dielectric layer 16 is, for example, sputtered in an oxidizing atmosphere containing argon and oxygen using a metal target made of metal contained in the electric film as a sputtering target. Form a film. During the film formation, as described above, a part of the metal film is oxidized to become the metal oxide layer 17, and the remaining part is not oxidized to become the metal layer 151.

The adhesive film to be the adhesive layer 18 is formed, for example, by sputtering in an atmosphere containing argon and nitrogen using a metal target such as titanium as a sputtering target. The protective film to be the protective layer 19 is formed, for example, by performing sputtering in an oxidizing atmosphere containing argon and oxygen using a metal target such as titanium as a sputtering target.

3 and 4, on the transparent substrate 11, a dielectric film to be the first dielectric layer 13, a silver film to be the silver layer 14, a nitride film to be the nitride layer 152, a metal layer 151, a metal film to be the metal oxide layer 17, and a dielectric film to be the second dielectric layer 16 are sequentially formed, and then heat treatment for strengthening or bending can be performed. If necessary, an adhesive film to be the adhesive layer 18 and a protective film to be the protective layer 19 are sequentially formed on the second dielectric layer 16. The heat treatment is preferably performed, for example, in air at 650 to 750 ° C. for 1 to 10 minutes. In addition, about the film | membrane similar to a non-heat-treated product, it can form into a film fundamentally similarly to a non-heat-treated product.

In the case where the metal layer 151 as shown in FIG. 3 is not provided, the thickness of the metal film is such that all of the metal film is oxidized when the dielectric film to be the second dielectric layer 16 is formed. On the other hand, in the case of the one having the metal layer 151 as shown in FIG. 4, the thickness of the metal film is set so that all of the metal film is not oxidized during the formation of the dielectric film to be the second dielectric layer 16.

Further, the nitride film to be the nitride layer 152 is formed by sputtering in an atmosphere containing argon and nitrogen, for example, using a metal target made of metal contained in the nitride film as a sputtering target.

The protective film serving as the protective layer 19 is formed by sputtering in a non-oxidizing atmosphere using, for example, a carbon target as a sputtering target. When a carbon film is formed as a protective film, it disappears by a subsequent heat treatment for strengthening or bending.

FIG. 5 shows one embodiment of the double glazing.
For example, the multilayer glass 20 is disposed so that the laminate 10 and the counter substrate 21 are spaced apart from each other with a spacer 22 interposed therebetween. A primary sealant 23 seals between the laminate 10 and the spacer 22 and between the counter substrate 21 and the spacer 22. Further, the peripheral edge between the laminated body 10 and the counter substrate 21 is sealed by the secondary sealing material 24. A desiccant 27 for suppressing condensation in the hollow layer 26 through the through hole 25 is disposed inside the spacer 22. The hollow layer 26 is filled with air or argon gas. Usually, the laminate 10 is disposed on the outdoor side with respect to the counter substrate 21. Moreover, the laminated body 10 is arrange | positioned so that the hollow layer 26 side may become the laminated film 12 side.

As mentioned above, although embodiment of this invention was described, these embodiment is shown as an example and does not limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. For example, although a laminated body is suitable for buildings, it is not necessarily limited to buildings, and can be used for vehicles such as automobiles as far as applicable. Further, the configuration of the laminated film is not limited to the above-described configuration, and other layers can be included as necessary and within the limits not departing from the object of the present invention.

Hereinafter, a detailed description will be given with reference to examples.
In addition, this invention is not limited at all by these Examples.

(Example 1)
Film formation was performed by the sputtering method with the film configuration shown in Table 1, and a laminate (non-heat-treated product) having the configuration shown in FIG. 2 was manufactured. Note that the configurations and thicknesses shown in Table 1 are the configurations and thicknesses when the respective films are formed, and do not necessarily match the configurations and thicknesses in the final form.

In the table, the dielectric film (1) is the first dielectric layer 13, the silver film is the silver layer 14, the metal film is partly oxidized to become the metal oxide layer 17, and the remainder is not oxidized and is a metal layer. 151, the dielectric film (2) becomes the second dielectric layer 16, the adhesive film becomes the adhesive layer 18 by oxidation, and the protective film becomes the protective layer 19. In the case of this example, the metal oxide layer 17, the adhesive layer 18, and the protective layer 19 all have a refractive index outside the range of 1.9 to 2.1. Therefore, the second dielectric layer 16 is not included.

As the sputtering apparatus, an in-line type sputtering apparatus equipped with a target for forming each film in the sputtering chamber was used. A 3 mm thick soda lime glass plate was introduced into this in-line type sputtering apparatus, and evacuated in the load lock chamber until the degree of vacuum was 2 × 10 ⁻⁶ Torr or less. Subsequently, a glass plate was introduced into the sputtering chamber, and films were sequentially formed with the film configurations shown in Table 1.

That is, as the dielectric film (1), a tin-zinc oxide film (a ratio of tin to 50% by mass with respect to the total amount of tin and zinc) and an aluminum zinc oxide film (aluminum with respect to the total amount of aluminum and zinc) Is a silver film, a titanium film as the metal film, and an aluminum zinc oxide film as the dielectric film (2) (the ratio of aluminum to the total amount of aluminum and zinc is 5.0). And tin-zinc oxide film (the ratio of tin to 50% by mass with respect to the total amount of tin and zinc), titanium nitride film (TiNx (x = 1.0)) as an adhesive film As a protective film, a zirconium titanium oxide film (the ratio of titanium oxide to the total amount of zirconium oxide and titanium oxide is 45% by mass) It was deposited, to produce a laminate.

The tin-zinc oxide film uses a zinc-tin alloy target (the ratio of tin to 50% by mass with respect to the total amount of zinc and tin) and introduces argon (Ar) and oxygen (O ₂ ). (The ratio of the gas pressure of argon and oxygen (P _Ar / PO ₂ ) was 10/9), and the power density was 3.6 W / cm ² .

The aluminum zinc oxide film uses an alloy target of zinc and aluminum (a ratio of aluminum with respect to the total amount of zinc and aluminum is 5.0 atomic%) and introduces argon (Ar) and oxygen (O ₂ ) (the ratio of the gas pressure of argon and oxygen (P _Ar / P _O2 ) is 10/9), and the power density was 3.6 W / cm ² .

The silver film was formed using a silver target with an introduction gas of Ar 100% and a power density of 1.4 W / cm ² .

The titanium film was formed using a titanium target with an introduction gas of Ar 100% and a power density of 0.7 W / cm ² .

The titanium nitride film uses a titanium target, and the introduced gas is a mixed gas of argon (Ar) and oxygen (O ₂ ) (the ratio of the gas pressure of argon and oxygen (P _Ar / P _O2 ) is 70/30). The film was formed with a power density of 3.6 W / cm ² .

The zirconium-titanium oxide film uses an alloy target of zirconium and titanium (the ratio of titanium to the total amount of zirconium and titanium is 45% by mass), and the introduced gas is argon (Ar) and oxygen (O ₂ ). (The ratio of the gas pressure of argon and oxygen (P _Ar / PO ₂ ) was 10/9), and the power density was 3.6 W / cm ² .

(Example 2)
As shown in Table 1, a laminate (non-heat treated product) was manufactured in the same manner as in Example 1 except that no titanium nitride film was provided.

(Example 3)
Film formation and heat treatment were performed by the sputtering method with the film configuration shown in Table 2, and a laminate (heat treatment product) having the metal layer 151 and the nitride layer 152 as the light absorption layer 15 as shown in FIG. 4 was manufactured. The heat treatment was performed in air at 730 ° C. for 6 minutes.

In the table, the dielectric film (1) is the first dielectric layer 13, the silver film is the silver layer 14, the nitride film is the nitride layer 152, and the metal film is partially oxidized to form the metal oxide layer 17 The remainder is not oxidized and becomes the metal layer 151 of the light absorption layer 15, the dielectric film (2) becomes the second dielectric layer 16, and the adhesive film becomes the adhesive layer 18 by oxidation. The protective film is formed as a protective layer, but disappears by the subsequent heat treatment.

Note that the nitride film (CrNx (x = 1.0)) uses a Cr target, and the introduced gas is a mixed gas of argon (Ar) and oxygen (O ₂ ) (ratio of gas pressure between argon and oxygen ( The film was formed with P _Ar / PO ₂ ) of 80/20) and a power density of 1.4 W / cm ² . The protective film was formed by using a carbon target with an introduction gas of Ar 100% and a power density of 2.1 W / cm ² . Other layers were formed under the same conditions as in Example 1.

Next, with respect to the laminates (sample number 5) of Examples 1 to 3, the visible light transmittance (T _v ), the visible light reflectance (R _v1 ) on the substrate side, and the visible light reflectance (R _v2 ) on the film side Asked. Moreover, the solar heat gain rate (SHGC) when it was set as the multilayer glass as shown in FIG. 5 was calculated | required. Table 3 shows the results of the visible light transmittance (T _v ), the visible light reflectance (R _v1 , R _v2 ), and the solar heat gain rate (SHGC).

For the laminates of Examples 1 to 3 (number of samples: 5), the a ^* b ^* in the CIE-Lab colorimetric method of transmitted light and reflected light (substrate side and film side) was determined. The results are shown in FIGS.

The visible light transmittance (T _v ) and the visible light reflectance (R _v ) were measured by measuring the visible light transmittance at a wavelength of 300 to 2500 nm using a Hitachi U-4100 spectrophotometer, and specified in JIS R3106: 1998. Calculated according to

The transmitted light and reflected light were calculated in accordance with JIS Z 8729 by measuring a ^* and b ^* in the L ^* a ^* b ^* color system based on JIS Z 8722.

As shown in FIG. 5, the solar heat acquisition rate (SHGC) is a glass plate (thickness 6 mm) for the transparent substrate 11 of the laminated film 12, and a glass plate (thickness 6 mm) for the counter substrate 21. It calculated | required about the multilayer glass 20 which used the hollow layer 26 as the air layer (thickness 12mm).

As is apparent from Table 3 and FIGS. 6 to 11, the laminates of Examples 1 to 3 having a predetermined laminate structure have a visible light transmittance (T _v ) of 66 to 72% and a visible light reflectance on the substrate side. (R _v1 ) is 20 to 25%, visible light reflectance (R _v2 ) on the film side is 13 to 20%, reflectance difference (R _v1 −R _v2 ) is 3.5% or more, and a ^{* of} transmitted light is -4 to -1 and b ^* are 3 to 8, a ^* of the reflected light on the substrate side is -4 to 1 and b ^* is -13 to -8, and a ^* of the reflected light on the film side is -1 to 7 and b ^* satisfies −20 to −13, and the solar radiation acquisition rate (SHGC) satisfies 0.37 to 0.43. In addition, the laminates of Examples 1 to 3 have good productivity.

(Comparative Example 1)
As shown in Table 4, a laminate (non-heat treated product) was manufactured in the same manner as in Example 1 by changing the thicknesses of the dielectric films (1) and (2) and the metal film.

(Comparative Example 2)
As shown in Table 5, laminates (heat-treated products) were manufactured in the same manner as in Example 3 by changing the thicknesses of the dielectric films (1) and (2) and the metal film.

By the method described above, the visible light transmittance (T _v ), the visible light reflectance (R _v1 , R _v2 ), the color tone of transmitted and reflected light (a ^* b ^* ), and the solar heat gain (SHGC) Asked. The results are shown in Tables 6 and 7.

The relationship between the thickness immediately after the formation of each film and the thickness after the formation of all the films (hereinafter referred to as the thickness after the formation of all films) is as shown below. The thicknesses of the dielectric films (1), (2), the silver film, and the protective film (zirconium titanium oxide and carbon) after film formation are all the same as the thickness immediately after the film formation. . The thickness of the entire metal film (titanium) after film formation is oxidized and increased during the film formation of other films, and is therefore about twice the thickness immediately after film formation. The thickness of the adhesive film after the entire film is formed is oxidized and increased at the time of forming other films, so that the thickness is less than 1.5 times that immediately after the film formation.

Further, the relationship between the thickness immediately after the film formation and the thickness after the heat treatment is as shown below. The thicknesses of the dielectric films (1), (2), the silver film, and the protective film (zirconium titanium oxide) after the heat treatment are all the same as the thickness immediately after the film formation. Since the thickness of the metal film (titanium) after the heat treatment is oxidized and increased during the heat treatment, it is about twice the thickness immediately after the film formation. Since the thickness of the adhesive film after the heat treatment is increased by oxidation during the heat treatment, the thickness is less than 1.5 times that immediately after the film formation. The protective film (carbon) disappears due to oxidation during heat treatment.

DESCRIPTION OF SYMBOLS 10 ... Laminated body, 11 ... Transparent substrate, 12 ... Laminated film, 13 ... 1st dielectric layer, 14 ... Silver layer, 15 ... Light absorption layer, 16 ... 2nd dielectric layer, 17 ... Metal oxide layer 18 ... Adhesive layer, 19 ... Protective layer, 20 ... Multi-layer glass, 21 ... Counter substrate, 22 ... Spacer, 23 ... Primary sealing material, 24 ... Secondary sealing material, 25 ... Through hole, 26 ... Hollow layer, 27 ... Desiccant, 151 ... Metal layer, 152 ... Nitride layer.

Claims

A transparent substrate, and a laminated film provided on the transparent substrate,
The laminated film includes, in order from the transparent substrate side, a first dielectric layer having a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm. A silver layer having a geometric thickness, a light absorbing layer having a geometric thickness of 1 to 6 nm, and a second having a refractive index of 1.9 to 2.1 and a geometric thickness of 35 to 48 nm A laminate having a dielectric layer.
The laminate according to claim 1, wherein the light absorption layer has a metal layer.
The laminate according to claim 1, wherein the light absorption layer has a metal nitride layer.
The laminate according to claim 1, wherein the light absorption layer has a metal nitride layer and a metal layer in order from the silver layer side.
The laminate according to claim 3 or 4, wherein the metal nitride layer is made of chromium nitride.
The laminate according to claim 4 or 5, wherein the metal layer is mainly composed of titanium.
The laminated body has a visible light transmittance (T v ) of 66 to 72%, a visible light reflectance (R v1 ) on the transparent substrate side of 20 to 25%, and a visible light reflectance (R v2 ) on the laminated film side. 7. The laminate according to any one of claims 1 to 6, wherein the content is 13 to 20%.
The reflectance difference (R v1 -R v2 ) between the visible light reflectance (R v1 ) on the transparent substrate side and the visible light reflectance (R v2 ) on the laminated film side is 3.5% or more. The laminated body of any one of thru | or 7.
The laminate, L * a * b * in the color system, a transmitted light a * -4 to -1 and b * 3-8, wherein the a * -4-reflected light of the transparent substrate 1 The laminate according to any one of claims 1 to 8, wherein b * is -13 to -8, a * of the reflected light on the laminated film side is -1 to 7, and b * is -20 to -11. .
The laminate according to any one of claims 1 to 9,
A multi-layer glass having a counter substrate disposed to face the laminated film side of the laminated body.
The multilayer glass according to claim 10, wherein the multilayer glass has a solar heat gain rate of 0.37 to 0.43.