JP6631686B2 - Transparent substrate with laminated film and window glass - Google Patents

Description

  The present invention relates to a transparent substrate with a laminated film and a method for producing the same, and more particularly to a transparent substrate with a laminated film having excellent durability in addition to high heat shielding properties, low heat insulating properties and high color rendering properties, and a transparent substrate with the laminated film. Regarding window glass.

  When considering the energy saving performance of architectural glazing in a hot region, for example, a region of low latitude to middle latitude such as Southeast Asia, it is required to have high heat shielding performance and appropriate visible light transmittance. On the other hand, the heat insulation performance is not considered unlike the cold region. In a cold region, the temperature difference between the room and the outside is very large, and there is a large amount of heat flowing out of the room.Therefore, high insulation performance is desired, but in a hot region, the temperature difference is relatively small and the amount of heat flowing into the room is small. Therefore, the need for high heat insulation performance is low. Therefore, a window glass for construction is required to have an appropriate visible light transmittance and high heat shielding performance.

  Here, it is necessary to lower the emissivity in order to give the window glass high heat-shielding performance, but the architectural window glass is also required to satisfy various optical characteristics. Specifically, the transmitted color looks natural without coloring, the reflected color is a preferred color, the visible light transmittance is within a predetermined range, the outdoor reflectance and the indoor Are not more than a predetermined range.

  As a window glass that achieves the above function, a single-pane window glass in which a silver-based optical multilayer film including a metal layer containing silver as a main component is formed on a glass substrate can be considered. However, conventionally, the silver-based optical multilayer film has been used by being provided inside a multi-layered glass having high heat insulation performance and exhibiting high heat shielding performance, and in a state where it is exposed, it is chemically durable. This is a problem in that sufficient mechanical durability cannot be obtained.

  Further, for example, there is known a glass article in which a heat-shielding film containing doped tin oxide or the like having chemical durability and mechanical durability is formed on a heat ray absorbing glass colored green or blue (see, for example, patents). Reference 1). In such a glass article, high visible light transmittance and high heat shielding performance are obtained, but there is a problem in that the color rendering properties are not sufficient.

  Thus, in a combination of a transparent substrate such as a glass substrate and various coating films, the transparent substrate and the coating film satisfying the above various characteristics suitable for use as a window glass in a hot region from low to middle latitudes are combined. At the present time, a high heat-shielding window glass has not been obtained.

JP-T-2005-529823

  The present invention has been made to solve the above problems, suitable for use as a veneer in a hot region of low latitude to middle latitude, having an appropriate visible light transmittance, high heat shielding and An object of the present invention is to provide a transparent substrate with a laminated film which is excellent in durability in addition to high color rendering properties, and a window glass having the transparent substrate with the laminated film.

  The transparent substrate with a laminated film of the present invention has a transparent substrate and a laminated film in which a transparent conductive layer, a nitrogen-containing light absorbing layer and a dielectric layer are laminated on the transparent substrate in this order from the transparent substrate side. A transparent substrate with a laminated film, wherein the thickness of the transparent conductive layer is 10 to 200 nm, the thickness of the nitrogen-containing light absorbing layer is more than 10 nm and 60 nm or less, and the thickness of the dielectric layer is 20 ８０80 nm.

  The present invention provides a window glass having the above-mentioned transparent substrate with a laminated film of the present invention, wherein the transparent substrate is a single plate, and the laminated film is exposed to the indoor side.

  According to the present invention, a laminated film having a suitable visible light transmittance suitable for use as a veneer in a hot region of low latitude to middle latitude, and having excellent durability in addition to high heat shielding properties and high color rendering properties. And a window glass having the transparent substrate with the laminated film.

It is sectional drawing which shows an example of embodiment of the transparent substrate with a laminated film. It is sectional drawing which shows another example of embodiment of the transparent substrate with a laminated film. It is sectional drawing when using an example of the transparent substrate with a laminated film of this invention as a window glass.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not construed as being limited to the following description.

[Transparent substrate with laminated film]
FIG. 1 is a sectional view showing an example of an embodiment of a transparent substrate with a laminated film of the present invention. FIG. 2 is a sectional view showing another example of the embodiment of the transparent substrate with a laminated film of the present invention.

  A transparent substrate with a laminated film 10A shown in FIG. 1 has a laminated film 12A on a transparent substrate 11, and the laminated film 12A is formed by forming a transparent conductive layer 13 and a nitrogen-containing light absorbing layer 14 in this order from the transparent substrate 11 side. It is composed.

(Transparent substrate)
The transparent substrate 11 is not particularly limited, and for example, a glass substrate having an inorganic transparency such as a window glass for a building, a float glass generally used, or a soda-lime glass manufactured by a roll-out method can be used. . As the glass substrate, a colorless one such as clear glass and high transmission glass can be used. As the transparent substrate 11, an organic transparent substrate may be used. Examples of the organic transparent substrate include a transparent substrate made of an acrylic resin such as polymethyl methacrylate, an aromatic polycarbonate resin such as polyphenylene carbonate, and an aromatic polyester resin such as polyethylene terephthalate (PET).

  When the visible light transmittance (Tv) of the transparent substrate with a laminated film 10A is set to an appropriate range, for example, 35 to 65% described later, the visible light transmittance (Tv) of the transparent substrate 11 is 80 to 92. % Is preferable, and 83 to 90% is more preferable. Considering such visible light transmittance, the transparent substrate 11 is preferably a colorless glass such as a clear glass or a high transmission glass. In addition, colorless glass is preferable from the viewpoint of obtaining high color rendering properties.

  In this specification, the visible light transmittance (Tv) is measured in accordance with ISO9050: 2003. Further, in the present specification, the optical characteristics are obtained by measuring with a “D65 light source 10-degree field of view” as a light source, unless otherwise specified.

  As the transparent substrate 11, various types of tempered glass such as air-cooled tempered glass and chemically tempered glass can be used. Further, 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 such that the visible light transmittance (Tv) of the transparent substrate 11 itself can be in the above range and sufficient mechanical strength can be ensured. 20 mm is preferred.

  The transparent conductive layer 13 is mainly composed of, for example, a metal oxide capable of forming a transparent layer on the transparent substrate 11 and having conductivity (hereinafter, referred to as “transparent conductive metal oxide”). It is not particularly limited as long as it is a layer to be formed.

  Examples of the transparent conductive metal oxide include a metal oxide doped with an element other than the metal constituting the metal oxide itself. Specifically, indium oxide doped with at least one selected from tin, titanium, tungsten, molybdenum, zinc and hydrogen; tin oxide doped with at least one selected from antimony, indium, tantalum, chlorine and fluorine A zinc oxide doped with at least one selected from indium, aluminum, tin, gallium, fluorine and boron. The transparent conductive metal oxide may be used alone or in combination of two or more to form the transparent conductive layer 13.

The transparent conductive layer 13 is preferably made of a transparent conductive metal oxide mainly composed of indium oxide (ITO) doped with tin from the viewpoint of reducing the resistance, and more preferably made of only ITO. The doping amount of tin in the ITO, is preferably 1 to 20 mass% as a content of SnO ₂ with respect to the total amount of _In 2 _{O 3} and SnO _2, and more preferably from 5 to 15% by mass.

  The thickness of the transparent conductive layer 13 is not particularly limited as long as the obtained transparent substrate with a laminated film 10A has an appropriate visible light transmittance and can achieve high heat shielding properties and high color rendering properties. The thickness of the transparent conductive layer 13 may be, for example, 10 to 600 nm, preferably 10 to 200 nm, and more preferably 50 to 150 nm.

  The method for forming the transparent conductive layer 13 is not particularly limited, but is usually manufactured by a method involving heat treatment as described later. The state before the heat treatment of the transparent conductive layer 13 is referred to as a precursor layer of the transparent conductive layer 13. Although the precursor layer of the transparent conductive layer 13 and the transparent conductive layer 13 after the heat treatment have substantially the same composition, the degree of oxidation is adjusted by being appropriately oxidized by oxygen contained in the atmosphere or the transparent substrate during the heat treatment, The transparent conductive layer 13 having a desired resistance value is formed. Usually, in the heat treatment, the heat treatment does not affect the thickness of the transparent conductive layer. Further, when the thickness of the transparent conductive layer 13, that is, the thickness of the precursor layer is the above-mentioned thickness, there is an effect that the degree of oxidation does not become uneven in the depth direction of the layer.

  The nitrogen-containing light-absorbing layer 14 has a light-absorbing property made of, for example, a metal nitride and / or oxynitride that can be formed on the transparent substrate 11 (hereinafter, “nitrogen-containing light-absorbing metal compound”). ) Is not particularly limited.

  In the transparent substrate with a laminated film 10A shown in FIG. 1, a transparent conductive layer 13 and a nitrogen-containing light absorption layer 14 are formed in this order from the transparent substrate 11 side. In addition, as long as the obtained transparent substrate 10A with a laminated film has an appropriate visible light transmittance and can achieve high heat shielding properties and high color rendering properties, the nitrogen-containing light absorbing layer 14, the transparent conductive The layers 13 may be formed in this order.

  As the light absorbing property of the nitrogen-containing light absorbing layer 14, a property of absorbing an appropriate amount of light in a wide range from the visible light region to the infrared region is preferable. When the nitrogen-containing light absorbing layer 14 has such light absorbing properties, the obtained transparent substrate with a laminated film 10A has an appropriate visible light transmittance, and can achieve high heat shielding properties and high color rendering properties.

  In the transparent substrate with a laminated film 10A, the transparent conductive layer 13 and the nitrogen-containing light absorption layer 14 are provided so as to be in contact with each other. With such a configuration, for example, at the time of heat treatment when manufacturing the transparent substrate with a laminated film 10A by the manufacturing method involving the heat treatment, oxygen is transferred between the nitrogen-containing light absorbing layer 14 and the transparent conductive layer 13; It can play a role in appropriately adjusting the degree of oxidation of the transparent conductive layer 13. That is, in the manufacturing process, even if the precursor layer of the transparent conductive layer 13 contains excessive oxygen at the time of heat treatment, the oxygen is transferred to the precursor layer of the nitrogen-containing light absorption layer 14 so that the degree of oxidation is more preferable. It is considered that the transparent conductive layer 13 having low resistance is finally obtained.

  In this case, the nitrogen-containing light-absorbing metal compound constituting the nitrogen-containing light-absorbing layer 14 is a component obtained by oxidizing the components constituting the precursor layer during the heat treatment. Here, when the nitrogen-containing light absorbing layer 14 is not in contact with the transparent conductive layer 13 and there is a layer (hereinafter referred to as an oxygen barrier layer) having an ability to block the transfer of oxygen, the nitrogen-containing light absorbing layer after the heat treatment is used. The oxidation degree of the nitrogen-containing light-absorbing metal compound forming the layer 14 is lower than that in the case where the layer 14 is in contact with the transparent conductive layer 13.

  Specific examples of the nitrogen-containing light-absorbing metal compound mainly constituting the nitrogen-containing light absorption layer 14 include zirconium nitride, chromium nitride, titanium nitride, niobium nitride, hafnium nitride, zirconium oxynitride, chromium oxynitride, and titanium oxynitride. , Niobium oxynitride, and hafnium oxynitride. As the nitrogen-containing light-absorbing metal compound, the metal nitrides exemplified above are preferable. When the nitrogen-containing light-absorbing metal compound is an oxynitride of the metal exemplified above, the ratio of oxygen to 1 mol of nitrogen in the compound is preferably 0.5 mol or less, more preferably 0.2 mol or less. . The nitrogen-containing light-absorbing metal compound may be used alone or in combination of two or more to form the nitrogen-containing light-absorbing layer 14.

The nitrogen-containing light-absorbing layer 14 is preferably made of a nitrogen-containing light-absorbing metal compound mainly composed of titanium nitride, and is preferably made of only titanium nitride or titanium oxynitride. Note that the titanium nitride does not necessarily need to be composed of titanium nitride having a stoichiometric composition ratio (Ti: N = 1: 1). It may be made of titanium. The same applies to nitrides of other metals described above. Further, in the present specification, a metal nitride or oxide represented by a nitriding + metal name or an oxidizing + metal name is a stoichiometric composition ratio or a non-stoichiometric composition ratio unless otherwise specified. Represents a nitride or an oxide. If necessary, for example, also be described as TiN _x if titanium nitride.

  Further, for example, when the precursor layer of the nitrogen-containing light absorption layer 14 is made of titanium nitride and is heat-treated as described above, the titanium nitride of the precursor layer is oxidized to titanium oxynitride. That is, the nitrogen-containing light absorbing layer 14 thus obtained is made of titanium oxynitride. In this case, the ratio of oxygen to 1 mol of nitrogen is preferably 0.5 mol or less, more preferably 0.2 mol or less, as described above. preferable.

  The thickness of the nitrogen-containing light absorbing layer 14 is not particularly limited as long as the obtained transparent substrate with a laminated film 10A has an appropriate visible light transmittance and can achieve high heat shielding properties and high color rendering properties. Therefore, the thickness of the nitrogen-containing light absorption layer 14 is more than 10 nm, preferably 20 to 60 nm, more preferably 25 to 50 nm. Note that the above preferred range is a case where the transparent conductive layer 13 and the nitrogen-containing light absorption layer 14 are formed in order from the transparent substrate 11 side, like the transparent substrate with a laminated film 10A shown in FIG. The thickness of the transparent conductive layer 13 shown above is also a preferable thickness in the lamination order.

  When the transparent conductive layer 13 and the nitrogen-containing light absorption layer 14 are formed in this order from the transparent substrate 11 side, the thickness of the nitrogen-containing light absorption layer 14 is 10 nm. It is super, preferably 20 to 60 nm, more preferably 25 to 50 nm. In this case, the thickness of the transparent conductive layer 13 is preferably from 10 to 200 nm, more preferably from 50 to 150 nm.

  FIG. 2 is a cross-sectional view of a transparent substrate with a laminated film 10B in which a laminated film 12B is formed on the transparent substrate 11 instead of the laminated film 12A on the transparent substrate with a laminated film 10A shown in FIG. The laminated film 12B includes a transparent conductive layer 13, a nitrogen-containing light absorbing layer 14, and a dielectric layer 15 formed in this order from the transparent substrate 11 side. The laminated film 12B can be the same as the laminated film 12A except for the dielectric layer 15.

  The dielectric layer 15 has a function of improving the mechanical durability and chemical durability of the laminated film 12B, and suppressing the nitrogen-containing light absorbing layer 14 from being oxidized by oxygen in the atmosphere. The dielectric layer 15 is not particularly limited as long as it has the above function. For example, aluminum, silicon nitride which may be doped with boron, a metal nitride such as aluminum nitride, aluminum, boron or the like is doped. It can be made of a dielectric containing a metal compound selected from metal oxynitrides such as silicon oxynitride and aluminum oxynitride, and metal oxides such as tin zinc oxide which may be used.

  The dielectric layer 15 mainly composed of at least one selected from silicon nitride, silicon oxynitride, silicon nitride or silicon oxynitride doped with aluminum and / or boron, aluminum nitride, aluminum oxynitride, and tin zinc oxide is preferable. . The dielectric layer 15 may be formed by using one kind of the metal compound as a dielectric or by using two or more kinds in combination.

  Like the above-mentioned titanium nitride, silicon nitride does not necessarily need to be composed of silicon nitride (Si: N = 3: 4) having a stoichiometric composition ratio. It may be composed of silicon nitride having a composition ratio. The same applies to aluminum nitride.

  The dielectric layer 15 is particularly preferably made of a material mainly composed of silicon nitride doped with aluminum and / or boron. Aluminum and boron are additional elements that are usually added to a sputtering target to facilitate sputtering of silicon nitride. The content of the additional element is preferably 15% by mass or less in the total amount of silicon nitride and the additional element.

  The thickness of the dielectric layer 15 is not particularly limited as long as the obtained transparent substrate with a laminated film 10B has an appropriate visible light transmittance and can achieve high heat shielding properties and high color rendering properties. Specifically, the thickness of the dielectric layer 15 is preferably from 20 to 80 nm, more preferably from 30 to 70 nm.

  2, a transparent conductive layer 13, a nitrogen-containing light absorption layer 14, and a dielectric layer 15 are formed in this order from the transparent substrate 11 side. Like the transparent substrate with a laminated film 10A, also in the transparent substrate with a laminated film 10B, each layer constituting the laminated film has an appropriate visible light transmittance, and also has a high heat shielding property, a low heat insulating property and a high color rendering property. If it can be achieved, the nitrogen-containing light absorbing layer 14, the transparent conductive layer 13, and the dielectric layer 15 may be formed in this order from the transparent substrate 11 side.

  When the laminated film in the transparent substrate with a laminated film has a transparent conductive layer, a nitrogen-containing light absorbing layer and a dielectric layer, the order of lamination of the three layers in the laminated film is as follows: the transparent conductive layer, the nitrogen-containing light It is preferable to use an absorption layer and a dielectric layer. With such a laminated film, the color tone of the reflected light on the transparent substrate side can be adjusted by the thickness of the transparent conductive layer, and the color tone of the reflected light on the laminated film side can be adjusted by the film thickness of the dielectric layer. Have.

  The thickness of the dielectric layer 15 depends on the case where the laminated film 12B is formed in the order of the transparent conductive layer 13, the nitrogen-containing light absorbing layer 14, and the dielectric layer 15 from the transparent substrate 11 side. There is no difference from the case where the nitrogen-containing light absorbing layer 14, the transparent conductive layer 13, and the dielectric layer 15 are formed in this order from the side.

  As for the dielectric layer 15 of the transparent substrate with laminated film 10B, when the transparent substrate with laminated film 10B is produced by a production method involving heat treatment in the same manner as the transparent substrate with laminated film 10A, the precursor layer of the dielectric layer 15 is heat-treated. The subsequent dielectric layer 15 has substantially the same composition, but is appropriately oxidized by oxygen contained in the atmosphere or the transparent substrate during the heat treatment.

  In the transparent substrate with a laminated film 10B, when the laminated film is formed in the order of the nitrogen-containing light absorbing layer 14, the transparent conductive layer 13, and the dielectric layer 15 from the transparent substrate 11 side, the transparent conductive layer 13 and the dielectric layer 15 are in contact with each other. With such a configuration, for example, when oxygen is contained so that the atmosphere of the heat treatment when producing the transparent substrate with a laminated film 10B by the production method involving the above-described heat treatment is air, the nitrogen-containing light absorbing layer 14 and the dielectric layer 15 can serve to prevent or suppress the transparent conductive layer 13 from being excessively oxidized. That is, in the manufacturing process, during the heat treatment, the precursor layer of the transparent conductive layer 13 is oxidized by oxygen in the air or oxygen contained in the transparent substrate 10B, but the nitrogen-containing light absorption layer 14 and the dielectric layer 15 are appropriately It is considered that by blocking oxygen, the degree of oxidation is adjusted to a more preferable degree, and the transparent conductive layer 13 having low resistance is finally obtained.

  In this case, as described above, the nitrogen-containing light-absorbing metal compound constituting the nitrogen-containing light-absorbing layer 14 is a component obtained by oxidizing the component constituting the precursor layer during the heat treatment. The metal compound which is a dielectric composing the dielectric layer 15 is a component obtained by oxidizing a component composing the precursor layer during the heat treatment.

  Although not shown, other layers may be formed on the laminated film 12A and the laminated film 12B as necessary, in addition to the above-described layers, as long as it is necessary and within a range not inconsistent with the gist of the present invention. For example, functions as a barrier layer between the transparent substrate 11 and the transparent conductive layer 13, between the transparent conductive layer 13 and the nitrogen-containing light absorption layer 14, between the nitrogen-containing light absorption layer 14 and the dielectric layer 15. A metal layer, an oxide layer, a nitride layer, a carbide layer, or a composite compound layer thereof may be provided. Specifically, a metal layer, an oxide layer, a nitride layer, a carbide layer, or a composite compound containing an element such as titanium, zirconium, niobium, tantalum, chromium, zinc, aluminum, gallium, indium, silicon, or tin Layers.

The transparent substrate with a laminated film of the present invention, having the above-described configuration, has an appropriate visible light transmittance, can achieve high heat shielding properties and high color rendering properties, and is excellent in durability. The transparent substrate with a laminated film of the present invention having such characteristics can be used as a window glass as a single plate, for example, as shown in FIG. FIG. 3 is a cross-sectional view when one example of a transparent substrate with a laminated film of the present invention is used as a single pane as a window glass. A window glass 30 shown in FIG. 3 includes a transparent substrate 11 and a transparent substrate 10 with a laminated film having a laminated film 12 formed on the transparent substrate 11, and is used in a state where the laminated film 12 is exposed to the indoor atmosphere. Is done.
Specifically, the transparent substrate with a laminated film of the present invention preferably satisfies the following characteristics.

  In the transparent substrate with a laminated film of the present invention, the total solar energy transmission (g value) measured in conformity with ISO9050: 2003 is preferably 0.44 or less, more preferably 0.40 or less, and 0.34 or less. The following are particularly preferred. Here, when the transparent substrate with the laminated film is used as shown in FIG. 3, the g value is emitted to the laminated film side when the solar radiation incident from the transparent substrate side of the transparent substrate with the laminated film is set to 1. It is a value indicating the ratio of solar radiation heat. From the g value, it is possible to know the heat shielding property, that is, how much heat (solar heat) generated by sunlight is blocked.

  In the transparent substrate with a laminated film of the present invention, the g value is directly transmitted heat (hereinafter, also referred to as “transmitted heat”) with respect to the amount of solar radiation incident from the transparent substrate side, and is absorbed and then released to the laminated film side. Heat (hereinafter also referred to as “radiant heat”). The g value is represented by a number between 0 and 1. The g value can be specifically calculated by measuring the spectral characteristics of the transparent substrate with a laminated film and introducing the measured value into a predetermined formula. As the g value is smaller, the ratio of the total amount of transmitted heat and radiated heat to the amount of solar heat incident from the transparent substrate side of the transparent substrate with a laminated film is smaller.

  In the transparent substrate with a laminated film of the present invention, the visible light transmittance (Tv) measured according to ISO9050: 2003 is preferably 35% or more. The visible light transmittance (Tv) is preferably 65% or less from the viewpoint of antiglare properties required for window glasses in low latitude to middle latitude regions such as Southeast Asia where daylight is strong. The visible light transmittance (Tv) is particularly preferably from 40 to 60%.

  Regarding the design of building windows, the larger the ratio of window area to the total area of the building side, the more visible light can be taken from the sun into the building, but the amount of solar heat that is simultaneously taken in is large. Become. In general large buildings, the ratio of window area to the total area of the building side called WWR (Window to Wall Ratio) is often 0.4 or more, and many buildings exceed 0.7. Exists.

Here, in a hot region from low to middle latitudes, the total amount of heat that is transmitted from the side of the building to the inside of the building through windows and walls and the amount of heat that enters through the windows as solar radiation is the total area of the building OTTV (Overall Thermal Transfer Value) is known as a value divided by the total area of the windows. In recent years, there has been an increasing demand for improving the energy-saving performance of buildings, and reducing the OTTV to 50 W / m ² or less is becoming a guide. In general, since the amount of heat flowing into and out of the window is larger than that of the wall, in order to satisfy the OTTV of 50 W / m ² , the ratio of the wall has to be increased and the WWR has to be reduced. That is, if the heat inflow and outflow from the window can be reduced, the WWR can be increased while the OTTV satisfies 50 W / m ² or less.

When the transparent substrate with a laminated film is used as shown in FIG. 3, the OTTV is set to 50 W / m ² or less, for example, when the g value of the transparent substrate with the laminated film 10 constituting the window glass 30 is in the above preferable range. Can be widened to about 0.3. If the g value is 0.4 or less, the WWR can be widened to about 0.35, and if the g value is 0.34 or less, the WWR can be widened to about 0.4.

  In the above example, the WWR is set to 0.3 or more for the purpose of enhancing the lighting property from the window. If the building has a WWR of about 0.3 or more, by setting the visible light transmittance (Tv) within the above range, it is possible to sufficiently light the building. A higher WWR is preferable from the viewpoint of daylighting properties.

  Further, a good balance relationship between the visible light transmittance (Tv) and the g value is obtained by the selection coefficient calculated by the formula of Tv / (g value × 100) using the g value and the visible light transmittance (Tv). Can be estimated. From the viewpoint of achieving appropriate visible light transmittance and high shielding properties, the transparent substrate with a laminated film of the present invention preferably has a selectivity coefficient of 1.1 or more, more preferably 1.2 or more.

  Furthermore, in the transparent substrate with a laminated film of the present invention, the color rendering of transmitted light evaluated by an average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) is 90% or more. Is preferred. When the color rendering property evaluated in this way is 90% or more, when the transparent substrate with a laminated film is used as shown in FIG. 3, the appearance when the window glass 30 is viewed from the outside of the building is natural. It becomes a neutral color. The color rendering property is preferably at least 92%, more preferably at least 94%. In the present specification, “color rendering property” means color rendering property measured by the above method unless otherwise specified.

  In the transparent substrate with a laminated film of the present invention, from the viewpoint of durability, particularly chemical durability, the surface of the laminated film is measured by observing the surface of the laminated film with a microscope (50 times) after a three-day sweat resistance test based on ISO12870. It is preferable that the number of defects in the range of 1 mm × 1 mm (hereinafter, simply referred to as “the number of defects by the sweat resistance test”) is 50 or less.

  In the sweat resistance test, specifically, an artificial sweat containing 50 g / L of lactic acid and 100 g / L of sodium chloride was poured into a closed container, and the transparent substrate with the laminated film was separated from the artificial sweat in the closed container. Can be performed by observing the surface of the laminated film with a microscope after disposing and keeping the container in a sealed state at 55 ± 5 ° C. for 3 days.

  In addition, the defect after the above-mentioned sweat resistance test observed with a microscope (50 times) is specifically discoloration and peeling. In the present specification, the number of defects evaluated in the sweat resistance test refers to the sum of the numbers of the two unless otherwise specified. Note that these determinations are made visually. The number of defects in the sweat resistance test is more preferably 5 or less.

In the transparent substrate with a laminated film of the present invention, the color tone of the reflected light on the transparent substrate side is preferably such that a ^* is 5 or less over the total reflection angle in CIE1976L ^* a ^* b ^* chromaticity coordinates, and a ^* is 2 The following is more preferred. If a ^* is 5 or less over the total reflection angle in the color tone of the reflected light on the transparent substrate side, when a transparent substrate with a laminated film is used as shown in FIG. It is preferable because the reddishness of the reflected light is suppressed from any angle.

In addition, it is preferable that various colors can be designed because it greatly affects the reflection color on the transparent substrate side and the appearance of the building. Specifically, the color tone of the reflected light having a reflection angle of 0 degree should be green. For example, -20 ≦ a ^* ≦ −5 and -5 ≦ b ^* ≦ 2, -7 ≦ a ^* ≦ 2-25 ≦ b ^* ≦ -7 for a blue tone, and -4 for an achromatic color. ≦ a ^* ≦ 2 and -4 ≦ b ^* ≦ 2 are preferred. Note that the reflected light having a reflection angle of 0 degrees refers to reflected light in a direction orthogonal to the surface of the stacked film. Here, the reflection color tone with a reflection angle of 0 degree is described. However, since the reflection of 0 degree cannot be actually measured, the reflection light measurement is performed at the reflection angle of 5 to 15 degrees, at which the color hardly changes from 0 degree. It is common to do. Hereinafter, although the reflection angle is described as 0 degree for convenience, there is no difference when any one of the reflection angles of 5 to 15 degrees is used.

Further, in the transparent substrate with a laminated film of the present invention, the color tone of the reflected light having a reflection angle of 0 degree on the laminated film side is preferably such that a ^* is 5 or less in CIE1976L ^* a ^* b ^* chromaticity coordinates. ^* Is more preferably 2 or less. If a ^* is 5 or less in the color tone of the reflected light having a reflection angle of 0 degree on the laminated film side, when a transparent substrate with a laminated film is used as shown in FIG. This is preferable because the red tint of the reflected light is suppressed. In the above, a ^* is preferably 0 or more. Furthermore, in order to suppress yellow tint, b ^* is preferably 0 or less, more preferably -35 ≦ b ^* ≦ 0, and even more preferably −35 ≦ b ^* ≦ −10.

Further, in the transparent substrate with a laminated film of the present invention, the visible light reflectance (Rv ₁ ) on the transparent substrate side is preferably 20% or less, and the visible light reflectance (Rv ₂ ) on the laminated film side is preferably 15% or less. . The visible light reflectance (Rv) is measured according to ISO9050: 2003.

  The manufacturing method of the transparent substrate with a laminated film of the present invention is not particularly limited as long as the laminated film having the above configuration is formed on the transparent substrate. The transparent substrate with a laminated film of the present invention, for example, on the transparent substrate, the transparent conductive layer and the nitrogen-containing light absorption layer respectively by the following heat treatment, the precursor layer of the transparent conductive layer and the nitrogen-containing light absorption Forming a precursor layer of the layer to obtain a coated transparent substrate, and heat-treating the coated transparent substrate in an air at 550 to 750 ° C. for 1 to 30 minutes, or in an air at 150 to 450 ° C. Heat treatment for 15 minutes to 4 hours.

  When the laminated film of the transparent substrate with a laminated film has a dielectric layer, a precursor layer of the dielectric layer to be the dielectric layer is formed by the heat treatment together with the two precursor layers in the coating step. The same applies to the case where the transparent substrate with a laminated film has another layer.

  In the case of manufacturing a transparent substrate with a laminated film by the above method, first, in a coating step, a surface of the transparent substrate is cleaned, and a precursor layer of each layer is formed on the surface. The film formation method is not particularly limited, and physical vapor deposition (vacuum vapor deposition, ion plating, sputtering), chemical vapor deposition (thermal CVD, plasma CVD, light CVD), ion beam sputtering Etc. can be applied. When the area of the transparent substrate is large, the direct current or alternating current dual sputtering method is preferable because the uniformity of the thickness is easily controlled and the productivity is excellent.

  For example, when a transparent conductive layer precursor layer is formed by a sputtering method, the transparent conductive layer precursor layer can be formed under normal processing conditions using a transparent conductive metal oxide target. The thickness can be adjusted by adjusting the type of sputtering gas, reaction temperature, and reaction time. Similarly, a precursor layer of the nitrogen-containing light absorption layer and a precursor layer of the dielectric layer are formed. The stacking order of each precursor layer can be the same as the stacking order of the obtained laminated film.

  Note that the composition of a material such as a target used for forming a precursor layer of each of the above layers is appropriately adjusted depending on the atmosphere in the heat treatment step described below. When a controlled atmosphere such as an inert gas atmosphere containing no oxidizing gas or a vacuum atmosphere can be set in the heat treatment step, the resulting transparent conductive layer, the nitrogen-containing light absorbing layer, and the material forming the dielectric layer can be used. The composition is the same as the composition of the constituent material of the precursor layer. When the atmosphere in the heat treatment process contains an oxidizing gas such as air, the material such as a transparent conductive layer, a nitrogen-containing light absorption layer, and a dielectric layer that is finally obtained in consideration of oxidation of the material during the heat treatment. The material composition of the precursor layer is selected so that the composition becomes a predetermined composition.

  Next, the coated transparent substrate is heat-treated. The heat treatment temperature is preferably 550 to 750 ° C, more preferably 600 to 750 ° C, and particularly preferably 600 to 720 ° C. When the heat treatment is performed at such a temperature, a glass substrate is used as the transparent substrate, and an effect is obtained in which a transparent substrate with a laminated film reinforced with sufficient reliability can be obtained.

  The heat treatment temperature may also be between 150 and 450C. In this case, 200 to 400 ° C is more preferable, and 250 to 350 ° C is particularly preferable. When the heat treatment is performed at such a temperature, a resin substrate can be used as the transparent substrate. When the transparent substrate is a glass substrate, it cannot be strengthened, but has an effect that an inexpensive apparatus can be used because of low-temperature treatment.

  The heat treatment time is preferably 1 to 30 minutes when the heat treatment temperature is 550 to 750 ° C. When the heat treatment temperature is 150 to 450 ° C., the heat treatment time is preferably 15 minutes to 4 hours. The heat treatment method is such that, by using the precursor layer adjusted according to the atmosphere, for example, using a heating furnace having an airtight structure, the heat treatment is performed under an atmosphere controlled to an inert gas atmosphere containing no oxidizing gas or a vacuum atmosphere. Or a method of heating the coated transparent substrate in a heating furnace installed in the atmosphere. Heat treatment using a heating furnace installed in the atmosphere, that is, a heating furnace having a simple structure is advantageous in terms of economy and workability.

  Although the embodiments of the present invention have been described above, these embodiments are presented as examples and do not limit the scope of the invention. These new embodiments can be implemented in other various forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. For example, the transparent substrate with a laminated film is suitable for buildings, but is not necessarily limited to buildings, and may be used for vehicles such as automobiles as far as applicable.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Note that the present invention is not limited to these.

(Example 1)
As a transparent substrate, soda lime glass (FL6, manufactured by Asahi Glass Co., Ltd.) having a thickness of 6.0 mm was prepared. After washing this glass substrate, it was set on a substrate holder.

A composite oxide sintered body target having a SnO ₂ content of 10% by mass with respect to the total amount of In ₂ O ₃ and SnO ₂ (hereinafter also referred to as “ITO composite oxide sintered body target”) and metal Ti A silicon target containing 10% by mass of aluminum (hereinafter referred to as a SiAl target) was attached to a cathode for performing intermittent DC magnetron sputtering. The intermittent cycle was 5 μs for the ON time and 45 μs for the OFF time.

  Next, after the inside of the film formation chamber was evacuated to vacuum, an ITO layer having a thickness of 96 nm was formed on a glass substrate by an intermittent DC magnetron sputtering method using an ITO composite oxide sintered body target. Here, only argon was used as a sputtering gas, and the pressure during sputtering was 3 mTorr. The composition of the formed ITO layer was equivalent to that of the target. Note that a small amount of oxygen was introduced into the sputtering gas.

Next, a titanium nitride layer (TiN _x layer) having a thickness of 33 nm was formed on the ITO layer by an intermittent DC magnetron sputtering method using a metal Ti target. The sputtering gas used was argon and nitrogen, and the ratio of argon / nitrogen was 17/3. The pressure during sputtering was 3 mTorr.

Next, an Al-doped silicon nitride layer (SiN _x : Al layer) having a thickness of 55 nm was formed by an intermittent DC magnetron sputtering method using a SiAl target. Here, argon and nitrogen were used as sputtering gases, and the ratio of argon / nitrogen was 9/7. The pressure during sputtering was 3 mTorr. Thus, on the glass substrate, in order from the glass substrate side, an ITO layer which is a precursor layer of the transparent conductive layer, a TiN _x layer which is a precursor layer of the nitrogen-containing light absorption layer, and a SiN _x layer which is a precursor layer of the dielectric layer : A coated glass substrate on which an Al layer was formed was prepared.

  Note that the glass substrate was not heated during the formation of any of the layers. The obtained coated glass substrate is air-cooled and strengthened, that is, subjected to a heat treatment at 650 ° C. for 5 minutes in the air in an electric firing furnace, and a transparent conductive layer made of ITO is sequentially formed on the glass substrate from the glass substrate side. A transparent substrate A with a laminated film was obtained in which a nitrogen-containing light absorbing layer made of titanium oxynitride oxidized with TiNx and a dielectric layer made of silicon oxynitride doped with Al oxidized with SiNx: Al were formed.

(Example 2)
In Example 1, as a coated glass substrate, a coated glass substrate having a thickness of an ITO layer of 72 nm, a thickness of a titanium nitride layer of 42 nm, and a thickness of an Al-doped silicon nitride layer of 59 nm was prepared. A transparent substrate B with a laminated film was obtained in the same manner as in Example 1.

(Example 3)
In Example 1, as a coated glass substrate, except that an ITO layer having a thickness of 131 nm, a titanium nitride layer having a thickness of 32 nm, and an Al-doped silicon nitride layer having a thickness of 40 nm was prepared, A transparent substrate C with a laminated film was obtained in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, as a coated glass substrate, a coated glass substrate was prepared in which the thickness of the ITO layer was 96 nm, the thickness of the titanium nitride layer was 5 nm, and the thickness of the Al-doped silicon nitride layer was 55 nm. A transparent substrate D with a laminated film was obtained in the same manner as in Example 1.

(Comparative Example 2)
When a green heat ray absorbing glass (manufactured by Asahi Glass Co., Ltd., indicated as “TG” in Table 1) having a thickness of 6 mm is formed as a transparent substrate, Chemical Vapor Deposition (installed on a float line for manufacturing glass) ( A SiOC layer (80 nm) and a Sb-doped SnO ₂ layer (320 nm) were formed in this order by a CVD) apparatus to obtain a transparent substrate E with a laminated film.

(Comparative Example 3)
As a transparent substrate, soda lime glass (FL6, manufactured by Asahi Glass Co., Ltd.) having a thickness of 6.0 mm was used, and a silicon nitride layer (10 nm) and a chromium nitride layer were formed on the transparent substrate by the same sputtering apparatus as in Example 1. (10 nm) and a silicon nitride layer (20 nm) were formed in that order to obtain a transparent substrate F with a laminated film.

  Next, the following evaluation was performed about the transparent substrate with a laminated film of an Example and a comparative example. The results are shown in Table 1 together with the constituent materials and thickness of each layer of the laminated film. In Examples 1 to 3 and Comparative Example 1, the constituent material of each layer of the laminated film is the constituent material of the precursor layer.

(optical properties)
Using a Hitachi spectrophotometer (U-4100 type), a spectroscopic measurement of the transparent substrate with a laminated film was performed. In accordance with ISO9050: 2003, g value when light is incident from a transparent substrate, visible light transmittance (Tv), visible light reflectance (Rv ₁ ) on the transparent substrate side, and visible light reflectance on the laminated film side (Rv ₂ ) was determined. The color rendering of transmitted light evaluated by the average color rendering index (Ra) was determined in accordance with JIS Z8726 (1990).

Further, a selection coefficient (Tv / (g value × 100)) was calculated from the visible light transmittance (Tv) and the g value. Further, the color tone (Rc ₁ ) of the reflected light on the transparent substrate side of the transparent substrate with the laminated film and the color tone (Rc ₂ ) of the reflected light on the laminated film side, specifically, the CIE1976L ^* a ^* b ^* chromaticity coordinates a ^* and b ^* were measured at a reflection angle of 10 degrees according to JIS Z 8722, and determined according to JIS Z 8729. Table 1 shows the maximum values of a ^* and b ^* among the values measured over the total reflection angle on the transparent substrate side.

(durability)
[Sweat resistance test]
A sweat resistance test was performed according to ISO12870. That is, the artificial sweat was injected into the closed container, the transparent substrate with the laminated film was placed in the closed container apart from the artificial sweat, and then kept in a sealed state at 55 ± 5 ° C. for 3 days. The artificial sweat contains 50 g / L of lactic acid and 100 g / L of sodium chloride. Thereafter, the transparent substrate with the laminated film was taken out of the sealed container, the surface of the laminated film was observed with a microscope (50 times), the number of defects in a range of 1 mm × 1 mm was visually measured, and evaluated according to the following criteria.

<Evaluation criteria>
5; 101 or more defects 4; 51 to 100 defects 3; 31 to 50 defects 2; 6 to 30 defects 1; 0 to 5 defects

[Chemical resistance test]
According to JIS R 3221, a test was conducted in which a transparent substrate with a laminated film was immersed in each of 1N-NaOH and 1N-HCl at a temperature of 23 ° C. for 6 hours, and then washed with pure water. The case where the change in haze before and after the test was 4% or less was “A”, and the case where the change exceeded 4% was “C”.

[Cooling cycle]
The transparent substrate with the laminated film was repeatedly subjected to a cooling / heating cycle of −30 ° C. × 5 hours to 80 ° C. × 5 hours (95% RH) for 90 days. After that, the appearance of the transparent substrate with the laminated film was visually inspected. In the table, "A" indicates that there is no deterioration such as corrosion and film peeling visually, and "C" indicates that there is deterioration such as corrosion and film peeling visually.

[Weather resistance test]
A super-xenon lamp (180 W / m ² ) was irradiated to the laminated film surface of the transparent substrate with the laminated film for 2000 hours. After that, the appearance of the transparent substrate with the laminated film was visually inspected. In the table, "A" indicates that there is no deterioration such as corrosion and film peeling visually, and "C" indicates that there is deterioration such as corrosion and film peeling visually.

[Salt resistance test]
The operation of holding the laminated film surface of the transparent substrate with the laminated film for 4 days while spray-supplying 5% NaCl on the surface of the laminated film was repeated four times with one cycle of drying in three days. Thereafter, a visual inspection was performed on the transparent substrate with the laminated film. In the table, "A" indicates that there is no deterioration such as corrosion and film peeling visually, and "C" indicates that there is deterioration such as corrosion and film peeling visually.

[Taber test]
The group B test of JIS R 3221 was repeated 100 times on the laminated film surface of the transparent substrate with the laminated film. The case where the change in haze before and after the test was 4% or less was “A”, and the case where the change exceeded 4% was “C”.

  10A, 10B, 10: transparent substrate with laminated film, 11: transparent substrate, 12A, 12B, 12: laminated film, 13: transparent conductive layer, 14: nitrogen-containing light absorbing layer, 15: dielectric layer, 30: window glass

Claims (5)

A transparent substrate and a laminated substrate having a laminated film, on the transparent substrate, a transparent conductive layer, a nitrogen-containing light-absorbing layer and a dielectric layer laminated in that order from the transparent substrate side,
The thickness of the transparent electrically conductive layer is 10 to 200 nm, the thickness of the nitrogen-containing light absorbing layer has a 10nm ultra and 60nm or less, the thickness of the dielectric layer is Ri 20~80nm der, the laminated film wherein that having a barrier layer between the transparent conductive layer and the nitrogen-containing light absorbing layer, a transparent substrate with film stack. The barrier layer is a metal layer, an oxide layer, a nitride layer, a carbide layer, or a composite compound layer containing an element of titanium, zirconium, niobium, tantalum, chromium, zinc, aluminum, gallium, indium, silicon, or tin. it is either, laminated film-coated transparent substrate as claimed in claim 1. The transparent substrate is air cooling tempering glass, laminated film with a transparent substrate according to claim 1 or 2. The nitrogen-containing light-absorbing layer is mainly composed of a nitrogen-containing light-absorbing metal oxynitride, and the ratio of oxygen to 1 mol of nitrogen in the nitrogen-containing light-absorbing metal oxynitride is 0.5 mol or less. Item 4. The transparent substrate with a laminated film according to any one of Items 1 to 3 . It is a window glass which has the transparent substrate with a laminated film as described in any one of Claims 1-4 , Comprising: The said transparent substrate is a single plate, The window glass in which the laminated film is exposed to the indoor side.

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