JP6459374B2 - Transparent substrate with window glass and laminated film - Google Patents

Description

  The present invention relates to a window glass and a transparent substrate with a laminated film.

  When considering the energy-saving performance of building window glass in a hot region, for example, a region from low latitude to mid-latitude such as Southeast Asia, it is required to have a high visible light transmittance and a high heat shielding performance. On the other hand, although it is not conscious about heat insulation performance, when a window glass has high heat insulation performance, the solar radiation heat taken in the room | chamber interior is not discharge | released but the cooling load will rise as a result. Therefore, in addition to high visible light transmittance and high heat shielding performance, low heat insulation performance is required for architectural window glass.

  Here, it is necessary to lower the emissivity in order to give the window glass high heat shielding performance, but it is known that if the emissivity is excessively lowered, the heat insulation performance is increased. It was necessary to adjust appropriately. Furthermore, architectural window glass is required to have a property that transmitted light and reflected light are close to natural light, that is, high color rendering properties.

  As a window glass that achieves the above functions, a single-panel 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 is conceivable. However, in the past, the silver-based optical multilayer film has been used within the double-glazed glass having high heat insulation performance and has exhibited high heat shielding performance. And it was a problem in that mechanical durability could not be sufficiently obtained.

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

  In this way, in combination of a transparent substrate such as a glass substrate and various coating films, the transparent substrate and the coating film satisfying the above-mentioned various characteristics suitable for use as a window glass in a low-latitude to mid-latitude hot region. At present, no window glass with high heat shielding properties has been obtained.

JP 2005-529823 A

  The present invention has been made to solve the above-described problems, and provides a highly heat-insulating window glass and a transparent substrate with a highly heat-insulating laminated film, which are suitable for use in a hot region from low to middle latitudes. With the goal.

The window glass of the first aspect of the present invention comprises a transparent substrate and a transparent substrate with a laminated film having a laminated film formed on the transparent substrate, and is used in a state where the laminated film is exposed to the indoor air. The heat transmissivity (U value) measured in accordance with JIS R3106 / 3107 (1998) is 3.4 to 4.7 W / m ² · K, and the solar heat gain (η value) is 0.17 to 0.44 and a visible light transmittance (Tv) of 35% or more, and a color rendering property 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, and the number of defects in the range of 1 mm × 1 mm, which is measured by observing the surface of the laminated film with a microscope (50 times) after a 3-day sweat resistance test according to ISO12870, is 50 or less.

  The window glass of the second aspect of the present invention comprises a transparent substrate and a transparent substrate with a laminated film having a laminated film formed on the transparent substrate, and is used in a state where the laminated film is exposed to the indoor air. And calculated by the equation Tv / (η value × 100) using the solar heat gain (η value) and visible light transmittance (Tv) measured according to JIS R3106 / 3107 (1998). The selection coefficient is 1.1 or more, and the color rendering properties of transmitted light evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) is 90% or more. The number of defects in the range of 1 mm × 1 mm, which is measured by observing the surface of the laminated film with a microscope (50 times) after a compliant 3-day sweat resistance test, is 50 or less.

The transparent substrate with a laminated film according to the third aspect of the present invention includes a transparent substrate and a laminated film formed on the transparent substrate, and the thermal conductivity measured in accordance with JIS R3106 / 3107 (1998). (U value) is 3.4 to 4.7 W / m ² · K, solar heat gain (η value) measured on the laminated film side is 0.17 to 0.44, and visible light transmittance (Tv) ) Is 35% or more, and the color rendering properties of transmitted light evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) is 90% or more.

  The transparent substrate with a laminated film according to the fourth aspect of the present invention has a laminated film including a transparent substrate and a metal layer mainly composed of silver formed on the transparent substrate, and has a resistance to resistance for 3 days according to ISO12870. The number of defects in the range of 1 mm × 1 mm measured by observing the surface of the laminated film with a microscope after the sweat test is 50 or less.

  According to the present invention, it is possible to provide a highly heat-insulating window glass and a highly heat-insulating transparent substrate with a laminated film that are suitable for use in a hot region from low to middle latitudes.

It is sectional drawing which shows an example at the time of use of one Embodiment of the window glass of this invention. It is sectional drawing of one Embodiment of a transparent substrate with a laminated film. It is sectional drawing which shows the modification of one Embodiment of the transparent substrate with a laminated film. It is sectional drawing which shows another embodiment of the transparent substrate with a laminated film. It is sectional drawing which shows the modification of another embodiment of the transparent substrate with a laminated film.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, this invention is limited to the following description and is not interpreted.

[Transparent substrate with window glass and laminated film]
FIG. 1 is a cross-sectional view showing an example when the window glass of the embodiment of the present invention is used. 2 and 3 are enlarged cross-sectional views showing an embodiment of a transparent substrate with a laminated film constituting the window glass of the present invention and a modification thereof. 4 and 5 are enlarged sectional views showing another embodiment of a transparent substrate with a laminated film constituting the window glass of the present invention and a modification thereof.

  As shown in FIG. 1, a window glass 30 according to an embodiment of the present invention includes a transparent substrate 10 and a transparent substrate with a laminated film 10 having a laminated film 12 formed on the transparent substrate 11. Used in a state exposed to the indoor air. In this specification, the “window glass” refers to a window glass body, such as a handle attached for opening and closing the window glass in use, a frame body such as a sash for attaching the window glass to the window frame, and the like. The window glass itself, not including any accessories.

In the window glass of the first aspect of the present invention, the transparent substrate 10 with a laminated film has the following physical property values (1-a) to (3-a) measured according to JIS R3106 / 3107 (1998). And the following physical property values of (4-a) and (5-a) are satisfied.
(1-a) Thermal conductivity (U value) is 3.4 to 4.7 W / m ² · K.
(2-a) Solar heat acquisition rate (η value) is 0.17 to 0.44.
(3-a) Visible light transmittance (Tv) is 35% or more.
(4-a) The color rendering properties of transmitted light evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) is 90% or more.
(5-a) The number of defects in the range of 1 mm × 1 mm (hereinafter simply referred to as “sweat resistance test” measured by observing the surface of the laminated film with a microscope (50 ×) after a 3-day sweat resistance test according to ISO12870. Is referred to as “the number of defects due to”) is 50 or less.

The larger the ratio of the area of the window to the total area of the side of the building, the more visible light can be taken into the building from sunlight, but the amount of solar heat taken in at the same time also increases. In general large buildings, the ratio of the window area to the total area of the side of the building called WWR (Window to Wall Ratio) is often 0.4 or more, and many buildings exceed 0.7. Exists. Also, in the low-latitude to mid-latitude hot areas, the total amount of heat transmitted from the side of the building through the windows and walls to the inside of the building and the amount of heat that enters through the windows as solar heat (walls and windows). OTTV (Overall Thermal Transfer Value) is known as a value divided by (total area). For example, if the thermal insulation performance required for the window glass in hot regions is shown using these indices, it is required that the OTTV be 50 W / m ² or less in a building having a WWR of 0.4 or more.

When the transparent substrate 10 with a laminated film constituting the window glass 30 satisfies the above (1-a) and (2-a), for example, in a building having a WWR of 0.4 or more, OTTV is 50 W / m ^2. It is possible to:

The heat transmission coefficient (U value) is preferably ^{3.4~4.4W / m 2 · K, 3.4~4.2W} / m 2 · K being more preferred. The heat transmissivity (U value) indicates the amount of heat (W) that passes 1 m ² per hour when the temperature difference is 1 degree between the inside and outside of the transparent substrate 10 with a laminated film, and is an index for measuring heat insulation. It means that it is excellent in heat insulation, so that a heat transmissivity (U value) is small.

  Further, the solar heat gain rate (η value) is preferably 0.17 to 0.40, more preferably 0.17 to 0.35. Here, the solar heat acquisition rate (η value) is a value indicating the ratio of the amount of heat flowing into the laminated film 12 side when the solar energy incident from the transparent substrate 11 side of the transparent substrate 10 with laminated film is taken as 1. . From the solar heat acquisition rate (η value), it is possible to know the degree of heat shielding, that is, how much heat generated by sunlight (sun heat) is blocked.

  The solar heat acquisition rate is the heat directly transmitted to the solar energy incident from the transparent substrate 11 side (hereinafter also referred to as “transmission heat”) and the heat absorbed and then released to the laminated film 12 side (hereinafter “ It is also the ratio of the total amount of heat. The solar heat acquisition rate is represented by a number between 0 and 1. Note that the solar heat acquisition rate can be calculated by measuring the spectral characteristics and emissivity of the laminated film-equipped transparent substrate 10 and introducing them into a predetermined calculation formula. The smaller the solar heat acquisition rate, the smaller the ratio of the total amount of transmitted heat and radiant heat to the amount of solar heat incident from the transparent substrate 11 side in the transparent substrate 10 with a laminated film.

  In the above example, WWR is set to 0.4 or more for the purpose of improving the daylighting from the window. If the building has a WWR of approximately 0.4 or more, the visible light transmittance (Tv) is set in the above range (3-a), so that lighting in the building can be sufficient. The visible light transmittance (Tv) is preferably 65% or less from the viewpoint of antiglare properties required for window glass in low latitude to middle latitude areas such as Southeast Asia where sunlight is strong in the daytime. The visible light transmittance (Tv) is particularly preferably 40 to 60%.

  When the color rendering property according to (4-a) is 90% or more, the appearance when the window glass 30 is viewed from the outside of the building is a natural intermediate color. The color rendering property is preferably 91% or more, and more preferably 92% or more.

  As shown in FIG. 1, the transparent substrate 10 with a laminated film is used in a state where the laminated film 12 is exposed to the indoor air. Therefore, it is essential to satisfy the physical property values shown in the above (5-a) from the viewpoint of durability.

  Specifically, the sweat resistance test was performed by injecting artificial sweat containing 50 g / L of lactic acid and 100 g / L of sodium chloride into a sealed container, and separating the artificial sweat from the artificial sweat into the sealed container. 10 is placed, sealed, and held at 55 ± 5 ° C. for 3 days, and then the surface of the laminated film 12 can be observed with a microscope.

  Specifically, the defects observed with a microscope (50 times) are silver aggregation, discoloration and peeling. In this specification, the number of defects evaluated by the sweat resistance test means the total number of these three members unless otherwise specified. These determinations are made visually through a microscope (50 times). The number of defects in the sweat resistance test is preferably 30 or less, and more preferably 5 or less.

  The physical properties of the transparent substrate with a laminated film constituting the window glass of the first aspect of the present invention described above are summarized in Table 1 below. In Table 1, rows are physical property items, columns are physical property values, (a) indicates an essential range, (b) indicates a preferable range, and (c) indicates a more preferable range. (1) The range of the (a) column of U values is denoted as (1-a). The range of the physical property value of the transparent substrate with a laminated film may be a combination of (a), (b), and (c) selected from each of the items (1) to (5). .

  The transparent substrate with a laminated film constituting the window glass of the first aspect of the present invention is provided with a laminated film in which the range of the column (a) of each item of (1) to (5) shown in Table 1 is essential. The combination of the range of the most preferable physical property value in this case is a combination of (1-c), (2-c), (3-c), (4-c) and (5-c). is there.

In the window glass of the first aspect of the present invention, the transparent substrate with a laminated film has the physical property values shown in Table 1 described above. In the window glass of the second aspect of the present invention, the transparent substrate with a laminated film satisfies the following physical property values of (6-a), and the above-mentioned (4-a) and (5-a). It satisfies the physical property values.
(6-a) Using the solar heat acquisition rate (η value) and visible light transmittance (Tv) measured according to JIS R3106 / 3107 (1998), Tv / (η value × 100) The calculated selection coefficient is 1.1 or more.

  The selection coefficient is an index for checking the balance between the visible light transmittance (Tv) and the solar heat gain (η value). If the selection coefficient is in the above range, moderate visible light permeability and high shielding properties are obtained. Can be realized. The selection coefficient is preferably 1.2 or more, and more preferably 1.25 or more.

  The physical properties of the transparent substrate with a laminated film in the second aspect of the present invention are summarized in the following Table 2 as described above. In Table 2, rows are physical property items, columns are physical property values, (a) is an essential range, (b) is a preferred range, and (c) is a more preferred range. (4) The range of the (a) row of color rendering properties is shown as (4-a). The range of the physical property values of the transparent substrate with the laminated film is a combination of (a), (b), and (c) selected from the items (4), (5), and (6). It may be.

  The transparent substrate with a laminated film constituting the window glass of the second aspect of the present invention must have the range (a) of each item of (4), (5) and (6) shown in Table 2 as essential. The combination of the range of the most preferable physical property value in this case is a combination of (4-c), (6-c) and (5-c).

Even if the transparent substrate with a laminated film in the window glass of the present invention is of the first aspect according to the essential physical property range of Table 1 above, it is of the second aspect according to the essential physical property range of Table 2 above. Even if it is, the color tone of the reflected light on the transparent substrate side is preferably C ^* 1976L ^* a ^* b ^* chromaticity coordinates, and a ^* ≦ 10 and b ^* ≦ 5. When a ^* ≦ 10 and b ^* ≦ 5, redness of reflected light on the transparent substrate side is suppressed, which is preferable. a ^* is more preferably −25 ≦ a ^* ≦ 7, and further preferably −15 ≦ a ^* ≦ 3. b ^* is more preferably −25 ≦ b ^* ≦ 5, and further preferably −23 ≦ b ^* ≦ 5.

In the transparent substrate with laminated film according to the first and second aspects, the color tone of the reflected light on the laminated film side is preferably a ^* ≦ 15 and b ^* ≦ 5 in the above coordinates. When a ^* ≦ 15 and b ^* ≦ 5, redness of reflected light on the laminated film side is suppressed, which is preferable. a ^* is more preferably −25 ≦ a ^* ≦ 15, further preferably −15 ≦ a ^* ≦ 12, and particularly preferably −15 ≦ a ^* ≦ 8. b ^* is more preferably −35 ≦ b ^* ≦ 0, and further preferably −30 ≦ b ^* ≦ 0.

Furthermore, the visible light reflectance (Rv ₁ ) on the transparent substrate side of the transparent substrate with the laminated film is preferably 25% or less, and the visible light reflectance (Rv ₂ ) on the laminated film side is preferably 20% or less. The visible light reflectance (Rv) is specified in JIS R3106: 1998.

  The present invention, as a third aspect, is a transparent substrate with a laminated film having a transparent substrate and a laminated film formed on the transparent substrate, and the above (1-a), (2-a), (3 A transparent substrate with a laminated film satisfying the characteristics of -a) and (4-a) is provided. The transparent substrate with a laminated film of the third aspect of the present invention that satisfies such characteristics is hereinafter referred to as a transparent substrate with a laminated film (A). It is preferable from the viewpoint of durability that the transparent substrate with laminated film (A) further satisfies the physical property values shown in (5-a) above.

  The physical property values of the transparent substrate with laminated film (A) will be described with reference to Table 1 above. The physical property values of the transparent substrate with laminated film (A) are the physical property items (1) to (4) in Table 1. , Each of (a), (b), and (c) may be selected and combined. The physical property value of the transparent substrate with laminated film (A) may be a combination of (5-a), (5-b) or (5-c). Thus, when selecting the physical property that the transparent substrate with laminated film (A) should have, the number of defects in the sweat resistance test of (5) is an arbitrary item. The most preferable combination of physical property values in the transparent substrate with laminated film (A) is a combination of (1-c), (2-c), (3-c), (4-c) and (5-c) It is.

  The present invention provides, as a fourth aspect, a transparent substrate with a laminated film comprising a transparent substrate and a laminated film comprising a metal layer mainly composed of silver formed on the transparent substrate, the above (5-a) A transparent substrate with a laminated film having the above characteristics as essential physical property values is provided. Such a transparent substrate with a laminated film of the fourth aspect of the present invention is hereinafter referred to as a transparent substrate with a laminated film (B).

  In the transparent substrate with laminated film (B), the number of defects in the sweat resistance test preferably has the above-mentioned characteristic (5-b), and more preferably has the above-mentioned characteristic (5-c). In the transparent substrate (B) with a laminated film, the laminated film includes a metal layer mainly composed of silver, thereby achieving the condition (a) in the physical property items (1) to (4) in Table 1. It can be said.

  Applications of the transparent substrate with laminated film (A) and the transparent substrate with laminated film (B) are not limited. As described above, the laminated film may be used as a window glass with a single plate exposed to the indoor air, or may be used as laminated glass or multilayer glass. In addition, when using a transparent substrate (A) with a laminated film as a window glass by a single plate as mentioned above, what satisfies the characteristic of said (5-a) is used.

  As the laminated glass, for example, a laminated glass having a configuration in which two transparent substrates arranged opposite to each other sandwich an intermediate film and are bonded by the intermediate film. A transparent substrate with a laminated film (A) and a transparent substrate with a laminated film (B) can be used as one or both of such laminated glass transparent substrates. In that case, the laminated film may be disposed on the intermediate film side or may be exposed to the atmosphere. The laminated glass may have three or more transparent substrates.

  Examples of the multi-layer glass include a multi-layer glass having a configuration in which two transparent substrates arranged opposite to each other are sealed at the periphery thereof with a spacer and an intermediate layer is formed between the opposing transparent substrates. A transparent substrate with a laminated film (A) and a transparent substrate with a laminated film (B) can be used for one or both of the transparent substrates of such multilayer glass. In that case, the laminated film may be disposed on the intermediate layer side or may be exposed to the atmosphere. The multilayer glass may have three or more transparent substrates.

  In addition, when using a laminated film with a laminated film exposed to air | atmosphere when using a laminated substrate with a laminated film (A) as a transparent substrate of a laminated glass or a multilayer glass as mentioned above, said (5-a) Those satisfying these characteristics are used.

  Here, in this specification, “glass” such as window glass, laminated glass, and multi-layer glass is not necessarily limited to those using an inorganic glass substrate, and is obtained using a transparent substrate containing organic glass. Used in the concept of transparent articles.

[Configuration of transparent substrate with laminated film]
The transparent substrate with laminated film in the window glass of the first aspect of the present invention, the transparent substrate with laminated film in the window glass of the second aspect, and the transparent substrate with laminated film (A) are all laminated films. For example, it is composed of a laminated film including a metal layer mainly composed of silver, or a laminated film including a transparent conductive layer and a nitrogen-containing light absorbing layer. The laminated film which the transparent substrate with laminated film (B) has is a laminated film including a metal layer mainly composed of silver as described above.

  Hereinafter, each component of the transparent substrate with a laminated film according to the present invention will be described for each constitution of the laminated film with reference to the drawings. FIG. 2 is a cross-sectional view of an example of a transparent substrate with a laminated film having a transparent substrate and a laminated film containing a metal layer mainly composed of silver. FIG. 3 is a cross-sectional view of a modified example of a transparent substrate with a laminated film having a transparent substrate and a laminated film containing a metal layer mainly composed of silver. FIG. 4 is a cross-sectional view of an example of a transparent substrate with a laminated film having a transparent substrate, a laminated film including a transparent conductive layer and a nitrogen-containing light absorbing layer. FIG. 5 is a cross-sectional view of a modified example of a transparent substrate with a laminated film having a laminated film including a transparent substrate, a transparent conductive layer, and a nitrogen-containing light absorbing layer.

First, a transparent substrate with a laminated film having a transparent substrate and a laminated film containing a metal layer mainly composed of silver as shown in FIG. 2 or FIG. 3 will be described.
A transparent substrate with a laminated film 10A shown in FIG. 2 includes a transparent substrate 11 and a laminated film 12A including a metal layer 123 mainly composed of silver on the transparent substrate 11.

(Transparent substrate)
The transparent substrate 11 is not specifically limited, For example, the glass substrate which has inorganic transparency, such as a window glass for buildings, the float glass normally used, or the soda-lime glass manufactured by the roll-out method can be used. . As a glass substrate, colorless things, such as clear glass and highly transmissive glass, etc. can be used. An organic transparent substrate may be used as the transparent substrate 11. Examples of the organic transparent substrate include transparent substrates made of acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET).

  In order to set the visible light transmittance (Tv) as the transparent substrate with laminated film 10A within the above range, the visible light transmittance (Tv) of the transparent substrate 11 is preferably 80 to 92%, more preferably 83 to 92%. . Considering such visible light transmittance, colorless glass such as clear glass and high transmittance glass is preferable. Further, colorless glass is preferable from the viewpoint of obtaining high color rendering properties.

  As the transparent substrate 11, various tempered glass 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. Although the thickness of the transparent substrate 11 is not necessarily limited, the thickness which can make visible light transmittance | permeability (Tv) of transparent substrate 11 itself into the said range, and can ensure sufficient mechanical strength is preferable, for example, 0.5- 20 mm is preferred.

(Laminated film including metal layer mainly composed of silver)
A laminated film 12A that the transparent substrate with laminated film 10A shown in FIG. 2 has on the transparent substrate 11 includes, in order from the transparent substrate 11 side, a first silicon nitride layer 121, a first chromium-containing layer 122, and silver. A metal layer 123, a second chromium-containing layer 124, and a second silicon nitride layer 125 are formed and configured. The transparent substrate with laminated film 10A is excellent because the metal layer mainly composed of silver is sandwiched between the two chromium-containing layers and further sandwiched between the two silicon nitride layers. Chemical durability, mechanical durability, and thermal durability.

  The metal layer 123 contains silver as a main component. In this specification, containing a component as a main component means that the ratio of the component contained as a main component with respect to all the components exceeds 50% by mass. The metal layer 123 preferably contains at least one metal selected from palladium, gold, chromium, cobalt, and nickel in addition to silver as a main component. Hereinafter, at least one metal selected from palladium, gold, chromium, cobalt, and nickel is also referred to as a metal M. The content of the metal M in the metal layer 123 is preferably a ratio of 0.1 to 10% by mass with respect to the total amount of silver and the metal M. Hereinafter, the content of the metal M refers to the ratio (mass%) of the metal M to the total amount of silver and the metal M unless otherwise specified.

  When the metal layer 123 mainly composed of silver contains the metal M preferably in the above-described content, the physical property items (1) to (4) and (6) of the laminated substrate with the laminated film 10A are within a predetermined range. Easy to adjust. Further, the durability of the laminated substrate with transparent film 10A, particularly the chemical durability such as the sweat resistance of the laminated film 12A, for example, the physical property item (5) can be improved within a predetermined range. Furthermore, when the metal layer 123 contains the metal M preferably in the above content, the mechanical durability is also improved. The reason why the mechanical durability is improved is presumed that the hardness of the metal layer 123 is improved by the solid solution of the metal M, and the strength of the entire laminated film 12A structure is improved. When the durability of the laminated film 12A is improved, the transparent substrate with laminated film 10A is suitable for use in a state where the laminated film 12A is exposed to the atmosphere.

  As said metal M, 1 type chosen from palladium, gold | metal | money, chromium, cobalt, and nickel may be used independently, and 2 or more types may be used together. Among these, as the metal M, palladium, gold and the like are preferable when one kind is used alone. As the combination of two or more, nickel and gold, nickel and palladium, etc. are preferable.

  The optimum amount of the metal M content in the metal layer 123 varies depending on the type of the metal M. When palladium is used as the metal M, the ratio of palladium to the total amount of silver and palladium is preferably 1 to 5% by mass. Similarly, it is preferable that the content is 1 to 10% by mass for gold, 0.1 to 5% by mass for chromium, 0.1 to 5% by mass for cobalt, and 0.1 to 7% by mass for nickel. When nickel and gold are used in combination, it is preferable to contain 0.1 to 7% by mass of nickel and 1 to 10% by mass of gold (however, the total of nickel and gold is 10% by mass or less). .

  The metal layer 123 can contain additive elements other than silver and metal M. Examples of the additive element include metal elements such as copper and titanium. When the additive element is contained, the total content of the additive elements is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less in all components constituting the metal layer 123.

  The thickness of the metal layer 123 is preferably 10 to 30 nm. When the thickness of the metal layer 123 is 10 nm or more, the above physical property items (1) to (4) and (6) of the transparent substrate with laminated film 10A are within a predetermined range, and durability, particularly the chemistry of the laminated film 12A. Durability, for example, the physical property item (5) is improved within a predetermined range. When the thickness of the metal layer 123 is 30 nm or less, the above physical property items (1) to (4) and (6) of the transparent substrate with laminated film 10A are within a predetermined range, and the productivity of the laminated film 12A is also improved. It becomes good. The thickness of the metal layer represents a geometric thickness (the same applies hereinafter).

The first chromium-containing layer 122 is made of chromium (Cr), a nickel chromium alloy (NiCr alloy), a chromium partial nitride obtained by nitriding a part of these, or a nickel chromium alloy partial nitride. As a partial nitride of chromium, CrN _x (0.5 <x <1.5) is preferable. As a partial nitride of the nickel chromium alloy, NiCrN _x (0.5 <x <1.5)) is preferable. From the viewpoint of the thermal durability of the transparent substrate with laminated film 10A, the first chromium-containing layer 122 is preferably made of non-nitrided chromium (Cr) or a nickel chromium alloy (NiCr alloy).

When the first chromium-containing layer 122 is made of a nickel-chromium alloy (NiCr alloy) or a partial nitride (NiCrN _x ) of a nickel-chromium alloy partially nitrided, the chromium content relative to the total amount of chromium and nickel Is preferably 10% by mass or more, and more preferably 15% by mass or more. The first chromium-containing layer 122 is formed so as to be in contact with the metal layer 123.

  The second chromium-containing layer 124 is composed of the same components as the first chromium-containing layer 122 and is formed so as to be in contact with the metal layer 123. Note that the first chromium-containing layer 122 and the second chromium-containing layer 124 do not necessarily have the same composition and may have different compositions.

  The first chromium-containing layer 122 and the second chromium-containing layer 124 are used as a light absorbing layer that absorbs visible light and improves heat shielding properties, and when the heat treatment is performed as necessary, the metal layer 123 is oxidized. It functions as a barrier layer or the like that suppresses

  The thickness of the first chromium-containing layer 122 and the second chromium-containing layer 124 is preferably 0.5 to 10 nm. Note that the thickness of the first chromium-containing layer 122 and the thickness of the second chromium-containing layer 124 may be the same or different from each other. When the thickness of the 1st chromium content layer 122 and the 2nd chromium content layer 124 is 0.5 nm or more, the above-mentioned physical property item (1)-(4), (6) of transparent substrate 10A with a laminated film is predetermined. The durability, particularly the chemical durability of the laminated film 12A, for example, the physical property item (5) is improved to a predetermined range. Moreover, when the thickness of the 1st chromium content layer 122 and the 2nd chromium content layer 124 is 10 nm or less, the item (1)-(4), (6) of the above-mentioned physical property of 10 A of transparent substrates with a laminated film is predetermined. The productivity of the laminated film 12A is also good.

  The first silicon nitride layer 121 and the second silicon nitride layer 125 function so as to adjust the reflectance in the visible region and the like to make the optical characteristics of the laminated film 12A have desired characteristics. Further, the first silicon nitride layer 121 and the second silicon nitride layer 125 function to improve the durability of the laminated film 12A.

The first silicon nitride layer 121 and the second silicon nitride layer 125 are not necessarily made of silicon nitride having a stoichiometric composition ratio (Si: N = 3: 4). For example, the composition ratio is deviated from this. It may be made of silicon nitride having a non-stoichiometric composition ratio. In this specification, a nitride or oxide of a metal represented by nitriding + metal name or oxidation + metal name is nitriding with a stoichiometric composition ratio or a non-stoichiometric composition ratio unless otherwise specified. Indicates an object or oxide. If necessary, for example, silicon nitride may be described as SiN _x .

  In addition, the first silicon nitride layer 121 and the second silicon nitride layer 125 do not necessarily need to be made of only silicon nitride, and an element added to the sputtering target to facilitate sputtering, for example, a conductive material such as aluminum. It can contain an additive element that imparts properties. The content of the additive element is preferably 15% by mass or less in the total amount of silicon nitride and the additive element. Note that the silicon nitrides constituting the first silicon nitride layer 121 and the second silicon nitride layer 125 do not need to have the same composition, and may have different compositions.

  The thickness of the first silicon nitride layer 121 is preferably 25 to 70 nm. The thickness of the second silicon nitride layer 125 is preferably 35 to 70 nm. When the thickness of the first silicon nitride layer 121 is 25 nm or more and the thickness of the second silicon nitride layer 125 is 35 nm or more, the physical property items (1) to (4), ( 6) tends to fall within a predetermined range, and its durability, particularly the chemical durability of the laminated film 12A, for example, the item (5) of the above physical properties is improved within the predetermined range. When the thicknesses of the first silicon nitride layer 121 and the second silicon nitride layer 125 are 70 nm or less, the above-mentioned physical property items (1) to (4) and (6) of the transparent substrate with laminated film 10A are predetermined. The productivity of the laminated film 12A is also good.

  Here, the transparent substrate with laminated film 10A is roughly classified into a non-heat treated product and a heat treated product. The non-heat treated product is a final product in which only the laminated film 12A is formed and is a final product, and heat treatment for strengthening or bending is not performed after the film formation. The heat-treated product is a final product in a final form by performing heat treatment for strengthening or bending after the film formation of the laminated film 12A. The transparent substrate with laminated film 10A may be either a non-heat treated product or a heat treated product.

  Note that the transparent substrate with laminated film 10A may be manufactured by forming the layers in the above order, and each layer is not necessarily formed after the entire film formation and further after the heat treatment. It is not necessary that the time state, such as composition, thickness, etc., be strictly maintained. However, for the transparent substrate with laminated film 10A, the change of each layer at the time of film formation or heat treatment is basically suppressed, so that each layer remains in the state at the time of film formation even after the entire film formation or heat treatment. It is preferable to maintain. The physical property items (1) to (6) may be within a predetermined range after the film formation, that is, in a state where the heat treatment is not performed. It is preferable to be within the same range.

  In particular, when the transparent substrate with laminated film 10A is a heat treated product, and the heat treatment for obtaining this is a heat treatment in which the surface temperature of a non-heat treated product having the same configuration as that of the laminated substrate with laminated film 10A is heated to 600 ° C. or higher. The first chromium-containing layer 122 preferably has a thickness of 2.0 to 10 nm, and the second chromium-containing layer 124 preferably has a thickness of 2.0 to 10 nm. Outside the above range, mechanical durability (scratch resistance) may not be sufficient in the laminated film 12A of the laminated substrate 10A with a laminated film obtained as a heat-treated product.

  FIG. 3 is a cross-sectional view of a transparent substrate 10B with a laminated film in which the laminated film 12B is formed on the transparent substrate 11 instead of the laminated film 12A in the transparent substrate 10A with the laminated film shown in FIG. The laminated film 12B includes, in order from the transparent substrate 11 side, a first silicon nitride layer 121, a first chromium-containing layer 122, a metal layer 123 mainly composed of silver, a second chromium-containing layer 124, and a second silicon nitride. A layer 125 and a protective layer 126 are formed. The laminated film 12B can be the same as the laminated film 12A except for the protective layer 126.

  The protective layer 126 has a function of improving the mechanical durability of the laminated film 12B, particularly the scratch resistance of the surface. The protective layer 126 is not particularly limited as long as it improves mechanical durability. For example, a carbon layer containing carbon as a main component is preferable. Note that when the protective layer 126 is a carbon film, it disappears when heat treatment is performed, but the scratch resistance from film formation to heat treatment can be improved. On the other hand, in the non-heat treated product, when the protective layer 126 which is a carbon film is formed, the scratch resistance can be improved by reducing the friction coefficient of the outermost surface.

  The thickness of the protective layer 126 is preferably 1 nm or more. When the thickness of the protective layer 126 is 1 nm or more, the mechanical durability is effectively improved. If the thickness of the protective layer 126 is 15 nm, it is sufficient to ensure mechanical durability, and by making it less than this, the productivity of the protective layer 126 is improved. The thickness of the protective layer 126 is more preferably 10 nm or less, and further preferably 6 nm or less.

  Although not shown, in addition to the above-described layers, other layers may be formed on the laminated film 12A and the laminated film 12B as necessary and within the limits not departing from the spirit of the present invention. For example, a light absorption layer, a barrier layer, or the like between the first silicon nitride layer 121 and the first chromium-containing layer 122 or between the second chromium-containing layer 124 and the second silicon nitride layer 125. A metal layer, an oxide layer, a nitride layer, a carbide layer, or a composite compound layer thereof functioning as the above may be provided. Specifically, a metal layer, oxide layer, nitride layer, carbide layer, or composite compound containing an element such as titanium, zirconium, niobium, tantalum, chromium, zinc, aluminum, gallium, indium, silicon, or tin Layer.

The transparent substrate with laminated film 10A shown in FIG. 2 and the transparent substrate with laminated film 10B shown in FIG. 3 can be manufactured by the following method, for example.
The transparent substrates with laminated films 10A and 10B are obtained by cleaning each surface of the transparent substrate 11 and then forming each layer on the surface. The film forming method is not particularly limited, and physical vapor deposition (vacuum vapor deposition, ion plating, sputtering), chemical vapor deposition (thermal CVD, plasma CVD, photo CVD), ion beam sputtering Etc. can be applied. When the area of the transparent substrate 11 is large, the uniformity of thickness is easy to control and the productivity is excellent, so the direct current or alternating current dual sputtering method is preferable.

  The first silicon nitride layer 121 and the second silicon nitride layer 125 are formed using, for example, a target containing silicon as a main component as a sputtering target in an atmosphere containing only nitrogen or an atmosphere containing nitrogen and argon. A film is formed by sputtering.

  The first chromium-containing layer 122 and the second chromium-containing layer 124 are formed by using, for example, a target mainly containing chromium or a nickel chromium alloy as a sputtering target, or an atmosphere containing only argon, or nitrogen and argon. A film is formed by sputtering in an atmosphere containing

  The metal layer 123 contains, for example, silver as a main component as a sputtering target, and contains at least one metal (metal M) selected from palladium, gold, chromium, cobalt, and nickel, in a total amount of silver and the metal. Using a target contained at a ratio of 0.1 to 10% by mass, sputtering is performed in an atmosphere containing only argon to form a film.

  When the transparent substrate with laminated film 10B has, for example, a carbon layer containing carbon as a main component as the protective layer 126, the carbon layer is sputtered in an atmosphere containing only argon using a carbon target. To form a film.

  As described above, non-heat-treated products of the transparent substrates 10A and 10B with laminated films are obtained. When the transparent substrates with laminated films 10A and 10B are heat-treated, the transparent substrates with laminated films 10A and 10B obtained above are subjected to, for example, a heating temperature for bending or bending according to the purpose in a heating furnace. For a predetermined time at the heating temperature. For example, for the transparent substrates 10A and 10B with a laminated film using a float glass substrate as the transparent substrate, when the air cooling of the glass substrate is performed, the heat treatment is performed as the surface temperature of the transparent substrates 10A and 10B with the laminated film. 1 to 30 minutes are preferable at 500 to 700 ° C.

Next, the transparent substrate with a laminated film having a laminated substrate including the transparent substrate, the transparent conductive layer, and the nitrogen-containing light absorbing layer shown in FIG. 4 or FIG. 5 will be described.
A transparent substrate with a laminated film 10 </ b> C illustrated in FIG. 4 includes a transparent substrate 11 and a laminated film 12 </ b> C including a transparent conductive layer 221 and a nitrogen-containing light absorption layer 222 on the transparent substrate 11. The transparent substrate 11 can be made in the same manner as the transparent substrate with a laminated film 10A shown in FIG.

(Laminated film including transparent conductive layer and nitrogen-containing light absorption layer)
The laminated film 12C that the transparent substrate with laminated film 10C shown in FIG. 4 has on the transparent substrate 11 is configured by sequentially forming the transparent conductive layer 221 and the nitrogen-containing light absorbing layer 222 from the transparent substrate 11 side.

  As the transparent conductive layer 221, 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”) is mainly used. There is no particular limitation as long as it is a layer.

  Examples of the transparent conductive metal oxide include a metal oxide doped with an element other than a 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 And 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 221.

The transparent conductive layer 221 is preferably made of a transparent conductive metal oxide mainly composed of indium oxide doped with tin (ITO) from the viewpoint of low 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 221 is not particularly limited as long as the physical property items (1) to (6) are within a predetermined range. The thickness of the transparent conductive layer 221 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 221 is not particularly limited, but it is usually produced by a method involving heat treatment as described later. The mode before the heat treatment of the transparent conductive layer 221 is referred to as a precursor layer of the transparent conductive layer 221. The precursor layer of the transparent conductive layer 221 and the transparent conductive layer 221 after the heat treatment have substantially the same composition, but the degree of oxidation is adjusted by being appropriately oxidized by the oxygen contained in the atmosphere or the transparent substrate during the heat treatment, A transparent conductive layer 221 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 221, that is, the thickness of the precursor layer thereof is the above thickness, there is an effect that non-uniformity in the degree of oxidation does not occur in the depth direction of the layer.

  The nitrogen-containing light-absorbing layer 222 has, for example, a light-absorbing layer made of a metal nitride and / or oxynitride that can be formed on the transparent substrate 11 (hereinafter, “nitrogen-containing light-absorbing metal compound”). It is not particularly limited as long as it is a layer mainly composed of. In the transparent substrate with a laminated film 10C shown in FIG. 4, the transparent conductive layer 221 and the nitrogen-containing light absorption layer 222 are formed in this order from the transparent substrate 11, but the physical property items (1) to (6) are changed. From the viewpoint of setting within a predetermined range, the nitrogen-containing light absorbing layer 222 and the transparent conductive layer 221 may be formed in this order from the transparent substrate 11 side.

  The light absorptivity of the nitrogen-containing light absorption layer 222 is preferably a property of absorbing an appropriate amount of light over a wide range from the visible light region to the infrared region. When the nitrogen-containing light absorption layer 222 has such light absorptivity, the physical property items (1) to (4) and (6) in the obtained transparent substrate with laminated film 10C are set within a predetermined range. Can contribute.

  In the transparent substrate with laminated film 10C, the transparent conductive layer 221 and the nitrogen-containing light absorption layer 222 are provided so as to be in contact with each other. With such a configuration, for example, during the heat treatment when producing the laminated film-coated transparent substrate 10C by the production method involving the heat treatment, oxygen is transferred between the nitrogen-containing light absorbing layer 222 and the transparent conductive layer 221. The transparent conductive layer 221 can play a role of appropriately adjusting the degree of oxidation. That is, in the manufacturing process, even when oxygen is excessively contained in the precursor layer of the transparent conductive layer 221 during the heat treatment, the degree of oxidation is more preferable by passing oxygen to the precursor layer of the nitrogen-containing light absorption layer 222. It is considered that the transparent conductive layer 221 having a low resistance is finally obtained.

  In this case, the nitrogen-containing light absorbing metal compound constituting the nitrogen-containing light absorbing layer 222 is a component obtained by oxidizing the components constituting the precursor layer during the heat treatment. Here, when the nitrogen-containing light absorption layer 222 is not in contact with the transparent conductive layer 221 and there is a layer having an ability to block oxygen transfer (hereinafter referred to as an oxygen barrier layer), the nitrogen-containing light absorption after the heat treatment is performed. The degree of oxidation of the nitrogen-containing light-absorbing metal compound constituting the layer 222 is lower than that in contact with the transparent conductive layer 221.

  Specific examples of the nitrogen-containing light-absorbing metal compound mainly constituting the nitrogen-containing light absorption layer 222 include zirconium nitride, chromium nitride, titanium nitride, niobium nitride, hafnium nitride, zirconium oxynitride, chromium oxynitride, and titanium oxynitride. , Niobium oxynitride, hafnium oxynitride, and the like. 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 thereof to form the nitrogen-containing light-absorbing layer 222.

  The nitrogen-containing light absorbing layer 222 is preferably made of a nitrogen-containing light-absorbing metal compound mainly composed of titanium nitride, and is preferably made of only titanium nitride. Titanium nitride does not necessarily need to be made of titanium nitride having a stoichiometric composition ratio (Ti: N = 1: 1). For example, so-called non-stoichiometric composition ratio nitriding in which the composition ratio deviates from the titanium nitride is not necessary. It may be made of titanium. The same applies to the other metal nitrides described above.

  For example, when the precursor layer of the nitrogen-containing light absorption layer 222 is made of titanium nitride and is heat-treated as described above, the titanium nitride in the precursor layer is oxidized to titanium oxynitride. That is, the nitrogen-containing light absorption layer 222 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, and more preferably 0.2 mol or less, as described above. preferable.

  The thickness of the nitrogen-containing light absorption layer 222 is not particularly limited as long as it is a thickness that allows the above physical property items (1) to (6) to be within a predetermined range. Therefore, the thickness of the nitrogen-containing light absorption layer 222 is more than 10 nm, preferably 20 to 60 nm, and more preferably 25 to 50 nm. In addition, the said preferable range is a case where the transparent conductive layer 221 and the nitrogen containing light absorption layer 222 are formed in order from the transparent substrate 11 side like the transparent substrate 10C with a laminated film shown in FIG. The thickness of the transparent conductive layer 221 shown above is also a preferable thickness in the stacking order.

  When the transparent conductive layer 221 and the nitrogen-containing light absorption layer 222 are formed in the order of the nitrogen-containing light absorption layer 222 and the transparent conductive layer 221 from the transparent substrate 11 side, the thickness of the nitrogen-containing light absorption layer 222 is 10 nm. 20 to 60 nm is preferable, and 25 to 50 nm is more preferable. In this case, the thickness of the transparent conductive layer 221 is preferably 10 to 200 nm, and more preferably 50 to 150 nm.

  FIG. 5 shows a cross-sectional view of a transparent substrate with laminated film 10D having a structure in which a laminated film 12D is formed on the transparent substrate 11 instead of the laminated film 12C in the transparent substrate with laminated film 10C shown in FIG. The laminated film 12D is configured by forming a transparent conductive layer 221, a nitrogen-containing light absorption layer 222, and a dielectric layer 223 in this order from the transparent substrate 11 side. The laminated film 12D can be the same as the laminated film 12C except for the dielectric layer 223.

  The dielectric layer 223 has a function of improving the mechanical durability and chemical durability of the laminated film 12D and suppressing the nitrogen-containing light absorption layer 222 from being oxidized by oxygen in the atmosphere. The dielectric layer 223 is not particularly limited as long as it has the above-mentioned function. For example, the dielectric layer 223 may be doped with metal nitride such as silicon nitride or aluminum nitride, which may be doped with aluminum or boron, or doped with aluminum or boron. It may be composed of a dielectric containing a metal compound selected from metal oxynitrides such as silicon oxynitride and aluminum oxynitride, which may be used, and metal oxides such as tin zinc oxide.

  The dielectric layer 223 mainly composed of at least one selected from silicon nitride, silicon oxynitride, silicon nitride doped with aluminum and / or boron, silicon oxynitride, aluminum nitride, aluminum oxynitride, and tin zinc oxide is preferable. . The dielectric metal layer 223 may be formed by using one kind of the metal compound as the dielectric alone or using two or more kinds in combination.

  The dielectric layer 223 is preferably made of a material mainly composed of silicon nitride which may be doped with aluminum and / or boron. For example, it can be set as the structure similar to the 1st silicon nitride layer 121 and the 2nd silicon nitride layer 125 in 10 A of transparent substrates with laminated film shown in the said FIG.

  The thickness of the dielectric layer 223 is not particularly limited as long as the physical property items (1) to (6) are within a predetermined range. Specifically, the thickness of the dielectric layer 223 is preferably 20 to 80 nm, and more preferably 30 to 70 nm.

  In the transparent substrate 10D with a laminated film shown in FIG. 5, a transparent conductive layer 221, a nitrogen-containing light absorption layer 222, and a dielectric layer 223 are formed in this order from the transparent substrate 11 side. Similarly to the transparent substrate with laminated film 10C, in the transparent substrate with laminated film 10D, each layer constituting the laminated film has an appropriate visible light transmittance, and has high heat shielding properties, low heat insulation properties, and high color rendering properties. If it can be achieved, the nitrogen-containing light absorbing layer 222, the transparent conductive layer 221 and the dielectric layer 223 may be formed in this order from the transparent substrate 11 side.

  When the laminated film in the transparent substrate with the 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 the transparent conductive layer and the nitrogen-containing light in order from the transparent substrate side. It is preferable to use an absorption layer and a dielectric layer. By using such a laminated film, the color tone of reflected light on the transparent substrate side can be adjusted by the film thickness of the transparent conductive layer, and the color tone of reflected light on the laminated film side can be adjusted by the film thickness of the dielectric layer. Have.

  Although not shown, in addition to the above-described layers, other layers may be formed on the laminated film 12C and the laminated film 12D as necessary and within the limits of the gist of the present invention. For example, it functions as a barrier layer or the like between the transparent substrate 11 and the transparent conductive layer 221, between the transparent conductive layer 221 and the nitrogen-containing light absorption layer 222, or between the nitrogen-containing light absorption layer 222 and the dielectric layer 223. 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, oxide layer, nitride layer, carbide layer, or composite compound containing an element such as titanium, zirconium, niobium, tantalum, chromium, zinc, aluminum, gallium, indium, silicon, or tin Layer.

The transparent substrate with laminated film 10C shown in FIG. 4 and the transparent substrate with laminated film 10D shown in FIG. 5 can be manufactured, for example, by the following method.
The transparent substrates with laminated films 10C and 10D are obtained by cleaning the surface of the transparent substrate 11, forming a precursor layer of each layer on the surface, and then performing heat treatment. The film forming method is not particularly limited, and the same method as exemplified in the above-mentioned transparent substrate with laminated film 10A, 10B can be applied.

  For example, when the precursor layer of the transparent conductive layer 221 is formed by a sputtering method, the precursor layer of the transparent conductive layer 221 can be formed under normal processing conditions using a transparent conductive metal oxide target. The thickness can be adjusted by adjusting the sputtering gas type, reaction temperature, and reaction time. Similarly, a precursor layer of the nitrogen-containing light absorption layer 222 and a precursor layer of the dielectric layer 223 are formed.

  Next, the transparent substrate with a precursor layer 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 the transparent substrate with laminated film 10C, 10D can be obtained with an effect that is reinforced with sufficient reliability.

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

  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 not particularly limited. For example, the method of heating the said transparent substrate with a precursor layer with the heating furnace installed in air | atmosphere is mentioned. That is, in the heat treatment step, the heat treatment may not be performed in an atmosphere controlled to an inert gas atmosphere or a vacuum atmosphere that does not contain an oxidizing gas, for example, using an airtight heating furnace. Thereby, a heating furnace having a simple structure can be used, which is preferable.

  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, the transparent substrate with a laminated film is suitable for buildings, but is not necessarily limited to buildings, and can be used for vehicles such as automobiles to the extent applicable.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these.

Example 1
A 3 mm thick soda lime glass plate (FL3, manufactured by Asahi Glass Co., Ltd.) was prepared as a transparent substrate, and each film was formed on one main surface thereof by sputtering to have the film configuration and thickness shown in Table 3. A transparent substrate A with a laminated film having a laminated film on the transparent substrate was produced. In Table 3, each of the transparent substrate and the laminated film is described in the order of lamination from the left. Each film is indicated by a constituent material and a thickness indicated by a number in parentheses (the unit is all [nm]).

  An in-line sputtering apparatus is used for film formation, and a silicon target containing 10% by mass of aluminum, a nickel chromium target containing 80% by mass of nickel, and a silver palladium target containing 1% by mass of palladium in the sputtering chamber. , And a carbon target.

The cleaned soda lime glass plate was introduced into this in-line type sputtering apparatus, and evacuated until the degree of vacuum became 2 × 10 ⁻⁶ Torr or less in the load lock chamber. Subsequently, a soda lime glass plate was introduced into the sputtering chamber, a silicon nitride layer containing aluminum as the first silicon nitride layer (SiN _x : Al layer), and a nickel chromium alloy layer (NiCr layer as the first chromium containing layer). ), A silver-palladium alloy layer (AgPd layer) as the metal layer, a nickel-chromium alloy layer (NiCr layer) as the second chromium-containing layer, and a silicon nitride layer containing aluminum as the second silicon nitride layer (SiN _x : Al Layer) were sequentially formed to form a laminated film. The film forming conditions for each layer are as follows. The film forming pressure was 3 to 5 mTorr.

The silicon nitride layer (SiN _x : Al layer) uses a silicon target containing 10% by mass of aluminum, nitrogen / argon = 3/7 in terms of flow rate, and power density of 3.6 W / cm ^2. The film was formed as follows.

The nickel chrome alloy layer (NiCr layer) was formed using a nickel chrome target containing 80% by mass of nickel with an introduction gas of 100% argon and a power density of 0.4 W / cm ² .

The silver-palladium alloy layer (AgPd layer) is formed using a silver-palladium target containing 99% by mass of silver and 1% by mass of palladium, with an introduction gas of 100% and a power density of 0.7 W / cm ^2. Went.

(Example 2)
A 6.0 mm thick soda lime glass (Asahi Glass Co., Ltd., FL6) was prepared as a transparent substrate, and this glass substrate was washed and then set on a substrate holder.

A composite oxide sintered body target (hereinafter also referred to as “ITO 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 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 period was set to 5 μs for the ON time and 45 μs for the OFF time.

  Next, after evacuating the film formation chamber to vacuum, an ITO layer having a thickness of 96 nm was formed on the glass substrate by an intermittent direct current magnetron sputtering method using an ITO composite oxide sintered target. Here, only argon was used as the sputtering gas, and the pressure during sputtering was 3 mTorr. The composition of the deposited ITO layer was equivalent to the target. 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 intermittent DC magnetron sputtering using a metal Ti target. The sputtering gas used was argon and nitrogen, and the argon / nitrogen ratio 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 using a SiAl target by intermittent direct current magnetron sputtering. Here, argon and nitrogen were used as the sputtering gas, and the ratio of argon / nitrogen was 9/7. The pressure during sputtering was 3 mTorr.

  Note that the glass substrate was not heated at the time of forming any layer. The obtained glass plate with a precursor layer was subjected to air-cooling strengthening treatment, that is, heat treatment at 650 ° C. for 5 minutes in the air in an electric firing furnace, to obtain a transparent substrate B with a laminated film. Table 3 shows the structure of the laminated film before the heat treatment.

(Example 3)
In Example 2, as a glass substrate with coating, except that a glass substrate with coating was prepared in which the thickness of the ITO layer was 72 nm, the thickness of the titanium nitride layer was 42 nm, and the thickness of the Al-doped silicon nitride layer was 59 nm, A transparent substrate C with a laminated film was obtained in the same manner as Example 2.

(Example 4)
In Example 2, as the glass substrate with coating, except that a glass substrate with coating was prepared with a thickness of the ITO layer of 131 nm, a thickness of the titanium nitride layer of 32 nm, and a thickness of the Al-doped silicon nitride layer of 40 nm, A transparent substrate D with a laminated film was obtained in the same manner as Example 2.

(Comparative Example 1)
As a transparent substrate, soda lime glass (FL3, manufactured by Asahi Glass Co., Ltd.) having a thickness of 3.0 mm was used, and an Al-doped zinc oxide layer (Al: ZnO layer) was formed on the transparent substrate by the same sputtering apparatus as in Example 1. ), A silver-palladium alloy layer (AgPd layer), an Al-doped zinc sacrificial layer (Al: Zn), and an Al-doped zinc oxide layer (Al: ZnO layer) similar to those in Example 1 are formed in that order, and a laminated film is provided. A transparent substrate E was obtained. In addition, for all Al-doped zinc oxide layers (Al: ZnO layers), carbon dioxide gas was introduced using a zinc aluminum metal target containing 2% by mass of aluminum so that the film forming pressure was 4.5 mTorr. The film was formed with a power density of 3.6 W / cm ² . In addition, the Al-doped zinc sacrificial layer (Al: Zn) uses a zinc aluminum metal target containing 2% by mass of aluminum, introduces argon so that the film forming pressure is 4 mTorr, and the power density is set to 0.00. The film was formed at 1 W / cm ² .
The Al-doped zinc sacrificial layer is a layer that is included in the Al-doped zinc oxide layer (Al: ZnO layer) formed thereon and does not remain as such.

(Comparative Example 2)
In Example 2, as a glass substrate with coating, except that a glass substrate with coating with an ITO layer thickness of 96 nm, a titanium nitride layer thickness of 5 nm, and an Al-doped silicon nitride layer thickness of 55 nm was prepared, A transparent substrate F with a laminated film was obtained in the same manner as Example 2.

(Comparative Example 3)
As a transparent substrate, when manufacturing a green heat ray absorbing glass (made by Asahi Glass Co., Ltd., shown as “TG” in Table 3) having a thickness of 6 mm, a Chemical Vapor Deposition installed on a float line for producing the glass ( With a CVD apparatus, an SiOC layer (80 nm) and an Sb-doped SnO ₂ layer (320 nm) were formed in this order, and a transparent substrate H with a laminated film was obtained.

(Comparative Example 4)
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 2. (10 nm) and a silicon nitride layer (20 nm) were formed in that order to obtain a transparent substrate I 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 4.

(optical properties)
A Hitachi spectrophotometer (U-3100 type) was used to perform spectroscopic measurement of a transparent substrate with a laminated film. Based on JIS R3106 / 3107 (1998), the heat transmissivity (U value), the solar heat acquisition rate (η value) when light enters from the transparent substrate, and the visible light transmittance (Tv) were determined. Further, the color rendering properties of transmitted light evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) was determined. Furthermore, the selection coefficient (Tv / (η value × 100)) was calculated from the visible light transmittance (Tv) and the solar heat acquisition rate (η value).

(Durability; sweat resistance test)
A sweat resistance test was performed according to ISO12870. That is, artificial sweat was poured into a sealed container, and a transparent substrate with a laminated film was placed in the sealed container away 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 from the sealed container, the surface of the laminated film was observed with a microscope (50 times), the number of defects in the range of 1 mm × 1 mm was visually measured, and evaluated according to the following criteria.

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

30 ... Window glass, 10 ... Transparent substrate with laminated film, 11 ... Transparent substrate, 12 ... Laminated film,
10A, 10B, 10C, 10D ... Transparent substrate with laminated film 12A, 12B, 12C, 12D ... laminated film 121 ... first silicon nitride layer, 122 ... first chromium-containing layer, 123 ... silver layer, 124 ... first 2 chromium-containing layers, 125 ... second silicon nitride layer, 126 ... protective layer 221 ... transparent conductive layer, 222 ... nitrogen-containing light absorbing layer, 223 ... dielectric layer

Claims (10)

A transparent substrate having laminated films which have a the formed product layer film on the transparent substrate and the transparent substrate,
The laminated film is formed in order from the transparent substrate side, a first silicon nitride layer having a thickness of 25 to 70 nm, a first chromium-containing layer having a thickness of 0.5 to 10 nm, and a thickness of 10 to 30 nm. A metal layer containing more than 50% by weight of silver, a second chromium-containing layer having a thickness of 0.5 to 10 nm, and a second silicon nitride layer having a thickness of 35 to 70 nm,
The transparent substrate with a laminated film has 50 or less defects in the range of 1 mm × 1 mm, which is measured by observing the surface of the laminated film with a microscope (50 times) after a 3-day sweat resistance test according to ISO12870. Transparent substrate with laminated film. Wherein the metal layer further palladium, gold, chromium, cobalt and at least one laminated film with a transparent substrate according to claim 1 further comprising a metal selected from nickel. In the metal layer, the content of at least one metal selected from palladium, gold, chromium, cobalt and nickel is at least one metal selected from palladium, gold, chromium, cobalt and nickel and silver. The transparent substrate with a laminated film according to claim 2, wherein the content is 0.1 to 10% by mass with respect to the total amount. The transparent substrate with a laminated film according to claim 2 or 3, wherein the metal layer further contains at least one metal selected from copper and titanium. The first chromium-containing layer and the second chromium-containing layer are each independently made of chromium or a nickel chromium alloy, a chromium partial nitride obtained by nitriding a part thereof, or a nickel nitride alloy partial nitride. The transparent substrate with a laminated film according to any one of claims 1 to 4. The said laminated film is a transparent substrate with a laminated film of any one of Claims 1-5 which has a layer containing carbon on the said 2nd silicon nitride layer. The transparent substrate with a laminated film according to claim 1, wherein the transparent substrate is made of colorless glass. The transparent substrate with a laminated film has a thermal conductivity (U value) measured in accordance with JIS R3106 / 3107 (1998) of 3.4 to 4.7 W / m ² · K, measured on the laminated film side. The solar radiation heat gain (η value) is 0.17 to 0.44, the visible light transmittance (Tv) is 35% or more, and an average color rendering property using a D65 light source according to JIS Z8726 (1990). The transparent substrate with a laminated film according to any one of claims 1 to 7, wherein the color rendering property of transmitted light evaluated by the evaluation number (Ra) is 90% or more . The transparent substrate with a laminated film is obtained by using a solar heat acquisition rate (η value) and a visible light transmittance (Tv) measured on the laminated film side in accordance with JIS R3106 / 3107 (1998). The selection coefficient calculated by the equation of (η value × 100) is 1.1 or more, and the transmitted light is evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990). The transparent substrate with a laminated film according to any one of claims 1 to 7, wherein the color rendering property is 90% or more . The transparent substrate with a laminated film according to any one of claims 1 to 9 , which is used for multilayer glass or laminated glass.

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