JP6601419B2 - Glass plate with laminated film and multilayer glass - Google Patents

Description

  The present invention relates to a laminated film-attached glass plate and a multilayer glass, and particularly relates to a laminated film-attached glass plate and a multilayer glass suitable for tempered glass.

  When considering the energy saving performance of architectural window glass, for example, a plate glass with a low emissivity laminated film called Low-E glass is used to achieve high heat shielding performance. Here, high heat insulation can be achieved by reducing the solar heat gain of the glass, but to reduce the solar heat gain, it is necessary to lower the visible light transmittance.

  Generally, in the Low-E glass, when the visible light transmittance is lowered in order to reduce the solar heat gain rate, the reflectance becomes too high. On the other hand, if the reflectance is lowered to a certain extent, the reflection color tone when viewed from the sheet glass side, that is, the outside of the building, tends to be reddish, and the design is impaired. In commercial buildings, blinds are often installed indoors, and if the transmitted color tone of the glass is yellowish, the design when viewed from the outside of the building is also impaired.

  As an attempt to solve such a problem, for example, Patent Document 1 describes a technique for adjusting the film thickness of a metal layer and a dielectric layer mainly composed of silver constituting a low emissivity laminated film. . However, with the technique described in Patent Document 1, it has been difficult to say that the heat insulation performance and the design properties when viewed from the plate glass side are sufficiently satisfactory.

JP 2014-76918 A

  The present invention aims to provide a glass sheet with a laminated film capable of achieving both high heat shielding performance and a good external appearance when it is made into a multilayer glass, and a multilayer glass using the glass sheet with the laminated film And

The glass plate with a laminated film according to one embodiment of the present invention is provided with a glass plate having a reinforced main surface on a rectangular glass plate and one main surface of the glass plate, and on two or more end surfaces of the glass plate. It is a glass plate with a laminated film having a laminated film that is not provided, and the laminated film is a glass plate with a laminated film having the following characteristics in the following multilayer glass using the laminated film.
The laminated film is formed on one main surface of a first transparent glass plate having a thickness of 5 mm to form a glass plate with a laminated film for testing, and the glass plate with the laminated film for testing and a glass plate having a thickness of 6 mm. The transparent glass plate of 2 is spaced apart from the main surface of the second transparent glass plate through a spacer disposed at the periphery thereof so that the laminated film surface of the glass plate with the laminated film for test faces one main surface. In the multilayer glass produced so as to have an air layer having a thickness of 12 mm between the glass plate with a laminated film for testing and the second transparent glass plate,
The solar heat acquisition rate (g value) on the second transparent glass plate side with respect to solar radiation from the glass plate side with the test laminate film, measured in accordance with ISO 9050: 2003, is 0.265 or less,
ISO9050: For transmitted light obtained by irradiating the visible light as defined in 2003, and a ^{b *} is 1 or less by CIE 1976 L ^* a ^* b ^* chromaticity coordinates,
The visible light reflectance measured on the basis of ISO 9050: 2003 on the side of the glass plate with a laminated film for test is 20% or less.

  Moreover, the glass plate with a laminated film of another embodiment of the present invention is provided with a reinforced main surface on a rectangular glass plate and one main surface of the glass plate, and on two or more end surfaces of the glass plate. Is provided, and the laminated film is formed by stacking n + 1 (n is an integer of 2 or more) metal layers containing silver as a main component and n + 1 laminated so as to sandwich the metal layer, respectively. The first metal layer closest to the glass plate among the metal layers is made of at least one metal selected from palladium, gold, chromium, cobalt and nickel, silver and the metal 6% by mass or more with respect to the total amount, and when the ratio is less than 9% by mass, the first metal layer and the second metal layer second closest to the glass plate The thickness of the dielectric layer in between is 100 nm or less, or In addition, at least one of the first metal layer and the metal layer other than the first metal layer is independently selected from silver, at least one metal selected from palladium, gold, chromium, cobalt, and nickel. The total content of the metal in the metal layer containing 1.5% by mass or more with respect to the total amount of the metal and 1.5% by mass or more of the metal is 4% by mass. The glass plate with a laminated film is as described above, and the thickness of the dielectric layer between the first metal layer and the second metal layer closest to the glass plate is 95 nm or less.

The multilayer glass according to an aspect of the present invention is provided on a first glass plate having a reinforced main surface having a rectangular shape and one main surface of the first glass plate, and the first glass plate A glass plate with a laminated film having a laminated film that is not provided on two or more end faces of the glass, and a second glass having a rectangular main surface disposed with a gap through the glass plate with the laminated film and a spacer. A double-glazed glass having the following characteristics.
The solar heat acquisition rate (g value) on the second glass plate side with respect to the solar radiation from the laminated film-attached glass plate side measured according to ISO 9050: 2003 is 0.265 or less.
ISO9050: For transmitted light obtained by irradiating the visible light as defined in 2003, ^{b *} is 1 or less by CIE1976L ^* a ^* b ^* chromaticity coordinates.
The visible light reflectance on the side of the glass plate with a laminated film, measured according to ISO 9050: 2003, is 20% or less.

  ADVANTAGE OF THE INVENTION According to this invention, when it is set as a multilayer glass, the glass plate with a laminated film and multilayer glass which can make high heat-shielding performance and the favorable external appearance compatible can be provided.

It is a front view which shows a glass plate with a laminated film schematically. It is sectional drawing in the XX line of the glass plate with a laminated film shown to FIG. 1A. It is sectional drawing which shows an example of a multilayer glass. It is sectional drawing of one Embodiment of the glass plate with a laminated film. It is sectional drawing which shows the modification of one Embodiment of the glass plate 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.

[Glass plate with laminated film]
1A and 1B are a front view schematically showing a laminated film-attached glass plate according to an embodiment of the present invention and a cross-sectional view taken along line XX. A glass plate 10 with a laminated film according to an embodiment of the present invention shown in FIGS. 1A and 1B has a reinforced glass plate 1 and a laminated film 2 provided on one main surface 1 s of the glass plate 1. The glass plate 1 has a main surface 1s having a rectangular shape and four end surfaces 1t. The laminated film 2 is not provided on the end surface 1 t of the glass plate 1. In addition, in the glass plate with a laminated film of the embodiment of the present invention, up to two of the four end faces may have a laminated film. The laminated film 2 can impart the following properties (1-a) to (3-a) to the multilayer glass when the multilayer glass having the following specific configuration is produced using the multilayer film 2. It is a low emissivity laminated film.

  The multilayer glass for evaluating the laminated film is a glass plate with a laminated film for testing by forming the laminated film on one main surface of a first transparent glass plate having a thickness of 5 mm. A laminated film surface of the glass sheet with a test laminated film is the second transparent glass through a spacer disposed on the periphery of a glass sheet with the laminated film and a second transparent glass plate having a thickness of 6 mm. It is made to be spaced so as to face one main surface of the plate, and to have an air layer having a thickness of 12 mm between the glass plate with a laminated film for test and the second transparent glass plate. The multilayer glass thus produced has the following properties (1-a), (2-a), and (3-a).

(1-a) The solar heat acquisition rate (g value) on the second transparent glass plate side with respect to the solar radiation from the glass plate side with a laminated film for test, measured according to ISO 9050: 2003, is 0. 265 or less.
(2-a) ISO9050: for transmitted light obtained by irradiating the visible light as defined in 2003, ^{b *} is 1 or less by CIE1976L ^* a ^* b ^* chromaticity coordinates.
(3-a) The visible light reflectance on the side of the glass plate with a test laminate film, measured in accordance with ISO 9050: 2003, is 20% or less.

  Hereinafter, the glass plate 1 and the laminated film 2 which the glass plate 10 with a laminated film of embodiment has are demonstrated.

(Glass plate)
The glass plate 1 is not particularly limited as long as the reinforced main surface is a rectangular plate-like glass. For example, the glass plate 1 is manufactured by a window glass for buildings, a commonly used float glass, or a roll-out method. A glass plate having inorganic transparency such as soda-lime glass can be used. The glass plate strengthening method includes air cooling strengthening, chemical strengthening, etc., and the glass plate 1 is preferably a glass plate strengthened by air cooling. The glass plate 1 may be strengthened before the laminated film 2 is provided on the main surface, and as described later, a non-heat treated product in which the laminated film is formed on the main surface of the glass plate is heat-treated at the time of manufacture. It is good also as the glass plate 1 strengthened by air-cooling. The latter is preferred in embodiments of the present invention.

  The glass plate 1 is appropriately selected according to the performance required as the glass plate 10 with a laminated film. When using the laminated film-attached glass plate 10 as a part of the multi-layer glass, if a certain level of visible light transmittance is required, the glass plate 1 is preferably a colorless glass such as a transparent glass or a high-transmission glass. . Further, colorless glass is preferable from the viewpoint of obtaining high color rendering properties.

  As the glass plate 1, 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 glass plate 1 is not necessarily limited, the thickness which can ensure sufficient mechanical strength is preferable, for example, 0.5-20 mm is suitable, keeping the visible light transmittance | permeability of the glass plate 1 more than fixed. is there.

  The shape of the glass plate 1 is not particularly limited as long as it is a plate shape and has a pair of rectangular main surfaces. The flat plate shape in which the pair of main surfaces are flat surfaces or the curved plate shape in which the entire or part of the pair of main surfaces has a curvature may be used. Note that the main surface is rectangular means that the main surface has a substantially rectangular shape. For example, a glass plate obtained by cutting off the corners of the peripheral portion is included in the category.

(Laminated film)
In the glass plate 10 with the laminated film, the laminated film 2 is provided over the entire surface on the main surface 1 s of the glass plate 1, but is not provided on the four end surfaces 1 t of the glass plate 1. In the glass plate with laminated film of the embodiment, one or two of the four end faces of the glass plate may have a laminated film, but it is preferable that no laminated film is provided on any of the four end faces. .

  The glass plate with a laminated film of the embodiment of the present invention is used alone or in combination with other members as laminated glass or multilayer glass, and is usually used by being fitted into a window. FIG. 2 shows a cross-sectional view of an example of the multilayer glass of the embodiment of the present invention using the laminated film-attached glass plate 10 as a constituent member. The multi-layer glass 3 is composed of a glass plate 10 with a laminated film having a first transparent glass plate 1 and a laminated film 2 and a second transparent glass plate 32 via a spacer 33 disposed on the periphery thereof. It is the structure separated so that it may have the intermediate | middle layer 34 in between. In the multilayer glass 3, the laminated film 2 surface of the laminated film-attached glass plate 10 is spaced so as to face one main surface of the second transparent glass plate 32.

  In the glass sheet with a laminated film of the embodiment of the present invention and the multilayer glass using the same, since the laminated film is not provided on two or more end faces of the glass sheet, preferably all the end faces, it is fitted into a window of a building or the like. It is preferable because there is an effect of suppressing deterioration of the laminated film by a material containing a plasticizer, such as a setting block and a glazing channel, and an effect of suppressing a decrease in adhesive strength of the meshed glass with a rust preventive material.

  In the glass plate 10 with a laminated film, the laminated film 2 has a low emissivity that satisfies all of the above (1-a) to (3-a) when evaluated as a multilayer glass for evaluation of the specific configuration. It is a laminated film.

<Characteristics of laminated film>
The laminated film 2 is, for example, a multi-layer glass having a configuration similar to that shown in FIG. 2, the intermediate layer 34 is an air layer, the thickness t1 of the first transparent glass plate 1, and the second transparent glass. The plate thickness t2 of the plate 32 and the thickness t3 of the intermediate layer (air layer) 34 can be evaluated by a multi-layer glass (hereinafter referred to as “multi-layer glass 30”) of 5 mm, 6 mm, and 12 mm, respectively. In this case, the transparent glass plate 1 having a thickness of 5 mm on which the laminated film 2 to be evaluated is provided is referred to as “a glass plate 10x with a laminated film for test”.

Here, the transparent glass plate used for the above evaluation and the like in this specification has a visible light transmittance of 80% or more measured in accordance with ISO 9050: 2003 regardless of the thickness, and is defined in ISO 9050: 2003. The CIE 1976L ^* a ^* b ^* chromaticity coordinates of the transmitted light obtained by irradiating visible light is glass whose absolute values of a ^* and b ^* are both 5 or less.

In this specification, the visible light transmittance measured in conformity with ISO 9050: 2003 is denoted as “Tv” and the visible light reflectance is denoted as “Rv” as necessary. Moreover, the transmitted light obtained by irradiating visible light defined by ISO 9050: 2003 is also simply referred to as “transmitted light”, and the reflected light obtained by irradiating visible light defined by ISO 9050: 2003 is similarly Also simply called “reflected light”. CIE1976L ^* a ^* b ^* b ^* and a ^* based on chromaticity coordinates are also simply referred to as “b ^* ” and “a ^* ”, respectively.

  Hereinafter, the characteristic of the laminated film in the glass plate with a laminated film of the embodiment evaluated using the multilayer glass for evaluation, for example, the multilayer glass 30, will be described. In addition, although the following description describes as the characteristic of the multilayer glass 30, all of these originate in the characteristic of the laminated film 2. FIG. In the multilayer glass using the laminated film-attached glass plate of the embodiment, the laminated film-attached glass plate is usually prepared so as to face the other glass plate with a gap between the laminated film and the laminated film. The attached glass plate side is exposed to the outdoors, and the opposite glass plate side is used indoors. The evaluation using the multilayer glass 30 is an evaluation assuming such use.

  In the multi-layer glass 30 using the laminated film 2, (1-a) on the second transparent glass plate 32 side with respect to solar radiation from the glass plate with test laminated film 10x side, measured according to ISO 9050: 2003. The solar heat gain rate (g value) is 0.265 or less. The solar heat gain rate (g value) is preferably 0.257 or less.

  Here, the solar heat acquisition rate (g value) is on the second transparent glass plate 32 side (indoor side) when the solar energy incident from the glass plate 10x side (outdoor side) with the test laminated film is taken as 1. It is a value indicating the ratio of the amount of heat flowing in. From the solar heat acquisition rate (g 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 that directly permeates the solar energy incident from the glass plate with test laminated film 10x side (outdoor side) (hereinafter also referred to as “transmitted heat”) and is absorbed after that. This is the ratio of the total amount of heat with the heat released to the glass plate 32 side (inside the room) (hereinafter also referred to as “radiant heat”). The solar heat acquisition rate is represented by a number between 0 and 1.

  The solar heat acquisition rate can be calculated by measuring the spectral characteristics and emissivity of the multilayer glass 30 and introducing them into a predetermined calculation formula. The smaller the solar heat acquisition rate, the smaller the ratio of the total heat quantity of the transmitted heat and the radiant heat to the solar heat quantity incident from the glass film 10x side with the laminated film for testing in the multilayer glass 30.

In the multi-layer glass 30 using the laminated film 2, (2-a) the transmitted light obtained by irradiating visible light specified in ISO 9050: 2003 has a b ^* of 1 according to CIE1976L ^* a ^* b ^* chromaticity coordinates. It is as follows.

  Even if the transmitted light is transmitted light that enters the glass plate 10x side (outdoor side) with the laminated glass 30 for test of the multilayer glass 30 and transmits to the second transparent glass plate 32 side (indoor side), the multilayer glass 30 The same applies to the transmitted light that is incident from the second transparent glass plate 32 side (indoor side) 30 and transmitted to the glass plate with test laminated film 10x side (outdoor side). May be used.

The b ^* of the light transmitted through the multilayer glass 30 is preferably b ^* ≦ 0. If b ^* of the transmitted light is within the above-mentioned range in the multi-layer glass 30, when the sunlight incident from the glass plate with test laminated film 10x side (outdoor side) hits a blind installed indoors, yellow It does not have a shabby color.

In the multilayer glass 30 using the laminated film 2, the visible light reflectance on the glass plate 10x side with a laminated film for test, measured in accordance with (3-a) ISO 9050: 2003, is 20% or less. Hereinafter, the visible light reflectance on the glass plate 10x side with a test laminated film measured in accordance with ISO 9050: 2003 is also referred to as Rv _out . Rv _out is preferably 18% or less. If Rv _out is in the above range in the multilayer glass 30, reflection is not too high when the glass is viewed from the outdoor side, and the appearance is excellent in design.

  In the multilayer glass 30 using the laminated film 2, the following (4-a), (2-a), (3-a), It preferably has one or more properties selected from 5-a), (6-a), (7-a) and (8-a). It is more preferable to have all the characteristics (4-a) to (8-a).

(4-a) The visible light reflectance on the second transparent glass plate side measured in accordance with ISO 9050: 2003 is 20% or less.
(5-a) The difference between the visible light reflectance on the glass plate with a test laminated film side measured in accordance with ISO 9050: 2003 and the visible light reflectance on the second transparent glass plate side is 10%. It is as follows.
(6-a) CIE 1976 L ^* a ^* b of each reflected light obtained by irradiating the test laminated film-attached glass plate side and the second transparent glass plate side with visible light defined in ISO 9050: 2003 ^{* A *} and b ^* by chromaticity coordinates are both 2 or less.
(7-a) Visible light transmittance measured in accordance with ISO 9050: 2003 is 30% or more.
(8-a) The color rendering properties of transmitted light evaluated by an average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) is 85% or more.

Similar to the above Rv _out , the visible light reflectance on the front side of the second transparent glass plate 32 measured in accordance with ISO 9050: 2003 is also referred to as Rv _in . Rv _in the above preferably 20% or less as (4-a), more preferably 18% or less, and particularly preferably 16%. Since the multilayer glass 30 has the characteristic (4-a), it is possible to suppress reflection in the room due to the reflected light on the second transparent glass plate 32 side (indoor side).

The difference between Rv _out and Rv _in is preferably 10% or less, more preferably 9% or less, and particularly preferably 8% or less, as described in (5-a) above. Note _that the difference _{Rv out} and _{Rv in,} refers to a value obtained by subtracting one value from having a large value of _{Rv out} and _{Rv in} small. Since the double-glazed glass 30 has the above-mentioned characteristic (5-a), it is easy to adjust the color tone with excellent design properties on both the outdoor side and the indoor side.

The CIE1976L ^* a ^* b ^* chromaticity coordinate a ^* and b ^* in the reflected light on the glass plate with test laminated film 10x side and the reflected light on the second transparent glass plate 32 side are as described in (6-a) above. Is preferably 2 or less. Since the multilayer glass 30 has the above-mentioned characteristic (6-a), the red light of the reflected light on the glass plate with test laminated film 10x side (outdoor side) and the second transparent glass plate 32 side (indoor side). , And yellowishness can be suppressed.

The a ^* of the reflected light on the glass plate with test laminated film 10x side (outdoor side) is more preferably -20 to 1, and particularly preferably -15 to 0. The b ^* of the reflected light on the glass plate with test laminated film 10x side (outdoor side) is more preferably −30 to 1, and particularly preferably −25 to 0. More preferably -20～1 of ^{a *} is the reflected light of the second transparent glass plate 32 side (indoor side), and particularly preferably -15～0. The b ^* of the reflected light on the second transparent glass plate 32 side (inside the room) is more preferably −30 to 1, and particularly preferably −25 to 0.

  The Tv of the multilayer glass 30 is preferably 30% or more as described in (7-a) above. Since the double-glazed glass 30 has the characteristics (7-a) described above, it is possible to obtain sufficient lighting in the building. The Tv of the multilayer glass 30 is preferably 60% or less from the viewpoint of antiglare properties. The Tv of the multilayer glass 30 is particularly preferably 35 to 55%.

  The color rendering properties of the transmitted light evaluated by the average color rendering index (Ra) using a D65 light source in accordance with JIS Z8726 (1990) of the multilayer glass 30 is 85% or more as described in (8-a) above. is there. When the color rendering property according to (8-a) is 85% or more, the appearance when the double glazing 30 is viewed from the outside of the building becomes a natural intermediate color. The color rendering property is preferably 87% or more, and more preferably 90% or more.

  In the above, the case where the characteristic of the laminated film of the glass plate with a laminated film of the embodiment of the present invention was evaluated by the multilayer glass using the glass plate with a laminated film for test was described. Each of the glass plate with a laminated film for test used above and the structure of the multilayer glass using the same is a structure for evaluating the laminated film of the glass sheet with a laminated film of the embodiment, and is a laminate of the present invention. The structure of the film-attached glass plate is not limited to the structure of the test laminated film-attached glass plate. The use of the laminated film-attached glass plate of the present invention is not limited to the multilayer glass, and the configuration of the multilayer glass of the embodiment of the present invention is the configuration of the multilayer glass for the evaluation. It is not limited.

The glass plate with a laminated film of the embodiment of the present invention preferably has a haze value of 2% or less in order to ensure transparency. The haze value of the laminated film-attached glass plate is more preferably 1% or less. In a glass plate with a laminated film, the haze value of the glass plate is usually about 0.0 to 0.1%, and the haze value of the entire glass plate with a laminated film largely depends on the haze value of the laminated film. That is, the laminated film must have characteristics satisfying (1-a), (2-a), and (3-a) in the above evaluation, and is selected from (4-a) to (8-a) Preferably, the laminated film has a haze value of 2% or less when a glass plate with a laminated film is obtained.

  The structure and manufacturing method of the laminated film in the laminated film-attached glass plate of the embodiment are as described below. When the glass plate is an air-cooled tempered glass plate or a curved plate-like glass plate, the precursor of the laminated film-attached glass plate may be heat-treated at, for example, 600 ° C. or more to obtain the laminated film-attached glass plate of the embodiment. . That is, by heat-treating a glass plate to, for example, 600 ° C. or more, a laminated film is formed on one main surface as an air-cooled tempered glass plate or a curved glass plate to obtain a laminated film-attached glass plate. Instead of forming the precursor of the laminated film on the glass plate before the heat treatment, and heat treating this to obtain a glass plate with a laminated film in which the glass plate is an air-cooled tempered glass plate or a curved glass plate. Sometimes. A curved glass plate is a curved glass plate reinforced by heat treatment. In such a case, the constituent material of the laminated film is selected as described below so that the heat-treated laminated film has a haze value of 2% or less of the laminated film-attached glass plate.

  The laminated film-attached glass plate of the embodiment has a diameter observed in a range of 100 mm × 100 mm on the surface of the laminated film after a moisture resistance test in which the laminated film-attached glass plate is stored at 50 ° C. and 90% RH for 2 weeks. The number of white spots of 0.5 mm or more is preferably 5 or less. If the surface of the laminated film after the moisture resistance test satisfies the above conditions, for example, when producing a multi-layer glass using the laminated film-attached glass plate of the embodiment, sufficient moisture resistance when storing the laminated film-attached glass plate It can be said that it has sex.

<Configuration of laminated film>
If the laminated film in the glass plate with laminated film of the embodiment has characteristics satisfying (1-a), (2-a) and (3-a) in the above evaluation, the configuration is not particularly limited. Examples of the laminated film that can satisfy the characteristics of (1-a), (2-a), and (3-a) in the above evaluation include a laminated film (X) or a laminated film (Y) having the following configuration. .

  The laminated film (X) has n layers (n is an integer of 2 or more) of metal layers containing silver as a main component, and n + 1 dielectric layers laminated so as to sandwich the metal layer, Of the metal layers, the first metal layer closest to the glass plate is 6% by mass of at least one metal selected from palladium, gold, chromium, cobalt and nickel with respect to the total amount of silver and the metal. It contains in the above ratio. However, when the ratio of the metal to the total amount of silver and the metal is 6% by mass or more and less than 9% by mass, between the first metal layer and the second metal layer second closest to the glass plate. The dielectric layer has a thickness of 100 nm or less. When the ratio of the metal to the total amount of silver and the metal is 9% by mass or more, the dielectric between the first metal layer and the second metal layer second closest to the glass plate The thickness of the layer is not particularly limited. In the present specification, the thicknesses of the metal layer, dielectric layer, and other layers constituting the laminated film represent geometric thicknesses.

  The laminated film (Y) has n layers (n is an integer of 2 or more) of metal layers containing silver as a main component and n + 1 dielectric layers laminated so as to sandwich the metal layers. In the laminated film (Y), the first metal layer closest to the glass plate among the metal layers is composed of at least one metal selected from palladium, gold, chromium, cobalt, and nickel, silver and the metal. It contains in the ratio of 1.5 mass% or more with respect to a total amount, and at least 1 layer of the said metal layers other than a said 1st metal layer among the said metal layers is palladium, gold | metal | money, chromium, cobalt, and nickel At least one metal selected from the group consisting of 1.5% by mass or more based on the total amount of silver and the metal. Furthermore, in the laminated film (Y), the total content of the metals in the metal layer containing the metal at a ratio of 1.5% by mass or more is 4% by mass or more. The laminated film (Y) includes the dielectric layer between the first metal layer and the second metal layer second closest to the glass plate while the configuration of the n metal layers satisfies the above-described condition. Is 95 nm or less.

  The metal layer of the laminated film (X) and the laminated film (Y) that is a metal layer containing silver as a main component (n is an integer of 2 or more) plays a role of imparting low radiation to the laminated film. is there. In addition, in this specification, containing a certain component as a main component means that the ratio of the component contained as a main component with respect to all the structural components exceeds 50 mass%. In the laminated film (X) and the laminated film (Y), at least one metal selected from palladium, gold, chromium, cobalt and nickel is used as the specific metal layer in the metal layer containing n layers of silver as a main component. In the laminated body (X), the first metal layer closest to the glass plate and the second closest one are essential as necessary in the laminated body (Y). By setting the thickness of the dielectric layer between the second metal layer within the above range, all the characteristics of (1-a), (2-a) and (3-a) can be achieved in the above evaluation. It is said.

  In the laminated film (X), the number of metal layers containing silver as a main component may be 2 or more, preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2. FIG. 3 is a cross-sectional view of an embodiment of a laminated film-attached glass plate 10A having a laminated film in which the number of metal layers containing silver as a main component is 2 as the laminated film (X). The laminated film-attached glass plate 10 </ b> A has a laminated film 2 </ b> A on one main surface 1 s of the glass plate 1.

The laminated film 2A includes a first dielectric layer 21, a first metal layer 22, a second dielectric layer 23, a second metal layer 24, and a third dielectric layer 25 in order from the glass plate 1 side. Have. The first metal layer 22 and the second metal layer 24 are both metal layers containing silver as a main component. The first metal layer 22 contains at least one metal selected from palladium, gold, chromium, cobalt and nickel in a proportion of 6% by mass or more based on the total amount of silver and the metal. In addition, in the 1st metal layer 22, when the ratio of the said metal with respect to the total amount of silver and the said metal is 6 mass% or more and less than 9 mass%, between the 1st metal layer 22 and the 2nd metal layer 24 The thickness of the second dielectric layer 23 in between is 100 nm or less. In the first metal layer 22, when the ratio of the metal to the total amount of silver and the metal is 9% by mass or more, the thickness of the second dielectric layer 23 is not particularly limited. In each layer, the side close to the glass plate 1 is called “glass plate side”, and the opposite side is called “surface side”.
Hereinafter, each layer constituting the laminated film 2A will be described.

  The first metal layer 22 contains silver as a main component, and in addition to silver as a main component, at least one metal selected from palladium, gold, chromium, cobalt, and nickel is a total amount of silver and the metal. It contains in the ratio of 6 mass% or more with respect to. Hereinafter, at least one metal selected from palladium, gold, chromium, cobalt, and nickel is also referred to as a metal M. Moreover, the ratio (mass%) of the metal M with respect to the total amount of silver and the metal M is called content of the metal M. As for content of the metal M in the 1st metal layer 22, 7.5 mass% or more is more preferable, and 9 mass% or more is especially preferable. The upper limit of the content of the metal M in the first metal layer 22 is preferably about 30% by mass from the balance between effect and economy.

  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 and gold are preferable, and palladium is particularly preferable. The metal M is a metal that easily forms a solid solution with silver, which is the main material of the first metal layer 22. By using the metal M, the haze value of the laminated film 2A obtained by the heat treatment does not greatly increase even if the heat treatment is performed in the strengthening process or bending process of the glass plate.

  The first metal layer 22 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 element is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less in all the components constituting the first metal layer 22. preferable.

  The second metal layer 24 is not particularly limited as long as it is a metal layer containing silver as a main component. The second metal layer 24 may contain the same metal M as that of the first metal layer 22 as necessary. A preferred embodiment of the metal M is the same as that of the first metal layer 22. In addition, about content of the metal M in case the 2nd metal layer 24 contains the metal M, it depends on the performance calculated | required by the laminated film.

  Regarding the thicknesses of the first metal layer 22 and the second metal layer 24, the ratio of the thickness of the second metal layer 24 to the thickness of the first metal layer 22 is 0.8 to 1.6. It is preferable that it exists in the range. The ratio value of the two metal layers is more preferably 0.85 to 1.5, and particularly preferably 0.9 to 1.4. Specifically, the thickness of the first metal layer 22 is preferably 8 to 25 nm, and more preferably 10 to 20 nm. The thickness of the second metal layer 24 is preferably 10 to 30 nm, more preferably 12 to 25 nm after satisfying the value of the above ratio.

  As the first dielectric layer 21, the second dielectric layer 23, and the third dielectric layer 25 in the laminated film 2A, the metal layer is sandwiched between laminated films each having a metal layer containing silver as a main component. A dielectric layer generally used in the form can be used without particular limitation. Specifically, a dielectric layer containing oxides, nitrides, oxynitrides or the like of metals or elements that can be formed on the glass plate 1, the first metal layer 22, or the second metal layer 24 is provided. Can be mentioned. Examples of the metal and element include zinc, tin, titanium, silicon, aluminum, chromium, nickel, niobium, and alloys thereof. In addition to the above metals and elements, for example, tin, aluminum, chromium, titanium, silicon, boron, magnesium, gallium are included in the metal and element oxides, nitrides, oxynitrides, and the like constituting the dielectric layer. An element selected from the above may be doped in the form of an oxide, nitride, or oxynitride.

  Note that the nitride layer and the oxynitride layer have a large stress change due to the heat treatment, and the stress accumulated in the film by the heat treatment causes the stability of the metal layer to be lost. The structure which does not have a nitride layer or an oxynitride layer between the metal layer nearest to the laminated film surface among the said metal layers and a glass plate is preferable. In the laminated film 2A, at least the first dielectric layer 21 and the second dielectric layer 23 are preferably neither a nitride layer nor an oxynitride layer from the viewpoint of film formation efficiency. More preferably, all of the first dielectric layer 21, the second dielectric layer 23, and the third dielectric layer 25 are preferably oxide layers.

  Among the oxide layers, the first dielectric layer 21, the second dielectric layer 23, and the third dielectric layer 25 include a first metal layer 22 containing silver as a main component, a second dielectric layer 25, and a second dielectric layer 25. Since the metal layer 24 is sandwiched, the metal layers 22 and 24 can be made homogeneous and dense, and a dielectric layer capable of improving adhesion to the metal layers 22 and 24, for example, containing an oxide of zinc A dielectric layer is preferred.

  When the dielectric layers 21, 23 and 25 are dielectric layers containing zinc oxide, oxide constituent elements other than zinc can be contained. Examples of oxide constituent elements other than zinc include tin, aluminum, chromium, titanium, silicon, boron, magnesium, and gallium, and these can contain one or more. By containing an oxide constituent element other than zinc, the adhesiveness with the layer in contact with this layer can be improved, and the visible light transmittance can be improved.

Tin, aluminum, chromium, titanium, silicon, boron, magnesium, and gallium, which are oxide constituent elements other than zinc, are included in the dielectric layers 21, 23, and 25, for example, tin oxide (SnO ₂ ), aluminum oxide (Al ₂ ). O ₃ ), chromium oxide (Cr ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), boron oxide (B ₂ O ₃ ), magnesium oxide (MgO), gallium oxide (Ga ₂ O ₃ ) Or as a composite oxide thereof. As oxide constituent elements other than zinc, aluminum and tin are preferable because they are inexpensive. Aluminum is preferable because it is an inexpensive material and can increase the deposition rate. Tin is also preferable because it is a relatively inexpensive material.

  In the case where an oxide constituent element other than zinc is contained in the dielectric layer containing zinc oxide, in the total amount (in 100 mass%) of zinc and oxide constituent elements other than zinc (excluding oxygen), zinc It is preferable to make oxide constituent elements other than 1 to 50 mass%. Visible light transmittance can be effectively improved by making the ratio of oxide constituent elements other than zinc into 1 mass% or more. Moreover, stability of the metal layers 22 and 24 formed between the dielectric layers 21, 23, and 25 can be ensured by setting the ratio of oxide constituent elements other than zinc to 50 mass% or less.

  In the laminated film 2A, when the content of the metal M in the first metal layer 22 is 9% by mass or more, the thicknesses of the first to third dielectric layers 21, 23, and 25 are not necessarily limited. It is not a thing. About the thickness of the 1st, 3rd dielectric material layers 21 and 25, 10-50 nm is respectively independently preferable, and 20-45 nm is more preferable. Further, the thickness of the second dielectric layer 23 sandwiched between the first metal layer 22 and the second metal layer 24 is thicker than the thickness of the first and third dielectric layers 21 and 25. 60-120 nm is preferable and 70-110 nm is more preferable. In the laminated film (X), the content of the metal M in the first metal layer 22 is set to 9% by mass or more, and the thicknesses of the dielectric layers 21, 23, and 25 are set in the above ranges, whereby the visible light reflectance is increased. Can be made lower and a good reflection color tone can be realized.

  On the other hand, in the laminated film 2A, when the content of the metal M in the first metal layer 22 is 6 mass% or more and less than 9 mass%, it is sandwiched between the first metal layer 22 and the second metal layer 24. The thickness of the second dielectric layer 23 is 100 nm or less. About the thickness of the 2nd dielectric material layer 23, 60-100 nm is preferable and 70-100 nm is more preferable. The thicknesses of the first dielectric layer 21 and the third dielectric layer 25 are not necessarily limited, but both are preferably thinner than the thickness of the second dielectric layer 23. Specifically, the thickness of the first dielectric layer 21 and the third dielectric layer 25 is the first dielectric when the content of the metal M in the first metal layer 22 is 9% by mass or more. The thickness can be the same as that of the body layer 21 and the third dielectric layer 25. In the laminated film (X), the content of the metal M in the first metal layer 22 is 6 mass% or more and less than 9 mass%, and the thickness of the dielectric layers 21, 23, 25 is in the above range, Visible light reflectance can be further lowered, and a good reflection color tone can be realized.

  Similarly to the laminated film (X), the number of layers of the metal layer containing silver as a main component may be 2 or more, preferably 2 to 4, more preferably 2 or 3, for the laminated film (Y). 2 is particularly preferred. When the number of metal layers containing silver as a main component is 2, the content of the metal M is 1.5% by mass or more in any metal layer, and the total content of the metal M in each layer is 4%. It is at least mass%. When the number of metal layers containing silver as a main component is 3 or more, at least one of the metal layers closest to the glass plate and the remaining metal layers has a ratio of 1.5% by mass or more of metal M. The total content of metal M in each layer is 4% by mass or more. The content of the metal M may be the same or different in each metal layer.

  The more preferable content of the metal M in each metal layer is 4% by mass or more and particularly preferably 7% by mass or more in the metal layer closest to the glass plate. Furthermore, in the other metal layer containing 1.5% by mass or more of metal M, the content of metal M is more preferably 2% by mass or more, and particularly preferably 2.5% by mass or more. In the metal layer in which the content of the metal M is not specified, the metal M may or may not be contained. When the metal M is contained, the content is preferably 1.5% by mass or more. The upper limit of the content of the metal M in each metal layer is preferably about 20% by mass.

  As the laminated structure in the laminated film (Y), for example, the same laminated structure as the laminated film 2A of the laminated film 10A shown in FIG. 3, that is, the first dielectric layer, And a structure having a second metal layer, a second dielectric layer, a second metal layer, and a third dielectric layer. The laminated film (Y) is the same as the laminated film (X) except that the metal layer is different in the content of the metal M in the first metal layer and the second metal layer. A configuration is preferred.

  When the laminated film (Y) having the same laminated structure as the laminated film 2A is used, the dielectric film is the laminated film (X) except that the thickness of the second dielectric layer is different. The same configuration is preferable. In the laminated film (Y), the thickness of the second dielectric layer sandwiched between the first metal layer and the second metal layer is 95 nm or less. The thickness of the second dielectric layer is preferably 60 to 95 nm, and more preferably 70 to 95 nm. The thicknesses of the first dielectric layer and the third dielectric layer are not necessarily limited, but both are preferably thinner than the thickness of the second dielectric layer. Specifically, the thicknesses of the first dielectric layer and the third dielectric layer can be made similar to the thicknesses of the first dielectric layer and the third dielectric layer in the laminated film (X). In the laminated film (Y), the metal layer is configured as described above, and the thickness of the dielectric layer is set in the above range, whereby the visible light reflectance can be further lowered and a good reflection color tone can be realized. Can do.

  In the laminated film, when the number of metal layers containing silver as a main component is 2, the laminated film (X) wherein the content of the metal M in the first metal layer close to the glass plate is 6% by mass or more. Even so, the content of the metal M in the first metal layer close to the glass plate and the second metal layer far from the glass plate is 1.5% by mass or more, and the content of the metal M in each layer Even if it is the said laminated film (Y) whose sum total is 4 mass% or more, it is preferable that a laminated film is a layer structure which shows a cross section in FIG.

  FIG. 4 is a cross-sectional view showing a modification of one embodiment of the laminated film-attached glass plate. The laminated film-attached glass plate 10 </ b> B has a laminated film 2 </ b> B on one main surface 1 s of the glass plate 1. The laminated film 2B includes, in order from the glass plate 1, the first dielectric layer 21, the first metal layer 22, the first barrier layer 26, the second dielectric layer 23, the second metal layer 24, Two barrier layers 27, a third dielectric layer 25, and a protective layer 28.

  Both the first metal layer 22 and the second metal layer 24 can be the same as the first metal layer 22 and the second metal layer 24 of the laminated film 2A in the laminated film-attached glass plate 10A.

  The first dielectric layer 21 includes a first amorphous dielectric layer 211 and a first crystalline dielectric layer 212 from the glass plate side. The second dielectric layer 23 includes a second crystalline dielectric layer 231, a second amorphous dielectric layer 232, and a third crystalline dielectric layer 233 from the glass plate side. Further, the third dielectric layer 25 includes a fourth crystalline dielectric layer 251 and a third amorphous dielectric layer 252 from the glass plate side.

  In the laminated film 2B, the first, second, and third dielectric layers 21, 23, and 25 have the crystalline dielectric layer and the amorphous dielectric layer, respectively, and sandwich the first metal layer 22 therebetween. The third crystalline dielectric layer 233 and the fourth crystalline dielectric layer are arranged such that the first crystalline dielectric layer 212 and the second crystalline dielectric layer 231 sandwich the second metal layer 24 therebetween. 251 is arranged, and first, second, and third amorphous dielectric layers 211, 232, and 252 are arranged on both sides thereof.

  In the laminated film 2B, the total thickness of each layer constituting the first dielectric layer 21, that is, the thickness of the first dielectric layer 21 is the case of either the laminated film (X) or the laminated film (Y). The thickness can be the same as the thickness of the laminated film (X) and the laminated film (Y) in the laminated film 2A. The same applies to the thickness of the second dielectric layer 23 and the thickness of the third dielectric layer 25.

  The laminated film 2B has a first barrier layer 26 and a second barrier layer 27 on the surface side of the first metal layer 22 and the second metal layer 24 so as to be in contact with the metal layers, respectively. The protective layer 28 is provided on the surface side of the third dielectric layer 25 on the surface side.

  As described above, the laminated film in the glass plate with a laminated film of the embodiment preferably has a structure in which no nitride layer or oxynitride layer is provided between the metal layer closest to the laminated film surface of the metal layers and the glass plate. In the laminated film 2B, at least the first dielectric layer 21, the first barrier layer 26, and the second dielectric layer 23 are neither a nitride layer nor an oxynitride layer from the viewpoint of film formation efficiency. It is preferable. More preferably, the first dielectric layer 21, the first barrier layer 26, the second dielectric layer 23, the second barrier layer 27, and the third dielectric layer 25 are all oxide layers. Is preferred.

  The first to fourth crystalline dielectric layers 212, 231, 233 and 251 are arranged so as to sandwich the first and second metal layers 22 and 24 as described above, and are highly crystalline dielectric layers. It is. The crystalline dielectric layer can be made dense by making the first metal layer 22 and the second metal layer 24 formed therebetween uniform by crystallization or the like.

  As a constituent material of the crystalline dielectric layers 212, 231, 233, and 251, a dielectric material having a high crystallinity among the above-described dielectric materials as materials constituting the dielectric layers 21, 23, 25, etc. in the laminated film 2A. A material can be appropriately selected and used. Among the dielectric materials described above, as a dielectric material having high crystallinity, specifically, an oxide of zinc or zinc containing an oxide constituent element other than zinc such as aluminum, titanium, tin, or the like. Oxides are preferred.

Among these, an oxide of zinc containing aluminum is particularly preferable in terms of crystallinity, film formation rate, and economy. When aluminum is contained in the oxide of zinc, it is contained in the form of aluminum oxide (Al ₂ O ₃ ) or a composite oxide of zinc and aluminum as described above. The content of aluminum in the zinc oxide containing aluminum is preferably 1 to 10% by mass, and preferably 1 to 5% by mass in the total amount of zinc and aluminum (in 100% by mass). It is more preferable.

  The thicknesses of the first to fourth crystalline dielectric layers 212, 231, 233, and 251 are each preferably 3 to 15 nm independently. By setting the thickness of the crystalline dielectric layers 212, 231, 233, and 251 to 3 nm or more, crystallization can be promoted, and the first and second metal layers 22 and 24 formed therebetween are made homogeneous. It can be precise. If the thickness of the crystalline dielectric layers 212, 231, 233, and 251 is 15 nm, it is sufficient for promoting crystallization. By making the thickness less than this, the crystalline dielectric layers 212, 231, 233 are reduced. , 251 can be prevented from deteriorating the characteristics of the first and second metal layers 22 and 24 due to the rough surface. The thickness of the crystalline dielectric layers 212, 231, 233, and 251 is 5 from the viewpoint of making the first and second metal layers 22 and 24 more homogeneous and dense, and having excellent characteristics. ˜11 nm is more preferable.

  A first barrier layer 26 and a second barrier layer 27 are disposed on the surface sides of the first and second metal layers 22 and 24 so as to be in contact with the metal layers, respectively. Therefore, the second crystalline dielectric layer disposed on the surface side of the first and second metal layers 22, 24 among the first to fourth crystalline dielectric layers 212, 231, 233, 251. 231 and the fourth crystalline dielectric layer 251 are arranged on the surface side of the first and second metal layers 22 and 24 with the first barrier layer 26 and the second barrier layer 27 interposed therebetween. However, the function of making the first and second metal layers 22 and 24 homogeneous and dense is that the first crystal disposed on the glass plate side of the first and second metal layers 22 and 24 This can be sufficiently achieved by using the conductive dielectric layer 212 and the third crystalline dielectric layer 233 together.

  The first, second, and third amorphous dielectric layers 211, 232, and 252 are first to fourth crystalline dielectric layers 212 provided so as to sandwich the first and second metal layers 22 and 24 therebetween. , 231, 233, 251, or an amorphous dielectric layer disposed above and below. Since the amorphous dielectric layer does not grow crystal grains, it is possible to ensure the flatness of the entire laminated film 2B by providing the amorphous dielectric layer between or above and below the crystalline dielectric layer.

  As a constituent material of the amorphous dielectric layers 211, 232, 252, an amorphous dielectric material is appropriately selected from the above-described dielectric materials as materials constituting the dielectric layers 21, 23, 25, etc. in the laminated film 2A. It can be selected and used. Among the dielectric materials described above, as an amorphous dielectric material, specifically, an oxide of zinc containing 10% by mass or more of an oxide constituent element other than zinc, such as tin, aluminum, titanium, etc. Etc. are preferred.

Among these, zinc oxide containing tin is particularly preferable in terms of non-crystallinity and economy. When tin is contained in the zinc oxide, it is contained in the form of tin oxide (SnO ₂ ) or a composite oxide of zinc and tin as described above. In order to obtain sufficient non-crystallinity, the tin content in the zinc oxide containing tin is 20 to 80% by mass in the total amount of zinc and tin (in 100% by mass). Is preferable, and it is more preferable to set it as 30-70 mass%.

  The thicknesses of the first, second and third amorphous dielectric layers 211, 232 and 252 are preferably 5 to 45 nm independently for the thicknesses of the first and third amorphous dielectric layers 211 and 252. 10 to 35 nm is more preferable. Further, regarding the thickness of the second amorphous dielectric layer 232 sandwiched between the second crystalline dielectric layer 231 and the third crystalline dielectric layer 233, the laminated film 2B has the laminated film (X), Considering whether it belongs to one of the laminated films (Y), the thickness of the second dielectric layer 23 is set to be within the thickness range in each case described above.

  When the laminated film 2B is the laminated film (X) and the content of the metal M in the first metal layer 22 is 9% by mass or more, the thickness of the second amorphous dielectric layer 232 is 30 to 30%. 100 nm is preferable and 40-80 nm is more preferable. When the multilayer film 2B is the multilayer film (X) and the content of the metal M in the first metal layer 22 is 6 mass% or more and less than 9 mass%, the thickness of the second amorphous dielectric layer 232 Is preferably 50 to 90 nm, more preferably 60 to 90 nm. When the laminated film 2B is a laminated film (Y), the thickness of the second amorphous dielectric layer 232 is preferably 50 to 85 nm, and more preferably 60 to 85 nm.

  By making the thicknesses of the first, second, and third amorphous dielectric layers 211, 232, and 252 within the above ranges, the visible light transmittance is increased while ensuring the flatness of the entire laminated film 2B. In addition, the film formation time can be shortened appropriately and the productivity can be improved.

  The first barrier layer 26 and the second barrier layer 27 are the first metal layer 22 and the second barrier layer 27, respectively, when the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251 are formed. It is provided to suppress oxidation of the metal layer 24.

  The constituent materials of the first barrier layer 26 and the second barrier layer 27 are not particularly limited as long as they can suppress the oxidation. The constituent materials of the first and second barrier layers 26 and 27 include, for example, titanium, zinc aluminum alloy, nickel chrome alloy, or oxides thereof, and have a metal or stoichiometric composition. On the other hand, those made of an oxide deficient in oxygen can be mentioned. By using a metal or an oxide-deficient material for the stoichiometric composition, the first metal layer 22 is oxidized during the formation of the second crystalline dielectric layer 231, and the fourth The oxidation of the second metal layer 24 during the formation of the crystalline dielectric layer 251 can be suppressed.

  The first and second barrier layers 26 and 27 are preferably composed mainly of titanium or an oxide of titanium. The thing which has an oxide of titanium as a main component is what contains 50 atomic% or more of titanium in the total amount (100 atomic%) of oxide constituent elements (except oxygen) other than titanium and titanium.

The first and second barrier layers 26 and 27 can contain a constituent element other than titanium. Examples of constituent elements other than titanium include niobium, tantalum, zirconium, silicon, tungsten, and molybdenum, and these can contain one or more of them. Titanium, niobium, tantalum, tungsten, and molybdenum are included in the oxidation barrier layer, for example, TiO _x (x <2), Nb ₂ O _x (x <5), Ta ₂ O _x (x <5), ZrO _x ( x <2), SiO _x (x <2), WO _x (x <3), MoO _x (x <3), or a composite thereof.

In the case where the first and second barrier layers 26 and 27 contain constituent elements other than titanium, titanium is included in the total amount (100 atomic%) of titanium and constituent elements other than titanium from the viewpoint of reducing material costs. The constituent elements other than are preferably 30 atomic percent or less, more preferably 20 atomic percent or less, and even more preferably 10 atomic percent or less. The first and second barrier layers 26 and 27 are preferably made of only titanium or an oxide of titanium, and particularly TiO _x (1) which is an oxide deficient in oxygen with respect to the stoichiometric composition. <X <2) is preferable.

  The first and second barrier layers 26 and 27 are partly or wholly oxidized when the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251 are formed. Therefore, after the second crystalline dielectric layer 231 and the fourth crystalline dielectric layer 251 are formed, it is not always necessary to be made of an oxide deficient in oxygen with respect to the stoichiometric composition. It may be composed of an oxide layer having a stoichiometric composition formed by oxidation and an unoxidized layer remaining without being oxidized, or only an oxide layer having a stoichiometric composition formed by oxidation. It may be made up of.

  The thicknesses of the first and second barrier layers 26 and 27 are preferably 1 nm or more independently of each other. By setting the thickness of the first and second barrier layers 26 and 27 to 1 nm or more, the oxidation of the first metal layer 22 and the second metal layer 24 can be effectively suppressed. The thicknesses of the first and second barrier layers 26 and 27 are not particularly limited as long as they are 1 nm or more, but in order to suppress oxidation of the first metal layer 22 and the second metal layer 24. If it is less than 10 nm, the visible light transmittance can be effectively increased.

  The protective layer 28 has a function of improving the durability of the multilayer film 2B, particularly the surface scratch resistance, and a function as a barrier against moisture and oxygen during heat treatment. The protective layer 28 is not particularly limited as long as it improves the above function. For example, the protective layer 28 mainly composed of oxynitride such as titanium, silicon, or aluminum is preferable. Further, although it disappears when heat treatment is performed, a carbon layer containing carbon as a main component that can improve the scratch resistance from film formation to heat treatment may be provided on the outermost layer of the protective layer 28. On the other hand, in the non-heat treated product before the heat treatment, the protective layer 28 is preferably a layer mainly composed of titanium oxide in advance.

  The thickness of the protective layer 28 is preferably 1 nm or more. When the thickness of the protective layer 28 is 1 nm or more, the durability is effectively improved. If the thickness of the protective layer 28 is 15 nm, it is sufficient for ensuring the durability, and by making it less than this, the productivity of the protective layer 28 is improved. The thickness of the protective layer 28 is more preferably 10 nm or less, and further preferably 6 nm or less.

(Manufacture of laminated glass sheets)
In the production of the laminated film-attached glass plate of the embodiment, the respective layers constituting the laminated film are formed in that order on one principal surface of the glass plate having a larger principal surface than the laminated film-attached glass plate to be produced by a conventional method. A film forming step of forming a film, and a cutting step of cutting the glass plate with the laminated film after the film forming step into a desired size having a rectangular main surface. The strengthening of the glass plate in the laminated film-attached glass plate is usually performed by air-cooling strengthening, and specifically by performing a heat treatment (heat treatment step) after laminating the respective layers. As an order of each process, it is essential that a cutting process is performed after a film-forming process. The order of the heat treatment steps is not limited, but it is preferable to perform the heat treatment after the cutting step.

  When forming the laminated film, the main surface on which the laminated film of the glass plate is formed is cleaned, and each layer of the laminated film is sequentially formed on the main 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.

  Hereinafter, the film forming method of each layer will be specifically described with reference to the glass plate with laminated film 10A shown in FIG. 3 and the glass plate with laminated film 10B shown in FIG. 3 and 4 are shown in a state where they have already been cut, but in actuality, the film formation of each layer is larger than the glass plate with a laminated film to be manufactured. The film is formed on one main surface of the glass plate.

  The method for forming the first, second, and third dielectric layers 21, 23, and 25 in the laminated film 2A of the laminated film-attached glass plate 10A is not particularly limited. For example, the film can be formed by selecting a sputtering target and an atmospheric gas corresponding to the constituent materials and performing sputtering by a conventional method. When these dielectric layers are provided, for example, as metal oxide layers, the film is formed by reactive sputtering in a sputtering gas with a sufficiently high oxidizing gas concentration using a metal target as a sputtering target. can do. As the metal target, for example, a metal target containing zinc is preferably used.

  The metal target containing zinc can contain oxide constituent elements other than zinc. Examples of oxide constituent elements other than zinc include tin, aluminum, chromium, titanium, silicon, boron, magnesium, and gallium, and these can contain one or more kinds. When the oxide constituent elements other than zinc are contained, the oxide constituent elements other than zinc are preferably 1 to 50 mass% in the total amount (100 mass%) of zinc and the oxide constituent elements other than zinc. .

  When the first to fourth crystalline dielectric layers 212, 231, 233, and 251 in the laminated film 2B of the laminated film glass plate 10B are formed as, for example, zinc oxide layers containing aluminum. In the above, by performing reactive sputtering using a metal target containing 1 to 10% by mass of aluminum in a desired ratio of zinc and aluminum, for example, in the total amount of zinc and aluminum (in 100% by mass). A film can be formed.

  Similarly, the first, second, and third amorphous dielectric layers 211, 232, and 252 in the laminated film 2B of the laminated glass plate 10B are formed as, for example, zinc oxide layers containing tin. In this case, reactive sputtering is performed using a metal target containing 30 to 70% by mass of tin and zinc in a desired ratio, for example, in a total amount of zinc and tin (in 100% by mass). A film can be formed by performing.

  The method for forming the first metal layer 22 and the second metal layer 24 is not particularly limited. The first metal layer 22 and the second metal layer 24 contain, for example, silver as a main component as a sputtering target, and at least one metal M selected from palladium, gold, chromium, cobalt, and nickel is silver. Film formation can be performed by performing sputtering in an atmosphere containing only an inert gas such as argon, using a target that is contained in a predetermined ratio with respect to the total amount of metal and metal M.

  Specifically, when the laminated film has the structure of the laminated film (X), the sputter target used for forming the first metal layer 22 contains silver as a main component, and the metal M contains silver and metal. A target containing 6% by mass or more of the total amount with M is used, and the second metal layer 24 uses a target containing silver as a main component as a sputter target. In the case of the laminated film (Y) configuration, the sputter target used for forming the first metal layer 22 and the second metal layer 24 are each independently a metal containing silver as a main component as a sputter target. M is contained in a ratio of 1.5% by mass or more with respect to the total amount of silver and metal M, and the content of metal M with respect to the total amount of silver and metal M in first metal layer 22 ( Mass%) and a target in which the total content (mass%) of metal M with respect to the total amount of silver and metal M in second metal layer 24 is 4 mass% or more is used.

  The first barrier layer 26 and the second barrier layer 27 are preferably formed by sputtering using a metal target such as titanium or a reducing oxide target and using an inert gas as a sputtering gas.

  When the laminated film 2B of the laminated film-attached glass plate 10B includes, for example, a titanium oxynitride layer as the protective layer 28, the titanium oxynitride layer is formed, for example, as follows. The layer is obtained by heat treatment as described below. The titanium nitride layer can be formed by sputtering in a sputtering gas atmosphere made of a mixed gas of argon and nitrogen using a titanium target. For example, when the protective layer 28 has a carbon layer containing carbon as a main component, the carbon layer is sputtered in an atmosphere containing only an inert gas such as argon using a carbon target. And film formation may be performed.

  After forming the laminated film, the glass plate with the laminated film is cut into a desired product shape. In order to cut | disconnect the glass plate in which the laminated film was formed, the laminated film is not provided in the end surface of 2 or more as for the glass plate with a laminated film of embodiment of this invention. In the method of forming a film after cutting into a product shape, the laminated film is also formed on the end face of the glass plate.

  As described above, the non-heat treated product of the laminated film-attached glass plate is obtained. When the non-heat treated product thus obtained is subjected to heat treatment to obtain the laminated film-attached glass plate of the embodiment, these are treated as precursors, and the laminated film-attached glass plate obtained by heat treatment is used in the present invention. The glass plate with the laminated film of the embodiment is used.

  When obtaining a glass sheet with a laminated film as a heat-treated product, the precursor of the glass sheet with a laminated film obtained above is used in a heating furnace according to the purpose, for example, for heating temperature or bending for strengthening. Heat at a heating temperature for a predetermined time. For example, for the precursor of a glass plate with a laminated film using a float glass substrate as the glass plate, when performing air-cooling strengthening of the glass substrate, the heat treatment is performed as the surface temperature of the precursor of the glass plate with a laminated film. 1 to 30 minutes are preferable at 500 to 700 ° C.

Further, as a method for forming the first metal layer 22 and the second metal layer 24, for example, the following methods are known.
Two types of metal targets containing silver and metal M are prepared so that the content of metal M is different. Metal obtained by laminating metal films having different metal M contents such that the film thickness and the content of metal M are the desired values as the finally obtained metal layer using the two types of targets obtained A layer precursor is obtained. By firing this precursor, a metal layer mainly composed of silver containing a predetermined amount of metal M is obtained as a single layer having a uniform composition.

  In the glass plate with a laminated film of the embodiment, the other layers constituting the laminated film are formed in the same manner as described above, and when the metal layer is formed by such a method, the desired size is obtained after the film formation. By cutting into a rectangular shape, a precursor of the laminated film-attached glass plate in which at least the metal layer is not in the final form is obtained. As a condition for firing the precursor of the laminated film-attached glass plate so that the metal layer becomes a single layer of uniform composition, the surface temperature of the precursor of the laminated film-attached glass plate is 500 to 700 ° C. Firing conditions are preferred.

  It is preferable that the glass plate with a laminated film according to the embodiment of the present invention has a haze value of 2% or less even in the case where the heat treatment is performed under the temperature condition of, for example, 600 ° C. or more in the manufacturing process.

  The use of the laminated film-attached glass plate of the embodiment of the present invention is not limited. For example, it can be used as a constituent member of low-radiation laminated glass or multilayer glass. It is preferable to use it as a constituent member of a double-glazed glass.

  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. The glass plate with a laminated film of the embodiment can be used for one of such laminated glass transparent substrates. In that case, the laminated film is used by being disposed on the intermediate film side. The other transparent substrate is preferably a transparent glass plate. When such a laminated glass is used as a window glass, the laminated glass-attached glass plate side is used as an outdoor side. Note that 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. The glass plate with a laminated film of the embodiment can be used on one of such transparent substrates of multi-layer glass. In that case, the laminated film is disposed on the intermediate layer side. The other transparent substrate is preferably a transparent glass plate. The intermediate layer is preferably an air layer or an inert gas such as argon. When such a multi-layer glass is used as a window glass, it is used so that the glass plate side with a laminated film becomes the outdoor side. Note that the multi-layer glass may have three or more transparent substrates.

[Multilayer glass]
The multilayer glass of the embodiment of the present invention is configured by using the laminated film-attached glass plate of the embodiment on one of the transparent substrates of the multilayer glass and using the second transparent glass plate as the other transparent substrate. The FIG. 2 shows a cross-sectional view of an example of the multilayer glass of the embodiment of the present invention. The multi-layer glass 3 is an example in which the laminated film-attached glass plate 10 is used as a constituent member, and the laminated film 2 surface of the laminated film-attached glass plate 10 is opposed to one main surface of the second transparent glass plate 32. Are spaced apart. In addition, the multilayer glass 3 has an intermediate layer 34 between the laminated film-attached glass plate 10 and the second transparent glass plate 32 by spacers 33 arranged on the periphery.

The multilayer glass of the embodiment of the present invention has the following properties (1-b), (2-b), and (3-b).
(1-b) The solar heat acquisition rate (g value) on the second glass plate side with respect to the solar radiation from the laminated film-attached glass plate side measured in accordance with ISO 9050: 2003 is 0.265 or less. is there.
(2-b) ISO9050: for transmitted light obtained by irradiating the visible light as defined in 2003, ^{b *} is 1 or less by CIE1976L ^* a ^* b ^* chromaticity coordinates.
(3-b) The visible light reflectance on the side of the glass plate with a laminated film, measured in accordance with ISO 9050: 2003, is 20% or less.

  The characteristics (1-b) to (3-b) are characteristics corresponding to (1-a) to (3-a) in the evaluation of the laminated film-attached glass plate of the embodiment of the present invention, respectively. Regarding (1-b) to (3-b) in the multilayer glass of the embodiment of the present invention, the preferred range is the same as the preferred range in (1-a) to (3-a). Furthermore, the multilayer glass of the embodiment of the present invention preferably has characteristics corresponding to (4-a) to (8-a) in the evaluation of the laminated film-attached glass plate of the embodiment of the present invention, in particular. A preferable range in these characteristics is more 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 glass plate with a laminated film of the present invention will be specifically described with reference to examples. The present invention is not limited to these. Examples 1, 2, and 8 are examples, and examples 3 to 7 are comparative examples.

(Examples 1-8)
As a glass plate with a laminated film, 1 to 8 glass plates with a laminated film having the constitution shown in Table 1 were produced. That is, a soda lime glass plate (manufactured by Asahi Glass Co., Ltd. (FL5, FL6), 100 mm × 180 mm × 5 mmt, 100 mm × 180 mm × 6 mmt) is used as the glass plate, and DC sputtering is performed on one main surface by the following method. After forming the precursor of the laminated film by cutting, it is cut and fired to form each film so as to have the film configuration and thickness shown in Table 1, and laminated on one main surface of the glass plate A glass plate with a laminated film having a film and having no laminated film on four end faces was produced.

  In Table 1, each film of the glass plate 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]). Moreover, the symbol of the constituent material concerning Examples 1-8 shown in Table 1 is the following meanings, and it is as follows also about the thickness of the layer without the display of thickness. In addition, the glass plate with a laminated film of 1-8 is a glass plate with a laminated film of the structure similar to glass plate 10B with a laminated film which shows a cross section in FIG.

FL5; manufactured by Asahi Glass Co., Ltd., soda lime glass plate, FL5 (5 mmt)
FL6; manufactured by Asahi Glass Co., Ltd., soda lime glass plate, FL6 (6 mmt)
SZO: Zinc and tin oxide layer (SnZn oxide layer)
AZO: Zinc and aluminum oxide layer (AlZn oxide layer). When there is no description of the thickness, the layer thickness is 10 nm.
AgPd: layer in which palladium is doped in silver. In Table 1, the number after AgPd indicates the ratio (mass%) of palladium to the total amount of palladium and silver.
TiOx: a layer made of titanium oxide having a stoichiometric composition ratio or a non-stoichiometric composition ratio, or a layer thickness of 4 nm when no thickness is described.
TiOxNy: a layer composed of titanium oxynitride having a stoichiometric composition ratio or a non-stoichiometric composition ratio, and when there is no description of the thickness, the layer thickness is 3.5 nm.

(1) Film Formation of Laminated Film Precursor In Examples 1 to 8, the precursor of the laminated film is formed on the glass plate by the following method, and the first zinc and tin oxide layer (SnZn oxide layer). , First zinc and aluminum oxide layer (AlZn oxide layer), first silver palladium one layer (AgPd1 layer = a layer containing 1% by mass of Pd with respect to the total amount of Ag and Pd) or first Silver palladium 1 layer (AgPd1 layer) and silver palladium 30 layer (AgPd30 layer = a layer containing 30% by mass of Pd based on the total amount of Ag and Pd), a first titanium layer (Ti barrier layer), a second layer Zinc and aluminum oxide layer, second zinc and tin oxide layer, third zinc and aluminum oxide layer, second silver palladium one layer (AgPd1 layer) or second silver palladium one layer (AgPd1 layer) and 30 layers of silver and palladium (AgPd30 layer), a second titanium layer, a fourth oxide layer of zinc and aluminum, a third oxide layer of zinc and tin, and a titanium nitride layer (TiNx layer) are sequentially formed. Thus, a thin film stack was formed.

The in-line type sputtering apparatus used for sputtering contains a titanium target (Ti target), a target made of a zinc alloy containing 50% by mass of tin (SnZn alloy target), and 2% by mass of aluminum in the film forming chamber. A target made of a zinc alloy (AlZn alloy target), a silver target containing 1% by mass of palladium (AgPd1 target), and a silver target containing 30% by mass of palladium (AgPd30 target) were placed on the cathode. And while introduce | transducing the wash | cleaned glass plate into a load lock chamber, the whole vacuum chamber was evacuated to 2.0 * 10 <^-4> Pa, and each layer was formed as shown below.

<SnZn oxide layer>
Argon and oxygen were introduced into the vacuum chamber at 30:70 sccm as discharge gases, and formed by reactive DC magnetron sputtering using the SnZn alloy target described above. The sputtering target was 70 × 200 mm ² and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa.

<AlZn oxide layer>
Oxygen was introduced into the vacuum chamber as a discharge gas at 100 sccm and formed by DC magnetron sputtering using the AlZn alloy target described above. The sputtering target was 70 × 200 mm ² and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. The thickness of the AlZn oxide layer was all 10.0 nm.

<AgPd1 layer>
Argon was introduced into the vacuum chamber by 50 sccm as a discharge gas and formed by DC magnetron sputtering using the above AgPd1 target. The sputtering target was 70 × 200 mm ² and 100 W was applied as the sputtering power.

<AgPd layer>
Argon was introduced into the vacuum chamber as a discharge gas by 50 sccm, and the above-described AgPd1 target and AgPd30 target were successively used in this order and formed by DC magnetron sputtering. In either case, the sputtering target was 70 × 200 mm ² and 100 W was applied as the sputtering power. The continuously formed AgPd1 layer and AgPd30 layer are formed into a single AgPd layer by the following heat treatment (firing) after the production of the laminated film precursor on the glass plate, and the total thickness of each is determined as the final AgPd layer. The layer thickness was taken.

<Ti barrier layer>
Argon was introduced into the vacuum chamber as a discharge gas at 100 sccm, and the magnet was formed by DC magnetron sputtering using the Ti target described above. The sputtering target was 70 × 200 mm ² and 50 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. The thickness of the Ti barrier layer was all 4.0 nm. The Ti barrier layer is a layer existing as a TiOx layer in the laminated film of the finally obtained glass plate with laminated film.

<Ti nitride layer>
Argon and nitrogen were introduced into the vacuum chamber at 70:30 sccm as discharge gases, and formed by DC magnetron sputtering using the Ti target described above. The sputtering target was 70 × 200 mm ² and 500 W was applied as the sputtering power. At this time, the pressure in the vacuum chamber was 0.4 Pa. The thickness of the TiNx layer was all set to 3.5 nm. The TiNx layer is a layer present as a TiOxNy layer in the laminated film of the finally obtained glass plate with laminated film.

(2) Cutting On the one main surface of the glass plate, the glass plate with the precursor of the laminated film obtained above is cut with a glass cutter so that the size of the main surface becomes a rectangular shape of 70 mm × 100 mm. The precursor examples 1-8 of the glass plate with a laminated film which did not have the precursor of a laminated film in the 4 end surface of a glass plate, and do not have the precursor of a laminated film were obtained.

(3) Firing (heat treatment)
Precursor examples 1 to 7 of the glass plate with laminated film produced above were baked for 5 minutes at a set temperature of 700 ° C. using a desktop electric furnace, and the precursor example 8 was set to 4 at a set temperature of 750 ° C. The glass plate with laminated films of Examples 1 to 8 having the laminated constitution shown in Table 1 was obtained by baking for a minute. The maximum temperature reached on the glass plate surface at this time was 650 ° C. The Pd content (mass% of Pd with respect to the total amount of Ag and Pd) in the AgPd layer after firing was measured using a fluorescent X-ray “ZSX-100e” manufactured by Rigaku or ICP-OES “SPS3100” manufactured by Hitachi High-Tech. did.

(Evaluation)
The glass plates with laminated films 1 to 8 obtained above were evaluated as follows. In the multilayer glass for evaluation described below, the multilayer glass using the laminated film-attached glass plates of Examples 1, 2, and 8 is the multilayer glass of the examples of the present invention.

  Using the spectrophotometer spectrophotometer and emissivity measurement results for the glass plates with laminated films 1 to 8, the double-layer glass having the following constitution, that is, the double-layer for evaluation having the same constitution as shown in FIG. The performance of the glass 30 was determined by calculation.

  The multi-layer glass uses a transparent glass plate having a thickness of 6 mm as a transparent counter substrate (second transparent glass plate 32 in the multi-layer glass 30) facing the glass plate with the multi-layer film, and is transparently opposed to the glass plate with the multi-layer film. The thickness of the intermediate layer between the substrate and the substrate was 12 mm, and the intermediate layer was filled with air. The spectrophotometer measurement was performed using “U4100” manufactured by HITACHI. The emissivity was measured by using a conversion formula between the measurement result and the surface resistance value (Rs) of the FT / IR “Frontier Gold” manufactured by Perkin Elmer, Inc., which was obtained in advance. When the vertical emissivity was less than 0.03 in the conversion formula, the vertical emissivity was calculated as 0.03.

  In addition, the measurement of the surface resistance value (Rs) of the laminated film surface of the glass plate with a laminated film of 1-8 was performed using the portable surface resistance measuring instrument "STRATOMETER" made from NAYY.

<Multilayer glass; Optical properties>
About the multilayer glass for evaluation using the glass plate with a laminated film of 1-8, the solar heat acquisition rate (g value) in the transparent counter substrate side with respect to the solar radiation from the glass plate side with a laminated film, visible light transmittance ( Tv), visible light reflectance (Rv _out ) on the side of the laminated film-attached glass plate, and visible light reflectance (Rv _in ) on the transparent counter substrate side were determined. The solar heat acquisition rate (g), visible light transmittance (Tv), and visible light reflectance (Rv) were determined based on ISO 9050: 2003.

<Multilayer glass; Optical properties (color tone)>
About the multilayer glass for evaluation using the glass plate with a laminated film of 1-8, the transmitted light obtained by irradiating the visible light prescribed | regulated to ISO9050: 2003, the reflected light of the glass plate with a laminated film, and transparent With respect to the reflected light on the counter substrate side, a ^* and b ^* by CIE1976L ^* a ^* b ^* chromaticity coordinates were obtained.

<Multilayer glass; Color rendering properties>
About the multilayer glass for evaluation using the glass plate with a laminated film of 1-8, the color rendering of the transmitted light evaluated by average color rendering index (Ra) using D65 light source based on JISZ8726 (1990) Seeking sex.

<Glass plate with laminated film; haze value>
The haze value (H (%)) of the glass plate with a laminated film of 1-8 was measured. The haze measurement was performed using a haze meter “HZ-2 type” manufactured by Suga Test Instruments Co., Ltd.

<Glass plate with laminated film; moisture resistance>
The number of white spots with a diameter of 0.5 mm or more observed in a predetermined range on the surface of the laminated film after a moisture resistance test in which the glass plates with laminated films 1 to 8 are stored at 50 ° C. and 90% RH for 2 weeks. It was observed visually. The case where the number of white spots per 100 mm × 100 mm was 5 or less was marked as “◯”.
Table 2 shows the evaluation results obtained above.

  DESCRIPTION OF SYMBOLS 10 ... Glass plate with laminated film, 1 ... Glass plate (first transparent glass plate), 2 ... Laminated film, 3 ... Multi-layer glass, 10 ... Glass plate with laminated film, 32 ... Second transparent glass plate, 33 ... Spacer, 34 ... Intermediate layer, 10A, 10B ... Glass plate with laminated film, 2A, 2B ... Laminated film, 21 ... First dielectric layer, 22 ... First metal layer, 23 ... Second dielectric Layer, 24 ... second metal layer, 25 ... third dielectric layer, 26 ... first barrier layer, 27 ... first barrier layer, 28 ... protective layer.

Claims (9)

A reinforced main surface is a rectangular glass plate,
A laminated film provided on one main surface of the glass plate and not provided on two or more end surfaces of the glass plate;
The laminated film is
Having two metal layers containing silver as a main component and three dielectric layers laminated so as to sandwich the metal layers,
The metal layer and the dielectric layer are in order from the glass plate side, from the first dielectric layer, the first metal layer, the second dielectric layer, the second metal layer, and the third dielectric layer. Become
The first dielectric layer includes a first amorphous dielectric layer laminated from the glass plate side, and a first crystalline dielectric layer,
The second dielectric layer comprises a second crystalline dielectric layer laminated from the glass plate side, a second amorphous dielectric layer, and a third crystalline dielectric layer,
The third dielectric layer comprises a fourth crystalline dielectric layer laminated from the glass plate side, and a third amorphous dielectric layer,
Before SL first metal layer, palladium, gold, chromium, at least one metal selected from cobalt and nickel, in a proportion of more than 6% by weight relative to the total amount of silver and the metal, provided that If the ratio is less than 9% by weight is 100nm or less thickness before Symbol second dielectric layer,
Glass plate with laminated film. A reinforced main surface is a rectangular glass plate,
A laminated film provided on one main surface of the glass plate and not provided on two or more end surfaces of the glass plate;
The laminated film is
Having two metal layers containing silver as a main component and three dielectric layers laminated so as to sandwich the metal layers ,
The metal layer and the dielectric layer are in order from the glass plate side, from the first dielectric layer, the first metal layer, the second dielectric layer, the second metal layer, and the third dielectric layer. Become
The first dielectric layer includes a first amorphous dielectric layer laminated from the glass plate side, and a first crystalline dielectric layer,
The second dielectric layer comprises a second crystalline dielectric layer laminated from the glass plate side, a second amorphous dielectric layer, and a third crystalline dielectric layer,
The third dielectric layer comprises a fourth crystalline dielectric layer laminated from the glass plate side, and a third amorphous dielectric layer,
Each of the first metal layer and the second metal layer independently includes at least one metal selected from palladium, gold, chromium, cobalt, and nickel with respect to the total amount of silver and the metal. A total content of the metal content in the first metal layer and the metal content in the second metal layer is 4% by mass or more, The thickness of the second dielectric layer is 95 nm or less
Glass plate with laminated film. The said laminated film is a glass plate with a laminated film of Claim 1 or 2 which does not have a nitride layer or an oxynitride layer between a said 2nd metal layer and the said glass plate. The laminated film includes, in order from the glass plate side, the first dielectric layer, the first metal layer, the first barrier layer, the second dielectric layer, the second metal layer, and the second metal layer. The glass plate with a laminated film according to any one of claims 1 to 3, comprising a barrier layer, a third dielectric layer, and a protective layer . 5. The first dielectric layer, the first barrier layer, the second dielectric layer, the second barrier layer, and the third dielectric layer are all oxide layers. The glass plate with a laminated film of description . For thickness before Symbol first metal layer, the ratio of the thickness of the second metal layer is laminated according to any one of claims 1 to 5 in the range of 0.9 to 1.4 Glass plate with film. The first crystalline dielectric layer, the second crystalline dielectric layer, the third crystalline dielectric layer, and the fourth crystalline dielectric layer are zinc oxide containing aluminum. The glass plate with a laminated film according to any one of claims 1 to 6, comprising: The glass plate with a laminated film according to claim 7, wherein the content of aluminum in the zinc oxide containing aluminum is 1 to 10 mass% with respect to the total amount of zinc and aluminum. A glass plate with a laminated film according to any one of claims 1 to 8,
A second glass plate having a rectangular main surface arranged with a space between the glass plate with the laminated film and a spacer;
Multi-layer glass comprising .

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