JP6673349B2 - Film laminate and laminated glass - Google Patents

Description

  The present invention relates to a heat-insulating film laminate and a laminated glass having such a film laminate.

  When increasing the heat insulation of buildings and vehicles, a film laminate having heat shielding properties is often used. This film laminate is formed by laminating a plurality of layers including a heat ray reflection functional layer on a base. When the film laminate is installed in a building, a window of a vehicle, or the like, heat shielding properties can be obtained by the infrared ray reflection effect of the heat ray reflection function layer.

  Such a film laminate is provided, for example, in the form of a film, and is used by bonding the film laminate to a member to be installed. Alternatively, in the film laminate, the substrate is formed of a rigid bulk material such as a glass plate, and is used as it is.

JP 2011-520755 A

  In general, the film stack includes a thin layer made of silver or a silver alloy (hereinafter, referred to as “silver layer”). This is because silver exhibits a good heat ray reflection function and hardly absorbs light in a visible light wavelength region. That is, by providing the silver layer in the film laminate, good heat shielding properties and high transparency can be obtained.

  By the way, when indicating the heat shielding property of the film laminate, an index called selectivity Se represented by Tv / g is often used. Here, Tv (%) is the visible light transmittance (%) of the film stack, and g (%) is the solar heat gain (%) of the film stack. The solar radiation heat acquisition rate g (%) is defined as heat (transmitted heat) transmitted directly to the opposite side (second side) with respect to the total solar heat incident from the substrate side (first side) of the film stack. , Expressed as a percentage of the sum of the heat absorbed within the film stack and subsequently released to the second side of the film stack.

  In the film laminate, the higher the visible light transmittance Tv (%) and the lower the solar radiation heat acquisition rate g (%), that is, the greater the selectivity Se, the higher the transparency and the higher the heat shielding performance of the film laminate. It can be said that it is high.

  Since the film stack including the silver layer as described above generally has high selectivity Se, it can be said that the film stack is transparent and has good heat shielding properties.

  However, the silver layer has poor environmental resistance and may oxidize or deteriorate with use. Further, when such a phenomenon occurs in the silver layer, there may be a problem that the transparency and the heat shielding property of the film laminate are reduced.

  The present invention has been made in view of such a background, and an object of the present invention is to provide a film laminate having high selectivity and good environmental resistance. Another object of the present invention is to provide a laminated glass including such a film laminate.

In the present invention, a film laminate having a laminated film on a transparent substrate,
The laminated film has one or two or more functional layers,
The laminated film has a first portion, the first portion including a first dielectric layer, a first functional layer on the first dielectric layer, and a second functional layer on the functional layer. The first functional layer is a functional layer farthest from the transparent substrate among the one or two or more functional layers,
The first functional layer is composed of zirconium nitride ZrN _x,
The first functional layer has a refractive index n of less than 1.2 at a wavelength of 500 nm, an extinction coefficient k of more than 6 at a wavelength of 1500 nm,
In the film laminate, when a visible light transmittance measured from the transparent substrate side to an outermost layer of the laminated film is Tv (%) and a solar heat gain is g (%), Tv / g is obtained. Is represented by the following formula (1):

1.1 ≦ Se (1)

A film laminate satisfying the above is provided.

  According to the present invention, it is possible to provide a film laminate having high selectivity and good environmental resistance. Further, in the present invention, a laminated glass including such a film laminate can be provided.

1 is a cross-sectional view illustrating a schematic configuration of a film stack according to an embodiment of the present invention. FIG. 6 is a cross-sectional view illustrating a schematic configuration of another film stack according to an embodiment of the present invention. It is the graph which plotted the relationship between the visible light transmittance Tv (%) and the solar radiation gain g (%) obtained in each film laminate. 35 is a chart showing in-plane X-ray diffraction results of first functional layers obtained in the film stacks according to Examples 56 and 65.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

(Film laminate according to one embodiment of the present invention)
FIG. 1 is a schematic cross-sectional view of a film stack (hereinafter, referred to as a “first film stack”) according to an embodiment of the present invention.

  As shown in FIG. 1, the first film stack 100 includes a transparent substrate 110 and a stacked film 120.

  The transparent substrate 110 has a role of supporting the laminated film 120 provided on the upper part. The transparent substrate 110 has a first surface 112 and a second surface 114, and the laminated film 120 is provided on the transparent substrate 110 on the side of the first surface 112.

  The laminated film 120 includes a plurality of layers. For example, in the example shown in FIG. 1, the laminated film 120 includes a first dielectric layer 122, a first seed layer 125, a first functional layer 130, a first sacrificial layer 132, and a second dielectric layer. 135 and the top layer 140 are arranged in this order.

  However, this is only an example, and the stacked film 120 may have another configuration. For example, in the laminated film 120 illustrated in FIG. 1, a sacrificial layer may be provided between the first dielectric layer 122 and the first seed layer 125, or may be used instead of the first seed layer 125. A sacrifice layer may be provided. The top layer 140 can also be omitted if necessary.

  The first seed layer 125 in the stacked film 120 has a role of promoting the crystal growth of the first functional layer 130 provided immediately above.

  Further, the first sacrificial layer 132 in the laminated film 120 suppresses the adjacent layer (for example, the first functional layer 130) from being deteriorated by heat during the heat treatment of the laminated film 120 (or a part thereof). Has the role of Further, the top layer 140 is provided as a protective layer of the first film stack 100, and has a role of protecting the stacked film 120.

  Here, in the first film laminate 100, a continuous portion from the first dielectric layer 122 to the second dielectric layer 135 in the laminated film 120 is the most basic main portion of the laminated film 120. Therefore, in the present application, this continuous portion is particularly referred to as a first portion 145. Note that, as described above, since the first seed layer 125 and the first sacrificial layer 132 are layers that are arbitrarily provided, these layers do not necessarily need to be present in the first portion 145. .

The first functional layer 130 has a heat ray reflection function. More specifically, the first functional layer 130 is formed of a zirconium nitride ZrN _x, the refractive index n at a wavelength of 500nm is less than 1.2, characterized in that the extinction coefficient k at a wavelength of 1500nm is greater than 6 Having.

In the first film stack 100, the presence of the first portion 145 allows visible light to pass through the second surface 114 of the transparent substrate 110 toward the outermost layer of the stacked film 120. When the rate is Tv (%) and the solar heat gain is g (%), the selectivity Se represented by Tv / g is represented by the following equation (1):

1.1 ≦ Se (1)

Meet.

  As described above, a so-called “silver layer” made of thin silver or a silver alloy has a problem that environmental resistance is not so good. For this reason, although the film laminate having the laminated film including the silver layer shows a good heat ray reflection function at the initial stage, the silver layer is oxidized and degraded with use time, thereby causing the transparency of the film laminate to be increased. In addition, there may be a problem that the heat shielding property is reduced.

On the other hand, in the first film stack 100, the first functional layer 130 is characterized in that it is made of zirconium nitride ZrN _x instead of silver. That is, in the first film stack 100, as a first functional layer 130 for expressing the heat ray reflecting function, zirconium nitride ZrN _x is used.

The zirconium nitride ZrN _x, compared to silver and silver alloys are excellent materials in environmental resistance, hardly occurs the problem that the first functional layer 130 is deteriorated with use time. Therefore, the first functional layer 130 can stably maintain the heat ray reflection function over a long period of time.

However, according to the inventors of the present application, when zirconium nitride ZrN _x is used as the first functional layer 130 of the film stack, the film stack often does not show proper permeability and heat shielding. It recognized.

Thus, in the first film laminate 100, the zirconium nitride ZrN _x forming the first functional layer 130 has a refractive index n of less than 1.2 at a wavelength of 500 nm and an extinction coefficient k of 6 at a wavelength of 1500 nm. Is also configured to be large. By setting the refractive index n and the extinction coefficient k of zirconium nitride ZrN _x in such ranges, a film laminate having good transmittance and heat shielding properties can be provided.

  Further, in the first film laminate 100, the selectivity Se satisfies the above-described expression (1), and can achieve both high transmittance and high heat shielding.

  With such an effect, the first film laminate 100 can stably exhibit high transparency and good heat shielding properties.

Note that the above-described selectivity Se is generally

2.00> Se Equation (2)

It is.

(Example of application of first film stack 100)
The following embodiments can be considered as application examples of the first film stack 100 having the above-described features. However, these application examples are merely examples, and application examples of the first film stack 100 are not limited thereto.

(First form)
The first film laminate 100 may be used, for example, in the form of a film attached to a member to be installed. In this case, it is preferable that the transparent substrate 110 is formed of a thin member having a thickness of, for example, 0.5 mm or less so as to have flexibility. Thereby, the first film laminate 100 can be easily attached to the member to be installed.

  The member to be installed may be, for example, a glass plate or the like.

(Second form)
The first film laminate 100 may be used as a member such as a building member or a vehicle member, for example, in the “as is” form. In this case, it is preferable that the transparent substrate 110 be made of a member having a size of, for example, 0.5 mm or more so as to have rigidity. For example, the transparent substrate 110 may be configured by a glass substrate.

  When the transparent substrate 110 is formed of a glass substrate, the first film laminate 100 may be used as one glass member for laminated glass.

  In general, the laminated glass has first and second glass sheets, and an intermediate film disposed between the two glass sheets and joining the two glass sheets. The first film laminate 100 can be applied as one or both glass plates of the laminated glass. In this case, the first film laminate 100 may be used such that the side of the transparent substrate 110 is “inside”, that is, the intermediate film side, or may be used such that the side of the laminated film 120 is “inside”. good.

  When the transparent substrate 110 is formed of a glass substrate, the first film stack 100 may be used as a single glass member for a double-glazing unit.

  In general, the double glazing has first and second glass plates and a space layer provided between the two glass plates. The first film laminate 100 can be applied as one or both glass plates of the double-glazed glass. In this case, the first film laminate 100 may be used such that the side of the transparent substrate 110 is “inside”, that is, the space layer side, or may be used such that the side of the laminated film 120 is “inside”. good.

  Various other uses are assumed as application examples of the first film stack 100.

(Each member constituting the first film laminate)
Next, each member constituting the first film stack 100 having the above-described features will be described in more detail. In the following description, for the sake of clarity, reference numerals shown in FIG.

(Transparent substrate 110)
The material forming the transparent base 110 is not particularly limited.

  The transparent substrate 110 may be made of glass, resin, plastic, or the like.

  The thickness of the transparent substrate 110 is not particularly limited, and an appropriate thickness is selected depending on the intended use of the first film stack 100.

  For example, when the first film laminate 100 is used in the above-described first mode, that is, as a film, the transparent substrate 110 may have a thickness of 0.01 mm to 1 mm.

  Further, for example, when the first film laminate 100 is used as a glass member for the above-described second embodiment, particularly for laminated glass or double-glazed glass, the transparent substrate 110 is formed of a glass substrate and has a thickness of 0.5 mm. It may have a thickness of up to 20 mm.

(First dielectric layer 122 and second dielectric layer 135)
The first dielectric layer 122 may be composed of, for example, a layer containing at least one of silicon nitride, silicon nitride containing aluminum, and silicon nitride containing zirconium. Alternatively, the first dielectric layer 122 may be composed of, for example, a layer containing at least one of ITO (indium tin oxide), tin oxide, titanium oxide, zirconium oxide, zinc oxide, and Zr ₃ N _4. good.

  The first dielectric layer 122 may contain oxygen. Note that the first dielectric layer 122 may be a single-layer film or a stacked film including different types of films.

Further, the first dielectric layer 122 may include a “crystallinity improving material” in a region (hereinafter, referred to as an “upper region”) in contact with the first functional layer 130. Here, the “crystallinity improving material” means a material capable of increasing the crystallinity of the first functional layer 130 disposed thereon, for example, ZrN _x (here, X> 1.2). , NbN _x (where X> 1), TiN _x (where 0.9 <X <1.1 or X> 1.2), and the like.

  When the first dielectric layer 122 has such a “crystallinity improving material”, the refractive index n of the first functional layer 130 at a wavelength of 500 nm can be further reduced, and the extinction coefficient at a wavelength of 1500 nm. k can be further improved.

  In the present application, an orientation index P obtained by an in-plane X-ray diffraction method is introduced as an index indicating the effect of improving the crystallinity of the first functional layer 130. It is to be noted that the in-plane X-ray diffraction method is employed in this method because even if the second dielectric layer 135 and the like exist on the first functional layer 130, It is because it can evaluate appropriately.

  The orientation index P is determined as follows:

ここで、Ｍａｘ［ａ，ｂ，ｃ］は、ａ〜ｃのうちの最大値を表し、Ｍｉｎ［ａ，ｂ，ｃ］は、ａ〜ｃのうちの最小値を表す。

Here, Max [a, b, c] represents the maximum value of a to c, and Min [a, b, c] represents the minimum value of a to c.

Further, Is (111) can be obtained from the peak intensity I (111) at the plane orientation (111) obtained by in-plane X-ray diffraction of the first functional layer 130 (ZrN _x ). Similarly, Is (200) can be obtained from the peak intensity I (200) at the plane orientation (200) obtained by in-plane X-ray diffraction of the first functional layer 130 (ZrN _x ), and Is (220). ) Can be obtained from the peak intensity I (220) at the plane orientation (220) obtained by in-plane X-ray diffraction of the first functional layer 130 (ZrN _x ). Here, the peak intensity I (111) is the maximum intensity and the peak intensity I ( 200) is the maximum intensity in the range of ± 1 ° around the diffraction angle 2θ of 39.4 °, and the peak intensity I (220) is the maximum intensity in the range of ± 1 ° around the diffraction angle 2θ of 56.9 °. Can be obtained from strength.

More specifically, Is (111), Is (200), and Is (220) are each represented by the following formula:

Is (111) = I (111) / 99 Equation (4) Is (200) = I (200) / 85 Equation (5) Is (220) = I (220) / 48 Equation (6)

Can be obtained from In addition, the peak height after a background process is used for each peak intensity.

  Here, the divisor (the denominator on the right side) in the expressions (4) to (6) is (111) of the ZrN powder pattern obtained from the inorganic material database (AtomWork) of the National Institute for Materials Science (AtomWork). 200) and (220), ie, 99:85:48.

That is, for Is (111), Is (200) and Is (220), the peak intensity obtained by in-plane X-ray diffraction of the first functional layer 130 (ZrN _x ) is normalized by the peak intensity of the powder pattern. Value can be regarded as

The orientation index P represented by the above equation (3) indicates how much the orientation of the first functional layer 130 (ZrN _x ) is deviated from the powder pattern. Therefore, it can be said that the larger the orientation index P is, the more the first functional layer 130 (ZrN _x ) is oriented in a specific direction.

  Generally, when the first dielectric layer 122 does not include the crystallinity improving material in the upper region, the orientation index P of the first functional layer 130 is around 1. On the other hand, when the first dielectric layer 122 has a crystallinity improving material in the upper region, the orientation index P of the first functional layer 130 is 2 or more.

  The thickness of the first dielectric layer 122 may be, for example, in a range of 3 nm to 300 nm.

  The first dielectric layer 122 may be provided by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, or the like) or a chemical vapor deposition method (CVD method, or the like). good. Among these film forming methods, a sputtering method is particularly preferable.

  The same can be said for the second dielectric layer 135 as for the first dielectric layer 122. The material and / or thickness of the second dielectric layer 135 may be the same as or different from that of the first dielectric layer 122.

(First functional layer 130)
As described above, the first functional layer 130 is comprised of zirconium nitride ZrN _x. Here, x is preferably in the range of 0.9 <x <1.0. When the upper region of the first dielectric layer 122 has the above-described crystallinity improving material, the first functional layer 130 preferably has a range of 0.9 <x <1.1. When the upper region of the first dielectric layer 122 has the above-described crystallinity improving material, the crystal orientation of the first functional layer 130 is aligned to a certain direction. Thereby, the orientation of the first functional layer 130 is increased, and there is no room for excess nitrogen to enter the grain boundary, and an ideal crystal can be obtained in a wider range of x.

By setting x in the range of 0.9 <x <1.0, a layer of zirconium nitride ZrN _x having a refractive index n of less than 1.2 at a wavelength of 500 nm and an extinction coefficient k of greater than 6 at a wavelength of 1500 nm. Can be obtained relatively easily. In the present embodiment, 0.9 <x <1.0, the stoichiometric ratio is relatively close, and the amount of nitrogen is suppressed, so that nitrogen does not enter between lattices. Can be obtained.

  The thickness of the first functional layer 130 is, for example, in a range of 1 nm to 60 nm.

  The first functional layer 130 may be formed by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, or the like) or a chemical vapor deposition method (CVD method, or the like). . Among these film forming methods, a sputtering method is particularly preferable.

In the sputtering method, the deposition conditions (e.g., temperature of the transparent substrate during film formation, film formation pressure, the composition of the incoming gas, the target composition, and post heat treatment temperature) by controlling the composition of the zirconium nitride ZrN _x, That is, the value of x can be adjusted. Further, by controlling the film formation conditions, zirconium nitride ZrN _x having the above-described refractive index n and extinction coefficient k can be formed relatively easily.

Incidentally, zirconium nitride ZrN _x constituting the first functional layer 130, an impurity (for example, carbon and oxygen, etc.) which are inevitably introduced during deposition may comprise about up to 3at%. When using a sputtering method, zirconium nitride ZrN _x constituting the first functional layer 130, impurities (e.g., contained in the target containing Zr, Hf, Ti, V, Nb, Ta, Cr, Mo, W, O, C, etc.) at a maximum of about 3 at%.

(First seed layer 125 and first sacrificial layer 132)
As described above, the first seed layer 125 and the first sacrificial layer 132 are layers that are arbitrarily provided, and may be formed of a plurality of layers, respectively, or may be omitted.

  If provided, the first seed layer 125 is made of, for example, a single metal such as Zr, Ti, or Si, or a metal nitride such as TiN. The thickness of the first seed layer 125 may be, for example, in a range of 1 nm to 10 nm. On the other hand, the first sacrificial layer 132 is made of, for example, Zn, Zr, Ti, and NiCr. The thickness of the first sacrificial layer 132 may be, for example, in the range of 1 nm to 10 nm.

  Note that the first seed layer 125 may contain oxygen.

  These layers may be formed by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, or the like) or a chemical vapor deposition method (CVD method, or the like). Among these film forming methods, a sputtering method is particularly preferable.

In particular, the first seed layer 125 may be made of ZrN _x (where X> 1.2), NbN _x (where X> 1), or TiN _x (where 0.9 <X <1.1 or X>). 1.2).

(Top layer 140)
As described above, the top layer 140 is an optional layer and may be omitted. In particular, in the configuration shown in FIG. 1, when the second dielectric layer 135 also functions as a protective layer, it is not necessary to provide the top layer 140.

If installed, the top layer 140 is made of, for example, SiO ₂ , TiN or C. The thickness of the top layer 140 may be, for example, in the range of 1 nm to 10 nm.

  The top layer 140 may be formed by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, or the like) or a chemical vapor deposition method (CVD method, or the like). Among these film forming methods, a sputtering method is particularly preferable.

(Laminated film 120)
Laminate layer 120, a first functional layer 130 has a layer comprised of zirconium nitride ZrN _x having the characteristics as described above. This material has better mechanical durability and chemical durability than silver. Therefore, when the laminated film 120 has only a single functional layer (that is, the first functional layer 130), it is possible to provide the film laminated body 100 having good environmental resistance.

On the other hand, as described later, if the laminated film has a plurality of functional layers, a functional layer located outermost of the laminated film is comprised of zirconium nitride ZrN _x. In this case, one or more of the “inner” functional layers may be made of a material other than zirconium nitride ZrN _x .

The outermost functional layer positioned by configuring with zirconium nitride ZrN _x having the characteristics as described above, the entire multilayer film can exhibit excellent environmental resistance.

(Another film laminate according to one embodiment of the present invention)
Next, another film laminate according to an embodiment of the present invention will be described with reference to FIG.

  FIG. 2 is a schematic cross-sectional view of another film stack (hereinafter, referred to as “second film stack”) according to an embodiment of the present invention.

  As shown in FIG. 2, the second film stack 200 includes a transparent substrate 210 and a stacked film 220.

  The transparent substrate 210 has a role of supporting the laminated film 220 provided on the upper part. The transparent substrate 210 has a first surface 212 and a second surface 214, and the laminated film 220 is provided on the transparent substrate 210 on the first surface 212 side.

  The laminated film 220 has a basic portion composed of a first dielectric layer 222, a first functional layer 230, and a second dielectric layer 235, that is, a first portion 245.

  Although not shown in FIG. 2, the first portion 245 may further include a first seed layer and / or a first sacrificial layer as described above. In this case, the first seed layer is disposed between the first dielectric layer 222 and the first functional layer 230, and the first sacrificial layer is formed between the first functional layer 230 and the second dielectric layer 230. 235.

  As described above, when the first dielectric layer 222 having the upper region of the crystallinity improving material is disposed immediately below the first functional layer 230, the orientation index P of the first functional layer 230 becomes 2 or more. In addition, the crystallinity of the first functional layer 230 is improved.

  Further, the stacked film 220 has a top layer 240 above the first portion 245. However, the top layer 240 may be omitted. The role of the top layer 240 is the same as the role of the top layer 140 in the first film stack 100 described above.

Here, the first functional layer 230 present in the first portion 245 is composed of zirconium nitride ZrN _x, the refractive index n at a wavelength of 500nm is less than 1.2, the extinction coefficient k at a wavelength of 1500nm is 6 It has the feature that it is larger.

In the second film laminate 200, the visible light transmittance measured from the side of the second surface 214 of the transparent substrate 210 toward the outermost layer of the laminated film 220 is defined as Tv (%). When the rate is g (%), the selectivity Se represented by Tv / g is represented by the following equation (1):

1.1 ≦ Se (1)

Meet.

  Therefore, also in the second film laminate 200, high transparency and good heat shielding properties can be stably exhibited, similarly to the case of the first film laminate 100.

  Note that the laminated film 220 further includes a third dielectric layer 250 and a second functional layer on the lower side of the first portion 245, that is, on the side closer to the transparent substrate 210, in the order closer to the first surface 212. 255.

  When the laminated film 220 has such a configuration, it is possible to relatively easily adjust the color and / or the selectivity Se as compared with the first film laminated body 100.

Note that the third dielectric layer 250 may have an upper region made of a crystallinity improving material as in the case of the above-described first dielectric layer. If the second functional layer 255 is formed of ZrN _x material, by arranging the third dielectric layer 250 having a top region of the crystalline enhancing material as described above, the second functional layer 255 crystal Can be enhanced.

(Each member constituting the second film laminate)
Next, each member constituting the second film stack 200 shown in FIG. 2 will be described in more detail.

  However, in the second film laminate 200, the transparent substrate 210, the first portion 245, and the top layer 240 are described with respect to each member of the first film laminate 100 as shown in FIG. Can be referenced. Thus, here, only the third dielectric layer 250 and the second functional layer 255 will be described. Further, in the following description, for the sake of clarity, the reference numerals shown in FIG.

(Third dielectric layer 250)
The third dielectric layer 250 may be composed of, for example, a layer containing at least one of silicon nitride, silicon nitride containing aluminum, and silicon nitride containing zirconium. Alternatively, the third dielectric layer 250 may be composed of, for example, a layer containing at least one of ITO (indium tin oxide), tin oxide, titanium oxide, zirconium oxide, zinc oxide, and Zr ₃ N _4. good.

  The thickness of the third dielectric layer 250 may be, for example, in a range of 3 nm to 300 nm.

  The third dielectric layer 250 may be formed by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, etc.) or a chemical vapor deposition method (CVD method, etc.). good. Among these film forming methods, a sputtering method is particularly preferable.

  Note that the third dielectric layer 250 may have the same composition as the first dielectric layer 222 and / or the second dielectric layer 235.

(Second functional layer 255)
The second functional layer 255 may be made of any material as long as it is a transparent and conductive material.

The second functional layer 255 may be, for example, ITO (indium tin oxide). Further, the second functional layer 255 may be made of the same zirconium nitride ZrN _x as the first functional layer 230.

  Note that a thin layer made of silver or a silver alloy, that is, a “silver layer” can be used for the second functional layer 255. Even if such a silver layer is used for the second functional layer 255, the first portion 245 having good environmental resistance exists above the second functional layer 255; This is because 245 functions as a protective barrier for the second functional layer 255.

  Note that when a silver layer is used as the second functional layer 255, the second functional layer 255 may include a plurality of layers. For example, the second functional layer 255 may have a three-layer structure of a first metal layer / a silver layer / a second metal layer.

  The thickness of the second functional layer 255 is, for example, in the range of 1 nm to 500 nm.

  The second functional layer 255 may be formed by, for example, a physical vapor deposition method (physical vapor deposition method, PVD method, sputtering method, or the like) or a chemical vapor deposition method (CVD method, or the like). . Among these film forming methods, a sputtering method is particularly preferable.

  The configuration and features of the second film stack 200 have been described above with reference to FIG.

  However, this is only an example, and the second film stack 200 may have another configuration. For example, in the second film stack 200 shown in FIG. 2, the third dielectric layer 250 may be omitted. In this case, the second functional layer 255 is directly provided on the first surface 212 of the transparent base 210.

  Alternatively, in the second film stack 200 shown in FIG. 2, a pair of another functional layer and a dielectric layer may be provided below the third dielectric layer 250 and further from the side near the first surface 212. However, one or more may be installed. The number of such sets may be, for example, two, three, or four or more. In this case, adjustment of the color and / or selectivity Se of the film stack becomes easier.

  In the present invention, it is apparent to those skilled in the art that, besides this, the film laminate can have various layer configurations.

  Next, examples of the present invention will be described. In the following description, Example 1 to Example 9, Example 31 to Example 39, and Example 41 to Example 44 are Examples, and Examples 21 to 26, Example 51 to Example 55, and Examples 65 to 67 are examples. Is a comparative example. Examples 56 to 64 are working examples.

(Example 1)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

The laminated film had a three-layer structure of a first dielectric layer / first functional layer / second dielectric layer from the side close to the glass substrate. The first dielectric layer is made of silicon nitride containing aluminum (target thickness: 46 nm), the first functional layer is made of ZrN _x (target thickness: 42 nm), and the second dielectric layer is made of silicon nitride containing aluminum. (The target film thickness was 56 nm).

  Each of these layers was formed by a sputtering method. More specifically, a Si-10 wt% Al target is used for forming the first dielectric layer, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) is used as a discharge gas. It was used. The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was heated to 300 ° C. when the first functional layer was formed.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as “film stack according to Example 1”) was manufactured.

(Examples 2 and 3)
In the same manner as in Example 1, a film laminate (referred to as “film laminate according to Example 2” and “film laminate according to Example 3”, respectively) was manufactured.

  However, in Examples 2 and 3, the thickness of each layer was changed from that in Example 1.

(Examples 4 to 6)
In the same manner as in Example 1, a film stack (each referred to as “film stack according to Examples 4 to 6”) was manufactured.

  However, in Examples 4 to 6, the thickness of each layer was changed from that in Example 1. In Examples 4 to 6, the glass substrate was not heated during the formation of the first functional layer. After the completion of the formation of the second dielectric layer, the glass substrate was heated to 600 ° C. and kept at 600 ° C. for 20 minutes.

(Examples 7 to 9)
In the same manner as in Example 1, a film stack (each referred to as “film stack according to Examples 7 to 9”) was manufactured.

  However, in Examples 7 to 9, the thickness of each layer was changed from that in Example 1. In Examples 7 to 9, the glass substrate was not heated during the formation of the first functional layer. Further, even after the formation of the second dielectric layer, no heat treatment was performed.

(Examples 21 to 22)
In the same manner as in Example 1, a film laminate (each referred to as “film laminate according to Examples 21 to 22”) was manufactured.

  However, in Examples 21 to 22, the thickness of each layer was changed from that in Example 1. In Examples 21 to 22, the ratio of argon to nitrogen in the mixed gas used for forming the first functional layer was argon: nitrogen = 6.3: 1 (sccm). The pressure during film formation was 0.35 Pa.

  Note that, in these examples, the glass substrate was not heated when forming the first functional layer. Further, even after the formation of the second dielectric layer, no heat treatment was performed.

(Examples 23 to 24)
In the same manner as in Example 1, a film stack (each referred to as a “film stack according to Examples 23 to 24”) was manufactured.

  However, in Examples 23 to 24, the thickness of each layer was changed from that in Example 1. In Examples 23 to 24, the ratio of argon to nitrogen in the mixed gas used for forming the first functional layer was 1: 1 (sccm). The pressure during film formation was 0.26 Pa.

  Note that, in these examples, the glass substrate was not heated when forming the first functional layer. Further, even after the formation of the second dielectric layer, no heat treatment was performed.

(Example 25)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The laminated film had a structure of first dielectric layer / first functional layer / second dielectric layer from the side close to the glass substrate. The first dielectric layer had a two-layer structure of silicon nitride (target thickness: 20 nm) and silicon oxide (target thickness: 40 nm). The first functional layer was made of niobium nitride (target thickness: 30 nm), and the second dielectric layer was made of silicon nitride containing aluminum (target thickness: 30 nm).

  Each of these layers was formed by a sputtering method. More specifically, of the first dielectric layer, an Si target of 10 wt% is used for forming a silicon nitride film, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)). The pressure during film formation was 0.4 Pa. In the first dielectric layer, a silicon target was used for forming a silicon oxide film, and a mixed gas of argon and oxygen (argon: oxygen = 30: 70 (sccm)) was used as a discharge gas. . The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Nb target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 10: 20 (sccm)) was used as a discharge gas. The pressure during film formation was 0.25 Pa. Note that the glass substrate was not heated during the formation of the first functional layer.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 25”) was manufactured.

(Example 26)
A film laminate (hereinafter, referred to as “film laminate according to Example 26”) was manufactured in the same manner as in Example 7 described above.

  However, in Example 26, the thickness of each layer was changed from that of Example 7. Chromium nitride (target film thickness: 10 nm) was used as the first functional layer.

  For the formation of the first functional layer, a Cr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 5: 25 (sccm)) was used as a discharge gas. The pressure during film formation was 0.28 Pa. Note that the glass substrate was not heated during the formation of the first functional layer.

(Example 31)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The laminated film has a five-layer structure of a third dielectric layer / second functional layer / first dielectric layer / first functional layer / second dielectric layer from the side close to the glass substrate. did.

The third dielectric layer is made of silicon nitride containing aluminum (target thickness: 25 nm), the second functional layer is made of ZrN _x (target thickness: 19 nm), and the first dielectric layer is made of silicon nitride containing aluminum. (Target thickness 91 nm), the first functional layer was ZrN _x (target thickness 40 nm), and the second dielectric layer was aluminum-containing silicon nitride (target thickness 38 nm).

  Each of these layers was formed by a sputtering method. More specifically, a Si-10 wt% Al target is used for forming the third dielectric layer, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) is used as a discharge gas. It was used. The pressure during film formation was 0.4 Pa.

  A Zr target was used for forming the second functional layer, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was heated to 300 ° C. when the second functional layer was formed.

  In forming the first dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was heated to 300 ° C. when the first functional layer was formed.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 31”) was manufactured.

(Examples 32 and 33)
In the same manner as in Example 31, a film laminate (referred to as “film laminate according to Example 32” and “film laminate according to Example 33”, respectively) was manufactured.

  However, in Examples 32 and 33, the thickness of each layer was changed from that of Example 31.

(Examples 34 to 36)
In the same manner as in Example 31, a film laminate (each referred to as “film laminate according to Examples 34 to 36”) was produced.

  However, in Examples 34 to 36, the thickness of each layer was changed from that of Example 31. In Examples 34 to 36, the glass substrate was not heated during the formation of the first functional layer. After the completion of the formation of the second dielectric layer, the glass substrate was heated to 600 ° C.

(Examples 37 to 39)
In the same manner as in Example 31, a film stack (each referred to as a “film stack according to Examples 37 to 39”) was manufactured.

  However, in Examples 37 to 39, the thickness of each layer was changed from that of Example 31. In Examples 37 to 39, the glass substrate was not heated when forming any of the layers. Further, the heat treatment was not performed even after all the layers were formed.

(Example 41)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The laminated film had a structure of a third dielectric layer / second functional layer / first dielectric layer / first functional layer / second dielectric layer from the side close to the glass substrate.

The third dielectric layer was made of silicon nitride containing aluminum (target film thickness: 28 nm). The second functional layer was silver (target thickness: 15.5 nm), and two sacrificial layers of a nickel-chromium alloy (target thickness: 1 nm) were provided so as to sandwich the second functional layer. The first dielectric layer was made of silicon nitride containing aluminum (target thickness: 97.5 nm). The first functional layer was made of ZrN _x (target film thickness 25.5 nm), and the second dielectric layer was made of silicon nitride containing aluminum (target film thickness 48 nm).

  Each of these layers was formed by a sputtering method. More specifically, a Si-10 wt% Al target is used for forming the third dielectric layer, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) is used as a discharge gas. It was used. The pressure during film formation was 0.4 Pa.

  Ni-20 wt% Cr and Ag targets were used for forming the second functional layer, and argon was used as a discharge gas. The pressure during film formation was 0.47.

  In forming the first dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was heated to 300 ° C. when the first functional layer was formed.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 41”) was manufactured.

(Example 42)
A film laminate (hereinafter, referred to as “film laminate according to Example 42”) was manufactured in the same manner as in Example 41 described above.

  However, in Example 42, the thickness of each layer was changed from that of Example 41. In Example 42, the glass substrate was not heated during the formation of the first functional layer. Instead, the glass substrate was heated to 600 ° C. after all layers were formed.

(Example 43)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The laminated film had a four-layer structure of a second functional layer / first dielectric layer / first functional layer / second dielectric layer from the side closer to the glass substrate.

The second functional layer was made of tin-doped indium oxide (target thickness: 55 nm). The first dielectric layer was made of silicon nitride containing aluminum (target thickness: 13 nm). The first functional layer was made of ZrN _x (target film thickness: 20 nm), and the second dielectric layer was made of silicon nitride containing aluminum (target film thickness: 54 nm).

  Each of these layers was formed by a sputtering method. More specifically, an ITO target was used for forming the second functional layer.

  For forming the first dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa. After the formation of all layers, a heat treatment at 300 ° C. was performed for 2 hours.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 43”) was manufactured.

(Example 44)
A film laminate (hereinafter, referred to as “film laminate according to Example 44”) was manufactured in the same manner as in Example 43 described above.

However, in Example 44, the thickness of each layer was changed from that in Example 43. In Example 44, Zr ₃ N ₄ (target film thickness: 5 nm) was used as the first dielectric layer. Further, in Example 44, after the formation of all the layers was completed, the glass substrate was heated to 600 ° C.

(Examples 51 to 52)
In the same manner as in Example 31, a film stack (each referred to as a “film stack according to Examples 51 to 52”) was manufactured.

  However, in Examples 51 to 52, the thickness of each layer was changed from that of Example 31. In Examples 51 to 52, the ratio of argon to nitrogen in the mixed gas used for forming the first functional layer was argon: nitrogen = 6.3: 1 (sccm).

  Note that, in these examples, the glass substrate was not heated when forming the first functional layer. Further, even after the formation of the second dielectric layer, no heat treatment was performed.

(Examples 53 to 54)
In the same manner as in Example 31, a film stack (each referred to as a “film stack according to Examples 53 to 54”) was manufactured.

  However, in Examples 53 to 54, the thickness of each layer was changed from that of Example 31. In Examples 53 to 54, the ratio of argon to nitrogen was 1: 1 (sccm) in the mixed gas used for forming the first functional layer.

  Note that, in these examples, the glass substrate was not heated when forming the first functional layer. Further, even after the formation of the second dielectric layer, no heat treatment was performed.

(Example 55)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The configuration of the laminated film was a configuration of a third dielectric layer / second functional layer / first dielectric layer / first functional layer / second dielectric layer from the side closer to the glass substrate. The third dielectric layer was made of silicon nitride containing aluminum (target thickness: 40 nm). The second functional layer was made of niobium nitride (target thickness: 12 nm). The second dielectric layer was made of silicon nitride containing aluminum (target film thickness: 80 nm). The first functional layer was made of niobium nitride (target thickness: 13 nm), and the second dielectric layer was made of silicon nitride containing aluminum (target thickness: 35 nm).

  Each of these layers was formed by a sputtering method. More specifically, a Si-10 wt% Al target is used for forming the third dielectric layer, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) is used as a discharge gas. It was used. The pressure during film formation was 0.4 Pa.

  For forming the second functional layer, a Nb target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 10: 20 (sccm)) was used as a discharge gas. The pressure during film formation was 0.25 Pa.

  In forming the first dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  For forming the first functional layer, a Nb target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 10: 20 (sccm)) was used as a discharge gas. The pressure during film formation was 0.25 Pa. Note that the glass substrate was not heated during the formation of the first functional layer.

  For forming the second dielectric layer, a Si-10 wt% Al target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 55”) was manufactured.

  Table 1 below summarizes the configurations and layer thicknesses of the film stacks according to the respective examples.

（評価）
次に、各例に係る膜積層体を用いて、以下の評価を行った。

(Evaluation)
Next, the following evaluation was performed using the film laminate according to each example.

(Zr: N ratio)
Zirconium nitride ZrN constituting a first functional layer using the film stacks according to Examples 4 to 9, Example 21 to Example 24, Example 34 to Example 39, Example 42 to Example 44, and Example 51 to Example 54 The element ratio of Zr to N in _x was measured using Rutherford Backscattering Spectrometry (RBS).

(Refractive index n and extinction coefficient k)
Using the film laminate according to each example, the refractive index n of the first functional layer at a wavelength of 500 nm and the extinction coefficient k at a wavelength of 1500 nm were determined as follows. For each of the laminates, the spectrum was measured using a spectrophotometer (U-4100: manufactured by Hitachi, Ltd.), and the polarization information was measured using a spectroscopic ellipsometer (M-2000: manufactured by JA Woollam). . Using the obtained spectral transmission and reflection spectra and polarization information, an optical model was fitted to determine a refractive index n and an extinction coefficient k.

(Visible light transmittance Tv and solar heat gain g)
Using the film stack according to each example, the visible light transmittance Tv (%) and the solar heat gain g (%) were measured as follows.

  For each of the laminates, the visible light transmittance Tv was calculated using the measured spectral transmission spectrum in accordance with JIS R3106, and the emissivity was measured using an emissivity measuring device (TSS-5X: manufactured by Japan Sensor Co., Ltd.). The solar radiation heat gain g was calculated according to ISO 9050.

  From the obtained visible light transmittance Tv (%) and solar heat gain g (%), selectivity Se was calculated in accordance with the above-described equation (1).

Table 2 below summarizes the evaluation results obtained for the film laminate according to each example. From Table 2, the first functional layers according to Examples 21 to 26 and Examples 51 to 55 have a refractive index n of light of 1.2 or more at a wavelength of 500 nm and an extinction coefficient of light at a wavelength of 1500 nm. k is less than 6. On the other hand, the first functional layer ZrN _{x according} to Examples 1 to 9, Example 31 to Example 39, and Examples 41 to 44 has a refractive index n of light of less than 1.2 at a wavelength of 500 nm and a wavelength of light of less than 1.2. The extinction coefficient k at 1500 nm is larger than 6.

図３には、各例に係る膜積層体において得られた可視光透過率Ｔｖ（％）と日射熱取得率ｇ（％）の関係を示す。

FIG. 3 shows the relationship between the visible light transmittance Tv (%) and the solar heat gain g (%) obtained in the film stack according to each example.

  From FIG. 3, it can be seen that Tv / g <1.1 in each of the film stacks according to Examples 21 to 26 and Examples 51 to 55. On the other hand, the film laminates according to Examples 1 to 9, Example 31 to Example 39, and Examples 41 to 44 satisfy the relationship of Tv / g ≧ 1.1, and have high transmittance and good heat shielding properties. Was found to have both.

(Durability test)
A durability test was performed using the three types of film laminates according to the following method. Each film stack has the following configuration.

(Film laminate A)
Glass substrate (100 mm × width 100 mm × thickness 2.8 mm) + Si ₃ N ₄ layer (40 nm) + ZrN _x layer (13 nm) + Si ₃ N ₄ layer (58 nm)
(Film laminate B)
Glass substrate (2.8 mm) + Si ₃ N ₄ layer (25 nm) + ZrN _x layer (19 nm) + Si ₃ N ₄ layer (91 nm) + ZrN _x layer (40 nm) + Si ₃ N ₄ layer (38 nm)
(Film laminate C)
Glass substrate (2.8 mm) + Si ₃ N ₄ layer (40 nm) + NiCr layer (2.5 nm) + Ag layer (8 nm) + NiCr layer (2.5 nm) + Si ₃ N ₄ layer (58 nm)
In each of the film stacks A to C, each layer was formed by a sputtering method.

In the film stacks A to C, the Si ₃ N ₄ layer is formed by using a Si target and using a mixed gas of argon and nitrogen (argon: nitrogen = 70: 30 (sccm)) as a discharge gas. A film was formed. In the film stacks A and B, the conditions for forming the ZrN _x layer are the same as in the case of Example 1 described above. In the film stack C, the conditions for forming the NiCr layer / Ag layer / NiCr layer are the same as in the case of Example 42 described above.

  As a durability test, the following two types of evaluations were performed.

(Evaluation of mechanical durability)
The film laminate was immersed in water using an Erichsen tester (Model 494 tester: manufactured by Eriksen).

  Next, an abrasive (Scotch Bright # 7448B: manufactured by Sumitomo 3M Limited) was brought into contact with the laminated film side of the film laminated body. The abrasive has dimensions of 90 mm × 40 mm. A load of 324 g was applied to this abrasive, and the abrasive was reciprocated 1000 times on the laminated film. Thereafter, the film laminate was collected, and the state of the laminated film was observed from the surface side with an optical microscope. The observation location was a region of 5 mm × 5 mm substantially at the center of the film stack.

  As a result of the observation, it was determined that a film laminate having five or less flaws (flaws having a width of 1 μm or more) generated in the laminated film had good mechanical durability. Further, a film laminate having six or more flaws (flaws having a width of 1 μm or more) was judged to have poor mechanical durability.

  Table 3 below shows the evaluation results of the mechanical durability of each of the film laminates A to C.

この結果から、機能層としてＺｒＮ_ｘ層を有する膜積層体ＡおよびＢは、機能層として銀層を有する膜積層体Ｃよりも良好な機械的耐久性を示すことが確認された。

From these results, it was confirmed that the film laminates A and B having the ZrN _x layer as the functional layer exhibited better mechanical durability than the film laminate C having the silver layer as the functional layer.

(Evaluation of chemical durability)
As an evaluation of the chemical durability of the film laminates A to C, a sweat resistance test, a chemical resistance test, and a moisture resistance test were performed.

(Sweat resistance test)
The sweat resistance test was performed by a method according to ISO12870.

  First, artificial sweat was injected into the closed container. The artificial sweat contains 50 g / L of lactic acid and 100 g / L of sodium chloride. The film laminates A to C were introduced into the sealed container while being separated from the artificial sweat liquid.

  Next, the sealed container was closed, and the inside was kept at 55 ° C. ± 5 ° C. for one day. Thereafter, the film laminates A to C were taken out of the sealed container, and the appearance was visually observed.

  As a result of the observation, a film in which deterioration such as corrosion and peeling did not occur in the laminated film was judged as “○ (good sweat resistance)”, and a film in which deterioration occurred was judged as “x”.

(Chemical resistance test)
The chemical resistance test was performed as follows.

  Each membrane stack was immersed in a 1N NaOH solution at 23 ° C. for 6 hours. Next, the film stack was washed with pure water, and then immersed in a 1N-HCl solution at 23 ° C. for 6 hours. Thereafter, the film laminate was washed with pure water, and the appearance was visually observed.

  As a result of the observation, a film in which deterioration such as corrosion and peeling did not occur in the laminated film was determined as “○ (good chemical resistance)”, and a film in which deterioration occurred was determined as “x”.

(Moisture resistance test)
The moisture resistance test was performed as follows.

  Each film laminate was kept in a constant temperature / humidity tester (KCH-1000: manufactured by Tokyo Rika Kikai) set at a temperature of 60 ° C. and a humidity of 95% RH for 2 weeks. Thereafter, the film laminate was taken out, and the appearance was visually observed.

As a result of the observation, a film laminate having 5 defects / 10 cm ² or less (white spots) observed on the surface of the laminated film was judged as “「 (good moisture resistance) ”, and the others were judged as“ x ”. .

  Table 4 below summarizes the evaluation results of the chemical durability of each of the film laminates A to C.

この結果から、機能層としてＺｒＮ_ｘ層を有する膜積層体ＡおよびＢは、機能層として銀層を有する膜積層体Ｃよりも良好な化学的耐久性を示すことが確認された。

From these results, it was confirmed that the film laminates A and B having the ZrN _x layer as the functional layer exhibited better chemical durability than the film laminate C having the silver layer as the functional layer.

(Example 56)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The configuration of the laminated film is as follows: from the side close to the glass substrate, a third dielectric layer (including the upper region) / a second functional layer / a first dielectric layer (including the upper region) / the first functional layer / The structure of the second dielectric layer.

  Each of these layers was formed by a sputtering method.

The first functional layer was made of ZrN _x (thickness: 20 nm), and the second functional layer was made of ZrN _x (thickness: 21 nm).

  For forming the first and second functional layers, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was not heated when forming any of the functional layers.

The first dielectric layer was aluminum-containing silicon nitride (80 nm thick) having an upper region (10 nm thick) made of ZrN _x (x> 1.2). The second dielectric layer was made of aluminum-containing silicon nitride (film thickness: 80 nm). The third dielectric layer was aluminum-containing silicon nitride (25 nm thick) having an upper region (5 nm thick) made of ZrN _x (x> 1.2).

  The following two-stage processing was performed for forming the first dielectric layer.

  First, an aluminum-containing silicon nitride film was formed using a Si-10 wt% Al target. As a discharge gas, a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used, and the pressure during film formation was 0.4 Pa.

  Next, an upper region was formed on the aluminum-containing silicon nitride film. For the film formation in the upper region, a Zr target was used, and nitrogen gas (100 sccm) was used as a discharge gas. The pressure during film formation was 0.5 Pa.

  The third dielectric layer was formed in the same manner.

  On the other hand, the second dielectric layer was formed using a Si-10 wt% Al target. A mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas, and the pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 56”) was manufactured.

(Examples 57 to 58)
In the same manner as in Example 56, a film laminate (referred to as “film laminate according to Example 57” and “film laminate according to Example 58,” respectively) was produced.

  However, in Examples 57 to 58, the thickness of each layer was changed from that in Example 56.

(Example 59)
By the following method, a laminated film was formed on one surface of a glass substrate to produce a film laminated body.

  As the glass substrate, soda lime glass having a size of 100 mm long × 100 mm wide × 2.8 mm thick was used.

  The configuration of the laminated film is, from the side close to the glass substrate, a third dielectric layer / a second functional layer / a first dielectric layer (including an upper region) / a first functional layer / a second dielectric layer The structure was a layer.

  Each of these layers was formed by a sputtering method.

The first functional layer was made of ZrN _x (thickness 13 nm), and the second functional layer was made of ZrN _x (thickness 15 nm).

  For forming the first and second functional layers, a Zr target was used, and a mixed gas of argon and nitrogen (argon: nitrogen = 4.6: 1 (sccm)) was used as a discharge gas. The pressure during film formation was 0.26 Pa. Note that the glass substrate was not heated when forming any of the functional layers.

The first dielectric layer has an upper region (thickness 5 nm) formed of NbN _x, and an aluminum-containing silicon nitride (thickness 96 nm). The second dielectric layer was made of aluminum-containing silicon nitride (42 nm thick). The third dielectric layer was made of aluminum-containing silicon nitride (film thickness: 10 nm).

  The following two-stage processing was performed for forming the first dielectric layer.

  First, an aluminum-containing silicon nitride film was formed using a Si-10 wt% Al target. As a discharge gas, a mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used, and the pressure during film formation was 0.4 Pa.

  Next, an upper region was formed on the aluminum-containing silicon nitride film. An Nb target was used for film formation in the upper region, and nitrogen gas (80 sccm) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  On the other hand, the second and third dielectric layers were formed using a Si-10 wt% Al target. A mixed gas of argon and nitrogen (argon: nitrogen = 30: 70 (sccm)) was used as a discharge gas, and the pressure during film formation was 0.4 Pa.

  Thus, a film stack (hereinafter, referred to as a “film stack according to Example 59”) was manufactured.

(Example 60)
A film laminate (referred to as “film laminate according to Example 60”) was manufactured in the same manner as in Example 59.

  However, in Example 60, the thickness of each layer was changed from that in Example 59.

(Example 61)
A film laminate (referred to as “film laminate according to Example 61”) was manufactured in the same manner as in Example 56.

However, in Example 61, the upper region of the upper region, and a third dielectric layer of the first dielectric layer are all set to TiN _x. In Example 61, the thickness of each layer was changed from that in Example 56.

  For the film formation in the upper region of the first dielectric layer, a Ti target was used, and a nitrogen gas (80 sccm) was used as a discharge gas. The pressure during film formation was 0.4 Pa.

  The upper region of the third dielectric layer was formed by the same method.

(Example 62)
A film laminate (referred to as “film laminate according to Example 62”) was produced in the same manner as in Example 61.

  However, in Example 62, the thickness of each layer was changed from that in Example 61.

(Example 63)
A film laminate (referred to as “film laminate according to Example 63”) was produced in the same manner as in Example 61.

  However, in Example 63, a Ti target was used to form the upper region of the first dielectric layer and the upper region of the third dielectric layer, and a mixed gas of argon and nitrogen (argon) was used as a discharge gas. : Nitrogen = 40: 7 (sccm)). The pressure during film formation was 0.4 Pa. In Example 63, the thickness of each layer was changed from that in Example 61.

(Example 64)
A film laminate (referred to as “film laminate according to Example 64”) was manufactured in the same manner as in Example 63.

  However, in Example 64, the thickness of each layer was changed from that in Example 63.

(Example 65 to Example 67)
The film stacks of Examples 65, 66, and 67 were manufactured by the same method as the film stacks of Examples 37, 38, and 39, respectively.

  Table 5 below summarizes the configurations and layer thicknesses of the film stacks according to the respective examples.

（各特性の評価）
次に、例５６〜例６７に係る膜積層体を用いて、前述の方法により、第１の機能層のＺｒ：Ｎ比、屈折率ｎ、消衰係数ｋ、可視光透過率Ｔｖ、日射熱取得率ｇ、およびセレクティビティの評価を実施した。

(Evaluation of each characteristic)
Next, the Zr: N ratio, the refractive index n, the extinction coefficient k, the visible light transmittance Tv, and the solar heat of the first functional layer were obtained by using the film laminates according to Examples 56 to 67 by the method described above. The acquisition rate g and the selectivity were evaluated.

  The results are summarized in Table 6 below.

表６に示すように、例５６〜例６７に係る膜積層体は、いずれも、セレクティビティが１．１を超えていることがわかる。このように、例５６〜例６７に係る膜積層体は、いずれも高い透過性と良好な遮熱性を有することがわかった。

As shown in Table 6, it can be seen that the film stacks according to Examples 56 to 67 all have a selectivity exceeding 1.1. Thus, it was found that all of the film laminates according to Examples 56 to 67 had high transmittance and good heat shielding properties.

(Evaluation of orientation index P)
Next, in the film laminates according to Examples 56 to 67, the orientation index P defined as described above was evaluated.

  For the in-plane X-ray diffraction measurement of the first functional layer, an in-plane XRD apparatus (ATX-G manufactured by Rigaku Corporation: radiation source CuKα) was used.

The measurement conditions are as follows:
CuKα extraction with a multilayer mirror;
2θχ / φ scan in the in-plane direction at a constant angle of incidence;
Incident angle 0.5 degrees;
In-plane X-ray divergence angle 0.5 degrees (limited by slits).

  In each of the film laminates, the orientation index P was calculated from the obtained in-plane X-ray diffraction results by using the above-mentioned equation (3).

  Table 7 below summarizes the orientation indices P obtained in the film stacks according to Examples 56 to 67.

表７から、第１の誘電体層が結晶性向上材料からなる上部領域を有さない、例６５〜例６７に係る膜積層体では、第１の機能層の配向指数Ｐが１．３５程度と、あまり大きくないことがわかった。これに対して、第１の誘電体層が結晶性向上材料からなる上部領域を有する例５６〜例６４に係る膜積層体では、第１の機能層の配向指数Ｐが少なくとも２を超えることがわかった。

From Table 7, it is found that in the film laminates according to Examples 65 to 67 in which the first dielectric layer has no upper region made of the crystallinity improving material, the orientation index P of the first functional layer is about 1.35. It turned out that it was not so big. On the other hand, in the film stacks according to Examples 56 to 64 in which the first dielectric layer has the upper region made of the crystallinity improving material, the orientation index P of the first functional layer may exceed at least 2. all right.

  FIG. 4 also shows in-plane X-ray diffraction results of the first functional layer obtained in the film stacks according to Example 56 and Example 65.

  From FIG. 4, it can be seen that the peak intensity of the plane orientation (220) of ZrNx is significantly increased in the film stack according to Example 56 as compared with the film stack according to Example 65.

  Thus, it has been confirmed that the use of the first dielectric layer having the upper region made of the crystallinity improving material improves the crystallinity of the first functional layer.

(Other evaluations)
Using the film laminate according to Example 56, the above-described tests of the evaluation of mechanical durability, the evaluation of chemical durability, the sweat resistance test, the chemical resistance test, and the moisture resistance test were performed.

  As a result, in the film laminate according to Example 56, good results were obtained in any of the tests.

  This application claims priority based on Japanese Patent Application No. 2015-118546 filed on June 11, 2015 and Japanese Patent Application No. 2016-13322 filed on January 27, 2016. The entire contents of the Japanese application are incorporated herein by reference.

REFERENCE SIGNS LIST 100 First film laminate 110 Transparent substrate 112 First surface 114 Second surface 120 Laminated film 122 First dielectric layer 125 First seed layer 130 First functional layer 132 First sacrificial layer 135 First 2 dielectric layer 140 top layer 145 first portion 200 second film laminate 210 transparent substrate 212 first surface 214 second surface 220 laminated film 222 first dielectric layer 230 first functional layer 235 Second dielectric layer 240 Top layer 245 First part 250 Third dielectric layer 255 Second functional layer

Claims (11)

A film laminate having a laminated film on a transparent substrate,
The laminated film has one or two or more functional layers,
The laminated film has a first portion, the first portion including a first dielectric layer, a first functional layer on the first dielectric layer, and a second functional layer on the functional layer. The first functional layer is a functional layer farthest from the transparent substrate among the one or two or more functional layers,
The first functional layer is composed of zirconium nitride ZrN _x,
The first functional layer has a refractive index n of less than 1.2 at a wavelength of 500 nm, an extinction coefficient k of more than 6 at a wavelength of 1500 nm,
In the film laminate, when a visible light transmittance measured from the transparent substrate side to an outermost layer of the laminated film is Tv (%) and a solar heat gain is g (%), Tv / g is obtained. Is represented by the following formula (1):

1.1 ≦ Se (1)

Meet the,
The first functional layer has the following formula (3)

A film laminate having an orientation index P of 2 or more :
Here, Max [a, b, c] represents the maximum value of a to c, Min [a, b, c] represents the minimum value of a to c,
Is (111), Is (200) and Is (220) indicate the peak intensities of the plane orientations (111), (200) and (220) obtained by in-plane X-ray diffraction of the first functional layer, respectively. , I (111), I (200) and I (220), respectively,

Is (111) = I (111) / 99
Is (200) = I (200) / 85
Is (220) = I (220) / 48

Obtained from   The film laminate according to claim 1, wherein the visible light transmittance Tv (%) exceeds 30%.   The film laminate according to claim 1, wherein the solar radiation heat acquisition rate g (%) is less than 50%. 4. The film laminate according to claim 1, wherein _x in the zirconium nitride ZrN _x satisfies 0.9 <x <1.0. 5.   The first dielectric layer and / or the second dielectric layer include at least one material selected from the group consisting of silicon nitride, silicon nitride containing aluminum, and silicon nitride containing zirconium. The film laminate according to claim 1. The first dielectric layer and / or the second dielectric layer may include at least one material selected from the group consisting of ITO, tin oxide, titanium oxide, zirconium oxide, zinc oxide, and Zr ₃ N _4. The film laminate according to any one of claims 1 to 5, comprising: The laminated film further includes a second functional layer on a side closer to the transparent substrate than the first functional layer,
Functional layer of said second, ITO, including silver or ZrN _x, film laminate according to any one of claims 1 to 6. Regions of the first dielectric layer that are in contact with the first functional layer are ZrN _x (here, X> 1.2), NbN _x (here, X> 1), TiN _x (where 0.9 <). The film laminate according to any one of claims 1 to 7 , comprising a material selected from the group consisting of X <1.1 and X> 1.2). The film laminate according to any one of claims 1 to 8 , wherein the transparent substrate is a glass substrate. The film laminate according to any one of claims 1 to 9 , wherein the film laminate has a form of a film. A laminated glass constituted by connecting the first and second glass plates to each other via an intermediate film,
A laminated glass, wherein the first or second glass plate has the film laminate according to claim 10 .

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