JP2019147277A - Laminate - Google Patents

Abstract

To provide a laminate which is suitable for window application, which has solar insolation shielding and heat insulation properties due to excellent infrared reflection performance by setting thickness of metal films on the upper and lower sides of the infrared reflection layer in a specified range and has excellent durability against corrosion of the metal film.SOLUTION: A laminate at least includes a substrate, a heat ray reflection layer, and a protective layer in this order. The heat ray reflection layer has: a first metal oxide film; a first metal film; a second metal film; a third metal film; and a second metal oxide film in this order from the side of the substrate. The first metal film is directly in contact with one face of the second metal film and further the third metal film is directly in contact with the other face of the second metal film. Both of the first metal film and the third metal film include palladium, chromium, molybdenum, wolfram, vanadium, niobium, cobalt, nickel, titanium, zirconium or alloys of them as a main component, and the second metal film includes silver as a main component. When the thickness of the first metal film is represented by L1 and the thickness of the third metal film is represented by L3, the ratio of L3 to L1 (L3/L1) is 0.5 to 1.5.SELECTED DRAWING: None

Description

  The present invention relates to a laminate suitable for window pasting applications.

  Conventionally, a laminated body in which a heat ray reflective layer in which metal films / metal oxide films are alternately laminated and a protective layer are formed in this order on a transparent substrate made of synthetic resin or the like has been provided in a house or a building. Used in openings (lighting parts) such as window glass. These laminated bodies suppress the inflow of solar heat (near infrared light) from the outside to the room due to the infrared reflection performance of the metal film (that is, shield from solar radiation), and further heat from the room to the outside (far infrared glands) Can be suppressed (ie, insulated), and an energy saving effect can be obtained throughout the year. Furthermore, by laminating a metal oxide film with a high refractive index, the visible light transmittance is improved and appearance visibility is ensured. By laminating a protective layer, the metal film and the metal oxide film are protected, and durability is improved. It is expressed. In such a laminate, in order to obtain a laminate having high infrared reflection performance and excellent heat insulation, the protective layer is thinned to suppress the infrared absorptivity of the protective layer located on the indoor side of the metal film. Therefore, the durability against corrosion of the metal film tends to decrease.

  Here, in Patent Document 1, aluminum, copper, gold, nickel, and silver are formed on a transparent film base material in order to obtain a laminated film that is excellent in infrared reflection performance and further excellent in durability. By laminating an infrared reflective layer made of an alloy such as, and further covering both sides of this infrared reflective layer with a light-absorbing metal film such as nickel, chromium, niobium, etc. that can protect this infrared reflective layer, A laminate is disclosed in which the durability of the infrared reflective layer against metal corrosion is improved.

Special table 2013-521160 gazette

  In the laminated body disclosed in Patent Document 1, a laminated body in which the upper and lower sides of an infrared reflecting layer made of an alloy such as silver are sandwiched between metal films made of a nickel-chromium alloy is disclosed. And it is thought by the structure of said laminated body that durability of this laminated body can be excellent. However, on the other hand, no investigation has been made on the thickness of the upper and lower metal films protecting the infrared reflecting layer, and there is a problem that the durability against corrosion of silver is not always sufficient.

  Therefore, in view of such a problem, the present invention has a solar radiation shielding property and a heat insulating property due to excellent infrared reflection performance by making the thickness of the metal film above and below the infrared reflection layer into a specific range, and corrosion of the metal film. It is intended to provide a laminate suitable for window pasting applications having excellent durability against the above.

The present invention is a laminated body that adopts the following configuration in order to solve such problems. That is,
(1) At least a base material, a heat ray reflective layer, and a protective layer are provided in this order, and the heat ray reflective layer includes a first metal oxide film, a first metal film, a second metal film, Three metal films and a second metal oxide film, the first metal film is in direct contact with one surface of the second metal film, and the third metal film is In direct contact with the other surface of the second metal film, and the first metal film and the third metal film are all palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, The main metal is titanium, zirconium or an alloy thereof, the second metal film is mainly silver, the thickness of the first metal film is L1, and the thickness of the third metal film When L3 is L3, the ratio of L3 to L1 (L3 / L1) is 0.5 or more Is 1.5 or less, the laminate,
(2) When the thickness of the first metal film is L1, and the thickness of the third metal film is L3, the laminated body according to (1), wherein L1 ≧ L3,
(3) The laminate of (1) or (2), wherein the total thickness of the first metal film and the third metal film is 2 nm or more and 10 nm or less,
(4) The laminate of (1) to (3), wherein the first metal film and the third metal film are mainly composed of titanium,
(5) The laminated body according to any one of (1) to (4), wherein the first metal oxide film and the second metal oxide film are mainly composed of an oxide of a composite metal of zinc and tin. ,
(6) The protective layer has a first protective layer and a second protective layer in this order from the second metal oxide film side, and the first protective layer is an inorganic protective layer, The laminated body according to any one of (1) to (5), wherein the second protective layer is an organic protective layer,
(7) The first protective layer contains carbon, nitrogen, oxygen, and silicon, and the ratio between the number of carbon atoms (C) and the number of nitrogen atoms (N) in the first protective layer ( The laminate according to any one of (1) to (6), wherein the number of carbon atoms (C) / the number of nitrogen atoms (N)) is 0.5 to 2.5.

  ADVANTAGE OF THE INVENTION According to this invention, it is a laminated body which is excellent in solar radiation shielding property and heat insulation by the outstanding infrared reflective performance, Comprising: The laminated body suitable for the window sticking use excellent in the durability with respect to corrosion of a metal film can be provided. .

  The laminate of the present invention includes at least a base material, a heat ray reflective layer, and a protective layer in this order, and the heat ray reflective layer includes a first metal oxide film, a first metal film, A metal film, a third metal film, and a second metal oxide film, wherein the first metal film is in direct contact with one surface of the second metal film; and The metal film is in direct contact with the other surface of the second metal film, and the first metal film and the third metal film are all palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, Nickel, titanium, zirconium or an alloy thereof is a main component, the second metal film is a main component of silver, the thickness of the first metal film is L1, and the third metal film is When the thickness is L3, the ratio of L3 to L1 (L3 / L1) is 0. More than, less than or equal to 1.5.

  As described above, the laminate of the present invention includes a first metal film mainly composed of palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium, or an alloy thereof, and a third metal. By providing the film with a specific thickness, even when the protective layer is thinned, the metal film has excellent durability against corrosion.

<Base material>
First, the base material with which the laminated body of this invention is provided is demonstrated. The base material is not particularly limited as long as it has excellent visible light transmission performance, but when used for window pasting, a film containing a synthetic resin from the viewpoint of flexibility and excellent handleability. It is preferable that Here, examples of the synthetic resin include polyethylene terephthalate, polycarbonate, acrylic, and nylon. Among these, a heat ray reflective layer (hereinafter referred to as a heat ray reflective layer) including the first metal oxide film, the first metal film, the second metal film, and the second metal oxide film is formed. In view of the heat resistance required, polyethylene terephthalate is more preferable.

  Further, from the viewpoint of improving the adhesion between the base material and the heat ray reflective layer, it is preferable to subject at least the surface of the base material on which the heat ray reflective layer is laminated to a surface treatment such as corona treatment, plasma treatment or saponification. .

  Next, although there is no restriction | limiting in particular about the thickness of a base material, When it considers the mechanical strength, heat resistance, and the handleability at the time of using for a window sticking use, it is preferable that it is 10-150 micrometers. By making the thickness 10 μm or more, it is possible to suppress the generation of wrinkles due to heat shrinkage in the surface treatment process of the base material and the formation process of the heat ray reflective layer, and to prevent the window from being damaged and to prevent crime. Can be granted. On the other hand, when the thickness is set to 150 μm or less, the amount of necessary materials can be reduced and the environmental load can be reduced, and the flexibility of the laminate is improved, so that the laminate is applied to a window or the like. This makes it possible to improve the workability.

  Furthermore, it is preferable to form an undercoat layer made of a synthetic resin such as an acrylic resin or a urethane resin on the surface of the base material in contact with the heat ray reflective layer. By forming the undercoat layer, the surface of the base material is smoothed, the adhesion between the base material and the heat ray reflective layer is improved, and the corrosion resistance of the silver-based metal film is improved. The rigidity of the substrate is increased and the scratch resistance tends to be improved. The thickness of the undercoat layer is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, the upper limit value is preferably 5.0 μm or less, and more preferably 3.0 μm or less.

<Heat ray reflective layer>
Next, the heat ray reflective layer with which the laminated body of this invention is provided is demonstrated. The heat ray reflective layer
The first metal oxide film, the first metal film, the second metal film, the third metal film, and the second metal oxide film are provided in this order from the substrate side, and silver is the main component. By reflecting infrared rays with the second metal film, solar radiation shielding properties and heat insulation properties are expressed, and reflection of visible light is reduced with the first metal oxide film and the second metal oxide film. The visible light permeability of the body can be made excellent. In the present application, infrared is a concept including both near infrared and far infrared.

  Further, the first metal oxide film is a layer disposed on the base side of the second metal film mainly containing silver, and the second metal oxide film is a second metal oxide mainly containing silver. It is a layer disposed on the protective layer side of the metal film, and also has a function as a protective film that improves the durability against corrosion of the second metal film mainly composed of silver. In other words, the first metal oxide film disposed on the base material side of the second metal film containing silver as a main component is a construction sprayed between the window glass and the base material when it is constructed as a window pasting film. When the liquid evaporates from the back surface of the base material to the protective layer side, this construction liquid contributes to suppressing silver corrosion of the second metal film. Moreover, the 2nd metal oxide film arrange | positioned at the protective layer side contributes to suppressing the corrosion of the silver of the metal film which has silver as a main component, when constructing and using as a window pasting film.

  The first metal film mainly composed of palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium or an alloy thereof is based on the second metal film mainly composed of silver. It is a film that is disposed on the material side and serves as a base in direct contact with the second metal film. The third metal film is disposed on the protective layer side of the second metal film containing silver as a main component, and is in direct contact with the second metal film, like the second metal oxide film. It is a film | membrane which has a function which protects a film | membrane. Although details will be described later, sandwiching a second metal film mainly composed of silver between the first metal film and the third metal film contributes to suppression of silver corrosion.

<First metal film / third metal film>
The first metal film and the third metal film of the present invention are composed mainly of palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium, or an alloy thereof.

  The first metal film is a film serving as a base for the second metal film containing silver as a main component. All of the metals described above have a high melting point, a high surface energy, and a tendency to form a wettable surface. Therefore, when used as the base of the second metal film containing silver as a main component, silver is used. The second metal film having the main component is uniformly and densely formed, the contact area with the substance that corrodes silver is reduced, and the corrosion resistance of the second metal film having the main component of silver is improved. . Here, the main component is palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium or an alloy thereof. The total metal component contained in the first metal film is 100% by mass. In some cases, the content exceeds 50% by mass, and the content of the metal described above is more preferably 90% by mass or more.

  The metal group described above is a group of metals having a melting point of 1400 ° C. or higher excluding those with poor durability, those with toxicity, and rare metals that are difficult to industrially use. Generally, a metal having a high melting point tends to have a high surface energy. Therefore, when forming a second metal film mainly composed of silver, all of the atoms constituting the metal film mainly composed of silver are formed. It is estimated that it has the effect of homogenization and further densification.

  The first metal film needs to be in direct contact with the second metal film from the viewpoint of expressing the effect of uniformly and densifying the second metal film containing silver as a main component. . For example, when a metal oxide film or another metal film is disposed between the first metal film and the second metal film, the first metal film is uniformly made of the second metal film mainly composed of silver. The effect of densification cannot be expressed.

  Next, the third metal film is a film that is disposed so as to be in direct contact with the protective layer side of the second metal film containing silver as a main component, and protects the second metal film. In general, a metal film has a lower water vapor transmission rate than a metal oxide film. Therefore, even in a thin film, salts contained in moisture, hand sweat, etc. in the atmosphere contain silver as a main component. The effect which suppresses reaching | attaining this metal film is high. Among them, palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium or their alloys are chemically stable and highly resistant to acids and salts, so that silver can be used for a long time. It has the effect of protecting the second metal film as the main component.

  Furthermore, the first metal film and the third metal film are made of titanium, which is chemically stable and has corrosion resistance equivalent to that of noble metals such as platinum and gold, and is inexpensive. It is particularly preferred to use a laminate having excellent corrosion resistance of the second metal film containing silver as a main component at a low cost.

  Next, in the laminate of the present invention, the ratio (L3 / L1) when the thickness L3 of the third metal film is set to the thickness L1 of the first metal film is 0.5 or more and 1.5 or less. is there. If the ratio between the thickness L1 of the first metal film and the thickness L3 of the third metal film is out of the above range, the corrosion resistance of the second metal film containing silver as a main component tends to decrease. The reason is not clear, but the first metal film and the third metal film are both arranged so as to be in direct contact with the second metal film containing silver as a main component, and have a high surface energy. It is a wet film. Therefore, since a force acts in the direction of spreading the second metal film that is in direct contact with the second metal film, if L3 / L1 is out of the above-described range, the second metal film applied to each of the upper and lower surfaces of the second metal film It is presumed that the difference in the force acting in the direction of wetting and spreading increases and defects occur in the second metal film.

  Furthermore, it is preferable that L1 ≧ L3 in the thickness L1 of the first metal film and the thickness L3 of the third metal film. The first metal film and the third metal film have an effect of improving the corrosion resistance of the second metal film containing silver as a main component, and the effect is higher in the first metal film. . On the other hand, since the first metal film and the third metal film are metal films, they have a property of absorbing visible light. Therefore, by setting L1 ≧ L3, it is possible to minimize the decrease in visible light transmittance and improve the corrosion resistance of the second metal film containing silver as a main component.

  Further, the total thickness of the first metal film and the third metal film is preferably 2 nm or more, and is preferably 4 nm or more for the reason of further improving the corrosion resistance and visible light transmission performance. It is more preferable. On the other hand, the upper limit is preferably 10 nm or less, and more preferably 8 nm or less. By setting the thickness of the first metal film and the third metal film to 2 nm or more, the first metal film becomes the base of the second metal film mainly composed of silver, and the second metal film is made uniform. It is possible to obtain a laminate that is densified and exhibits the effect that the third metal film protects the second metal film, improves the corrosion resistance of silver, and has excellent durability. The effect becomes more remarkable when the total thickness is 4 nm or more. Further, by setting the total thickness to 10 nm or less, the visible light absorption performance of the metal film can be kept low, and the visible light transmission performance can be improved. Moreover, the laminated body which was more excellent in visible light transmission performance can be obtained by setting it as 6 nm or less.

  When forming the first metal film included in the laminate by sputtering, by using the above-described sputtering target material of metal or an alloy thereof and forming the film using argon gas in an atmosphere not containing oxygen. Can be obtained.

<Second metal film>
The second metal film of the present invention is mainly composed of silver excellent in infrared reflection performance. Here, the main component means that the content of silver contained in the second metal film exceeds 50% by mass when the total metal component of the metal film is 100% by mass. It is preferable that it is 90 mass% or more. Furthermore, in order to improve the corrosion resistance of silver, it is preferable to use an alloy in which one or more of gold, copper, palladium, zinc, tin and the like are added in addition to silver. Among these metals, it is preferable to contain gold from the viewpoint of making silver more excellent in corrosion resistance, and it is more preferable to contain tin in addition to gold. By including gold and tin in addition to silver, the second metal film can provide corrosion resistance against atmospheric moisture due to the effect of gold, and corrosion resistance against salts contained in hand sweat due to the effect of tin. Can be granted. From the viewpoint of improving the above-described corrosion resistance of silver, the gold content is preferably 2.0% by mass or more when all the components of the metal film are 100% by mass, and 3.0% by mass. The above is particularly preferable. The upper limit of the gold content in the metal film is not particularly limited, but is 5.0% by mass or less because it is not possible to obtain the effect of improving the corrosion resistance of the laminate in accordance with the cost increase due to the increase in the content. It is preferable that Further, the content of tin is preferably 1.0% by mass or more when the total component of the metal film is 100% by mass, and the upper limit is from the viewpoint of further improving the visible light transmission performance of the laminate. The content is preferably 2.5% by mass or less.

  About the thickness of a 2nd metal film, it is preferable to select suitably in the range of 10-25 nm from the reason for improving the infrared reflective performance and visible light transmission performance of a laminated body more. Specifically, the infrared reflection performance of the laminate is excellent when the thickness of the second metal film is 10 nm or more, and the visible light transmission is achieved when the thickness of the second metal film is 25 nm or less. The performance is excellent. In addition, when the thickness of the second metal film is 25 nm or less, an effect that the amount of metal used is reduced and the productivity of the laminate is improved is also obtained.

<Metal oxide film>
By providing the first metal oxide film and the second metal oxide film, the laminate of the present invention has excellent visible light transmission performance, and these metal oxide films function as a protective film. By doing so, the silver has excellent corrosion resistance.

  By adopting a metal oxide film having a high refractive index at a wavelength of 500 nm for the first metal oxide film and the second metal oxide film included in the laminate of the present invention, reflection of visible light of the laminate is performed. And the visible light permeability of the laminate can be improved. Examples of the metal oxide having a high refractive index include oxides such as titanium, niobium, zinc, tin, and indium, but the laminate of the present invention is used for window pasting that is used for a long time in an environment where it is exposed to sunlight. When used, it is preferable to use a metal oxide film composed mainly of an oxide of a composite metal of zinc and tin. Both zinc and tin oxides have a high refractive index and do not show a strong photocatalytic reaction under the energy of sunlight. Therefore, when used for window application, a laminate with excellent visible light transmission performance and durability is obtained. Can do. Here, the main component means that the total content of zinc and tin exceeds 90% by mass when the total metal components in the metal oxide film are 100% by mass. Furthermore, it is preferable to make content of zinc into 10-40 mass%. Zinc oxide has high conductivity and is excellent in productivity when formed by sputtering, but has poor moisture resistance as compared with tin oxide, and therefore tends to be easily deteriorated by moisture in the atmosphere. is there. Therefore, by setting the zinc content in the above-described range, a metal oxide film having excellent productivity and excellent moisture resistance can be obtained.

  In addition, from the viewpoint of the first metal oxide film and the second metal oxide film that are particularly excellent in performance as a protective film that suppresses corrosion of silver, in the laminate of the present invention, the metal oxide film is It is preferable to contain nitrogen, and the nitrogen content is equivalent to the ratio of nitrogen (N) to zinc (Zn) and tin (Sn) considering the equivalent of each element in the metal oxide film (3N / (2Zn + 4Sn)) More preferably, it is 0.010 to 0.025. Since the metal oxide film contains nitrogen, the degree of freedom in the molecular level in the film increases, distortion is eliminated, and the densification improves barrier properties against substances that corrode silver. It is estimated that. This equivalence ratio is determined by analyzing the number of atoms of nitrogen, zinc, and tin contained in the metal oxide thin film by an X-ray photoelectron spectroscopy (XPS) method as described in the Examples section. Is substituted for N, Zn, and Sn of 3N / (2Zn + 4Sn), respectively.

  Furthermore, it is preferable that the first metal oxide film and the second metal oxide film sufficiently contain oxygen from the viewpoint of improving the visible light transmittance of the laminate. The film containing nitrogen and oxygen like the first metal oxide film and the second metal oxide film provided in the present invention described above is an atmosphere of oxygen gas or carbon dioxide gas in addition to nitrogen gas. It can obtain by forming into a film. However, oxygen gas contains only oxygen atoms in the molecule and easily binds to zinc or tin to form an oxide. Therefore, the first metal oxide film and the second metal oxide film are mixed with nitrogen and oxygen. It is preferable to form the film in an atmosphere of nitrogen gas and carbon dioxide gas from the viewpoint of containing it and having excellent performance as a protective film and excellent visible light permeability.

  The thickness of the first metal oxide film and the second metal oxide film is preferably 10 nm or more, and more preferably 30 nm or more. On the other hand, the upper limit is preferably 100 nm or less, and more preferably 60 nm or less. By setting the thickness of the first metal oxide film and / or the second metal oxide film to 10 nm or more, it is possible to suppress the reflection of visible light and obtain a laminate having excellent visible light transmission performance. . On the other hand, even if the thickness of the first metal oxide film and / or the second metal oxide thin film exceeds 100 nm, not only the material cost increases, but the visible light transmission performance cannot be further improved. .

  For the thicknesses of the first metal film, the second metal film, the third metal film, the first metal oxide thin film, and the second metal oxide film, use a transmission electron microscope (TEM). The composition of each layer can be used and analyzed. Details of the composition of each layer are described in the Examples section, but can be measured using an X-ray photoelectron spectrometer (ESCA). In addition, these metal films, the first metal oxide film, the second metal oxide film, and the metal suboxide film are formed by vapor deposition methods such as vacuum deposition, sputtering, and ion plating. Although the film can be formed, it is preferable to use the sputtering method among the vapor phase growth methods because the variety of materials that can be formed is wide and a high-quality film can be obtained.

<Protective layer>
Next, the protective layer with which the laminated body of this invention is provided has a function which protects a heat ray reflective layer, and it is preferable that it is a layer located in the outermost surface of a laminated body. By providing the protective layer, not only the corrosion resistance of the laminate is further improved, but also the scratch resistance of the laminate is excellent. In other words, when the laminate is used as a window pasting film for the protective layer, it is resistant to scratches on the construction spatula used at the time of construction, from components that corrode silver in the atmosphere at the time of use, and dirt components such as hand sweat. The barrier property which suppresses deterioration of the 2nd metal film which has as a main component is calculated | required.

  From the viewpoint described above, the protective layer has the first protective layer and the second protective layer in this order from the substrate side, the first protective layer is an inorganic protective layer, and the second protective layer is An organic protective layer is preferred.

  The inorganic protective layer can be formed by a known method such as a vacuum deposition method, a sputtering method, or an ion plating method in the same manner as a metal film or a metal oxide film, and absorbs infrared rays due to the properties of the inorganic substance. It is difficult, has high hardness, is dense, and has high barrier properties. On the other hand, since it is difficult to increase the film thickness due to the manufacturing method, when a scratch is generated on the surface, the metal film located under the inorganic protective layer tends to be damaged.

  On the other hand, the organic protective layer can be formed by a known method such as a gravure coating method, a reverse roll coating method, a dip coating method, and can be thickened as a whole. When it hits, it has the characteristic that the crack which reaches a metal film does not arise easily. On the other hand, since the organic substance has the property of absorbing infrared rays, the infrared reflection performance tends to be reduced as a laminate by increasing the film thickness. In order to take advantage of the characteristics of the inorganic protective layer and the organic protective layer described above, the combined use of the inorganic protective layer and the organic protective layer is a barrier that protects the metal film and prevents the metal film from deteriorating. It is preferable at the point which can balance the property. Further, from the viewpoint of making the best use of the characteristics of each protective layer, it is preferable to use an inorganic protective layer for the first protective layer located on the substrate side and an organic protective layer for the outermost layer. In this case, after forming the metal film, the metal oxide film, and the inorganic protective layer in the same process, the organic protective layer can be laminated, which is preferable from the viewpoint of productivity.

  Next, the preferable form of an inorganic type protective layer and an organic type protective layer is demonstrated. First, the inorganic protective layer contains carbon, nitrogen, oxygen, and silicon from the viewpoint of high hardness and better barrier properties, and further includes carbon contained in the inorganic protective layer. The ratio of the numbers of atoms (C) and nitrogen atoms (N) (number of carbon atoms (C) / number of nitrogen atoms (N)) is preferably 0.5 to 2.5. When the inorganic protective layer contains carbon and nitrogen in addition to oxygen and silicon, the degree of freedom is increased at the molecular level, distortion is eliminated, the inorganic protective layer is densified, and the barrier of the inorganic protective layer Is estimated to improve. Further, since the film hardness is improved and scratches are difficult to be made during construction, it is presumed that the durability of the laminated body as a window pasting film is improved. The effect is that the ratio of the number of carbon atoms (C) and nitrogen atoms (N) contained in the inorganic protective layer (the number of carbon atoms (C) / the number of nitrogen atoms (N)) is 0. It becomes more remarkable in the range of 5 to 2.5, preferably 0.7 or more and 2.0 or less, more preferably 1.0 or more and 1.5 or less. The thickness of the inorganic protective layer is preferably 10 nm or more, and more preferably 15 nm or more. By setting the thickness of the inorganic protective layer to 10 nm or more, the scratch resistance of the inorganic protective layer can be further improved, and excellent barrier properties of the protective layer can be secured, and durability sufficient as a laminate. Can be obtained. The effect becomes more remarkable by setting the thickness to 15 nm or more. Further, the thickness of the inorganic protective layer is preferably 50 nm or less, and more preferably 30 nm or less. By making the thickness of the inorganic protective layer 50 nm or less, the visible light transmission performance can be further improved, and the corrected emissivity (infrared absorptance) of the inorganic protective layer can be lowered. .

  Next, an acrylic resin, a urethane resin, a fluororesin, a silicone resin, or the like can be used for the organic protective layer. Furthermore, by containing a fluororesin and a silicone resin, it is possible to improve the contact angle of the organic protective layer with respect to water, suppressing the penetration of moisture such as condensed water, and mainly containing silver. This is preferable in that the corrosion of the second metal film as a component can be further suppressed. The contact angle of the organic protective layer with respect to water is preferably 60 ° or more, more preferably 80 ° or more, and further preferably 100 ° or more.

  The thickness of the organic protective layer is preferably 200 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less. On the other hand, the film thickness lower limit is preferably 10 nm or more, and more preferably 30 nm or more. By setting the thickness of the organic protective layer in the above-described range, the modified emissivity (infrared absorption rate) of the organic protective layer can be lowered.

<Characteristics of laminate>
The laminate of the present invention has an infrared reflectance of 85% or more at a wavelength of 5.5 to 50 μm measured from the protective layer side, and a solar heat gain rate at a wavelength of 300 to 2500 nm measured from the protective layer side is It is preferable that it is 0.62 or less. By setting the infrared reflectance and the solar heat acquisition rate within the above-described ranges, a laminated body having a high energy saving effect can be obtained. In addition, it becomes a laminated body which was excellent by heat insulation because the infrared reflectance of wavelength 5.5-50 micrometers is 85% or more, and the solar radiation heat acquisition rate of wavelength 300-2500 nm was 0.62 or less, and was excellent by solar radiation shielding. It becomes a laminate. Moreover, as a means which makes the infrared reflectance of a laminated body and the solar heat acquisition rate into said range, making the structure of a laminated body the structure of the laminated body of this invention, etc. are mentioned.

  Hereinafter, the present invention will be described more specifically with reference to examples. The production method of the test specimen for evaluation used for the measurement of the characteristic values shown in the examples and the measurement / calculation method of the characteristic values are as follows.

A. Preparation of test specimen for evaluation (1) The laminate is cut into a 50 mm square.
(2) An adhesive layer is formed on the base material side surface of the film cut in the item (1).
(3) Next, it is bonded to a 3 mm thick float glass through the adhesive layer formed in the item (2). Bonding is carried out in accordance with “Glass Film Construction Manual 3rd Edition (published by Japan Window Film Industry Association)”.

B. Composition of each layer
(1) Using an X-ray photoelectron spectrometer PHI5000 VersaProbe II (manufactured by ULVAC-PHI Co., Ltd.), the spectrum of the bond energy peak between each element is measured (photoemission angle 45 degrees), and the number of atoms of each element is calculated. At this time, measurement is performed after all the layers stacked on the layer to be measured are removed by etching.

C. The thickness of each film (1) Measured using an analytical electron microscope TITAN 80-300 (FEI) and an EDX detector r-TEM / SuperUTW (EDAX) (acceleration voltage 200 kV).

D. Composition of each film
(1) Using an X-ray photoelectron spectrometer PHI5000 VersaProbe II (manufactured by ULVAC-PHI Co., Ltd.), the spectrum of the bond energy peak between each element is measured (photoemission angle 45 degrees), and the number of atoms of each element is calculated. At this time, measurement is performed after all the layers stacked on the film to be measured are removed by etching.

E. Equivalent ratio of nitrogen to zinc and tin of metal oxide film (1) The number of atoms of zinc (Zn), tin (Sn), and nitrogen (N) is calculated by the method described in the item B.
(2) By substituting the number of nitrogen atoms, the number of zinc atoms, and the number of tin atoms into N, Zn, and Sn in the formula of 3N / (2Zn + 4Sn) considering the equivalent of each element, zinc and The equivalent ratio of nitrogen to tin (3N / (2Zn + 4Sn)) is calculated.

F. C / N ratio of the first protective layer (1) The number of atoms constituting the protective layer is calculated by the method described in item B. Note that the atomic number% of a specific atom (for example, carbon) is calculated by dividing the number of atoms of the same atom by the number of atoms of all atoms contained in the protective layer and multiplying the obtained value by 100. Note that elements whose atomic percentage is less than 1% are excluded. In addition, since carbon may be detected due to contamination of the analytical device or the test specimen, the test specimen that does not contain carbon in the protective layer (carbon is not introduced in the manufacturing process) is used as a blank. The content is the number of atoms contained.
(2) The C / N ratio is calculated by dividing the atomic percentage of carbon (C) by the atomic percentage of nitrogen (N).

G. Corrosion resistance of metal film (durability of laminate)
(1) Measuring method:
i) 50 μL of artificial sweat (lactic acid 5%, NaCl 10%: JIS B7285) is dropped on the surface of the test specimen for evaluation prepared in the item A, and left in a constant temperature and humidity chamber (temperature 23 ° C., humidity 90%).
ii) After standing for 1, 3, 5, 10 hours, taking out and washing with water, the corrosion state is observed with a shape measurement laser microscope VK-X110 (manufactured by Keyence Corporation). The objective lens is 5 times.
(2) Criteria “A”: no corrosion (discoloration), no peeling of thin metal.
“B”: There was slight corrosion (discoloration), and there was no peeling of thin metal.
“C”: Corrosion (discoloration) is present, and thin metal is peeled off.
Here, the silver corrosion of the metal film first causes discoloration when the silver corrosion occurs, and further, the metal film exfoliates when the corrosion progresses greatly.

H. Far-infrared reflectance (1) Standard: Conforms to JIS R3106-1998 (2) Measurement method:
i) Using a spectrophotometer “IR Prestige-21 (manufactured by Shimadzu Corporation)” and a specular reflection measuring unit “SRM-8000A (manufactured by Shimadzu Corporation)”, spectral reflection of a test specimen for evaluation having a wavelength of 5 to 25 μm. Measure the rate. An Al vapor deposition mirror was used for the standard plate. ii) Extract the spectral reflectance at the selected wavelengths of the numbers λ1 (wavelength 5.5 μm) to λ30 (wavelength 50 μm) described in Appendix 3 of the JIS text from the spectral reflectance. In addition, the value of (lambda) 24 (wavelength 23.3 micrometers) is used for the reflectance of (lambda) 25 (wavelength 25.2 micrometers)-(lambda) 30 (wavelength 50 micrometers). iii) Multiply the extracted spectral reflectance by the standard reflectance of the Al vapor deposition mirror described in Appendix 3 of the JIS text to obtain the reflectance of the evaluation specimen at the selected wavelength of λ1 to λ30. iv) Let the average value of the reflectance be the far-infrared reflectance.

I. Solar heat acquisition rate (1) Standard: Conforms to JIS R3106-1998 (2) Measurement method:
i) Using a spectrophotometer “UV-3150 (manufactured by Shimadzu Corporation)”, the spectral transmittance and spectral reflectance of the test specimen for evaluation at a wavelength of 300 to 2500 nm are measured at 1 nm intervals. ii) After multiplying the transmittance / reflectance by the weight coefficient described in Appendix 2 of the JIS text, the total value is calculated to be the solar transmittance / reflectance (%). iii) The solar heat acquisition rate is calculated using the calculation formula in 8.4 of the JIS text.
(3) Measurement conditions: scan speed “high speed”, resolution capability “10 nm”.

J. et al. Visible light transmittance (1) Standard: based on JIS R 3106-1998 (2) Measurement method i) Using spectrophotometer “UV-3150 (manufactured by Shimadzu Corporation)”, wavelength of test specimen for evaluation: 380-780 nm The spectral transmittance and the spectral reflectance are measured at 1 nm intervals. ii) After multiplying the transmittance by the weight coefficient described in the JIS text, the total value is calculated to obtain the visible light transmittance (%).
(3) Measurement conditions: scan speed “high speed”, resolution capability “10 nm”.

[Example 1]
As a base material, a hard coat film “Tough Top” (registered trademark) THS (manufactured by Toray Film Processing Co., Ltd.) provided with an undercoat layer was used.

  Next, a first metal having a thickness of 30 nm is formed on the undercoat layer of the base material using a metal oxide sputtering target material having a metal composition of tin (Sn): zinc (Zn) = 65 mass%: 35 mass%. An oxide film was formed (sputtering gas was argon: oxygen = 95%: 5% (flow rate ratio)). Subsequently, a first metal film having a thickness of 1 nm was formed on the first metal oxide film using a metal sputtering target material having a titanium (Ti) content of 100 mass% (sputtering gas is Argon 100%). Next, a thickness of 12 nm is formed on the first metal film using a metal sputtering target material having a silver (Ag) content of 97.0 mass% and a gold (Au) content of 3.0 mass%. The second metal film was formed (sputtering gas was argon = 100%). Furthermore, a 1 nm-thick third metal film was formed using the same sputtering target material as the first metal film (sputtering gas is argon = 100%). Next, a second metal oxide film having a thickness of 30 nm is formed using the same metal oxide sputtering target material as the first metal oxide thin film ((sputtering gas is argon: oxygen = 95%: 5 % (Flow rate ratio)), a heat ray reflective layer made of the first metal oxide film / first metal film / second metal film / third metal film / second metal oxide is formed on the substrate. did.

  Next, an inorganic protective layer having a thickness of 15 nm is formed on the heat ray reflective layer using a Si sputtering target material (sputtering gas is argon: carbon dioxide: nitrogen = 76%: 16%: 8%), and the laminate is formed. Obtained.

[Example 2]
A laminate was obtained in the same manner as in Example 1 except that the thicknesses of the first metal film and the third metal film were changed to 2 nm.

[Example 3]
A laminate was obtained in the same manner as in Example 1 except that the thickness of the first metal film and the third metal film was changed to 3 nm.

[Example 4]
A laminate was obtained in the same manner as in Example 1 except that the thickness of the first metal film and the third metal film was changed to 5 nm.

[Example 5]
A laminate was obtained in the same manner as in Example 1 except that the thickness of the first metal film was changed to 3 nm and the thickness of the third metal film was changed to 2 nm.

[Example 6]
A laminate was obtained in the same manner as in Example 1 except that the thickness of the first metal film was changed to 5 nm and the thickness of the third metal film was changed to 3 nm.

[Example 7]
Example 1 except that the content of niobium (Nb) was changed to 100% by mass and the thickness was 3 nm each for the sputtering target material when forming the first metal film and the third metal film A laminate was obtained by the same method as in (Sputtering gas: Argon 100%).

[Example 8]
Example 1 except that the content of tungsten (W) was changed to 100% by mass and the thickness was 3 nm for the sputtering target material when forming the first metal film and the third metal film, respectively. A laminate was obtained by the same method as in (Sputtering gas: Argon 100%).

[Example 9]
The same method as in Example 2 except that the sputtering gas used when forming the first and second metal oxide films was changed to argon: carbon dioxide: nitrogen = 90%: 7%: 3%. A laminate was obtained.

[Example 10]
Example 2 except that the sputtering gas used when forming the first and second metal oxide films was changed to argon: carbon dioxide: nitrogen = 75%: 17.5%: 7.5%. A laminate was obtained in the same manner.

[Example 11]
Lamination was carried out in the same manner as in Example 10 except that the sputtering gas for forming the first protective layer was changed to argon: oxygen: carbon dioxide: nitrogen = 74%: 5%: 14%: 7%. Got the body.

[Example 12]
Lamination was performed in the same manner as in Example 10 except that the sputtering gas for forming the first protective layer was changed to argon: oxygen: carbon dioxide: nitrogen = 78%: 7%: 10%: 5%. Got the body.

[Example 13]
The sputtering target material for forming the second metal film has a silver (Ag) content of 97.0% by mass, a gold (Au) content of 2.0% by mass, and a tin (Sn) content. Was changed to a sputtering target material of 1.0% by mass, and a laminate was produced in the same manner as in Example 10 except that the thickness was 12 nm.

[Example 14]
After laminating the heat ray reflective layer and the first protective layer by the same method as in Example 13, a second protective layer was formed by coating at 10 nm to obtain a laminate. In addition, the fluorine-type coating agent "Novec1720 (made by 3M company)" was used for the 2nd protective layer.

[Comparative Example 1]
A laminate was obtained in the same manner as in Example 1 except that the first metal film and the third metal film were not provided.

[Comparative Example 2]
A laminate was obtained in the same manner as in Example 1 except that the first metal film was changed to 3 nm and the third metal film was changed to 1 nm.

[Comparative Example 3]
A laminate was obtained in the same manner as in Example 1 except that the first metal film was changed to 5 nm and the third metal film was changed to 1.5 nm.

  About each test body of Examples 1-14 and Comparative Examples 1-3, using the measurement method mentioned above, infrared reflectivity, solar heat acquisition rate, visible light transmittance, corrosion resistance, 3N of metal oxide film ( The results of measuring the C / N ratio of 2Zn + 4Sn) and the first protective layer are shown in Table 1, Table 2, and Table 3.

  A metal film mainly composed of titanium is disposed on the first metal film and the third metal film, and the thickness L1 of the first metal film and the thickness L3 of the third metal film are 1 nm, 2 nm, respectively. Example 1 to Example 4 in which L3 / L1 was 1.0, and Example 3 in which L3 / L1 = 2 nm / 3 nm (0.67) was set, and L3 / L1 = 3 nm / 5 nm (3 nm, 5 nm) 0.60), Comparative Example 1, L3 / L1 = 1 nm / 3 nm (0.33), Comparative Example 2, L3 without the first metal film and the third metal film /L1=1.5 nm / 5 nm (0.30), compared with Comparative Example 3 where the corrosion resistance is improved, the evaluation at the time when 1 h has elapsed is “A”, and the evaluation at the time when 10 h has elapsed The determination was “B” (Comparative Example 1: 1 h determination “C”, Comparative Example 2, 3:10 h determination “C”). In addition, the corrosion resistance is similarly improved in Examples 7 and 8 in which the first metal film and the second metal film are changed to niobium and tungsten, and the evaluation is “A” in the evaluation after 1 hour. there were.

  Furthermore, a first metal film having the same composition and thickness as in Example 3 is disposed, nitrogen is contained in the first metal oxide film and the second oxide film, and 3N / (2Zn + 4Sn) is set to 0. In Examples 9 and 10 in the range of .010 to 0.025, the corrosion resistance was further improved, and the evaluation was “A” even in the evaluation of 3 h (Example 3: 3 h determination “B”). .

  Further, in the same manner as in Example 10, up to the second metal oxide film was formed, and the C / N ratio of the first protective layer was in the range of 0.010 to 0.025, Example 11, The corrosion resistance of No. 12 was judged as “A” in 3 hours as in Example 10.

  Next, from Example 10, only the composition of the second metal film was changed, and in Example 13 in which gold and tin were contained in silver, the corrosion resistance was further improved. (Example 10: 5h determination “B”).

  Finally, Example 14 in which the second protective layer was laminated on the laminate of Example 13 was most excellent in corrosion resistance, and the judgment was “A” at 10 h.

  In all the test bodies, the far-infrared reflectance, which is an index of heat insulation, the solar heat acquisition rate, which is an index of heat shielding, and the visible light transmittance, which is an index of transparency, were good values.

  Since the laminated body of the present invention has high levels of solar shading and heat insulation and is excellent in durability, it can be suitably used for window glass in houses and buildings.

Claims (7)

At least a substrate, a heat ray reflective layer, and a protective layer are provided in this order,
The heat ray reflective layer has a first metal oxide film, a first metal film, a second metal film, a third metal film, and a second metal oxide film from the substrate side,
The first metal film is in direct contact with one surface of the second metal film, and the third metal film is in direct contact with the other surface of the second metal film;
The first metal film and the third metal film are all composed mainly of palladium, chromium, molybdenum, tungsten, vanadium, niobium, cobalt, nickel, titanium, zirconium or an alloy thereof,
The second metal film is mainly composed of silver,
When the thickness of the first metal film is L1, and the thickness of the third metal film is L3, the ratio of L3 to L1 (L3 / L1) is 0.5 or more and 1.5 or less, Laminated body.   The laminate according to claim 1, wherein L1 ≧ L3 in the thickness L1 of the first metal film and the thickness L3 of the third metal film.   The laminate according to claim 1 or 2, wherein a total thickness of the first metal film and the third metal film is 2 nm or more and 10 nm or less.   The laminate according to any one of claims 1 to 3, wherein each of the first metal film and the third metal film has titanium as a main component.   The laminate according to any one of claims 1 to 4, wherein each of the first metal oxide film and the second metal oxide film is mainly composed of an oxide of a composite metal of zinc and tin.   The protective layer has a first protective layer and a second protective layer in this order from the second metal oxide film side, the first protective layer is an inorganic protective layer, The laminate according to any one of claims 1 to 5, wherein the protective layer is an organic protective layer.   The first protective layer contains carbon, nitrogen, oxygen, and silicon, and the ratio between the number of carbon atoms (C) and the number of nitrogen atoms (N) in the first protective layer (carbon atoms ( The laminate according to any one of claims 1 to 6, wherein C) number of atoms / number of nitrogen atoms (N) is 0.5 to 2.5.