JPWO2018105456A1 - Laminate - Google Patents

Abstract

At least a substrate, a heat ray reflective layer, and a protective layer are provided in this order, and the heat ray reflective layer is at least a first metal oxide thin film, a metal thin film mainly composed of silver, and a composite metal oxynitriding of zinc and tin The second metal oxide thin film mainly comprising a material is provided in this order from the substrate side, and the equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in the second metal oxide thin film The laminated body whose (3N / (2Zn + 4Sn)) is 0.005-0.030. Provided is a laminate suitable for window pasting, which is particularly excellent in durability of a metal thin film, even when a thinned protective layer is employed to express solar radiation shielding properties and heat insulation properties at a high level.

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 thin films / metal oxide thin films are alternately laminated on a transparent polymer film, and a protective layer are sequentially formed in openings such as window glass provided in a house or a building. in use. These laminated bodies can suppress the inflow of solar heat (near infrared) from the outside to the room and the outflow of heating heat (far infrared gland) from the room to the outside by the infrared reflective function of the metal thin film. , Energy saving effect can be obtained throughout the year. Furthermore, by laminating a metal oxide thin film with a high refractive index, transparency is improved and appearance visibility is secured. By laminating a protective layer, the metal thin film and the metal oxide thin film are protected, and durability is exhibited. ing.

  As the above-mentioned laminate, for example, after alternately laminating metal thin films such as gold, silver, and copper and metal oxide films on a transparent polymer film, the heat ray shielding performance is obtained by further laminating silicon oxide or acrylic resin as a protective layer. The transparent laminated body which has is proposed (refer patent document 1).

JP 2012-135888 A

  In the transparent laminate described in Patent Document 1, a material containing silicon oxide or acrylic resin is used for the protective layer in order to obtain a transparent laminate suitable for window pasting that has both high solar shielding properties and high heat insulation properties. Furthermore, the corrected emissivity (infrared absorptivity) of the protective layer is lowered by reducing the thickness of the protective layer. However, the present inventor can obtain a transparent laminate having a low correction emissivity and an excellent solar radiation shielding property and heat insulating property when the thinned protective layer is used like the above transparent laminate, while the protective layer is a thin film. Therefore, the present inventors have found a problem that the metal thin film is liable to deteriorate during construction or use and there is a tendency that sufficient durability cannot be obtained. Therefore, in view of such problems, the present invention is particularly suitable for window pasting, which is excellent in durability of a metal thin film, even when a thinned protective layer is employed to express solar radiation shielding and heat insulation at a high level. It is intended to provide a suitable laminate.

  The present invention is a laminated body that adopts the following configuration in order to solve such problems.

  (1) At least a substrate, a heat ray reflective layer, and a protective layer are provided in this order, and the heat ray reflective layer is at least a first metal oxide thin film, a metal thin film mainly composed of silver, and a composite metal of zinc and tin. A second metal oxide thin film mainly composed of oxynitride of the second metal oxide in this order from the base material side, and nitrogen (N) with respect to zinc (Zn) and tin (Sn) in the second metal oxide thin film A laminate having an equivalent ratio (3N / (2Zn + 4Sn)) of 0.005 to 0.030.

  (2) The equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in the second metal oxide thin film (3N / (2Zn + 4Sn)) is from 0.010 to 0.030. Laminated body.

  (3) The first metal oxide thin film is mainly composed of oxynitride of a composite metal of zinc and tin, and nitrogen (N) with respect to zinc (Zn) and tin (Sn) in the first metal oxide thin film ) Equivalent ratio (3N / (2Zn + 4Sn)) is 0.005 to 0.030, and the laminate of (1) or (2).

  (4) The equivalent ratio (3N / (2Zn + 4Sn)) of nitrogen (N) to zinc (Zn) and tin (Sn) in the first metal oxide thin film is 0.010 to 0.030. (3) Laminated body.

  (5) The protective layer contains carbon, nitrogen, oxygen, and silicon, and the ratio of the number of carbon atoms (C) to the number of nitrogen atoms (N) in the protective layer (of carbon atoms (C) The laminate according to any one of (1) to (4), wherein the number of atoms / the number of nitrogen atoms (N) is 0.5 to 2.5.

  (6) The laminated body according to any one of (1) to (5), wherein the protective layer has a thickness of 10 nm to 50 nm.

  According to the present invention, in order to express solar shading and heat insulation at a high level, even when a thinned protective layer is adopted, it is excellent in durability, and deterioration of the metal thin film is suppressed. It is possible to provide a suitable laminate.

  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 at least a first metal oxide thin film, a metal thin film mainly composed of silver, and zinc and tin. And a second metal oxide thin film mainly composed of a composite metal oxynitride from the substrate side in this order, and with respect to zinc (Zn) and tin (Sn) in the second metal oxide thin film The equivalent ratio of nitrogen (N) (3N / (2Zn + 4Sn)) is 0.005 to 0.030.

  The substrate used in the present invention is not particularly limited as long as it has excellent visible light transmission performance. However, when used for window pasting applications, it is a synthetic resin from the viewpoint of flexibility and excellent handleability. It is preferable that it is a film containing. Here, the synthetic resin is preferably, for example, polyethylene terephthalate, polycarbonate, acrylic, nylon, etc., and at least a first metal oxide thin film, a metal thin film mainly composed of silver, and a composite metal oxynitriding of zinc and tin Considering the heat resistance, cost, etc. required for forming a heat ray reflective layer (hereinafter referred to as a heat ray reflective layer) comprising the second metal oxide thin film mainly comprising an object in this order from the substrate side, polyethylene Terephthalate is more preferred. In addition, from the viewpoint of improving the adhesion between the substrate and the heat ray reflective layer, an easy adhesion layer is provided on the surface of the substrate on which the heat ray reflective layer is laminated, or surface treatment such as corona treatment, plasma treatment, saponification, etc. It is preferable to apply. Here, examples of the resin used for the easy adhesion layer include polyester, acrylic, and urethane. Although there is no restriction | limiting in particular about the thickness of a base material, When the mechanical strength, heat resistance, and the handleability at the time of using for a window sticking use are considered, it is preferable that it is 10-150 micrometers. By making the thickness 10 μm or more, generation of wrinkles due to thermal contraction can be suppressed in the surface treatment process of the base material and the heat ray reflective layer forming process, and the window breakage prevention performance and crime prevention performance are imparted. can do. On the other hand, when the thickness is 150 μm or less, the amount of necessary materials can be reduced, leading to a reduction in environmental load, and the flexibility of the laminate improves, so that the laminate can be applied to windows and the like. The workability can be made better.

  Next, the heat ray reflective layer includes at least a first metal oxide thin film, a metal thin film mainly composed of silver, and a second metal oxide thin film in this order from the base material side. By reflecting infrared rays with a metal thin film as a component, the solar heat insulation and heat insulation properties are expressed, and the first and second metal oxides reduce the interface reflection of visible light and express visible light transmission performance. Can do.

  In addition, the second metal oxide thin film located on the metal thin film containing silver as a main component, that is, on the protective layer side of the metal thin film is a metal thin film when applied and used as a window pasting film, like the protective layer. It can also serve as a protective layer that suppresses silver degradation. On the other hand, since the first metal oxide thin film is located on the base side of the metal thin film, the construction liquid sprayed between the window glass and the base material is protected from the back side of the base material when it is applied as a window pasting film. When evaporating in the layer direction, it can play a role of suppressing deterioration of silver from this construction liquid. That is, the second metal oxide thin film plays a role of suppressing silver deterioration during construction and use, and the first metal oxide thin film can play a role of mainly suppressing silver deterioration due to construction.

  From the viewpoint described above, that is, from the viewpoint that the performance of the second metal oxide thin film as a protective layer for suppressing the deterioration of silver of the metal thin film is extremely excellent, in the laminate of the present invention, the second The metal oxide thin film is mainly composed of a composite metal oxynitride of zinc and tin, and the equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in consideration of the equivalent of each element ( 3N / (2Zn + 4Sn)) is 0.005 to 0.030. This equivalent ratio is analyzed by the number of atoms of nitrogen, zinc, and tin contained in the second metal oxide thin film by the X-ray photoelectron spectroscopy (XPS) method, as described in the Examples section. Is calculated by substituting the value of the number of atoms for N, Zn, and Sn of 3N / (2Zn + 4Sn), respectively. Here, the main component is 50% by mass when the content of the composite metal of zinc and tin contained in the second metal oxide thin film is 100% by mass of all the components of the second metal oxide thin film. As long as the content of the oxynitride of the composite metal of zinc and tin exceeds 50% by mass, a metal other than zinc and tin may be included, and the second metal oxide The thin film may be composed only of a composite metal oxynitride of zinc and tin. The first metal oxide thin film preferably has the same composition as the second metal oxide thin film.

  When the second metal oxide thin film contains, as a main component, a composite metal oxynitride of zinc and tin having a high refractive index at a wavelength of 500 nm, the visible light transmission performance of the laminate can be improved. Furthermore, when these compounds contain a specific amount of nitrogen, the performance as a protective layer for suppressing deterioration of silver contained in the metal thin film becomes more remarkable. The second metal oxide thin film contains a composite metal oxynitride of zinc and tin as a main component, and the second metal oxide thin film contains a specific amount of nitrogen. It is presumed that the degree of freedom at the molecular level in the film is increased, distortion is eliminated, and the film is densified, thereby improving the barrier property against a substance that degrades silver in the metal thin film of the film. The effect is that the above-mentioned value of 3N / (2Zn + 4Sn) is expressed from 0.005 or more, and the lower limit of the value of 3N / (2Zn + 4Sn) is 0.010 or more from the viewpoint that this effect becomes more excellent. It is particularly preferred. Furthermore, by setting the value of 3N / (2Zn + 4Sn) to 0.010 or more, the adhesion between the second metal oxide thin film and the metal thin film tends to be improved. Here, the adhesion between the layers of the second metal oxide thin film and the metal thin film tends to be lower at the end of the laminate than at the portions other than the end of the laminate. And in the laminate excellent in the adhesion between the second metal oxide thin film and the metal thin film, the peeling of the second metal oxide thin film at the end of the laminate can be further suppressed, so the end of the laminate It is also preferable from the point that corrosion from can be further suppressed. On the other hand, by setting the upper limit of (3N / (2Zn + 4Sn) to 0.030 or less, preferably 0.020 or less, the performance of the second metal oxide thin film as a protective layer that suppresses the deterioration of silver in the metal thin film is improved. Here, when there are many nitrogen atoms (3N / (2Zn + 4Sn)) exceeds 0.030, the reason why the function as a protective layer for suppressing the deterioration of silver contained in the metal thin film is reduced. In regard to, when the abundance of nitrogen atoms exceeds a certain level, the flexibility of the second metal oxide thin film decreases, and defects occur in the structure of the second metal oxide thin film during the winding process during manufacturing, etc. On the other hand, when the number of nitrogen atoms is small and the value of 3N / (2Zn + 4Sn) is less than 0.005, the function as a protective layer for suppressing deterioration of silver contained in the metal thin film is reduced. Visible In the case where the first metal oxide thin film is the same as the second metal oxide thin film, the above-mentioned first absorption is increased. The same can be said for metal oxide thin films.

  In addition, since the first and second metal oxide thin films contain oxygen, the visible light transmission performance of the laminate can be improved, and the adhesion with the metal thin film can be further improved. The durability as a window pasting film can be improved. Regarding the oxygen atom content of at least one of the first and second metal oxide thin films, the equivalent ratio of oxygen (O) to zinc (Zn) and tin (Sn) considering the equivalent of each element ( 2O / 2Zn + 4Sn)) is preferably 0.65 to 0.75. By setting this ratio to 0.65 or more, there can be obtained a laminate having no visible oxygen deficiency and excellent visible light transmission performance. On the other hand, by setting the equivalent ratio to 0.75 or less, nitrogen with respect to zinc (Zn) and tin (Sn) of the first and / or second metal oxide thin film having the equivalent ratio of 0.75 or less. The equivalent ratio (3N / (2Zn + 4Sn)) of (N) can be made higher, and the first and / or second metal oxide thin film has a barrier property against a substance that deteriorates silver of the metal thin film. It can be made excellent. The larger the value of the equivalent ratio of oxygen (O) to zinc (Zn) and tin (Sn), the more the zinc or tin is oxidized, and the zinc (Zn) of the first and second metal oxide thin films. ) And the equivalent ratio of nitrogen (N) to tin (Sn) (3N / (2Zn + 4Sn)) will be lower.

  Like the second metal oxide thin film provided in the present invention, a layer containing nitrogen can be obtained by forming a film in an atmosphere of nitrogen gas, and the layer containing oxygen can be obtained from oxygen gas or carbon dioxide gas. It can be obtained by forming a film in an atmosphere. However, in the film formation of the second metal oxide thin film containing nitrogen and oxygen, the oxygen gas contains only oxygen atoms in the molecule and is easy to bond with zinc or tin to form an oxide. From the viewpoint of increasing the value of the equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn), it is preferable to form a film in an atmosphere of carbon dioxide gas.

  The number of atoms of zinc, tin, nitrogen, etc. in the oxynitride of the composite metal of zinc and tin, which is the main constituent material of the second metal oxide thin film, is well-known such as X-ray photoelectron spectroscopy (XPS) method. It can measure using the method of this.

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

  The metal thin film used in the present invention is mainly composed of silver excellent in infrared reflection performance. Here, the main component means that the silver content contained in the metal thin film exceeds 50% by mass when all the components of the metal thin film are 100% by mass, and the silver content is 90% by mass or more. It is preferable that Further, for the purpose of improving the corrosion resistance of silver, it is also preferable to use an alloy in which one or more of gold, copper, palladium, bismuth, nickel, niobium, magnesium, zinc, tin and the like are added in addition to silver. Among these metals, it is particularly preferable to contain gold and / or palladium in addition to silver from the viewpoint of achieving both infrared reflection performance and corrosion resistance. Moreover, although there is no restriction | limiting in particular in content of gold | metal | money and / or palladium, From a viewpoint of corrosion resistance and cost, when all the components of a metal thin film are 100 mass%, a gold atom and a palladium atom are 2 mass in total. % Or more, and more preferably 3% by mass or more. The upper limit is preferably 5% by mass or less. If it is less, the effect of suppressing silver corrosion cannot be obtained. On the other hand, if the amount is too large, an improvement effect commensurate with the cost increase cannot be obtained only by an increase in cost. Although there is no restriction | limiting in particular about the thickness of a metal thin film, It is preferable to select suitably in the range of 5-20 nm in view of the required infrared reflective performance and visible light transmission performance. If the thickness is thin, the visible light transmission performance is excellent, but the infrared reflection performance is degraded. On the other hand, if it is too thick, the visible light transmission performance is lowered, the amount of metal used is increased, and this is not economically preferable.

  In addition, about the thickness of a metal thin film, the 1st, and 2nd metal oxide thin film, it can analyze by using well-known methods, such as a transmission electron microscope (TEM), or an optical film thickness meter, etc. suitably. . These metal thin films and the first and second metal oxide thin films can be formed by a vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method. It is preferable to use a sputtering method because of the wide variety of types and high quality films that can be obtained.

  Next, the protective layer used in the present invention has a function of protecting the metal thin film and the first and second metal oxide thin films, and is preferably a layer located on the outermost surface of the laminate. Therefore, when used as a windowed film for the protective layer, from the viewpoint of obtaining durability to maintain the quality of the windowed film during use, it is a metal thin film from atmospheric moisture and deposits such as harmful substances, condensed water, and dirt. The barrier property which suppresses deterioration of is required. Furthermore, since the protective layer is required to have high transparency without hindering the infrared reflection function of the metal thin film, it is necessary to express the performance with a thin film.

  From the viewpoint described above, the protective layer contains carbon, nitrogen, oxygen, and silicon, and the ratio of the number of atoms of carbon atoms (C) and nitrogen atoms (N) contained in the protective layer ( The number of carbon atoms (C) / nitrogen atom (N)) is preferably 0.5 to 2.5. By including carbon and nitrogen in addition to oxygen and silicon in the protective layer, the degree of freedom is increased at the molecular level, the strain is eliminated, the protective layer is densified, and the barrier property of the protective layer is improved. The 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 atoms of carbon atoms (C) and nitrogen atoms (N) contained in the protective layer (number of carbon atoms (C) / number of nitrogen atoms (N)) is 0.5 to 0.5. It becomes more prominent in the range of 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 protective layer is preferably 10 nm or more, and more preferably 15 nm or more. By making the thickness of the protective layer 10 nm or more, the scratch resistance of the protective layer can be further improved, the excellent barrier properties of the protective layer can be ensured, and sufficient durability as a laminate can be obtained. . The said effect becomes more remarkable by thickness being 15 nm or more. Moreover, it is preferable that the thickness of a protective layer is 50 nm or less, and it is more preferable that it is 30 nm or less. By making the thickness of the protective layer 50 nm or less, the visible light transmission performance can be further improved, and the modified emissivity (infrared absorptance) of the protective layer can be lowered. These protective layers can be formed by vapor deposition methods such as vacuum deposition, sputtering, CVD, ion plating, etc., but metal thin films and first and second metal oxide thin films It is preferable to form a film by a sputtering method in the same manner as described above.

  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 was cut into a 50 mm square.
(2) An adhesive layer was formed on the base-side surface of the film cut in the item (1).
(3) Next, it was bonded to 3 mm thick float glass through the adhesive layer formed in the item (2). The bonding was performed according to “Glass Film Construction Manual 3rd Edition (published by Japan Window Film Industry Association)”.

B. Equivalent ratio of nitrogen to zinc and tin in the first or second metal oxide thin film (1) Measurement method / calculation method i) Between each element using an X-ray photoelectron spectrometer PHI5000 VersaProbeII (manufactured by ULVAC-PHI Co., Ltd.) The spectrum of the binding energy peak of was measured. At this time, the measurement was performed after all the layers stacked on the layer to be measured were removed by etching.
ii) Calculate the number of atoms of the element contained in the first or second metal oxide thin film from the spectrum, and consider the equivalent of each element to N, Zn, and Sn in the formula of 3N / (2Zn + 4Sn) By substituting the number of nitrogen atoms, the number of zinc atoms, and the number of tin atoms, respectively, the equivalent ratio of nitrogen to zinc and tin (3N / (2Zn + 4Sn)) was calculated. In addition, the number of atoms of the element contained in the first or second metal oxide thin film is calculated from the spectrum, and the equivalent of each element is taken into consideration, and oxygen of 2O / (2Zn + 4Sn) is added to O, Zn, and Sn. The equivalent ratio of oxygen (2O / (2Zn + 4Sn)) was calculated by substituting the number of atoms, the number of zinc atoms, and the number of tin atoms, respectively.

C. Ratio of the number of atoms contained in the protective layer (1) Measurement method / calculation method i) The spectrum of the bond energy peak between each element was measured using an X-ray photoelectron spectrometer PHI5000 VersaProbeII (manufactured by ULVAC-PHI Co., Ltd.). In addition, since the element which is not originally contained may be detected due to the contamination of the analyzer or the test specimen, the measurement was performed after etching the surface of the protective layer. Furthermore, since carbon (C) is easily detected as a contaminant, a test body that does not contain carbon in the protective layer (carbon is not introduced in the manufacturing process) may be used as a blank.
ii) The number of atoms of the elements constituting the protective layer was calculated from the spectrum, and calculated by dividing the number of carbon (C) atoms by the number of nitrogen (N) atoms.

D. Barrier properties (durability)
(1) Measurement method i) 50 μl of an aqueous NaCl solution (0.5 wt%) is dropped on the protective layer side surface of the laminate of the test specimen for evaluation prepared in Section A, and the temperature is kept at 60 ° C. , Humidity 90%) for 3 hours.
ii) After standing for 3 hours, the sample was taken out, and the state of corrosion of the laminate of the test specimen for evaluation was observed with a shape measurement laser microscope VK-X110 (manufactured by Keyence Corporation). In addition, the objective lens used 10 times.
(2) Criteria “A”: no corrosion (discoloration), no peeling of metal layer, “B”: slight corrosion (discoloration), no peeling of metal layer, “C”: corrosion (discoloration), metal There is delamination. Here, although the corrosion of silver in the metal thin film progresses slightly, a discoloration point appears as it progresses, and further, when the corrosion of silver in the metal thin film progresses greatly, peeling of the metal layer appears.

E. Far-infrared reflectivity (1) standard: compliant with JIS R3106-1998 (2) Measurement method i) Spectrophotometer “IR Prestige-21 (manufactured by Shimadzu Corporation)”, specular reflection measurement unit “SRM-8000A” The spectral reflectance of the test specimen for evaluation at a wavelength of 5 to 25 μm was measured using “manufactured by Shimadzu Corporation”. An Al vapor deposition mirror was used for the standard plate. ii) Spectral reflectances at selected wavelengths of numbers λ1 (wavelength 5.5 μm) to λ30 (wavelength 50 μm) described in Appendix 3 of the JIS text were extracted from the spectral reflectances. In addition, the value of (lambda) 24 (wavelength 23.3 micrometers) was used for the reflectance of (lambda) 25 (wavelength 25.2 micrometers)-(lambda) 30 (wavelength 50 micrometers). iii) Each of the extracted spectral reflectances is multiplied 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) The average value of the reflectance was taken as the far-infrared reflectance.
(3) Measurement conditions: Wavelength range “5 to 25 μm”, avodis coefficient “Happ-Genzel”, number of integrations “20 times”, resolution “4.0 cm ⁻¹ ”.

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

G. 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 were measured at 1 nm intervals. ii) After multiplying the transmittance by the weight coefficient described in the JIS text, the total value was calculated and made visible light transmittance (%).
(3) Measurement conditions: scan speed “high speed”, resolution capability “10 nm”.

H. Adhesion test (cross-cut method)
(1) Standard: Conforms to JIS K5600-5-6-1999 (2) Measurement method:
i) A cross-cut spacing spacer (Cortech Co., Ltd .: model number CROSSSCUT GUIDE 1.0) and a cutter knife are used to cut the test specimen for evaluation 6 times in the vertical direction and 6 times in the horizontal direction at 1 mm intervals (by this operation) 5 × 5 = 25 grids are produced). ii) A transparent pressure-sensitive adhesive tape (manufactured by Nitto Denko Corporation: 31B) is pressure-bonded onto the lattice prepared in i), and the pressure-bonded tape is peeled off in the direction of 60 degrees.
(3) Judgment Criteria Here, “no separation of the entire surface of the lattice” means that there is no lattice that completely separates the entire lattice of 25 squares. “There is a whole surface peeling of the lattice” means that at least a part of the lattice of 25 squares has a lattice that peels the whole surface. “No partial peeling of the lattice” indicates that no peeling occurs in a part of the lattice in all of the 25 square lattices. “With partial peeling of the lattice” indicates that at least a portion of the lattice of 25 squares is observed to be peeled off at a portion of the lattice. That is, in the test body with extremely excellent adhesion, the entire surface of the lattice is not peeled off, and the lattice is partially peeled off. In the test specimen with excellent adhesion, the occurrence of delamination is observed in a part of the lattice in at least a part of the 25-mass lattice, but the entire surface of the 25-mass lattice is not delaminated and the entire lattice is not exfoliated. In addition, there is partial peeling of the lattice. In the test piece with poor adhesion, peeling occurred on the entire surface of the lattice in at least a part of the lattice of 25 squares, indicating that the entire surface of the lattice was peeled off. It is clear that the adhesion of the specimen with the entire surface peeling of the grid is inferior to that of the specimen with the partial peeling of the grid. For specimens with peeling of the entire surface of the grid, there is no problem with the presence or absence of partial peeling of the grid.
“A”: no peeling of the entire grating and no partial peeling of the grating “B”: no peeling of the entire grating and part of the grating “C”: peeling of the entire grating.

[Example 1]
As the substrate, a hard coat film “Tough Top” (registered trademark) THS (manufactured by Toray Film Processing Co., Ltd.) was used.

  Next, a first metal oxide thin film 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: zinc = 65 mass%: 35 mass%. (The sputtering gas was argon: oxygen dioxide: nitrogen = 95%: 3.5%: 1.5% (flow rate ratio)). Subsequently, on the first metal oxide thin film, a sputtering target material having a silver content of 97% by mass and a gold content of 3% by mass is used. A metal thin film was formed (sputtering gas was argon = 100%). Further, a masking layer having a thickness of 2 nm is formed using the same sputtering target material as the first metal oxide thin film (sputtering gas is argon: oxygen = 98%: 2% (flow rate ratio)), and the metal thin film is formed. Masked. Next, a second metal oxide thin film having a thickness of 30 nm is formed on the masking layer using the same sputtering target material as the first metal oxide thin film (sputtering gas is argon: oxygen dioxide: nitrogen = 95). %: 3.5%: 1.5% (flow rate ratio)), and a heat ray reflective layer composed of the first metal oxide thin film / metal thin film / masking layer / second metal oxide thin film was formed on the substrate. .

  Next, a protective layer having a thickness of 25 nm is formed on the heat ray reflective layer using a Si sputtering target material (sputtering gas is argon: oxygen: carbon dioxide: nitrogen = 47%: 8%: 32%: 13%), A laminate was obtained.

[Example 2]
The same method as in Example 1 except that the sputtering gas used when forming the first and second metal oxide thin films was changed to argon: carbon dioxide: nitrogen = 90%: 7%: 3%. A laminate was obtained.

[Example 3]
Example 1 except that the sputtering gas used when forming the first and second metal oxide thin films was changed to argon: carbon dioxide: nitrogen = 85%: 10.5%: 4.5% A laminate was obtained in the same manner.

[Example 4]
The same method as in Example 1 except that the sputtering gas used when forming the first and second metal oxide thin films was changed to argon: carbon dioxide: nitrogen = 80%: 14%: 6%. A laminate was obtained.

[Example 5]
Example 1 except that the sputtering gas used when forming the first and second metal oxide thin films was changed to argon: carbon dioxide: nitrogen = 75%: 17.5%: 7.5% A laminate was obtained in the same manner.

[Example 6]
A laminate was obtained in the same manner as in Example 3 except that the sputtering gas for forming the first metal oxide thin film was changed to argon: oxygen = 90%: 10%.

[Example 7]
A laminated body is obtained in the same manner as in Example 3 except that the sputtering gas for forming the protective layer is changed to argon: oxygen: carbon dioxide: nitrogen = 73%: 5%: 15%: 7%. It was.

[Example 8]
A laminated body is obtained in the same manner as in Example 3 except that the sputtering gas for forming the protective layer is changed to argon: oxygen: carbon dioxide: nitrogen = 76%: 10%: 7%: 7%. It was.

[Comparative Example 1]
A laminate was obtained in the same manner as in Example 1 except that the sputtering gas for forming the first and second metal oxide thin films was changed to argon: oxygen = 90%: 10%.

[Comparative Example 2]
The same method as in Example 1 except that the sputtering gas used when forming the first and second metal oxide thin films was changed to argon: carbon dioxide: nitrogen = 90%: 8%: 2%. A laminate was obtained.

[Comparative Example 3]
A laminate was obtained in the same manner as in Example 1 except that the sputtering gas for forming the first and second metal oxide thin films was changed to argon: nitrogen = 50%: 50%.

  About each test body of Examples 1-5, using the measuring method mentioned above, the number of contained atoms, barrier property (durability), adhesiveness, far-infrared reflectance, solar heat acquisition rate, visible light transmittance, etc. were measured. A result is shown in Table 1, About each test body of Examples 6-8 and Comparative Examples 1-3, using the measuring method mentioned above, the number of contained atoms, barrier property (durability), adhesiveness, far-infrared reflectance, Table 2 shows the results of measurement of solar heat acquisition rate, visible light transmittance, and the like.

  Nitrogen is introduced into the first metal oxide thin film and the second metal oxide thin film, and the equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in each layer (3N / (2Zn + 4Sn)) is set to 0. 0.005 to 0.030, and the ratio of the number of carbon atoms (C) and the number of nitrogen atoms (N) as a protective layer (number of carbon atoms (C) / number of nitrogen atoms (N) ) Was excellent in durability, and the determination was “B” or more. Among them, Example 2 in which (3N / (2Zn + 4Sn)) of the first metal oxide thin film was set to 0.010 and (3N / (2Zn + 4Sn)) of the second metal oxide thin film was set to 0.011. Example 3 in which (3N / (2Zn + 4Sn)) was 0.017 in each of the first metal oxide thin film and the second metal oxide thin film, (3N / (2Zn + 4Sn)) of the first metal oxide thin film Example 4 in which 0.018 was 0.018 and (3N / (2Zn + 4Sn)) of the second metal oxide thin film was 0.019 was particularly excellent in durability, and the determination was “A”.

  Further, in Example 6 in which the second metal oxide thin film was formed by the same method as in Example 3 and the first metal oxide thin film without introducing nitrogen was used, the durability was judged as “B”. In comparison with Example 3, the durability tended to decrease.

  Further, the first and second metal oxide thin films were formed by the same method as in Example 3, and the number of carbon atoms (C) / nitrogen atoms (N) in the protective layer was 2.6. In Example 7 and Example 8 in which the number of carbon atoms (C) in the protective layer / the number of nitrogen atoms (N) is 0.2, the durability tends to be lower than in Example 3. The durability was “B” judgment.

  Moreover, about the adhesiveness, the determination in the test bodies of Examples 1 to 8 is “B” or more, and in particular, in Examples 2 to 5, 7, and 8 in which (3N / (2Zn + 4Sn)) is 0.010 or more. Was "A". 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.

  On the other hand, Comparative Example 1 in which the same protective layer as Example 1 was formed without introducing nitrogen into the second metal oxide thin film and the first metal oxide thin film was inferior in durability, and the durability was “C It was a judgment.

  Further, nitrogen is introduced into the second metal oxide thin film and the first metal oxide thin film, and the equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in each layer (3N / (2Zn + 4Sn)) Comparative Example 2 in which the protective layer was formed by the same method as in Example 1 and over 0.030, and Comparative Example 3 in which the protective layer was formed by the same method as in Example 1 were both durable. The durability was “C” judgment.

  Regarding the adhesion, Comparative Example 1 containing no nitrogen and Comparative Example 2 in which (3N / (2Zn + 4Sn)) was 0.002 were “B” determination, and Comparative Example 3 was “A” determination.

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 (6)

At least a substrate, a heat ray reflective layer, and a protective layer are provided in this order,
The heat ray reflective layer is based on at least a first metal oxide thin film, a metal thin film mainly composed of silver, and a second metal oxide thin film mainly composed of a composite metal oxynitride of zinc and tin. Prepared in this order from the side,
The laminated body whose equivalent ratio (3N / (2Zn + 4Sn)) of nitrogen (N) with respect to zinc (Zn) and tin (Sn) in said 2nd metal oxide thin film is 0.005-0.030.   The equivalent ratio (3N / (2Zn + 4Sn)) of nitrogen (N) to zinc (Zn) and tin (Sn) in the second metal oxide thin film is 0.010 to 0.030. 1. The laminate according to 1. The first metal oxide thin film is mainly composed of a composite metal oxynitride of zinc and tin,
The equivalent ratio (3N / (2Zn + 4Sn)) of nitrogen (N) to zinc (Zn) and tin (Sn) in the first metal oxide thin film is 0.005 to 0.030. Laminated body.   The equivalent ratio of nitrogen (N) to zinc (Zn) and tin (Sn) in the first metal oxide thin film (3N / (2Zn + 4Sn)) is 0.010 to 0.030. 3. The laminate according to 3. The protective layer contains carbon, nitrogen, oxygen and silicon;
The ratio of the number of carbon atoms (C) and the number of nitrogen atoms (N) in the protective layer (number of carbon atoms (C) / number of nitrogen atoms (N)) is 0.5-2. The laminate according to any one of claims 1 to 4, which is 5. The laminated body in any one of Claims 1-5 whose thickness of the said protective layer is 10 nm-50 nm.