JP2012207444A - Method for adjusting solar radiation in wire-reinforced window glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for adjusting solar radiation in a wire-reinforced window glass which can increase solar shading performance while securing the daylighting property.SOLUTION: Transparent rolling screen sheet materials 10 and 30 each comprises a screen base material 14 comprising a transparent high polymer film and a transparent laminate film 12 bonded to at least one surface of the screen base material 14, in which the transparent laminate film 12 comprises a laminate structure part 18 with solar shading performance at least on one surface of a film base material 16 comprising the transparent high polymer film. The transparent rolling screen sheet materials 10 and 30 are arranged on the indoor side along the indoor-side glass surface of a wire-reinforced window glass 40, apart from the indoor-side glass surface within a range of 1-300 mm.

Description

  The present invention relates to a solar radiation adjustment method suitable for the case where a meshed glass is used for a window glass of a building such as a building or a house or a window glass of a vehicle such as an automobile.

  Conventionally, measures for reducing the heat caused by solar radiation have been studied for the purpose of enhancing the comfort of buildings such as buildings and houses and vehicles such as automobiles. As one of such measures, there is a method of shielding the room by using a curtain or a blind for the window glass. Moreover, the method of suppressing the indoor temperature rise by a heat ray by using the window glass provided with the function to cut a heat ray is mentioned.

  Examples of the latter method include a method in which the glass laminate described in Patent Document 1 is used for a window glass. Patent Document 1 discloses a glass laminate in which a heat ray reflective layer is laminated on a glass substrate.

JP 2000-229380 A

  In a window glass of a building such as a building or a house, or a window glass of a vehicle such as an automobile, a net-like metal wire is embedded in the glass sheet or between a pair of glass sheets for the purpose of strengthening the glass, preventing crime, shielding electromagnetic waves, etc. Reticulated glass may be used.

  In the case of using meshed glass for the window glass, if the heat ray reflective layer is laminated on the glass substrate as in Patent Document 1 and the function of cutting the heat rays is given to the meshed window glass, the window glass can easily absorb solar radiation. Become. Since glass has poor thermal conductivity, the temperature difference between the portion of the window glass that has been exposed to solar radiation and the portion that has not received solar radiation may increase, and the glass may heat crack. For this reason, the glass with a net having a function of cutting heat rays in the glass cannot be used as the window glass. Similarly, when a functional film that cuts heat rays is directly attached to a window glass, the glass may similarly cause thermal cracking.

  On the other hand, curtains and blinds are intended to block light. Therefore, when using these, it is inferior to daylighting property. In the first place, curtains and blinds have a low function of shielding solar radiation.

  Thus, when netted glass is used for the window glass, the conventional measures to reduce the heat caused by solar radiation cannot be adopted. In such a case, the heat caused by solar radiation is reduced while ensuring daylighting. There was no effective method.

  The problem to be solved by the present invention is to provide a solar radiation adjusting method for a window glass with a net that can enhance the solar shading while securing the daylighting property.

  In order to solve the above-mentioned problems, a method for adjusting the solar radiation of a mesh window glass according to the present invention comprises a screen substrate made of a transparent polymer film, and a transparent laminated film bonded to at least one surface of the screen substrate. A transparent roll screen having a laminated structure portion having solar radiation shielding properties on at least one surface of a film substrate made of a transparent polymer film, wherein the transparent laminated film has a glass surface on the indoor side with respect to the netted window glass. It is a gist to arrange | position in the indoor side along the glass surface of an indoor side separated within the range of 1-300 mm from.

At this time, the transparent roll screen is preferably set to a visible light transmittance of 65% or more, a solar radiation shielding coefficient of 0.69 or less, a visible light reflectance of 10% or less, and a haze of 2.0 or less. The transparent roll screen has a visible light transmittance of 65% or more, a solar shading coefficient of 0.69 or less, a thermal conductivity of 5.0 W / m ² · K or less, a visible light reflectance of 10% or less, and a haze of 2.0 or less. It is preferable that it is set to.

  And it is preferable to arrange | position the said laminated structure part indoors rather than the said screen base material. At this time, it is preferable that the film base material of the transparent laminated film is further arranged on the screen base material side with respect to the laminated structure portion, and the laminated structure portion is arranged on the indoor side with respect to the film base material.

  And it is preferable that the said laminated structure part is comprised by what laminated | stacked the metal oxide layer and metal layer containing an organic content. Moreover, it is preferable to have a barrier layer mainly composed of a metal oxide on at least one surface of the metal layer. The metal oxide layer is preferably a titanium oxide layer. The metal layer is preferably a silver layer or a silver alloy layer. Moreover, it is preferable that the said barrier layer is mainly comprised from a titanium oxide.

  According to the solar radiation adjusting method of the mesh window glass according to the present invention, the interior side of the mesh window glass is separated from the indoor glass surface by a specific distance, and has solar radiation shielding properties along the indoor glass surface. Since the transparent roll screen is arranged, the solar radiation shielding property itself is not in close contact with the glass of the window glass, and heat due to the absorption of sunlight can be prevented from being transmitted to the window glass. . For this reason, when the countermeasure which reduces the heat by solar radiation is taken, it can suppress that the thermal crack of a mesh window glass generate | occur | produces. Therefore, it is possible to enhance the solar shading while securing the daylighting property.

  At this time, when the transparent roll screen has specific optical physical properties, it is particularly excellent in the effect of improving the sun shielding property while ensuring the daylighting property. Moreover, when the heat transmissivity of the said transparent roll screen is set to the specific range, it is excellent also in heat insulation. Therefore, heating efficiency can be improved when the heating device is used indoors for measures against cold such as winter.

  And if the said laminated structure part is arrange | positioned indoors rather than a screen base material, since a heat insulation effect is exhibited by the laminated structure part before heating heat is absorbed by a screen base material, heating efficiency can be improved. At this time, when the film base of the transparent laminated film is further arranged on the screen base side with respect to the laminated structure, and the laminated structure is arranged on the indoor side with respect to the film base, heating heat is applied to the film base. Since the heat insulating effect is exhibited by the laminated structure before being absorbed, the heating efficiency can be further improved.

  And when the said laminated structure part is comprised by what laminated | stacked the metal oxide layer and metal layer containing an organic content, since a laminated structure part is excellent in a softness | flexibility, it is excellent in the softness | flexibility of a transparent roll screen. . For this reason, it is excellent in the winding-up property of a transparent roll screen.

  And when the barrier layer mainly comprised from a metal oxide is formed in the at least one surface of the said metal layer, the spreading | diffusion by the solar radiation of the metal element which comprises each metal layer can be suppressed. Therefore, it becomes easy to maintain the visible light transmittance and the solar radiation shielding property over a long period of time, and it is possible to contribute to improvement of durability and reliability.

  Further, when the metal oxide layer is a titanium oxide layer, it is easy to obtain a relatively high refractive index, so that it is easy to improve visible light transmittance. Moreover, when the said metal layer is a silver layer or a silver alloy layer, it is excellent in the balance of visible light transmittance | permeability and solar radiation shielding property. Moreover, when the said barrier layer is mainly comprised from a titanium oxide, it is easy to suppress the spreading | diffusion by the solar radiation of a metal layer, such as silver, and heat.

It is sectional drawing which showed one Embodiment of the sheet material of the transparent roll screen applied to this invention. It is sectional drawing which showed other embodiment of the sheet | seat material of the transparent roll screen applied to this invention. It is sectional drawing which showed the example of application of the sheet material of the transparent roll screen for demonstrating the solar radiation adjustment method of the window glass with a mesh | network concerning this invention.

  Below, the solar radiation adjustment method (henceforth this solar radiation adjustment method) of the net window glass which concerns on this invention is demonstrated in detail.

  This solar radiation adjustment method is a method of performing solar radiation adjustment by using a specific transparent roll screen (hereinafter, also referred to as the present roll screen) for a mesh window glass.

  The window glass with a mesh is configured by embedding a mesh-like metal wire in a sheet glass or between a pair of sheet glasses. Examples of the glass include normal float glass, semi-tempered glass, and tempered glass. What is necessary is just to determine the thickness of glass suitably according to a use etc.

  This roll screen is composed of a sheet material and a winding member for winding the sheet material. As the winding member, a known winding member conventionally known in a roll screen can be used. The sheet material of this roll screen is composed of a screen base material and a transparent laminated film bonded to the screen base material. A transparent laminated film is comprised from what was provided with the film base material and the laminated structure part laminated | stacked on the film base material. A film base material is a base material used as the base for forming a laminated structure part. The laminated structure has a function of shielding solar radiation. The laminated structure part may be formed only on one side of the film substrate, or may be formed on both sides.

  In this roll screen, a transparent polymer film is used as the screen substrate and the film substrate of the transparent laminated film in order to ensure transparency. Moreover, the solar radiation shielding function is obtained by the laminated structure part of the transparent laminated film.

  The transparent polymer film constituting the screen base material has excellent visible light permeability in order to ensure daylighting. Examples of such a polymer material include polyethylene terephthalate (PET) and polycarbonate (PC). The thickness of the screen base material is preferably about 10 to 200 μm from the viewpoint of obtaining sufficient durability and rigidity during operation of the roll screen and the like, and excellent flexibility. More preferably, it is 50-150 micrometers, More preferably, it is 75-125 micrometers.

  As the transparent polymer film constituting the film substrate of the transparent laminated film, any film can be used as long as it has excellent visible light permeability and can form a thin film on its surface without hindrance. For the film substrate of the screen substrate and the transparent laminated film, the same kind of polymer material may be used, or different kinds of polymer materials may be used.

  Specifically, as the polymer material of the transparent polymer film constituting the film substrate, for example, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, polyimide, Illustrate polymer materials such as polyamide, polybutylene terephthalate, polyethylene naphthalate, polysulfone, polyethersulfone, polyetheretherketone, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, cycloolefin polymer, etc. Can do. These may be contained alone or in combination of two or more. Also, two or more kinds of transparent polymers can be laminated and used.

  Among these, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, and the like can be exemplified as preferable from the viewpoint of excellent transparency, durability, workability, and the like.

  The thickness of the film substrate can be variously adjusted in consideration of the use, the type of material, optical characteristics, durability, and the like. The lower limit value of the thickness of the film substrate is preferably 25 μm or more, more preferably 50 μm or more, from the viewpoint that wrinkles are difficult to occur during processing and breakage is difficult. On the other hand, the upper limit value of the thickness of the film substrate is preferably 500 μm or less, more preferably 250 μm or less, from the viewpoints of easy winding and economy.

  The laminated structure part of the transparent laminated film may be abbreviated as a metal oxide layer (hereinafter sometimes abbreviated as “MO layer”) and a metal layer (hereinafter abbreviated as “M layer”). At least). Examples of the basic structure of the laminated structure portion include a laminated structure portion in which metal oxide layers (MO layers) containing organic components and metal layers (M layers) are alternately laminated. A barrier layer (hereinafter sometimes abbreviated as “B layer”) may be further formed on one or both surfaces of the metal layer (M layer).

  In a transparent laminated film, the metal oxide layer containing an organic component exhibits functions such as enhancing transparency (excellent transparency in the visible light region) by being laminated together with the metal layer. It can function as a refractive index layer. Here, the high refractive index means a case where the refractive index for light of 633 nm is 1.7 or more. In the transparent laminated film, the metal layer can mainly function as a solar radiation shielding layer. Since the transparent laminated film has such a laminated structure portion, it has good visible light transparency and solar shading.

  The laminated structure part can be formed by a laminating step of laminating a metal oxide layer containing an organic component and a metal layer on at least one surface of a film substrate of a transparent laminated film. Although the lamination process varies depending on the configuration of the above-described laminated structure portion, it can be basically formed by sequentially stacking each layer by a method optimal for forming each layer.

  The transparent laminated film preferably includes a protective layer on the laminated structure part for the purpose of protecting the laminated structure part from external damage and the like. Examples of the material constituting the protective layer include acrylic resins. The thickness of the protective layer is preferably in the range of 1 to 2 μm from the viewpoint of the balance between the protective function, adhesion, transparency, cost and the like. From the viewpoint of suppressing absorption of infrared rays, it is more preferably in the range of 1 to 1.5 μm, and still more preferably in the range of 1 to 1.2 μm.

  The protective layer may be composed of a single layer or a plurality of layers. When the protective layer is composed of a plurality of layers, the plurality of layers may be formed of a material containing different types of resins, or may be formed of a material containing the same type of resin. The protective layer is prepared by, for example, diluting the material in a suitable solvent and coating it on the transparent laminate using a coating method, and then, if necessary, suitable for the material such as heat, light, water, etc. It can be formed by curing with a curing means.

  The sheet material of the present roll screen often touches both outer sides due to the property used as a roll screen. For this reason, it is preferable that the sheet material of the present roll screen includes a hard coat layer as the outermost layer of the sheet material. The hard coat layer can be formed of, for example, a urethane material. The hard coat layer can be formed, for example, by coating a coating liquid containing a urethane material on a transparent polymer film.

  The sheet material of the present roll screen is constituted by using the screen base material and the transparent laminated film having the above-described configuration, etc., so that the visible light transmittance is 65% or more, the solar radiation shielding coefficient is 0.69 or less, and the visible light reflectance is 10%. Hereinafter, the haze is preferably set to 2.0 or less. When it has such an optical characteristic, it is especially excellent in the effect which improves solar shading property, ensuring lighting property.

  A preferable range of the visible light transmittance of the sheet material is 70% or more. Preferable ranges of the solar radiation shielding coefficient of the sheet material include 0.60 or less and 0.50 or less. Preferable ranges of the visible light reflectance of the sheet material include 9.5% or less and 9.0% or less. Preferable ranges of the haze of the sheet material include 1.5 or less and 1.0 or less.

  At this time, if the heat transmissivity of the roll screen is set within a specific range, the heat insulation is excellent. Therefore, heating efficiency can be improved when the heating device is used indoors for measures against cold such as winter.

  The suitable lamination | stacking form about the sheet | seat material of this roll screen which consists of the above structure is demonstrated. 1 and 2 are sectional views showing an embodiment of a sheet material of a transparent roll screen applied to the present invention.

  As shown in FIG. 1, in the sheet material 10 of the first embodiment, the transparent laminated film 12 is bonded to the screen base material 14 via the adhesive layer 22 on the protective layer 20 side of the transparent laminated film 12. For this reason, in the sheet material 10 of the first embodiment, the screen base material 14 and the film base material 16 are arranged outside the laminated structure portion 18, and the laminated structure portion 18 is sandwiched between them. Hard coat layers 24 a and 24 b as protective films are formed on the outer side of the screen base material 14 and the outer side of the film base material 16.

  As shown in FIG. 2, the sheet material 30 of the second embodiment is such that the transparent laminated film 12 is bonded to the screen substrate 14 via the adhesive layer 22 on the film substrate 16 side of the transparent laminated film 12. Yes. For this reason, in the sheet material 30 of the second embodiment, the screen base material 14 and the film base material 16 are arranged on the same surface side with respect to the laminated structure portion 18. In the sheet material 30 of the second embodiment, hard coat layers 24a and 24b as protective films are formed on the outside of the screen base material 14 and the protective layer 20, respectively.

  And the solar radiation preparation method using the sheet | seat materials 10 and 30 of such this roll screen is demonstrated. 3 (a) and 3 (b) are cross-sectional views showing an application example of the sheet material of the present roll screen for explaining the method for adjusting the solar radiation of the mesh window glass according to the present invention.

  As shown in FIGS. 3 (a) and 3 (b), the present solar radiation adjustment method separates the sheet materials 10 and 30 of the roll screen having such a configuration from the glass surface on the indoor side with respect to the netted window glass 40. Then, it is arranged on the indoor side along the glass surface on the indoor side. By separating the sheet materials 10 and 30 of the present roll screen from the glass surface of the mesh window glass 40, the solar radiation shielding property itself is not in close contact with the glass of the mesh window glass 40, and heat caused by absorption of solar radiation. Can be prevented from being transmitted to the mesh window glass 40. For this reason, when the countermeasure which reduces the heat by solar radiation is taken, it can suppress that the thermal crack of the mesh window glass 40 generate | occur | produces. Moreover, since the clearance gap between the meshed window glass 40 and the sheet | seat materials 10 and 30 of this roll screen becomes an air layer, this can improve heat insulation.

  The distance which separates the sheet | seat materials 10 and 30 of this roll screen with respect to the window glass 40 with a net | network is set in the range of 1-300 mm from the glass surface of an indoor side. When the distance separating the sheet materials 10 and 30 is short, heat due to absorption of solar radiation is easily transmitted from the sheet materials 10 and 30 of the present roll screen to the mesh window glass 40. On the other hand, when the distance separating the sheet materials 10 and 30 is long, heat due to the absorption of solar radiation becomes difficult to be transmitted to the mesh window glass 40, but the sheet materials 10 and 30 of the present roll screen and the mesh window glass 40 The solar radiation adjustment effect tends to be weakened by solar radiation incident from between. Moreover, as distance which separates the sheet | seat materials 10 and 30, More preferably, it exists in the range of 50-250 mm, More preferably, it exists in the range of 100-200 mm.

  Further, as shown in FIGS. 3A and 3B, the laminated structure 18 can be disposed on the indoor side of the screen base material 14 in any of the configurations of FIGS. The screen substrate 14 is made of a polymer material and may absorb infrared rays. In particular, PET and the like tend to absorb infrared rays. The laminated structure 18 has solar radiation shielding properties (near infrared reflectance) and also has far infrared reflectance. Then, by arranging the laminated structure portion 18 on the indoor side of the screen base material 14, the heat insulating effect is exhibited by the laminated structure portion 18 before the indoor heating heat is absorbed by the screen base material 14. Efficiency can be improved.

  Further, in the configuration of FIG. 2, the film base 16 of the transparent laminated film 12 is further arranged on the screen base 14 side than the laminated structure portion 18. For this reason, as shown in FIG. 3B, the laminated structure portion 18 is disposed on the indoor side of the film base material 16. Thereby, since the heat insulation effect is exhibited by the laminated structure portion 18 before the heating heat is absorbed by the film base material 16 formed of the polymer material, the heating efficiency can be further improved. And if it is the structure of FIG. 2, it is easy to set the heat | fever flow rate of the sheet | seat material 30 of this roll screen to the above-mentioned specific range. In the configuration of FIG. 2, as shown in FIG. 3B, the protective layer 20 is disposed on the indoor side of the laminated structure portion 18. For this reason, it is preferable to reduce the thickness of the protective layer 18 within a range of 1 to 1.5 μm, for example, from the viewpoint of suppressing the absorption of heating heat in the protective layer 18. More preferably, it is in the range of 1 to 1.2 μm.

  And when the said laminated structure part is comprised by what laminated | stacked the metal oxide layer and metal layer containing an organic content, since a laminated structure part is excellent in a softness | flexibility, it is excellent in the softness | flexibility of a transparent roll screen. . For this reason, it is excellent in the winding-up property of a transparent roll screen.

  Specifically, the basic unit of the laminated structure portion of the transparent laminated film is, for example, from the transparent polymer film side, MO layer | B layer / M layer / B layer, MO layer | M layer / B layer, MO layer │From the first basic unit such as B layer / M layer, or transparent polymer film side, B layer / M layer / B layer│MO layer, M layer / B layer│MO layer, B layer / M layer│MO layer The second basic unit can be exemplified. Note that “|” means a layer separation. “/” Means that the B layer is attached to the M layer.

  In the stacked structure portion, one or more basic units selected from the first basic units may be singularly or plurally stacked, or one or more basic units selected from the second basic units may be singular. Alternatively, a plurality of layers may be laminated repeatedly.

  Among these, from the viewpoint of easily suppressing the elements constituting the M layer from diffusing into the MO layer, the MO layer | B layer / M layer / B layer unit is determined as long as it is the first basic unit. In the case of the second basic unit, a unit of B layer / M layer / B layer | MO layer can be suitably selected.

  Of the thin film layers constituting the laminated structure, the thin film layer disposed in contact with the transparent polymer film is preferably a metal oxide layer (MO layer) containing an organic component. There are advantages such as excellent optical characteristics such as high visible light transmission and low visible light reflection. Moreover, the thin film layer arrange | positioned at the outermost layer among the thin film layers which comprise a laminated structure part is good in it being a metal oxide layer (MO layer) containing an organic content.

  The number of laminated structures can be varied in consideration of optical characteristics such as visible light transparency and solar shading, the material and film thickness of each thin film layer, manufacturing cost, and the like. The number of stacked layers is preferably 2 to 10 layers, and more preferably odd layers such as 3 layers, 5 layers, 7 layers, and 9 layers. More preferably, from the viewpoint of production cost and the like, the number of layers is 3 layers, 5 layers, and 7 layers.

  More specifically, the laminated structure is more easily formed from the MO polymer layer (first layer) | layer B from the transparent polymer film side, from the viewpoint of easy balance between transparency and solar shading and manufacturing cost reduction. / M layer / B layer (second layer) | MO layer (third layer), MO layer (first layer) | B layer / M layer (second layer) | MO layer (third layer), MO layer ( First layer) | M layer / B layer (second layer) | MO layer (third layer), MO layer (first layer) | M layer (second layer) | MO layer (third layer), etc. 3 Layer stack structure, MO layer (first layer) | B layer / M layer / B layer (second layer) | MO layer (third layer) | B layer / M layer / B layer (fourth layer) | MO Layer (5th layer), MO layer (1st layer) | B layer / M layer (2nd layer) | MO layer (3rd layer) | B layer / M layer (4th layer) | MO layer (5 layers) Eye), MO layer (first layer) | M layer / B layer (second layer) | MO layer (third layer) | M layer / B layer (fourth layer) ) | MO layer (5th layer), MO layer (1st layer) | M layer (2nd layer) | MO layer (3rd layer) | M layer (4th layer) | MO layer (5th layer), etc. 5 layer laminated structure, MO layer (1st layer) | B layer / M layer / B layer (2nd layer) | MO layer (3rd layer) | B layer / M layer / B layer (4th layer) │MO layer (5th layer) │B layer / M layer / B layer (6th layer) │MO layer (7th layer), MO layer (1st layer) │B layer / M layer (2nd layer) │ MO layer (3rd layer) | B layer / M layer (4th layer) | MO layer (5th layer) | B layer / M layer (6th layer) | MO layer (7th layer), MO layer (1 Layer) | M layer / B layer (2nd layer) | MO layer (3rd layer) | M layer / B layer (4th layer) | MO layer (5th layer) | M layer / B layer (6 layers) Eye) | MO layer (7th layer), MO layer (1st layer) | M layer (2nd layer) | MO layer (3rd layer) | M layer (4th layer) | MO layer (5th layer) │M layer (6th layer) │M It can be exemplified a seven-layer laminated structure, such as a layer (seventh layer) as a preferred structure.

  In addition, since the B layer is a thin film layer accompanying the M layer, the number of layers in the present application is counted as one M layer including the B layer and one MO layer.

  In the present film, each thin film layer may be formed at a time or may be formed in a divided manner. In addition, some or all of the thin film layers included in the stacked structure portion may be divided and formed. When each thin film layer is composed of a plurality of divided layers, the number of divisions may be the same or different for each thin film layer. Note that the divided layers are not counted as the number of stacked layers, but one thin film layer formed by aggregating a plurality of divided layers is counted as one layer.

  In this film, the composition or material of each thin film layer may be formed from the same composition or material, or may be formed from different compositions or materials. This also applies to the case where each thin film layer is composed of a plurality of divided layers. Moreover, the film thickness of each thin film layer may be substantially the same, and may differ for each film.

  Hereinafter, the metal oxide layer (MO layer) and metal layer (M layer) constituting the laminated structure part of the film, and the barrier layer (B layer) that may optionally constitute the laminated structure part of the film are described in more detail. Explained.

<Metal oxide layer>
Specific examples of the metal oxide include titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, magnesium oxide, and aluminum oxide. Products, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined.

As the metal oxide, titanium oxide (TiO ₂ ), ITO, zinc oxide (ZnO), tin oxide (SnO ₂ ), and the like are particularly preferable from the viewpoint of a relatively large refractive index with respect to visible light. It can be illustrated. These may be contained alone or in combination of two or more.

  Here, the metal oxide layer is mainly composed of the metal oxide described above, but may contain an organic component in addition to the metal oxide. It is because the softness | flexibility of this film can be improved more by containing an organic content. Specific examples of this type of organic component include components derived from the material for forming the metal oxide layer, such as components derived from the starting material of the sol-gel method.

  More specifically, examples of the organic component include organic metal compounds (including decomposition products thereof) such as metal alkoxides, metal acylates, and metal chelates of the above-described metal oxides, and the above organic metals. Examples thereof include various additives such as an organic compound (described later) that reacts with a compound to form an ultraviolet-absorbing chelate. These may be contained alone or in combination of two or more.

  The lower limit of the content of the organic component contained in the metal oxide layer is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably, from the viewpoint of easily imparting flexibility. It is good that it is 7% by mass or more. On the other hand, the upper limit of the content of the organic component contained in the metal oxide layer is preferably 30% by mass or less, from the viewpoint of easily ensuring a high refractive index and easily ensuring solvent resistance. More preferably, it is 25 mass% or less, More preferably, it is good in it being 20 mass% or less.

  In addition, content of the said organic content can be investigated using a X ray photoelectron spectroscopy (XPS) etc. Moreover, the kind of said organic content can be investigated using infrared spectroscopy (IR) (infrared absorption analysis) etc.

  The film thickness of the metal oxide layer can be adjusted in consideration of solar shading, visibility, reflection color, and the like.

  The lower limit of the film thickness of the metal oxide layer is preferably 10 nm or more, more preferably 15 nm, from the viewpoints of easily suppressing the red and yellow colors of the reflected color and easily obtaining high transparency. As described above, more preferably, it is 20 nm or more. On the other hand, the upper limit value of the film thickness of the metal oxide layer is preferably 90 nm or less, more preferably 85 nm, from the viewpoint that it is easy to suppress the green color of the reflected color and high transparency is easily obtained. Hereinafter, more preferably, it is 80 nm or less.

  The metal oxide layer having the above structure can be formed by either a vapor phase method or a liquid phase method. The liquid phase method does not need to be evacuated or use a large electric power as compared with the gas phase method. Therefore, it is advantageous in terms of cost, and is excellent in productivity.

  As the liquid phase method, a sol-gel method can be suitably used from the viewpoint of easily leaving an organic component.

  More specifically, as the sol-gel method, for example, a coating liquid containing a metal organometallic compound that constitutes a metal oxide is coated in a thin film shape, and this is dried as necessary to obtain a metal oxide. Examples include a method of forming a precursor layer of a physical layer and then hydrolyzing and condensing an organometallic compound in the precursor layer to synthesize an oxide of a metal constituting the organometallic compound. . According to this, a metal oxide layer containing a metal oxide as a main component and containing an organic component can be formed. Hereinafter, the above method will be described in detail.

  The coating liquid can be prepared by dissolving the organometallic compound in a suitable solvent. In this case, specific examples of the organometallic compound include organic compounds of metals such as titanium, zinc, indium, tin, magnesium, aluminum, zirconium, niobium, cerium, silicon, hafnium, and lead. Can do. These may be contained alone or in combination of two or more.

  Specific examples of the organometallic compound include metal alkoxides, metal acylates, and metal chelates of the above metals. A metal chelate is preferable from the viewpoint of stability in air.

  As the organic metal compound, in particular, a metal organic compound that can be a metal oxide having a high refractive index can be preferably used. Examples of such organometallic compounds include organic titanium compounds.

  Specific examples of the organic titanium compound include M-O-R bonds such as tetra-n-butoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, and tetramethoxy titanium (R represents an alkyl group). , M represents a titanium atom) and an acylate of titanium having an M—O—CO—R bond (R represents an alkyl group and M represents a titanium atom) such as isopropoxy titanium stearate. Examples thereof include titanium chelates such as diisopropoxy titanium bisacetylacetonate, dihydroxy bis lactato titanium, diisopropoxy bis triethanolaminato titanium, diisopropoxy bis ethyl acetoacetate titanium, and the like. These may be used alone or in combination. These may be either monomers or multimers.

  The content of the organometallic compound in the coating liquid is preferably from 1 to 20% by mass, more preferably from 3 to 20% from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. It is good if it exists in the range of 15 mass%, More preferably, 5-10 mass%.

  Specific examples of the solvent for dissolving the organometallic compound include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, acetonitrile, acetone and methyl ethyl ketone. Examples thereof include ketones such as tetrahydrofuran, cycloethers such as dioxane, acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene, and the like. These may be used alone or in combination.

  At this time, the amount of the solvent is preferably 5 to 100 times the amount of the solid content weight of the organometallic compound from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. More preferably, the amount is 7 to 30 times, and further preferably 10 to 20 times.

  When the amount of the solvent is more than 100 times, the film thickness that can be formed by a single coating becomes thin, and a tendency to require many coatings to obtain a desired film thickness is observed. On the other hand, when the amount is less than 5 times, the film thickness becomes too thick, and there is a tendency that the hydrolysis / condensation reaction of the organometallic compound does not proceed sufficiently. Therefore, the amount of the solvent is preferably selected in consideration of these.

  In addition, the coating liquid may contain water as necessary from the viewpoint of promoting hydrolysis by a sol-gel method and facilitating a high refractive index.

  The coating liquid is prepared, for example, by mixing an organometallic compound weighed so as to have a predetermined ratio, an appropriate amount of solvent, and other components added as necessary, with a stirring means such as a stirrer for a predetermined time. It can be prepared by a method such as stirring and mixing. In this case, the components may be mixed at a time or may be mixed in a plurality of times.

  In addition, as a coating method of the coating liquid, from the viewpoint of easy uniform coating, a micro gravure method, a gravure method, a reverse roll coating method, a die coating method, a knife coating method, a dip coating method, a spin coating method, a bar coating method, and the like. Various wet coating methods such as a coating method can be exemplified as suitable ones. These may be appropriately selected and used, and one or more may be used in combination.

  Further, when the coated coating liquid is dried, it may be dried using a known drying apparatus. In this case, as the drying conditions, specifically, for example, a temperature range of 80 ° C to 120 ° C, Examples of the drying time include 0.5 minutes to 5 minutes.

  Specific examples of means for hydrolyzing and condensing the organometallic compound in the precursor layer include various means such as irradiation with light energy such as ultraviolet rays, electron beams, and X-rays, and heating. can do. These may be used alone or in combination of two or more. Among these, preferably, irradiation with light energy, particularly ultraviolet irradiation can be suitably used. Compared with other means, it is possible to produce a metal oxide at a low temperature in a short time, and it is difficult to give heat load such as thermal degradation to the transparent polymer film (especially in the case of ultraviolet irradiation, There is an advantage that simple equipment can be used.) In addition, there is an advantage that an organic metal compound (including a decomposition product thereof) or the like is easily left as an organic component.

  In this case, specific examples of the ultraviolet irradiator to be used include a mercury lamp, a xenon lamp, a deuterium lamp, an excimer lamp, a metal halide lamp, and the like. These may be used alone or in combination of two or more.

  Further, the amount of light energy to be irradiated can be variously adjusted in consideration of the type of the organometallic compound mainly forming the precursor layer, the thickness of the coating layer, and the like. However, if the amount of light energy to be irradiated is too small, it is difficult to increase the refractive index of the metal oxide layer. On the other hand, if the amount of light energy to be irradiated is excessively large, the transparent polymer film may be deformed by heat generated during the light energy irradiation. Therefore, these should be noted.

When the light energy to be irradiated is ultraviolet light, the light amount is preferably 300 to 8000 mJ / cm at a measurement wavelength of 300 to 390 nm from the viewpoint of the refractive index of the metal oxide layer, damage to the transparent polymer film, and the like. ² , more preferably in the range of 500 to 5000 mJ / cm ² .

  When light energy irradiation is used as a means for hydrolyzing and condensing the organometallic compound in the precursor layer, it reacts with the organometallic compound in the coating liquid described above to absorb light (for example, absorbs ultraviolet rays). It is preferable to add an additive such as an organic compound that forms a chelate. When the additive is added to the coating solution that is the starting solution, light energy is irradiated where the light-absorbing chelate has been formed in advance, so that the metal oxide layer is formed at a relatively low temperature. This is because a high refractive index can be easily achieved.

  Specific examples of the additive include additives such as β diketones, alkoxy alcohols, and alkanolamines. More specifically, examples of the β diketones include acetylacetone, benzoylacetone, ethyl acetoacetate, methyl acetoacetate, diethyl malonate, and the like. Examples of the alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-methoxy-2-propanol, and the like. Examples of the alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. These may be used alone or in combination.

  Of these, β diketones are particularly preferred, and acetylacetone can be most preferably used.

  The blending ratio of the additive is preferably 0.1 to 1 mol of the metal atom in the organometallic compound from the viewpoint of easiness in increasing the refractive index and stability in the state of the coating film. It is good that it is in the range of 2 times mole, more preferably 0.5 to 1.5 times mole.

<Metal layer>
Specific examples of the metal of the metal layer include silver, gold, platinum, copper, aluminum, chromium, titanium, zinc, tin, nickel, cobalt, niobium, tantalum, tungsten, zirconium, lead, palladium, indium and the like. These metals, alloys of these metals, etc. can be illustrated. These may be contained alone or in combination of two or more.

  The metal is preferably silver or a silver alloy from the viewpoints of excellent visible light transparency, heat ray reflectivity, conductivity, and the like during lamination. More preferably, from the viewpoint of improving durability against environment such as heat, light, and water vapor, the main component is silver, and at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium is included. It should be a silver alloy. More preferably, a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), a silver alloy containing titanium (Ag—Ti alloy), or the like may be used. This is because there are advantages such as a large silver diffusion suppression effect and cost advantage.

  In the case of using a silver alloy containing copper, in addition to silver and copper, for example, other elements and inevitable impurities may be contained as long as they do not adversely affect the aggregation / diffusion suppression effect of silver.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Bi, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc. in Ag-Cu alloys Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing copper, the lower limit of the copper content is preferably 1 atomic% or more, more preferably 2 atomic% or more, and even more preferably 3 atomic% or more, from the viewpoint of obtaining the effect of addition. It is good to be. On the other hand, the upper limit of the copper content is preferably 20 atomic% or less, more preferably 10 atomic%, from the viewpoint of manufacturability such as easy to ensure high transparency and easy production of a sputtering target. Hereinafter, it is more preferable that it is 5 atomic% or less.

  Further, when using a silver alloy containing bismuth, in addition to silver and bismuth, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc., in Ag-Bi alloys Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing bismuth, the lower limit of the bismuth content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining the effect of addition. It may be 0.1 atomic% or more. On the other hand, the upper limit of the bismuth content is preferably 5 atomic% or less, more preferably 2 atomic% or less, and still more preferably 1 atomic% from the viewpoint of manufacturability such as easy production of a sputtering target. It is good to be below.

  In addition, when using a silver alloy containing titanium, other than silver and titanium, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, Bi, etc., Ag-Ti system Elements that can be precipitated as a single phase in the alloy; Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing titanium, the lower limit value of the titanium content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining an addition effect. It may be 0.1 atomic% or more. On the other hand, the upper limit of the content of titanium is preferably 2 atomic% or less, more preferably 1.75 atomic% or less, and still more preferably, from the viewpoint that a complete solid solution is easily obtained when it is formed into a film. Is preferably 1.5 atomic% or less.

  Note that the proportion of subelements such as copper, bismuth and titanium can be measured using ICP analysis. Further, the metal (including alloy) constituting the metal layer may be partially oxidized.

  The lower limit of the thickness of the metal layer is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more from the viewpoints of stability, heat ray reflectivity, and the like. On the other hand, the upper limit value of the thickness of the metal layer is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less, from the viewpoint of transparency of visible light, economy, and the like.

  Here, as a method for forming the metal layer, specifically, for example, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, MBE, laser ablation, thermal CVD, etc. Examples thereof include a vapor phase method such as a chemical vapor deposition method (CVD) such as a plasma CVD method. The metal layer may be formed using any one of these methods, or may be formed using two or more methods.

  Of these methods, sputtering methods such as a DC magnetron sputtering method and an RF magnetron sputtering method can be preferably used from the viewpoint of obtaining a dense film quality and relatively easy film thickness control.

  In addition, the metal layer may be oxidized within the range which does not impair the function of a metal layer by receiving the post-oxidation etc. which are mentioned later.

<Barrier layer>
In the present film, the barrier layer mainly has a barrier function that suppresses diffusion of elements constituting the metal layer into the metal oxide layer. Further, by interposing between the metal oxide layer and the metal layer, it is possible to contribute to improving the adhesion between them.

  Note that the barrier layer may have discontinuous portions such as floating islands as long as the diffusion can be suppressed.

  Specific examples of the metal oxide constituting the barrier layer include, for example, titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, and magnesium oxide. And aluminum oxide, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined. Note that the barrier layer may contain inevitable impurities in addition to the metal oxide.

  Here, the barrier layer is mainly composed of a metal oxide contained in the metal oxide layer from the viewpoint of excellent diffusion suppression effect of the metal constituting the metal layer and excellent adhesion. good.

More specifically, for example, when a TiO ₂ layer is selected as the metal oxide layer, the barrier layer is a titanium oxide layer mainly composed of an oxide of Ti that is a metal contained in the TiO ₂ layer. Good to have.

  When the barrier layer is a titanium oxide layer, the barrier layer may be a thin film layer formed as titanium oxide from the beginning, or a thin film layer formed by post-oxidation of a metal Ti layer, Alternatively, it may be a thin film layer formed by post-oxidizing a partially oxidized titanium oxide layer.

  The barrier layer is mainly composed of a metal oxide in the same manner as the metal oxide layer, but is set to be thinner than the metal oxide layer. This is because the diffusion of the metal constituting the metal layer occurs at the atomic level, so that it is not necessary to increase the film thickness to a sufficient level to ensure a sufficient refractive index. Moreover, by forming it thinly, the film-forming cost is reduced correspondingly, and it can contribute to the reduction of the manufacturing cost of this film.

  The lower limit value of the thickness of the barrier layer is preferably 1 nm or more, more preferably 1.5 nm or more, and still more preferably 2 nm or more, from the viewpoint of easily ensuring barrier properties. On the other hand, the upper limit value of the thickness of the barrier layer is preferably 15 nm or less, more preferably 10 nm or less, and still more preferably 8 nm or less, from the viewpoint of economy and the like.

  When the barrier layer is mainly composed of titanium oxide, the lower limit value of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is 1.0 / 4.0 or more from the viewpoint of barrier properties and the like. Preferably, 1.0 / 3.8 or higher, more preferably 1.0 / 3.5 or higher, even more preferably 1.0 / 3.0 or higher, most preferably 1.0 / 2.8. It is good to be above.

  When the barrier layer is mainly composed of titanium oxide, the upper limit of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is preferably 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, more preferably 1.0 / 1.0 or less, even more preferably 1.0 / 1.2 or less, most preferably 1 0.0 / 1.5 or less is preferable.

  The Ti / O ratio can be calculated from the composition of the layer. As a composition analysis method of the layer, energy dispersive X-ray fluorescence analysis (EDX) can be preferably used from the viewpoint of enabling comparatively accurate analysis of the composition of an extremely thin thin film layer.

  A specific composition analysis method will be described. First, using an ultrathin section method (microtome) or the like, a test piece having a thickness of 100 nm or less in the cross-sectional direction of the laminated structure including the layer to be analyzed is prepared. Next, the position of the laminated structure portion and the layer is confirmed with a transmission electron microscope (TEM) from the cross-sectional direction. Next, an electron beam is emitted from the electron gun of the EDX apparatus and is incident on the vicinity of the center of the film thickness of the layer to be analyzed. Electrons incident from the surface of the test specimen enter to a certain depth and generate various electron beams and X-rays. By detecting and analyzing characteristic X-rays at this time, the constituent elements of the layer can be analyzed.

  In this film, the gas phase method can be suitably used as the barrier layer from the viewpoint that a dense film can be formed and a thin film layer of about several nm to several tens of nm can be formed with a uniform film thickness.

  Specific examples of the vapor phase method include physical vapor deposition methods (PVD) such as vacuum deposition, sputtering, ion plating, MBE, and laser ablation, thermal CVD, and plasma CVD. Examples thereof include chemical vapor deposition (CVD) and the like. As the vapor phase method, a sputtering method such as a DC magnetron sputtering method or an RF magnetron sputtering method is preferable from the viewpoint of excellent adhesion at the film interface as compared with a vacuum deposition method and the like and easy control of the film thickness. Can be used.

  Note that each barrier layer that can be included in the stacked structure portion may be formed by using any one of these vapor phase methods, or by using two or more methods. It may be formed.

  The barrier layer may be formed as a metal oxide layer from the beginning by using the above-described vapor phase method, or a metal layer or a partially oxidized metal oxide layer is once formed. Later, it can be formed by oxidizing it afterwards. The partially oxidized metal oxide layer refers to a metal oxide layer that has room for further oxidation.

  When forming a metal oxide layer from the beginning, specifically, for example, a gas containing oxygen as a reactive gas is mixed with an inert gas such as argon or neon as a sputtering gas, and the metal and oxygen are mixed. A thin film may be formed while reacting (reactive sputtering method). For example, when a titanium oxide layer having the Ti / O ratio is obtained by using the reactive sputtering method, the oxygen concentration in the atmosphere (the volume ratio of the gas containing oxygen to the inert gas) is the film thickness range described above. The optimum ratio may be appropriately selected in consideration of the above.

  On the other hand, after forming a metal layer or a partially oxidized metal oxide layer and then post-oxidizing it, specifically, after forming the above-described laminated structure on the transparent polymer film, What is necessary is just to post-oxidize the metal layer in a laminated structure part, or the metal oxide layer partially oxidized. Note that a sputtering method or the like may be used for forming the metal layer, and the above-described reactive sputtering method or the like may be used for forming the partially oxidized metal oxide layer.

  Examples of the post-oxidation technique include heat treatment, pressure treatment, chemical treatment, and natural oxidation. Of these post-oxidation techniques, heat treatment is preferable from the viewpoint of enabling post-oxidation relatively easily and reliably. Examples of the heat treatment include, for example, a method in which the transparent polymer film having the laminated structure described above is present in a heating atmosphere such as a heating furnace, a method of immersing in warm water, a method of microwave heating, Examples thereof include a method of energizing and heating the metal layer, the partially oxidized metal oxide layer, and the like. These may be performed in combination of one or two or more.

  As heating conditions at the time of the heat treatment, specifically, for example, preferably 30 ° C. to 60 ° C., more preferably 32 ° C. to 57 ° C., more preferably 35 ° C. to 55 ° C., heating When present in the atmosphere, the heating time is preferably selected from 5 days or longer, more preferably 10 days or longer, and even more preferably 15 days or longer. This is because the post-oxidation effect, the suppression of thermal deformation and fusion of the transparent polymer film, and the like are good within the above heating conditions.

  The heating atmosphere during the heat treatment is preferably an atmosphere containing oxygen or moisture, such as in the air, a high oxygen atmosphere, or a high humidity atmosphere. Particularly preferably, it is in the air from the viewpoint of manufacturability and cost reduction.

  When the post-oxidation thin film described above is included in the laminated structure portion, since the moisture and oxygen contained in the metal oxide layer are consumed during post-oxidation, the metal oxidation is performed even when exposed to sunlight. The physical layer becomes difficult to chemically react. Specifically, for example, when the metal oxide layer is formed by a sol-gel method, since the moisture and oxygen contained in the metal oxide layer are consumed during post-oxidation, the metal oxide layer The starting material (metal alkoxide, etc.) by the sol-gel method remaining in the layer and moisture (adsorbed water, etc.), oxygen, etc. are difficult to undergo a sol-gel curing reaction by sunlight. Therefore, it is possible to relieve internal stress caused by volume change such as curing shrinkage, and it is easy to suppress interfacial peeling of the laminated structure portion, and to improve durability against sunlight.

  Hereinafter, the present invention will be described in detail using examples.

<Preparation of transparent laminated film (1)>
(Preparation of coating solution)
A coating solution used for forming a TiO ₂ layer by a sol-gel method was prepared. That is, tetra-n-butoxytitanium tetramer (manufactured by Nippon Soda Co., Ltd., “B4”) as titanium alkoxide, and acetylacetone as an additive that forms an ultraviolet-absorbing chelate, n-butanol and isopropyl It mix | blended with the mixed solvent with alcohol, and this was mixed for 10 minutes using the stirrer, and the coating liquid was prepared. At this time, the composition of tetra-n-butoxy titanium tetramer / acetylacetone / n-butanol / isopropyl alcohol was 6.75% by mass / 3.38% by mass / 59.87% by mass / 30.00% by mass, respectively. did.

(Lamination of each layer)
A TiO ₂ layer was formed as a first layer on one side of a 50 μm thick polyethylene terephthalate film (Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) by the following procedure.

That is, the coating liquid was continuously applied to the PET surface side of the PET film with a gravure roll having a predetermined groove volume using a micro gravure coater. Subsequently, the coating film was dried at 100 ° C. for 80 seconds using an in-line drying furnace to form a precursor layer of TiO ₂ layer. Then, using an in-line ultraviolet irradiator [high pressure mercury lamp (160 W / cm)], the precursor layer was continuously irradiated with ultraviolet rays for 1.5 seconds at the same linear velocity as that during the coating. Thus, a TiO ₂ layer (first layer) was formed on the PET film by a sol-gel method using ultraviolet energy during sol-gel curing (hereinafter sometimes abbreviated as “(sol gel + UV)”).

Next, each thin film constituting the second layer was formed on the first layer. That is, a lower metal Ti layer was formed by sputtering on the first TiO ₂ layer using a DC magnetron sputtering apparatus. Next, an Ag—Cu alloy layer was formed on the lower metal Ti layer by sputtering. Next, an upper metal Ti layer was formed on the Ag—Cu alloy layer by sputtering.

At this time, the film formation conditions of the upper and lower metal Ti layers were as follows: Ti target (purity 4N), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas: Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds.

The film formation conditions of the Ag—Cu alloy thin film are as follows: Ag—Cu alloy target (Cu content: 4 atom%), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas: Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds.

Next, as the third layer, a TiO ₂ layer by (sol gel + UV) was formed on the _second layer. Here, the film forming procedure according to the first layer is performed twice to obtain a predetermined film thickness.

  Next, as the fourth layer, each thin film constituting the fourth layer was formed on the third layer. Here, a film forming procedure according to the second layer was performed.

However, when the Ag—Cu alloy thin film was formed, the film formation conditions described above were as follows: Ag—Cu alloy target (Cu content: 4 atomic%), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas : Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.8 (kW), and film formation time: 1.1 seconds, thereby changing the film thickness.

Next, as the fifth layer, a TiO ₂ layer having the same configuration as the third layer (sol gel + UV) was formed on the fourth layer.

  Next, as the sixth layer, each thin film having the same configuration as the second layer was formed on the fifth layer.

Next, as the seventh layer, a TiO ₂ layer by (sol gel + UV) was formed on the sixth layer. Here, a predetermined film thickness is obtained by performing the film formation procedure according to the first layer once.

  Thereafter, the transparent laminated film obtained through the above-described lamination step is heat-treated in a heating furnace at 40 ° C. for 300 hours, so that the metal Ti layer / Ag—Cu alloy layer / metal contained in the laminated structure portion. The Ti layer (2, 4, 6th layer) was post-oxidized.

(Formation of protective layer)
An ultraviolet curable acrylic resin (manufactured by DIC Graphics, “UC Sealer TE014”) was diluted with MEK to a concentration of 20% to prepare a coating solution. Next, the prepared coating liquid was applied to the surface of the laminated structure part of the film with the laminated structure part produced as described above, dried at 100 ° C. for 2 minutes, and further irradiated with ultraviolet rays of 400 mJ / cm ² . This formed the protective layer which consists of an acrylic resin (hardened | cured material) on the surface of a transparent laminated part.

  Thus, a transparent laminated film (1) having a 7-layer laminated structure was produced.

<Preparation of transparent laminated film (2)>
A transparent laminated film (2) having a 7-layer laminated structure was produced in the same manner as the transparent laminated film (1) except that the thickness of the protective layer was changed.

<Preparation of transparent laminated film (3)>
A transparent laminated film (3) having a three-layer laminated structure is produced in the same manner as the transparent laminated film (2) except that the third layer is formed in the same procedure as the lamination procedure of each layer of the transparent laminated film (1). did.

<Production of Roll Screen Sheet Material (1)>
The protective layer side of the transparent laminated film (1) was bonded to a polyethylene terephthalate film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) (adhesive layer thickness). 22 μm). Subsequently, a UV curable hard coat agent (“LCH” manufactured by Toyo Ink Co., Ltd.) was applied to both outer side surfaces, dried and cured to form a hard coat layer. Thus, a roll screen sheet material (1) was produced.

<Production of Roll Screen Sheet Material (2)>
A roll screen sheet material (2) was produced in the same manner as the roll screen sheet material (1) except that the PET film side of the transparent laminated film (1) was bonded to the polyethylene terephthalate film using an adhesive.

<Production of Roll Screen Sheet Material (3)>
In the same manner as the production of the roll screen sheet material (2) except that the transparent laminated film (2) having a three-layer laminated structure is used instead of the transparent laminated film (1) having a seven-layer laminated structure, a roll A screen sheet material (3) was produced.

  Table 1 shows the detailed layer structure of the transparent laminated films (1) to (3). Table 2 shows the detailed layer structure of the sheet materials (1) to (3). In addition, Table 2 summarizes the physical property data of the sheet materials (1) to (3). The measuring method is as follows.

<Visible light transmittance>
In accordance with JIS A5759, a transmission spectrum with a wavelength of 300 to 1000 nm was measured using a spectrophotometer (“UV3100” manufactured by Shimadzu Corporation), and the visible light transmittance was calculated.

<Sunlight shielding coefficient>
Based on JIS R3106, the vertical emissivity of the glass surface and the film surface was calculated | required, and the solar radiation shielding coefficient was calculated | required based on JISA5759.

<Visible light reflectance>
In accordance with JIS A5759, a spectrophotometer (“UV3100” manufactured by Shimadzu Corporation) was used to measure a reflection spectrum at a wavelength of 300 to 1000 nm, and the visible light reflectance was calculated.

<Haze>
Based on JIS K7105, the haze value was calculated | required using the haze meter (Suga Test Instruments Co., Ltd. product HGM-2DP).

<Heat transmissibility>
Based on JIS R3106, the vertical emissivity of the glass surface and the film surface was determined, and the thermal transmissivity was determined based on JIS A5759.

According to the sheet material (1), the visible light transmittance is 65% or more, the solar radiation shielding coefficient is 0.69 or less, the visible light reflectance is 10% or less, and the haze is 2.0 or less. For this reason, it turns out that it is highly transparent and is excellent in solar shading. According to the sheet material (2), the visible light transmittance is 65% or more, the solar radiation shielding coefficient is 0.69 or less, the thermal conductivity is 5.0 W / m ² · K or less, the visible light reflectance is 10% or less, and the haze is 2.0. Satisfies the following: For this reason, it turns out that it is highly transparent, is excellent in solar radiation shielding property, and is excellent also in heat insulation. According to the sheet material (3), the visible light transmittance is 65% or more, the thermal conductivity is 5.0 W / m ² · K or less, and the haze is 2.0 or less. For this reason, it turns out that it is highly transparent and excellent in heat insulation.

  Therefore, by using these sheet materials, it is possible to reduce the heat caused by solar radiation, reduce the cold in winter, or improve the heating efficiency while ensuring the daylighting property. And, by disposing the transparent roll screen having this sheet material in a range of 1 to 300 mm from the glass surface on the indoor side with respect to the window glass, the indoor roll glass is disposed on the indoor side along the glass surface on the indoor side. Such solar radiation adjustment can be performed without causing thermal cracking of the window glass.

  Although the embodiments and examples of the present invention have been described above, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. .

DESCRIPTION OF SYMBOLS 10,30 Roll screen sheet material 12 Transparent laminated film 14 Screen base material 16 Sheet base material 18 Laminated structure part

Claims (10)

  A screen substrate made of a transparent polymer film, and a transparent laminated film bonded to at least one surface of the screen substrate, wherein the transparent laminated film is formed on at least one surface of the film substrate made of a transparent polymer film. The transparent roll screen having a structure having a laminated structure having solar radiation shielding property is separated from the glass window on the interior side within the range of 1 to 300 mm from the indoor glass surface along the indoor glass surface. The solar radiation adjustment method of the window glass with a mesh characterized by arrange | positioning.   The said transparent roll screen is set to visible light transmittance 65% or more, solar radiation shielding coefficient 0.69 or less, visible light reflectance 10% or less, and haze 2.0 or less. Solar radiation adjustment method for a glass window. The transparent roll screen has a visible light transmittance of 65% or more, a solar radiation shielding coefficient of 0.69 or less, a thermal conductivity of 5.0 W / m ² · K or less, a visible light reflectance of 10% or less, and a haze of 2.0 or less. The method for adjusting solar radiation of a mesh window glass according to claim 1.   4. The method for adjusting solar radiation of a meshed window glass according to claim 1, wherein the laminated structure portion is disposed on the indoor side of the screen base material. 5.   The film base material of the transparent laminated film is disposed on the screen base material side with respect to the laminated structure portion, and the laminated structure portion is disposed on the indoor side with respect to the film base material. Solar radiation adjustment method for a glass window.   6. The mesh window glass according to claim 1, wherein the laminated structure portion is formed by laminating a metal oxide layer containing an organic component and a metal layer. Solar radiation adjustment method.   The solar radiation adjusting method for a mesh window glass according to any one of claims 1 to 6, further comprising a barrier layer mainly composed of a metal oxide on at least one surface of the metal layer.   The said metal oxide layer is a titanium oxide layer, The solar radiation adjustment method of the mesh window glass of any one of Claim 1 to 7 characterized by the above-mentioned.   The said metal layer is a silver layer or a silver alloy layer, The solar radiation adjustment method of the meshed window glass of any one of Claim 1 to 8 characterized by the above-mentioned.   The method for adjusting solar radiation of a mesh window glass according to any one of claims 1 to 9, wherein the barrier layer is mainly composed of titanium oxide.

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