JPS6254955B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a window that exhibits an energy saving effect.
More specifically, the present invention relates to a window with excellent heat insulation effect, which is a combination of double-glazed glass and a selectively transparent film. Recently, energy conservation has been required in architectural styles, and for this purpose, building materials, building windows, windows and doors of refrigerated storage cases, train windows, greenhouse windows, etc., are double-glazed or selectively permeable. Glass windows equipped with films are being developed. In order to further improve the insulation properties of windows, attempts have been made to replace double-glazed windows with triple or quadruple-paned windows; Moreover, the spacers around the glass plates and the window frames that house the glass windows need to be made stronger to accommodate this increase in weight. Increased weight and cost are the reasons why multi-layer windows cannot be implemented more efficiently. Furthermore, multi-layer windows have the inconvenience of having to replace the entire window glass frame if one glass pane breaks. Therefore, attempts have been made to create a thermal insulation effect equivalent to that of triple-glazed windows by extending a material that has the same thermal insulation effect as window glass inside double-glazed windows. This material is a kind of selectively transparent film, in which a thin film of metal or metal oxide is formed on the surface (one or both sides) of an organic film, and mainly reflects radiation (infrared rays). As such an improvement, the present inventors also proposed in Japanese Unexamined Patent Publication No. 54-85283 that a selective light-transmitting film in which a thin film of metal or metal oxide is formed on one side of an organic film is attached to the inside of a transparent plate of a double-paned window. I suggested something to wear. According to the example, this configuration also has sufficient heat insulation performance with a heat transfer coefficient of 1.6, but when a thin film of metal or metal oxide is formed on both sides, the heat transfer coefficient is 1.0 (see Comparative Example 2 below).
However, depending on the application, further improvement is required. When forming a selectively transparent thin film on both sides of this organic film, it takes twice as long to form a thin film on only one side of the film. There is a concern that surface flaws may occur on one side. This surface flaw is thought to be caused by the detachment of a thin film that does not have high scratch resistance due to friction between the roll and the first surface. Therefore, by forming a thin film of metal oxide or the like on only one side of an organic film, it is possible to develop an excellent selective light transmitting film that has the same heat insulation effect as a thin film formed on both sides. A product with no scratches due to processing (scratches would reduce transparency) is obtained, and processability is also improved. After examining various conditions for single-sided processing, the inventor found that by selecting a material with appropriate shape and physical properties as a transparent organic film, it is possible to obtain a film that has the same level of heat insulation effect as a double-sided processed film. The present invention was developed based on this knowledge. That is, in the present invention, a transparent organic film (A) is used as a selective light transmitting film (E) as a support, and a metal oxide (D) is layered on one side of the support, or a high refractive index thin film layer is provided on one side of the transparent organic film (A). A selectively transparent film (E) laminated with (B) and a metal thin film layer (C) is placed between two transparent plates (F) with a gap between them so as not to contact either of the transparent plates. It is a window that is set up so that
The basic infrared absorption capacity q of the organic film (A) is
0.3 or less, and the thickness of the organic film is d
(μm), there is a relationship of q・d≦4 (μm), and the infrared reflectance of the processed film surface of the selectively transparent film (E) is 70% or more. This is a distinctive window. The present invention will be explained. The transparent organic film (A) that serves as a support for the selectively transparent film (E) that constitutes a part of the window of the present invention has a film thickness (d) of 2 to 60 μm, preferably 4 to 30 μm.
A material in the μm range is preferable. This organic film has a visible light transmittance of 60% or more. Examples of the material for this film include polyolefins such as polyethylene and polypropylene, polymethacrylonitrile, polyacrylonitrile, ionomers, acrylonitrile rubber, nitrile butadiene, acrylonitrile-styrene, and the like. In particular, polyethylene or polypropylene, which are polymers with low basic infrared absorption ability, are preferred. Basic infrared absorption capacity q of transparent organic film (A)
must be 0.3 or less, and the following equation d·q≦4 (μm) is required for the thicknesses d (μm) and q of the organic film. If these conditions are not met, thin film processing on only one side is required.
It is not possible to obtain the same insulation effect as double-sided processing. The basic infrared absorption capacity q is determined as follows. Film thickness 3000Å on a suitable film or glass substrate
or more silver is deposited. On top of this, a transparent organic film (A) is laminated to a thickness of 2 μm using a dry method or a melting method. Its infrared reflectance is 3 to 25 μm.
Measure in the wavelength range of On the other hand, the energy radiated from a blackbody at 300〓 (27℃) is picked up every 0.2μm, and the product of the radiant energy and infrared reflectance according to each wavelength is calculated every 0.2μm. Find the sum in the wavelength domain. Then, the sum is normalized by dividing it by the sum of the radiant energy intensity in the region of 3 to 25 μm. This value is the energy radiated from 300〓 (3~25μ
m area) is reflected overall. The film thickness of silver is 3000 Å or more, and the transmittance of infrared rays is zero, so if you calculate the difference in this normalized reflectance from 1, it will be the infrared absorption ability of the transparent organic film. This value is defined as the basic infrared absorption capacity q. Radiant energy in the 3-25 μm region is at room temperature.
300〓 corresponds to about 85% of the total black body radiant energy. The basic infrared absorption capacity takes a value between 0 and 1. Even if the basic infrared absorption capacity is 0.3 or less, if the thickness d (μm) of the transparent organic film becomes larger than necessary, the heat insulation performance will be reduced. q×d≦
When the condition of 4 (μm) is met, the selective light transmitting film (E) has its heat insulation performance. Examples of the high refractive index thin film layer (B) used in the window of the present invention include thin film layers made of titanium dioxide, titanium oxide, bismuth oxide, zinc sulfide, tin oxide, indium oxide, and the like. This thin film layer can also be applied by sputtering, ion plating, vacuum deposition or chemical coating. As an example of chemical coating,
For example, a titanium oxide thin film layer can be provided by applying an organic solvent containing an alkyl titanate as a solute. Such alkyl titanates are represented by the general formula TilOmRn (where R is an alkyl group and l, m, and n are positive integers). Among these, m=4+(l-1)×3, n
=4+(l-1)x2, and those with l=1 to 30 are easy to coat or have good performance as a high refractive index thin film layer.
Examples of preferred alkyl titanates include tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrastearyl titanate, tetra-2-ethylhexyl titanate,
Examples include diisopropoxytitanium bisacetylacetonate. By adjusting the conditions for film formation of alkyl titanate, it is possible to leave alkyl groups in the thin film layer, and the amount can be controlled.
By adjusting the content to 0.1 to 10% by weight, it is possible to obtain a selective light transmitting film (E) with improved adhesion to the metal layer or organic film and excellent transparency over a wide wavelength range. . The high refractive index thin film layer of the present invention has the effect of increasing the transparency of the metal thin film layer (C), and has a refractive index of 1.6 or more, preferably 1.8 or more with respect to visible light, and each layer has a refractive index of 1.6 or more, preferably 1.8 or more. The film thickness is 50-600Å,
Preferably it is 120-400 Å. Materials for the metal thin film layer (C) constituting the selectively transparent film used in the window of the present invention include silver,
gold, copper, aluminum, nickel, palladium,
Tin and alloys or mixtures thereof are used. In particular, silver, gold, copper, alloys or mixtures thereof are preferably used. Its film thickness is 50~600
Å, preferably 75 to 200 Å, because this range is suitable when both the transparency and heat insulation of the window are taken into consideration. As a method for forming this metal thin film layer, for example, vacuum evaporation method, cathode sputtering method, plasma spraying method, vapor phase plating method, chemical plating method, electroplating method, and combinations thereof can be applied. The vacuum deposition method is advantageous because the deposition is performed efficiently, and the sputtering method is advantageous because it can reduce temporal fluctuations in the composition of the metal thin film. The metal thin film layer can be one layer, but it can also be multilayered by combining different metals. Particularly preferable metal thin film layers (C) include (a) 75-
A metal thin film layer (b) 75 which is a 220 Å silver and copper alloy layer, and the proportion of copper in the alloy layer is 5 to 20% by weight.
A metal thin film, etc., which is a 220 Å alloy layer of silver, gold, and copper, in which the proportion of gold in the alloy layer is 5 to 30% by weight, the proportion of copper is 3 to 15% by weight, and the balance is silver. . They are superior to single films and other compositions in their resistance to light and heat. Examples of metal oxide (D) thin films include In ₂ O ₃ , SnO ₂ ,
Examples include Cd ₂ SnO ₄ , and the film thickness is preferably in the range of 2000 to 4000 Å. Other elements can also be added to further improve the infrared reflectance. For example, a system to which SnO ₂ is added is preferable for In ₂ O ₃ . As a method for forming the metal oxide, a method suitable for the composition may be selected from among vacuum evaporation, cathode sputtering, reactive evaporation, chemical reaction spraying, and the like. These metal oxide thin film layers (D)
is provided on the organic film (A) surface, but an undercoat may be provided if necessary to increase adhesive strength. Further, in order to increase the scratch resistance, a protective layer may be further laminated on the metal oxide thin film layer within a range that does not impair the intended effects of the present invention. A selective light transmitting film (E) is obtained by laminating a high refractive index thin film layer (B) and a metal thin film layer (C) on the surface of a transparent organic film (A). This lamination order may include a film in which a high refractive index thin film layer (B) is provided on the organic film (A) surface, followed by a metal thin film layer (C), a film in which the metal thin film layer (C) is laminated in the reverse order, or a film in which a metal thin film layer (C) is laminated on the organic film (A) surface. There is a structure such as a film in which a high refractive index thin film layer (B) is further laminated on the surface C). The selective light transmitting film (E), which is a film in which a metal thin film layer (C) is sandwiched between two high refractive index thin film layers in a sandwich pattern, has excellent properties and is therefore preferably used for the window of the present invention. In addition to the film embodiments described above, the selective light transmitting film (E) constituting the window of the present invention may be a film comprising a support film (A) and a metal oxide (D). There is also Note that a transparent protective layer can be provided on the outermost layer (processed surface) of the selectively transparent film as long as it does not impair the heat insulating effect aimed at by the present invention. This protective layer is preferably a thin film layer made of acrylic resin, polyolefin resin, or the like, which has excellent scratch resistance. The selective light transmitting film (E) in the present invention is obtained by the method described above, and has a visible light (500 nm) transmittance of 60.
%, preferably 70% or more, the basic infrared absorption capacity q of the transparent organic film support serving as a component is 0.3 or less, and the film thickness d (μm) and q of the transparent organic film is q・d≦4(μm)
It satisfies the following. The transparent plate (F) constituting the window of the present invention may be any plate having transparency that functions as a window.
Although not particularly limited, examples include glass plates, acrylic plates, polycarbonate plates, and the like. The thickness of these is approximately 1 mm to 10 mm, preferably 2 mm to
5 mm, and may be slightly colored for the purpose of blocking heat rays, blocking sunlight, or for aesthetic purposes. In particular, transparent plates with a transmittance of 80% or more (500 nm) are preferable for south-facing windows of buildings that utilize sunlight effectively, or for vehicle windows that should not obstruct the view. used. From the viewpoint of heat insulation, it is preferable that the two transparent plates (F) are arranged in parallel with a gap of 5 mm or more, preferably 10 mm or more between them. The selectively transparent film (E) is preferably stretched between two transparent plates (F) without loosening. For example, various known simple means can be applied, such as using a shrinkable film and heat setting it after construction, or hanging the film by attaching a weight or a spring to one end of the film. If necessary, around the two transparent plates,
From the viewpoint of the durability of the film, it is possible to include the selectively transparent film (E) and seal it with a sealant. As the sealant, polysulfide-based, silicone-based, and butyl rubber-based resins, which are usually used in double-glazed window types, can be used. When silver is mainly used as the metal layer (B), a hot melt type of butyl rubber or a dual type of butyl rubber on the inside of the window and silicone or polysulfide on the outside can be applied. Furthermore, when a desiccant is used in the window, it may be any of the commonly used silica gel, molecular sieve, or a mixture of both. In order to further increase the heat insulation properties, argon, SF ₆ or CO ₂ can be filled as the gas in the multilayer instead of air. From the viewpoint of durability, N ₂ encapsulation is also a preferred embodiment. Furthermore, it is unnecessary to explain that a transparent plate can be further added to the window of the present invention to form a triple-paned window without impairing the intended effects of the present invention. The window of the present invention has a heat transfer coefficient of 1.2 (Kcal/
m ² , hr, deg), and compared to normal glass windows (thermal transmission coefficient 5.4 Kcal/m ² , hr, deg) and double glass windows (thermal transmission coefficient 3.0 Kcal/m ² , hr, deg). , can be significantly lower. In the Sapporo area, located at 43° north latitude, the amount of heat that escapes through glass windows or double-glazed windows in a typical house during the six months of winter is approximately 600 Mcal/
m ² , 380 Mcal/m ² . By using the window of the present invention, the amount of heat that escapes can be reduced to approximately half or less, to 210 Mcal/m ² . This energy saving effect is achieved at the most economical kerosene price (10 yen/
Mcal), it becomes 3900 yen/m ² . In this way, the window of the present invention can be used as an energy-saving window.
It is very effective as a window not only for Japan, which has limited energy resources, but also for cold countries such as northern regions. Since the window of the present invention has the above-mentioned effects, it can be used not only for general houses, buildings, vehicles, ships, and aircraft windows, but also for refrigerator cases, window windows, solar water heaters, and peep windows for heating elements. be used effectively. The details of the present invention will be shown below in Examples. The infrared reflectance was measured by attaching a reflectance measuring device to a Hitachi EPI-type infrared spectrometer and setting the reflectance of a glass slide with approximately 3000 Å of silver vapor-deposited as 100%. The sample value was calculated taking into account the body radiant energy distribution (300〓). The amount of organic substance contained in the titanium oxide thin film layer is determined by cutting the molded product of the laminate of the present invention, which has transparent conductivity or selective light transmission, into small pieces of about 2 mm in size, and adding 1000 parts by weight of water to the molded product, which has a size of about 2 mm. , to a solution prepared by mixing 20 parts by weight of ethyl alcohol and 1 part by weight of hydrochloric acid,
Organic components were extracted by immersion at room temperature for 24 hours, and then analyzed using a gas chromatograph mass spectrometer (Shimadzu Corporation).
LKB-9000), a glass column with a diameter of 3 mm and a length of 3 m was filled with 100 parts by weight of Chromosorb W (60 to 80 mesh) to which 30 parts by weight of PEG-20 was attached, and the mass fragment graphite method was used. The ions were determined by quantitative determination. Example 1 A biaxially stretched polypropylene film with a thickness of 25 μm and a light transmittance (500 nm) of 86% was coated with 250 μm as the first layer.
A titanium oxide thin film layer with a thickness of 193Å, and a metal thin film layer of silver and copper with a thickness of 193Å as the second layer (the weight ratio of silver and copper is
90:10), a titanium oxide thin film layer of 160 Å as the third layer, and polymethacrylonitrile with a thickness of about 0.1 μm were successively laminated. (The obtained laminated film is hereinafter abbreviated as laminated film-1) The titanium oxide thin film layer was provided by a sputtering method using argon gas at a vacuum degree of 3×10 ⁻⁴ Torr. The metal thin film layer is made of an alloy of silver and copper (silver content 90% by weight, copper content 10% by weight) in a vacuum of 5 × 10 ^-5 Torr.
was heated in an aluminum crucible and vacuum deposited. Visible light of laminate-1 (500nm)
The transmittance was 74%, and the infrared reflectance on the processed surface side was 93%. Furthermore, since the basic infrared absorption capacity q of this organic film made of polypropylene film is 0.13 and the thickness d (μm) of the transparent organic film is 25 μm, q·d=3.3 μm. Laminate-1 was stretched and fixed at a position where the air layer was exactly in the middle of a glass plate with a thickness of 20 mm to make a double-glazed window. The heat transmission coefficient of the obtained window was 1.1Kcal/m ² ,
It was hr and deg. Comparative Example 1 The heat transmission coefficient of a similar double-glazed window without laminate-1 was 2.7 Kcal/ ^m2 ·h·°C. Comparative Example 2 Laminated body 2, in which the same selective light transmission layer was provided on both sides of the same polypropylene film, was spread in the middle between the glass plates in an air layer with a thickness of 20 mm in the same manner as in Example 1, using the same method as in Example 2. The heat transmission coefficient was determined.
The value was 1.0 (Kcal/ ^m2 ·h·°C). Example 2 A polymethacrylonitrile film with a thickness of 8 μm and a light transmittance (500 nm) of 86% was coated as the first layer.
A 250 Å titanium oxide thin film layer, a 140 Å metal thin film layer made of silver and copper (the weight ratio of silver and copper is 90:10) as the second layer, and a 300 Å titanium oxide thin film layer as the third layer were laminated in this order. (The obtained laminated film is hereinafter abbreviated as laminate-3). The titanium oxide thin film layer is made of 3 parts of tetrabutyl titanate and isopropyl alcohol.
A solution consisting of 65 parts of normal hexane and 32 parts of normal hexane was applied using a bar coater and heated at 100°C for 20 minutes. The metal thin film layer is made of an alloy of silver and copper (silver content 90% by weight, copper content 10% by weight) in a vacuum of 5 × 10 ^-5 Torr.
was heated in an aluminum pot and vacuum-deposited. The content of butyl groups contained in the first and third titanium oxide thin film layers was 2.0% by weight (as determined by mass fragment graphing for mass No. 56). The visible light (500nm) transmittance of laminate-3 is
80%, and the infrared light reflectance was 93%. The basic infrared absorption capacity was 0.16. The heat transmission coefficient of the laminate-3, which was determined in the same manner as in Example-1, was 1.15 (Kcal/m ² ·h·°C). Example 3 An indium oxide film was provided on the surface of a 25 μm thick polypropylene film by sputtering. In sputtering, the degree of vacuum is increased to 2x by adjusting the introduction speed and exhaust speed of a mixed gas in which the molar ratio of argon and oxygen is 95:5 mol%.
The temperature was maintained at 10 ^-5 Torr and the substrate temperature was 80°C. The thickness of the obtained indium oxide film is 4000Å
It was hot. The infrared reflectance of the processed surface of the laminate (hereinafter referred to as laminate-4) in which indium oxide was coated on a polypropylene film was 82%. In addition, the heat transmission coefficient was 1.2 (Kcal/m ² · h · °C). Example 4 A 250 Å thin titanium oxide film layer was provided as the first layer, a 95 Å thin gold film layer was provided as the second layer, and a 0.1 μm thick polymethacrylonitrile layer was provided as the third layer on one side of a 30 μm thick polyethylene film. Ta. The first titanium oxide thin film layer was provided by a sputtering method. The second layer of gold was similarly provided by the sputtering method. The third layer of polymethacrylonitrile was provided by a dry method using cyclohexanone as a solvent. The infrared reflectance of the processed surface was 86%. The heat transmission coefficient was 1.15 (Kcal/m ² ·h ·°C). Comparative Example 3 Laminated body 6 was produced under exactly the same conditions as in Example 2, except that the polyacrylonitrile film was changed to 50 μm. The infrared reflectance of the processed surface of laminate-6 is 86%, and the basic infrared absorption capacity is
Since it was 0.22, the product with the film thickness was 11 μm. The K value of this laminate is 1.4 (Kcal/ ^m2・h・℃)
It was hot. Comparative Example 4 Laminated body 7 was produced under exactly the same conditions as in Example 1 except that the thickness of the polypropylene film was changed to 80 μm. The infrared reflectance of the processed surface of laminate-7 was 93%, and since the basic infrared absorption capacity was 0.13, the product with the film thickness was 10.4 μm. The K value of this laminate is 1.4 (Kcal/ ^m2・h・
℃). Comparative Example 5 In Example 2, the transparent organic film (A) was a polyethylene terephthalate film with a thickness of 25 μm.
Laminate-8 was obtained by laminating under the same conditions except that the following conditions were changed. Since the basic infrared absorption capacity of polyethylene terephthalate film is 0.7, the product with the film thickness d was 17.5 μm. The K value of laminate-8 is 1.4 (Kcal/ ^m2・h・℃)
It was hot. Table 1 summarizes Examples 1-4 and Comparative Examples 1-5. Comparative Example 2 is a film processed on both sides, and has a K value of 1.0 (Kcal/m ² ·h·° C.). It can be seen that in the examples of the present invention, the K value is in the range of 1.1 to 1.2, which is superior to the K value of 1.4 in Comparative Examples 3 to 5. 【table】

Claims (1)

[Claims] 1. A metal oxide (D) is provided on one side of a transparent organic film (A) between two transparent plates (F), or a high refractive index thin film layer (B) and a metal A window in which a selectively transparent film (E) provided with a thin film layer (C) is disposed on one side of the transparent plate (F) with a gap so as not to come into contact with any of the organic film (A); The basic infrared absorption capacity q of the organic film (A) is 0.3 or less, and when the film thickness of the organic film (A) is d (μm), q・d≦4 (μm), and the selective light transmitting film (A) A window characterized in that the infrared reflectance of the film surface subjected to the processing described in E) is 70% or more. 2. The window according to claim 1, wherein the organic film (A) is a polypropylene film.