JPH0519497B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a laminated plate made by laminating a pair of transparent plates made of glass, synthetic resin, etc. with an interlayer film made of a transparent synthetic resin. Something with performance. This heat ray reflective laminated plate is suitable for use as a window glass for a vehicle or a window glass for a building. [Summary of the Invention] The present invention provides a laminated board in which first and second transparent plates are laminated with a transparent resin film, in which a heat ray reflective film coated on the inner surface of the first transparent plate is attached to a pair of It consists of a metal oxide layer and a noble metal layer with a sheet resistance of 4 to 10 Ω□ interposed between the pair of metal oxide layers, and the sum of the thicknesses of the pair of metal oxides is 500 to 900 Å, and The ratio of the film thicknesses of the pair of metal oxide layers is 1.1 to 1.6, and the color tone of the reflected light of the laminated plate is the color tone a of the Hunter color system.
and b, −1≦a≦1 and −1≦b
≦1, and the visible light reflectance of the laminated plate is
By configuring it so that it is less than 10%, it has high strength, does not scatter fragments in the event of breakage, and is highly safe.It also has excellent heat ray reflection performance, and has low visible light transmittance. It is possible to provide a heat ray reflective laminated board that has a nearly achromatic color and good appearance despite its high ratio. [Prior Art] Laminated glass, in which a pair of glass plates made of float glass or the like are bonded together with an interlayer made of a transparent synthetic resin such as polyvinyl butyral, has been known. This type of laminated glass is made up of multiple layers of glass and an interlayer film that bonds the pair of glass sheets together, so it has great strength and even if the glass sheet breaks, it will not break. Since the fragments are attached to the interlayer film, the fragments do not scatter, making it highly safe. However, when such laminated glass is used as vehicle or architectural window glass, a large amount of solar radiant energy propagates into the vehicle or building, especially in midsummer. temperature rises more than necessary. On the other hand, U.S. Patent No. 4,337,990 discloses a heat ray reflective glass constructed by sequentially forming a first metal oxide layer, a noble metal layer, and a second metal oxide layer on a single sheet of glass. ing. In this heat-reflecting glass, due to the interference between the first and second metal oxide layers and the noble metal layer, the reflectance of light at a wavelength of 550 nm, which has high visibility, is low and the visible light transmittance is high. As such, the thicknesses of the first metal oxide layer and the second metal oxide layer are approximately equal to each other. [Problems to be Solved by the Invention] In the reflection component curve of the heat-reflecting glass disclosed in the above US patent, reflection is stronger on the longer wavelength side (red region) and the shorter wavelength side (blue region) of the visible region. For this reason, in the heat ray reflective glass, the reflected color tone of the light incident from the glass plate side and the light incident from the second metal oxide layer side are both purple, giving a glare sensation. Therefore, if the above heat ray reflective glass is used as window glass for vehicles such as automobiles or buildings,
One drawback was that the color could not be harmonized with the vehicle body or building exterior color. [Means for Solving the Problems] The present invention was invented in order to correct the above-mentioned drawbacks. A heat ray reflective film is attached to the inner surface of the first transparent plate so as to be interposed between the first transparent plate and the transparent resin film. , the heat ray reflective film is composed of a laminate formed by sequentially forming a first metal oxide layer, a noble metal layer and a second metal oxide layer on the inner surface of the first transparent plate; 1 metal oxide layer and the second metal oxide layer.
The sum of the thicknesses of the metal oxide layers is 500 to 900 Å, and the ratio of the thickness of the first metal oxide layer to the second metal oxide layer, or the sum of the thicknesses of the second metal oxide layer The ratio of the film thickness to the first metal oxide layer is 1.1 to 1.6, preferably 1.2 to 1.5,
The sheet resistance of the noble metal layer is 4 to 10 Ω/□, and the color tone of the light reflected from the laminated plate is -1≦ for the color tone indications a and b of Hunter Pixel Color.
The present invention relates to a heat ray reflective laminated plate that satisfies a≦1 and -1≦b≦1 and has a visible light reflectance of 10% or less. In the present invention, the sheet resistance of the noble metal layer is 4 to 4.
The reason for setting it to 10Ω/□ is as follows. In other words, generally speaking, the sheet resistance is 4Ω/□
If it is smaller than , the visible light reflectance is too large and the color tone becomes noticeable, so the color tone a and b of the Hunter color system for the light reflected from the laminated board is -
It will not fall between 1 and 1. On the contrary, if the sheet resistance exceeds 100 Ω/□, there is no reproducibility in the heat ray reflection performance, and there is also a risk that the visible light reflectance may decrease due to oxidation of the noble metal layer. In this case, if silver is used as the noble metal layer, generally speaking, the thickness of this noble metal layer when the sheet resistance is 4Ω/□ is 130 to 270, depending on how it is made.
The thickness of this precious metal layer when the sheet resistance is 10Ω/□ is about 60 to 150Ω, depending on its construction.
It will be about Å. Therefore, when using silver alone or a layer containing silver as a main component, the noble metal layer may have a thickness of 60 to 270 Å. In the present invention, the first and second transparent plates are
A glass plate made of float glass or the like is preferable, and may be colored if necessary as long as it has the required visible light transmittance. Further, the thickness of the first and second transparent plates can be arbitrarily selected depending on the application, but generally speaking, the thickness may be about 0.5 to 5 mm, preferably about 1 to 3 mm. In the present invention, the sum of the thicknesses of the first metal oxide layer and the second metal oxide layer is 500 to 900 Å, and the thickness of the first metal oxide layer relative to the second metal oxide layer is or the ratio of the film thickness of the second metal oxide layer to the first metal oxide layer is 1.1 to 1.6, the color tone representations a and b of the Hunter color system for the light reflected from the laminated plate
can very easily take values between -1 and 1, respectively. As a result, a laminated glass with an inconspicuous color tone can be obtained. In the present invention, the refractive index of the first metal oxide layer and the second metal oxide layer are respectively:
It may be between 1.9 and 2.1. Further, the respective thicknesses of the first metal oxide layer and the second metal oxide layer may be approximately 190 to 690 Å. In the present invention, the metal oxides constituting the first metal oxide layer and the second metal oxide layer include tin oxide, indium oxide, indium oxide containing tin oxide (hereinafter referred to as "ITO"), Either zinc or antimony oxide can be used. In this case, the first metal oxide layer and the second metal oxide layer may be of the same type of oxide, or may be of different types of oxides. In addition, usually as the above tin oxide,
Indium oxide (In 2 O 3 ) can be used as stannic oxide (SnO ₂ ), as indium oxide, or as indium oxide (In ₂ O ₃ ).
Zinc oxide (ZnO) in a narrow sense is used as zinc oxide, and diantimony pentoxide (Sb ₂ O ₅ ) is used as antimony oxide. In the present invention, the noble metal layer may include gold, silver, copper,
It may be made of one or more of palladium and rhodium. In particular, silver
Among these noble metals, the noble metal is preferably made of silver because it absorbs the least amount of light in the visible range. However, silver alone does not necessarily have good chemical resistance such as moisture resistance, alkali resistance, and acid resistance.
It is more preferable to contain a small amount of at least one of copper, palladium and rhodium.
In this case, by including these noble metals, the color tone of the noble metal layer may change compared to when silver alone is used, and the visible light transmittance may decrease. Therefore, the above content is preferably 2% or less for each of gold and copper, and preferably 1% or less for palladium and rhodium. Furthermore, even when a plurality of types of these are contained, the total content is preferably 2% or less. Further, the thickness of the noble metal layer may generally be about 30 to 300 Å. In the present invention, the transparent resin film has approximately the same refractive index as the transparent plate (for example, about 1.52 in the case of a glass plate), and The material is not particularly limited as long as it has good adhesion and is transparent in the visible range. As the transparent resin film, for example, a film made of polyvinyl alcohol resin such as polyvinyl butyral, vinyl acetate resin such as ethylene vinyl acetate, thermoplastic polyurethane resin, or polyvinyl chloride resin can be used. ,
In particular, it is preferable to use a film made of polyvinyl butyral. In addition, its thickness is 0.05~
It may be 0.4 mm, preferably 0.1-0.2 mm. In the present invention, the visible light transmittance of the laminated plate is 80
% or more, and if the solar transmittance (transmittance of solar radiant energy) is less than 75%, even though visible light can sufficiently pass through the heat-reflective plywood,
Because solar radiant energy is blocked to some extent,
Particularly preferred. When manufacturing the heat ray reflective laminated plate according to the present invention, usually a first metal oxide layer, a noble metal layer and a second metal oxide layer are sequentially formed on the inner surface of a first glass plate, After this first glass plate, sheet-shaped transparent resin film, and second glass plate are laminated in sequence, this laminate is heated to 130 to 180°C and pressurized at a pressure of 1 to 5 kg/cm ^2. In this way, the transparent resin film is thermally fused to the second metal oxide layer of the first glass plate and to the inner surface of the second glass plate, respectively. This laminate is then cut and sized around its periphery. When the heat-reflective laminated sheet according to the present invention is used as dense glass for vehicles or buildings, the heat-reflective laminated sheet is usually such that the first transparent plate on the side to which the heat-reflective film is applied is the vehicle. or attached to a vehicle or building so that it is outside the building. In this case, the color tone of the light reflected from the heat-reflective laminate is substantially the same on the outside and inside of the car or building. However, since the outside of a vehicle or building is usually bright and the inside is dark, reflected light on the outside and transmitted light on the inside become a problem. According to the heat ray reflective laminated plate of the present invention, reflected light is nearly achromatic, and visible light can be sufficiently transmitted. [Example] Next, an example of the present invention will be described based on the attached drawings. First, for example, 0.4Pa (Pascal [Newton/
In a mixed atmosphere of argon gas and oxygen gas maintained at a temperature of 2.0 m ² ]), a sintered body of a mixture of tin oxide and indium oxide is sputtered onto a glass plate 10 having a thickness of 2.1 mm, for example. To,
For example, 238 Å thick ITO (indium oxide containing tin oxide, consisting of 10% tin oxide and 90% indium oxide)
The same applies hereinafter) was formed. Next, in an argon gas atmosphere maintained at 0.4 Pa, a noble metal made of silver and having a sheet resistance of, for example, 9 Ω/gate is sputtered onto the first metal oxide layer 11 by sputtering using silver as a target. Layer 12 was formed. Furthermore, in a mixed atmosphere of argon gas and oxygen gas maintained at 0.4 Pa, a sputtering method was used to target a sintered body of a mixture of tin oxide and indium oxide.
A second metal oxide layer 13 made of ITO and having a thickness of 262 Å, for example, was formed on the noble metal layer 12. Next, on the second metal oxide layer 13 of the glass plate 10, a transparent resin film 14 made of a polyvinyl butyral film having a thickness of, for example, 0.15 mm and a film of, for example, 2.1 mm thick are applied.
Thick glass plates 15 were sequentially laminated. Next, the polyvinyl butyral film 14 is bonded to the second metal oxide layer 13 of the glass plate 10 by heating this laminate to, for example, 150° C. and applying a pressure of, for example, 3 Kg/cm ² . They were each heat-sealed to the glass plate 15. Next, the periphery of this laminate was cut to size it to a desired size, and as a result, a transparent heat-reflective laminated board as shown in the drawing was obtained. In this case, the first metal oxide layer 11 is made of ITO.
The second metal oxide layer 13 can be changed to ZnO or ITO.
to ZnO or SnO ₂ or noble metal layer 12
Ag to Ag−0.5%Cu (silver containing 0.5% copper)
Alternatively, a heat ray reflective laminated board was manufactured in the same manner by changing to Ag-1% Au (silver containing 1% gold). In addition, the thickness of the first and second metal oxide layers 11 and 13 was varied in the range of 200 to 540 Å, and the sheet resistance of the noble metal layer 12 was varied in the range of 6 to 9 Ω/□. Similarly, a heat ray reflective laminate was manufactured. Tables 1 to 12 listed below each show examples of the present invention of heat ray reflective laminated plates obtained as described above. Furthermore, Table 13 similarly shows reference examples of the present invention. The compositions of the first metal oxide layer 11, the noble metal layer 12, and the second metal oxide layer 13 of the heat ray reflective laminated plates shown in Tables 1 to 13 are as follows. Examples Table 1 ITO/Ag/ITO system Table 2 ITO/Ag/ITO system Table 3 ITO/Ag/ITO system Table 4 ITO/Ag/ITO system Table 5 ITO/Ag/ITO system Table 6 ITO/Ag/ITO system Table 7 ITO/Ag/ITO system Table 8 ITO/Ag/ITO system Table 9 ZnO/Ag/SnO ₂ system Table 10 ZnO/Ag/SnO system Table 11 ITO/Ag/ Ag-0.5%Cu/ITO system Table 12 ITO/Ag/Ag-1%Au/ITO system comparison example Table 13 ITO/Ag/ITO system

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

〔Effect of the invention〕

As described above, the present invention has a multilayer structure in which a first transparent plate having a heat ray reflective film coated on its inner surface and a second transparent plate are laminated with a transparent resin film, so that the strength is increased. is large and difficult to break. In addition, since the first transparent plate and the second transparent plate are bonded together with a transparent resin film, even if the transparent plate breaks, the pieces of the transparent plate will stick to the intermediate film, so the pieces will scatter. Therefore, it is highly safe. Further, the heat ray reflective film adhered to the inner surface of the first transparent plate includes a pair of metal oxide layers and a sheet resistance of 4 to 10
Ω/□ noble metal layer, the sum of the thicknesses of the pair of metal oxide layers is 500 to 900 Å, and the ratio of the thicknesses of the pair of metal oxide layers is 1.1 to 1.6,
The color tone of the reflected light of the laminated plate satisfies -1≦a≦1 and -1≦b≦1 for color tone representations a and b of the Hunter color system, and the visible light reflectance of the laminated plate is 10 % or less. Therefore, according to the present invention, it has excellent heat ray reflection performance, and
It is possible to provide a heat ray reflective laminated board that has a relatively achromatic color and good appearance despite its relatively high visible light transmittance.

[Brief explanation of the drawing]

The drawing is a longitudinal cross-sectional view of a portion of a heat-reflective laminated plate according to the present invention. In addition, in the symbols used in the drawings, 10... glass plate, 11... first metal oxide layer, 12...
Noble metal layer, 13... Second metal oxide layer, 14...
...Transparent resin film, 15...Glass plate.

Claims (1)

[Scope of Claims] 1 A laminated board made by laminating a first and a second transparent plate with a transparent resin film, wherein the first transparent plate and the transparent plate are attached to the inner surface of the first transparent plate. To be interposed between the resin film,
A heat ray reflective film is deposited, and the heat ray reflective film is formed by sequentially forming a first metal oxide layer, a noble metal layer, and a second metal oxide layer on the inner surface of the first transparent plate. The sum of the thicknesses of the first metal oxide layer and the second metal oxide layer is 500 to 900 Å, and the second metal of the first metal oxide layer The ratio of the film thickness to the oxide layer or the ratio of the film thickness of the second metal oxide layer to the first metal oxide layer is 1.1 to 1.6, and the sheet resistance of the noble metal constituting the noble metal layer is , 4 to 10Ω/□, and the color tone of the light reflected from the laminated plate is −1≦a for the color tone representations a and b of the Hunter color system.
1. A heat-reflective laminated board that satisfies ≦1 and -1≦b≦1, and has a visible light reflectance of 10% or less. 2 The first and second transparent plates each have
The heat ray reflective laminated plate according to claim 1, which is a glass plate. 3. The heat ray reflective laminated plate according to claim 1 or 2, wherein the first metal oxide layer and the second metal oxide layer each have a refractive index of 1.9 to 2.1. 4 The ratio of the thickness of the first metal oxide layer to the second metal oxide layer or the ratio of the thickness of the second metal oxide layer to the first metal oxide layer is 1.2 to 4. The heat ray reflective laminated board according to claim 1, 2 or 3, wherein the heat ray reflective laminated board is 1.5. 5. The metal oxide constituting each of the first metal oxide layer and the second metal oxide layer is any one of tin oxide, indium oxide, tin oxide-containing indium oxide, zinc oxide, and antimony oxide. (However, the first metal oxide layer and the second metal oxide layer may be of the same type of metal oxide or may be of different types of metal oxide. The heat ray reflective laminated board according to any one of claims 1 to 4, characterized in that: 6. The heat ray reflective property according to any one of claims 1 to 5, wherein the noble metal layer is made of one or more of gold, silver, copper, palladium, or rhodium. Laminated board. 7 The noble metal layer contains silver as a main component, and
The heat ray reflective laminated board according to any one of claims 1 to 6, characterized in that it contains a small amount of at least one of gold, copper, palladium, and rhodium. 8. The heat ray reflective laminated board according to any one of claims 1 to 6, wherein the noble metal layer is silver. 9. The heat ray reflective laminated board according to any one of claims 1 to 8, wherein the transparent resin film is made of polyvinyl butyral. 10. The heat ray according to any one of claims 1 to 9, characterized in that the visible light reflectance of the laminated plate is 80% or more, and the solar transmittance of the laminated plate is 75% or less. Reflective laminate.