JPS6250294B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a selective light transmitting laminate having excellent performance of transmitting light in the visible region and reflecting light in the infrared region. Specifically, by layering a material selected from the group consisting of Ti, Zr, In, Si, C, Co, and Ni on and in contact with the heat ray reflective layer mainly composed of silver, light,
The resistance to heat, gas, etc. has been significantly improved, especially
In a deterioration test at 90°C, the infrared reflectance at a wavelength of 10μ usually decreases to 85% of its initial value for about 1,000 hours or more, often for about 5,000 hours or more. More specifically, a transparent sheet-like base material (A); a heat ray reflective layer (D) with a thickness of 50 to 300 Å mainly composed of silver on the sheet-like base material (A); a sheet-like base material (A) and the high refractive index transparent thin film layer (B ₁ ) provided between the heat ray reflective layer (D), or the high refractive index transparent thin film layer (B ₂ ) provided on the heat ray reflective layer D, or the high refractive index Both transparent thin film layers (B ₁ ) and (B ₂ ); Ti, Zr, In, Si, C , Co, and Ni with a thickness of 3 to 100 Å.
The thin film layer (C) is a selective light transmitting laminate provided on and in contact with the heat ray reflection prevention layer (D). Regarding laminates having heat ray reflective ability or electrical conductivity, U.S. Patent Nos. 3698946 and 3962488
No. 4017661 and specification No. 4020389, JP-A-Sho
Publication No. 51-66841, British Patent No. 1307642,
French patent no. 2043002, Belgian patent no. 693528
No., Canadian Patent No. 840513, West German Patent No. 2813394
Many proposals have been made in the specifications of European Patent Application No. 80302985 and European Patent Application No. 80302985. The selective light transmitting laminate is transparent to light in the visible light range, for example, but has the ability to reflect infrared light, so it is useful as a transparent heat insulating film.
Therefore, it can be used in solar energy collectors (water heaters), solar thermal power generation, greenhouses, building windows, refrigerated and frozen cases, etc. Particularly in modern buildings, the function of transparent heat-insulating windows that can prevent solar energy utilization and energy dissipation from windows that occupy a large proportion of the wall surface will become increasingly important in the future. Furthermore, it is of great importance as a film for greenhouses, which is necessary for the cultivation of agricultural chemicals such as wild daisies and citrus fruits, and for the cultivation of fruits. As described above, selective light transmitting laminates are important from the viewpoint of solar energy utilization, and the industry has desired that homogeneous, high-performance films can be supplied industrially at low cost and in large quantities. Conventionally known selective light transmitting laminates include metal thin films such as gold, copper, silver, and palladium, compound semiconductor films such as indium oxide, tin oxide, and copper iodide, and gold, silver, and copper thin films. It is known that conductive metal films such as palladium are made selectively transparent over a certain wavelength range. As a selective transmission film with high infrared light reflecting ability, an indium oxide film or a tin oxide film with a thickness of several thousand angstroms, and a laminated film of a metal film and a transparent conductor film are known. however,
At present, transparent conductive films or selective light transmitting films with excellent performance have not yet been produced industrially at low cost. The above-mentioned West German Patent Publication No. 2813394 discloses a transparent conductive laminate having the following structure. (A) Transparent solid substrate; (B) Titanium oxide thin film layer in contact with the above substrate (A); (C) Conductive metal thin film layer in contact with the above (B) layer; (D) On the above (C) layer a titanium oxide thin film layer in contact with; (E) optionally a transparent protective layer in contact with the above (D) layer, provided that (i) the above substrate (A) is a film-like synthetic resin layer; (ii) The above (B) is a titanium oxide layer formed from an organic titanium compound; Furthermore, the conductive metal thin film layer (C) is an alloy of Ag and Cu,
In particular, it is shown that the proportion of Cu is preferably 1 to 30% by weight. DE 2828576 discloses that metal thin film layers selected from gold, silver, copper, aluminum and alloys of two or more of these are preferred. In addition, European Patent Application Publication No. 0007224 discloses (A) a solid substrate; (B) a high refractive index transparent thin film layer formed on the solid substrate; (C) the above (B) as a heat ray reflective and conductive laminate; (D) A transparent heat-reflecting layer of conductive metal formed on the above layer; The transparent protective layer (D″) is clarified. It also shows that the above layer (C) is preferably a silver layer containing 3 to 30% by weight of gold. In any of the prior documents, on a heat ray reflective layer mainly composed of silver,
A laminate having heat ray reflection and conductivity that has a thin film layer obtained by laminating materials selected from the group consisting of Ti, Zr, Si, In, C, Co, and Ni has not been disclosed. The present inventor has discovered that the performance of a selectively permeable laminate having a heat ray reflective layer and a high refractive index transparent thin film layer mainly composed of silver deteriorates due to environmental factors such as heat, light, and gas. Focusing on the technical issue of causing this problem, we conducted research to develop a technology that could easily and inexpensively overcome this issue. As a result, Ti, Zr,
By interposing a thin film layer obtained by stacking materials selected from the group consisting of Si, In, C, Co, and Ni, the above environmental factors such as heat, light, gas, etc.
It has been discovered that the above-mentioned technical problem, which is assumed to be caused by the surface diffusion of Ag, can be overcome, and the environmental durability of the selective light transmitting laminate can be greatly improved. Furthermore, the intervening layer can be formed on the heat-reflecting surface mainly composed of silver by existing methods such as vacuum evaporation and sputtering, but in this case, the material forming the intervening layer may be its oxide or other compound. I learned that it should be formed under conditions that prevent it from converting into a state as much as possible. Namely, Ti, Zr, Si, In, C,
I learned that it should be laminated in the state of a material selected from the group of Co and Ni. As will be shown in many examples later, this laminate has many excellent properties. In particular, it has excellent heat resistance; for example, in a deterioration test at 90℃, the time it takes for the infrared reflectance at a wavelength of 10μ to drop to 85% of its initial value is approximately 1000 hours or more, often 5000 hours or more. The present inventors have learned that it is possible to provide a selectively transparent laminate having the following properties. Accordingly, it is an object of the present invention to provide various improved selective light transmitting laminates having superior performance. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The selective light transmitting laminate of the present invention includes: (1) a transparent sheet-like base material (A); (2) a 50-300 Å thick hot wire mainly composed of silver on the sheet-like base material (A); Reflective layer (D); (3) High refractive index transparent thin film layer (B ₁ ) provided between the sheet-like base material (A) and the heat ray reflective layer (D), or provided on the heat ray reflective layer (D). a high refractive index transparent thin film layer (B ₂ ), or both the high refractive index transparent thin film layer (B ₁ ) and (B ₂ ); (4) a transparent top layer (E) provided as necessary; It basically consists of Ti, Zr,
Thin film layer (C) with a thickness of 3 to 100 Å obtained by laminating materials selected from the group consisting of In, Si, C, Co, and Ni.
is provided in contact with the heat ray reflection prevention layer (D). Furthermore, an additional thin film layer (C) can be provided below and in contact with the heat ray reflective layer (D). In the present invention, the transparent sheet-like base material (A) is an organic or inorganic solid base material, or a combination thereof. Sheet type refers to film, sheet,
This is a name that includes shapes such as plates. In addition, "transparent" is a term that includes both a colored and transparent state. The organic molded product of the sheet-like base material (A) is preferably a synthetic resin. For example, polyethylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, acrylic resin, ABS resin, polystyrene resin, polyacetal resin, polyethylene resin,
Thermoplastic resins such as polypropylene resins, polyamide resins, and fluorine resins, thermosetting resins such as epoxy resins, sialyl phthalate resins, phenolic resins, and urea resins, as well as polyvinyl alcohol, polyacrylonitrile, polyurethane, and aromatic resins. Examples include sheet-shaped molded products of solvent-soluble resins such as polyamide, polyamide, and polyimide resins. These may be used alone or as a mixture of two or more as homopolymers or copolymers. Inorganic molded products include soda, glass, vitreous materials such as borosilicate glass and silicate glass, metal oxides such as alumina, magnesia, zirconia, and silica, compound semiconductors such as potassium-arsenic, indium-phosphorus, and silicon. , molded products of semiconductors such as germanium. The heat ray reflective layer (D) used in the present invention is a layer containing silver as a main component and having a thickness of 50 to 300 Å. This may contain other metals or metal compounds as long as the desired effects of the present invention are not impaired. for example,
Au, Cu, Al, In, Zn, Sn, etc. are used,
Particularly preferred are Au and Cu. For example, copper from 0.1
By adding 30% by weight of silver, preferably 0.3 to 15% by weight, the light resistance of the resulting laminate is significantly improved, and by adding 3 to 30% by weight of gold, the heat resistance is improved. The thickness of this heat ray reflective layer (D) is 50 to 300 Å, preferably 70 to 200 Å. If it is less than 50 Å, the infrared reflectance and heat resistance will be too low, and if it is too thick and exceeds 300 Å, the visible light transmittance will decrease.
Not for practical use. The heat ray reflective layer (D) can be formed by existing methods such as vacuum deposition and sputtering. The thickness of the thin film layer (C), which is an important feature in the laminate of the present invention, is 3 to 100 Å, and includes Ti, Zr, In,
It is obtained by laminating materials selected from the group consisting of Si, C, Co, and Ni. This layer is provided in contact with the heat ray reflective layer (D), or in a structure in which the heat ray reflective layer (D) is sandwiched, so that it is in contact with the heat ray reflective layer (D). These can be formed using existing methods such as vacuum deposition and sputtering. At this time, the above-mentioned substance is formed under conditions that minimize conversion into its oxide or compound state. A slight degree of oxidation, for example in the case of Ti, is acceptable if x of TiOx is 1.3 or less, preferably 1.0 or less, but it is preferable to select conditions such that oxidation to a degree that exceeds this does not occur. The same is true for other metals, y/x of MxOy is 1.0
The following are preferred. The thin film layer (C) uses Ti, Zr, Si, In, C, Co, Ni, and mixtures thereof, and further contains trace amounts of other metals and metal compounds to the extent that the object of the present invention is not impaired. be able to. The thickness of this layer (C) is 3 to 100 Å, preferably 10 to 100 Å.
50 Å, but when the thin film layer (C) is provided only on the heat ray reflective layer (D), or when it is provided on both the top and bottom,
In addition, it is appropriately changed and selected depending on the type of substance forming the thin film layer (C). For example, when the thin film layer (C) is provided in contact only with the heat ray reflective layer (D), the minimum film thickness is 25
Å, particularly 30 Å is preferred. Further, when the thin film layer (C) is provided above and below the heat ray reflective layer (D), the total minimum film thickness is preferably 10 Å, particularly 15 Å. Such an optimum film thickness can be appropriately selected depending on the type of substance forming the thin film layer (C). for example,
In the former case, Ti is 30 Å or more, Si,
For Co, Zr, C, Ni, and In, a film thickness of 25 Å or more can be exemplified. In the latter case, the total film thickness is 10 Å or more in the case of Ti, Si, and Zr. If the film thickness is too thin, the effect of improving durability will be small, and if it exceeds 100 Å, the transmittance in the visible light region will drop significantly, making it unsuitable for the purpose of a selective light transmitting laminate. In addition, as illustrated above, when the thin film layer (C) is provided both above and below the heat ray reflective layer (D), the thin film layer
There is an advantage that the film thickness of (C) can be thin. In the present invention, the high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) are made of one or more metals selected from titanium, indium, zinc, tin, yttrium, erbium, zirconium, cerium, tantalum, and hafnium. Zinc oxide or sulfide. These are transparent to visible light and have a high refractive index in visible light, with a refractive index of 1.6 or more, preferably 1.8.
It is particularly preferably 2.0 or more. From these viewpoints, titanium oxide is particularly preferred as the high refractive index transparent thin film layers (B ₁ ) and (B ₂ ). The film thickness of the high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) is 50 to 500
Å, particularly preferably 150 to 400 Å. Outside this range, visible light transmittance decreases. The high refractive index transparent thin film layers (B ₁ ) and (B ₂ )
can be provided by methods such as sputtering, vacuum deposition, ion plating, and wet coating. The wet coating method is a method in which, for example, a metal alcoholate solution is hydrolyzed to obtain an oxide layer. Taking as an example an organic titanate compound that forms a titanium oxide film, the alkyl group is not particularly limited, and examples include ethyl, propyl, isopropyl, butyl, stearyl, 2-ethylhexyl, and two types of these alkyl titanates. A condensate obtained by mixing the above and condensing the mixture may also be used. Although organic silicate itself forms a film with a low refractive index, it may be added as long as the overall refractive index does not become 1.6 or less. A solution obtained by diluting these metal alcoholates and their condensates with a suitable solvent may be applied and dried, and the solvent in this case may be used as long as it satisfies conditions such as solubility and boiling point. In general, hydrocarbons such as n-heptane and cyclohexane, mixed solvents such as ligroinsolvent naphtha, petroleum benzine, and petroleum ether, alcoholic solvents such as ethanol, propanol, butanol, and mixed solvents thereof are preferably used. It is also effective to add a catalyst to accelerate the curing of the transparent high refractive index thin film layer formed from metal alcoholate. Any catalyst may be used as long as it promotes hydrolysis and condensation reactions. Examples include sodium acetate, potassium acetate, naphthenic acid metal salts, and the like. Furthermore, addition of silicon alkylate is effective for mixing different types of metal alcohols, for example, for curing titanium alcoholate. In the selective light transmitting laminate of the present invention, at least one of the high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) is necessary. Of course, both (B ₁ ) and (B ₂ ) may be provided. The combination consisting of a heat ray reflective layer (D) and a thin film layer (C) is not limited to one, and other similar combinations can be stacked on top of this combination, so that the heat ray reflective layer (D) and the thin film layer (D) are alternately stacked. It is also possible to have a structure in which multiple layers are laminated. The laminate of the present invention may be provided with a transparent protective layer (E) on the uppermost surface. Such a protective layer (E) can suppress the influence of external environmental factors on the surface hardness, light resistance, gas resistance, water resistance, etc. of the laminate. Examples of substances that can be used to form such a transparent protective layer (E) include acrylic resins such as polymethyl methacrylate, polyacrylonitrile resins, polymethacrylonitrile resins, and polymers obtained from ethyl silicate. In addition to organic substances such as silicone resin, polyester resin, and fluororesin, inorganic substances such as silicon oxide can be mentioned. Polypropylene, polyethylene, etc. are also used. Examples of methods for forming the transparent protective layer (E) include existing methods such as coating and film lamination. Further, the thickness of these films must be within a range that exhibits a protective effect without reducing the heat ray reflection ability, which is the objective of the present invention, and may be changed as appropriate depending on the material and application. The selective light transmitting laminate thus obtained has excellent durability and can be advantageously used for heat ray reflection applications, but it can also be used for other applications that utilize its conductivity, such as electrode electroluminescent materials for liquid crystal displays. It is also used in fields such as electronics, such as electrodes, electrodes for photoconductive photoreceptors, and surface heating elements with antistatic layers. The visible light transmittance, durability, and infrared reflectance of the laminate of the present invention are determined by the film thicknesses of the heat ray reflective layer (D), thin film layer (C), and high refractive index transparent thin film layers (B ₁ ) and (B ₂ ). It can be changed freely by adjusting. The visible light transmittance is at least 50% or more, preferably 60% or more, and the average infrared reflectance is at least 70%, preferably 80% or more. Next, a method of calculating visible light transmittance and average infrared reflectance will be explained. To determine the visible light transmittance, first
Measure the transmittance from 450 to 700 mμ, and calculate the product of solar energy intensity and transmittance every 50 mμ. The visible light transmittance is normalized by dividing the total sum by the total solar energy intensity in the range of 450 to 700 mμ. On the other hand, in order to obtain the average infrared reflectance, first the infrared reflectance is measured in the range of 3 to 25μ. On the other hand, 300
〓The energy radiated from a black body at (27℃)
The product of the radiant energy and the infrared reflectance according to each wavelength is calculated every 0.2 μm, and the sum is calculated in the wavelength range of 3 to 25 μm. Then, the total sum is normalized by dividing it by the total sum of radiant energy intensity in the 3 to 25 μm region. This value represents the reflectance of energy (3 to 25 μm) radiated from a 300〓 black body.
The radiant energy in the 3 to 25 μm region corresponds to about 85% of the total black body radiant energy of 300 mm. Hereinafter, a more specific explanation of the present invention will be shown in Examples. All "parts" in the examples are based on weight. Examples 1 to 3, Comparative Examples 1 to 2 A film with a thickness of 300 Å was placed on a biaxially stretched polyethylene terephthalate film (A) with a light transmittance of 86% and a film thickness of 50 μm.
titanium oxide thin film layer (B ₁ ), 150 Å thick thin film layer made of silver and copper alloy (D) (92 wt% silver, 8 wt% copper), metallic titanium layer (C), and 280 Å thick titanium oxide thin film The layers (B ₂ ) were sequentially laminated to obtain a selectively transparent laminate. The titanium oxide thin film layer is made of 3 parts of tetramer of tetrabutyl titanate and 97% of isopropyl alcohol.
Apply a solution consisting of
Heat and set for 3 minutes. The silver-copper alloy layer was formed by direct current sputtering, targeting a silver-copper alloy (92% by weight silver, 8% by weight copper). The metal titanium layer was provided by vacuum evaporation using electron beam heating, and the film thickness is shown in Table 1. The selective light transmitting laminate was placed in a hot air dryer set at 90°C to perform a heat deterioration acceleration test, and the time required for the infrared light reflectance (10 μ) to reach 85% of the initial value was measured as the deterioration time. did. Table 1 shows the results, as well as the visible light transmittance and average infrared reflectance before the accelerated heat deterioration test. Furthermore, a laminate without a metal titanium layer was also shown as a comparative example.

[Table] As can be seen, in the case of no metallic titanium layer, the heat resistance is poor and the deterioration time is very short.
On the other hand, if the thickness of the titanium metal layer exceeds 100 Å, the visible light transmittance will drop significantly, making it unusable. Examples 4 and 5, Comparative Examples 3 and 4 In the same manner as in Example 1, a 300 Å thin layer of titanium oxide (B ₁ ) and a 150 Å layer of silver and copper alloy were formed on a biaxially stretched polyethylene terephthalate film (A). a thin film layer (D), a metallic titanium layer (C) of various thicknesses, and
280 Å titanium oxide thin film layers (B ₂ ) are laminated in sequence,
A laminate having selective light transmittance was obtained. However, in this case, the titanium oxide thin film layer was provided by low-temperature sputtering using a target formed from commercially available high-purity titanium dioxide powder. The sputtering conditions are as follows: The vacuum chamber is set to high vacuum (5×
10 ^-6 torr), then Ar gas was pumped to 5×10 ^-3 torr.
A titanium oxide thin film layer was formed using a high-frequency electric field. The high frequency sputtering output is 500W, the distance between the part to be sputtered and the target is 10cm, and the sputtering time is 300Å with a sputtering time of 20 minutes.
A titanium oxide thin film layer with a thickness of 280 Å was obtained in 18 minutes. Visible light transmittance, average infrared reflectance, and initial value of infrared light reflectance (10
μ) Deterioration time is shown in Table-2.

[Table] As can be seen from the table, heat resistance is poor when there is no metallic titanium layer, and when the thickness of the metallic titanium layer exceeds 100 Å, the visible light transmittance decreases significantly. Examples 6 and 7, Comparative Examples 5 and 6 Biaxially oriented polyethylene terephthalate film
(A) 300 Å thick titanium oxide thin film layer (B ₁ ) on top, 150 Å thin film layer made of silver and copper alloy (D) (92% silver by weight)
In a laminate in which 280 Å titanium oxide thin film layers (B ₂ ) were sequentially provided, various metallic titanium layers (C) were provided between the silver-copper alloy layer and the titanium oxide thin film layer, and their characteristics were evaluated. are shown in Table-3. Among the titanium oxide thin film layer forming methods, the one written as TBT method is one formed from a tetramer of tetrabutyl titanate as in Examples 1 to 3.
Examples 4 to 5 are those written as sputtering method.
It was formed by sputtering in the same way as . The metallic titanium layer was provided by vacuum evaporation using an electron beam.

[Table] Examples 8 to 11, Comparative Examples 7 to 9 The antireflection layer was made of titanium oxide formed by an ion plating method, instead of a titanium oxide thin film layer formed from a tetramer of tetrabutyl titanate. Example 1 was repeated except that the thin film layers of zirconium oxide and tantalum oxide were substituted and the thickness of the titanium metal layer was changed to the values shown in Table 4. Ion plating was performed under the following conditions. Oxygen gas partial pressure 5×10 ⁴ torr High frequency power (13.56MHz) 200W All film thicknesses were set at 300Å. The results are shown in Table-4.

[Table] Examples 12, 13, Comparative Example 10 A film with a thickness of 300 Å was placed on a biaxially stretched polyethylene terephthalate film (A) with a light transmittance of 86% and a film thickness of 50 μm.
a titanium oxide thin film layer (B ₁ ), a 150 Å thick thin film layer (D) made of an alloy of silver and copper (92 wt% silver, 8 wt% copper), a silicon layer (C), and a 280 Å thick titanium oxide thin film layer. (B ₂ ) were sequentially laminated to obtain a selective light transmitting laminate. The titanium oxide thin film layers (B ₁ ) and (B ₂ ) were each formed by applying a solution consisting of 3 parts of tetrabutyl titanate and 97 parts of isopropyl alcohol using a bar coater and heating at 120° C. for 3 minutes. Silver-copper alloy metal (D) is silver-copper alloy (silver 92% by weight,
Copper (8% by weight) was targeted and deposited by direct current sputtering. The silicon layer (C) was provided by vacuum deposition using electron beam heating, and the film thickness is shown in Table 5. Table 5 shows the visible light transmittance and average infrared reflectance before the accelerated heat deterioration test. Furthermore, a laminate without the silicon layer (C) was also shown as a comparative example.

[Table] As can be seen, in the case of no silicon layer (C), the heat resistance is poor and the deterioration time is very short. On the other hand, if the thickness of the silicon layer (C) exceeds 100 Å, the visible light transmittance decreases significantly, making it unsuitable for practical use. Examples 14, 15, Comparative Examples 11, 12 In the same manner as in Example 1, a 300 Å titanium oxide thin film layer (B ₁ ), a 150 Å silver layer (D), and a metal were deposited on a biaxially stretched polyethylene terephthalate film (A). Layers of various thicknesses deposited as titanium (C) and titanium oxide thin film layers (B ₂ ) of 280 Å were successively laminated to obtain a laminate having permselectivity. The titanium oxide thin film layer was provided in the same manner as in Example 1. The results are shown in Table-6.

[Table] From this table, even if the heat ray reflective layer (D) is made only of silver, heat resistance will be poor if there is no titanium layer, and if the titanium layer exceeds 100 Å, the visible light transmittance will decrease, making it unsuitable for practical use. I understand. Examples 16, 17 Biaxially oriented polyethylene terephthalate film
On top of (A) are a 300 Å titanium oxide thin film layer (A), a 300 Å titanium oxide thin film layer (B ₁ ), a 150 Å thin film layer made of silver and gold alloy (D) (92% silver by weight), and a 280 Å thin film layer (B 1 ). In a laminate in which titanium oxide thin film layers (B ₂ ) are sequentially provided, a silicon layer is provided between the silver and gold alloy layer and the titanium oxide thin film layers (B ₁ ) and (B ₂ ), respectively,
Table 7 shows the results of evaluating its characteristics. The method for forming the titanium oxide thin film layers (B ₁ ) and (B ₂ ) is written as the TBT method in Example 1, and the sputtering method is written as in Example 4.
It was formed in the same manner as. Silicon layer (C)
was provided by vacuum evaporation using an electron beam.

[Table] Examples 18 to 21 Instead of a titanium oxide thin film layer formed from a tetramer of tetrabutyl titanate, the antireflection layer was made of titanium oxide, zirium oxide, and tantalum oxide formed by an ion plating method. Example 12 was repeated except that the thin film layer was replaced and the thickness of the metal silicon was set to the value shown in Table 8. Ion plating was performed under the same conditions as in Example 8.

[Table] Examples 22 to 24, Comparative Example 13 A film with a thickness of 300 Å was placed on a biaxially stretched polyethylene terephthalate film (A) with a light transmittance of 86% and a film thickness of 50 μm.
Titanium oxide thin film layer (B ₁ ), carbon film layer (C), thickness
Thin film layer (D) consisting of a 150 Å silver and copper alloy (silver 92
(% by weight, 8% by weight of copper), a carbon layer (C), and a 280 Å titanium oxide thin film layer (B ₂ ) were sequentially laminated to obtain a selective light transmitting laminate. Titanium oxide layer (B ₁ ), (B ₂ ) and silver-copper alloy layer (D)
was provided in the same manner as in Example 1. The carbon film layer (C) was formed by vacuum deposition using electron beam heating, and the film thickness is shown in Table 9. The results are shown in Table-9.

[Table] When the thickness of the carbon layer exceeds 100 Å, the visible light transmittance increases. A thin layer of titanium (B ₁ ), a thin layer of silver and copper alloy of 150 Å (D), a carbon layer of various thicknesses (C) and a layer of 280 Å
Titanium oxide thin film layers (B ₂ ) were sequentially laminated to obtain a laminate having selective light transmittance. The results are shown in Table-10.

[Table] Examples 28 to 31 Titanium oxide thin film layers (B ₁ ) and (B ₂ ) were formed by ion plating instead of the titanium oxide thin film layer formed from the tetramer of tetrable titanate. Example 22 was repeated except that the carbon layer thickness was changed to the value shown in Table 11, and the thickness of the carbon layer was changed to the value shown in Table 11. Ion plating was performed under the same conditions as in Example 8. The results are shown in Table-11.

[Table] Examples 32 to 34, Comparative Examples 15 and 16 A film with a thickness of 300 Å was placed on a biaxially stretched polyethylene terephthalate film (A) with a light transmittance of 86% and a film thickness of 50 μm.
a titanium oxide thin film layer (B ₁ ), a 150 Å thick thin film layer (D) made of a silver and copper alloy (95% by weight of silver, 5% by weight of copper), a metallic cobalt layer (C), and a 280 Å thick titanium oxide thin film The layers (B ₂ ) were sequentially laminated to obtain a selectively transparent laminate. The titanium oxide thin film layers B ₁ and B ₂ were provided in the same manner as in Example 1. The silver-copper alloy layer (D) is a silver-copper alloy (silver 95% by weight,
A target of 5% by weight of copper was applied by direct current sputtering. The metal cobalt layer (C) was provided by vacuum evaporation using electron beam heating, and the film layers are shown in Table 12. Table 12 shows the results.

[Table] As can be seen, in the case without the metal cobalt layer (C), the heat resistance is poor and the deterioration time is very short. On the other hand, if the metal cobalt layer (C) exceeds 100 Å, the visible light transmittance decreases significantly, making it unsuitable for practical use. Examples 35 to 37, Comparative Examples 17 and 18 Laminated bodies having selective light transmittance were obtained using the same configuration as Example 32, but using metal nickel instead of metal cobalt. The nickel metal was provided by vacuum evaporation using electron beam heating. Table 13 shows the initial characteristics and 90°C aging time (hr) of those samples.

[Table] As can be seen, in the case without the metal nickel layer (C), the heat resistance is poor and the deterioration time is very short. On the other hand, if the thickness of the metal nickel layer (C) exceeds 100 Å, the visible light transmittance will drop significantly, making it unusable. Examples 38-41, comparative rows 19-21 In the same manner as in Example 32, a 300 Å titanium oxide thin film layer (B ₁ ), a 150 Å silver and copper alloy layer was applied on a biaxially oriented polyethylene terephthalate film (A). A thin film layer (D) having various thicknesses, a metallic cobalt layer (C) of various thicknesses, or a metallic nickel layer and a titanium oxide thin film layer (B ₂ ) of 280 Å were sequentially laminated to obtain a laminate having selective light transmittance. The titanium oxide thin film layers (B ₁ ) and (B ₂ ) were prepared in Example 4,
It was set up in the same way as 5. The results are shown in Table-14.

[Table] As can be seen, heat resistance is poor when there is no metallic nickel or metallic cobalt layer in the metal layer (C), and visible light transmittance decreases significantly when the thickness of these layers exceeds 100 Å. . Examples 42-45 Biaxially oriented polyethylene terephthalate film
(A) 300 Å thick titanium oxide thin film layer (B ₁ ) on top, 150 Å thin film layer made of silver and copper alloy (D) (92% silver by weight)
In the laminate in which titanium oxide thin film layers (B ₂ ) of 280 Å are sequentially provided, a silver-copper alloy layer (D) is interposed between the titanium oxide thin film layers (B ₁ ) and (B ₂ ), and various metals are placed between the titanium oxide thin film layers (B 1 ) and (B 2 ). Table 15 shows the results of evaluating the characteristics of a cobalt layer (C) or metal nickel layer (C). Titanium oxide thin film layer (B ₁ ), (B ₂ ) formal method,
Those labeled as TBT method were formed from a tetramer of tetrabutyl titanate as in Example 32, and those labeled as sputtering method were formed by sputtering as in Example 38. . The metal cobalt layer and the metal nickel layer were provided by vacuum evaporation using an electron beam.

[Table] Examples 46 to 49, Comparative Examples 22 to 24 The antireflection layer was made of titanium oxide formed by an ion plating method, instead of a titanium oxide thin film layer formed from a tetramer of tetrable titanate. Example 32 was repeated except that the thin film layers of zirconium oxide and tantalum oxide were substituted and the thickness of the metal cobalt layer or metal nickel layer was changed to the values shown in Table 16. Ion plating was performed in the same manner as in Example 8. The results are shown in Table-16.

[Table] Examples 50 to 53 Same configuration as Example 7, except that the titanium oxide thin film layer formed by the TBT method was replaced with a zirconium oxide thin film layer formed from tetrabutoxyzirconate as the _B1 and _B2 layers, and further, A laminate was formed by replacing the thin film layer (D) made of an alloy of silver and copper with a 160 Å single silver layer and a silver-gold alloy layer.
The zirconium oxide thin film layer was formed by applying a solution consisting of 7 parts of tetrabutoxyzirconate, 40 parts of n-hexane, 20 parts of ligroin, and 33 parts of n-butanol using a bar coater and drying at 130°C for 5 minutes. The silver and silver-gold alloy layers were formed by direct current sputtering, targeting silver and silver-gold alloy (90% by weight silver, 10% by weight gold), respectively. The results are shown in Table-17.

[Table] Examples 54 to 58, Comparative Example 25 A laminate was created in the same manner as in Example 7, except that layers B ₁ and B ₂ and layers C ₁ and C ₂ were configured as shown in Table 18 below. . Transparent protective layer (E) on the surface of each laminate
Wet coating from cyclohexanone solution as
A polymethacrylonitrile layer with a thickness of 2 μm was provided by a method. Their characteristics are also shown in Table 18.

[Table] Examples 59 and 60 Laminated bodies were prepared in the same manner as in Example 7, except that the metal titanium layers (C ₁ ) and (C ₂ ) had the thicknesses shown in Table 19 below. Their characteristics are also shown in Table 19 below.

【table】

Claims (1)

[Claims] 1. A transparent sheet-like base material (A); A heat ray reflective layer (D) with a thickness of 50 to 300 Å mainly composed of silver on the sheet-like base material (A); A high refractive index transparent thin film layer (B ₁ ) provided between the base material (A) and the heat ray reflective layer (D), or a high refractive index transparent thin film layer (B ₂ ) provided on the heat ray reflective layer (D). ), or both of the high refractive index transparent thin film layers (B ₁ ) and (B ₂ ); a transparent protective layer (E) provided on the top surface if necessary; a laminate basically consisting of; Ti; , Zr, In, Si, C, Co, and Ni with a thickness of 3 to 100 Å.
A selective light transmitting laminate in which a thin film layer (C) is provided on and in contact with a heat ray reflection prevention layer (D). 2. The selective light transmitting laminate according to claim 1, wherein the thin film layer (C) is laminated in contact with both sides of the heat ray reflection prevention layer (D). 3. The selective light transmitting laminate according to claim 1, wherein the heat ray reflection prevention layer (D) is mainly composed of silver containing 0.1 to 30% by weight of copper and/or 3 to 30% by weight of gold. body. 4 The high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) are
titanium, indium, zinc, tin, yttrium,
The selective light transmitting laminate according to claim 1, which is an oxide or zinc sulfide of one or more metals selected from erbium, zirconium, cerium, tantalum, and hafnium. 5 The high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) are formed from an organic titanium compound, and have an organic group of 0.1
The selective light transmitting laminate according to claim 1, which contains titanium oxide in an amount of 5% by weight. 6 The high refractive index transparent thin film layers (B ₁ ) and (B ₂ ) are 50
The selective light transmitting laminate according to claim 1, which has a film thickness of ~500 Å. 7. The selective light transmitting laminate according to claim 1, wherein the thin film layer (C) has a minimum thickness of 25 Å. 8. The selective light transmitting laminate according to claim 2, wherein the total minimum thickness of the thin film layers (C) provided above and below the heat ray reflection prevention layer (D) is 10 Å. 9 Visible light transmittance is 50% or more, average infrared reflectance is
The selective light transmitting laminate according to claim 1, wherein the selective light transmittance is 70% or more.