KR880000988B1 - Selective light transmission laminate - Google Patents

Abstract

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Description

Selective light transmission laminate

The present invention relates to a laminate which selectively transmits light having various excellent properties of transmitting visible light and reflecting heat waves or infrared rays. More specifically, the present invention relates to a selective light-transmitting laminate having improved resistance to light, heat, gas, etc., in particular, Ti, Zr, In, SI, C, on the surface of the silver-containing metal layer that reflects heat waves By providing a layer deposited as a selective material from Co and Ni, it relates to a selective light transmissive laminate which is significantly improved in resistance to thermal degradation represented by a degradation time of at least about 1,000 hours (often more than about 5,000 hours).

In particular, the present invention relates to a selective light transmissive laminate composed of the following layers, characterized by a thin layer deposited as a material selected from Ti, Zr, In, SI, C, Co and Ni with a thickness of 3-100 kPa (C) is characterized in that it is configured in contact with the layer (D):

(1) the base layer (A) of the transparent sheet structure,

(2) a heat wave reflection layer (D) of a silver-containing metal formed on the layer (A) and having a thickness of 50-300 kPa,

(3), a thin transparent layer (B ₁ ) having a high refractive index disposed between layers (A) and (D), a thin transparent layer (B ₂ ) having a high refractive index on layer (D), or both layers (B ₁ ) And (B ₂ ) both (optional),

(4) Top transparent layer (E) on layer (D) (optional).

Numerous studies on heat wave reflection or conductive laminates and the like have been recorded in the following patents: US Pat. Nos. 3698946, 3962488, 4017661 and 4020389, Japanese Patent Application No. 66841/76, British Patent 1307642, and French Patent No. 2043002 , Belgian Patent No. 673528, Canadian Patent No. 840513, Federal Republic of Germany Publication Nos. 2813394 and 2828576 and European Patent Application No. 8030985.

Optionally, light transmitting laminates are useful as transparent thermal insulation layers because the laminate is transparent to visible light but can reflect infrared radiation (including near infrared light). Thus, the laminate can be used for solar integrators (water heaters), solar energy generation, window sections of greenhouses and window sections of frozen and cooled glass showcases.

In particular, the laminate is of increasing importance because the window acts as a transparent thermal insulation window that prevents energy dissipation and uses solar energy in a modern building that occupies most of the building wall. This laminate is also important as a film in greenhouses used to grow vegetables and fruits.

As such, selective light transmissive laminates are important in that they utilize solar energy, and it is technically desirable to provide a large amount of inexpensive and effective films.

Known thin transparent laminates of electrically conductive metals described in the above patents (i) thin layers of metals such as gold, copper, silver and palladium, (ii) thin layers of semiconductor compounds such as indium oxide, tin oxide and copper iodide Layer and (iii) a thin layer of electrically conductive metal, such as gold, silver copper and palladium, which is optionally transparent at certain wavelengths. It is known that laminates of indium or tin oxide layers of several thousand angstroms thick and metal layers and transparent conductive layers are selectively transparent and have a high ability to reflect infrared light. However, transparent electrically conductive films or selective and transmissive films with good action have not been produced at low prices.

In the aforementioned Federal Republic of Germany Publication No. 2813394, an electrically conductive transparent laminate composed of:

(A) a transparent solid substrate,

(B) a thin layer of titanium oxide in contact with the base layer (A),

(C) a thin layer of electrically conductive metal in contact with said layer (B),

(D) a thin layer of titanium oxide in contact with layer (C),

(E) Top transparent layer in contact with layer (D) (optional).

By the way, here are the following features:

(i) the base layer (A) is a film-forming synthetic resin layer,

(ii) The layer (B) is a titanium oxide layer derived from a layer of an organic titanium compound and containing an organic residual group in the organic titanium compound.

In this patent, a thin metal layer containing both silver and copper is known to be good as a thin layer (C) of electrically conductive metal. In particular, it is preferable to use layer (C) composed of silver and copper as 1-30% of the total weight of silver and copper.

In Federal Republic No. 2828576, the use of thin layers of metals selected from gold, silver, copper aluminum and at least two of these alloys or mixtures is described.

In European Patent Application Publication No. 0007224

(A) molded solid substrate,

(B) a thin transparent layer having a high refractive index in contact with the base layer (A),

(C) a transparent heat wave reflecting layer of an electrically conductive metal in contact with the layer (B),

(D) a thin transparent layer (D ') having a high refractive index in contact with the layer (C) and a top transparent layer (D ") (optionally) in contact with the thin transparent layer (D'), the layer ( C) describes a heat wave reflecting or electrically conductive laminate, characterized in that the amount of silver is a layer composed of silver and gold with 3-30% of the total weight of silver and gold.

However, in any of the prior art, a heat wave reflecting or electrically conductive laminate having a layer deposited in contact with a heat wave reflecting Ag-containing metal layer as a material selected from Ti, Zr, SI, In, C, Co and Ni is described. Not.

In the present invention, as described above, the selective light transmissive laminate having a thin transparent layer having a high refractive index imparted on the heat wave reflecting Ag-containing metal layer shows that the action is reduced by the influence of heat, gas around the light, and the like.

In order to overcome these technical difficulties, studies have shown that a material selected from Ti, Zr, Si, In, C, Co and Ni provides a thin layer deposited on or both above and below a heat wave reflecting layer of a silver-containing metal. It is possible to overcome the technical difficulties due to the surface diffusion of silver in the heat wave reflecting silver-containing metal layer caused by conditions such as light and gas, and to produce a selective light transmitting laminate having a significantly improved resistance to ambient conditions.

Thin layers of such materials can be formed on hot-wave reflecting silver-containing metal layers by known methods such as vacuum deposition and sputtering. It is understood that the material forming this layer should be deposited under conditions that are not converted to its oxides or other compounds, in particular thin layers should be deposited as materials selected from Ti, Zr, Si, In, C, Co and Ni. Paid.

Thus, selective light transmissive laminates can be provided that can impart high resistance to thermal degradation, which has been demonstrated with a number of excellent properties, in particular, a degradation time of at least about 1,000 hours (often more than about 5,000 hours), where the degradation time is determined by It is defined as the time that elapses until the infrared reflectance at 9.8 or 10 micron wavelength is reduced by 90% and by 85% in the degradation experiment.

It is therefore an object of the present invention to provide selective light transmissive laminates having various improved and excellent properties.

These and other objects and advantages of the present invention will become more apparent from the following description.

The laminate according to the invention consists of:

(1) the base layer (A) of the transparent sheet structure,

(2) a heat wave reflecting layer (D) of a silver-containing metal having a thickness of 50-300 kPa formed on the layer (A),

(3) a thin transparent layer (B ₁ ) having a high refractive index disposed between layers (A) and (B), a thin transparent layer (B ₂ ) having a high refractive index on layer (D), or both layers (B ₁ ); (B ₂ ), or both layers (B1) and (B ₂ ) (optionally),

(4) Top transparent layer (E) on layer (D) (optional).

Here, the laminate has a thickness of 3 to 100 GPa and a thin layer (C) deposited as a material selected from Ti, Zr, In, Si, C, Co and Ni is formed in contact with the layer (D). It features.

In another embodiment, layer (C) may also be formed in contact below layer (D).

The base layer A may be a molded solid base composed of organic, inorganic or mixtures thereof. In the present invention, the term " transparent sheet-like structure " means to include shapes such as films, sheets and plates, and the term " transparent " means to include colored and transparent states.

In the base layer (A), the organic material is preferably an organic synthetic resin. Specific examples of the resin include thermoplastic resins such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylic resin, ABS resin, polystyrene polyacetal, polyethylene, polypropylene, polyamide and fluorocarbon resin; Thermosetting resins such as epoxy, diallyl portate, silicone, unsaturated polyester, phenol and urea resin; And solvent soluble resins such as polyvinyl alcohol, polyacrylonitrile, polyurethane, aromatic polyamides and polyimides. These are in the form of homopolymers or copolymers and can be used singly or as a mixture.

Molded solid substrates composed of inorganic materials include glass materials such as soda glass, borosilicate glass and silicate glass, metal oxides such as alumina, silica, magnesia and zirconia and semiconductors such as gallium-arsenic, indium-phosphorus, silicon- and germanium It can be molded into.

The heat wave reflecting layer (D) of the silver containing metal having a thickness of 50-300 mm 3 may be an Ag layer, or may be Ag and another metal or metal compound layer. Examples of metals or metal compounds that may be present with silver may be Au, Cu, Al, In, Zn and Sn (particularly Au and Cu) and their compounds. For example, the Ag-containing metal layer (D) may comprise an Ag layer, an Ag layer containing up to 30% by weight Cu, an Ag layer containing up to 30% by weight Ag, up to 30% by weight Cu and up to 30% by weight Ag layer containing Au. The light resistance of the selective light transmitting laminate according to the present invention can be improved by mixing copper with 0.1-30% by weight (preferably 0.3-15% by weight) of silver. Heat resistance for the laminate of the present invention can be improved by containing 3-30% by weight of copper in silver.

The thickness of the heat-wave reflecting layer D of the silver containing metal is preferably 50-300 kPa (70-200 kPa). If the thickness of the layer (D) is too small, 50 kPa or less, the infrared reflectance and heat resistance of the laminate tend to decrease. If the thickness of the layer (D) is too large, such as 300 kPa or more, the visible light transmittance of the laminate is reduced and practically unusable.

In order to form a thin silver containing metal layer (D), a well-known method can be used. For example, a vacuum deposition method, a cathode sputtering method, a plasma flame spraying method, a gas phase plating method, an electroless plating method, an electroplating method, a chemical coating method, and a mixture thereof may be used.

Layer C, having a thickness of 3-100 microns and deposited as a material selected from Ti, Zr, Si, In, C, Co and Ni, is an important feature of the selective light transmissive laminate of the present invention, and is known as vacuum deposition and cathode sputtering. By means of a method formed on the layer (D) or both above and below the layer (D).

At least the material is then deposited under conditions that are not converted to that oxide or other compound. For Ti, smaller degrees of oxidation, such as TiOx generation, where X is less than 1.3 (preferably less than 1), can be tolerated. It is desirable to select conditions so that partial or complete oxidation outside of this level cannot occur. The same applies to the other materials forming the layer C. For example, the tolerance of partial oxidation is MOx, where M is a metal and X is about 1.0 or less.

Layer C deposited as a material (including a mixture of two or more of these metals) selected from Ti, Zr, Si, In, C, Co and Ni may also contain very small amounts of another metal or metal compound.

The thickness of layer C is 3-100 kPa (preferably 10-50 kPa). The thickness of layer C varies suitably depending on the material forming layer C, and depending on whether it is constructed only on layer D or both above and below layer D. For example, when layer C is constructed in contact only on layer D, its minimum thickness is preferably 25 mm 3, in particular 30 mm 3. When layer C is constructed in contact with both above and below layer D, the total minimum thickness of both layers C is preferably 10 ns, in particular 15 ns. The thickness of layer C may be selected depending on the type of material forming layer C. For example, in the former case, the thickness of the layer C may be at least 30 mW for Ti, and at least 25 mW for Si, Co, In, Zr, C, and Ni. In the latter case, the overall thickness may be at least 10 mm 3 for Ti, Si and Zr.

If the thickness of layer C is too small outside the above defined range, there is little effect in improving the durability of the laminate. On the other hand, if it is too large beyond 100 kHz, the transmittance of the laminate in the visible region is significantly reduced so that the resulting laminate selectively does not sufficiently transmit light. When layer C is configured both above and below layer D, the thickness of each layer C is smaller.

The laminate of the present invention may comprise a thin transparent layer (B ₁ ) and / or B ₂ ) having a high refractive index. Thin transparent layers (B ₁ ) and / or (B ₂ ) with high refractive indices are formed from Ti, In, Zn, Sn, Y, Er, Zr, Ce, Ta, Ge and Hf, including mixtures of two or more of them. Oxide layer or ZnS layer of the selected metal. The refractive index of layer (B ₁ ) or (B ₂ ) is at least 1.6 (preferably at least 1.8 and particularly preferably at least 2.0) and the visible light transmittance is at least 60% (preferably at least 75%).

Thin layers of titanium oxide are particularly good as layers (B ₁ ) and / or (B ₂ ).

The thickness of layer (B ₁ ) or (B ₂ ) is 50-500 mm 3, particularly preferably 150-400 mm 3. Thickness outside the prescribed range tends to reduce the visible light transmittance of the laminate. The thin transparent layers (B ₁ ) and / or (B ₂ ) can be formed by known methods such as sputtering, ion plating, vacuum deposition, wet coating, and the like.

The wet coating method consists of coating a solution of a metal alcoholate or the like and hydrolyzing the coating to form a metal oxide layer. For the purposes of the present invention, organotitanic compounds such as organotitanate compounds such as tetrabutoxy titanate; Organic zirconate compounds such as tetrabutoxy zirconate; Organoaluminum compounds such as aluminum tri-secondary-butoxide; And an organic germanium compound such as tetrabutoxy germanium may be used as the material for forming the metal oxide layer. Since the alkoxy group bonded to the metal atom can be transesterified or polycondensed by a known method, the compounds can be used in the present invention. Several kinds of metal alkoxides may be used by mixing or polycondensation, in which case the metal alkoxide may have different metal atoms.

For example, in the case of organotitanates taken as examples of metal alkoxides, the alkyl group may be ethyl, propyl, isopropyl, butyl, 2-0ethylhexyl, stearyl, and the like, condensing two or more of these tetraalkyl titanates The condensate obtained by this can also be used. Or as described above, metal alkoxides of various metals, for example aluminum tri-secondary-butoxide, aluminum tri-iso-propoxide-tetrabutoxy zirconate and tetrabutoxy germanium are condensed or mixed Can be used.

The organic silicate compound capable of forming a film having a low refractive index alone, such as monomethyltrimethoxysilane or monoethyltriethoxysilane, may be mixed at a rate such that the refractive index of the entire metal oxide layer does not decrease beyond 1.6. .

The layers can be formed by diluting the metal alkoxide compound or its condensation product or mixture thereof in a suitable solvent, coating the resulting solution, and drying the coated layer to induce polymerization. The solvent used for this purpose must satisfy certain values for solubility, boiling point and inertness in the metal alkoxide (the property of not inhibiting crosslinking of the metal alkoxide by condensation). Examples of solvents include hydrocarbons such as n-heptane and cyclohexane, hydrocarbon mixtures such as ligroin, solvent naphtha, petroleum benzine and petroleum ether and mixtures thereof.

It may be effective to add a catalyst to promote the production of a transparent layer having a high refractive index. The catalyst may be any one that promotes the hydrolysis and condensation of the metal alkoxide, and examples thereof include fine acetate, potassium acetate and metal naphthenate. Mixing of various kinds of metal alkoxides is an effective method such that addition of silicon alkoxide is effective for titanium alkoxide curing.

Constituting at least one of layers (B ₁ ) and (B ₂ ) is essential for the selective light transmitting laminate of the present invention. The laminate does not necessarily comprise only one combination of layer D and layers or layers (C), two or more such combinations may be present in the laminate of the invention.

The laminate of the present invention may also include a top transparent layer (E) as an optional layer. The top layer E serves to improve the surface hardness, light resistance, gas resistance, water resistance and the like of the laminate. Examples of materials that can be used to form this top layer (E) include organic materials, for example polymethyl methacrylate resins, polyacrylonitrile resins, acrylic resins such as polymethacrylonitrile resins, poly Polyolefin resins such as propylene; Polymers derived from ethyl silicates; Polyester resin; Fluorine-containing resins; Inorganic materials such as silicon oxide.

The top layer E can be formed by known methods such as coating, film lamination and vacuum deposition. The thickness of the top layer E can be chosen as appropriate. For example, 0.05-10 microns (preferably 0.1-5 microns). A layer can be constructed below the top worm to improve adhesion and the like.

The laminate of the present invention formed as described above is excellent in durability, and is advantageous for use in a wide range of applications for heat wave reflection by heat wave reflectivity, and may be advantageous for use in a wide range of electrotechnical applications due to electrical conductivity. .

For example, the selective light transmitting laminate of the present invention may be used as a selective light transmitting material for effectively utilizing sunlight or may be used as an energy saving material by using a thermal insulating material. Moreover, the present laminate can be used as a panel heater by using a transparent electrode, a photoconductive photosensitive material, an antistatic layer, and electrical conductivity for liquid crystal display and electroluminescence.

Visible light transmittance and surface resistance of the laminate of the present invention by controlling the thickness of the thin metal layer (D), the thin layer (C), the layer (B ₁ ) and / or (B ₂ ) of the silver-containing metal and their lamination method. And the infrared reflectance can be freely changed as needed.

Typical uses for the laminate thus obtained are as heaters, such as transparent electrically conductive laminates in antistatic or photoconductive photosensitive layers, panel light emitters such as liquid crystal electroluminescent or transparent electrodes for solid state displays, and removal heaters for window of automobiles. Transparent panel heaters and transparent thermal insulation laminates used in glass parts of window panes in buildings, greenhouses and frozen and cooled glass showcases.

Selective light transmissive laminates of the present invention exhibit at least 50% visible light transmission and at least 70% average infrared reflectance (preferably at least 60% visible light transmission and at least 80% average infrared transmission).

The present invention is explained in detail by the following examples.

All parts in these examples are by weight unless otherwise indicated. The visible light transmittance and average infrared reflectance of the laminate are determined by the following method.

Visible light transmittance

The transmittance is measured in the visible region of 450 to 700 mu m. The product of the intensity and transmittance of solar energy is calculated every wavelength increments of 50 μm, and the sum of the products in this region is divided by the total intensity of solar energy at 450-700 μm. The obtained value is defined as visible light transmittance (%).

[Mean infrared reflectance]

Infrared reflectance was measured by an infrared spectrophotometer (model EPI-II, manufactured by Hitachi, Ltd.) consisting of a reflection measuring device.

The measurement is performed in the infrared wavelength region of 3 to 25 mu m. The energy radiated from the blackbody at 300 ° K (27 ° C.) is measured at wavelength increments of 0.2 μm, and the product of radiation energy and infrared reflectance corresponding to each wavelength is calculated at wavelength increments of 0.2 μm. The sum of the enemies is calculated in the wavelength range of 3 to 25 mu m. The sum of the enemies is divided by the total intensity of the radiant energy in the wavelength range of 3 to 25 μm. The obtained value represents the average reflectance (wavelength region of 3 to 25 mu m) of the energy radiated from the black body at 300 ° K.

The radiant energy in the wavelength range of 3 to 25 mu m corresponds to about 85% of the total radiated energy of the blackbody at 300 ° K.

[Examples 1-3 and Comparative Examples 1 and 2]

300 Å thick titanium oxide layer (layer B ₁ ), 150, thick silver and copper alloy layer (92 wt% silver and 8 wt% copper) (layer (D), metal titanium layer (layer C) and 280 두께 thickness The phosphorus titanium oxide layer (layer B ₂ ) was successively laminated to a biaxially oriented polyethylene terephthalate film having a light transmittance of 86% and a thickness of 50 microns to obtain a laminate that selectively transmits light.

Each titanium oxide layer was formed by coating by a bar coater with a solution consisting of 3 parts of tetramer and 97 parts of isopropyl alcohol of tetrabutyl titanate and heating the coated layer at 120 ° C. for 3 minutes.

The silver-copper alloy layer was formed by DC sputtering using a silver-copper alloy composed of 92 wt% silver and 8 wt% copper as targets.

A metal titanium layer (layer C deposited with Ti) was formed in each thickness shown in Table 1 by vacuum deposition using electron beam heating.

Selective light transmitting laminates were injected into a hot air dryer maintained at 90 ° C. for resistance to accelerated thermal degradation. The time elapsed until the infrared reflectance (wavelength 10 microns) of the sample was reduced to 85% of the initial value was defined as the deterioration time.

Table 1 shows the visible light transmittance and the average infrared reflectance before the experiment and their experimental results.

Comparative Example 1 shows the same laminate except that layer C was left out.

TABLE 1

From the results shown in Table 1, the thermal resistance of the laminate when it does not include the layer C deposited as Ti is very weak and the deterioration time is very short, and when the thickness of the metal titanium layer exceeds 100 GPa, the laminate becomes visible light. It can be seen that it is not suitable for use because of the significant decrease in transmittance.

[Examples 4 and 5 and Comparative Examples 3 and 4]

Titanium oxide layer (B ₁ ) having a thickness of 300 μs, alloy layer (D) of silver and copper having a thickness of 150 μs, metal titanium layer (C) of each thickness shown in Table 2, and titanium oxide layer having a thickness of 280 μs (B ₂₎ ) Was successively laminated on a biaxially oriented polyethylene terephthalate film (layer A) to obtain a selective light transmitting laminate in the same manner as in Example 1.

Each titanium oxide layer B ₁ , B ₂ was formed by low temperature sputtering using a target formed from a high purity commercially available titanium dioxide powder. The vacuum vessel was made high vacuum (5 × 10 ⁻⁶ torr) and argon gas was introduced at a pressure of 5 × 10 ⁻³ torr. Sputtering was performed in a high frequency electric field in the vessel. The output of high frequency sputtering was 500W, and the distance between the substrate and the target was adjusted to 10 cm. Titanium oxide layer B ₁ was formed by performing sputtering for 20 minutes, and titanium oxide layer B ₂ was formed by performing sputtering for 18 minutes.

In Table 2, the degradation time of the laminate in relation to the visible light transmittance, the average infrared reflectance, the initial infrared reflectance (10 microns) and the thickness of the metal titanium layer C ₁ is shown.

TABLE 2

From the experimental results shown in Table 2, the heat resistance of the laminate becomes weak when the laminate does not contain the metal titanium layer C, and the visible light transmittance of the laminate is significantly reduced when the thickness of the metal titanium layer exceeds 100 GPa. It can be seen.

[Examples 6 and 7 and Comparative Examples 5 and 6]

Of the titanium oxide layer (B ₁₎ having a thickness of 300Å, having a thickness of 150Å silver and copper alloy layer (D) (92 wt%) and a thickness of the orientation of 280Å of titanium oxide layer (B ₂₎ a biaxial polyethylene terephthalate In a laminate obtained by continuously forming on a phthalate film (layer A), each of the various metal titanium layers (C) deposited as Ti is a silver-copper alloy layer (D) and a titanium oxide layer (B ₁ ) or (B ₂ ) formed between. As a result, various properties of the resulting laminate were measured, and the results are shown in Table 3.

Titanium oxide layers B ₁ and B ₂ were formed from tetramers of tetrabutyl titanate by the TBF method or by the sputtering method as in Examples 4 and 5 as in Examples 1-3.

The metal titanium layer C was formed by vacuum deposition using an electron beam.

TABLE 3

[Example 8-11 and Comparative Example 7-9]

Example 7 was repeated except that the layer of titanium oxide, zirconium oxide or tantalum oxide formed by the ion plating method was used as the antireflection layer instead of the titanium oxide film layer formed from the tetramer of tetrabutyl titanate, and the metal titanium The thickness of layer C deposited as was varied as shown in Table 4. Ion plating was carried out under the following conditions.

Oxygen gas partial pressure: 5 × 10 ^-4 torr

High frequency power (13.56 MHz): 200 W

The thickness of the reflection suppression layer was 300 kPa in all examples and comparative examples. The results are shown in Table 4.

TABLE 4

[Examples 12 and 13 and Comparative Example 10]

The light transmittance of the titanium oxide layer (B ₁ ) having a thickness of 300 μs, the silver and copper alloy layer (D) having a thickness of 150 μs, the silicon layer (C) deposited as Si, and the titanium oxide film layer (B ₂ ) having a thickness of 280 μs This was 86% and was successively laminated to a biaxially oriented polyethylene terephthalate film (A) having a thickness of 50 microns to obtain a selective light transmitting laminate.

Titanium oxide film layers B ₁ and B ₂ and alloy layer D were formed as in Example 1.

Silicon layer C was formed to the thickness shown in Table 5 by vacuum deposition using electron beam heating. The results are shown in Table 5. Comparative Example 8 showed the laminate showing the same laminate but without the silicon layer C.

TABLE 5

From the results shown in Table 5, it can be seen that when the thickness of the silicon layer exceeds 100 GPa, the laminate is not suitable for practical use due to the severe decrease in visible light transmittance.

[Examples 14 and 15 and Comparative Examples 11 and 12]

The selective light transmissive laminate was formed by successively laminating a titanium oxide layer B ₂ having a thickness of 300 GPa in a biaxially oriented polyethylene terephthalate film (layer A) in the same manner as in Example 1.

Titanium oxide film layers B ₁ and B ₂ were formed in the same manner as in Example 1. The results are shown in Table 6.

TABLE 6

From the results shown in Table 6, it can be seen that the heat resistance is weakened when the laminate does not contain the titanium layer C, and the visible light transmittance of the laminate is significantly reduced when the thickness of the titanium layer C exceeds 100 GPa.

[Examples 16 and 17]

Titanium oxide layer B ₁ having a thickness of 300 μs, silver and gold alloy layer D having a thickness of 150 μs (92 wt%), and titanium oxide layer B ₂ having a thickness of 280 μs were successively laminated on a biaxially oriented polyethylene terephthalate film (layer A). In the laminate obtained by the above, a silicon layer having each thickness shown in Table 7 was formed between the silver-gold alloy layer D and each titanium oxide film layer B ₁ and B ₂ . The results are shown in Table 7.

Titanium oxide film layers B ₁ and B ₂ were formed by the TBT method or the sputtering method as in Examples 12 and 13 and Examples 14 and 15.

Silicon layer C was formed by vacuum deposition using an electron beam.

TABLE 7

Example 18-21

Example 12 was repeated except that the layer of titanium oxide, zirconium oxide or tantalum oxide formed by the ion plating method was used as the antireflection layer instead of the titanium oxide layer formed from the tetramer of tetrabutyl titanate, and the silicon metal layer was The thickness was changed as in Table 8.

Ion plating was carried out under the same conditions as in Example 8. The results are shown in Table 8.

TABLE 8

[Examples 22-24 and Comparative Example 13]

Titanium oxide layer (B ₁ ) having a thickness of 300 kPa, carbon layer (C), silver and copper alloy layer (D) having a thickness of 150 kPa (92 wt% silver and 8 wt% copper), carbon layer (C) and thickness A 280 티타늄 titanium oxide layer (B ₂ ) was successively laminated to a biaxially oriented polyethylene terephthalate film (layer A) having a light transmittance of 86% and a thickness of 50 microns to obtain a selective light transmitting laminate.

The titanium oxide layers B ₁ and B ₂ and the silver-copper alloy layer were formed in the same manner as in Example 12.

Layer C deposited with carbon was formed by vacuum deposition using electron beam heating, the thicknesses of which are shown in Table 9. The results are shown in Table 9.

TABLE 9

From the result shown in Table 9, when the thickness of carbon layer C exceeds 100 GPa, it turns out that visible ray transmittance remarkably decreases.

[Examples 25-27 and Comparative Example 14]

Performing the titanium oxide layer (B _1), a titanium oxide layer (B ₂₎ having a thickness of 150Å-in and a copper alloy layer (D), a thickness of the carbon layer C and a thickness of 280Å as shown in Table 10 having a thickness of 300Å Example 22 The selective light transmissive laminate was obtained by successively stacking on biaxially oriented polyethylene terephthalate (layer A) in the same manner as in. The results are shown in Table 10.

TABLE 10

From the results shown in Table 10, it can be seen that the thermal resistance of the laminate is weak when the laminate does not contain the carbon layer C, and the visible light transmittance of the laminate is greatly reduced when the thickness of the carbon layer C exceeds 100 GPa. .

Example 28-31

Example 22 was repeated except that the layer of titanium oxide, zirconium oxide or tantalum oxide formed by the ion plating method was used as a reflection inhibiting layer instead of the titanium oxide layer formed from the tetramer of tetrabutyl titanate, and the carbon layer was The thickness was changed as in Table 11.

Ion plating was carried out under the same conditions as in Example 8. The results are shown in Table 11.

TABLE 11

[Examples 32 and 34 and Comparative Examples 15 and 16]

Titanium oxide layer (B ₁ ) having a thickness of 300 μs, silver and copper alloy layer (D) having a thickness of 150 μs (95% of silver and 5% by weight of copper), metal cobalt layer (C) deposited with Co, and having a thickness of 280 μs The titanium oxide film layer (B ₂ ) was successively laminated to a biaxially oriented polyethylene terephthalate film (layer A) having a light transmittance of 86% and a thickness of 50 microns to obtain a selective and permeable laminate.

Titanium oxide layers B ₁ and B ₂ and a silver-copper alloy layer were formed as in Example 1.

The metal cobalt layer C was formed at each thickness shown in Table 12 in vacuum deposition using electron beam heating. The results are shown in Table 12.

TABLE 12

The results shown in Table 12 show that the heat resistance is weak when the laminate does not contain the metal cobalt layer C, and the visible light transmittance of the laminate is greatly reduced when the thickness of the metal cobalt layer C exceeds 100 GPa.

[Examples 35 and 37 and Comparative Examples 17 and 18]

Example 32 was repeated except that metal nickel was used instead of metal cobalt. The metal nickel layer C was formed by vacuum deposition using electron beam heating.

Table 13 shows the thickness and the resultant values of the metal titanium layer.

TABLE 13

From the results shown in Table 13, when the laminate does not contain the metal nickel layer C, the laminate has a weak thermal resistance, a very short deterioration time, and visible light of the laminate when the thickness of the metal nickel layer C exceeds 100 GPa. It can be seen that the transmittance is greatly reduced, making it practically unavailable.

[Examples 38-41 and Comparative Examples 19-21]

A titanium oxide layer (B ₁ ) having a thickness of 300 μs, a silver and a copper alloy layer having a thickness of 150 μs, a metal cobalt or nickel layer C deposited with Co or Ni shown in Table 14, and a titanium oxide layer B ₂ having a thickness of 280 μs were carried out. It was successively laminated to the biaxially oriented polyethylene terephthalate film (layer A) in the same manner as in Example 32 to obtain a selective light transmitting laminate.

Titanium oxide film layers B ₁ and B ₂ were formed in the same manner as in Examples 4 and 5. The results are shown in Table 14.

TABLE 14

From the results shown in Table 14, when the laminate does not contain metal cobalt or nickel layer C, the heat resistance of the laminate is weak, and when the thickness of the metal cobalt or nickel layer C exceeds 100 GPa, the visible light transmittance of the laminate is large. It can be seen that the decrease.

[Example 42-45]

A titanium oxide layer B ₁ having a thickness of 300 GPa, a silver and copper alloy layer D (92 wt% silver), and a titanium oxide layer B ₂ having a thickness of 280 GPa were successively laminated to a biaxially oriented polyethylene terephthalate film (layer A). Cobalt or nickel layer C in the laminate was composed between the silver-copper alloy layer D and each titanium oxide layer B ₁ and B ₂ .

Titanium oxide film layers B ₁ and B ₂ were formed by the TBT method in Example 32 or the sputtering method in Example 38.

The metal cobalt layer and the metal nickel layer C were formed by vacuum deposition using an electron beam. The results are shown in Table 15.

TABLE 15

[Examples 46-49 and Comparative Examples 22-24]

Example 32 was repeated except that a layer of titanium oxide, zirconium oxide or tantalum oxide formed by the ion plating method was used as the antireflection layer instead of the titanium oxide layer formed from the tetramer of tetrabutyl titanate, and metal cobalt or The thickness of the nickel layer was changed as shown in Table 16.

Ion plating was carried out under the same conditions as in Example 8. The results are shown in Table 16.

TABLE 16

Example 50-53

The laminate was produced in the same manner as in Example 7, except that the titanium oxide layer obtained by the TBT method as the layers B ₁ and B ₂ was replaced with a thin zirconium oxide layer formed of tetrabutoxy zirconate. Alloy layer D was changed to a silver, silver-gold alloy- or silver-copper alloy layer having a thickness of 160 kPa.

A zirconium oxide layer was formed by coating with a solution consisting of 7 parts tetrabutoxy zirconate, 40 parts n-hexane, 20 parts ligroin and 33 parts n-butanol and drying the coating at 130 ° C. for 5 minutes.

The silver layer, the silver-gold alloy layer and the silver-copper alloy layer are target silver or silver-gold alloys (90% silver and 10% gold) or silver-copper alloys (92% silver and 8% copper) Was formed by DC sputtering. The results are shown in Table 17.

TABLE 17

[Example 54-58 and Comparative Example 25]

The laminate was produced in the same manner as in Example 7, except that layers c and layers B ₁ and B ₂ were formed as shown in Table 18. A top transparent layer (E) having a thickness of 2 microns was formed on the laminate surface by wet coating with a solution of polyacrylonitrile in cyclohexanone. The properties of the resulting laminates are shown in Table 18.

TABLE 18

[Examples 59 and 60]

The laminate was produced in the same manner as in Example 7, except that the thickness of the metal titanium layer C was changed as shown in Table 19. The properties of the laminate are shown in Table 19.

TABLE 19

Example 61 and Comparative Example 26

A metal titanium layer (layer C) having a thickness of 10 μs, a silver and copper alloy layer (92 weight% and 9 weight% of silver) having a thickness of 80 μs, and a metal titanium layer (layer C ′) having a thickness of 30 μs are 84 Successive laminations were made on a axially oriented polyethylene terephthalate film having a thickness of 20 microns and a thickness of 20 microns to obtain a selective light transmitting laminate.

The metal titanium layer and the alloy layer were formed by DC sputtering using metal titanium and silver-copper alloys.

The optional light transmissive laminate has a 75% visible light transmission and an 87% average infrared reflectance.

The laminate was injected into a hot air dryer maintained at 90 ° C. The time that elapsed until the infrared reflectance of the sample decreased to 85% of the initial value was 2500 hours.

The laminate was produced in the same manner as in Example 61 except that layers (C) and (C ′) were omitted.

The laminate had an average infrared reflectance of 82%, reduced by 85% at 450 hours.

Claims (9)

(A) The heat wave reflecting layer (D) and (C) of a silver-containing metal formed on the base layer (A) and (B) layer (A) of the transparent sheet structure and having a thickness of 50-300Å, optionally, the layer (A). A high refractive index thin transparent layer (B ₁ ) disposed between and (D), a thin transparent layer (B ₂ ) having a high refractive index on layer (D), or both layers (B ₁ ) and (B ₂ ), and (d) Optionally, in the selective light transmitting laminate composed of the top transparent layer (E) on the layer (D), the thickness is 3-100 GPa and is selected from Ti, Zr, In, Si, C, Co and Ni. Laminate, characterized in that the thin layer (C) is deposited in contact with the layer (D). 2. The laminate according to claim 1, wherein layer (C) is configured to further contact under layer (D). The laminate according to claim 1, wherein the layer (D) is an Ag layer, an Ag layer containing up to 30% by weight of Cu, or an Ag layer containing up to 30% by weight of Au. The method of claim 1, wherein the layers (B ₁ ) and (B ₂ ) are each a metal oxide layer or a ZnS layer selected from Ti, In, Zn, Sn, Y, Er, Zr, Ce, Ta and Hf. Laminate. The laminate according to claim 1, wherein each of layers (B ₁ ) and (B ₂ ) is a thin layer of titanium oxide derived from an organic titanium compound and containing an organic residual group of the organotitanium compound. The laminate according to claim 1, wherein each of the layers (B ₁ ) and (B ₂ ) has a thickness of 50-500 mm 3. The laminate according to claim 1, wherein the minimum thickness of the layer (C) is 25 mm 3. The laminated body of Claim 2 whose minimum total thickness of two layers (C) is 10 microseconds. The laminate according to claim 1, wherein the laminate has a visible light transmittance of at least 50% and an average infrared reflectance of at least 70%.