JPS5836448A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate in which at least one side of a metal thin film layer is covered with a transparent (high refractive index) thin film layer.
The present invention relates to a laminate having chemically formed modified transparent (high refractive index) thin film layers.

In general, in a laminate in which conductive metal thin films such as gold, silver, steel, and various alloys containing these as main components are sandwiched between transparent high refractive index dielectric layers, specific properties can be achieved by controlling the thickness of each constituent thin film. It is known that it is possible to obtain a material that selectively reflects light in a wavelength range. In particular, a laminate that selectively reflects infrared wavelength regions is important as a heat ray reflective film from the viewpoints of energy saving in buildings, aS, etc., solar energy utilization, and the like. In addition, since such a laminate is transparent in the visible range and has high electrical conductivity, it is used as a transparent conductive laminate as a transparent surface heating element.

Electrical applications such as transparent electrostatic shields and transparent electrodes are important.

Such a laminate includes Tie, /Ag/Tie.

Zn8/Ag/ZnS and B i,O,/A
Stacks such as u/B i , O, etc. have been proposed.

The main methods for forming these films have been physical formation methods such as vacuum evaporation method 1, reactive evaporation method, and sputtering method.

However, physical methods such as vacuum evaporation and sputtering often have problems in terms of industrial viability and adhesion to organic substrates, etc., and surface mold retaining layers when forming metal oxide thin films. This is because the technology for stably growing a metal oxide thin film on an organic substrate using these physical methods has not yet been established, and furthermore, it is possible to coat either the top, bottom, or both sides of the metal oxide thin film. This means that the technology for covering metal oxides with thin metal oxide films has not yet been perfected on an industrial scale.

As a solution to this problem, the present inventors have already proposed a method in which a transparent high refractive index thin film layer is formed from an organometallic compound such as a metal alkoxide by chemical means.

That is, to give a typical example, by applying an organic solvent solution of alkyl titanate onto a substrate and treating it at a relatively low temperature, a titanium oxide thin film layer with a high refractive index can be formed, and this and a metal thin film layer can be formed. When combined with K, the Tie has an infrared reflectance of 95 cm or more and a visible light (soo@μ) transmittance of Fuller or more.
,/Ag/Tie.

It has become possible to economically produce a three-layer laminate. −
Moreover, since the processing temperature is low, it is also possible to use an organic polymer substrate such as polyethylene terephthalate as a substrate, which has extremely superior performance economically than forming a laminate continuously on the film. This made it possible to obtain a laminate.

Although the above method is an excellent method, the formed titanium oxide layer has some chemical defects, so it is difficult to use a titanium oxide layer formed by physical means such as sputtering. Depending on the conditions of use, the durability may be inferior to that of the original case.

As a result of intensive research to improve this drawback, the present inventors found that the acid basicity, that is, the pH, of the transparent/clear thin film layer or the transparent high refractive index thin film layer in contact with the metal layer is in the range of 10≧pH≧5. We have discovered that certain things are extremely effective in suppressing deterioration, and have arrived at the present invention. That is, 1
, a transparent substrate and a transparent thin film layer on one or both sides)
In a laminate mainly consisting of a metal thin film layer in contact with
≧5, preferably 2. A molded product substrate and a transparent thin film layer (B) on one or both sides.
) and a metal thin film that is in contact with the laminate. The laminate according to item 1 above, which is a metal oxide formed by a coating method, especially: L The laminate according to item 1 or 2, wherein the thin film factor is a metal thin film layer containing at least 60% by weight of -.

Although there is no need to specifically limit the term ``seirei thing basics'' used in the present invention, S
It is necessary to have transparency with a transmittance at OO@μ of at least 50 inches or more, preferably 75 inches or more, and molded product substrates that meet this condition include transparent organic polymer materials, It may be a molded product of an inorganic material such as glass or a metal oxide, or a composite of both, but from the viewpoint of industrial productivity of the laminate, it is preferable to use an organic polymer material, and in particular, a film-form product is preferable. preferable.

Polyethylene tele 7 tanto film, nine film on I#.

polycarbonate film, polypropylene film,
Polyethylene film, polyethylene film, polysulfone film.

A polyether sulfone film or the like is preferably used.

The metal thin film layer (2) used in the laminate of the present invention may be made of any metal or alloy with low absorption loss in the visible light region and high electrical conductivity. Other metals to be included include gold.

Steel, aluminum, and nickel metal are preferred, but any metal may be included as long as it does not reduce the properties of silver. The content of silver is an important factor governing the optical properties of the resulting laminate, and it should be contained at least 50% by weight, preferably 60% by weight or more.
It is preferable to be there. In addition, in order to obtain a selective light transmitting film with high 4IK infrared reflectivity, two materials selected from the three elements of gold, silver, and steel are used.
A thin metal film layer of 111 or an alloy of three metals is preferred.

The thickness of the metal thin film layer is not particularly limited as long as it has the required characteristics of a transparent conductive or selectively transparent film, but in order to have infrared light reflective ability or conductivity, at least a certain range of thickness is required. It is necessary to have continuity. The film thickness from the island structure to the continuous structure is preferably about SOA or more and about 6000A or less from the viewpoint of transparency to visible light. Since the thickness of the metal thin film layer is thin, the light transmission area expands,
In order to increase transparency, a film thickness of 200^ or less is preferable, and in order to provide sufficient conductivity or infrared light reflecting ability, a film thickness of 70X or more is preferable.

Methods for forming the metal thin film layer include, for example, vacuum evaporation, cathode sputtering, ion blating, etc.
Either method is possible, but in the case of a laminate using a synthetic footwear substrate, if the surface of the substrate such as a sheet or film is smooth, the uniformity of the formed thin film, the ease of manufacturing, and the speed of film formation. From this point of view, the cathode sputtering method is preferable, and the cathode sputtering method is particularly suitable when forming an alloy thin film.

In the present invention, the transparent thin film layer (B) is a transparent high refractive index thin film layer (B
-1), and in this case, the layer in contact with the metal thin film factor is a transparent high refractive index thin film layer (
B-1) is preferable. The transparent high refractive index thin film layer (B-1) has a refractive index of 1.6 or more, preferably 14 or more with respect to visible light, a visible light transmittance of go1 or more, preferably 9o- or more, and Film thickness is 2°X ~ 5o
oX, preferably +tsoX to 4ooX. The acid-basicity of such a transparent high refractive index thin film layer is preferably 10≧pH≧5 as determined by the measuring method described later.

In order to increase the durability of the final product laminate, it is necessary to stabilize the metal thin film layer, and it is preferable that the acid/basicity of the transparent (high refractive index) thin film layer is pH≧5. If the requirements for heat resistance and light resistance are high, pH≧5.
．． 5 is particularly preferable. In addition, from the viewpoint of the optical properties of the laminate, it is important that the transparent high refractive index thin film layer has high transparency, and from the viewpoint of stabilizing the metal thin film layer, pH≦lO
It is preferable that pH≦9, and when the optical properties (visible light transmittance) are highly required, it is preferable that pH≦9. From these, the acid/basicity of the transparent high refractive index thin film layer is preferably 10≧pH≧5, particularly preferably 9≧PH≧
It is 5.5.

Examples of such substances include organic titanate compounds such as tetrazthoxytitanate, ferrous zirconate compounds such as tetrazthoxydyl':
-propyl9/l/ :l nate, tetra-1go
-Propylzirco*-),? Tora-n-butylzirconate, Tetra-is.

-butyl dilphinate, organoaluminum compounds such as aluminum tri5ee-cytoxide, organosilicate compounds such as monomethyltrimethoxysilane,
Organogermanium compounds, for example organometallic compounds such as tetraptoxyglumanicum, and metal alkoxide compounds can be used for the purpose of the present invention. Furthermore, these 7
Cetyl acetonates are also preferably used (hereinafter,
May be collectively referred to as ``metal alkoxides, etc.'')
. Since these compounds can transesterify and condense the alkoxy groups bonded to metal atoms using known methods, the metal alkoxides etc. that can be used for the purpose of the present invention are Any metal alkoxide or the like may be used as long as it has an acid/basicity, that is, 10≧pH≧5. In addition, such metal alkoxides, etc. can be prepared by mixing several types of metal alkoxides, etc.
Alternatively, they may be used in a condensed form, and in this case, metal alkoxides having different metal atoms may be mixed or condensed together. From the viewpoint of acid-base neutralization, this mixing or condensation can be achieved by using an equivalent amount of metal alkoxide and/or metal 7-sylate, etc. whose pH is <5.
) When metal alkoxides and/or metal acylates having pH 10 are mixed or condensed, the acid basicity of the resulting mixture or condensate falls within the range of 10 > pH > 5, and a compound that meets the objective K of the present invention is obtained. It has the meaning of being received. In the same sense, a small amount of metal alkoxide and/or metal 7 sylate with pH<5 and 10≧
Mixing or condensation of a large amount of metal alphoxides and/or metal acylates with pH≧5, pH) 10,
It is also possible to mix or condense a small amount of metal alkoxide and/or all-chain acylate with a large amount of metal alkoxide and/or metal acylate whose pH is 10≧pH≧5.
It is possible to obtain mixtures or condensates with an acid-basicity of 0≧pH≧5.

As described above, any metal alkoxide etc. used in the present invention may be used as long as the acid basicity of the compound is 10≧pH≧5, and conversely, when using a compound with pH <5. From the viewpoint of neutralization, metal alkoxides and/or metal acylates with high basicity, or organic amine compounds such as triethanolamine, n-butyl amine, etc. are added, or potassium hydroxide, sodium hydroxide, etc. After washing with a solvent such as alcohol containing an alkali hydroxide, or neutralizing and washing with potassium carbonate, sodium carbonate, etc., the metal alkoxide and/or metal acylate group is distilled off using vacuum distillation to make the pH ≧5. I can do things.

In addition, when using the compounds of p) () and 10, from the viewpoint of neutralization, metal alphoxides and/or metal acylates with high acidity, or organic acids such as acetic acid, lactic acid, etc. are added, or minato sulfuric acid, etc. The pH can be adjusted to 10 by washing with water, or by neutralizing and washing with citric acid, oxalic acid, etc., and then distilling metal alphoxide, etc. under reduced pressure. in general,
Since metal alphoxide is made from metal chlorides, it tends to contain acidic substances during the manufacturing process. It is effective in the present invention to remove or neutralize this acidic substance so that the pH of the metal alkoxide becomes 10≧pH≧5, and if the metal alkoxide itself has a pH<5,
Neutralize by adding other metal alkoxides and basic compounds such as those mentioned above, and adjust the pH of the metal alkoxide to 10≧p.
It is effective to set H≧5.3゜On the other hand, if the metal alkoxide itself has a pH of 10, neutralize it by adding other whole alkoxides and acidic compounds such as citric acid, tartaric acid, and oxalic acid. , the pH of the metal alkoxide is 1G.
Setting the pH to ≧5 is also effective. As described above, the metal alphoxide can be modified in various ways to meet the objectives of the present invention.

The metal alkoxides and the like that meet the purpose of the present invention are enumerated using organic titanate compounds as an example. The furkyl group is not particularly limited and includes ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, stearyl, etc. Condensates obtained by condensing two or more of these tetraalkyl titanates may also be used.

In addition, as mentioned above, other metal alkoxide compounds such as monomethyltrimethoxysilane, monoethyltriethoxysilane, aluminumtrily 5eC-butoxide, aluminumtrily 1go-propoxide, tetrabutoxyzirconate, tetrabutoxygermanium compounds, etc. It can also be used by condensation or mixing with well-known dissimilar metal alkoxides.

In order to form the transparent high refractive index thin film layer (B-1) referred to in the present invention by a wet coating method, the above-mentioned metal alkoxides, etc., or their condensates or mixtures are diluted in an appropriate solvent. All you have to do is apply a solution and let it dry.

In this case, the solvent may be used as long as it satisfies conditions such as solubility, boiling point, and inertness (not suppressing the condensation network reaction of the metal alkoxide) with respect to the metal alkoxide.

Examples of these solvents include hydrocarbon-based solvents such as n-hebutane and cyclohexane, and ligroin.

Solvent naphtha, petroleum benzene, petroleum ether mixed solvents, ethanol, and propatools.

Alcohol solvents such as butanol and mixed solvents thereof are preferably used.

It is also possible to wash these solvents in advance with basic compounds and acidic compounds, such as potassium chloride, sodium carbonate, citric acid, oxalic acid, etc., so that they do not affect acid-bases such as metal alkoxides. It is.

Conversely, a basic compound 1 such as an organic amine compound or an alkali hydroxide compound can be added to these solvents to keep the solution of metal alkoxide or the like basic. Furthermore, it is also possible to keep the solution of metal alkoxide etc. acidic by adding acidic compounds such as citric acid, oxalic acid, sulfuric acid, hydrochloric acid, lactic acid, etc. to these solvents, and these methods are also effective in the present invention. be.

It is also effective to add a catalyst to accelerate the hardening of the transparent high refractive index thin film layer formed from metal alkoxide or the like. The catalyst is used for hydrolysis of metal alkoxides, etc.
Anything that promotes the condensation reaction may be used. Examples include sodium acetate, potassium acetate, metal salts of heptathenate, and the like. Also, mixing different types of metal alkoxides, etc.
For example, for curing titanium alkoxide, silicon 7/
I; It is an effective means, just as the addition of co-oxide is effective.

In the present invention, the measurement of acid-base ratios such as metal alkoxides can be carried out by various known methods.

For example, there are methods such as the pH electrode method, the pH test paper method, and the application of the solid acid basicity measurement method. The pH electrode method will be described here.

(11fIJ standard sample preparation method and measurementMetal flukoxide gin was weighed so4, distilled water tooy
and hydrolyze it. At this time, the mixture was stirred under N atmosphere for 5 hours and the precipitate was separated. If the resulting liquid was separated into two phases, the water portion was separated and used as a sample.

・The distilled water in this case is distilled water obtained by adding a small amount of potassium hydroxide and potassium permanganate to 7-I-exchanged water and then distilling it, and it is stored so as not to absorb carbon dioxide gas. . Take a sample 209, JISZ8802pH
By measuring methods such as those shown in II.
Measure H. In this measurement, the determination that lO≧pH≧5 is a condition for the metal alkoxide, etc. used.

In addition, the pi of the transparent high refractive index thin film layer (B-1) formed from metal alkoxide can also be measured. For example, take a transparent high refractive index thin film layer with a thickness of 50X formed from a fathom and cut it into as thin a layer as possible.Immerse the cut pieces in distilled water in a toy and heat them at 50°C for 2 hours in an ultrasonic cleaner.
After extraction, the solution was left to stand for 24 hours, and after separation, the pH was measured using the method described above. The condition is that lO≧pH≧5 between acid and base in the formed laminate.

Furthermore, it is also effective to determine the pH using a reagent found in JIS K-8004, etc., and it is also possible to estimate it by applying the method of measuring solid acid basicity.

゛No matter which method is used, the acid-base ratio between the metal alkoxide used and the formed transparent thin film layer is 10≧pH≧5.
If it is judged as such, it will be towed.

Furthermore, the laminate of the present invention does not suffer from damage even if a transparent protective layer is formed on the transparent high refractive index thin film layer (B-1) formed on the metal thin film element for the purpose of protecting the laminate. . Such a transparent protective layer may be made of any material as long as it does not impair the intended optical properties of the laminate and improves environmental contamination resistance and surface hardness. , sio in the case of inorganic compounds.

Transparent oxides such as TtO, l ZrO, e AltOs are preferred, and in the case of organic compounds, polymethacrylonitrile and polyalkyl methacrylate resins.

Acrylic resins such as polyacrylonitrile are preferably used, and transparent resins such as polystyrene resins are also preferably used.

Further, a stretched polypropylene film, a polyethylene film, etc. may be laminated and used.

The purpose of this protective layer is to have a thickness that exhibits the intended protective effect of the protective layer, preferably from 0.05μ to 304μ, and preferably from II#K O-'I sm to 20μ. used.

Hereinafter, a detailed explanation of the present invention will be given by way of examples.

Example 1 A first layer was applied to a biaxially stretched polyethylene terephthalate film having a light transmittance of 86-2 and a thickness of 75 Ir1ft to a thickness of 3.
00A titanium oxide thin film layer, second layer and tin thickness 140X
A thin film layer consisting of silver and copper (90 weight % silver, 10 layers of copper [1st and 3rd layers are titanium oxide thin film layers with a thickness of 300A are sequentially laminated, and has transparent conductivity and selective light transmittance. The body was formed on the film.

The titanium oxide thin film layer has pH=S, SO in the pH measurement method.
obtained by coating with tetrabutoxy titanate.

7 parts of tetrabutoxy titanate (Nanatsumar).

A solution consisting of 70 parts of normal hexane and 23 parts of n-7' tanol was coated with a bar coater and heated to 120°C. The pH of the transparent thin film layer formed from the obtained tetrabutoxy titanate was determined by the reagent method and the pHl1 standard method.
H=6.0O.

The thin film layer made of silver and copper was formed using a silver-copper alloy (90% by weight of silver, 10% by weight of copper) by a low-temperature magnetron sputtering method.

The resulting laminate had a visible light transmittance of 72 inches, a surface resistance of 10 Ω/hole, and an infrared reflectance of 95 inches. The obtained film was placed in a gear-operated open tester kept at 90°C, and the infrared light reflectance was measured after 2,000 hours.
The infrared light reflectance was maintained at 80 inches or more.

Comparative Example 1 The first and third titanium oxide layers were formed from a solution consisting of 7 parts of tetrabutyl titanate (7 parts) at pH-4, 5, 70 parts of n-hexane, and 23 parts of n-butanol. A laminated film was produced in the same manner as in Example 1 except for the following.

The pH of the formed thin film was 4.3.

The light transmittance of the obtained film was 71 cm, and the surface resistance was 15
The infrared reflectance was 93Ω/mouth.

As a result of conducting a thermal deterioration acceleration test in the same manner as in Example 1, the infrared light reflectance became 5oIs or less after about 1,000 hours.

Comparative Example 2 The titanium oxide thin film layer of the first layer and the three irises layers was treated with a solution 10 consisting of 7 parts of tetrabutyl titanate (monomer), 70 parts of Normanhexane, and 23 parts of n-7' tanol at pH-4 and 5.
A laminated film was prepared in the same manner as in Example 1, except that 2I of potassium hydroxide was added to 0g of the sample and the resulting precipitate was separated from the solution.

The pH of the titanium oxide thin film layer was 12.0.

The light transmittance of the obtained laminate was 50 inches, and white turbidity was observed. The surface resistance was 15 Ω/hole, and the infrared reflectance was 8 f1. As a result of conducting a thermal deterioration acceleration test in the same manner as in Example 1, the surface layer became white for about 1000 hours and the infrared light reflectance became 80 or less.

Example 2 The transparent high refractive index thin film layers of the first layer and the three irises layers were adjusted to pH = 6.2.
A laminate was formed in the same manner as in Example 1, except that the zirconium oxide thin film layer was replaced with a zirconium oxide thin film layer formed from 0% tetrabutoxyzirconate.

The zirconium oxide layer contains 7 parts of tetragutoxysilfnate, 40 parts of normal hexane, and 2 parts of ligroin.
A solution consisting of 0 parts of n-butanol and 33 parts of n-butanol was applied using a bar coater and dried at 130°C for 5 minutes.

The pH of the obtained zirconium oxide thin film layer was 6.4.
It was 0.

The resulting laminate had a visible light transmittance of 64%, an infrared light reflectance of ss%, and a surface resistance of 12Ω/hole.

As a result of conducting a thermal deterioration acceleration test in the same manner as in Example 1, the infrared light reflectance remained at ss% or higher even after 2,000 hours.

Example 3 First layer, I! Three layers of transparent high folded book thin film layer PH-6,3
A laminate was formed in the same manner as in Example 1, except that the alumina thin film layer was replaced with an alumina thin film layer formed from 0% aluminum tri-5ec-butoxide. The alumina thin film layer consists of aluminum tris@7 parts of e-butoxide, 10 parts of n-hexane, 50 parts of ligroin, and 33 parts of n-butanol.
A solution consisting of 1.5 mm was coated with a bar coater and dried for 130'' CS minutes.

The pH of the obtained alumina oxide thin film layer was 7.30.

The resulting laminate had a visible light transmittance of 61%, an infrared light reflectance of sa%, and a surface resistance of 12Ω/hole.

As a result of conducting a thermal deterioration acceleration test in the same manner as in Example 1, the infrared light reflectance S3% or more was maintained even after 2,000 hours.

Example 4 The first and third transparent high refractive index thin film layers are formed from a mixture of a condensate of monomethyltrinidoxysilane (mainly consisting of a tetramer) and 'tetrabutoxytitanate in an equal weight ratio.
A laminate was formed in the same manner as in Example 1 except that a titanium oxide thin film layer containing silicon oxide was used instead.

The pH of the monomethyltriethoxysilane condensate and tetrabutoxytitanate mixture was 6.15. The titanium oxide thin film layer containing silicon oxide was prepared using 7 parts of a mixture of monomethyltriethoxysilane condensate and tetrabutoxy titanate, 10 parts of n-hexane, and 30@1 ligroin.
1. A solution consisting of 20 parts of n-butanol and 33 parts of 1so-purpanol was coated with a bar coater and dried at 130° C. for 5 minutes.

The pH of the obtained titanium oxide thin film layer containing silicon oxide was 6.80.

Visible light transmittance ss%, infrared reflectance 9 of the obtained laminate
3%, and the surface resistance was 12Ω/mouth.

As a result of conducting a thermal deterioration acceleration test in the same manner as in Example 1, an infrared light reflectance of 80- or higher was maintained even after 2,000 hours.

Examples 1s to 8 and Comparative Examples 3 and 4 On the polyester film used in Example 1, a metal thin film having a thickness of 150 A and consisting of 90% by weight of silver and 10% by weight of copper was formed by magnetone sputtering. A titanium oxide thin film layer with a thickness of 2 GOA made of tetrabutoxy titanate having various pH values was formed on the metal thin film.

The method for forming the titanium oxide thin film layer was the same as in Example 1.

A protective layer of polymethacrylonitrile was formed on the obtained laminate. The polymethacrylonitrile protective layer is 3 parts polymethacrylonitrile.

A solution consisting of 47 parts of cyclohexanone and sO parts of methyl ethyl ketone was applied using a bar coater and dried at 1'40°C for 5 minutes.

Table 1 shows the optical properties of the laminate and the results of a 2,000-hour thermal deterioration acceleration test conducted in the same manner as in Example 1.

Table 1 Examples 9 to 12 The first and third titanium oxide thin film layers were formed in the same manner as in Example 1, except that the metal thin film layers with different silver and steel contents were formed with a thickness of 150A. Formed. A protective layer made of polymethacrylonitrile and having a thickness of 0.2 μm was provided on the surface of the obtained laminate in the same manner as in Example 5.

The pH of the titanium oxide thin film layer was in the range of 5.60 to 6.10.

The laminate was subjected to a thermal deterioration acceleration test for 2.0.00 hours in the same manner as in Example 1, and the results are shown in Table 2.

Table 2 Example 13 Laminated body top K obtained in Example 24, Tagrack A-3s
o and Takenate A-10 (both manufactured by Takeda Pharmaceutical Company Ltd.)
Methyl isobutyl ketone solution (A-31010 parts, A
-102 parts) was coated using a bar coater, and after air drying, a polypropylene stretched film was laminated thereon. The resulting laminate had a visible light transmittance of 60% and an infrared light reflectance of 85qIb.

This laminate was subjected to the same accelerated thermal deterioration test as in Example 1, and as a result, it maintained a reflectance of 80- or more even after 3,000 hours.

Example 14 The metal thin film layer had a thickness of 130A, @SS wt%, gold 1
The first and third titanium oxide thin film layers were formed in the same manner as in Example 1, except that the metal thin film layers containing 5% by weight were formed. The pH of the obtained titanium oxide thin film layer was 5.90. The visible light transmission property of the obtained laminate was 74 cm,
The infrared light reflectance was 90%.Example 15 On the polyester film used in Example 1, a metal of 80 to 83% by weight of silver and 17 to 20% by weight of copper with a thickness of lSOX was deposited by vacuum deposition. A thin film layer was formed. [
The visible light transmittance of the obtained laminate was 66 inches, and the infrared light reflectance was 93 inches.

The pH of the obtained zirconium oxide thin film layer was 6.20.

This laminate was subjected to a thermal deterioration acceleration test in the same manner as in Example 1, and as a result of 2,000 hours, the reflectance was 8.
3% or more was maintained.

Example 16 ゛ A 100A thick zirconium oxide thin film layer made from tetrabutoxyzirconate with CPL (=6.0 O) was formed as a single layer on the polyester film used in Example 11, and a third layer with pH= 6.15 thick formed from 10% tetra-1so-pupoxy titanate
A laminate having selective light transmittance was obtained in the same manner as in Example 1 except that a 0A titanium oxide thin film layer was formed.

The pH of the formed zirconium oxide thin film layer was 6.30.

The titanium oxide layer contains 5 parts of tetra-1so-pupoxy titanate, 50 parts of ligroin, and 3 parts of 1so-propatool.
A thin film layer was obtained by applying a solution consisting of ls part of n-butanol using a bar coater and drying at 130°C for 3 minutes.

The pH of the titanium oxide thin film layer was measured by coating the present coating solution on the polyester film used in Example 1 to form a thin film, and found that the pH was 6.20.

The zirconium oxide thin film layer was created in the same manner as in Example 2.

The visible light transmittance of the obtained laminate was 69 inches, and the infrared light reflectance was 92 inches.

A thermal deterioration acceleration test was conducted in the same manner as in Example 1, but
Even after 2,000 hours, the reflectance remained at 80 degrees or higher.

Example 17 Titanium oxide thin film layers were formed as the first and third layers on the polyester film used in Example 1 using 5 parts of tetrabutyl titanate (monomer) with a pH of 4.5 and 6 parts of n-hexane.
It was formed from a solution in which 0.2 g of potassium hydroxide was added and dissolved in 100Ii of a solution consisting of 5 parts of n-tutanol and 30 parts of n-tutanol.

The film thickness is 200A for the first layer and 250X for the third layer.
and the pH is 8.2° pH = 8.2°, respectively.
7 (the third layer was measured including the first layer).

The metal thin film layer was formed in the same manner as in Example 1, and had a thickness of 140 Å and was made of 9% by weight of porcelain and 10% by weight of steel.

The resulting laminate had a visible light transmittance of 73%, a surface resistance of 10 Ω/hole, and an infrared reflectance of 93%.

The resulting laminate was tested for heat resistance in the same manner as in Example 1, but for 2,000 hours! ! The infrared light reflectance remained at 80 inches or more even after the test.

Example 18 A film of pH=6.
Using a target formed by forming titanium oxide powder (2), a high frequency magnet is used to create a
X10 Torr*Input power zw/d) A layer of 1M thicker than K was formed.

The p)l of the titanium oxide thin film layer was 6.3.

On this titanium oxide thin film layer, silver and copper (90% by weight of silver, 10% by weight of copper, 120% by weight,
A metal thin film layer was formed.

As the third layer, tetrabutoxyzirconate having p)I=6.2 was formed in the same manner as in Example 2.

The visible light transmittance of the obtained laminate was 7456. The surface resistance was 11Ω/hole, the infrared reflectance was 90%, and as a result of a heat resistance test conducted in the same manner as in Example 1, 2,000Ω
The infrared light reflectance was maintained at so% or higher over time.

Example 19 A metal thin film layer consisting of silver and copper (90 weight % silver, 10 weight % copper) was formed on the polyester film used in Example 1 in the same manner as in Example 1. On the thin film layer, 5 m of tetraztoxy titanate (monomer) with K pn = 5.3, 70 parts of n-hexane, n-
St consisting of y'tutar 25s was coated and dried using a bar coater to obtain a °C laminate.

The pH of the titanium oxide layer was 5.90.

The resulting laminate had a visible light transmittance of 67 inches and an infrared light reflectance of 90 inches. A solution consisting of 5 parts of a condensate of monomethyltrimethoxysilane (mainly composed of tetramers), 20 parts of ethanol, 60 parts of Impro/Wonol, and 15 parts of n-butanol was coated onto the laminate using a bar coater and dried to give a thick coating. Sa1
A protective layer of GOA was formed. There was almost no difference in the optical properties of the laminate after the protective layer was formed compared to before the protective layer was formed. In addition, as a result of the same heat resistance test as in Example 1, 2,000
The infrared light reflectance remained at 80 or higher over time.

Claims (1)

[Claims] 1. A molded product substrate and a transparent thin film layer (
In a laminate consisting of a metal thin film layer in contact with B), at least one of the transparent thin film layers (B) is made of a metal oxide, and the acid basicity of the metal oxide is 10≧p.
A laminate whose percentage characteristic is that H≧5. 2 The molded product substrate and one or both sides of the transparent thin film layer (B
In a laminate mainly consisting of a metal thin film layer in contact with IK; at least one of the transparent thin film layers CB+ is coated with a metal fluoride and/or acylate having an acid basicity in the range of 10≧pH≧5 by a wet coating method. The laminate according to claim 1, which is a formed metal oxide. 1. The laminate according to claim 1 or claim 2, wherein the thin film layer is a metal thin film layer containing at least 60 m of silver.