JPH0339281B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a light-transmitting sheet that transmits visible light and absorbs or reflects infrared rays. More specifically, the present invention relates to a selectively transparent sheet that transmits visible light and absorbs or reflects near-infrared light to infrared light.

In general, by controlling the thickness of each component thin film in a laminate in which conductive metal thin films such as gold, silver, copper, and various alloys containing these as main components are sandwiched between transparent high refractive index dielectric layers, specific wavelength ranges can be achieved. It is known that it is possible to obtain a material that selectively reflects the rays of light.

In particular, a laminate that is transparent in the visible region and selectively reflects the infrared wavelength region is effective as a heat ray reflective film from the viewpoint of energy conservation in buildings, houses, etc., and solar energy utilization. However, in order to further improve energy saving efficiency in the field of energy saving in buildings, houses, etc. and solar energy blocking, it is necessary to
m ~ 700nm), near infrared region (701nm ~ 2100nm)
It is more effective to give more selectivity to the transmission characteristics of the filter. In other words, insulation is achieved by reducing the transmission characteristics of the near-infrared rays, which are not felt by the human eye in the solar energy distribution, but which account for approximately 50% of the sun's reflected heat rays, and further improving the transmission characteristics of the visible rays. Furthermore, since it is effective and does not impair transparency in any way, it can be applied to various fields without affecting the surrounding environment or safety.

Examples of application fields include improving the heat insulation of monitoring windows during high-temperature work, improving the sense of heat and further improving the cooling effect by improving the shielding properties of solar energy that enters through the windows of buildings, cars, trains, and other vehicles.
Examples include improving the heat insulation of transparent food containers and further improving the cold retention effect in freezing and refrigerating cases.

(b) Prior Art Fabry-Perot filters are generally well known as optical interference filters having selective transmission properties. This is known as an interference filter that sandwiches a transparent dielectric material with a specific optical thickness between opposing semi-transparent mirrors and transmits only light of a specific wavelength. The US patent states that by applying this Fabry-Perot filter, it is possible to obtain a selective light transmitting sheet with high transmission characteristics in the visible region and high reflection characteristics in the near-infrared region.
It is shown in the specification of No. 3682528. According to it,
For example, the structure of substrate/metal layer/dielectric/metal layer is glass/Ni/Ag/Al ₂ O ₃ /Ni/Ag/Al ₂ O ₃ and the transmittance from 400 nm to 700 nm is 70%.
or more, and the reflectance is approximately 10% from 700nm.
A selective light transmitting laminate having a transmittance of 10% or less at 2500 nm and a reflectance of about 90% or more has been obtained.

In addition, heat-absorbing glass containing Fe oxide, which is known as a selectively transmitting material that is transparent in the visible light region and absorbs near-infrared light, has a visible light transmittance of 76% at a thickness of 5 mm, and is transparent to near-infrared light. It has a radiation transmittance of 57%.

In addition, in recent years, near-infrared light absorption filters containing organometallic complexes in an organic medium (Tokuko Showa) have been developed.
46-3452) or near-infrared light absorbing agricultural sheets (see Japanese Patent Laid-Open No. 49-31748).

(c) Problems However, when Fabry-Perot filters are used in building windows for energy-saving purposes such as blocking solar energy, it is essential to apply them to large areas, and using conventional metal compounds as transparent dielectrics is difficult to achieve on an industrial scale. production is impossible.

This means that the technology for uniformly covering a large area of the surface of a metal thin film layer with metal oxide or the like is still an incomplete technology.

If the metal oxide film is thin, less than 50 Å, it is possible to easily form a metal oxide film from the metal film by thermal oxidation, etc.
It can be said that it is impossible to uniformly produce an oxide film with a thickness of about 1000 Å, which is necessary for a Perot filter, over a large area on an industrial scale.

In other words, the Fabry-Perot filter, which uses a metal oxide as an interlayer, is suitable for precision optical applications that handle small areas, but is not suitable for solar energy shielding or energy conservation applications that require large areas.

In addition, in heat-absorbing glass, FeO and Fe ₂ O ₃ , which are oxides of Fe, have absorption not only in the near-infrared region but also in the visible region, which increases the absorption efficiency in the near-infrared region. When the color is improved, the absorption in the visible light region increases, the visible light transmittance decreases, and the visible light region becomes dark and colored.

A similar phenomenon is also observed in organometallic complexes that have absorption in the near-infrared region, and as expected, increasing the absorption effect in the near-infrared region decreases the visible light transmittance, making it darker and increasing the coloration. There were flaws.

(d) Means for solving the problem We have conducted intensive studies to apply a structure with superior selective light transmittance to applications such as blocking solar energy, saving energy, and blocking harmful heat rays.

As a result, a
By optically combining a light-selective transmitting structure consisting of a metal layer mainly composed of Ag and a thin film layer containing a near-infrared absorber having an absorption peak between 800 nm and 1200 nm, they compensate for each other's shortcomings. In addition, the mutual advantages increase synergistically, and the selectivity ratio of visible light and near-infrared light increases.It is transparent to visible light and reflects or absorbs most of near-infrared light. The present invention was achieved by discovering that it is possible to produce on an industrial scale a selectively transparent functional sheet with excellent solar energy blocking ability or heat ray blocking ability by reflecting infrared rays over a large area. In other words, the present invention provides a method for forming a film with a thickness of 40 Å to 180 Å containing 50% by weight or more of Ag metal.
Metal layer (A): Anti-reflection film layer made of dielectric material with a refractive index of 1.5 or more
(B); A thin film layer containing a near-infrared absorber having an absorption peak between 800 nm and 1200 nm; (C); and an organic polymer film (D). A light selective transmission functional sheet, which comprises each of the above layers. is (B)/(A)/(B)/(C)/(D), or (B)/(A)/(C)/(D), or (B)/(A)/(B) /(D)/(C), or (B)/(A)/(D)/(C), or (C)/(B)/(A)/(B)/(D) or (C) /(B)/(A)/(D) are sequentially laminated in the order, and the optical properties are an integrated visible light transmittance of 70% or more and an integrated near-infrared light transmittance of 50% or less. This is a permselective functional sheet.

The organic polymer film (D) referred to in the present invention does not need to be particularly limited, but for the purpose of applying the laminate of the present invention to a transparent window etc., 550n
It is necessary to have transparency with a transmittance at m of at least 50% or more, preferably 75% or more, and any conventionally known organic polymer film (D) that satisfies this condition may be used. Among them, polyethylene terephthalate film, polycarbonate film, polypropylene film, polyethylene film, polyethylene naphthalate film, polysulfone film, polyethersulfone film, nylon film, etc. are preferably used.

The thickness of the organic polymer film (D) can be appropriately selected depending on the purpose, but from the viewpoint of flexibility, it is preferably from 10 μm to 200 μm. Furthermore, the present invention may include coloring agents, ultraviolet absorbers, stabilizers, plasticizers, pigments, etc., to the extent that these organic polymer films do not impair the mechanical properties and optical properties of the organic polymer films. There is no problem with the organic polymer film used.

When adding an ultraviolet absorber, it is preferable to add it so that the integrated ultraviolet light transmittance is 10% or less.

The metal thin film layer (A) used in the laminate of the present invention may be made of any metal or alloy as long as it has low absorption loss in the visible light region and has high electrical conductivity. It is preferable to be there. Other metals that can be included include:
Gold, copper, aluminum, etc. are preferred, but any metal may be included as long as it does not reduce the properties of silver. The silver content is an important factor governing the optical properties of the resulting laminate, and is preferably at least 50% by weight.

In addition, in order to obtain a laminate with particularly high infrared reflectivity, a metal thin film layer (A) of an alloy consisting of two or three metals selected from the three elements of gold, silver, and copper, or a single layer of these metals may be used. Preferably, it is a metal thin film layer (A).

The thickness of the metal thin film layer (A) is not particularly limited as long as it satisfies the required optical properties of the obtained laminate, but in order to have infrared light reflection ability or electrical conductivity, , it is necessary to have continuity as a film in at least a certain area. It is preferable that the metal thin film has a thickness of about 40 Å or more when it changes from an island-like structure to a continuous structure, and that it is 180 Å or less in order to improve the visible light transmission characteristics, which is the object of the present invention.

In order for the laminate to have sufficient visible light transmittance, the thickness of the metal thin film layer (A) is particularly preferably about 150 Å or less.

The metal thin film layer (A) can be formed by any conventionally known method in addition to vacuum evaporation, cathode sputtering, ion plating, etc.; In order to form a stable film, film forming methods using high energy particles such as cathode sputtering and ion plating are preferred. In particular, when obtaining an alloy thin film, the cathode sputtering method is preferred from the viewpoint of uniformity of the alloy composition of the formed thin film and uniformity of the thickness of the formed thin film.

Furthermore, in order to stabilize the thin metal layer when forming the metal thin film layer (A), the material that will become the substrate can be pretreated by a known method. These methods include, for example, cleaning treatments such as ion bombardment, undercoating treatments such as coating with organic silicates, organic titanates, organic zirconate compounds, and/or metals such as Ni, Ti, Si, Bi, Zr, V,
There is a nucleation stabilization treatment in which Ta and oxides of these metals are preformed by sputtering, etc., and it is sufficient to select and use them as long as they do not adversely affect the optical properties of the laminate. . If these pre-treatments involve an increase in thickness, the thickness is preferably 100 Å or less. A treatment similar to this pre-treatment may be performed on the metal layer as a post-treatment.

The dielectric used for the antireflection film layer (B) of the present invention is effective if it has a refractive index of 1.5 or more and is transparent.

Dielectric materials suitable for these include organic polymers,
Examples include metal oxides and metal sulfides.

As the organic polymer, highly transparent resins such as acrylate resins such as polymethyl methacrylate, acrylic resins such as polymethacrylonitrile, polymers and copolymers such as polystyrene resins and phenoxy resins are preferred.

Metal oxides include titanium oxide, silicon oxide,
Zirconium oxide, zinc oxide, tin oxide, cerium oxide, aluminum oxide, etc. are preferably used. Zinc sulfide is preferably used as the metal sulfide.

In the case of organic polymers, the dielectric is formed by diluting and dissolving an appropriate resin in a dissolving solvent to an appropriate concentration, and if the area is small, using a suitable coating method such as spin coating or bar coater coating. In addition, in the case of a large area, it is possible to form the coating by a method such as a reverse roll coater method or a gravure roll coater method.

In the case of a metal oxide, it can be formed by a physical forming method such as a sputtering method or a vacuum evaporation method, or a chemical forming method such as a coating method such as a metal alkoxide method. In the sputtering method and vacuum evaporation method, the target oxide is used as a target or a deposition source, and the target oxide is reacted with oxidation. A dielectric layer made of a desired oxide can be formed by a reactive sputtering method, a reactive vacuum deposition method, or the like, which forms an oxide.

Further, when a metal alkoxide compound corresponding to the metal oxide is present, a dielectric layer made of the desired metal oxide can be formed by coating the metal alkoxide compound.

As the metal alkoxide compound, compounds such as titanium alkoxide, zirconium alkoxide, aluminum alkoxide, and alkoxysilane are used. Examples of titanium alkoxide compounds include tetraisopropyl titanate, tetrabutoxytitanate, and tetraisooctyltitanate; examples of zirconium alkoxide compounds include tetrabutoxyzirconate and tetraisopropylzirconate; and aluminum alkoxide compounds. Examples include aluminum butoxide and aluminum propoxide.
Examples of the alkoxysilane compound include compounds such as monomethyltrimethoxysilane, monoethyltriethoxysilane, and ethylsilicate.

Furthermore, chelated products such as acetylacetonates of these compounds can also be used, and these metal alkoxide compounds may be monomers or appropriate condensates (hereinafter collectively referred to as "metal alkoxides, etc."). ).

In these compounds, an alkoxy group bonded to a metal atom can be transesterified or condensed by a known method. Also, these compounds are
For example, it is possible to use a mixture of multiple components depending on the purpose, such as a mixture of an alkoxysilane compound and titanium alkoxide, and the refractive index of the thin film obtained by these operations can be controlled. things are possible.

Further, even if these metal alkoxides and the like contain additives such as condensation catalysts to an extent that does not impair their optical properties, the effects of the present invention will not be affected in any way.

A method for forming a dielectric material from metal alkoxide is to dissolve metal alkoxide, etc. at an appropriate concentration in a solvent that can dissolve metal alkoxide, etc. If the area is small, it can be coated with spin coating, a bar coater, a doctor knife, etc. If the area is large enough, it can be formed by coating with a gravure roll coater or the like and then drying.

The thickness of the anti-reflection film (B) formed by this method is preferably set so as to maximize the anti-reflection effect on the metal layer (A), but even if the film thickness deviates from the optimum thickness, the film will not reflect. An appropriate selection can be made as long as the preventive effect is achieved. Although it is related to the refractive index of the dielectric material constituting the anti-reflection film (B) and the thickness of the metal layer (A), the thickness of the anti-reflection film (B) is preferably from 50 Å to 1000 Å.

The thin film layer (C) containing a near-infrared absorber having an absorption peak between wavelengths of 800 nm to 1200 nm in the present invention is formed from an organic resin layer containing a near-infrared absorber.

Examples of near-infrared absorbers include
Iron compounds such as FeO, Cu ion compounds such as copper sulfate,
Copper complexes such as copper phthalocyanine are known, but as near-infrared absorbers suitable for the present invention, the following general formula as seen in Japanese Patent Publication No. 1983-3452 is used. C: carbon atom S: sulfur atom R: alkyl group M: bis[cis-1,2-bis(alkyl)ethylene-1,2-dithiolate] metal complex compound represented by a metal atom, or J.Am, Chem. Soc 88 43 (1966)
The [bis(toluene-3,4-dithiol)] metal complex compound shown by HBGray et al. is preferably used. In addition, Mitsui Toatsu Huain Co., Ltd.
Near-infrared absorber [IR ABSORBERPA-1001,
PA−1002, PA−1003, PA−1005, PA−1006〕
etc. can be easily used in the present invention.

In particular, [bis(1-methyl-3,4-dithiophenolate)nickel]tetrabutylammonium, [bis(1-methyl-3,4-dithiophenolate)platinum]tetrabutylammonium, [bis(1-methyl-3,4-dithiophenolate)platinum]tetrabutylammonium, chloro-3,4-dithiophenolate)nickel]tetrabutylammonium,
[Bis(1-chloro-3,4-dithiophenolate)platinum]tetrabutylammonium, etc.
A 3,4-dithiophenolate complex having a metal core such as Ni or Pt is preferably used in the present invention.

Such a near-infrared absorber can be mixed with a solution of a suitable organic resin such as an acrylate resin, an acrylic resin, a urethane resin, a styrene resin, a polyester resin, a vinyl acetate resin, an acetal resin, or a copolymer composition thereof in an appropriate solvent. Alternatively, by dissolving and coating, it is possible to form a thin film layer (C) containing a near-infrared absorber at an appropriate concentration to an arbitrary thickness.

Furthermore, if the near-infrared absorber is soluble in the organic polymer film (D) selected as the substrate, it can be mixed into the organic polymer film (D) by kneading or the like. In this case, the thin film layer (C) containing the near-infrared absorber may be omitted.

In addition, an organic sheet containing a near-infrared absorber,
For example, it is also possible to laminate a polymethyl methacrylate resin plate or a polyvinyl chloride resin plate with an organic polymer film (D), and use the combination as an organic polymer film (D) as a substrate.

The concentration of the near-infrared absorber contained in the thin film layer (C) or the organic polymer (D) is 0.01 to 30 parts by weight [0.01 phr (per
100 resin) to 30 phr], and it is necessary to select an appropriate concentration in relation to the compatibility with the organic resin used and the film thickness with the thin film layer (C).

The thickness of the thin film layer (C) may be appropriately determined depending on the concentration of the near-infrared absorber contained, taking into consideration the effect of the near-infrared absorbing ability. Considering the synergistic effect in the present invention, it is preferable that the near-infrared absorbent used at this time has a transmittance of 30% or less and 0.5% or more at the absorption peak (800 nm to 1200 nm).

Further, such a thin film layer (C) may contain a stabilizer, an ultraviolet absorber, an antioxidant, etc.

When adding an ultraviolet absorber, it is preferably added so that the integrated ultraviolet light transmittance is 10% or less.

The selective light transmission functional sheet of the present invention has the following characteristics: (1) It has excellent flexibility, (2) It is optically uniform over a large area, and (3) It has an integrated visible transmittance of 70% or more. It is extremely bright, has an integrated near-infrared transmittance of less than 50%, and has excellent solar energy blocking properties.

Such selective light transmission functional sheets are used depending on their purpose, but for example, when used for building windows, etc., they can be applied directly to the glass of the window etc. using an adhesive, or they can be applied to the glass as a layer. One possible method is to use it by spreading it between layers, and when it is used in the windows of automobiles, it can be inserted into laminated glass known as safety glass through polyvinyl butyral.

In this case, an adhesion promoter, an adhesive, or a pressure-sensitive adhesive may be applied to the selectively transmitting light functional sheet of the present invention by a known method before use.

In particular, when the selective light transmission functional sheet of the present invention is used in safety glass for automobiles, vehicles, aircraft, buildings, etc., the synergy of the metal layer containing Ag, the antireflection layer, and the near-infrared absorber Due to the effect, the transmittance in the visible part is high, and the reflectance in the visible part is less than 15%,
It is preferably 12% or less, most preferably 10% or less, which is almost equivalent to glass, and it is possible to obtain a structure with excellent solar energy shielding rate.

By using the laminate of the present invention in this way,
It is possible to obtain various structures with excellent properties that are unattainable with the prior art.

In this way, the selective light transmission functional sheet of the present invention can be used in an optimal manner depending on the purpose of use, and can be effectively used not only in controlling the incidence of solar energy but also in all fields of heat radiation prevention. can do.

The optical performance in the present invention was measured with a self-recording spectrophotometer model 330 manufactured by Hitachi, Ltd., and was determined by the integral ultraviolet transmittance of 300 ~ Calculated using 390nm, integrated visible transmittance, 400-700nm, and integrated near-infrared transmittance, 750-2100nm.

Moreover, in particular, the integral visible transmittance was also calculated by the JIS-R3212 method (400 to 760 nm), and the larger value obtained was adopted.

Examples of specific examples of the present invention will be described below.

Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 50 μm was used as a substrate, and on top of that a silver-copper alloy thin film layer with a thickness of 80 Å (containing 10% by weight copper) as the first layer, and a 200 Å thick layer as the second layer. a transparent dielectric layer formed from tetrabutoxyzirconate, and a near-infrared absorber made of polymethacrylonitrile with a thickness of 2μ as the third layer (near-infrared absorber was added at 10 phr).
A selectively transparent sheet consisting of a thin film layer was formed.

A silver-copper alloy thin film layer containing 10% by weight of copper was formed by DC magnetron sputtering at an Ar gas pressure of 5×10 ^-3 Torr, targeting a silver-copper alloy containing 10% by weight of copper.

The input power is per unit area of the target.
It was 2W/ ^cm2 .

The transparent dielectric layer is made by mixing tetrabutoxyzirconate monomers with 3 parts of butanol and 2 parts of n-hexane.
A solution containing 7% by weight of acetylacetone dissolved in a solvent consisting of 50% of tetrabutoxyzirconate and an equimolar amount of tetrabutoxyzirconate was coated using a bar coater and dried at 120°C for 3 minutes.

The thin film layer containing the near-infrared absorber made of polymethacronitrile is made of 10 parts of polymethacronitrile.
10 phr of [bis(1-methyl-3,4 dithiophenolate)nickel]tetra-n-butylammonium was dissolved in a mixed solvent of cyclohexanone/methyl ethyl ketone at a weight ratio of 1:1 to form a 10% by weight solution of polymethacronitrile. After coating with a bar coater, dry at 130℃ for 2 minutes to obtain the desired thickness.
A thin film layer containing a 2μ near-infrared absorber was formed.

The integrated visible transmittance (JIS-
R3212) was 82%, and near-infrared light transmittance was 37%.

Comparative Example 1 On the polyethylene terephthalate film used in Example 1, a first layer of an 80 Å thick Ag/Cu metal thin film layer was formed using the same method as in Example 1, and a 200 Å thick tetrabutoxyzirconium second layer was formed. A zirconium oxide layer was formed.

The resulting laminate had an integrated visible transmittance of 86% and a near-infrared light transmittance of 65%.

Comparative Example 2 A near-red absorber made of polymethacrylonitrile [bis(1-methyl-3,4-dithiophenolate)] having a thickness of 2μ was applied on the polyethylene terephthalate film used in Example 1 in the same manner as in Example 1.
A thin film layer containing tetrabutylammonium (nickel) was formed. The resulting laminate had an integrated visible transmittance of 87% and a near-infrared transmittance of 77%.

Example 2 On a 75 μm thick biaxially stretched polyethylene terephthalate film, a 10 Å thick pretreatment layer formed of metallic titanium, a 120 Å thick silver-copper alloy thin film layer containing 5% by weight of copper, a 20 Å thick A laminate was obtained by sequentially laminating a post-treatment layer made of metallic titanium and a 150 Å thick transparent dielectric layer made of titanium oxide made of tetrabutoxy titanate. A silver-copper alloy thin film layer containing 5% by weight of copper was formed in the same manner as in Example 1 by DC magnetron sputtering using the silver-copper alloy layer containing 5% by weight of copper as a target. The pre-treatment layer and post-treatment layer formed from metallic titanium target metallic titanium.
It was formed as a thin film of metallic titanium by RF magnetron sputtering. The transparent dielectric layer formed from tetrabutoxy titanate is made from butanol 3
5 wt.

The unprocessed surface (polyester back surface) of the obtained laminate has a thickness of polystyrene containing [bis(1-methyl-3,4-dithiophenolate)nickel]tetrabutylammonium as a near-infrared absorber.
A 4μ thin film layer was formed. The thin film layer containing the near-infrared absorber is made of bis(1 methyl 3,4 dithiophenolate) nickel tetrabutylammonium.
5phr, 20 parts polystyrene to methyl ethyl ketone
60 parts of toluene, coated with a bar coater, and dried at 120°C for 1 minute.

The integrated visible light transmittance of the obtained light selectively transmitting laminate was 82%, and the near-infrared light transmittance was 35%.

Example 3 A titanium oxide layer with a thickness of 100 Å, an Ag metal layer with a thickness of 100 Å, and a titanium oxide layer with a thickness of 200 Å were sequentially laminated on a biaxially stretched polyester film with a thickness of 50 μ, and near-infrared absorption was applied to the back side of the polyester film. A laminate was obtained in which a polymethacrylonitrile layer containing the agent was provided with a thickness of 2 μm.

Titanium oxide layers with thicknesses of 100 Å and 200 Å were created using RF magnetron sputtering using titanium oxide as a target at an Ar pressure of 5×10 ^-3 Torr and RF power.
The samples were obtained by adding 2 W/cm ² and varying the precipitation time. The Ag metal layer with a thickness of 100 Å was obtained by DC magnetron sputtering using Ag metal as a target at an Ar pressure of 5×10 ⁻³ Torr and a DC power of 3 W/cm ² .

The polymethacrylonitrile layer containing the near-infrared absorber was prepared using a solution consisting of 10 phr of [bis(1-methyl-3,4-dithiophenolate)nickel]tetrabutylammonium, 10 parts of polymethacrylonitrile, 40 parts of cyclohexanone, and 50 parts of methyl ethyl ketone. was coated with a bar coater and dried at 130°C for 2 minutes.

The resulting laminate had an integrated visible transmittance of 80% and a near-red transmittance of 32%.

Example 4 A polyvinyl butyral sheet having a thickness of 380 μm was laminated on both sides of the permselective sheet obtained in Example 3, and then both sides were sandwiched with a glass plate having a thickness of 3 mm. The laminate was held at a temperature of 90° C. for 60 minutes while applying a pressure of 1 kg/cm ² to completely adhere, and then further treated at a high temperature and pressure of 15 kg/cm ² at 120° C. The resulting laminate had an integrated visible transmittance of 75%, a near-infrared light transmittance of 28%, and an integrated visible reflectance of 11%.

Example 5 A biaxially stretched polyethylene terephthalate film with a thickness of 100 μm was used as a substrate, the first layer was a thin film layer containing a near-infrared absorber made of acrylonitrile-styrene copolymer with a thickness of 4 μm, and the second layer was gold. A silver metal layer with a thickness of 100 Å containing 20% by weight, and a transparent dielectric layer made of polystyrene with a thickness of 800 Å as the third layer were formed.

The thin film layer containing the near-infrared absorber was made of 10 parts of acrylonitrile-styrene copolymer (acrylonitrile 30 mol%), 60 parts of methyl ethyl ketone, 30 parts of cyclohexanone, [bis(1-methyl-3,4-dithiophenolate) platinum] tetral- Mix and dissolve butylammonium 10 phr and coat with a bar coater.
It was obtained by drying at 120°C for 2 minutes.

A silver metal layer containing 20% by weight of gold was obtained by using a DC magnetron sputtering method with an Ar pressure of 8×10 ^-3 Torr and a DC power of 3W/cm ² using a silver metal plate containing 20% by weight of gold as a target. Ta.

The transparent dielectric layer made of polystyrene is made by mixing 4 parts of polystyrene with 16 parts of toluene and methyl ethyl ketone.
Mix and dissolve in a solvent consisting of 70 parts and 10 parts of acetone, coat the solution with a bar coater, and then coat at 120℃ for 2 hours.
It was obtained by drying for a minute.

The resulting laminate had an integrated visible transmittance of 75% and a near-infrared transmittance of 36%.

Example 6 A biaxially stretched polyethylene terephthalate film with a thickness of 7 μm was used as the substrate, and the thickness was
A 90 Å silver metal layer containing 10% copper by weight is laminated in sequence, followed by a 300 Å thick zirconium oxide layer as the second layer, and a 15 μ thick layer containing a near-infrared absorber made of polyvinyl butyral as the third layer. A laminate was constructed.

A silver metal layer containing 10 wt% copper with a thickness of 90 Å is
It was formed by DC magnetron sputtering using a target made of a silver-copper alloy containing 10% by weight of copper.

The zirconium oxide layer with a thickness of 300 Å was made of 5 parts of tetrabutoxyzirconium monomer, 2 parts of acetylacetone, 50 parts of n-butanol, and n-hexane.
A solution consisting of 33 parts and 10 parts of isopropanol was coated using a bar coater and dried at 130°C for 3 minutes.

The layer containing a near-infrared absorber made of polyvinyl butyral with a thickness of 15μ is made of polyvinyl butyral.
After dissolving 2 phr of [bis(1-methyl-3,4 dithiophenolate) platinum]tetra-n-butylammonium in a solution consisting of 20 parts of ethanol, 15 parts of ethanol, and 65 parts of cyclohexanone, the solution was coated with a bar coater to 100 parts of cyclohexanone. It was obtained by drying at ℃ for 2 minutes.

The resulting laminate had an integrated visible transmittance of 82% and a near-infrared light transmittance of 32%.

Claims (1)

[Claims] 1. Thickness from 40 Å to 180 Å containing 50% by weight or more of Ag metal
Å metal layer (A); anti-reflection coating layer made of dielectric material with a refractive index of 1.5 or more
(B); A thin film layer containing a near-infrared absorber having an absorption peak between 800 nm and 1200 nm; (C); and an organic polymer film (D). A light selective transmission functional sheet, which comprises each of the above layers. is (B)/(A)/(B)/(C)/(D), or (B)/(A)/(C)/(D), or (B)/(A)/(B) /(D)/(C), or (B)/(A)/(D)/(C), or (C)/(B)/(A)/(B)/(D) or (C ) / (B) / (A) / (D) are sequentially laminated in the order, and the optical properties are that the laminated visible light transmittance is 70% or more and the integrated near-infrared light transmittance is 50% or less. Selective light transmission functional sheet.