JP4415953B2 - Selective permeable membrane coating solution, selective permeable membrane and selective permeable multilayer membrane - Google Patents

Description

  The present invention relates to a selective permeable membrane coating solution applicable to various transparent substrates such as glass, plastics, and more specifically, selectively transmits, reflects, and absorbs ultraviolet rays, heat rays, visible rays, and infrared rays according to purposes. And a permselective membrane and a permselective multilayer film.

  Due to the generation and expansion of the ozone hole, the amount of ultraviolet rays reaching the ground surface has increased remarkably, and adverse effects on the human body such as sunburn and skin cancer have become problems. In addition, ultraviolet rays enter through windows of houses, buildings, automobiles, show windows, etc., and fading, discoloration, and deterioration of furniture such as curtains, carpets, and sofas, paintings, and documents are also problematic.

  Conventionally used ultraviolet screening agents include titanium oxide, cerium oxide, zinc oxide, etc., but these have a low ultraviolet absorption rate on the long wavelength side (near 400 nm), including when these are used alone, 400 nm. It was not an ultraviolet shielding material for efficiently and sufficiently shielding nearby light.

  In addition, UV screening agents that use organic substances such as benzophenone have a high UV absorption rate near 400 nm, but they themselves decompose by absorbing UV rays, making it difficult to maintain stable UV blocking performance for a long period of time. Met.

  In addition, from the viewpoint of energy conservation, heat ray shielding glass that shields the inflow of solar energy from the window and reduces the cooling load in summer, and privacy protection glass that controls the transmittance in the visible light region have recently attracted attention. Has been. These glasses are used according to their preference, various colors, brightness, heat ray shielding rate, etc., but most of such functional films have conventionally been dry-type by sputtering or vapor deposition. Because it is manufactured by the method, it is not suitable for low-volume, multi-product production for the above-mentioned requirements, it cannot be said that it meets the detailed requirements for demand, and requires large equipment and complicated processes. Therefore, the cost as a product was very expensive.

Moreover, few of these glasses have an ultraviolet shielding function (particularly, a shielding function around 400 nm), and there is almost no glass that simultaneously controls ultraviolet rays, heat rays (sunlight), and visible light.
A colored film using an organic dye is also commercially available, but the organic dye is greatly deteriorated by ultraviolet rays or the like, and cannot be said to exhibit a sufficient effect.

In addition , the dry method used for the production of the functional film described above requires a large vacuum device, etc., and on-site processing work on glass already installed in houses, buildings, cars, etc. is carried out It was impossible.

  The present invention has been made in order to solve the above-mentioned conventional problems. The object of the present invention is to efficiently shield a wide range of ultraviolet rays having a wavelength of about 400 nm or less from around 400 nm. Compared with organic coloring dyes, it maintains its effect stably for a long time, and also has a heat ray shielding function, controls the transmittance in the visible light region, and mixes various inorganic fine particles to achieve a color tone according to the purpose. Providing a selective permeable membrane coating solution, a selective permeable membrane, and a selectively permeable multilayer membrane that can be applied to the already installed glass on site by selecting a binder using a simple and inexpensive coating method. That is.

  In order to solve the above-mentioned conventional problems, the present inventors have focused on inorganic fine particles having a specific average particle diameter excellent in weather resistance, and found that the intended purpose can be achieved by dispersing the fine particles, thereby completing the present invention. It came to do.

That is, in the first embodiment of the present invention, at least one of iron oxide fine particles and iron (III) oxide fine particles having an average particle size of 100 nm or less is 2.0 to 7.0% by weight, and the average particle size is Selective transmission in which 0.5 to 2.1% by weight of at least one of ruthenium oxide fine particles, titanium nitride fine particles, tantalum nitride fine particles, titanium silicide fine particles, molybdenum silicide fine particles, and lanthanum boride fine particles having a particle size of 100 nm or less is mixed and dispersed. This is a permselective membrane obtained by applying a coating solution for a membrane to a substrate and then curing it. The ultraviolet transmittance τ _uv is 6.25% or less, the solar transmittance τ _e is 66.28% or less, and visible light transmission is achieved. The rate τ _v is 26.99% or more.

Further, in the second embodiment of the present invention, at least one of a metal alkoxide of silicon, zirconium, titanium, and aluminum, a partial hydrolysis polymer of each metal alkoxide, or a synthetic resin is further formed on the above-described permselective membrane. It is characterized by a permselective multilayer film to which a film containing seeds is deposited.

Furthermore, in a third embodiment of the present invention, at least one of the iron oxide fine particles and iron oxide hydroxide (III) fine particles having an average particle size of 100 nm or less, which form the permselective membrane and the permselective multilayer membrane, is selected from two. At least one of ruthenium oxide fine particles, titanium nitride fine particles, tantalum nitride fine particles, titanium silicide fine particles, molybdenum silicide fine particles, and lanthanum boride fine particles having an average particle diameter of 100 nm or less and 0.0 to 7.0% by weight is 0.5%. And 2.1% by weight of a dispersion, and further containing at least one of silicon, zirconium, titanium, aluminum metal alkoxides, or partial hydrolysis polymers of metal alkoxides, and a binder. As a characteristic feature, the selective permeable membrane coating solution further contains a synthetic resin.

  As described above, according to the present invention, it is possible to efficiently shield a wide range of ultraviolet rays from around 400 nm and below, and to maintain the effect stably over a long period of time compared to conventional organic ultraviolet shielding agents and organic coloring dyes. Also, it has a heat ray shielding function, controls the transmittance in the visible light region, and by mixing various inorganic fine particles, a color tone according to the purpose can be obtained, and a binder is selected using a simple and inexpensive coating method. Thus, it is possible to provide a selectively permeable membrane coating solution, a selectively permeable membrane, and a selectively permeable multilayer membrane that can be applied on site to already installed glass.

As a result of intensive studies on inorganic fine particle materials that efficiently absorb ultraviolet rays on the long wavelength side (around 400 nm), the present inventors first focused on iron oxide and iron oxide hydroxide (III ) . When coated on a substrate using a coating solution in which iron oxide fine particles and iron (III) oxide fine particles are dispersed with an average particle size of 100 nm or less, it transmits light in the visible region and absorbs light in the ultraviolet region. It turns out that it will have.

  Next, as a result of research on inorganic fine particles such as ruthenium oxide fine particles, titanium nitride fine particles, tantalum nitride fine particles, titanium silicide fine particles, silicified molybdenum fine particles, and lanthanum boride fine particles, each of these inorganic fine particles is a powder having absorption in the visible light region. It was also found that in the thin film state dispersed as fine particles having an average particle size of 100 nm or less, it has a characteristic of transmitting light in the visible light region and shielding light in the near infrared region.

  As for the color tone, when the inorganic fine particles are dispersed in the form of fine particles having an average particle size of 100 nm or less, the iron oxide exhibits a red color, the iron oxide hydroxide (III) is a yellow color, and the ruthenium oxide is a green color. The titanium nitride fine particles are blue, the tantalum nitride fine particles are brown, the titanium silicide fine particles are gray, the molybdenum silicide fine particles are bronze, and the lanthanum boride fine particles are green.

In addition to the above inorganic materials, the same shows the equivalent of the properties can be listed below.
Pb ₂ Ru ₂ O _6.5 fine particles and Bi ₂ Ru ₂ O _7-x fine particles can be used instead of ruthenium oxide fine particles, and titanium nitride fine particles, tantalum nitride fine particles, titanium silicide fine particles, molybdenum silicide fine particles can be used. Zirconium nitride fine particles and hafnium nitride fine particles can be used instead of titanium boride, and titanium boride can be used instead of lanthanum boride fine particles. Furthermore, iron oxide hydroxide (III ) Instead of fine particles, it is also possible to use iron iron oxide or iron nitride.

  In the present invention, the average particle size of the inorganic fine particles in the coating solution needs to be 100 nm or less. When the average particle diameter is larger than 100 nm, the aggregated fine particles in the coating liquid are settled due to the aggregation of the fine particles in the dispersion. Further, fine particles having an average particle diameter exceeding 100 nm or coarse particles formed by agglomeration thereof are not preferable because they cause increase in film haze and decrease in visible light transmittance due to light scattering. The average particle size of the inorganic fine particles needs to be 100 nm or less for the reason described above. However, since the lowest average particle size that is economically available with the current technology is about 2 nm, this is the lower limit.

  The dispersion medium for the fine particles in the coating liquid is not particularly limited, and can be selected according to the coating conditions, coating environment, alkoxide in the coating liquid, synthetic resin binder, and the like. For example, organic substances such as water and alcohol Various solvents and the like can be used, and the pH may be adjusted by adding acid or alkali as necessary. Furthermore, in order to further improve the dispersion stability of the fine particles in the ink, various coupling agents, surfactants and the like can be added. The amount of each added at that time is 30% by weight or less, preferably 5% by weight or less based on the inorganic fine particles. The fine particle dispersion method can be arbitrarily selected as long as the fine particles are uniformly dispersed in the solution. Examples of the fine particle dispersion method include a ball mill, a sand mill, and an ultrasonic dispersion method.

  The permselective membrane in the present invention is a membrane in which the fine particles are deposited at a high density on a substrate to form a membrane. Each of the metal alkoxides of silicon, zirconium, titanium, and aluminum contained in the coating solution or alkoxides of these metals is used. The partially hydrolyzed polymer or the synthetic resin binder has an effect of improving the binding property of the fine particles to the substrate after coating and curing, and further improving the hardness of the film. Further, on the film thus obtained, a coating containing a metal alkoxy oxide such as silicon, zirconium, titanium or aluminum or a partially hydrolyzed polymer of these metal alkoxides or a synthetic resin is coated as a second layer. By attaching it, it becomes possible to further improve the binding force of the film containing fine particles as a main component to the substrate, the hardness and weather resistance of the film.

When the coating solution does not contain silicon, zirconium, titanium, and aluminum metal alkoxides, partially hydrolyzed polymer of these metal alkoxides, or synthetic resin, the film obtained after coating the coating solution on the substrate is formed on the substrate. A film structure in which only fine particles are deposited is obtained.
Even if it remains as it is, it shows selective permeability of light, but in the same manner as above, a coating solution containing each metal alkoxide of silicon, zirconium, titanium, and aluminum, a partially hydrolyzed polymer of these metal alkoxides, or a synthetic resin is applied. By forming a film and forming a multi-layer film, the coating liquid component fills the gap in which the fine particles of the first layer are deposited, thus reducing the film haze and improving the light transmittance in the visible light region. To improve the binding property of the fine particles to the substrate.

  As a method of depositing the film containing the fine particles as a main component with a film made of each metal alkoxide such as silicon, zirconium, titanium, and aluminum or a partially hydrolyzed polymer of these metal alkoxides, a sputtering method or a vapor deposition method may be used. Although possible, the coating method is effective because of the advantages such as the ease of the film forming process and the low film forming cost. This coating solution for coating contains one or more alkoxides such as silicon, zirconium, titanium and aluminum and partially hydrolyzed heavy compounds thereof in water or alcohol, and the content thereof is an oxidation obtained after heating. It is preferably 40% by weight or less in the total solution in terms of product. Moreover, it is also possible to adjust pH by adding an acid and an alkali as needed. An oxide film such as silicon, zirconium, titanium, or aluminum can be easily produced by applying such a liquid as a second layer on the film containing the fine particles as a main component and heating.

  The application method of the coating solution and the coating solution for the film is not particularly limited, and the treatment solution is flat, thin and even, such as spin coating, spray coating, dip coating, screen printing, and flow coating. Any method can be used as long as it can be applied.

  When the substrate heating temperature after application of the coating solution containing each metal alkoxide and its partially hydrolyzed polymer is less than 100 ° C., the polymerization reaction of the alkoxide and its partially hydrolyzed polymer contained in the coating film remains incomplete. In many cases, water or an organic solvent remains in the film and causes a reduction in the visible light transmittance of the film after heating. Therefore, the temperature is preferably 100 ° C. or higher, more preferably the boiling point temperature of the solvent in the coating solution. Heating is performed as described above.

  When a synthetic resin binder is used, it may be cured in accordance with each curing method. For example, an ultraviolet curable resin may be irradiated with an appropriate amount of ultraviolet light. Since it can be used, it can be applied to existing window glass in the field, expanding versatility.

  The coating liquid according to the present invention is a dispersion of the above-mentioned fine particles, and does not form the desired solar shading film by utilizing the decomposition or chemical reaction of the components of the coating liquid due to heat during firing, and thus has stable characteristics. A thin permeable membrane having a uniform thickness can be formed.

  The fine particle-dispersed film in the present invention is a film in which fine particles are deposited at a high density on a substrate to form a film. Each metal alkoxide of silicon, zirconium, titanium, and aluminum contained in a coating solution or a partial hydrolysis polymerization thereof. The product or the synthetic resin binder has an effect of improving the binding property of the fine particles to the substrate after the coating film is cured, and further improving the strength of the film.

  As described above, according to the present invention, by appropriately mixing the materials of the above-mentioned inorganic fine particles, it is possible to produce an ink that meets the purpose by adjusting the solar radiation transmittance and color tone of ultraviolet rays, visible rays, and infrared rays. In addition, since these fine particle materials are inorganic materials, they have extremely high weather resistance as compared with organic materials. For example, even if they are used in a portion exposed to sunlight (ultraviolet rays), the color and various characteristics hardly deteriorate.

In addition , in terms of the ability to produce a small amount of various types and a permselective membrane that meets the requirements, for example, when applying to a glass window of a single building, to reduce the heat of the window that is inserted into the western sun. In addition, it has a high sun-shielding effect, 1st floor windows with low visible light transmittance for privacy protection, strong sunlight in the daytime, fading furniture and curtains, and people sunburning It becomes possible to satisfy various requirements such as blending with a high UV shielding rate and blending according to the color tone of the room by a simple method. In addition, since these requests are mostly noticed when they are actually used, it is possible to prepare a coating solution according to the usage situation such as a window with a coating solution using a binder that cures at room temperature, and to apply it on site. It is possible and very useful.
[Example]

Examples of the present invention will be described below together with comparative examples.
[Reference Example 1]

Iron oxide (Fe ₂ O ₃ ) fine particles (average particle size 30 nm) 20 g, ethyl alcohol 69.5 g, diacetone alcohol (DAA) 10 g, and titanate coupling agent (Ajinomoto Co., Ltd. Preneact KR-44: trade name ) 0.5 g was mixed, and ball mill mixing was performed for 80 hours using zirconia balls having a diameter of 4 mm to prepare 100 g of a dispersion of iron oxide (Fe ₂ O ₃ ) (solution A).

  Next, 25 g of ethyl silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) having an average degree of polymerization of 4 to 5 is 25 g, 32 g of ethanol, 8 g of 5% hydrochloric acid aqueous solution, 70 g of ethyl silicate solution adjusted with 5 g of water, 30 g of ethanol. Were mixed uniformly to prepare 100 g of an ethylsilicate mixed solution (solution B).

Solution A and Solution B were diluted with ethanol so that the composition of Reference Example 1 shown in Table 1 was mixed, and 15 g of this solution was rotated on a 200 × 200 × 3 mm soda-lime-based plate glass substrate rotating at 200 rpm. The solution was dripped from the flask and shaken for 5 minutes. This was put in an electric furnace at 180 ° C. and heated for 30 minutes to obtain the intended film.

About the formed film | membrane, the transmittance | permeability of 200-1800 nm was measured using the spectrophotometer made from Hitachi, and the solar transmittance (τe) and the visible light transmittance (τv) according to JISR3106, the ultraviolet transmittance ( τuv) was calculated. Further, the transmittance at 400 nm (400 nm T%) was read. These results are shown in Table 2. Table 2 also shows the optical characteristics of the films obtained in Examples, Reference Examples and Comparative Examples 1 and 2 described below.
[Reference Example 2]

The iron oxide (Fe ₂ O ₃ ) concentration of solution A is diluted with ethanol to 3.0%, and 15 g of this solution is dropped from a beaker onto a 200 × 200 × 3 mm soda-lime-based plate glass substrate rotating at 200 rpm. The rotation was stopped after shaking for 5 minutes. Further, 15 g of a solution obtained by diluting the SiO ₂ concentration of solution B with ethanol to 3.0% was dropped from the beaker onto the coated substrate rotating at 200 rpm, shaken for 5 minutes, and then stopped rotating. This was put in an electric furnace at 180 ° C. and heated for 30 minutes to obtain the intended film. The optical properties of this film are shown in Table 2.
[Reference Example 3]

  Iron oxide (III) oxide (FeO (OH)) fine particles (average particle size 30 nm) 20 g, ethyl alcohol 69.5 g, diacetone alcohol (DAA) 10 g, and titanate coupling agent (Ajinomoto Co., Ltd., Plenact KR -44: 0.5 g of trade name) was mixed, and ball mill mixing was performed for 80 hours using zirconia balls having a diameter of 4 mm to prepare 100 g of an iron (III) oxide hydroxide (FeO (OH)) dispersion (solution C). ). Moreover, normal temperature hardening resin (normal temperature hardening type silicone resin) was diluted with ethanol, and it was set as 20% solid content solution (D liquid).

The liquid C and liquid D were diluted with ethanol so as to have the composition of Reference Example 3 in Table 1, and the target film was obtained by the same procedure as in Reference Example 1, and the optical characteristics of this film were measured. The optical properties of this film are shown in Table 2.
[Reference Example 4]

A liquid, C liquid, and D liquid were diluted with ethanol so that it might become a composition of the reference example 4 of Table 1, and the target film | membrane was obtained by the procedure similar to the reference example 1. FIG. The optical properties of this film are shown in Table 2.
[Example 5]

Ruthenium oxide fine particles (RuO ₂ ) (average particle size 40 nm) 20 g, ethyl alcohol 69.5 g, N-methyl-2-pyrrolidone 10 g, and titanate coupling agent (Ajinomoto Co., Ltd. Preneact KR-44: trade name) 0.5 g was mixed, and ball mill mixing was performed for 100 hours using zirconia balls having a diameter of 4 mm to prepare a dispersion 100 g of ruthenium oxide (RuO ₂ ) (solution E).

A liquid, E liquid, and B liquid were diluted with ethanol so that it might become a composition of Example 5 of Table 1, and the target film | membrane was obtained by the procedure similar to the reference example 1. FIG. The optical properties of this film are shown in Table 2.
[Example 6]

C liquid, E liquid, and B liquid were diluted with ethanol so as to have the composition of Example 6 in Table 1, and a target film was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Example 7]

Liquid C, liquid E and liquid B were diluted with ethanol so as to have the composition of Example 7 in Table 1, and the intended membrane was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Example 8]

Liquid C, liquid E and liquid B were diluted with ethanol so as to have the composition of Example 8 in Table 1, and the target membrane was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Example 9]

  Mixing 20 g of titanium nitride fine particles (TiN) (average particle size 30 nm), 69.5 g of diacetone alcohol, 10 g of N-methyl-2-pyrrolidone, and 0.5 g of silane coupling agent, and using zirconia balls having a diameter of 4 mm The mixture was ball milled for 100 hours to prepare 100 g of a titanium nitride (TiN) dispersion (liquid F).

Liquid C, liquid F and liquid B were diluted with ethanol so as to have the composition of Example 9 in Table 1, and the target membrane was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Reference Example 10]

Liquid F and liquid B were diluted with ethanol so as to have the composition of Reference Example 10 in Table 1, and the intended membrane was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Example 11]

Lanthanum boride fine particles (LaB ₆ ) (average particle size 40 nm) 20 g, diacetone alcohol 69.5 g, N-methyl-2-pyrrolidone 10 g, and silane coupling agent 0.5 g were mixed, and a zirconia ball having a diameter of 4 mm. Was used for 100 hours to prepare a dispersion of lanthanum boride (LaB ₆ ) 100 g (solution G).

A liquid, G liquid, and B liquid were diluted with ethanol so that it might become a composition of Example 11 of Table 1, and the target film | membrane was obtained by the procedure similar to the reference example 1. FIG. The optical properties of this film are shown in Table 2.
[Reference Example 12]

Liquid E and liquid B were diluted with ethanol so as to have the composition of Reference Example 12 in Table 1, and the intended membrane was obtained by the same procedure as in Reference Example 1 . The optical properties of this film are shown in Table 2.
[Example 13]

  20 g of tantalum nitride (TaN) fine particles (average particle size 40 nm), 69.5 g of diacetone alcohol, 10 g of N-methyl-2-pyrrolidone and 0.5 g of a silane coupling agent are mixed, and zirconia balls having a diameter of 4 mm are used. Ball mill mixing was performed for 100 hours to prepare 100 g of a tantalum nitride (TaN) dispersion (liquid H).

Liquid C, liquid H and liquid B were diluted with ethanol so as to have the composition of Example 13 in Table 1 and mixed well, and 15 g of this solution was rotated on a 200 × 200 × 3 mm soda-lime-based plate glass substrate rotating at 200 rpm. The solution was dropped from the beaker and shaken for 5 minutes as it was, and then the rotation was stopped. This was put in an electric furnace at 180 ° C. and heated for 15 minutes to obtain the intended film. The optical properties of this film are shown in Table 2 .
[Example 14]

Mixing titanium silicide (TiSi ₂ ) fine particles (average particle size 50 nm) 20 g, diacetone alcohol 69.5 g, N-methyl-2-pyrrolidone 10 g and silane coupling agent 0.5 g, and using zirconia balls having a diameter of 4 mm. The mixture was ball milled for 100 hours to prepare 100 g of a titanium silicide (TiSi ₂ ) dispersion (liquid I).

A solution, I solution, and B solution were diluted with ethanol so as to have the composition of Example 14 in Table 1 and mixed well, and 15 g of this solution was rotated at 200 rpm on a 200 × 200 × 3 mm soda-lime-based plate glass substrate. The solution was dropped from the beaker and shaken for 5 minutes as it was, and then the rotation was stopped. This was put in an electric furnace at 180 ° C. and heated for 15 minutes to obtain the intended film. The optical properties of this film are shown in Table 2 .
[Example 15]

Mixing 20 g of molybdenum silicide (MoSi ₂ ) fine particles (average particle size 45 nm), 69.5 g of diacetone alcohol, 10 g of N-methyl-2-pyrrolidone and 0.5 g of silane coupling agent, and using zirconia balls having a diameter of 4 mm The mixture was ball milled for 100 hours to prepare 100 g of a dispersion of molybdenum silicide (MoSi ₂ ) (solution J).

Liquid C, Liquid J and Liquid B were diluted with ethanol so as to have the composition of Example 15 in Table 1 and mixed well, and 15 g of this solution was rotated at 200 rpm on a 200 × 200 × 3 mm soda-lime-based plate glass substrate. The solution was dropped from the beaker and shaken for 5 minutes as it was, and then the rotation was stopped. This was put in an electric furnace at 180 ° C. and heated for 15 minutes to obtain the intended film. The optical properties of this film are shown in Table 2 .
[Comparative Example 1]

Titanium oxide (TiO ₂ ) fine particles (average particle size 50 nm) 30 g, ethyl alcohol 59.5 g, diacetone alcohol (DAA) 10 g, and titanate coupling agent (Ajinomoto Co., Ltd. Preneact KR-44: trade name) 0 0.5 g was mixed and ball mill mixing was performed for 100 hours using zirconia balls having a diameter of 4 mm to prepare 100 g of a titanium oxide dispersion (solution K ).

The liquid K and the liquid B were diluted with ethanol so as to have the composition of Comparative Example 1 shown in Table 1, and mixed sufficiently. The solution was added dropwise and shaken for 2 minutes. This was put in an electric furnace at 180 ° C. and heated for 15 minutes to obtain the intended film. The optical properties of this film are shown in Table 2.
[Comparative Example 2]

30 g of zinc oxide (ＯnO) fine particles (average particle size 45 nm), 59.5 g of ethyl alcohol, 10 g of diacetone alcohol (DAA), and titanate coupling agent (Plainact KR-44 manufactured by Ajinomoto Co., Inc.) 5 g was mixed and mixed with a ball mill for 100 hours using zirconia balls having a diameter of 4 mm to prepare 100 g of a zinc oxide dispersion (Liquid L ).

The liquids L and B were diluted with ethanol so as to have the composition of Comparative Example 2 in Table 1, and the intended membrane was obtained in the same procedure as Comparative Example 1. The optical properties of this film are shown in Table 2.

  From Table 2, in the examples according to the present invention, comparison is made over the optical characteristics of solar transmittance (τe), visible light transmittance (τv), ultraviolet transmittance (τuv) and transmittance at 400 nm (400 nm T%). It can be seen that the numerical values are superior to those of the examples and a desired color tone is obtained.

Claims (5)

At least one of iron oxide fine particles and iron (III) oxide fine particles having an average particle size of 100 nm or less is 2.0 to 7.0% by weight, ruthenium oxide fine particles and titanium nitride particles having an average particle size of 100 nm or less. After applying a selective permeable membrane coating solution in which 0.5 to 2.1 wt% of at least one of tantalum nitride fine particles, titanium silicide fine particles, silicified molybdenum fine particles, and lanthanum boride fine particles is mixed and dispersed to a substrate, A selectively permeable membrane obtained by curing, having an ultraviolet transmittance τ _uv Is 6.25% or less, solar transmittance τ _e 66.28% or less, visible light transmittance τ _v Is a permselective membrane, characterized in that it is 26.99% or more. A film containing at least one of a metal alkoxide of silicon, zirconium, titanium, and aluminum, a partially hydrolyzed polymer of each metal alkoxide, or a synthetic resin is deposited on the permselective membrane according to claim 1. A selectively permeable multilayer film characterized by being made. A selectively permeable membrane coating solution for forming the selectively permeable membrane according to claim 1 or 2,
    At least one of iron oxide fine particles and iron (III) oxide fine particles having an average particle size of 100 nm or less is 2.0 to 7.0% by weight, ruthenium oxide fine particles and titanium nitride particles having an average particle size of 100 nm or less. A coating for a selectively permeable membrane, characterized in that 0.5 to 2.1% by weight of at least one of tantalum nitride fine particles, titanium silicide fine particles, molybdenum silicide fine particles, and lanthanum boride fine particles is mixed and dispersed in a solvent. liquid. 4. The permselective membrane coating solution according to claim 3, further comprising at least one of silicon, zirconium, titanium, and aluminum metal alkoxides, or a partially hydrolyzed polymer of each metal alkoxide. The selective permeable membrane coating solution according to claim 3 or 4, further comprising a synthetic resin as a binder.