KR102141631B1 - Transmittance changeable film and method for manufacturing the same) - Google Patents

Abstract

This application relates to a variable transmittance film. The variable transmittance film of the present application includes an electrochromic layer and a transparent conductive material, and includes an electrode layer whose b value in the Lab color space is different from the electrochromic layer.

Description

Variable transmittance film and manufacturing method of variable transmittance film {TRANSMITTANCE CHANGEABLE FILM AND METHOD FOR MANUFACTURING THE SAME)}

The present application relates to a variable transmittance film and a method for manufacturing the variable transmittance film.

The variable transmittance film is widely used in smart windows that can control the transmittance of sunlight. The variable transmittance film can implement a performance in which the transmittance is changed by using a polymer dispersed liquid crystal or by using electrochromic color. In particular, when electrochromic color is used, a film having a large area can be manufactured with excellent durability and low cost. There are advantages.

However, when using electrochromic, there is a disadvantage in that it is dependent on the type of the electrochromic material since the color is expressed by coloring or bleaching by the oxidation or reduction reaction of the electrochromic material. In particular, the typical electrochromic materials, such as WO ₃ , Prussian Blue (PB), and Viologen, have a problem in that expression of colors is not free because most of them have a blue-based coloring color.

Furthermore, although various studies have been conducted on organic substances that are free to change the structure of molecules to express various colors, electrochromic materials require stability of electron transfer and excellent electrochromic properties, so it is easy to manufacture reliable electrochromic materials. Because it is not, a different approach to color diversification is needed.

An object of the present application is to provide a variable transmittance film capable of realizing various colors while maintaining excellent durability of the variable transmittance film.

The above and other other objects of the present application can be achieved by the present application described in detail below.

In an example related to the present application, the present application relates to a variable transmittance film. The variable transmittance film according to the present invention includes an electrochromic layer and a transparent conductive material, and an electrochromic layer and an electrode layer having different b values in Lab color space.

The b value of the Lab color space indicates the yellowness, and the larger the b value, the greater the yellow index. The b value of the electrode layer and the electrochromic layer is different means that the b value of the electrode layer is different from the b value measured when coloring the electrochromic material of the electrochromic layer and/or the b value measured when decoloring.

The variable transmittance film of the present application includes an electrode layer having a different b value from the electrochromic layer, and thus it is possible to provide a variable transmittance film having a desired optical color without changing the electrochromic material.

In particular, when the electrochromic layer has a negative b value due to decolorization and/or coloring, the electrode layer has a positive b value, or when the electrochromic layer has positive b value due to decolorization and/or coloring, The electrode layer may provide a variable transmittance film having a neutral color by having a negative b value.

In one example, the electrode layer further includes oxygen, and the content ratio of the oxygen may be 50% or less, 40% or less, 35% or less, or 30% or less compared to a transparent conductive material. The lower limit is not particularly limited, and may be, for example, 0.3% or more, 0.5% or more, or 1% or more. The oxygen content ratio may be changed by deposition power of a step of forming an electrode layer, process pressure, or partial pressure of injected oxygen. In addition, the oxygen content ratio, for example, can be derived by a method using an X-ray photoelectron microscope (X-ray photoelectron spectroscopy, XPS). The variable transmittance film of the present application can control the ratio of oxygen contained in the electrode layer, thereby changing the b value of the electrode layer, thereby providing a variable transmittance film having a desired optical color.

In one example, the electrode layer may have a b value of 0.5 or more, 0.7 or more, 1.0 or more, or 1.5 or more. The upper limit of the b value of the electrode layer is not particularly limited, and may be determined in consideration of the optical color development of the variable transmittance film, and may be, for example, 10 or less, 7 or less, or 5 or less.

The variable transmittance film of the present application includes the electrode layer having a value of b in the above range, thereby changing the color of the variable transmittance film due to the color-discoloration of the electrochromic layer, and having the desired optical color without changing the electrochromic material. It is possible to provide a variable film, which can also solve the durability problem of the electrochromic material.

In addition, when the electrochromic layer of the variable transmittance film exhibits a blue color when colored or discolored, for example, when the b value of the electrochromic layer is negative, the yellowness of the electrode layer increases as the b value of the electrode layer increases. As it becomes larger, it is possible to provide a variable transmittance film having a neutral color.

In one example, the thickness of the electrode layer of the present application may be preferably 10 nm or more, 15 nm or more, 20 nm or more, or 30 nm or more, and may be 500 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less, but is not limited thereto. When the electrode layer satisfies the above range, the b value of the electrode layer can be changed to provide a variable transmittance film having a desired optical color.

In one example, the transparent conductive oxide is ITO (Indium Tin Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium doped Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), IZO (Indium doped Zinc Oxide), NTO (Niobium doped Titanium Oxide), ZnO (Zinc Oxide), OMO (Oxide/Metal/Oxide) or CTO (Cadmium Tin Oxide), but is not limited thereto. In another example, the electrode layer may have a structure in which two or more conductive materials are stacked in a plurality of layers.

In one example, the electrochromic layer of the present application includes an electrochromic material, wherein the electrochromic material is a metal oxide, a prussian blue compound, a viologen compound, a phthalate compound, a pyridine compound, an anthraquinone compound, It may be an aminoquinone-based compound, a rare earth-based organometallic compound, a phthalocyanine-based compound, a petothiazine-based compound, a dye-based compound, a conductive polymer compound, or a combination thereof, but the electrochromic materials of the present application are not limited to the above materials. .

In one example, the metal oxide may be cobalt oxide, ruthenium oxide, iridium oxide, nickel oxide, chromium oxide, manganese oxide, iron oxide, titanium oxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide or tungsten oxide, , But is not limited thereto.

In another example of the present application, the present application relates to a method of manufacturing a variable transmittance film. The manufacturing method of the present application may include the step of forming an electrode layer by depositing a transparent conductive material on the substrate under an oxygen partial pressure of 30% or less. The oxygen partial pressure may be 25% or less or 20% or less in a range of 30% or less, but may be 0.5% or more or 1% or more, but is not limited thereto. The oxygen partial pressure (O ₂ partial pressure) may be, for example, an oxygen ratio in a mixed gas of argon and oxygen. In the manufacturing method of the present application, the oxygen content ratio of the electrode layer can be controlled by controlling the oxygen partial pressure in the above-described range in the step of forming the electrode layer, and accordingly, the b value of the electrode layer is changed to obtain the desired optical color without changing the electrochromic material It is possible to provide a variable film having transmittance.

The transparent conductive material is the same as described above, and the method of depositing the transparent conductive material to form the electrode layer is not particularly limited, and a known method can be used without limitation. For example, it may be formed by sputtering, electron beam evaporation, chemical vapor deposition, nanoparticle dispersion coating, and the like, but is not limited thereto.

In one example, the deposition power for forming the electrode layer is 1 W / cm ² at to 20 W / cm ² range can be more than 1 W / cm ² or more or ^{2 W / cm 2, 20 W} / cm 2 It may be 15 W/cm ² or less, or 10 W/cm ² or less. When the deposition power of the step of forming the electrode layer is adjusted within the above range, the oxygen content ratio of the electrode layer can be controlled, and thus the b value of the electrode layer can be changed to provide a variable transmittance film having a desired optical color.

In one example, the process pressure of the step of forming the electrode layer may be 1 mTorr or more, or 2 mTorr or more in a range of 1 mTorr to 10 mTorr, 10 mTorr or less, 8 mTorr Or less, or 5 mTorr It can be below. When the process pressure of the step of forming the electrode layer is adjusted within the above range, the oxygen content ratio of the electrode layer can be controlled, and thus a variable transmittance film having a desired optical color can be provided by changing the b value of the electrode layer.

In one example, the electrode layer may have a b value of 0.5 or more, 0.7 or more, 1.0 or more, or 1.5 or more. The upper limit of the b value of the electrode layer is not particularly limited, and may be determined in consideration of the optical color development of the variable transmittance film, and may be, for example, 10 or less, 7 or less, or 5 or less.

In one example, the manufacturing method may further include forming an electrochromic layer on the electrode layer. The electrochromic layer is formed to include an electrochromic material, and the electrochromic material is the same as mentioned above.

In one example, the substrate may have a transmittance to visible light of 80% or more, 85% or more, or 90% or more, but is not limited thereto. In another example, the substrate is a natural and synthetic polymer resin, plastic, and/or polyester (such as PET), polyimide (PI), polycarbonate, polysulfone, polyethylene naphthalate (PEN), ethylene vinyl acetate ( EVA), an acrylate polymer, a polyamide and a cyclic olefin polymer (COP) may be a substrate comprising at least one, and is not particularly limited as long as it is a transparent or substantially transparent substrate in the visible region.

In another example of the present application, the present application relates to an electrochromic device. The electrochromic device of the present application may include a variable transmittance film, an electrolyte layer, an ion storage layer, and a counter electrode layer according to an example of the present application. The electrochromic device includes an electrode layer having a different b value from the electrochromic layer, thereby providing an electrochromic device having a desired optical color without changing the electrochromic material.

In one example, the counter electrode layer may be configured in the same manner as the above-mentioned electrode layer.

In one example, the electrolyte layer may be configured to provide ions involved in a discoloration reaction. The type of electrolyte used in the electrolyte layer is not particularly limited, and for example, a liquid electrolyte, a gel polymer electrolyte, or an inorganic solid electrolyte may be used.

In one example, the ion storage layer of the present application may include an electrochromic material having complementary color development characteristics to the electrochromic material included in the electrochromic layer. Complementary color development characteristics refer to cases in which the types of reactions in which the electrochromic material can be colored are different from each other. For example, when an oxidative colorant is used in the ion storage layer, a reductive colorant is used in the electrochromic layer. It means the case. As the discoloration material having complementary color characteristics is included in the electrochromic layer and the ion storage layer, respectively, for example, the coloration of the electrochromic layer by reduction reaction and the ion storage layer by oxidation reaction can be simultaneously performed. , In the opposite case, the color change of the electrochromic layer and the ion storage layer may be simultaneously performed. As a result, coloring and decolorization of the entire device can be simultaneously performed. Such coloring and decoloring may be alternating depending on the polarity of the voltage applied to the device.

According to the transmittance variable film and the method for manufacturing the transmittance variable film of the present application, it is possible to provide an electrochromic device capable of realizing various colors while maintaining excellent durability by using an electrochromic material secured with reliability.

Hereinafter, the present application will be described in detail through examples. However, the protection scope of the present application is not limited by the examples described below.

Example 1

Deposition power by using ITO target on PET substrate 3 W/cm ² , An electrode layer having a thickness of 20 nm was prepared by a sputtering deposition method under process conditions of a process pressure of 3 mTorr and an oxygen partial pressure of 9.1%. The b value of the electrode layer formed using a Haze meter (COH-400, NIPPON DENSHOKU) was measured, and the results are shown in Table 1.

Example 2 to 4 and Comparative example One

An electrode layer was prepared in the same manner as in Example 1, except that the oxygen partial pressure conditions of the electrode forming process were changed as shown in Table 1 below, and the results are shown in Table 1.

Oxygen partial pressure (%) b-value (b*) Example 1 9.1 3.6 Example 2 16.7 2.2 Example 3 20 1.8 Example 4 25 1.4 Comparative Example 1 0 -2.1

In Table 1, it can be seen that when the thickness of the electrode layer is the same, the b value of the electrode layer can be adjusted according to the oxygen partial pressure.

Claims (12)

An electrochromic layer having a negative b-value and an electrochromic layer having a different b-value in the Lab color space, a b-value of 1.4 or more, and an electrode layer containing a transparent conductive material,
The electrode layer is a variable transmittance film formed by depositing a transparent conductive material on a substrate under an oxygen partial pressure of 0.5% to 25%. The variable transmittance film of claim 1, wherein the electrode layer further contains oxygen, and the content ratio of the oxygen is 50% or less compared to a transparent conductive material. delete According to claim 1, The transparent conductive material is ITO (Indium Tin Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium doped Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), Variable transmittance film which is Indium doped Zinc Oxide (IZO), Niobium doped Titanium Oxide (NTO), Zinc Oxide (ZnO), Oxide/Metal/Oxide (OMO) or Cadmium Tin Oxide (CTO). According to claim 1, wherein the electrochromic layer comprises an electrochromic material, the electrochromic material is a metal oxide, prussian blue compound, viologen compound, phthalate compound, pyridine compound, anthraquinone compound, amino, respectively A quinone-based compound, a rare-earth-based organometallic compound, a phthalocyanine-based compound, a petothiazine-based compound, a dye-based compound, a conductive polymer compound, or a combination thereof. The permeability of claim 5, wherein the metal oxide is cobalt oxide, ruthenium oxide, iridium oxide, nickel oxide, chromium oxide, manganese oxide, iron oxide, titanium oxide, vanadium oxide, niobium oxide, tantalum oxide, molybdenum oxide or tungsten oxide. Variable film. Depositing a transparent conductive material on the substrate under an oxygen partial pressure of 0.5% to 25% to form an electrode layer; And
And forming an electrochromic layer on the electrode layer,
The electrochromic layer has a negative b value, and the electrode layer has a b value of 1.4 or more. The deposition power of the step of forming the electrode layer is 1 W / cm ² To 20 W/cm ^{2 A} method of manufacturing a variable transmittance film. The method of claim 7, wherein the process pressure in the step of forming the electrode layer is 1 to 10 mTorr. delete The method of claim 7, wherein the substrate has a transmittance of 80% or more with respect to visible light. An electrochromic device comprising the variable transmittance film of claim 1, an electrolyte layer, an ion storage layer and a counter electrode layer.