KR101999352B1 - Electrochromic film for smart window with variable transmittance - Google Patents

Abstract

The present invention relates to an electrochromic film for a smart window in which transmittance is variable, and more particularly, to a color filter for a smart window, which is a transparent electrode for electrochromic display, It is an active type discoloration film that can be used for energy conservation by adjusting the solar energy transmittance according to the need. If it is easily cut and attached to various glass sizes, it is possible to form an electric shade, Since it is inexpensive, has excellent workability, and has no silver layer, it is not necessary to separately perform the process of removing the thin film of the free edge of the glass edge, and since a low power DC power source of several watts or less is used, There is no danger of short-circuiting, the oxidation resistance is excellent, and it can be stored in the form of a roll or a thin sheet. Since less risk of damage, to a color change film for smart windows is the transmittance which can secure the ease of handling a variable load.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a coloring film for a smart window,

The present invention relates to an electrochromic film for a smart window in which transmittance is variable, and more particularly, to a color filter for a smart window, which is a transparent electrode for electrochromic display, It is an active type discoloration film that can be used for energy conservation by adjusting the solar energy transmittance according to the need. If it is easily cut and attached to various glass sizes, it is possible to form an electric shade, Since it is inexpensive, has excellent workability, and has no silver layer, it is not necessary to separately perform the process of removing the thin film of the free edge of the glass edge, and since a low power DC power source of several watts or less is used, There is no danger of short-circuiting, the oxidation resistance is excellent, and it can be stored in the form of a roll or a thin sheet. Since less risk of damage, to a color change film for smart windows is the transmittance which can secure the ease of handling a variable load.

As the greenhouse gas reduction is urgent by 2015, the Korean government plans to reduce the greenhouse gas by 37% by 2030 and plan to expand the renewable energy and improve energy efficiency in the buildings. Energy building is rising rapidly.

However, domestic buildings are increasing by 8.7% annually. The energy consumption of the building is 24% of the total energy consumption in Korea, and the energy conservation measures This is urgent.

In particular, it is reported that 77% of the energy consumed in a building is due to indoor heating and cooling energy, and heat loss through windows is 20-45%.

In this regard, according to the DOE of the United States, it has been reported that the use of light control smart windows can save 40% or more of building energy and reduce the heating and cooling system capacity and building management cost by 25%, respectively.

Therefore, we have been focusing on developing the above-mentioned problem-solving techniques in various countries around the world starting from Sweden. Among them, we can exemplify electric shading technology using electric discoloration technology as an energy saving technology through windows.

These technologies have developed dynamic glasses such as Chromogenic, Thermotropic and Liquid Crystal, and EC (Electrochromic, electrochromic), which is one of the chromogenic technologies, has been applied to this technology. As a result, A window is opened.

However, the glass-type smart window is an application of electro-discoloration technology between several sheets of glass. Since the manufacturing process such as cutting, chamfering, cleaning, strengthening and bonding is very complicated, the cost is too high and standardization is difficult. And the defective ratio is high. In order to prevent the oxidation of the silver layer, the roiling thin film removing process must be separately performed.

In addition, there is a high risk of moisture penetration when the silicone finishes, so there is a great risk of oxidation and leakage, and it is difficult to standardize according to the connection of wires, so that there is a problem of resistance variation, and it is easy to break due to the nature of the material of glass, It has a low safety margin.

Moreover, it is necessary to make different sizes according to the size of the window to be constructed, and it is very difficult and inconvenient to maintain, store and transport due to such structural characteristics, and the construction cost is very expensive besides the manufacturing cost, have.

Examples of the improvement include a Supended Particle (SPD) method or a polymer dispersed liquid crystal (PDLC) method. However, in this case, the driving voltage is very high and there is no bistable, so electric energy consumption is relatively large. Power is required, so that it is difficult to achieve the intended energy saving effect.

In addition, most of silver (Ag) is used as an electrochromic electrode in a glass type smart window (Roy glass, etc.) applying EC, as shown in the following prior arts. It is because it is visible.

However, since silver (Ag) is easily contacted with oxygen or sulfur in the air, it can not achieve longevity and there is a limit in efficiency in proportion to the period of use.

In addition, in the case of the glass-shaped electric shoehorn disclosed in the prior art, since the stepwise processes are sequentially processed one by one, the manufacturing process is complicated and the continuous process is difficult. In addition, as described above, ) Is used as an electrode for electrochromic coloration, the above-mentioned problem can not be avoided.

Korean Patent No. 10-1656466 (Sep. 2016.), 'Ion Gel Smart Window Manufacturing Method' Korean Registered Patent No. 10-1656490 (Sep. 2016, Sep.), 'Adhesive Smart Window Film and Manufacturing Method Thereof' Korean Patent Laid-Open No. 10-2017-0024830 (Apr. 23, 2017), 'Smart Window Coating with Insulation Function'

Disclosure of Invention Technical Problem [8] The present invention has been made in view of the above-mentioned problems in the prior art, and it is an object of the present invention to provide a silver halide photovoltaic cell which is excellent in transparency and low- It is possible to form an electric shoehorn naturally, and thus it is possible to produce the product inexpensively, and it is excellent in workability, does not need to be subjected to a separate thin film removal process, has no risk of leakage, has excellent oxidation resistance, The present invention provides a color window film for smart windows, which can be rolled up and stored, without any risk of breakage, and has a variable transmissivity to ensure ease of storage and transportation.

In order to achieve the above-mentioned object, the present invention provides a transparent plastic film comprising: a base film (100); A silicon dioxide layer 110 sputtered on the upper surface of the base film 100; A first transparent electrode layer 120 sputtered with polycrystalline poly-ITO on the upper surface of the silicon dioxide layer 110; A layer 130 of a red color fading material sputtered with WO ₃ on the first transparent electrode layer 120; An electrolyte layer 140 sputtered with LiPON on the reducing coloring material layer 130; A layer of oxidative discoloration material 150 sputtered with NiO on the electrolyte layer 140; A second transparent electrode layer 160 sputtered on the oxidative discoloration material layer 150 to have at least one O (O) - M (Metal) - O (Oxide) structure; A barrier layer 170 sputtered on the upper surface of the second transparent electrode layer 160; And a protective film (180) laminated on the barrier layer (170), wherein the transmittance is variable; The silicon dioxide layer 110 is formed to have a refractive index relatively lower than that of the base film 100. The first transparent electrode layer 120 is formed to have a relatively higher refractive index than the silicon dioxide layer 110, The first transparent electrode layer 120 has a higher refractive index than the base film 100; The barrier layer 170 is formed by depositing a thermosetting plastic. The barrier layer 170 has a variable transmissivity.

At this time, the silicon dioxide layer 110, the first transparent electrode layer 120, the red coloring material layer 130, the electrolyte layer 140, the oxidative discoloration material layer 150, the second transparent electrode layer 160, The sputtering of the sputtering chamber 170 is sequentially batch-processed in one sputtering chamber 200; The sputtering unit 240 for sputtering is also connected to an RF power source 250 for generating a high frequency.

The second transparent electrode layer 160 includes a first oxide layer 160a, a first metal layer 160b, a second oxide layer 160c, a second metal layer 160d, a third oxide layer 160e, And the like.

The silicon dioxide layer 110 is also sputtered so as to be uniformly dispersed in a nano-size when the silicon dioxide layer 110 is formed.

According to the present invention, the transparent electrode for electrochromic coloring has good low-emissivity (low E) characteristics that reflect infrared rays without using a silver (Ag) layer, and can control the solar energy transmittance It is an active discoloration film that can be used. It can be easily cut to fit various glass sizes, and it can be used as an electric shade to form an electric shade. Therefore, production cost is lower than that of glass type, and workability is excellent. It does not need to be subjected to ROI thin film removal process, and because it uses a low power DC power source of several W or less, there is no risk of electric leakage in smart windows such as PDLC and SPD, and oxidation resistance is excellent. It is possible to reduce the risk of breakage because it can be stored and maintained, and it is possible to obtain an effect of securing ease of transportation .

1 is an exemplary cross-sectional view showing a layer structure of a color window for a smart window in which transmittance is variable according to the present invention.
FIG. 2 is an exemplary test photograph showing a change in thickness that can be formed by sputtering an oxide with respect to the roughness in the OMO implementation of the electrochromic electrode structure applied to the discoloration film according to the present invention.
FIG. 3 is a sample photograph of the surface cracking occurrence before and after the bending in the OMO implementation of FIG. 2 compared with ITO.
FIG. 4 is a schematic view showing a sputtering chamber for producing a discoloration film according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Before describing the present invention, the following specific structural or functional descriptions are merely illustrative for the purpose of describing an embodiment according to the concept of the present invention, and embodiments according to the concept of the present invention may be embodied in various forms, And should not be construed as limited to the embodiments described herein.

In addition, since the embodiments according to the concept of the present invention can make various changes and have various forms, specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the embodiments according to the concept of the present invention are not intended to limit the present invention to specific modes of operation, but include all modifications, equivalents and alternatives falling within the spirit and scope of the present invention.

The present invention is based on a dry sputtering process using a high frequency sputtering method rather than a vapor deposition method or a coating method which has been generally used in the past, useful.

That is, as described in the prior art, there is a problem in that the lifetime is shortened as described in the prior art, and since the density of the thin film is lower than that of sputtering and the high vacuum degree must be maintained compared with the sputtering, it is difficult to adjust the deposition rate, Is not easy to secure.

On the other hand, the high frequency sputtering utilized in the present invention is advantageous in that atoms and molecules of the material can be attached uniformly and densely on the surface of the adherend in the vicinity thereof by ion impacting the target material. In addition, the deposition rate can be easily controlled and the process can be easily adjusted.

In particular, the present invention realizes a transparent electrode of OMO (Oxide / Metal / Oxide) structure when forming an electrode for electrochromic formation, and is chemically stable and excellent in conductivity, and is suitable as an electrochromic electrode. ) Effect, it is possible to treat thin films with a very thin thickness by ensuring excellent surface uniformity of amorphous oxide while having Roy characteristics, and the electrochromic film manufactured using the film can drive at low driving voltage within a driving voltage of 3 V And is designed to provide excellent compatibility with energy savings.

In addition, this type of electrochromic method is advantageous in connection with IC (MCU, etc.), which is a core component of a control device, simplifies wiring, simplifies device structure and manufacturing process, and most importantly, It also has features that make it possible to get angry and make it look good on the interior window.

In addition, 'Electrochromic', which will be described below, is a technology that has been already commercialized, and refers to a phenomenon in which a color reversibly changes due to an electrochemical oxidation or reduction reaction depending on the direction of an electric field or current when a voltage is applied.

For example, WO ₃ , MoO ₃ , TiO ₃ and the like show color in a reduced state, which is called a Cathodic Coloration Material. V ₂ O ₅ , IrO ₂ , Nb ₂ O ₅ , NiO, Color, which is called anodic coloration material.

More specifically, as shown in FIG. 1, the coloring film for a smart window in which transmittance is variable according to the present invention includes PET, PP, COP film and the like as the base film 100.

Since the base film 100 has durability while maintaining transparency, it is used as a base film in the present invention. It is attached to a glass surface of two or three sides of a window where energy saving is required. For the reliability and durability PVB film or EVA film.

A silicon dioxide (SiO ₂ ) layer 110 is formed on the upper surface of the base film 100.

The silicon dioxide layer 110 is formed into a thin film by sputtering in the chamber. When the temperature of the base film 100 is increased by receiving heat through the electrochromic electrode, oxygen, oligomers, carbon, etc. Is prevented from moving toward the electrochromic electrode, thereby improving the durability and improving the index matching characteristics.

In particular, when the silicon dioxide is uniformly coated in accordance with the stoichiometric ratio, barrier properties of permeable materials including oxygen can be significantly enhanced, and adhesion between the interfaces can be significantly enhanced, do. .

In addition, the refractive index of the PET, which is the base film 100, is about 1.6, the refractive index of the silicon dioxide layer 110 is about 1.4, and the first and second electrochromic electrodes, that is, the first ITO (Poly ITO) Since the refractive index of the transparent electrode layer 120 corresponds to about 1.95, the transmittance can be increased by having the shape of high refractive index-low refractive index-high refractive index so as to perform index matching.

In addition, a first transparent electrode layer 120 is formed on the upper surface of the silicon dioxide layer 110.

The first transparent electrode layer 120 is a means for realizing an electric shading by applying power to the discoloration film according to the present invention to induce discoloration.

The first transparent electrode layer 120 according to the present invention is formed by sputtering poly (ITO) unlike the prior art.

That is, conventionally, since the ITO film is adhered to the substrate, a separate heat treatment process must be performed to stabilize the solvent. However, in the present invention, since poly ITO made of polycrystalline is immediately deposited by sputtering, batch processing is possible, and a separate heat treatment process is not required, so that the process can be simplified and the defect rate is also zeroed.

In addition, a reducing coloring material layer 130, an electrolyte layer 140, and an oxidizing coloring material layer 150 are sequentially sputtered on the upper surface of the first transparent electrode layer 120 to form a thin film.

At this time, since the reducing coloring material layer 130 and the oxidizing discoloration material layer 150 are already known as described in the prior art, detailed description of their functions and features will be omitted.

However, in the present invention, WO ₃ is used as the red coloring material layer 130, and NiO is used as the oxidizing discoloration material layer 150.

In addition, the electrolyte layer 140 differs from the conventional technology in that LiPON (lithium phosphorous oxy-nitride) is used instead of a conventional TaO thin film solid electrolyte.

For example, a commonly used TaO solid electrolyte is used in the form of a thin film of Ta ₂ O _{5. It} changes the optical properties of the material due to the injection and desorption of H + ions by the applied electric field, It is necessary to undergo a separate hydrotreatment process in order to induce hydrogen.

However, the LiPON used in the present invention can induce electrochromatography through injection and desorption of Li + ions even if it is used directly as a thin film solid electrolyte without needing a separate hydrotreatment process.

A second transparent electrode layer 160 is formed on the upper surface of the oxidative discoloration material layer 150 by sputtering.

The second transparent electrode layer 160 may be formed to correspond to the first transparent electrode layer 120. Thus, when a voltage is applied to both of them, an electric field is formed between them, and the injection and desorption of Li + ions are caused by the influence of the electric field, thereby inducing the electrochromism.

Here, in the present invention, the second transparent electrode layer 160 may have an OMO structure to maximize chemical stability while improving the conductivity. In particular, the present invention can improve the ROI characteristics according to the surface plasmon effect and improve the surface uniformity of the amorphous oxide Since the silver (Ag) is not used, there is no fear of corrosion, and in particular, the electrochromic electrode has a low resistance characteristic because it contains a metal layer and improves the conductivity.

That is, the second transparent electrode layer 160 according to the present invention has at least one O (Oxide Layer) -M (Oxide Layer) -O (Oxide Layer) structure.

For example, in the present invention, the first oxide layer 160a, the first metal layer 160b, the second oxide layer 160c, the second metal layer 160d, and the third oxide layer 160e ).

In particular, such an OMO electrode structure has an advantage in that the thickness of the layer can be reduced as much as possible by reducing the surface roughness of the oxide layer as shown in FIG. 2. In addition, in the banding test as shown in FIG. 3, However, since the OMO electrode structure contains an amorphous oxide, it does not cause cracks even after bending, and there is no risk of loss due to an increase in local resistance due to crack occurrence before and after bending, thereby enabling stable driving.

A barrier layer 170 is formed on the upper surface of the second transparent electrode layer 160.

The barrier layer 170 is formed by depositing a thermosetting plastic having superior flexibility and elasticity.

In addition, ionization treatment is more preferable in order to increase the density of the barrier layer 170. [

Thereafter, a protective film 180 is provided to protect the surface of the barrier layer 170. The protective film 180 may be provided by simply attaching the thin film type film.

The color change film for smart window having the variable transmittance according to the present invention having such a structure is continuously processed through the sputtering apparatus as shown in FIG.

For example, referring to FIG. 4, the sputtering apparatus includes a sputtering chamber 200.

The sputtering chamber 200 is maintained in a vacuum state and does not need to be kept in a very high vacuum state.

A sputtering drum 210 is rotatably installed at the center of the sputtering chamber 200. An unwinding roll 220 and a winding roll 230 ) Is installed.

At this time, the base film 100 is wound on the winding roll 220, the base film 100 is unwound from the winding roll 220, passed through the first tension roll 222, passed through the sputtering drum 210 The sputtering drum 210 is wound on the winding roll 230 in the form of a coil through the second tension roll 232 and the sputtering drum 210 is rotated in the advancing direction of the base film 100.

During the movement of the base film 100, sputtering for forming each layer described above proceeds in a region that is moved to the grounded state with respect to the sputtering drum 210.

A plurality of layer chambers LC1-LC11 for performing high-frequency sputtering are disposed on the lower side of the sputtering drum 210 so as to correspond to the radius of curvature of the sputtering drum 210, And are provided in a state in which they are separated from each other.

In the 1-11-layer chambers LC1-LC11, a material for forming each layer is sputtered to the surface of the substrate film 100 while being slowly grounded to the sputtering drum 210. [ (240), and the RF power source (250) is connected to the sputtering unit (240).

In this case, the reason why the RF power source 250 is used is to increase the electron density of the plasma to make a dense thin film and reduce pinholes, and particularly to easily coat an oxide target of nonconductive material such as WO 3 or NiO.

In addition, when a DC bias power source is connected to the sputtering drum 210, dissociated ions sputtered can be focused toward the sputtering drum 210, thereby further enhancing the sputtering efficiency.

That is, in the first layer chamber LC1, silicon dioxide is sputtered to form the silicon dioxide layer 110 on the surface of the base film 100. [

When the portion of the silicon dioxide layer 110 formed by the rotation of the sputtering drum 210 is positioned in the second layer chamber LC2, Poly ITO is sputtered in the second layer chamber LC2 to form the silicon dioxide layer 110. [ The first transparent electrode layer 120 is formed.

The third layer chamber LC3 is formed with the red coloring material layer 130 in the fourth layer chamber LC4 and the electrolyte layer 140 is formed in the fourth layer chamber LC4, Oxide, metal, oxide, and oxide are successively sputtered to form one second transparent electrode layer 160 in the sixth, seventh, eighth, ninth, and tenth layer chambers LC6, LC7, LC8, LC9, And the barrier layer 170 is formed in the eleventh layer chamber LC11.

As described above, according to the present invention, a discoloration film in which a layer necessary for a large number of discoloration is formed is produced only when a substrate film passes through one sputtering chamber 200, thereby improving process efficiency and productivity, Is zeroed and is expected to be a useful technique for ensuring the stability of the layer.

When power is applied to such a discoloration film, an electric field is formed between the two electrodes to cause discoloration, so that the transmittance of sunlight can be controlled. Thus, it is possible to realize an insulation function as well as an awning function.

100: substrate film
110: Silicon dioxide layer
120: first transparent electrode layer
130: Reduced coloring material layer
140: electrolyte layer
150: oxidative discoloration material layer
160: second transparent electrode layer
170: barrier layer
180: protective film

Claims (4)

A base film (100) which is a transparent plastic film; A silicon dioxide layer 110 sputtered on the upper surface of the base film 100; A first transparent electrode layer 120 sputtered with polycrystalline poly-ITO on the upper surface of the silicon dioxide layer 110; A layer 130 of a red color fading material sputtered with WO ₃ on the first transparent electrode layer 120; An electrolyte layer 140 sputtered with LiPON on the reducing coloring material layer 130; A layer of oxidative discoloration material 150 sputtered with NiO on the electrolyte layer 140; A second transparent electrode layer 160 sputtered on the oxidative discoloration material layer 150 to have at least one O (O) - M (Metal) - O (Oxide) structure; A barrier layer 170 sputtered on the upper surface of the second transparent electrode layer 160; And a protective film (180) laminated on the barrier layer (170), wherein the transmittance is variable;
The silicon dioxide layer 110 is formed to have a refractive index relatively lower than that of the base film 100. The first transparent electrode layer 120 is formed to have a relatively higher refractive index than the silicon dioxide layer 110, The first transparent electrode layer 120 has a higher refractive index than the base film 100;
Wherein the barrier layer (170) is formed by depositing a thermosetting plastic.
The method according to claim 1,
The second transparent electrode layer 160 and the barrier layer 170 are formed on the silicon dioxide layer 110, the first transparent electrode layer 120, the red coloring material layer 130, the electrolyte layer 140, the oxidative discoloration material layer 150, Are sequentially batch processed in one sputtering chamber 200; Wherein a sputtering unit (240) for sputtering is connected to an RF power source (250) for generating a high frequency.
The method according to claim 1,
The second transparent electrode layer 160 includes a first oxide layer 160a, a first metal layer 160b, a second oxide layer 160c, a second metal layer 160d, and a third oxide layer 160e Wherein the transmittance is variable.
The method according to claim 1,
Wherein the silicon dioxide layer is sputtered so as to be uniformly dispersed in a nano-size when forming the silicon dioxide layer (110).

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