KR101986348B1 - Color-changing film for smart window that can be colored more than two colors - Google Patents

Abstract

The present invention relates to a color changeable film for a smart window, capable of being changed into two or more colors. More specifically, the color changeable film for a smart window has excellent transmittance and Low E characteristics even without using silver (Ag) as an electrochromic electrode, naturally forms an electric shade only by cutting regardless of the size of glass, thereby requiring low production costs and having excellent constructability, removes an additional process of removing transparent conductive oxides (TCO), prevents danger of electric leakage, has excellent oxidation resistance, prevents danger of damage by being stored in a roll shape, secures easiness of storage, maintenance, transport, and loading, and improves design of external appearances by realizing various colors. In addition, the color changeable film for a smart window comprises an optical film, a silicon dioxide layer, a first transparent electrode layer, a first color changing layer, an interlayer transparent electrode layer, a second color changing layer, a second transparent electrode layer, a barrier layer, and a protective film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color-changing film for a smart window,

The present invention relates to a color change film for smart windows capable of multi-color change of more than two colors. More specifically, the present invention relates to a color change film for smart window which is excellent in transmittance and low E (low emissivity) characteristics without using Ag as an electrochromic electrode It is possible to naturally create an electric shade by cutting and pasting regardless of the glass size, so that the production cost is low, the workability is excellent, the separate transparent conductive oxide (TCO) removal process is not required, Since it is excellent in oxidation resistance and can be stored in roll form, there is no risk of breakage, and it is possible to secure the ease of storage, transportation and loading, and it is possible to realize various colors, To a discoloration film for smart windows capable of multi-discoloration.

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.

As a starting point in Sweden, various countries around the world have been devoted to developing the above-mentioned technologies for solving the above problems. Among them, the technology of electric shading using electric discoloration can be exemplified as an energy saving technique through windows.

Such technologies include glass-type smart windows such as Electrochromic, Thermochromic, and PDLC.

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. Therefore, there is a disadvantage that a separate TCO (Transparent Conductive Oxides) removal process must be 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 size according to the size of the window to be constructed. Due to such structural characteristics, it is very difficult and inconvenient to carry out the maintenance, storage and transportation, and the construction cost is very expensive besides the manufacturing cost. have.

As an example of the improvement, a Supended Particle (SPD) method or a polymer dispersed liquid crystal (PDLC) method can be exemplified. However, in this case, since the driving voltage is very high and there is no bistability, energy consumption is very large. It is difficult to achieve the intended energy saving effect.

In the case of a smart window (Roy glass, etc.) applying electrochromic (EC) electrochromic, most of the electrode (Ag) is used as an electrochromic electrode as shown in the following prior arts, And Roy characteristics.

However, since silver (Ag) causes corrosion, longevity can not be achieved and there is a limit in efficiency in proportion to the period of use.

In addition, in the case of the film-type electric canopy disclosed in the prior art, it is made of an adhesive type, and it is difficult to increase the longevity because each step process is sequentially processed.

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 it is possible to manufacture the electric shoehorn inexpensively, and it is excellent in workability, does not need to undergo a separate TCO (Transparent Conductive Oxides) removal process, has no risk of leakage current, It can be stored in a roll form, so there is no danger of breakage. It is possible to secure the ease of storage, transportation and loading, and it is also possible to realize various colors. There is a main purpose in providing a discoloration film.

The present invention provides, as means for achieving the above object, an optical film (100) which is a transparent base film including PET, PP, PC or PMMA; A silicon dioxide layer 110 sputtered on the top surface of the optical film 100; A first transparent electrode layer 120 sputtered with poly-ITO on the silicon dioxide layer 110; A first color conversion layer 130 formed by sequentially sputtering a first reducing coloring material layer 132, a first electrolyte layer 134, and a first oxidizing coloring material layer 136 on the first transparent electrode layer 120; )and; An interlayer transparent electrode layer 140 sputtered with poly ITO on the first color conversion layer 130; A second color conversion layer 150 formed by sequentially sputtering a second oxidative discoloration layer 152, a second electrolyte layer 154, and a second reduced coloring material layer 156 on the interlayer transparent electrode layer 140; and; A second transparent electrode layer 160 sputtered on the second color conversion 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 protection film (180) laminated on the barrier layer (170); The barrier layer 170 is an oxidation barrier layer formed by sputtering with an Al nitride. The barrier layer 170 is formed by spraying fine particles having a size of several micrometers or less on the surface of the barrier layer 170 at a collision speed of at least 100 m / s And the surface hardness and the internal residual stress are collapsed and the surface texture is refined. The present invention provides a discoloration film for a smart window, which is capable of multi-discoloring over two or more colors.

At this time, in order to constitute two layers, for example, oxidation and reduction change materials can be selected from the following table.

(Wherein R is reduced coloring and O means oxidation coloring)

That is, the first and second reducing color materials layers 132 and 156 are formed of TiO ₂ , which changes the color of transparent ↔ dark color, WO ₃ , which discolorates transparent ↔ tap water, MoO ₃ , which discolors transparent ↔ blue, And Nb ₂ O ₅ in which discoloration occurs; The first and second oxidative discoloring material layers 136 and 152 are formed of Cr ₂ O ₅ , which is discolored from yellow to soft blue, MnO ₂ , which is discolored to yellow to brown, FeO ₂ , which is discolored to transparent ↔ green, CoO _{2 in} which discoloration occurs, and NiO ₂ in which discoloration of black and transparent color is performed.

The first color conversion layer 130 including the first red coloring material layer 132 and the first oxidizing coloring material layer 136 may be formed of a transparent ↔ color (either black, yellow, green, blue or blue) Using a coloring material which is discolored as a coloring material; The second color conversion layer 150 including the second oxidative discoloration substance layer 152 and the second color change material layer 156 may be formed by using a coloring material that is discolored in reverse to the first color conversion layer 130 It is also characterized by its full shade.

In addition, an electrochromic layer can be formed by combining an oxidative discoloration layer and a reducing discoloration layer with an electrolyte interposed therebetween, and the electrochromic layer can have two color changes with respect to an electric current flowing in both directions.

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.

According to the present invention, it is possible to provide an electrochromic device which is excellent in transparency and loose characteristic without using Ag as an electrode for electrochromic production, and can be naturally formed by cutting and pasting regardless of the glass size, It is excellent in workability and does not need to be subjected to a separate TCO (Transparent Conductive Oxides) removal process, has no risk of electric leakage, has excellent oxidation resistance, can be rolled in a rolled form, It is possible to secure the easiness of carrying and to realize various colors, thereby improving the appearance design.

FIG. 1 is an exemplary cross-sectional view showing a layer structure of a discoloration film for a smart window capable of multi-discoloring over two or more colors 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.
5 is a schematic view showing an example of discoloration and coloring of the 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 type using a RF sputtering method rather than a deposition method or a coating method that has been generally used, and this method is particularly useful for forming an electrode for electrochromic use .

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 process very thin film by ensuring superior surface uniformity of amorphous oxide while having Roy characteristics, and it is designed to realize excellent compatibility with energy saving by enabling low power driving with driving voltage within 3V do.

In addition, this method has a merit of bonding with an IC, so that the device structure and manufacturing process are simple, and most of all, the temperature can be widely used up to 20-80 ° C and multi-color can be obtained.

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 ₂ 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 capable of multi-color change of more than two colors according to the present invention includes the optical film 100 as a base film.

The optical film 100 is a film having transparency including PET, PP, PC, and PMMA and has durability. Therefore, the optical film 100 is used as a base film in the present invention and is attached to a glass surface of a window where energy saving is required.

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

The silicon dioxide layer 110 is formed as a thin film by sputtering in the chamber. When the temperature of the optical 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.

Particularly, when the silicon dioxide is uniformly dispersed in the nano-size, the permeation blocking property of the permeable materials including oxygen can be significantly enhanced, and the interfacial bonding stability can be remarkably enhanced to completely prevent the peeling at the interface.

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.

A first color conversion layer 130, an interlayer transparent electrode layer 140, and a second color conversion layer 150 are sequentially sputtered on the upper surface of the first transparent electrode layer 120 to form a thin film.

1 and 5, the first color conversion layer 130 includes a first red color fading material layer 132 and a first red color fading material layer 132 sputtered on the upper surface of the first red color fading material layer 132, An electrolyte layer 134 and a first oxidative discoloration material layer 136 sputtered on the first electrolyte layer 134.

In addition, the interlayer transparent electrode layer 140 is also a transparent electrode formed by directly sputtering Poly ITO.

The second color conversion layer 150 includes a second oxidative discoloration material layer 152, a second electrolyte layer 154 sputtered on the upper surface of the second oxidative discoloration material layer 152, And a second red color discoloring material layer 156 sputtered onto layer 154.

Here, the first and second reducing color discoloring material layers 132 and 156 may be formed of a coloring material selected from the group consisting of WO ₃ , MoO ₃ , TiO ₂ and Nb ₂ O ₅ , The material layers 136 and 152 are made of a coloring material selected from the group consisting of Cr ₂ O ₅ , MnO ₂ , FeO ₂ , CoO ₂ and NiO ₂ .

In addition, in the case of V ₂ O ₅ , it can be used for both.

Thus, depending on the selected coloring material, two-layer discoloration may be made different from each other, thereby adding a sense of beauty and mystery. In other words, you can increase the beauty of the design by adjusting the degree of shading or choosing a color.

For example, in the case of TiO ₂ is made of a color change of the transparent ↔ heukcheong, V ₂ O _5, and Cr ₂ O ₅ is made of a color change of the yellow ↔ soft blue, MnO ₂ is formed of a color change of the yellow ↔ brown, FeO ₂ CoO ₂ is discolored to blue ↔ brown, NiO ₂ is discolored to black ↔ transparent, Nb ₂ O ₅ is discolored to soft ↔ yellow, and MoO ₃ has a transparent ↔ blue discoloration and WO ₃ has a transparent ↔ transparent discoloration. Therefore, various color changing films can be realized by their selection.

Accordingly, the first color conversion layer 130 may be formed of a coloring material that is color-changed to a transparent color (black, blue, green, blue, or tint), the second color conversion layer 150 may be a color- In other words, using a coloring material that changes color (black, yellow, green, blue, tint) ↔ transparent makes full shading possible.

Further, if the first and second color conversion layers 130 and 150 are made to be able to change color to different colors, it is possible to perform an awning function capable of changing the color of the mixed color. Therefore, the oxidation coloring material layer + oxidative discoloration material layer, A coloring material layer, a reducing coloring material layer and a reducing coloring material layer.

A second transparent electrode layer 160 is formed on the upper surface of the second color conversion 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 sputtering with Al nitride.

Since this nitride forms a film to harden the surface to prevent local elastic deformation and Al forms an oxide film to form an oxidation barrier layer, it has the effect of suppressing cracks and film peeling due to internal stress and enhancing stability .

In addition, in order to increase the fatigue strength of the barrier layer 170, the barrier layer 170 is formed and then subjected to a fine particle peening treatment.

In this case, the particle peening treatment is to collide fine particles having a size of several micrometers or less on the surface of the barrier layer 170 to eliminate the surface hardness and the internal residual stress, and to obtain a surface modification effect according to the fineness of the surface texture. s or more.

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 discoloration film for smart window capable of multi-discoloration of more than two colors 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.

The optical film 100 is unwound from the winding roll 220 and passes through the first tension roll 222 to move 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 optical film 100.

During the movement of the optical film 100, sputtering for forming each layer described above proceeds in a region where the optical film 100 is moved to the grounded state with 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 for sputtering onto the surface of the optical film 100 which is being moved slowly while being 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 reduce the pinhole and increase the filling rate of the film.

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 optical 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.

Although not shown in the third layer chamber LC3, the first color conversion layer 130 is sputtered by sputtering the first coloring material layer, the first electrolyte layer, and the first oxidizing coloring material layer, Forming; In the fourth layer chamber LC4, an interlayer transparent electrode 140 is formed by sputtering; Although not shown in the fifth layer chamber LC5, a second color conversion layer 150 is formed by sputtering a second oxidative discoloration material layer, a second electrolyte layer, and a second reduction color material layer to be further subdivided; In the sixth, seventh, eighth, ninth and tenth layer chambers LC6, LC7, LC8, LC9, and LC10, oxide, metal, oxide, metal, and oxide are sequentially sputtered to form one second transparent electrode layer 160; 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: Optical film
110: Silicon dioxide layer
120: first transparent electrode layer
130: first color conversion layer
140: interlayer transparent electrode layer
150: Second color conversion layer
160: second transparent electrode layer
170: barrier layer
180: protective film

Claims (4)

An optical film (100) which is a transparent base film including PET, PP, PC or PMMA; A silicon dioxide layer 110 sputtered on the top surface of the optical film 100; A first transparent electrode layer 120 sputtered with poly-ITO on the silicon dioxide layer 110; A first color conversion layer 130 formed by sequentially sputtering a first reducing coloring material layer 132, a first electrolyte layer 134, and a first oxidizing coloring material layer 136 on the first transparent electrode layer 120; )and; An interlayer transparent electrode layer 140 sputtered with poly ITO on the first color conversion layer 130; A second color conversion layer 150 formed by sequentially sputtering a second oxidative discoloration layer 152, a second electrolyte layer 154, and a second reduced coloring material layer 156 on the interlayer transparent electrode layer 140; and; A second transparent electrode layer 160 sputtered on the second color conversion 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 protection film (180) laminated on the barrier layer (170);
The barrier layer 170 is an oxidation barrier layer formed by sputtering with an Al nitride. The barrier layer 170 is formed by spraying fine particles having a size of several micrometers or less on the surface of the barrier layer 170 at a collision speed of at least 100 m / s Wherein the surface hardness and the internal residual stress are eliminated and the fine structure of the surface texture is finely processed.
The method according to claim 1,
The first and second reducing color materials layers 132 and 156 are made of TiO ₂ that changes color of transparent ↔ dark brown, WO _{3 that} discolor of transparent ↔ tap water, MoO _{3 that} discolor of transparent ↔ blue discoloration, And Nb ₂ O ₅ ;
The first and second oxidative discoloring material layers 136 and 152 are formed of Cr ₂ O ₅ , which is discolored from yellow to soft blue, MnO ₂ , which is discolored to yellow to brown, FeO ₂ , which is discolored to transparent ↔ green, CoO _{2 in} which discoloration occurs, and NiO ₂ in which discoloration of black and transparent is performed.
The method of claim 2,
The first color conversion layer 130 including the first red coloring material layer 132 and the first oxidizing coloring material layer 136 may be changed to a transparent ↔ color (one of black, blue, green and blue) A coloring material is used;
The second color conversion layer 150 including the second oxidative discoloration substance layer 152 and the second color change material layer 156 may be formed by using a coloring material that is discolored in reverse to the first color conversion layer 130 Which is characterized in that it is completely shaded.
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 Which is capable of multi-discoloration of more than two colors.

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