KR102583695B1 - Transparent conductive film for electrochromic film and method for manufacturing same - Google Patents

Abstract

The present invention relates to a transparent conductive film for electrochromic film and a manufacturing method thereof. It can be used in a transparent electrode layer of an electrochromic film and can ensure heat absorption resistance and high permeability.
In addition, the present invention relates to a transparent conductive film that lowers surface tension, exhibits water- and oil-repellent properties, and anti-pollution properties, as well as improved chemical resistance, optical properties, low coefficient of friction, and abrasion resistance, and a method of manufacturing the same.

Description

Transparent conductive film for electrochromic film and method for manufacturing same}

The present invention relates to a transparent conductive film for electrochromic film and a method of manufacturing the same, and specifically relates to a transparent conductive film having high light transmittance and a method of manufacturing the same.

In general, transparent conductive films are film-type, such as touch panels, electronic display labels (ESL), smart windows, liquid crystal displays (LCD), organic light-emitting device hybrid encaps (OLED hybrid encaps), organic solar cells, and electromagnetic interference shielding (EMI). Used in devices.

These transparent conductive films have high conductivity (for example, sheet resistance of 100 Ω/sq or less) and high transmittance in the visible light region, so they are used as electrodes for various light-receiving and light-emitting devices such as solar cells, liquid crystal displays, smart windows, etc. In addition, it is used as a transparent electromagnetic wave shield such as anti-static film and electromagnetic wave shield used in automobile window glass and building window glass, and as a transparent heating element such as heat ray reflection film and refrigeration showcase.

As transparent conductive films, tin oxide (SnO ₂ ) films doped with antimony or fluorine, zinc oxide (ZnO) films doped with aluminum or potassium, and indium oxide (In ₂ O ₃ ) films doped with tin are widely used. there is.

In addition, to obtain a flexible touch panel or display, conductive polymers can be used to coat the upper surface of a polymer substrate, but these films have problems such as low electrical conductivity or lack of transparency when exposed to the external environment, so their uses are limited. This happens.

Electrochromic film is a film whose color changes due to coloring and decolorization due to oxidation-reduction reactions at each anode and cathode depending on the applied potential. It is a film that allows the user to artificially control visible light and infrared light, and is available in various types. Inorganic oxides are used as electrode materials.

In general, the components that make up an electrochromic film are largely composed of five layers: a transparent electrode layer, an oxidizing electrode layer, an electrolyte layer, a cathode electrode layer, and a transparent electrode layer. In the case of a film form, an adhesive layer and a release film that allow it to be attached to glass or mirrors are included. It is possible to add

The transparent electrode layer constituting the electrochromic film can be a transparent conductive film, and it is necessary to develop a product that has heat-and-moisture resistance and high permeability.

KR 10-2013-0078764 A1

The object of the present invention relates to a transparent conductive film for electrochromic film and a method of manufacturing the same.

Another object of the present invention is to provide a transparent conductive film that can be used in a transparent electrode layer for an electrochromic film and can secure heat absorption resistance and high transmittance, and a method of manufacturing the same.

Another object of the present invention is to provide a transparent conductive film that not only exhibits water- and oil-repellent properties and anti-pollution properties by lowering surface tension, but also has improved chemical resistance, optical properties, low coefficient of friction, and abrasion resistance, and a method for manufacturing the same.

In order to achieve the above object, a transparent conductive film for electrochromic film according to an embodiment of the present invention includes a base film layer; A refractive index matching layer formed on the upper surface of the base film layer; a barrier layer formed on the upper surface of the refractive index matching layer; and a transparent conductive layer formed on the upper surface of the barrier layer, and has a moisture permeability of 3 mg/m ² /day or less.

The transparent conductive film includes a hard coating layer formed on the lower surface of the base film layer; And it may further include a water-repellent coating layer formed on the lower surface of the hard coating layer.

The water-repellent coating layer can be formed by combining a fluorine compound with the lower surface of the hard coating layer.

The base film layer is characterized by no precipitation of oligomers and no increase in haze when observed with the naked eye or a microscope at 180°C for 1 hour.

The base film layer and the refractive index matching layer have a refractive index of 1.5 to 2.

A method of manufacturing a transparent conductive film for an electrochromic film according to another embodiment of the present invention includes forming a refractive index matching layer having the same refractive index as the base layer by coating the upper surface of the base layer; depositing a barrier layer on the upper surface of the refractive index matching layer by PECVD; And it may include depositing a transparent conductive layer on the upper surface of the barrier layer by sputtering.

Forming a hard coating layer on the lower surface of the base layer by PECVD; And it may include applying a water-repellent coating layer to the lower surface of the hard coating layer, drying and curing.

Hereinafter, the present invention will be described in more detail.

A transparent conductive film for electrochromic film according to an embodiment of the present invention includes a base film layer; A refractive index matching layer formed on the upper surface of the base film layer; a barrier layer formed on the upper surface of the refractive index matching layer; and a transparent conductive layer formed on the upper surface of the barrier layer, and has a moisture permeability of 3 mg/m ² /day or less.

Transparent conductive materials (TCM), which are essential for next-generation electronic devices, are used in key materials that require high visible light transmittance and electrical conductivity.

A lot of research has been done on TCM, and it is used in devices such as flat panel displays and solar cells. Due to rapidly developing display and solar technologies, the demand for next-generation materials that are light in weight, flexible, low in price, and suitable for mass production is increasing.

In particular, electrochromic films can change absorbance or transmittance through electrochemical reactions of color-changing materials when an external voltage is applied, and are receiving a lot of attention as next-generation transparent displays.

These electrochromic films can be divided into three types depending on each driving type.

First, Type I electrochromic film refers to a device in which oxidation/reduction electrochromic material is dissolved in the electrolyte layer. The electrochromic material for these Type I electrochromic films is mostly viologen, and the discoloration of the film is mainly affected by diffusion due to differences in concentration of chemical species in the electrolyte.

In contrast, Type III electrochromic film refers to a film in which an oxidation/reduction electrochromic material is coated as a solid film on the electrode surface, so that it does not dissolve in the electrolyte layer.

Conductive polymers and metal oxides are mainly used as electrochromic materials for these Type III electrochromic films, and the operation of the device is mainly affected by electrochemical reactions caused by electronic transfer on the electrode surface.

Lastly, Type ± electrochromic film, which is an intermediate form between Type I and III, is a type in which only one of the oxidation/reduction electrochromic materials is dissolved in the electrolyte layer, and the other material uses a solid film on the electrode surface that is insoluble in the electrolyte. It refers to elements.

Recently, as the multifunctionalization of devices is pursued, research is being actively conducted on the development of devices that can implement additional functions in addition to the color change characteristics of electrochromic films.

The present invention relates to a transparent conductive film for electrochromic films, and can be used as a barrier film and transparent electrode layer of commonly used electrochromic films.

1 shows an electrochromic film according to an embodiment of the present invention, including a barrier film layer 100; Transparent electrode layer 200; Electrochromic layer (300); Transparent electrode layer 400; and a barrier layer 500 may be stacked in that order.

The transparent conductive film of the present invention can be used as the barrier film layer 100 and the transparent electrode layer 200 of the electrochromic film by laminating the transparent conductive film of the present invention on both sides of the electrochromic layer 300. It may be said that it is possible to manufacture it as an electrochromic film.

The transparent conductive film specifically includes a base film layer (10); A refractive index matching layer (20) formed on the upper surface of the base film layer (10); A barrier layer 30 formed on the upper surface of the refractive index matching layer 20; And it may include a transparent conductive layer 40 formed on the upper surface of the barrier layer 30.

In addition, a hard coating layer 50 may be formed on the lower surface of the base film layer 10, and a water-repellent coating layer 60 may be formed on the lower surface of the hard coating layer 50.

The transparent conductive film of the present invention has a moisture permeability of 3 mg/m ² /day or less, and is characterized by excellent moisture resistance.

Transparent conductive films can be included in solar cells, and cell efficiency is affected by humidity. In other words, the efficiency of solar cells is significantly affected by dust and humidity deposited on the cell surface. To prevent this problem, lowering the moisture permeability of the transparent conductive film can prevent the cell's efficiency from being reduced due to humidity. Additionally, in the case of touch screen panels, humidity affects touch sensitivity, making it difficult to obtain accurate operating characteristics.

By including the barrier layer 30, the transparent conductive film of the present invention reduces moisture permeability below a certain level, making it possible to provide a transparent conductive film with excellent moisture resistance.

The barrier layer 30 is formed by depositing oxides or nitrides of Si and Al metals through a PECVD process. In particular, the barrier layer 30 is characterized in that it reduces moisture permeability without significantly affecting visible light transmittance.

The oxide or nitride of the Si metal may be any one of SiO _x , SiO _x N _y , SiO _x C _y and SiC _x H _y O _z , and the oxide or nitride of the Al metal may be AlN or Al _x O _y . The barrier layer 30 can be formed to have a thickness of 0.01 to 1 μm or less. When formed within the above thickness range, it does not affect visible light transmittance and can be effective as a barrier layer 30 by lowering moisture permeability.

The barrier layer 30 is a deposition layer formed by the PECVD (Plasma Enhanced CVD) method. As an example, a gas composition containing an organic silicon compound as a deposition monomer material is used as a raw material, and a base film layer ( 10) By forming a silicon oxide deposition film using the organic silicon compound using the PE-CVD method, the adhesion of the stacked interface under high temperature and high humidity is improved, and by using the silicon oxide layer as an oligomer block layer, there is no shrinkage of the deposited film and dimensional stability can be improved. there is.

The barrier layer has a thickness of 20 to 300 nm and is formed as a single layer rather than multiple layers. The barrier layer can be formed to have a thickness of 20 to 300 nm, maintaining transparency and reducing moisture permeability.

In addition, heat and moisture resistance can be improved by forming a gas barrier deposition layer. The barrier layer 30 of the present invention is a thin film of organosilicon oxide in which organic components such as compounds having C-H bonds or Si-C bonds, organosilicon compounds of monomers as deposition raw materials, or such derivatives are formed by chemical bonding, etc. It can be contained, and due to the presence of this organic component, precipitation of oligomers is suppressed by the thin film layer of organosilicon oxide.

In this case, it is preferable to form an oligomer block layer using hydrocarbon (hydraulic carbon) having a CH ₃ structure as a basic structure as a compound contained in the thin film layer of the organosilicon oxide.

In order to prevent precipitation of oligomers, the film material formed on a plastic film substrate such as polyester is a continuous thin film of organosilicon oxide formed by using a deposition monomer gas such as an organosilicon compound. The deposition monomer gas, such as an organosilicon compound, and oxygen gas undergo a chemical reaction, and the reaction product forms a continuous thin film layer on the substrate. For details, among the components expressed as SiO _x C _y , x is in the range of 1.5 to 2.2, It is desirable for y to be in the range of 0.15 to 0.80, but more precisely, for x it is desirable to be in the range of 1.7 to 2.1, and for y to be in the range of 0.39 to 0.47.

In addition, unless an organosilicon compound containing a methyl group or an ethyl group is used for the organosilicon oxide containing an organic component and this is not deposited by the PECVD method, it is not possible to introduce a methyl group or an ethyl group as an organic component into the film.

Organosilicon compounds used to form a continuous thin film of carbon-containing organosilicon oxide that forms a release layer include the following monomer materials containing a methyl group or an ethyl group and with Si as the main ring, for example, hexamethyl Hydroxyloxylic acid (HMDSO), tetraethoxysilane (TEOS), tetramethyldimethylsilane (TMDSO), methyltrimethylsilane (MTMOS), tetramethoxysilane (TMOS), etc. can be used.

Regardless of the above examples, the monomer material may be any material as long as it is an organosilicon compound containing a Si atom and a CH ₃ or C ₂ H ₅ group and can be subjected to the PECVD method at room temperature and with an appropriate vapor pressure.

In the present invention, as the organosilicon compounds, raw materials such as hexamethyldimethylsiloxane (HMDSO), tetraethoxysilane (TEOS), and tetramethyldimethylsiloxane (TMDSO) are used because of their ease of handling and the formation of organosilicon oxides. This is preferable from the viewpoint of properties such as water repellency of the deposited film.

The base film layer 10 is a transparent film with a total light transmittance of 85% or more, and is characterized by being a base material that does not precipitate oligomers with the naked eye or under a microscope for up to 1 hour at 180°C and does not increase haze.

Specifically, it may be transparent PET, PI, COP, TAC, PP, etc., but as previously explained, it is a transparent film with a total light transmittance of 85% or more, and there is no precipitation of oligomers with the naked eye or under a microscope for up to 1 hour at 180°C, and there is no haze ( Since it is a substrate without an increase in haze, it is not limited to the above example and can be used without limitation.

The base film layer 10 is characterized in that it has a thickness of 12 to 125 ㎛.

The transparent conductive film of the present invention is characterized by being transparent, and when film layers having a different refractive index from the base film layer 10 are laminated or laminated, optical interference such as rainbow phenomenon, Newton ring, or interface reflection due to refractive index mismatch occurs. It can happen.

As described above, the transparent conductive film of the present invention includes a barrier layer 30 to reduce moisture permeability and a conductive layer 40 to exhibit conductive properties.

Both the barrier layer 30 and the conductive layer 40 are transparent, but their refractive index is different from that of the base film layer 10, so when they are directly laminated, optical interference may occur due to mismatch in refractive index.

In order to prevent the above problems, a refractive index matching layer 20 is formed on the upper surface of the base film layer 10.

The refractive index matching layer 20 is characterized in that the transmittance is increased by coating one or more layers of the refractive index matching layer 20 having the same refractive index as the base film layer 10.

The refractive index matching layer 20 includes melamine resin, which is chemically stable, strong, and contains a large amount of nitrogen element, and has excellent barrier properties.

The melamine resins include monomethylol melamine, dimethiol melamine, trimethiol melamine, tetramethiol melamine, pentamethylol melamine, hexamethylol melamine, ether-type melamine resin, imino melamine resin, methylated melamine resin, and butylated melamine resin. It may be selected from the group consisting of melamine resin and alkylated melamine resin.

The melamine resin is commercially available, for example, Cytech Industries Co., Ltd.'s J. CYMEL series product, Sumitomo Chemical's Sumitex Resin series (M-3, MK, M-6, MC, etc.) The product, methylated melamine resin (MW-22, MX-706, etc.) manufactured by Sanwa Chemical, is available as a commercial product.

The melamine resin is dissolved in an organic solvent, and there are no special restrictions on the organic solvent. Considering compatibility and applicability with the melamine resin, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) are used. ), cyclohexanone (CCH), xylene, etc. can be used.

In order to improve the curing speed of the melamine resin, an acid catalyst such as dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, and phosphoric acid may be further included.

The melamine resin is a thermosetting resin and has the characteristic of vaporizing immediately without melting when heated. Using the above characteristics, the refractive index matching layer 20 of the present invention can be formed by evaporating melamine at a temperature of 200° C. or higher under a vacuum state and forming the refractive index matching layer 20.

The transparent conductive layer 40 is coated with one or more layers of ITO by sputtering deposition or wet coating of PEDOT:PSS, and is characterized in that it exhibits conductive properties.

The operating principle of the sputtering manufacturing device using plasma of the present invention will be briefly described. When voltage is applied to the cathode (cathode) where ITO, the target layer material, is adhesively installed, electrons are emitted from the cathode. When the emitted electrons collide with gas atoms of argon gas, argon is ionized into Ar+. When argon is excited and energy is released, a glow discharge occurs and a plasma in which ions and electrons coexist is formed.

Ar+ ions in this plasma collide with the surface of ITO, the target layer material, due to a large potential difference, causing ITO atoms to protrude and deposit on the surface, forming a thin film.

When explaining the sputtering deposition conditions, the pressure in the vacuum chamber is reduced by a vacuum pump and the vacuum degree is 1*10 ^-1 to 1*10 ^-8 torr, preferably the vacuum degree is 1*10 ^-3 to 1*10 ^- It is preferable to adjust it to ⁵ torr, and the reaction rate of the substrate or gas is related to the film thickness, density, productivity, etc. of the ITO thin film layer to be formed, and is usually adjusted to 0.5 to 3 m/min per target, preferably 1 to 2 m/min. It is desirable. Argon gas and plasma generation power are related to the film thickness, density, productivity, etc. of the ITO thin film layer to be formed, and are generally preferably adjusted to 3 to 10 Kw per target.

A hard coating layer 50 is formed on the lower surface of the base film layer 10. The hard coating layer 50 is formed to be durable and has a pencil hardness of 1H or more, and more specifically, is characterized by the formation of a SiO ₂ thin film.

The SiO ₂ film is formed on the lower surface of the base film layer 10 by CVD at a relatively high substrate temperature of 100°C to 160°C, and is preferably deposited by PECVD. Deposition of the SiO ₂ film by PECVD method is as described previously.

The thickness of the hard coating layer is within the range of 0.1 to 2.5㎛, and the film layer constituting the transparent conductive film of the present invention may be formed of one layer or multiple layers within the range of 0.1 to 2.5㎛, unless the thickness is specifically limited. You can.

It may additionally include a water-repellent coating layer formed on the lower surface of the hard coating layer. The water-repellent coating layer contains a fluorine compound selected from the group consisting of Formula 1, Formula 2, and mixtures thereof, and can be formed into a water-repellent coating layer by modifying the lower surface of the hard coating layer:

[Formula 1]

[Formula 2]

here,

n and m are integers from 1 to 100.

By forming a water-repellent coating layer through a bonding reaction of the fluorine compound on the lower surface of the hard coating layer, a water-repellent effect with a contact angle of 110° or more can be exhibited.

This is because the fluorine compound is bonded to the hard coating layer, so that the compound is positioned in a direction perpendicular to the hard coating layer, and can exhibit a water repellent effect due to fluorine. The water-repellent coating layer exhibits water-repellent and oil-repellent properties, and not only has excellent stain and contamination prevention effects, but also improves chemical resistance, optical properties, low friction coefficient, and abrasion resistance properties by applying it as a coating layer.

The water-repellent coating layer may include 20 to 40 parts by weight of the fluorine compound and 1 to 5 parts by weight of the dispersant, based on 100 parts by weight of the organic solvent. When mixed and used within the above range, it is easy to form a water-repellent coating layer, and as described later, it has excellent bonding with a primer and can increase the water-repellent effect.

The organic solvent is selected from the group consisting of methyl ethyl ketone (MEK), toluene, and mixtures thereof, preferably methyl ethyl ketone, but is not limited to the above examples.

As the dispersant, a polyester-based dispersant can be used. Specifically, a polyester-based dispersion stabilizer consisting of a copolymer of 2-methoxypropyl acetate and 1-methoxy-2-propyl acetate is TEGO-Disperse 670 (manufacturer) : EVONIK) can be used, but is not limited to the above example and any dispersant that is obvious to those skilled in the art can be used without limitation.

However, when a reforming reaction is performed directly on the hard coating layer, the fluorine compound does not easily combine with SiO ₂ of the hard coating, making it difficult to form a water-repellent coating layer.

To this end, a primer is first coated on the lower surface of the hard coating layer, dried and cured to form a primer layer, then a fluorine compound is coated, and a drying and curing process is performed.

The primer uses an organopolysiloxane compound and may be a compound represented by the following formula (3):

[Formula 3]

here,

p and q are the same or different from each other and are each independently an integer from 1 to 100.

The primer is first applied to the lower surface of the hard coating layer to form a primer layer, and the primer layer can exhibit a high level of bonding strength with the hard coating layer.

The primer layer can then react with a fluorine compound to form a water-repellent coating layer.

The present invention can be used in the transparent electrode layer of an electrochromic film and can ensure heat absorption resistance and high permeability.

In addition, the present invention relates to a transparent conductive film that lowers surface tension, exhibits water- and oil-repellent properties, and anti-pollution properties, as well as improved chemical resistance, optical properties, low coefficient of friction, and abrasion resistance, and a method of manufacturing the same.

1 is a diagram of an electrochromic film according to an embodiment of the present invention.
Figure 2 is a diagram of a transparent conductive film according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement it. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

Manufacturing example

Preparation of transparent conductive film for electrochromic film

PET with a refractive index of 1.67 is used as a base film, and the thickness of the base film is 100㎛. Melimine resin (Sumimoto Chemicals M-3) was applied to one side of the base film, and the solvent was evaporated under temperature conditions of 200°C or higher to form a refractive index matching layer. The refractive index matching layer is characterized by a refractive index of 1.67, and was formed to have a thickness of 10 to 100 nm. The upper surface of the refractive index matching layer forms a SiO _x C _y layer by PECVD, and the thickness may be 20 to 300 nm. In the case of SiO _x C _y , x is 1.7 to 2.1, and y is 0.39 to 0.47. ITO was deposited on the upper surface of the barrier layer using a sputtering method.

A SiO ₂ film was deposited on the lower surface of the base film by PECVD and formed to a thickness of 0.1 to 2.5 μm.

A primer resin represented by the following formula (3) was applied to the lower surface of the SiO ₂ film to a thickness of 20 to 30 nm and dried at 80° C. for 1 to 3 minutes to form a primer layer:

[Formula 3]

After the primer layer was formed, the fluorine coating composition was applied to a thickness of 20 to 30 nm by dry coating using a coater, and dried at 140°C for 7 minutes to form a water-repellent coating layer.

The fluorine coating composition was prepared by mixing in the range shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Formula 1 10 20 30 40 50 - 15 Formula 2 - - - - - 30 15 menstruum 100 100 100 100 100 100 100 dispersant One One One One One One One

(unit weight) Comparative Example 1

To manufacture the transparent conductive film, it was prepared in the same manner as in Preparation Example except that a primer layer was not formed separately, and the fluorine coating composition used in Example 7 was used to form a coating layer.

Experimental Example 1

Appearance and contact angle measurements

On the surface where the fluorine coating layer was formed, whether the coating layer was formed evenly in appearance and the contact angle were measured.

In order to check the abrasion resistance properties, the contact angle after coating was checked to confirm that it was over 100 degrees, and after rubbing 5,000 times with a 1kg load with non-woven fabric, the contact angle was measured in the same manner to check whether the water repellent properties were maintained.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example Exterior Pass Pass Pass Pass Pass Pass Pass error contact angle 103° 113° 117° 113.5° 105° 116.5° 125.5° 91.5 Wear resistance 5,000 times 98.5° 112.5° 117.5° 113° 102.5° 117° 125° 90°

As a result of the above experiment, it was confirmed that in the case of the comparative example, the external surface was not formed evenly, and the contact angle was also less than 113°, which confirmed that the water-repellent properties were low.

In addition, in the case of Examples 2 to 4, it was confirmed that there was no change in water repellency properties even after conducting an abrasion resistance test in addition to excellent contact angles. In particular, Example 7 was confirmed to have very excellent water repellency properties.

Experimental Example 2

Reliability evaluation results

The following experiment was conducted to confirm the effects of the transparent conductive film on wear resistance, chemical resistance, etc.

(1) Wear resistance test

The contact angle was measured after rubbing 5,000 times with a 1kg load with a non-woven fabric.

(2) Chemical resistance test

The contact angle was measured after leaving the sample in a 5% NaOH aqueous solution for 10 minutes.

(3) Cosmetic resistance test

One hour after applying the foundation, the contact angle was measured.

(4) Salt spray

A 5% NaCl aqueous solution was sprayed for 10 minutes, and the contact angle was measured.

(5) Internal buffer solution

The contact angle was measured after immersing in an aqueous solution of 0.1 mol/L acetic acid and 0.1 mol/L sodium acetate for 10 minutes.

(6) ultraviolet rays

The contact angle was measured after QUV irradiation for 10 to 60 minutes.

(7) Thermal shock

After maintaining the temperature at -40 degrees and 80 degrees for 30 minutes each, the contact angle was measured 10 times.

(8) High temperature and humidity

After leaving for 1 hour at 80 degrees and 85% humidity, the contact angle was measured.

(9) Pencil strength

The contact angle was measured after drawing with a 1H pencil under a load of 500 g.

The experimental results are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example wear resistance before exam 105.1 113.25 115.5 116.51 106.2 115.29 116.82 90.2 after exam 94.87 107.12 109.32 109.77 96.66 109.14 110.81 80.0 Chemical resistance before exam 104.52 114.25 115.7 116.21 107.2 116.32 117.12 91.2 after exam 98.42 111.27 109.9 111.24 98.1 111.21 114.24 84.5 Cosmetics before exam 105.5 113.35 116.2 115.82 105.1 116.18 117.24 91.3 after exam 98.46 107.21 109.54 110.12 95.67 109.54 111.21 81.3 salt spray before exam 104.2 114.23 116.1 117.52 105.21 116.19 117.52 91.1 after exam 95.84 108.56 110.15 111.54 97.14 110.24 115.14 82.8 internal buffer before exam 104.1 113.25 115.51 116.52 106.2 116.29 115.82 90.2 after exam 92.1 106.24 110.11 110.54 98.3 112.18 113.21 82.3 UV-rays before exam 105.4 114.35 115.4 116.5 106.21 115.45 116.72 90.1 after exam - - - - - - - - thermal shock before exam 105.1 113.25 115.5 116.51 106.2 115.29 116.82 90.2 after exam 103.2 111.24 114.5 114.28 104.4 113.87 115.14 87.5 high temperature and humidity before exam 105.2 113.35 115.6 116.42 106.34 115.3 116.2 90.1 after exam 103.1 111.21 113.1 114.21 103.12 113.1 115.1 84.5 pencil strength before exam 104.1 114.15 113.5 115.5 107.1 116.3 117.2 91.1 after exam 104.1 114.15 113.5 115.5 107.1 116.3 117.2 91.1

(unit °)

According to the above experimental results, Examples 2 to 4, Example 6, and Example 7 showed excellent results in reliability evaluation. However, in all ultraviolet ray evaluations, it was confirmed that the contact angle could not be measured, confirming that reliability was not maintained by ultraviolet rays.

In other experiments, it was confirmed that it exhibited excellent physical properties with no significant change in contact angle.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims are also possible. falls within the scope of rights.

10: Base film layer
20: Refractive index matching layer
30: barrier layer
40: Transparent conductive layer
50: Hard coating layer
60: Water-repellent coating layer
100: barrier film layer
200: Transparent electrode layer
300: electrochromic layer
400: Transparent electrode layer
500: barrier layer

Claims (7)

Base film layer;
A refractive index matching layer formed on the upper surface of the base film layer;
a barrier layer formed on the upper surface of the refractive index matching layer;
A transparent conductive layer formed on the upper surface of the barrier layer;
A hard coating layer formed on the lower surface of the base film layer; and
It includes a water-repellent coating layer formed on the lower surface of the hard coating layer,
The water-repellent coating layer is formed by combining a fluorine compound with the lower surface of the hard coating layer,
Moisture permeability less than 3mg/m ² /day
Transparent conductive film for electrochromic films. delete delete According to paragraph 1,
The base film layer shows no precipitation of oligomers and no increase in haze when observed with the naked eye or microscope for 1 hour at 180°C.
Transparent conductive film for electrochromic films. According to paragraph 1,
The base film layer and the refractive index matching layer have a refractive index of 1.5 to 2.
Transparent conductive film for electrochromic films. Forming a refractive index matching layer having the same refractive index as the base layer by coating the upper surface of the base layer;
depositing a barrier layer on the upper surface of the refractive index matching layer by PECVD;
depositing a transparent conductive layer on the upper surface of the barrier layer by sputtering;
Forming a hard coating layer on the lower surface of the base layer by CVD; and
Comprising the steps of applying a water-repellent coating layer to the lower surface of the hard coating layer, drying and curing,
The water-repellent coating layer is formed by combining a fluorine compound on the lower surface of the hard coating layer.
Method for manufacturing transparent conductive film for electrochromic film. delete