TWI486973B - Transparent conductive multilayered film, producing method of the same, and touch panel containing the same - Google Patents

Description

Transparent conductive laminate film, method of manufacturing the same, and touch screen comprising the transparent conductive laminate film

The present invention relates to a transparent conductive film, and more particularly to a transparent conductive laminate film comprising a laminate having different refractive indices, a method for producing the same, and a use thereof.

The touch screen is an output device mounted on the surface of the display device and converting physical contact of the user's finger, stylus, etc. into an electronic signal, and is applied to a liquid crystal display or a plasma display panel. Panel) and EL (electro-luminescence) elements.

Such a touch screen is a special input device of the information display device, and is classified into a resistive type, a capacitive type, an ultrasonic type, an infrared type, and a surface acoustic wave type according to the implementation manner.

Recently, resistive and digital capacitive touch screens have been widely used in small portable devices such as mobile devices and navigation devices with increased usage and application range. In particular, the resistive operation is easy to implement, the manufacturing cost is low, and it is widely used in general touch screen mobile phones and navigation devices. Recently, however, it is simple to operate from the existing tabs and drags. The screen touch method is detached, and the behavior of a multi-touch multi-touch capacitive touch screen that is easy to implement in a smart phone and a high-end mobile device display is continuously expanding.

The capacitive touch screen comprises a touch pattern layer, and the touch pattern layer has an effect of generating an electrical signal corresponding to external physical contact, but in the case of a transparent conductive film for a capacitive touch screen, high visible light transmittance and transmission are required. The visibility of the transparent electrode pattern which is low in coloration and which is formed after the transparent electrode pattern etching process is good. In particular, the transparent conductive film used for the capacitive touch screen exhibits the hue of the display image without distortion, and the transmission coloring must be low, and the visibility of the pattern generated after the transparent electrode pattern etching process on the structure of the touch screen product is particularly low. Must be good. In order to obtain low transmission colorability and high pattern visibility, it is necessary to transmit the pattern and minimize the visibility of the naked eye, and for this, a laminated structure in which the amount of reflected light is reduced and the amount of transmission is increased is required. However, the transparent conductive film used in the existing touch screen generally has a suitable visible light transmittance for the resistive type. In the case of a film of a multilayer structure for overcoming this, even in the case of improving transmittance and ensuring durability and resistance stability against high temperature and high humidity (150 ° C, humidity 90%) and thermal shock, There is a problem that the production time increases as the lamination of the multilayer film leads to an increase in production time.

In order to solve the above problems, it has been conventionally known to form an intermediate layer having a refractive index larger than that of a transparent substrate and having a smaller refractive index than that of a transparent conductive layer, and to reduce the b* value of the transmitted light, so that the transmitted color becomes yellow and brown. Solved, but can not make a conductive laminate film with high transmittance used in the capacitive type.

Further, still another prior art for producing a conductive laminate film having high transmittance is proposed as a dry process in a process of forming an intermediate layer of a conductive laminate film of an oxide film having a low refractive index and a high refractive index. The method of sputtering into a film by physical vapor deposition (PVD) improves transmittance and durability. However, the formation of two layers of metal and inorganic oxides having a high refractive index and a low refractive index by sputtering requires a long film formation time and cannot be solved in a continuous roll-to-roll process. There is a need to increase the cost of manufacturing.

The present invention provides a transparent conductive laminate film having high light transmittance and low transmission coloring, and is capable of providing a small surface resistance change rate and excellent durability even in a harsh environment of high temperature and high humidity, and capable of improving visibility of a transparent electrode pattern while being capable of improving visibility of a transparent electrode pattern. A transparent conductive laminate film which reduces manufacturing cost and a method of manufacturing the same, and a touch screen comprising a transparent conductive laminate film.

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above problems, in a first aspect of the invention, there is provided a transparent conductive laminate film comprising: a light transparent substrate; laminated on a light transparent substrate by plasma chemical vapor deposition (PECVD) a first laminate having an inorganic oxide and having a refractive index of 1.3 to 2.5 up to a thickness of 10 nm to 300 nm; laminated on the first laminate to a thickness of 10 nm to 300 nm by plasma chemical vapor deposition a second laminate comprising an inorganic oxide different from the inorganic oxide contained in the first laminate; and a transparent conductive layer laminated on the second laminate to a thickness of 10 nm to 100 nm.

In one embodiment, in the case where the thickness of the transparent conductive layer is 50 nm or more, the refractive index of the second laminate is larger than the refractive index of the first laminate, but is not limited thereto.

In one embodiment, the total thickness of the first laminate and the second laminate is 50 to 350 nm, but is not limited thereto.

In one embodiment, the L, a*, b* value of the color difference meter of the second laminate has a transmission color coordinate value of -7<b*<2, but is not limited thereto.

In one embodiment, the transparent conductive layer contains one or more of indium tin oxide (ITO), antimony tin oxide (ATO), and indium zinc oxide (IZO), but is not limited thereto.

In one embodiment, the light transparent substrate comprises a plastic film, and the thickness of the light transparent substrate is 25 um to 350 um, but is not limited thereto.

In one embodiment, the transparent hard coat film is further disposed on one side or both sides of the light transparent substrate, but is not limited thereto.

According to a second aspect of the present invention, there is provided a method of producing a transparent conductive laminate film comprising: laminating an inorganic oxide on a light transparent substrate by plasma chemical vapor deposition (PECVD), having a refractive index of 1.3 a first laminate of ~2.5 to a thickness of 10 nm to 300 nm; laminating a first laminate comprising a different inorganic oxide than the inorganic oxide contained in the first laminate by plasma chemical vapor deposition The second laminate is to a thickness of 10 nm to 300 nm; and the transparent conductive layer is laminated on the second laminate to a thickness of 10 to 100 nm.

In one embodiment, the plasma chemical vapor deposition method comprises a roll-to-roll plasma chemical vapor deposition method, but is not limited thereto.

In one embodiment, the step of laminating the transparent conductive layer comprises using at least one method selected from the group consisting of a vapor deposition method, an ion etching method, a sputtering method, a chemical vapor deposition method, and an etching method, and The roll-to-roll process continuously forms a transparent conductive layer, but is not limited thereto.

In one embodiment, the method for producing a transparent conductive laminate film further comprises: after the step of laminating the transparent conductive layer, heat-treating at 120 ° C to 150 ° C to crystallize the transparent conductive layer, but is not limited thereto.

In a third aspect of the invention, a touch screen comprising a transparent conductive laminate film is provided, but is not limited thereto.

According to the present invention, by the process comprising laminating a laminate comprising a two-layer structure having an adjustable refractive index and a thickness on a light-transparent substrate by plasma chemical vapor deposition, the following effects can be obtained: a dense and stable transparent structure can be provided The conductive laminate film is capable of providing a transparent conductive laminate film having high visible light transmittance, low transmission coloration, small surface resistance change rate in a high temperature and high humidity environment, and high film durability.

On the other hand, since a process including a roll-to-roll type plasma chemical vapor deposition method is applied in the manufacture of a laminate including a two-layer structure having an adjustable refractive index and a thickness, and other PVD processes (sputtering, Compared with the electron beam deposition or the like, the film formation speed can be increased by 5 times to 7 times or more, and thus the effect of improving the productivity of a large area and reducing the manufacturing cost can be obtained.

In addition, a touch screen comprising a transparent conductive laminate film having high light transmittance, low transmission coloration, and small surface resistance change rate in a high temperature and high humidity environment can be used in various modes including capacitive and resistive touch screens. Apply without restrictions.

Embodiments and embodiments of the present invention are exemplified and described in detail below with reference to the accompanying drawings, so that those of ordinary skill in the art of the invention can be easily implemented.

However, the invention may be embodied in a variety of different forms and is not limited to the embodiments and embodiments described herein. Further, in the drawings, in order to clearly explain the present invention, portions that are not related to the description are omitted, and like reference numerals are added to the like parts throughout the specification.

Throughout the specification, if a part "includes" a component, it means that the other component is not excluded unless otherwise indicated, and may further include other components.

Throughout the specification, if a layer or component is "above" another layer or component, this does not only mean that a layer or component is connected to another layer or component, but also includes between two or two components. The presence of other layers or other components.

The term "basic [薬]", "substantially", etc., used throughout the specification, as used in the context of the meaning of the inherent manufacturing and material tolerances, may be used as the value or close to the value, to help The invention is understood to be used in order to prevent unscrupulous infringers from improperly utilizing disclosures that refer to correct or absolute values. The term "stage" or "stage of" used throughout the specification does not mean "stage for".

According to a first aspect of the present invention, there is provided a transparent conductive laminate film comprising: a light transparent substrate; laminated on a light transparent substrate by plasma chemical vapor deposition (PECVD) to 10 nm to 300 nm Thickness, comprising an inorganic oxide, having a first laminate having a refractive index of 1.3 to 2.5; laminating on the first laminate by plasma chemical vapor deposition to a thickness of 10 nm to 300 nm, including and first a second laminate of inorganic oxides having different inorganic oxides contained in the laminate; and a transparent conductive layer laminated on the second laminate to a thickness of 10 nm to 100 nm.

The first figure is a cross-sectional view of a transparent conductive laminate film 100 in one embodiment of the present invention. Hereinafter, an embodiment of the present invention will be described in detail with reference to the first drawings.

The inorganic oxide comprises a metal oxide or an amphoteric metal oxide, and as a specific example, is selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, aluminum oxide (aluminium). Oxide), tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide, silicon oxide, antimony tin One or more of the group consisting of oxide) and indium tin oxide, but is not limited thereto. In the illustrated embodiment, the inorganic oxide contains one or more selected from the group consisting of titanium oxide, cerium oxide, and zirconium oxide, but is not limited thereto. In the illustrated embodiment, in order to increase the visibility of the transparent electrode pattern, the inorganic oxide contains titanium oxide or cerium oxide, but is not limited thereto.

The first laminate 20 has a refractive index of 1.3 to 2.5 and a thickness of 10 to 300 nm, but is not limited thereto. The numerical range is the behavior of the light constituting the two-layer film in the deposition process using the plasma chemical vapor deposition method in the laminate including the first laminate 20 and the second laminate 30, and constitutes the multilayer laminate In the case of the physical properties of the laminate which must be considered, the stability of the laminate material is large in the numerical range, and the stress matching between the laminates is formed, and the refractive index change is small. As an example of the stress matching, titanium oxide (TiO ₂ ) is laminated on the first laminate 20 to have a refractive index of about 1.46, and the second laminate 30 is adjusted in refractive index using cerium oxide (SiO ₂ ) to constitute two. The laminate of the film, the titania-containing laminate is subjected to tensile force under external pressure, and the cerium oxide-containing laminate is subjected to compressive strain, and is capable of maintaining transparency to light. The advantage of the force balance of the substrate 10.

The second laminate 30 contains an inorganic oxide different from the metal oxide and/or inorganic oxide contained in the first laminate 20, and has a thickness of 10 nm to 300 nm, but is not limited thereto. In the illustrated embodiment, in the case where the first laminate 20 contains titanium oxide, the second laminate 30 contains a metal oxide other than titanium oxide or cerium oxide as an inorganic oxide. In this regard, the reason for including the different metal oxides and/or inorganic oxides is as described above because the stability of the laminate and the excellent light transmittance can be ensured.

In one embodiment, a transparent conductive laminate film 100 is provided, wherein, in the case where the thickness of the transparent conductive layer 40 is 50 nm or more, the refractive index of the second laminate 30 has a larger refractive index than that of the first laminate 20 The refractive index having a large refractive index is not limited thereto. In the case where the thickness of the transparent conductive layer 40 is 50 nm or more, the refractive index of the second laminate 30 must be higher than that of the first laminate 20, otherwise the effect of high light transmittance cannot be obtained.

In one embodiment, the total thickness of the first laminate 20 and the second laminate 30 is 50 to 350 nm, but is not limited thereto. In the illustrated embodiment, the total thickness of the first laminate 20 and the second laminate 30 is 90 to 310 nm, but is not limited thereto. The excellent stability of the laminate and high light transmittance can be ensured within the above numerical range.

The first laminate 20 and the second laminate 30 act as a buffer, and the surface resistance of the transparent conductive layer 40 improves the bending due to the external environment, particularly humidity and heat or film. The electrical stability of the impact. Further, the high density and dense film structure of the laminated oxide serves as a barrier function for preventing moisture generated by the transparent resin film substrate and diffusion of organic substances such as a solvent to the transparent conductor layer, thereby enhancing the buffering function against bending shock.

In one embodiment, a transparent conductive laminate film 100 having a transmission color coordinate value of -7 < b* < 2 in L, a*, b* values of a color difference meter having the second laminate 30 is provided. L, a*, and b* refer to the color difference table, and the L value represents brightness, which is represented by 0 to 100. Also, a* and b* are plane coordinate systems like the xy coordinate system, the horizontal axis means a* value, the vertical axis means b* value, the +a side represents red, the -a side represents green, and the +b side represents yellow. The -b side represents blue. In an exemplary embodiment of the present invention, a transparent conductive laminate film 100 having a transmission color coordinate value of -5 < b* < 3 in L, a*, b* values of a color difference meter is provided. In the numerical range, the complete transmittance and color coordinate value of the transparent conductive laminate film 100 can be achieved, and the local minimum reflectance wavelength of the surface of the two-layer laminate having different refractive indexes can be in the range of 350 to 500 nm. The lowest value is included. In the case of adjusting the thickness and refractive index of the laminate and depositing it by plasma chemical vapor deposition, the purple light or blue can be reduced within the numerical range of the color shift value of the color difference meter. The reflection of the colored light can also reduce the color of the transmitted light.

In one embodiment, the transparent conductive layer 40 includes one or more of indium tin oxide (ITO), antimony tin oxide (ATO), and indium zinc oxide (IZO), but is not limited thereto. The transparent conductive layer 40 contains a metal or a metal oxide, but is not limited thereto. In the illustrated embodiment, one or more selected from the group consisting of indium tin oxide (ITO), antimony tin oxide (ATO), and indium zinc oxide (IZO), gold, silver, copper, platinum, and nickel are included, but not Limited to this.

In one embodiment, the light transparent substrate 10 comprises a plastic film, and the thickness of the light transparent substrate is 25 to 350 um, but is not limited thereto. Therefore, the thickness range of the light transparent substrate is required from the viewpoint of transparency and productivity of the transparent conductive laminate film 100. The optically transparent substrate 10, if it is an optically transparent substance capable of ensuring the thickness and transparency of the substrate, may include a substrate which is appropriately selected by a skilled person as needed. In the illustrated embodiment, the optically transparent substrate 10 comprises, for example, selected from the group consisting of glass or polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate ( Polycarbonate, poly(methyl methacrylate) copolymer, triacetyl cellulose, polyolefin, polyamide, polyvinyl chloride One or more substrates in the group consisting of amorphous polyolefins, but are not limited thereto. The form of the light transparent substrate 10 is a sheet, a plate or a film, but is not limited thereto.

In one embodiment, the light transparent substrate 10 includes a transparent hard coat film on at least one side thereof, but is not limited thereto. In order to improve the surface hardness and bending of the light transparent substrate, the thickness of the transparent hard coat film is 2 to 15 μm, but is not limited thereto. In the illustrated embodiment, it is 3 to 15 um, but is not limited thereto. The hard coat film is one or more types of curable resins selected from the group consisting of melamine resins, urethane resins, alkyd resins, acrylic resins, and fluorene resins, but is not limited thereto.

According to a second aspect of the present invention, there is provided a method of manufacturing a transparent conductive laminate film 100 comprising: laminating an inorganic oxide on a light transparent substrate 10 by a plasma chemical vapor deposition method, having a refractive index of 1.3 a thickness of the first laminate of ~2.5 to a thickness of 10 nm to 300 nm; lamination of the inorganic layer different from the inorganic oxide contained in the first laminate 20 on the first laminate 20 by plasma chemical vapor deposition The second laminate of the oxide has a thickness of 30 to 10 nm to 300 nm; and the transparent conductive layer 40 is laminated on the second laminate 30 to a thickness of 10 to 100 nm.

In one embodiment, the plasma chemical vapor deposition method comprises a roll-to-roll plasma chemical vapor deposition method, but is not limited thereto. Plasma chemical vapor deposition is capable of forming a dense and uniform film of a laminate having high density and purity. On the other hand, in the case where the deposition rate is easily adjusted and deposited on the optical base film at a low temperature, it is possible to carry out inexpensive production. In order to obtain the best uniform film quality, the plasma chemical vapor deposition method can optimize the hydrodynamic parameters and heat transfer parameters such as the reaction gas flow according to the temperature distribution and the reactor position. In the illustrated embodiment, the gas may be supplied with high electrical energy at a low pressure, a reaction precursor is initiated by a plasma ion source that generates a plasma, and the activated reaction gas is moved to the reactor. In the middle, a phase transition is induced on the light-transparent substrate 10, and a desired film is formed at a low temperature. In the illustrated embodiment, the precursor used at this time forms a cerium oxide-containing layer using titanium ethoxide or titanium tetrachloride in the case of forming a titania-containing laminate. In the case of a laminate, TMDSO (tetramethyldisiloxane) + O ₂ or SiH ₄ + O _{2 is} used as the reaction precursor, but is not limited thereto. On the other hand, the plasma chemical vapor deposition method includes a roll-to-roll method, but is not limited thereto. The lamination film formation time of the first laminate 20 and the second laminate 30 by the plasma chemical vapor deposition method is short and the denseness and uniform distribution of the inorganic oxide of the laminate after film formation can be ensured. Thus, in addition to the roll-to-roll method, the continuous production of the transparent conductive laminate film 100 can be performed in order.

In one embodiment, the step of laminating the transparent conductive layer 40 includes using one or more selected from the group consisting of a vapor deposition method, an ion etching method, a sputtering method, a chemical vapor deposition method, and an etching method. The method and the roll-to-roll process continuously form a transparent conductive layer, but are not limited thereto.

In one embodiment, a method of manufacturing the transparent conductive laminate film 100 in which the transparent conductive layer 40 is crystallized by heat treatment at 120 ° C to 150 ° C after the step of laminating the transparent conductive layer 40 is further included, but is not limited thereto. . In the illustrated embodiment, the heat treatment further includes heat treatment at 120 ° C to 150 ° C for about 90 minutes, but is not limited thereto.

In a third aspect of the invention, a touch screen comprising a transparent conductive laminate film 100 is provided, but is not limited thereto. The touch screen is a capacitive touch screen, but is not limited to this, and a resistive touch screen can also be applied. In the illustrated embodiment, the transparent conductive laminate film 100 is used as a panel, and after forming an indium tin oxide (ITO) film on a glass plate as another panel, the transparent conductive glass is used to dispose the two panels by spacing. The indium tin oxide thin films are opposed to each other to manufacture a touch screen as a switch structure, but are not limited thereto.

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto.

[Example 1] Fabrication of the first laminate 20

On one side of a transparent resin film substrate composed of a PET film having a thickness of 125 μm, a GPI PECVD modulator was used as a plasma chemical vapor deposition device suitable for a large-area PECVD linear source.

PET was injected into the PECVD chamber, and a plasma ion source of a chamber maintained at a vacuum of 1 to 20 mtorr was supplied with a 40 kHz alternator, and Titanium Tetrachloride was injected into the PECVD reactor as a reaction precursor (Precusor). A phase transition was induced on the substrate to form a 34 nm thick TiO ₂ film having a refractive index of 2.32.

Lamination of the second laminate 30

As a production method of the first laminate 20, TMDSO and an atmosphere O _{2 were} injected as a reaction precursor (Precusor) into a PECVD reactor, and a 61 nm-thick SiO ₂ film having a refractive index of 1.45 was formed on the first laminate 20. The second laminate 30.

Lamination of transparent conductive layer 40

A film formed by injecting the second laminate 30 into the sputtering chamber was formed by RF magnetron sputtering. The objective is to use a sintered body containing 5 wt% of tin oxide and 95 wt% of indium oxide to maintain a chamber with an initial vacuum of 5.0×10 ^-5 torr, and 80% of argon and 20% of oxygen. A transparent conductive laminate film 100 was produced by laminating an ITO film as a 25 nm thick transparent conductive layer having a refractive index of 2.05 in an atmosphere of 4.0 × 10 ^-3 torr.

<Comparative Example 1>

The thickness of the transparent conductive layer was fixed at 25 nm, in order to investigate the transmittance and the transmission coloring value due to the intermediate layer structure, and the reliability against high temperature and high humidity, except that TiO ₂ of the first laminate 20 was not formed, A transparent conductive laminate film 100 having a SiO ₂ film having a refractive index of 1.45 and a thickness of 42 nm was produced in the same manner as in Example 1.

<Comparative Example 2>

In order to study the difference in thickness and resistance of the transparent conductive layer, the transmittance and the transmission coloring value due to the difference in refractive index, the first laminate 20 and the second laminate 30 are formed by an Electron Beam Evaporation process. .

A PET film having a thickness of 125 μm was injected into the deposition chamber, and the first laminate 20 (TiO ₂ ) and the second laminate 30 (SiO ₂ ) and the adjacent materials were respectively injected into the electron beam, maintaining an initial vacuum of 6.0×10 ^{− 6} torr, injecting oxygen while irradiating the electron beam to increase the reactivity of the inorganic oxide. The operation was carried out at an optimum oxygen partial pressure of an optical film of an inorganic oxide, that is, 5.0 × 10 ^-5 torr.

A TiO ₂ film having a thickness of 66 nm having a refractive index of 2.16 and a SiO ₂ film having a thickness of 1.43 and having a refractive index of 43 nm were produced. The thickness and formation method of ITO were carried out in the same manner as in Example 1 to produce a transparent conductive laminate film 100.

The transmittance, color coordinate value, surface resistance, reliability, and the like of the transparent conductive laminate film 100 manufactured in Example 1 according to an embodiment of the present invention were measured, and together with the results of Comparative Example 1 and Comparative Example 2, Table 1 below.

<Measurement method of average transmittance and color coordinate value>

The transmittance of the transparent conductive laminate film 100 according to an embodiment of the present invention was measured together with a comparative example, and the transmittance was measured using a Hitachi U4300 spectrophotometer, respectively, using a CIE color coordinate measurement method and a D75 source. .

<Measurement of Surface Resistance and Method of Measuring Resistance Change Rate>

The surface resistance Ro (ohm/cm ² ) of the ITO surface of the transparent conductive laminate film 100 placed at room temperature was measured by a four-terminal method, and then placed in a heating chamber at 60 ° C and 95% humidity. After standing for 240 hours, the ITO surface resistance R was measured, and the rate of change in surface resistance (R/Ro) was calculated to evaluate the reliability of high temperature and high humidity.

< Method for Measuring Refractive Index and Thickness of Thin Film >

The refractive index and film thickness of the TiO ₂ , SiO ₂ and ITO films formed on each layer were measured by phase modulation type spectroscopy (Phase Modulated Ellipsometry).

From Table 1, the reliability (R/Ro) of the surface resistance of ITO as a transparent laminate to high temperature and high humidity was confirmed, and in Example 1, two intermediate layers (first laminate and second) were formed from PEVCD. The case of the laminate) has more excellent characteristics than Comparative Example 1 in which only a single intermediate layer is formed of PEVCD and Comparative Example 2 in which two intermediate layers are formed by an electron beam deposition process. In this regard, as described above, the external thermal shock by the TiO ₂ and SiO ₂ layers corresponds to the tensile force and the contraction force, respectively, and it can be seen that the surface tension of the ITO film can be stabilized.

Further, the intermediate layers formed by the electron beams, that is, the first laminate 20 and the second laminate 30, exhibit a result of weak heat resistance and moisture shock caused by a low density and a loose film structure, and this result can be confirmed as utilization. The first laminate 20 and the second laminate 30 of the high-density and dense film structure formed by the PECVD process of the embodiment 1 of the embodiment of the present invention are excellent in reliability characteristics against external impact such as heat and moisture.

2A is a graph for measuring the reflectance of the transparent conductive laminate film 100 according to Example 1 of the present invention, and FIG. 2B is a graph for measuring the reflectance of the transparent conductive laminate film 100 according to Comparative Example 1.

As can be seen from Table 1, FIG. 2A and FIG. 2B, in Comparative Example 1, the numerical values of the transmission coloring are slightly different from those of Embodiment 1 according to an embodiment of the present invention, but it can be determined that the expression is low. Visible light transmittance values are not suitable for use in capacitive touch screens that require high transmittance values.

In Comparative Example 2, compared with Embodiment 1 according to an embodiment of the present invention, The transmittance values are values of the same degree, but it is seen that the b* value indicating the transmission coloration (yellow) is relatively high.

Further, comparing FIG. 2A and FIG. 2B, it can be confirmed that the case of Embodiment 1 according to an embodiment of the present invention is lower in reflectance in the visible light range than in Comparative Example 2, particularly in the wavelength range of 550 nm. It is confirmed by this that the light transmittance of the present invention is high.

[Embodiment 2]

In order to investigate the difference in thickness and resistance change of the transparent conductive layer, the transmittance and the transmitted color value due to the difference in refractive index, the transparent conductive layer 40 except that the thickness of the laminated TiO ₂ film was 61 nm and the thickness of the SiO ₂ film was 25 nm. A transparent conductive laminate film 100 was laminated in the same manner as in Example 1 except that the thickness was 40 nm.

<Comparative Example 3>

The thickness of the transparent conductive layer 40 was fixed as in Example 2, in order to investigate the change in transmittance and transmission coloration due to the structure of the intermediate layer, except that the thickness of the second laminate 30, that is, the thickness of SiO ₂ was changed to 24 nm, The transparent conductive laminate film 100 was produced in the same manner as in Example 1.

<Comparative Example 4>

Except that the thickness of the TiO ₂ layer as the first laminate 20 and the SiO ₂ layer as the second laminate 30 and the ITO as the transparent conductive layer 40 in Comparative Example 2 were 67 nm, 25 nm, and 40 nm, respectively, A transparent conductive film was produced in the same manner as in Comparative Example 2.

The transmittance and color coordinate value of the transparent conductive laminate film 100 manufactured according to Example 2 of one embodiment of the present invention were measured, which are shown together with the results of Comparative Example 3 and Comparative Example 4 in Table 2 below.

3A is a view for measuring the reflectance of the transparent conductive laminate film 100 according to Example 2 of the present invention, and FIG. 3B is a view for measuring the reflectance of the transparent conductive laminate film 100 according to Comparative Example 3.

As can be seen from Table 2, FIG. 3A and FIG. 3B, in Comparative Example 3, the transmission coloring value has a slight difference as compared with Embodiment 2 according to an embodiment of the present invention, but it can be determined that the low visible light is Transmittance values are not suitable for use in capacitive touch screens that require high transmittance values.

In Comparative Example 4, the transmittance values were values of the same degree as compared with Example 1 according to an embodiment of the present invention, but it was seen that the b* value indicating the transmission coloring (yellow) was relatively high.

Further, comparing FIGS. 3A and 3B, it can be confirmed that the case of Embodiment 2 according to an embodiment of the present invention is opposite to that of Comparative Example 5 in the visible light range. The light transmittance is low, particularly in the wavelength range of 550 nm, and it can be confirmed from this that the light transmittance of the present invention is high.

[Example 3]

In the case where the thickness of the transparent conductive layer 40 (ITO; refractive index 20.5) is 50 nm or more, the second laminate 20 and the second laminate 30 which are formed of optically transparent resin on PET require a second laminate. The refractive index of the body 30 is higher than the refractive index of the first laminate 20.

A first laminate 20 was formed by laminating a SiO ₂ layer having a refractive index of 1.45 to a thickness of 282 nm on PET, and TiO ₂ having a refractive index of 2.32 was laminated on the first laminate 20 to 57 nm, and a transparent conductive layer was laminated. The thickness of 40 was laminated to 70 nm to manufacture a transparent conductive laminate film 100.

<Comparative Example 5>

The thickness of the transparent conductive layer 40 was fixed in the same manner as in Example 3, in order to investigate the change in transmittance and transmission coloration due to the structure of the intermediate layer, except that the thickness of the second laminate 30, that is, SiO ₂ was changed to 55 nm, The transparent conductive laminate film 100 was produced in the same manner as in Comparative Example 1.

<Comparative Example 6>

The thickness of the SiO ₂ layer as the first laminate 20 and the TiO ₂ layer as the second laminate 30 and the ITO as the transparent conductive layer in Comparative Example 2 were 288 nm, 64 nm, and 70 nm, respectively, and compared. The transparent conductive film was produced in the same manner as in Example 2.

The transmittance and color coordinate value of the transparent conductive laminate film 100 manufactured according to Example 3 of one embodiment of the present invention were measured, which are shown together with the results of Comparative Example 5 and Comparative Example 6 in Table 3 below.

4A is a graph for measuring the reflectance of the transparent conductive laminate film 100 according to Example 3 of the present invention, and FIG. 4B is a graph for measuring the reflectance of the transparent conductive laminate film 100 according to Comparative Example 5.

As can be seen from the above Table 3, FIG. 4A and FIG. 4B, in Comparative Example 5, the transmission coloring value has a slight difference as compared with Embodiment 3 according to an embodiment of the present invention, but it can be determined that the expression is low. Visible light transmittance values are not suitable for use in capacitive touch screens that require high transmittance values.

In Comparative Example 6, the transmittance values were values of the same degree as compared with Example 1 according to an embodiment of the present invention, but it was seen that the b* value indicating the transmission coloring (yellow) was relatively high.

Further, comparing FIGS. 4A and 4B, it can be confirmed that the case of Embodiment 3 according to an embodiment of the present invention is lower in reflectance in the visible light range than in Comparative Example 5, particularly in the wavelength range of 550 nm. Low, through this you can be sure It is recognized that the light transmittance of the present invention is high.

According to the results of Embodiments 1 to 3 of an embodiment of the present invention, the present invention is excellent in ensuring high transmittance, low transmission coloring, and reliability characteristics of an external environment of high temperature and high humidity.

The present invention has been described in detail above with reference to the embodiments and embodiments, but it is understood that the present invention is not limited to the embodiments and examples described above, and various modifications may be made, and those skilled in the art may employ the techniques of the present invention. Various forms of various deformations are carried out within the spirit.

10‧‧‧Light transparent substrate

20‧‧‧First laminate

30‧‧‧Second laminate

40‧‧‧Transparent conductive layer

100‧‧‧Transparent conductive laminate film

Fig. 1 is a cross-sectional view showing a transparent conductive laminate film in an embodiment of the present invention.

Fig. 2A is a graph for measuring the reflectance of the transparent conductive laminate film of Example 1 according to the present invention.

Fig. 2B is a graph for measuring the reflectance of the transparent conductive laminate film according to Comparative Example 1.

Fig. 3A is a graph for measuring the reflectance of the transparent conductive laminate film of Example 2 according to the present invention.

Fig. 3B is a graph for measuring the reflectance of the transparent conductive laminate film according to Comparative Example 3.

Fig. 4A is a graph for measuring the reflectance of the transparent conductive laminate film according to Example 3 of the present invention.

Fig. 4B is a graph for measuring the reflectance of the transparent conductive laminate film according to Comparative Example 5.

10. . . Light transparent substrate

20. . . First laminate

30. . . Second laminate

40. . . Transparent conductive layer

100. . . Transparent conductive laminate film

Claims (9)

A transparent conductive laminate film comprising: a light transparent substrate; a first laminate laminated on the light transparent substrate by plasma chemical vapor deposition to a thickness of 10 nm to 300 nm, containing an inorganic oxide, having refraction a ratio of 1.3 to 2.5; a second laminate laminated on the first laminate to a thickness of 10 nm to 300 nm by plasma chemical vapor deposition, comprising inorganic oxide contained in the first laminate a different inorganic oxide; and a transparent conductive layer laminated on the second laminate to a thickness of 10 to 100 nm, wherein the second laminate is in the case where the thickness of the transparent conductive layer is 50 nm or more The refractive index is greater than the refractive index of the first laminate, and wherein the total thickness of the first laminate and the second laminate is 50 to 350 nm. The transparent conductive laminate film according to claim 1, wherein the transparent conductive layer contains one or more of indium tin oxide, antimony tin oxide, and indium zinc oxide. The transparent conductive laminate film according to claim 1, wherein the light transparent substrate comprises a glass or plastic film, and the light transparent substrate has a thickness of 25 um to 350 um. The transparent conductive laminate film according to claim 1, wherein the color difference meter of the second laminate has a transmission color coordinate value of -7 < b* < 2 in L, a*, b* values. The transparent conductive laminate film according to claim 1, further comprising: a transparent hard coating film on one side or both sides of the light transparent substrate. A method for manufacturing a transparent conductive laminate film comprising: Laminating a first laminate having an inorganic oxide and having a refractive index of 1.3 to 2.5 to a thickness of 10 nm to 300 nm on a light transparent substrate by a roll-to-roll plasma chemical vapor deposition method; using a roll-to-roll method a plasma chemical vapor deposition method, wherein a second laminate comprising an inorganic oxide different from the inorganic oxide contained in the first laminate is laminated on the first laminate to a thickness of 10 nm to 300 nm; And laminating a transparent conductive layer on the second laminate to a thickness of 10 to 100 nm, wherein the second laminate has a refractive index greater than the first layer in a case where the transparent conductive layer has a thickness of 50 nm or more The refractive index of the compact is large, and wherein the total thickness of the first laminate and the second laminate is 50 to 350 nm. The method for producing a transparent conductive laminate film according to claim 6, wherein the step of laminating the transparent conductive layer comprises using a method selected from the group consisting of vapor deposition, ion etching, sputtering, chemical vapor deposition, and One or more methods of the group consisting of etching methods and a roll-to-roll process continuously form the transparent conductive layer. The method for producing a transparent conductive laminate film according to claim 6, further comprising: after the step of laminating the transparent conductive layer, heat-treating at 120 ° C to 150 ° C to crystallize the transparent conductive layer. A touch screen comprising the transparent conductive laminate film according to any one of claims 1 to 5.