JP2012101544A - Transparent conductive layered film, method for producing the same, and touch panel including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive layered film which has high light transmission rate with less transmission coloring, a method for producing the same, and a touch panel including the same.SOLUTION: The transparent conductive layered film 100 is a laminate 100 including two layers 20 and 30 with adjusted refractive index and thickness which are formed on an optical transparent substrate 10 through a process including a plasma-enhanced chemical vapor deposition method, and has a precise and stable structure. This layered film has a high visible light transmission rate with less transmission coloring, a low change rate of surface resistance in high-temperature, high-humidity environments, and high thin film durability. The production cost thereof can be reduced while enhancing large-area productivity.

Description

  The present application relates to a transparent conductive laminated film including laminates having different refractive indexes, a method for producing the same, and uses thereof.

  A touch panel is a device that is attached to the surface of a display device and converts a physical contact of a user's finger, a touch pen, or the like into an electrical signal and outputs the signal, and includes a liquid crystal display device and a plasma display panel. panel) and EL (electro-luminescence) elements.

  Such a touch panel is a special input device for an information display device, and is classified into a resistance film method, a capacitance method, an ultrasonic method, an infrared method, an elastic wave method, and the like according to an implementation method.

  Recently, resistive film type and digital capacitance type touch panels have been widely applied to mobile devices such as mobile devices and navigation devices whose usage and application range have been expanded. In particular, the resistive film method is easy to implement, has a low manufacturing cost, and is widely used in general touch screen mobile phones and navigation devices. In addition, capacitive touch panels that are easy to implement various types of multi-touch, deviating from simple operations that can only be dragged, have recently been increasingly installed in smartphones and premium-grade mobile device displays. .

  The capacitive touch panel includes a touch pattern layer, and the touch pattern layer serves to generate an electrical signal in response to an external physical contact, and is used for the capacitive touch panel. In the case of the transparent conductive film to be formed, the visible light transmittance must be high, the transmission coloring should be low, and the visibility of the transparent electrode pattern generated after the transparent electrode pattern etching step should be good. In particular, a transparent conductive film used for a capacitive touch panel must have low transmission coloring in order to express the hue of a screen to be displayed without distortion. Due to the structure of the touch panel product, the transparent electrode pattern is etched. The visibility of the pattern generated after the process must be good. In order to obtain low transmission colorability and high pattern visibility, the transmission of the pattern must be minimized so that the amount of reflected light is reduced and transmission is increased. A laminated structure is required. However, the transparent conductive film used for the existing touch panel generally has a visible light transmittance suitable for the electric resistance film system. In the case of a film having a multilayer structure to overcome this, the transmittance may be improved, and durability and resistance stability against high temperature, high humidity (150 ° C., 90% humidity) and thermal shock may be ensured. There is a problem that a manufacturing cost is increased due to an increase in production time due to film lamination.

  In order to solve the above problem, conventionally, an intermediate layer having a refractive index larger than the refractive index of the transparent substrate and smaller than that of the transparent conductive layer is formed, and the color difference meter b * value of the transmitted light is reduced and transmitted. Although the problem of changing the color to yellow and brown was solved (Korea Published Patent No. 10-2005-0004165), it was not possible to produce a conductive laminated film having a high transmittance used for the capacitance method.

  Another conventional technique for producing a conductive laminated film having a high transmittance is a process of forming an intermediate layer of a conductive laminated film that forms an oxide film having a high refractive index and a low refractive index. As a dry process, among physical vapor deposition (PVD), a method of forming a film by sputtering was proposed to improve the transmittance and improve the durability. However, a two-layer metal and an inorganic oxide having a high refractive index and a low refractive index are formed by a sputtering method, and a long film formation time is required, and a roll-to-roll method is required. In the continuous production process, the manufacturing cost is high and the necessary problems cannot be solved.

  The present application provides a transparent conductive laminated film having a high light transmittance and a low transmission colorability, and has a low surface resistance change rate and excellent durability even in an environment where temperature and humidity are inferior. A transparent conductive laminated film that can reduce the manufacturing cost while improving visibility and a method for producing the same are provided, and a touch panel including the transparent conductive laminated film is provided.

  However, the problem to be solved by the present application is not limited to the problem mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

  In order to achieve the above object, a first aspect of the present application is an optically transparent substrate; a thickness of 10 nm to 300 nm on the optically transparent substrate using plasma-enhanced chemical vapor deposition (PECVD). A first laminated body including an inorganic oxide and having a refractive index of 1.3 to 2.5, and 10 nm to 300 nm on the first laminated body using a plasma-enhanced chemical vapor deposition method. A second laminated body including an inorganic oxide different from the inorganic oxide contained in the first laminated body, and a transparent conductive layer laminated to a thickness of 10 to 100 nm on the second laminated body. A transparent conductive laminated film comprising a layer is provided.

  In one embodiment, when the transparent conductive layer has a thickness of 50 nm or more, the refractive index of the second stacked body is higher than the refractive index of the first stacked body, but is not limited thereto.

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

  In one embodiment, the transmission color coordinate value of the L, a *, and b * values of the color difference meter of the second laminate is −7 <b * <2, but the present invention is not limited thereto.

  In one embodiment, the transparent conductive layer includes at least one selected from the group consisting of indium tin oxide (ITO), antimony tin oxide (ATO), and indium zinc oxide (IZO), but is not limited thereto. .

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

  In one embodiment, a transparent hard coat film is included on one or both surfaces of the optically transparent substrate, but the embodiment is not limited thereto.

  According to a second aspect of the present application, a plasma-enhanced chemical vapor is formed on an optically transparent substrate by adding a first laminate including an inorganic oxide and having a refractive index of 1.3 to 2.5 to a thickness of 10 nm to 300 nm. The second stacked body including an inorganic oxide different from the inorganic oxide included in the first stacked body is formed on the first stacked body to a thickness of 10 nm to 300 nm by stacking using a phase deposition method. -The manufacturing method of the transparent conductive laminated film including laminating | stacking using a reinforced chemical vapor deposition method and laminating | stacking a transparent conductive layer on the said 2nd laminated body in thickness of 10-100 nm is provided.

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

  In one embodiment, laminating the transparent conductive layer includes at least one method selected from the group consisting of vapor deposition, ion plating, sputtering, chemical vapor deposition, and plating, and a roll-to-roll process. However, the present invention is not limited to this.

  In one embodiment, the method for producing a transparent conductive laminated film further includes crystallizing the transparent conductive layer by laminating the transparent conductive layer and then heat-treating at 120 ° C. to 150 ° C., but is not limited thereto. .

  Although the 3rd side surface of this application provides the touch panel containing the said transparent conductive laminated film, it is not restricted to this.

  According to the present application, a transparent conductive material having a dense and stable structure through a process including a plasma-enhanced chemical vapor deposition method on a laminate including a two-layer structure in which a refractive index and a thickness are adjusted on an optically transparent substrate. Provided is a transparent conductive laminated film that can provide a laminated film, has high visible light transmittance, little transmission coloration, little change in surface resistance in a high temperature / high humidity environment, and high thin film durability. Can do.

  On the other hand, when a process including a roll-to-roll type plasma-enhanced chemical vapor deposition method is applied to manufacture a laminate including a two-layer structure in which the refractive index and the thickness are adjusted, other PVD processes (sputtering, electron beam) Compared with vapor deposition etc.), the film formation rate can be increased by 5 to 7 times or more, so that there is an effect that the large area productivity can be increased and the manufacturing cost can be reduced.

  Furthermore, in the touch panel including the transparent conductive laminated film having a low rate of change in surface resistance in a high temperature / humidity environment, a capacitive touch panel, a resistive film method, It can be used without limitation to various types of touch panels including touch panels.

FIG. 1 is a cross-sectional view of a transparent conductive laminated film in an embodiment of the present application. It is the graph which measured the reflectance of the transparent conductive laminated film by Example 1 of this application. 5 is a graph obtained by measuring the reflectance of a transparent conductive laminated film according to Comparative Example 1. It is the graph which measured the reflectance of the transparent conductive laminated film by Example 2 of this application. 6 is a graph obtained by measuring the reflectance of a transparent conductive laminated film according to Comparative Example 3. It is the graph which measured the reflectance of the transparent conductive laminated film by Example 2 of this application. 6 is a graph obtained by measuring the reflectance of a transparent conductive laminated film according to Comparative Example 5.

  Hereinafter, exemplary embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present application pertains can easily implement the present invention.

  However, the present application can be embodied in various different forms, and is not limited to the embodiments and examples described here. In order to clearly describe the present application in the drawings, portions not related to the description are omitted, and similar portions are denoted by similar reference numerals throughout the specification.

  Throughout this specification, when a part “includes” a component, this does not exclude other components unless specifically stated to the contrary, and further includes other components. Means you can.

  Throughout this application, if a layer or member is located "on" another layer or member, this is not only when the layer or member is in contact with the other layer or member, This includes the case where another layer or other member exists between two layers or two members.

  The terms “about”, “substantially”, etc., to the extent used throughout this specification, are expressed in or close to the numerical value when manufacturing and material tolerances inherent in the stated meaning are presented. Used in the sense and to help understand the present invention, exact or absolute numerical values are used to prevent unauthorized use of the disclosure content to which the conscientious infringer is referred. As used throughout this specification, the terms “steps” or “steps of” do not mean “steps for”.

  The first aspect of the present application is an optically transparent substrate; laminated on the optically transparent substrate to a thickness of 10 nm to 300 nm using plasma-enhanced chemical vapor deposition (PECVD), and an inorganic oxide Including a first laminate having a refractive index of 1.3 to 2.5, and a first laminate having a thickness of 10 nm to 300 nm on the first laminate using a plasma-enhanced chemical vapor deposition method. A transparent conductive laminate comprising a second laminate containing an inorganic oxide different from the inorganic oxide contained in one laminate, and a transparent conductive layer laminated to a thickness of 10 to 100 nm on the second laminate. Provide film.

  FIG. 1 is a cross-sectional view of a transparent conductive laminated film 100 in an embodiment of the present application. An embodiment of the present application will be described in detail below with reference to FIG.

  The inorganic oxide includes a metal oxide or an amphoteric metal oxide, and specific examples thereof include titanium oxide, zinc oxide, cerium oxide, and aluminum oxide. (Alumium oxide), tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide (silicon oxide), silicon oxide (silicon oxide) including one or more selected from the group consisting of antimony tin oxide and indium tin oxide. Not limited to this. In an exemplary embodiment, the inorganic oxide includes at least one selected from the group consisting of titanium oxide, silicon oxide, and zirconium oxide, but is not limited thereto. In an exemplary embodiment, in order to improve the visibility of the transparent electrode pattern, the inorganic oxide includes, but is not limited to, titanium oxide or silicon oxide.

The refractive index of the first stacked body 20 is 1.3 to 2.5, and the thickness is 10 to 300 nm, but is not limited thereto. The numerical value range includes the light behavior of the two-layer film and the multilayer laminate in the deposition process using the plasma-enhanced chemical vapor deposition method in the laminate including the first laminate 20 and the second laminate 30. However, the physical properties of the laminate must be taken into account, but the stability of the laminate material is large within the above numerical range, resulting in stress matching between the laminates, and a change in refractive index. Few. As an example of the stress matching, in the case of the first laminated body 20, titanium oxide (TiO ₂ ) is laminated to have a refractive index of about 1.46, and the second laminated body 30 is made of silicon oxide (SiO ₂ ). If the refractive index is adjusted to form a two-layer film laminate, the laminate containing titanium oxide will receive a tensile force when subjected to external stress, and will contain silicon oxide. The body has the advantage that it can receive a compressive strain to balance the force on the optically transparent substrate 10.

  The second stacked body 30 includes an inorganic oxide different from the metal oxide and / or inorganic oxide included in the first stacked body 20 and has a thickness of 10 nm to 300 nm, but is not limited thereto. In an exemplary embodiment, when the first stacked body 20 includes titanium oxide, the second stacked body 30 includes silicon oxide as a metal oxide or inorganic oxide excluding the titanium oxide. Thus, the reason for including different metal oxides and / or inorganic oxides is that, as described above, the stability of the laminate and the excellent optical transmittance can be ensured.

  In an exemplary embodiment, when the thickness of the transparent conductive layer 40 is 50 nm or more, the transparent conductive laminate including a refractive index of the second stacked body 30 that is higher than a refractive index of the first stacked body 20. Provide film, but not limited to this. When the thickness of the transparent conductive layer 40 is 50 nm or more, the high light-transmitting effect cannot be obtained unless the refractive index of the second stacked body 30 is higher than the refractive index of the first stacked body 20.

  In one embodiment, the total thickness of the first stacked body 20 and the second stacked body 30 is 50 to 350 nm, but is not limited thereto. In an exemplary embodiment, the total thickness of the first stacked body 20 and the second stacked body 30 is 90 to 310 nm, but is not limited thereto. Within the above numerical range, it is possible to ensure high stability of the laminate and excellent optical transmittance.

  The first laminated body 20 and the second laminated body 30 serve as a buffer and are affected by an impact such as humidity, heat, or film bending due to surface resistance of the transparent conductive layer 40 due to external resistance. Increases electrical stability. In addition, the high density and dense film structure of the oxide to be laminated, the role of the barrier that prevents the diffusion of organic substances such as moisture and solvent generated from the transparent resin film base material into the transparent conductor layer and the bending impact Improve the buffer function.

  In one embodiment, a transparent conductive laminated film is provided that includes the L, a *, and b * values of the color difference meter of the second laminated body 30 and the transmitted color coordinate value is −7 <b * <2. The L, a *, and b * mean a color difference table, and the L value represents lightness and is displayed from 0 to 100. The a * and b * are a plane coordinate system such as an xy coordinate system, the horizontal axis represents the a * value, the vertical axis represents the b * value, + a is red, and -a is Represents green, + b indicates yellow, and -b indicates blue. In an exemplary embodiment of the present application, there is provided a transparent conductive laminated film including transmission color coordinate values of L, a *, b * values of the color difference meter of −5 <b * <3. Within the numerical range, it is possible to embody the complete transmittance and color coordinate value of the transparent conductive laminated film, and the local minimum reflectance wavelength of the surface of the two-layer laminate having different refractive indexes is 350 to In the case where the refractive index and thickness of the laminate are adjusted and the deposition is performed using the plasma-enhanced chemical vapor deposition method, the numerical value of the transmission color coordinate value of the color difference meter can be obtained. Within the range, the reflection of purple light or blue light can be reduced, and the coloring of transmitted light can also be reduced.

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

  In one embodiment, the optically transparent substrate 10 includes a plastic film, and the thickness of the optically transparent substrate is 25 to 350 μm, but is not limited thereto. Therefore, it is desirable from the viewpoint of transparency and productivity of the transparent conductive laminated film within the range of the thickness of the optically transparent substrate. The optically transparent base material 10 includes a base material that can be appropriately selected by those skilled in the art as long as the thickness of the base material is an optically transparent substance that can ensure transparency. . In an exemplary embodiment, the optically transparent substrate 10 may be made of, for example, glass, polyethylene terephthalate (PET), polybutylene terephthalate, polycarbonate, poly (methyl methacrylate) copolymer (poly (methyl methacrylate) copolymer). poly (methylmethacrylate) copolymer), triacetyl cellulose (triacetyl cellulose), polyolefin (polyolefin), polyamide (polyamide), poly (vinyl chloride) (poly (chloro chloride)) and amorphous polyolefin (poly polyolefin). Including a substrate comprising one or more selected from the group consisting in), it is not limited thereto. The form of the optically transparent substrate 10 is a sheet, a plate, or a thin film, but is not limited thereto.

  In one embodiment, the optically transparent substrate 10 includes a transparent hard coat film on at least one surface thereof, but is not limited thereto. In order to improve the surface hardness and bendability of the optically transparent substrate, the thickness of the transparent hard coat film is 2 to 15 μm, but is not limited thereto. In the exemplary embodiment, it is 3 to 15 μm, but is not limited thereto. The hard coat film is a curable resin including at least one selected from the group consisting of a melanin resin, a urethane resin, an alkyd resin, an acrylic resin, and a silicone resin, but is not limited thereto.

  According to a second aspect of the present application, a plasma-enhanced chemical vapor is formed on an optically transparent substrate by adding a first laminate including an inorganic oxide and having a refractive index of 1.3 to 2.5 to a thickness of 10 nm to 300 nm. The second stacked body including an inorganic oxide different from the inorganic oxide included in the first stacked body is formed on the first stacked body to a thickness of 10 nm to 300 nm by stacking using a phase deposition method. -The manufacturing method of the transparent conductive laminated film including laminating | stacking using a reinforced chemical vapor deposition method and laminating | stacking the transparent conductive layer 40 on the said 2nd laminated body in thickness of 10-100 nm is provided.

In one embodiment, the plasma-enhanced chemical vapor deposition includes a roll-to-roll plasma-enhanced chemical vapor deposition, but is not limited thereto. The plasma-enhanced chemical vapor deposition method can form a dense and uniform film having a high density and purity. On the other hand, when the deposition rate is easily adjusted and deposited on the optical substrate film at a low temperature, it can be manufactured at low cost. The plasma-enhanced chemical vapor deposition method is applied by optimizing hydrodynamic elements such as temperature distribution and flow of reaction gas depending on the position of the reactor and heat transfer elements in order to obtain an optimal uniform film quality. be able to. In an exemplary embodiment, a reactant is activated through a plasma ion source that generates plasma by supplying high electrical energy to the gas at a low pressure, and the activated reactant gas is supplied to the reactor. The desired film can be formed at a low temperature by moving to induce a phase change on the optically transparent substrate. In an exemplary embodiment, when the precursor used at this time forms a laminate including titanium oxide, the precursor including titanium oxide is used by using titanium ethoxide or titanium tetrachloride. When forming a body, TMDSO (tetramethyldisiloxane) + O ₂ or SiH ₄ + O ₂ is used as a reaction precursor, but is not limited thereto. Meanwhile, the plasma-enhanced chemical vapor deposition method includes a roll-to-roll method, but is not limited thereto. The lamination of the first laminate and the second laminate through the plasma-enhanced chemical vapor deposition method has a fast film formation time, and the denseness and uniform distribution of the inorganic oxide of the laminate after the film formation. Through this, a continuous continuous production of the transparent conductive laminated film is possible including a roll-to-roll system.

  In one embodiment, laminating the transparent conductive layer includes at least one method selected from the group consisting of vapor deposition, ion plating, sputtering, chemical vapor deposition, and plating, and a roll-to-roll process. However, the present invention is not limited to this.

  In one embodiment, the method for producing a transparent conductive laminated film further includes crystallizing the transparent conductive layer by laminating the transparent conductive layer and then heat-treating at 120 ° C. to 150 ° C., but is not limited thereto. . In an exemplary embodiment, the heat treatment further includes heat treatment at 120 ° C. to 150 ° C. for about 90 minutes, but is not limited thereto.

  Although the 3rd side surface of this application provides the touch panel containing a transparent conductive laminated film, it is not restricted to this. The touch panel is a capacitive touch panel, but is not limited thereto, and can be applied to a resistive touch panel. In an exemplary embodiment, the transparent conductive laminated film is used as a panel plate, and an indium tin oxide (ITO) thin film is formed on the glass plate as the other panel plate, and then both panels are formed using transparent conductive glass. The touch panel as the switch structure is manufactured by arranging the plates so that the indium tin oxide thin films face each other with a spacer interposed therebetween, but the invention is not limited to this.

  Hereinafter, the present application will be described more specifically using examples, but the present application is not limited thereto.

Production of First Laminate A GPi PECVD modulator was used as a plasma enhanced chemical vapor deposition facility in which a large area PECVD linear source was applied to one surface of a transparent resin film substrate made of a PET film having a thickness of 125 um.

PET was injected into the PECVD chamber, power was applied from a 40 kHz AC generator to the plasma ion source in the chamber maintained at a vacuum of 1 to 20 mtorr, and titanium tetrachloride (PE) was used as a reaction precursor (Precusor). It was injected into the reactor to induce phase variation on the substrate to form a 34 nm thick TiO ₂ film having a refractive index of 2.32.

Lamination of Second Laminate As a method for producing the first laminate, TMDSO and atmospheric gas O ₂ are injected into the PECVD reactor as a reaction precursor (Precusor) on the first laminate, and a refractive index of 1 A second laminate having a 61 nm thick SiO ₂ film having a thickness of .45 was formed.

Lamination of Transparent Conductive Layer A film on which the second laminate was formed was injected into a sputtering chamber and formed by RF magnetron sputtering. The target was a 95 wt% indium oxide sintered body containing 5 wt% tin monoxide, and the initial vacuum of the chamber was maintained at 5.0 × 10 ⁻⁵ torr, and argon gas was 80% and oxygen gas was 20%. A transparent conductive laminated film was manufactured by laminating an ITO film as a 25 nm-thick transparent conductive layer having a refractive index of 2.05 in a 4.0 × 10 ⁻³ torr atmosphere under pressure.

<Comparative Example 1>
In order to fix the thickness of the transparent conductive layer to 25 nm, and to investigate the transmittance and transmission color due to the structure of the intermediate layer, and the reliability due to the high temperature and high humidity environment, TiO ₂ that is the first laminate is not formed. Except for the above, a transparent conductive laminated film having an 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 investigate the thickness and resistance change of the transparent conductive layer, and the difference between the transmittance and the transmission color value due to the difference in refractive index, the first and second laminates were formed through a vacuum deposition (Electron Beam Evaporation) process. .

A PET film having a thickness of 125 μm is injected into the vapor deposition chamber, the chemicals of the first laminate (TiO ₂ ) and the second laminate (SiO ₂ ) are respectively injected into the electron beam crucible, and an initial vacuum is set to 6. While maintaining an electron beam of 0 × 10 ⁻⁶ torr, oxygen gas was injected to increase the reactivity of the inorganic oxide. The operation was carried out at 5.0 × 10 ⁻⁵ torr, which is an optimized oxygen partial pressure of the inorganic oxide optical thin film.

A 66 nm thick TiO ₂ film having a refractive index of 2.16 and a 43 nm SiO ₂ film having a refractive index of 1.43 were produced. A transparent conductive laminated film was manufactured in the same manner as in Example 1 with respect to the thickness and formation method of ITO.

  The transmittance, color coordinate value, sheet resistance, reliability, and the like of the transparent conductive laminated film manufactured according to Example 1 according to an example of the present application are measured. Is shown in the following [Table 1].

<Measuring method of average transmittance and color coordinate value>
The transmittance of the transparent conductive laminated film according to one embodiment of the present application is measured together with a comparative example. The transmittance is measured using a Hitachi U4300 spectrophotometer, and the CIE color coordinate measurement method and the D75 source are measured. Each was measured using.

<Measurement of surface resistance and resistance change rate>
After measuring the surface resistance Ro (ohm / cm ² ) of the ITO surface of the transparent conductive laminated film that was measured using the 4-terminal method and left at room temperature, it was placed in a heating chamber and an atmosphere of 60 ° C. and 95% humidity After being allowed to stand for 240 hours, the ITO sheet resistance R was measured to determine the sheet resistance change rate (R / Ro), and the reliability of high temperature and high humidity was evaluated.

<Method for measuring refractive index and thickness of thin film>
A phase modulation spectroscopic ellipsometer was used to measure the refractive index and thickness of the TiO ₂ and SiO ₂ and ITO films formed in each layer.

As can be confirmed from the above [Table 1], the reliability (R / Ro) of the ITO sheet resistance as a transparent laminate with respect to high temperature and high humidity (R / Ro) in Example 1 is two intermediate layers (first laminate and first laminate). 2 layer) is formed by PECVD, but has superior characteristics to Comparative Example 1 in which only a single intermediate layer is formed by PECVD and Comparative Example 2 in which a two-layer intermediate is formed by an electronic beer deposition process. I understand that As mentioned above, it can be seen that the surface tension of the ITO film can be stabilized by the TiO ₂ and SiO ₂ layers corresponding to the tensile force and the contraction force against the external thermal shock, respectively.

  In addition, the first laminated body and the second laminated body, which are intermediate layers formed by an electron beam, show a result that is weak against heat and moisture shock due to a low density and a loose film structure. It is confirmed that the first laminate and the second laminate having a high density and a dense film structure through the PECVD process of Example 1 as an example have very excellent reliability characteristics against external impacts such as heat and moisture. it can.

  2a is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Example 1 of the present application, and FIG. 2b is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Comparative Example 1.

  As can be seen from Table 1 and FIGS. 2a and 2b, in Comparative Example 1, although there is a fine difference in numerical values of transmission coloring compared to Example 1 according to one example of the present application, low visible light transmittance is low. Since the value is expressed, it can be confirmed that it is unsuitable for use in a capacitive touch panel that requires a high transmittance value.

  In Comparative Example 2, it can be seen that the transmittance value is the same as that in Example 1 according to one example of the present application, but the b * value indicating transmission coloring (yellow) is relatively high.

  Furthermore, comparing FIG. 2a and FIG. 2b, it can be confirmed that the reflectance in the visible light region band is lower in the case of Example 1 according to the embodiment of the present application than in Comparative Example 3, especially in the 550 nm wavelength band. It can be confirmed that the light transmittance of the present application is high.

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

<Comparative Example 3>
In order to fix the thickness of the transparent conductive layer as in Example 2 and investigate the change in transmittance and transmission coloration due to the structure of the intermediate floor, the thickness of SiO ₂ as the second laminate was changed to 24 nm. A transparent conductive laminated film was produced in the same manner as in Comparative Example 1 except that.

<Comparative example 4>
In Comparative Example 2, the TiO ₂ layer as the first laminate, the SiO ₂ layer as the second laminate, and the ITO as the transparent conductive layer were compared with the thicknesses of 67 nm, 25 nm, and 40 nm, respectively. A transparent conductive film was produced in the same manner as in Example 2.

  The transmittance and color coordinate value of the transparent conductive laminated film manufactured according to Example 2 according to one example of the present application were measured, and the results are shown in the following [Table 2] together with Comparative Example 3 and Comparative Example 4. expressed.

  3a is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Example 2 of the present application, and FIG. 3b is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Comparative Example 3.

  [Table 2], FIG. 3a and FIG. 3b show that in Comparative Example 3, there is a fine difference in transmission coloring values compared to Example 2 according to one example of the present application, but a low visible light transmittance value. Therefore, it can be confirmed that it is unsuitable for use in a capacitive touch panel that requires a high transmittance value.

  In Comparative Example 4, it is understood that the b * value indicating the transmission coloring (yellow) is relatively high, although the transmittance value is the same as that in Example 1 according to one example of the present application.

  Further, comparing FIG. 3a and FIG. 3b, it can be confirmed that the reflectivity in the visible light region band is lower in the case of the second embodiment according to one embodiment of the present application than in the comparative example 5, particularly in the 550 nm wavelength band. It can be confirmed that the light transmittance of the present application is high.

  When the thickness of the transparent conductive layer (ITO; refractive index 20.5) is 50 nm or more, in the case of the first laminate and the second laminate formed on the PET as an optically transparent resin, the second laminate The refractive index is required to be higher than the refractive index of the first laminate.

A first laminated body is manufactured by laminating a SiO ₂ layer having a refractive index of 1.45 on PET to a thickness of 282 nm, and TiO ₂ having a refractive index of 2.32 is formed on the first laminated body to 57 nm. Laminated and laminated with the thickness of the transparent conductive layer being 70 nm to produce a transparent conductive laminated film.

<Comparative Example 5>
In order to fix the thickness of the transparent conductive layer in the same manner as in Example 3 and investigate the change in transmittance and transmission coloration due to the structure of the intermediate layer, the thickness of SiO ₂ as the second laminate was changed to 55 nm. A transparent conductive laminated film was produced in the same manner as in Comparative Example 1 except that.

<Comparative Example 6>
In Comparative Example 2, a comparison was made except that the thicknesses of the SiO ₂ layer as the first laminate, the TiO ₂ layer as the second laminate, and the ITO layer as the transparent conductive layer were 288 nm, 64 nm, and 70 nm, respectively. A transparent conductive film was produced in the same manner as in Example 2.

  The transmittance and color coordinate value of the transparent conductive laminated film manufactured according to Example 3 according to an example of the present application were measured, and the results are shown in the following [Table 3] together with Comparative Example 5 and Comparative Example 6. expressed.

  4a is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Example 2 of the present application, and FIG. 4b is a graph obtained by measuring the reflectance of the transparent conductive laminated film according to Comparative Example 5.

  According to [Table 3] and FIGS. 4a and 4b, in Comparative Example 5, although there is a fine difference in transmission coloring values compared to Example 3 according to one example of the present application, a low visible light transmittance value is obtained. Therefore, it can be confirmed that it is unsuitable for use in a capacitive touch panel that requires a high transmittance value.

  In the comparative example 6, it can be seen that the b * value indicating the transmission coloring (yellow) is relatively high, although the transmittance value is the same as that of the embodiment 1 according to the embodiment of the present application.

  Furthermore, comparing FIG. 4a and FIG. 4b, it can be confirmed that the reflectivity in the visible light region band is lower in the case of Example 3 according to the embodiment of the present application than in Comparative Example 5, particularly in the 550 nm wavelength band. It can confirm that it is low, and it can confirm that the light transmittance of this application is high through this.

  The results of Examples 1 to 3 as one example according to the present application show that the present application is very excellent in securing high transmittance, low transmission coloring, and reliability characteristics with respect to the external environment of high temperature and high humidity. To express.

  The present invention has been described in detail with reference to the embodiments and examples. However, the present invention is not limited to the embodiments and examples, and can be modified in various forms. It is apparent that many variations are possible by those having ordinary knowledge in the field.

DESCRIPTION OF SYMBOLS 10: Optically transparent base material 20: 1st laminated body 30: 2nd laminated body 40: Transparent conductive layer 100: Transparent conductive laminated film

Claims (12)

An optically transparent substrate;
The plasma-enhanced chemical vapor deposition (PECVD) is used to deposit a thickness of 10 nm to 300 nm on the optically transparent substrate, includes an inorganic oxide, and has a refractive index of 1.3 to 2.5. A first laminate;
A second layer containing an inorganic oxide different from the inorganic oxide included in the first stacked body and stacked to a thickness of 10 nm to 300 nm on the first stacked body using a plasma-enhanced chemical vapor deposition method. A laminate,
A transparent conductive laminated film comprising: a transparent conductive layer laminated to a thickness of 10 to 100 nm on the second laminate.   2. The transparent conductive laminated film according to claim 1, wherein when the thickness of the transparent conductive layer is 50 nm or more, the refractive index of the second laminated body is higher than the refractive index of the first laminated body.   The transparent conductive laminated film according to claim 1 or 2, wherein a total thickness of the first laminated body and the second laminated body is 50 to 350 nm.   4. The method according to claim 1, wherein the transparent conductive layer includes at least one selected from the group consisting of indium tin oxide (ITO), antimony tin oxide (ATO), and indium zinc oxide (IZO). 5. The transparent conductive laminated film as described.   The transparent conductive laminated film according to any one of claims 1 to 4, wherein the optically transparent substrate includes glass or a plastic film, and the thickness of the optically transparent substrate is 25 um to 350 um.   6. The transparent conductive material according to claim 1, wherein the color coordinate value of the color difference meter of the second laminated body is -7 <b * <2 in terms of L, a *, b * values. Laminated film.   The transparent conductive laminated film according to claim 1, wherein the optically transparent substrate includes a transparent hard coat film on one surface or both surfaces. Using a plasma-enhanced chemical vapor deposition method, a first laminate including an inorganic oxide and having a refractive index of 1.3 to 2.5 is formed on an optically transparent substrate to a thickness of 10 to 300 nm. Laminated,
A plasma-enhanced chemical vapor deposition method is applied to a second stacked body including an inorganic oxide different from the inorganic oxide included in the first stacked body to a thickness of 10 nm to 300 nm on the first stacked body. And laminated
A method for producing a transparent conductive laminated film, comprising: laminating a transparent conductive layer on the second laminate to a thickness of 10 to 100 nm.   The method for producing a transparent conductive laminated film according to claim 8, wherein the plasma-enhanced chemical vapor deposition method includes a roll-to-roll plasma-enhanced chemical vapor deposition method.   Laminating the transparent conductive layer is performed by using one or more methods selected from a group consisting of a vapor deposition method, an ion plating method, a sputtering method, a chemical vapor deposition method, and a plating method, and a roll-to-roll process. The manufacturing method of the transparent conductive laminated film of Claim 8 or 9 including forming a transparent conductive layer continuously.   The method for producing a transparent conductive laminated film according to any one of claims 8 to 10, further comprising crystallizing the transparent conductive layer by laminating the transparent conductive layer at 120 ° C to 150 ° C. .   The touch panel containing the transparent conductive laminated film as described in any one of Claim 1 to 7.

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