TW201115594A - Transparent electrically conductive film and touch panel using the same - Google Patents

Abstract

The present invention provides transparent electrically conductive film, which, when used in the front side of display, such as high definition liquid-crystal display and the like, as electrode film of touch panel has excellent recognition as well as excellent productivity and excellent pen sliding durability near its frame and a touch panel using the same. Provided is transparent electrically conductive film obtained by laminating high refractive index layer, low refractive index layer and transparent electrically conductive film layer on substrate made from transparent plastic film in this order, characterized by that the high refractive index layer is made out of inorganic film made from noncrystalline In-Sn complex oxide having tin oxide content ratio of 10 to 60 mass%; low refractive index layer is made out of inorganic film having refractive index of 1.30 to 1.60; transparent electrically conductive film layer is made out of inorganic film having refractive index of 1.80 to 2.20; a peak of the spectral transmittance of transparent electrically conductive film is at 450 nm to 530 nm; an entire light transmittance is not less than 90%; and the color b value is -2 to 2.

Description

201115594 6. Technical Field of the Invention The present invention relates to a method in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order on a substrate made of a transparent plastic film. A transparent conductive film or a transparent conductive sheet (hereinafter also referred to as a transparent conductive film) and a touch panel using the same. In particular, when a thin film for a touch panel of a display body such as a high-definition liquid crystal display is incorporated, the visibility is excellent and the pen sliding durability in the vicinity of the frame edge of the touch panel is excellent, so that the transparent display area can be expanded. Conductive film and touch panel using the same. [Prior Art] A transparent conductive film in which a transparent and low-resistance film is laminated on a substrate made of a transparent plastic film is widely used for its use in conductivity, such as liquid crystal display or electric excitation. Light (sometimes slightly EL) Uses in the electrical and electronic fields, such as flat-panel displays such as displays, or transparent electrodes of touch panels. In recent years, touch panels have been widely recognized as input interfaces, and particularly mobile terminal devices such as mobile information terminals, digital cameras, and digital cameras, and a housing for mounting a touch panel has been added to the display in order to omit the operation keys. On the other hand, the display quality of liquid crystal displays and the like for such mobile terminals has been increasing, and it is strongly expected that the visibility of the electrode film for touch panels incorporated in front of such a display body will not be lowered. . In other words, when the transmittance of the electrode film is low, the brightness of the display body such as a liquid crystal display is lowered and the display screen is darkened, so that it becomes difficult to view. Moreover, when the electrode film of the 201115594 is colored, the display color of the display color (especially white) of the liquid crystal display or the like is changed, and it becomes difficult to obtain a clear image. Therefore, it is expected that the transmittance of the electrode film is high and the coloring is small. On the other hand, it is expected that a display body such as a liquid crystal display will be enlarged. Therefore, the frame area (frame edge) including the display for display is narrower, and the frame edge is also expected to be narrower as the touch panel, and the vicinity of the frame edge of the touch panel is not stored in the frame to form the display. The state of the district. In the touch panel, a pair of transparent conductive substrates having a transparent conductive layer are disposed such that a transparent conductive layer faces each other with a spacer interposed therebetween. When the pen input is performed on the touch panel, the transparent conductive film on the fixed electrode side and the transparent conductive film on the movable electrode (thin film electrode) side are in contact with each other, but in particular, in the vicinity of the frame edge, the transparent conductive film on the movable electrode side Strong bending stress caused by the applied pen load. Therefore, it is desired that the transparent conductive film does not cause cracking or peeling or the like, and the transparent conductive film having excellent pen sliding durability in the vicinity of the frame edge is not caused by the strong bending stress caused by the application of the pen load. In order to improve the visibility, it has been proposed to laminate a layer having a different refractive index for use in antireflection processing or the like, and to use optical interference. In other words, it has been proposed to provide a layer having a refractive index difference between the transparent conductive film and the base film, and to use optical interference (Patent Documents 1 to 3). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The film system can be changed to 201115594. The visibility is good but the environmental stability or the pen sliding durability near the frame edge of the touch panel is problematic. In other words, as described in the first embodiment of Patent Document 1, a film having a low tin content with respect to indium formed after evacuating the vacuum chamber to a high vacuum state is used as a high refractive index layer in film formation or In the manufacturing process of the touch panel, the ITO film is likely to cause crystallization due to the related heat treatment. A transparent conductive film having an ITO film thus crystallized as a high refractive layer or a transparent conductive layer is used as a touch panel as an electrode film, and the pen sliding durability near the frame edge of the touch panel is poor. . Further, the touch panel of the transparent conductive film used as the high refractive layer of the titanium oxide film described in Patent Document 2 has a problem that an input position shift occurs when it is used outdoors. In addition, when the indium oxide film containing tin oxide and yttrium oxide described in Patent Document 3 is used as a high refractive index layer, since it contains a ruthenium oxide and becomes a hard and brittle film, the pen slip near the frame edge of the touch panel. Insufficient durability, and the film formation speed is slow, and the productivity is lowered. [Explanation] [Problems to be Solved by the Invention] That is, the object of the present invention is to provide a transparent conductive film and use the same in view of the above conventional problems. When used as an electrode film for a touch panel in front of a display body such as a high-definition liquid crystal display, the touch panel is excellent in visibility, excellent in productivity, and pen sliding durability near the frame edge (edge Excellent durability). [Means for Solving the Problem] The present invention has been made in view of the above circumstances, and the transparent conductive film and the touch panel which can solve the above problems are formed by the following constitution. 201115594 1. A transparent conductive film which is a transparent conductive film formed by laminating a high refractive index layer, a low refractive index layer and a transparent conductive film layer on a substrate made of a transparent plastic film. The high refractive index layer is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 1 〇 to 60% by mass, and the low refractive index layer is composed of an inorganic having a refractive index of 1.3 0 to 1.60. The transparent conductive film layer is composed of an inorganic film having a refractive index of 1.80 to 2.20, and the peak of the spectral transmittance of the transparent conductive film is 450 to 530 nm, and the total light transmittance is 90% or more. The color b値 is -2 to 2. 2. The transparent conductive film according to the above 1, wherein the high refractive index layer has a tin oxide content of 20 to 60% by mass. 3. The transparent conductive film according to the above 1. or 2. wherein the opposite surface of the surface of the substrate composed of the transparent plastic film laminated with the transparent conductive film layer is subjected to a low reflection treatment. 4. A transparent conductive sheet characterized in that the transparent conductive film of any one of the above-mentioned 1 to 3 is laminated on the opposite side of the surface of the transparent conductive film layer, and the transparent resin is bonded to the transparent resin Sheet. 5. A touch panel is a touch panel in which a pair of panels having a transparent conductive film layer are disposed with a transparent conductive film layer facing each other via a spacer, and at least one of the panels is characterized by The transparent conductive film or the transparent conductive sheet according to any one of the above 1 to 4. [Effect of the Invention] The transparent conductive film of the present invention is formed on a 201115594 substrate composed of a transparent plastic film, and has a structure in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in order. Since the peak of the transmittance is in a specific wavelength region, even if it is disposed in front of the high-definition display, the deterioration of visibility can be suppressed. Further, the high refractive index layer is a layer composed of an amorphous indium-tin composite oxide having a predetermined content of tin oxide, whereby the productivity is excellent and the mechanical strength against bending is improved. Therefore, when the pen sliding test is performed in the vicinity of the frame edge of the touch panel, the transparent conductive film is less likely to be peeled and cracked, and has the advantage of improving the durability of the pen sliding in the vicinity of the frame edge. [Embodiment] The transparent conductive film of the present invention is a transparent conductive film in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order on a substrate made of a transparent plastic film. . The following is a detailed description of each layer. (Substrate composed of a transparent plastic film) The substrate made of the transparent plastic film used in the present invention is required to be extended in the longitudinal direction and/or the width direction after the organic polymer is melted or extruded. Cooled, heat-fixed film. Examples of the organic polymer include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polypropylene terephthalate, nylon 6, and resistant. Polyester 4, nylon 66, nylon 12, polyimine, polyamidamine, polyether sulfur, polyetheretherketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, poly Partially dichloroethylene, polyvinyl alcohol, polyether phthalimide, polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, norbornene-based polymer, and the like. 201115594 Among these organic polymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, syndiotactic polystyrene, norbornene The polymer 'polycarbonate, polyarylate, etc. are suitable. Further, these organic polymers may be copolymerized with a small amount of monomers of other organic polymers, and other organic polymers may be mixed. The thickness of the base material composed of the transparent plastic film used in the present invention is preferably in the range of more than ΙΟμηη and 300 μmη, and the upper limit 値 is 260 μm, and the lower limit 値 is 7 〇 μηη. When the thickness of the plastic film is 1 〇μηη or less, the mechanical strength is insufficient. In particular, when the touch panel is used for a touch panel, the deformation of the pen input tends to be large, and it tends to be insufficient in durability. On the other hand, when the thickness exceeds 300 μm, when the touch panel is used, it is necessary to increase the pen load in order to deform the film. Therefore, the load applied to the transparent conductive film is inevitably increased, and the durability of the transparent conductive film is not good. The substrate made of the transparent plastic film used in the present invention is subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and the like, as long as the object of the present invention is not impaired. Surface activation treatment such as ozone treatment is also possible. In the present invention, the adhesion between the substrate and the transparent conductive thin film layer is improved, pen input durability, drug resistance, and prevention of precipitation of low molecular weight substances such as oligomers are performed. A cured layer containing a curable resin as a main component may be provided between the film layers. The curable resin is not particularly limited as long as it is cured by energy application such as heating, ultraviolet irradiation, or electron beam irradiation, and examples thereof include polyfluorene oxide resin, acrylic resin methacrylate resin, and epoxy resin. .201115594 Melamine resin, polyester resin, urethane resin, etc. From the viewpoint of productivity, a curable resin containing an ultraviolet curable resin as a main component is preferred. Examples of such an ultraviolet curable resin include a polyfunctional acrylate resin of acrylic acid or methacrylic acid ester of a polyhydric alcohol, a diisocyanate, a polyhydric alcohol, and a hydroxyalkyl ester of acrylic acid or methacrylic acid. A polyfunctional urethane acrylate resin or the like. If necessary, a monofunctional monomer such as vinylpyrrolidone, methyl methacrylate, styrene or the like may be added to the polyfunctional resin to be copolymerized. Further, in order to improve the adhesion between the transparent conductive film and the cured layer, it is effective to surface-treat the cured layer. Specific examples of the method include a discharge treatment method using irradiation of glow or corona discharge, a method of increasing a carbonyl group, a carboxyl group, or a hydrocarbon group, a chemical treatment method using an acid or a base treatment, and a polar group such as an amine group, a hydroxyl group, or a carbonyl group. Method, etc. The ultraviolet curable resin is usually used by adding a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and a known compound which absorbs ultraviolet rays to generate a radical is used. Examples of such a photopolymerization initiator include various benzoin, benzophenone, and benzophenone. The amount of the photopolymerization initiator to be added is preferably 1 to 5 parts by mass based on 1 part by mass of the ultraviolet curable resin. The concentration of the resin component in the coating liquid can be appropriately selected in consideration of the viscosity of the coating method and the like. For example, the ratio of the total amount of the ultraviolet curable resin and the photopolymerization initiator in the coating liquid is usually 20 to 80% by mass. Further, in the coating liquid, it is also possible to add other well-known additives as necessary.

LSI -10- 201115594 A coating agent such as a polysiloxane surfactant or a fluorine surfactant. In the present invention, the prepared coating liquid is applied onto a substrate composed of a transparent plastic film. The coating method is not particularly limited, and a conventional method such as a hard coating method, a gravure coating method, or a reverse roll coating method can be used. Further, the thickness of the cured layer is preferably in the range of 〇.1 to 15 μη. The lower limit 厚度 of the thickness of the cured layer is preferably 0.5 μηη, particularly preferably Ιμιη. Further, the upper limit of the thickness of the cured layer is preferably ΙΟμηη, particularly preferably 8 μm. When the thickness of the cured layer is less than 0.1, since the crosslinked structure cannot be formed sufficiently, the pen input durability or chemical resistance is liable to be lowered, and the adhesion due to the low molecular weight of the oligomer or the like is likely to occur. reduce. On the other hand, when the thickness of the cured layer exceeds 15 μm, the productivity tends to decrease. (High refractive index layer) The high refractive index layer in the present invention is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 10 to 60% by mass. More preferably, the content of tin oxide is 20 to 50% by mass, and more preferably 30 to 45% by mass. The high refractive index layer has at least a layer having a refractive index of a lower refractive index layer (refractive index of 1.3 to 1.60). The interference effect of light can be obtained by forming a layer having a refractive index of a lower refractive index layer on a transparent plastic film substrate. In general, TiO 2 , Nb 2 05, and 203 203 are used as the high refractive index layer. However, when a film of TiO 2 and Nb 20 5 is formed by sputtering, for example, the film formation rate is slow and the productivity is lowered. Therefore, from the viewpoint of productivity, indium oxide is preferred as the high refractive index layer. However, indium-tin composite oxidation [Si -11-201115594 film] having a low content of Ιι 203 or tin oxide is formed, although it is excellent in productivity, but is subjected to heat treatment in sputtering film formation or touch panel manufacturing engineering. The high refractive index layer is crystallized. In a touch panel manufactured using a transparent conductive film crystallized with a high refractive index layer, the pen sliding durability in the vicinity of the frame edge is poor. Therefore, it is preferred that no crystal grains are present in the high refractive index layer. Specifically, it is preferred that no crystal grains are observed in the measurement described in the column of the examples. Therefore, the high refractive index layer used in the present invention is composed of an indium-tin composite oxide in terms of productivity, and the content of tin oxide is 10 to 60% by mass. When the content of tin oxide is less than 1% by mass, it is difficult to suppress crystallization due to heat treatment in film formation or in a touch panel manufacturing process. On the other hand, when the content of tin oxide is more than 60% by mass, it is difficult to increase the target density, and abnormal discharge is likely to occur during production, which is not preferable from the viewpoint of productivity. In addition, even if the content of tin oxide is in the range of 1 〇 to 60% by mass, there is a case where crystallization occurs due to film formation conditions in a region where the content of tin oxide is low. In particular, when the ratio of the water pressure to the inert gas is low, crystallization is easy. In the case where the content of the tin oxide is low (e.g., 20% by mass or less), in particular, by increasing the ratio of the water pressure to the inert gas, crystallization can be suppressed. The ratio of the water partial pressure to the inert gas is preferably in accordance with the content of the tin oxide. However, for example, when the tin content is 10% by mass, 3x1 0_3 or more is preferable. In order to increase the ratio of the water pressure to the inert gas, the method of increasing the water content of the film by adjusting the vacuum exposure conditions before film formation, the method of making the film temperature high during film formation, and the method of intentionally introducing water vapor are mentioned. Any method. In addition, since the moisture content of the base film to be used is about the same, it is necessary to take the test [S1 -12-201115594 to determine the appropriate conditions. Further, crystallization can be suppressed by lowering the partial pressure ratio of oxygen. The film thickness of the high refractive index layer used in the present invention is preferably 35 to 50 nm, more preferably 38 to 48 nm. When it exceeds 50 nm, the high refractive index layer is easily crystallized during film formation or after heat treatment. Further, when it is less than 35 nm, it is difficult to improve the optical characteristics of the transparent conductive film. Further, the refractive index of the high refractive index layer is preferably from 1.70 to 2.50, more preferably from 1.90 to 2.30, particularly preferably from 1.90 to 2.10. As a film forming method of the high refractive index layer in the present invention, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the required film thickness. However, from the viewpoint of reducing film thickness unevenness, sputtering is preferred. In the sputtering method, there are generally a reactive sputtering method in which a reactive gas is introduced from a metal target to form a metal oxide, and a method of producing a metal oxide from an oxide target. In order to suppress the unevenness of the film thickness, it is preferred to use an oxide target. In order to suppress the influence on the conductivity of the transparent conductive film interposed between the low refractive index laminated layers, the high refractive index layer used in the present invention is preferably an insulator. Specifically, it is 1 Μ 06 Ω/□ or more. Therefore, when the indium-tin composite oxide layer is formed, it is preferred to set the reactive gas to a flow rate of 1.5 to 5 times the gas flow rate when the surface resistance 値 is the minimum 。. When it is less than 1.5 times, it is difficult to set the surface resistance 値 to the above range. In addition, when a gas flow rate exceeding 5.0 times is passed, a film having a stoichiometric ratio or higher in the film or a film having a large damage due to generation of an excess of oxygen anion is likely to be formed, and an unstable film is formed, which is lowered. Stability of transparent conductive film after environmental experiment" Therefore, in order to obtain stability in high temperature and high humidity environment (85 °C, 85% RH, 1000 r > L ^ i -13 - 201115594 hours), the gas flow rate It is preferable to set the surface resistance 値 to 1.5 to 3 times the gas flow rate which is the minimum enthalpy, and therefore the content of the tin oxide is preferably 20 to 60% by mass. When the amount is less than 20% by mass, the above gas flow rate is difficult to achieve a surface resistance 1 of 1 × 〇 6 ω / □ or more. (Low Refractive Index Layer) The refractive index of the low refractive index layer in the present invention is preferably from 1.30 to 1.60, more preferably from 1.4 to 1.50. Specifically, a transparent metal oxide such as Si 02 or Α12〇3, or SiO 2 may be mentioned. When the refractive index of the layer composed of the composite metal oxide such as Al203 is less than 1.30, the low refractive index layer becomes a porous film, and the electrical properties of the transparent conductive thin film layer formed thereon are inhibited. On the other hand, when the refractive index is more than 1.60, it is difficult to satisfy the above optical characteristics. The film thickness of the low refractive index layer can be appropriately selected as long as it satisfies the spectral transmittance, total light transmittance, and color 范围 of the scope of the invention of the present application. For example, the case of the Si〇2 film is preferably 45 to 60 nm, more preferably 50 to 58 nm. When the thickness exceeds 60 nm, the light transmittance of the transparent conductive film is improved, but coloring occurs to cause the spectral transmittance and the color b値 to deviate from the target. On the other hand, in the case of less than 45 nm, it is difficult to obtain the total light transmittance of the target. As a film forming method of the low refractive index layer in the present invention, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and the above method can be suitably used in accordance with the required film thickness. From the viewpoint of reducing film thickness unevenness, sputtering is preferred. Reactive DC or AC sputtering is generally used when forming by sputtering. In order to increase the film formation speed, resistance control for controlling the flow rate of the reactive gas is used to keep the voltage 値 of the DC or AC power source constant, or plasma irradiation method for controlling the flow rate of the reactive gas is used to make the electric element of the specific element m - 14 - 201115594 The luminous intensity in the slurry remains constant. (Transparent Conductive Thin Film Layer) The transparent conductive thin film layer of the present invention is composed of an inorganic thin film having a refractive index of 1.80 to 2.20. An inorganic film of 1.9 0 to 2.10 is more preferably an inorganic film of 1.93 to 2.05. When the refractive index of the transparent conductive film is less than 1.8, it is difficult to form a transparent conductive thin film layer having good conductivity. On the other hand, when the refractive index is more than 2.20, it is difficult to form a transparent conductive thin film layer having good conductivity, and further, the reflection at the interface between the air and the transparent conductive thin film layer becomes large, and it is difficult to satisfy the optical characteristics described above. Specific examples thereof include indium oxide, tin oxide, zinc oxide, indium-tin complex oxide, tin-bismuth composite oxide, and zinc-aluminum composite oxide 'indium-zinc composite oxide. Further, in order to adjust the refractive index, a metal oxide may be added as appropriate. Among these, an indium-tin composite oxide is suitable from the viewpoint of environmental stability and circuit processability. In the present invention, the transparent conductive film layer can be transparently conductive by setting the surface resistance 値 of the transparent conductive film to 50 to 5 000 Ω/□, more preferably 100 to 2000 Ω/□. The film is used in a touch panel or the like. When the surface resistance 値 is less than 100 Ω/□, the position recognition accuracy of the touch panel is deteriorated, and when it exceeds 2000 Ω/□, there is a case where it is necessary to increase the voltage applied between the electrodes of the touch panel, which is not preferable. Further, from the viewpoint of productivity, the transparent conductive film and the high refractive index layer are made of the same material, for example, an indium-tin composition is preferable. When the composition is different, it is necessary to have a target and a cathode for the high refractive index and the transparent conductive film, and the device is also a bulky device. [S1 -15- • 201115594 The layer structure of the transparent conductive film may be a single layer structure, and the laminated structure of two or more layers may be formed in the case of a transparent conductive film having a laminated structure of two or more layers. The metal oxides described above may be the same or different. The film thickness of the transparent conductive film is preferably 4 to 25 nm, more preferably 5 to 20 nm, still more preferably 8 to 18 urn. When the film thickness of the transparent conductive film is less than 4 nm, it is difficult to form a continuous film, and thus it is difficult to obtain good conductivity. On the other hand, when the film thickness of the transparent conductive film is thicker than 25 nm, the transparency is liable to be lowered, and it is difficult to obtain a film having mechanical strength capable of withstanding the bending stress near the frame edge of the touch panel. As a method of forming a transparent conductive film in the present invention, a vacuum deposition method such as a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the film thickness required. For example, in the case of a sputtering method, a general sputtering method using an oxide target or a reactive sputtering method using a metal target, etc., in this case, oxygen, nitrogen, or the like may be introduced as a reactive gas, or倂 Add ozone, plasma irradiation, ion assist and other means. Further, a bias voltage such as direct current, alternating current, or high frequency may be applied to the substrate insofar as the object of the present invention is not impaired. (Optical Characteristics of Transparent Conductive Film) The transparent conductive film of the present invention is formed by laminating a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer on a substrate composed of the above transparent plastic film. In the configuration, since there is a peak of transmittance in a specific wavelength region, it is possible to suppress a decrease in visibility even if it is disposed in front of a high-definition display. [S1 -16 * 201115594 The peak of the spectral transmittance of the transparent conductive film of the present invention is present at 45 0 to 5 3 Onm, so that the coloring is extremely small and the transmittance is excellent. Therefore, the transparent conductive film of the present invention is used for touch. When components such as a control panel are used, the visibility is excellent. Preferably, the peak transmittance of the spectral transmittance is 460 to 520 nm, and more preferably, the peak of the light transmittance is 470 to 510 nm. Further, since the transparent conductive film of the present invention has a total light transmittance of 90% or more, when the transparent conductive film of the present invention is used for a member such as a touch panel, it is possible to suppress a decrease in luminance of a liquid crystal display or the like. Further, since the color b 本 of the transparent conductive film of the present invention is -2 to 2, when the transparent conductive film of the present invention is used for a member such as a touch panel, it is possible to suppress damage to the display color of a display such as a liquid crystal display. . Preferably, the color b値 is -1.0 to 1.5, more preferably 0 to 1.5. (Preventing the generation of Newton's ring) In addition, for the purpose of preventing the generation of Newton's ring, the cured layer described in the description of the transparent plastic film has a center line average roughness (Ra) of 0.1 to 0.5 μm. The range of the method contains particles as well. When Ra is less than 0.1, it is difficult to prevent the Newton's ring from being generated. On the other hand, when Ra is more than 0.5 μΐη, the surface of the transparent conductive film is too thick, and the pen sliding durability is deteriorated. The particles to be contained in the cured layer are not particularly limited, and examples thereof include inorganic particles (for example, ceria, calcium carbonate, etc.), and heat-resistant organic particles (for example, polysiloxane particles, PTFE particles, polyimine particles, etc.). And crosslinked polymer particles (crosslinked PS particles, crosslinked acrylic particles, etc.). The average particle diameter of the particles (according to electron microscopy) is preferably 5 to 5 μm. Further, the content of the particles contained in the layer of the hardened LSi-17-201115594 is preferably 0.01 to 10% by mass. (hard coating) Further, in order to further improve the scratch resistance of the outermost layer (pen input surface) when the touch panel is used, on the opposite side of the surface of the transparent plastic film on which the transparent conductive film is formed (as a touch panel) The outermost pen input surface), preferably with a hard coat. The hardness of the hard coat layer is preferably 2H or more in pencil hardness. When the hardness is less than 2H, the hard coat layer as a transparent conductive film is insufficient in scratch resistance. The thickness of the hard coat layer is preferably 0.5 to 10 μm. When the thickness is less than 0.5 μm, it tends to be insufficient in scratch resistance, and when it is thicker than ΙΟμηη, it is not preferable from the viewpoint of productivity. The curable resin composition used for the hard coat layer is preferably a resin having an acrylate functional group, and examples thereof include a polyester resin having a lower molecular weight, a polyether resin, an acrylic resin, an epoxy resin, and an amine group. Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as acid ester resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols Things and so on. And 'as a reactive diluent, a large amount of ethyl (meth) acrylate, ethyl hexyl (meth) acrylate, styrene, methyl benzene, N-vinyl pyrrolidone, etc. are used in a large amount. Monofunctional monomers and polyfunctional monomers, such as trimethyl methoxide tri (meth) acrylate, hexane diol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol II (Meth)acrylic acid vinegar, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate vinegar, 1,6-hexanediol di(meth)acrylate, neopentyl Alcohol di(methyl)propene 201115594 enoate or the like. In the present invention, it is preferred to mix urethane acrylate as an oligomer, and to mix bis(penta) pentaerythritol pentoxide as a monomer. Further, as a hardening type resin composition used for the above hard coat layer, a mixture of a polyester acrylate and a polyurethane acrylate is particularly suitable. The polyester acrylate coating film is very hard and is suitable as a hard coat layer. However, when the polyester acrylate is coated alone, it has a problem that the punching resistance is low and it is easy to become brittle. Therefore, in order to impart impact resistance and flexibility to the coating film, it is preferred to use a polyurethane acrylate. In other words, by using polyurethane acrylate in polyester acrylate, the hardness of the coating film as a hard coat layer can be maintained, and the function of punching resistance and flexibility can be maintained. The blending ratio of the two is preferably 30 parts by mass or less based on 100 parts by mass of the polyester acrylate resin. When the addition ratio of the polyurethane acrylate resin is more than 30 parts by mass, the coating film is too soft and the punching resistance tends to be insufficient. The hardening method of the above-mentioned hardening type resin composition can be carried out by a usual hardening method, that is, a method of hardening by heating, electron beam or ultraviolet irradiation. For example, the case of electron beam hardening is based on Cockcroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, and dinam (^ An electron beam having an energy of 50 to 1 000 keV, preferably 100 to 300 keV, which is emitted by various electron beam accelerators such as a type 1 and a high frequency type. Moreover, in the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. may be used. -19- 201115594 In addition, in the case of ionizing radiation hardening, It is preferred to contain a photopolymerization initiator or a photosensitizer in the curable resin composition. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler-Benzoyl benzoate, α-Amyloxim ester, and tetrasulfide tetrasulfide. Tetramethyithiuram monosulfide, thioxanthone, etc. Further, as the photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine or the like is preferred. In order to impart anti-glare property to the hard coat layer, a method of dispersing inorganic particles such as CaC03 or SiO 2 to a curable resin or a method of forming irregularities on the surface of the hard coat layer is effective. For example, in order to form irregularities, after coating with a coating liquid containing a curable resin composition, a film having a convex shape on the surface is laminated, and ultraviolet rays are irradiated from the shaped film to harden the hardening resin, and only the peeling is performed. Obtained as a film. The above-mentioned shaped film can be formed by providing a desired convex shape on a base film such as polyethylene terephthalate having a release property (hereinafter sometimes referred to as PET) or on a base film such as PET. Slim convex layer, etc. The formation of the convex layer can be obtained, for example, by applying a resin composition composed of inorganic particles and a binder resin to a base film. As the binder resin, for example, an acrylic polyol crosslinked with a polyisocyanate is used, and as the inorganic particles, CaC03, SiO 2 or the like can be used. Further, other types of mat type PET in which inorganic particles such as SiO 2 are mixed may be used in the production of PET. When the coating film is laminated on the coating film of the ultraviolet curable resin, and the coating film is cured by irradiation with ultraviolet rays, and the film is a film having PET as a substrate -20-201115594, the short-wavelength side of the ultraviolet ray is absorbed. The film has the disadvantage of insufficient hardening of the ultraviolet curable resin. Therefore, it is necessary to use a coating film laminated on the coating film of the ultraviolet curable resin to have a total light transmittance of 20% or more. Further, when it is used in a touch panel, since the transmittance of visible light is further increased, it is also possible to perform low reflection treatment on the hard coat layer. This low reflection treatment is preferably a single layer or a layer of two or more layers having a refractive index different from the refractive index of the hard coat layer. In the case of a single layer structure, it is preferred to use a material having a smaller refractive index than the hard coat layer. Further, in the case of a multilayer structure of two or more layers, a layer adjacent to the hard coat layer is made of a material having a larger refractive index than the hard coat layer, and a layer having a smaller refractive index is preferably used as the layer thereon. As the material constituting such a low reflection treatment, the organic material or the inorganic material is not particularly limited as long as it satisfies the above refractive index. For example, a dielectric such as CaF2, MgF2, NaAlF4, SiO2, ThF4, Zr02, Nd203, Sn?2, Ti02, Ce02, ZnS, In2?3 is preferably used. The low-reflection treatment is a dry coating method such as a vacuum distillation method, a pendulum method, a CVD method, or an ion plating method, or a wet coating method such as a gravure coating method, a reverse roll coating method, or a die coating method. Furthermore, before the low-reflection treatment layer is laminated, corona discharge treatment, plasma treatment, sputtering uranium engraving treatment, electron beam irradiation treatment, external radiation treatment, primer coating may be performed on the hard coating layer. Surface treatment such as primer treatment, easy bonding treatment, and the like. (Transparent Conductive Sheet) [Si-21-201115594 The transparent conductive sheet of the present invention is bonded to the opposite side of the surface of the transparent conductive film of the present invention in which the transparent conductive film layer is laminated, and is adhered and transparent by a binder. The resin sheet was laminated. The transparent conductive sheet of the present invention can be used as a fixed electrode of a touch panel. That is, the substrate of the fixed electrode of the touch panel is changed from glass to the transparent resin sheet of the present invention, whereby a lightweight and non-cleavable touch panel can be produced. The binder is not particularly limited as long as it has transparency. For example, an acrylic binder, a polyoxynene binder, a rubber binder, or the like is suitable. The thickness of the binder is not particularly limited, but it is usually desirably set in the range of 1 to ΙΟΟμηη. When the thickness of the adhesive is less than the thickness of Ιμηι, it is difficult to obtain a practically non-problem adhesive property, and when it exceeds the thickness of 100 μm, it is not preferable from the viewpoint of productivity. The transparent resin sheet to be bonded by the adhesive is preferably used in a thickness of 〇. 5 to 5 in order to impart mechanical strength equivalent to that of glass. When the thickness of the transparent resin sheet is less than 〇5 mm, the mechanical strength is insufficient compared to the glass. On the other hand, when the thickness is more than 5 mm, it is too thick to be used in a touch panel. Further, the material of the transparent resin sheet can be the same as that of the above transparent plastic film. (Touch Panel) The touch panel is a pair of transparent conductive substrates (any of a film, a glass, and a sheet) having a transparent conductive film layer, and the transparent conductive film layers are disposed to face each other with a spacer interposed therebetween. When the characters are input by the pen, the opposing transparent conductive films are brought into contact with each other by the push of the pen, and the power source is turned ON, and the position of the pen on the touch panel can be detected. The text can be recognized from the trajectory of the pen by detecting the position of the pen continuously and correctly -22-201115594. In the touch panel of the present invention, the transparent conductive film of the present invention is used in at least one of the transparent conductive substrates. In this case, when the transparent conductive film of the present invention is used as the movable electrode of the present invention, the visibility is not lowered even if it is incorporated in a display such as a high-definition liquid crystal display, and the pen sliding durability is excellent. It can be a long-term stable touch panel. Fig. 1 shows an example of a touch panel using the transparent conductive film of the present invention. Further, Fig. 2 is a cross-sectional view showing a plastic touch panel which does not use a glass substrate, which is obtained by using the transparent conductive film of the present invention and a transparent conductive sheet. Since the plastic touch panel does not use glass, it is very light and does not crack due to smashing. [Examples] Hereinafter, the present invention will be described in further detail based on examples, but the present invention is not limited by the examples. Further, the properties of the transparent conductive film, the crystallinity of the high refractive index layer, the transparent conductive film, and the pen sliding durability test of the touch panel were measured by the following methods. (1) Total light transmittance The light transmittance was measured by NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS-K7136. (2) Surface resistance 値 According to JIS-K7 194, the measurement system is measured using the Mitsubishi Oil Chemical Co., Ltd. Lotest AMCP-T4 00. (3) Color (a値, b値) -23- 201115594 According to JIS-K7 105, the color is measured by the standard light C/2 using a color difference meter (Japan Electric Industrial Co., Ltd. 'ZE-2 0 0 0) b値. (4) Peak-wavelength of spectral transmittance The light is irradiated on the side of the transparent conductive film in the range of 380 to 780 nm by a spectrophotometer (Hitachi U-3500 type), and the measurement of indoor air as a transmittance is measured. According to the measurement result, the wavelength at which the transmittance is the largest is used as the peak wavelength. (5) Crystallinity of High Refractive Index Layer and Transparent Conductive Film A film sample sheet in which a high refractive index layer and a transparent conductive film are laminated is cut into a square of 300 μm χ 300 μm, and a sample holder for an ultramicrotome (Ultramicrotome) is used. Fix the film side to the front. Next, the knives were placed at an extremely acute angle with respect to the film surface of the observation site having a target of Ιμιη xl μιη or more, and cut at a thickness of 7 〇 nm. On the surface side of the conductive film of the slice and the portion where the film was not significantly damaged, the observation field of Ιμιη χ1 μπι was secured, and the transmission electron microscope (JE-2010, JEM-2010) was used to accelerate the voltage at 200 kV and the bright field observation magnification was 5 Photographic photography was performed 10,000 times to evaluate crystallinity. (6) The pen sliding durability test near the edge of the frame is offset from the inside of the bonding portion of the touch panel by a distance of 1.5 mm. A pen of polyacetal (front end shape: 0.8 sunning R) is applied with a load of 2.5 N. The touch panel was subjected to a linear sliding test of 10,000 times (reciprocating 5,000 times). At this time, the sliding distance is 30 ug and the sliding speed is 60 sec/sec. Furthermore, the gap between the upper and lower substrates of the touch panel is 15 〇 μηη. After this sliding durability test, first, it was visually observed whether or not the sliding portion was whitened. Further, the vicinity of the sliding portion was observed with a microscope to observe the presence or absence of [Si -24-201115594 crack generation. Further, the ON resistance (the resistance 可 when the movable electrode (thin film electrode) and the fixed electrode are in contact with each other when the sliding portion is pressed by the pen load 1. ON is measured. (7) Pen sliding durability test ’ 施加 A 2.5N load was applied to a pen made of polyacetal (front end shape: 〇.8mmR), and a linear sliding test was performed on the touch panel 100,000 times (reciprocating 50,000 times). At this time, the sliding distance is 30 circles and the sliding speed is 60 mi / sec. After this sliding durability test, first, it was visually observed whether or not the sliding portion was whitened. Further, a pen load of 0.5 N is applied to the sliding portion, and 20 is marked with a mark of 0 to evaluate whether the touch panel can correctly read the record. Further, the ON resistance (the resistance 値 when the movable electrode (thin film electrode) and the fixed electrode are in contact with each other when the sliding portion is pressed with a pen load of 0.5 N) is measured. (8) Environmental test under high temperature and high humidity LH43-12P manufactured by NAGANO Scientific Machinery Co., Ltd. was used to expose the transparent conductive film for 1,000 hours at 85 ° C and 85% RH. After the treatment, the surface resistance 値, the light transmittance, and the color were measured. (9) Film thickness of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer The thin film sample sheet in which the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer are laminated is cut into one surface xl〇nim The size is embedded in an epoxy resin for electron microscopy. This was attached to a sample holder of an ultramicrotome to prepare a thin section slice parallel to the short side of the embedded sample piece. Then, a photograph was taken by a transmission electron microscope (JE-2010, manufactured by JEOL Co., Ltd.) at an acceleration voltage of 200 kV and a bright field observation magnification of 10,000 times in a portion where the film of the slice was not significantly damaged, and the photograph was obtained from the obtained photograph. Film thickness: -25- 201115594 (ίο) The refractive index of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer is prepared for each layer on the tantalum wafer under the same film forming conditions. The refractive index of 550 nm was evaluated by an Ellipsometer (manufactured by Otsuka Electronics Co., Ltd., FE-500). Further, the spectral transmittance measurement data of the film provided with each layer was subjected to fitting using an optical simulation software to calculate the refractive index. At this time, the film thickness of each layer was evaluated by the above-mentioned film thickness evaluation method. Further, it was confirmed that the refractive index of each layer thus calculated and the refractive index of each layer on the germanium wafer were not greatly different. [Example 1] Toluene/MEK (80/20: as a solvent) was added to an acrylic resin (Seikabeam EXF-0 1 J, manufactured by Daisei Seiki Co., Ltd.) containing 1 part by mass of a photopolymerization initiator. The mixed solvent of the mass ratio was 50% by mass of the solid content, and the mixture was stirred and uniformly dissolved to prepare a coating liquid. A biaxially oriented transparent PET film (manufactured by Toyobo Co., Ltd., A43 40, thickness: 188 μm) having an easy-to-bond layer on both sides was coated with a Meyer Bar to form a coating film thickness to form 5 μm. After drying at 80 ° C for 1 minute, ultraviolet rays (light quantity: 300 mJ/cm 2 ) were irradiated by an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UB042-5AM-W type) to cure the coating film. Next, the coating film was applied to the reverse side in the same manner, and then heat-treated at 1 80 ° C for 1 minute to reduce the volatile component. Further, in order to vacuum-expose the biaxially aligned transparent PET film in which the cured layer is laminated, the rewinding treatment is performed in the vacuum processing chamber. The pressure at this time was 〇.〇〇2Pa, and the exposure time was 20 minutes. Moreover, the temperature of the center roll is 40 °C. -26- 201115594 Next, a high refractive index layer composed of an indium-tin composite oxide is formed on the cured layer. At this time, the pressure before the sputtering was set to 0.0001 Pa, and DC power of 2 W/cm 2 was applied using indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 6.9 g/cm 3 ) containing 36% by mass of tin oxide as a target. Further, Ar gas was flowed at a flow rate of 3 times the flow rate of 〇2 at a surface resistance 値 of 130 sccm and 02 gas, and a film was formed by DC magnetron sputtering in an atmosphere of 〇.4 Pa. However, it is not a normal DC, and in order to prevent arc discharge, a pulse of 5 μs width is applied at a cycle of 50 kHz using the RPG-100 manufactured by Japan ENI. Further, the center roll temperature was 〇 ° C and sputtering was performed. Furthermore, the oxygen partial pressure of the atmosphere is observed for a long time by a sputtering process monitor (manufactured by LEYBOLD INFICON Co., Ltd., XPR2), and is fed back to the oxygen flow meter and the DC power source to make the oxidation degree in the indium-tin composite oxide film constant. . As in the above manner, a high refractive index layer composed of an indium-tin composite oxide having a thickness of 45 nm is deposited. The surface resistivity 高 of the high refractive index layer thus obtained is 1 X 1 06 Ω/□ or more. Further, in order to form a SiO 2 film as a low refractive index layer on the high refractive layer, and use yttrium as a target, a DC magnetron sputtering method, a vacuum degree of 0.27 Pa, an Ar gas as a gas of 500 sccm, and 02 gas are used. Flowed at a flow rate of 80 sccm. Further, a chill roll of 〇 ° C was placed on the back surface of the substrate to cool the transparent plastic film. The target was supplied with power of 7.8 W/cm 2 at this time, and the dynamic rate was 23 nm.m / min. Further, when the voltage 値 in the film formation is observed for a long period of time, the flow meter is fed back to the oxygen gas to make the voltage 値 constant. As described above, a low refractive index layer having a thickness of 5 5 nm and a refractive index of 1.46 was deposited. -27-201115594 Next, a transparent conductive film made of an indium-tin composite oxide is formed on the low refractive index layer. At this time, the pressure before the splashing was set to 0.000 lPa, and the indium oxide containing 36% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density 6.9 g/cm 3 ) was used as a target, and DC power of 2 W/cm 2 was applied. Further, a film was formed by a DC magnetron sputtering method in which an Ar gas was 130 sccm and a gas flow rate of the 02 gas was minimized at a surface resistance 値. However, it is not a normal DC, and in order to prevent arc discharge, a pulse of 5 ps width is applied at a cycle of 50 kHz using a RPG-100 manufactured by ENI, Japan, and a center roll temperature of 10 ° C is used for sputtering. In addition, the oxygen partial pressure of the atmosphere is observed for a long time by a sputtering process monitor (XPR2 manufactured by LEYBOLD INFICON Co., Ltd.), and the oxygen flow meter and the DC power source are fed back to make the oxidation degree in the indium-tin composite oxide film constant. . As described above, a transparent conductive film composed of an indium-tin composite oxide having a thickness of 15 nm and a refractive index of 1.96 was deposited. <Production of Touch Panel> The transparent conductive film is used as one of the panels, and the other panel is an indium-tin composite oxide film having a thickness of 20 nm by plasma CVD on the glass substrate. A transparent conductive film (manufactured by Sakamoto Co., Ltd., S5 00) made of (tin oxide content·_1% by mass). The two panels were placed in a transparent conductive film with a diameter of 30 μm epoxide beads interposed therebetween to form a touch panel. [Example 2] In Example 1, as a target for producing a high refractive index layer, indium oxide containing bismuth by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.lg/cm 3 ), [Si - 28-201115594 A transparent conductive film was produced in the same manner as in Example 1 except that the gas flow rate was five times the flow rate at which the surface resistance 値 was the smallest. The surface resistivity 高 of the obtained high refractive index layer was 1 X 106 Ω/□ or more. Further, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1. Further, the ratio of the water pressure to the inert gas was 5 x 1 (T3. [Comparative Example 1] In Example 1, as a target for producing a high refractive index layer, in addition to indium oxide containing 5 mass% of tin oxide (Mitsui Metal Mining Co., Ltd. A transparent conductive film was produced in the same manner as in Example 1 except that the density was 7.1 g/cm 3 . Further, a transparent touch film was used to prepare a touch panel in the same manner as in Example 1. [Comparative Example 2 In the first embodiment, a transparent conductive film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was 70 nm. Further, the transparent conductive film was used in the same manner as in Example 1. [Comparative Example 3] A transparent conductive film was produced in the same manner as in Example 1 except that the film thickness of the low refractive index layer was 4 Onm in Example 1. Further, the transparent conductive film was used. A touch panel was produced in the same manner as in Example 1. [Example 3] A substrate/cured layer/high refractive index layer composed of a hard coat layer/biaxially oriented transparent PET film was produced in the same manner as in Example 1. Low refractive index layer / transparent conductive thin Layer laminate composed, on the hard coat layer is then sequentially laminated Ti02 film layer (refractive index: 2.30, thickness of 15nm), a thin film layer Si〇2 (off

Si -29-201115594 Emissivity: 1.46, film thickness: 29 nm), Ti〇2 film layer (refractive index · 2.30, film thickness: 109 nm), SiO 2 film layer (refractive index · 1.46, film thickness: 87 nm), thereby forming In order to form a TiO 2 film layer, titanium was used as a target, and a DC magnetron sputtering method was used, and a flow rate of 0.27 Pa, a gas of Ar gas of 500 sccm, and a gas of 02 gas of 80 sccm flowed. Further, a cooling roll having a surface temperature of 0 ° C was provided on the back surface of the substrate to cool the transparent plastic film. The power of 7.8 W/cm2 was supplied to the target at this time, and the dynamic rate was 23 nm.m/min. In order to form a SiO 2 film, ruthenium was used as a target, and a DC magnetron sputtering method was used to flow at a flow rate of 27.27 Pa, a gas of Ar gas of 50 〇SCCm, and a gas of 〇2 of 80 sccm. Further, a cooling roller of 〇 ° C was provided on the back surface of the substrate to cool the transparent plastic film. At this time, the target supplies 7.8 W/on 2 of power with a dynamic rate of 23 nm.m/min. Further, this transparent conductive film was used as one of the panels, and a touch panel was produced in the same manner as in the first embodiment. [Example 4] A transparent conductive film produced in the same manner as in Example 1 was bonded to a polycrystalline carbon sheet having a thickness of 1.0 IM1 by an acrylic adhesive to prepare a transparent, electrically conductive laminated sheet. The transparent conductive laminated sheet was used as a fixed electrode, and the transparent conductive film of Example 1 was used for a movable electrode, and a touch panel was produced in the same manner as in Example 1. [Example 5] A transparent conductive film was formed in the same manner as in Example 1 except that a film made of magnesium fluoride (MgF2) was formed as a film of the low refractive index.

[S -30- 201115594 At this time, the pressure before the sputtering is set to 0.0000 PaPa, and the target system is made of magnesium carbide (manufactured by Mitsui Metals Co., Ltd.), and the high frequency power of 13·56 2 of 2 W /cm 2 is applied, and the magnetic control is utilized. The sputtering method and the degree of vacuum were 0.27 Pa, and the Ar gas system as a gas was flowed at a flow rate of 50 〇SCCm to form a film. Moreover, the voltage 値 in the film formation is observed for a long time, and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a low refractive index layer having a thickness of 60 nm and a refractive index of 1.36 was deposited. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film. [Example 6] Example 1 was formed in the same manner as in Example 1 except that a film made of an aluminum-bismuth composite oxide (Al 203-SiO 2 ) was formed as a low refractive index layer on the cured layer. A transparent conductive film. At this time, the pressure before the sputtering was set to 0.001 lPa, and Al-Si (50: 50 wt%) (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied, by magnetron sputtering, The degree of vacuum was 〇.27 Pa, and the Ar gas system as a gas was flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and an 02 gas system to form a film. Moreover, the flow rate 値 in the film formation for a long time and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a low refractive index layer having a thickness of 50 nm and a refractive index of 1.55 was deposited. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film. [Example 7] In Example 1, as a target for producing a high refractive index layer, indium oxide containing 20% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density 7.0 g/era3), except for 〇2 gas A transparent conductive film was produced in the same manner as in Example 1 except that the flow rate was 4 times the flow rate at which the surface resistance 値 was the smallest. The surface resistance 値 of the obtained high refractive index layer was 1 χ 106 Ω/□ or more. Further, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1. [Example 8] A transparent conductive film was produced in the same manner as in Example 1 except that a gallium-doped zinc oxide film was used as the transparent conductive film. As the target system, zinc oxide containing 5% by mass of gallium oxide (manufactured by Tosoh Corporation) was used, and DC power of 2 W/cm 2 was applied. Further, the Ar gas is a 130 sccm' 〇 2 gas system, and the surface resistance 値 becomes the minimum flow rate, and a film is formed by DC magnetron sputtering in an atmosphere of 4. 4 Pa to obtain a transparent conductive layer having a thickness of 14 nm and a refractive index of 2.05. Film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film. [Example 9] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 40 nm. [Example 1] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the low refractive index layer was 5 Onm. [Example 1 1] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 1 Onm. [Example 1 2] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 2 2 nm.

LSI • 32-201115594 [Example 1 3] In Example 1, as a target for producing a high refractive index layer, indium oxide containing 55 mass% of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density 6.7 g/cm 3 ) In the same manner as in Example 1, a transparent conductive film was produced in the same manner as in Example 1 except that the gas flow rate was 2.5 times the flow rate at which the surface resistance was the smallest. The surface resistance 値 of the obtained high refractive index layer is 1 χΐ〇 6 Ω / □ or more. Further, a touch panel was produced in the same manner as in Example 1 using the transparent conductive film: [Comparative Example 4] A film composed of zirconium oxide-ruthenium composite oxide (Zr02-SiO 2 ) was used in Example 1. A transparent conductive film was formed in the same manner as in Example 1 except that a film was formed as a low refractive index layer. At this time, the pressure before the sputtering was set to 0.001 Pa, and ZrSi 2 (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied, and the DC magnetron sputtering method was used, and the degree of vacuum was 2727 Pa. The Ar gas system as a gas was flowed at a flow rate of 80 sccm at a flow rate of 500 sccm and a helium gas system to form a film. Moreover, the flow rate 値 in the film formation for a long time and the flow meter fed back to the oxygen makes the voltage 値 constant. As described above, a low refractive index layer having a thickness of 45 nm and a refractive index of 1.75 was deposited. [Comparative Example 5] A transparent conductive film was produced in the same manner as in Example 2 except that the pressure at the time of rewinding before film formation was further increased by one bit to 0.00 2 P P a . The ratio of the water pressure to the inert gas at this time was 1χ1〇_3. Further, using the transparent conductive film, a touch panel was produced in the same manner as in the first embodiment. [Comparative Example 6] r r- I ^ -33- 201115594 In Example 1, as a target for producing a high refractive index layer, indium oxide containing 75 mass% of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density 5.8) g/cm 3), 02 gas flow rate is twice the flow rate when the surface resistance 値 is the minimum. However, abnormal discharge often occurs during sputtering, and the high refractive index layer cannot be formed into a film. [Comparative Example 7] A transparent conductive film was produced in the same manner as in Example 1 except that the indium oxide film doped with titanium and tin was used for the transparent conductive film. As the target system, indium oxide: tin oxide: titanium oxide = 60: 10: 30% by weight (manufactured by Sumitomo Metal Mining Co., Ltd.) was used, and DC power of 2 W/cm 2 was applied. Further, the Ar gas system was flowed at a flow rate of the surface resistance 値 at a minimum of 130 sccm and an 02 gas system, and a film was formed by DC magnetron sputtering at an atmosphere of 0.4 Pa to obtain a transparent conductivity of 15 nm in thickness and 2.25 in refractive index. film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film. [Comparative Example 8] A transparent conductive film was produced in the same manner as in Example 1 except that the indium oxide film doped with antimony and tin was used for the transparent conductive film. Indium oxide: tin oxide: yttrium oxide = 60:10: 30% by weight (manufactured by Sumitomo Metal Mining Co., Ltd.) was used as a target system, and DC power of 2 W/cm 2 was applied. Further, the Ar gas system was flowed at a flow rate of a surface resistance 値 of 130 sccm and an 02 gas system, and a film was formed by DC magnetron sputtering in an atmosphere of 0.4 Pa to obtain a transparent conductive layer having a thickness of 18 nm and a refractive index of 1.75. film. Further, a touch panel was produced in the same manner as in Example 1 using the transparent conductive film. iSl-34-201115594 [Comparative Example 9] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 30 nm. [Comparative Example 1] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 60 nm. [Comparative Example 1 1] A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 30 nm.

Surface ship rate (0/□> (%) Color _ $ 値 严 高 高 高 曲率 曲率 曲率 导 导 导 导 导 1 1 1 1 1 1 1 1 1 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 * Shed 2 9 2 0 9 1 -1. 4 r 0. 6 485 ΙΜΚ 胙 AH than ft example i 9 2 0 9 1 -1 . 6 0. 5 480 Painted Alt Egg All 9 2 0 94 -3. 1 5 3 545 Egg yolk Egg AH 9 20 88 -0. 7 -1. 2 440 Non-financial 舴 AK 9 2 0 9 5 -1. 5 0. 8 50 0 冲 A寅μαχ " Stt example 4 9 2 0 9 1 —K 5 1. 3 490 •MM Non-ΑΚ SUM 5 9 20 9 1 -1. 5 1. 0 490 鲊All Non-Alt Yellow 916 9 2 0 Θ 1 -έ; ο 1. 3 4Θ0 Non-IM Non A 寅ΑύΝ 寅ΑύΝ / 9 2 0 9 1 -1.6 ο. β 490 and turtle selling 穽A 霣 蝴 8 8 15 0 0 9 1 -1. 9 1· 2 490 Non-AH Non-<1贵贾_019 9 2 0 9 1 -2. 0 1. 0 485 AH AH 1 u 9 2 0 9 1 -1. 9 1. 0 ABB ntM »A« (Gong A case 1 1 15 0 0 9 2 -1. 3 0 7 480 Difficult AIK F. Alt member I z 6 0 0 90 -1. 2 t. 6 500 穽Alt A A expensive Us example 1 12 00 d 1 -1. d 1, 2 490 A quality non-ah lUtt for 4 9 2 0 90 -2. 7 2. 5 49 0 Mixing non-A lean ratio I&M5 66 6 5 0 9 1 —1. 4 * 0. 8 485 Μ Μ Compare Example 7 1 0 0 0 0 89 -3. 4 2. d 490 Difficult to see Fu Jing Huang Comparative Example 8 2 0 0 0 0 9 2 -1. 1 0. 7 490 珅 ft 典 蜃 9 9 9 9 89 2. 9 -2. 1 440 Non-IM Non-AH iUft Example 1 v 9 2 0 92 -0. 8 2. 8 5 5 0 Mixing non-A yellow 1 1 3 5 0 8 β -0. 7 3. S 580 鼹 穽 穽 霣 霣 霣 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Initial 0Νimpedance値(kQ) Realized chick ONP straightening (KQ) Sliding part of crack initial ON curry (ΚΩ) Really difficult ONpiStft (ka) Solid foot 1 &20 9 1 —1. 8 1. 1 钿2 2 无Γ 2 2 f 16912 105 0 9 1 -2. 1 1 . 5 No 2 2 No 2 2 Comparative Example 1 82 0 9 1 -1. 6 0. 5 m 2 2 There are 2 > 1 000 Comparative Examples 2 820 94 — 3.1 5. 3 No 2 2 No. 2 2 Comparative example 3 82 0 K8 -0.7 -1. 2 No 2 2 No 2 2 Real detail “3 820 9 5 -1; 5 0. 8 No 2 2 No 2 2 Decoration 4 820 9 1 —1. 5 1.3 No 2 2 No 2 2 Solid foot 5 820 9 1 -1. 5 1.0 No 2 2 No 2 2 Hybrid β 820 9 1 -2. 0 1. 3 None 2 i No 2 2 Hybrid 7 820 9 1 -1. β 0. 9 No 2 2 No 2 2 Decoration Β t 500 9 1 -2. 1 1.5 Μ 2 2 No 2 2 Yi Na 820 9 1 -2. 0 1.0 No 2 2 No 2 2 Mu 1 1 0 82 0 9 1 -1.9 1. ό ^ - 2 2 . 2 2 Real Butterfly 1 1 82 0 9 2 — 1.3 0. 7 No 2 2 No 2 2 Real » 1 2 8 2 0 90 -1. 2 1. 5 No 2 2 No 2 2 Real κηι 3 820 9 1 - 1. β 1. 2 no 2 2 no 2 2 mm a 820 9〇1 -2· 7 2. 5 no 2 2 no 2 2 tiJSfflS 7 50 9 1 —1. β 1.0 no 2 2 yes. 2 >1 000 Comparison for β — — — — — — — — — Comparative Example 7 1 8000 89 —3. 9 3. 3 No 200 3 000 No 2 0 0 500 Comparative Example 8 30000 9 2 -2. 1 1.3 No S00 4000 No 500 800 019 820 89 -Ζ. 9 -2. 1 No 2 2 No 2 2 City example 0 820 92 . —0. 8 2. 8 No 2 2 No 2 2 Comparative Example 11 300 8 8 -0 7 - S = No 2 2 . No 2 2 According to the results of Tables 1 and 2, the transparent conductive film or the transparent conductive sheet touch panel described in Examples 1 to 13 which satisfies the scope of the invention of the present application. It is excellent in visual recognition, and applies a load of 2.5N to the polyacetal pen (front end shape: 0.8 surface R) near the frame edge, and after 10,000 sliding experiments, it will not Peeling or cracking occurred, and the ON resistance was not abnormal. On the other hand, a touch panel of a transparent conductive film or a transparent conductive sheet described in Comparative Example 1 in which the high refractive index layer is crystalline is used to form a polyacetal pen near the frame edge (front end shape: 〇.8imR) When a load of 2.5 N was applied and the sliding test was performed for 10,000 times, the ON resistance was abnormal. Further, when the pen sliding portion was evaluated by a microscope, peeling or cracking of the transparent conductive film was observed. Comparative Example 5 in which the transparent conductive film is crystalline is also the same as -36-201115594, and the film thickness of the low refractive index layer or the high refractive index layer or the transparent conductive film is relatively large [Comparative Examples 2, 1 and 11] The light transmittance is outside the range of the invention of the present application, and the transparency is poor, and the film thickness of the low refractive index layer or the high refractive index layer is relatively thin [Comparative Examples 3 and 9], and the color b is outside the scope of the invention of the present application, and the color is poor. A touch panel using these transparent conductive films is visually inferior. In Comparative Example 4 and Comparative Example 7, since the refractive index of the low refractive index layer or the transparent conductive film was high, the color b 値 was outside the range of the invention of the present application, and the color was poor. Comparative Examples 7 and 8 have excessive surface resistance and are not suitable for touch panel applications. Further, in Comparative Example 6, the ratio of tin oxide to indium oxide was too large, abnormal discharge was large, and abnormal discharge was excessive during sputtering, and film formation was impossible. [Industrial Applicability] The transparent conductive film or the transparent conductive sheet of the present invention is excellent in visual visibility and is even in contact when used for a touch panel disposed in front of a display body such as a high-definition liquid crystal display. There is no peeling or cracking near the frame edge of the control panel, and the pen sliding durability is excellent, and the position detection accuracy and display quality are also excellent, so that the narrow frame edge of the touch panel can be used for the mobile information terminal. A digital camera, a digital camera, etc., and a touch panel that strongly requires recording media miniaturization and a large display screen is particularly suitable. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view of a touch panel using a transparent conductive film of the present invention. Fig. 2 is an explanatory view of a touch panel using a transparent conductive film of the present invention without using a glass-37-201115594 substrate. [Description of main component symbols] 1 〇: transparent conductive film 1 1 : transparent plastic film (substrate) 1 2 : cured layer 1 3 : high refractive index layer 1 4 : low refractive index layer 1 5 : transparent conductive film Layer 1 6 : Hard coat layer 20 : Beads 3 0 : Glass plate 40 : Transparent conductive sheet 4 1 : Adhesive 42 : Transparent resin sheet - 38-

Claims (1)

.201115594 VII. Patent application scope: 1. A transparent conductive film is formed on a substrate composed of a transparent plastic film, and the high refractive index layer, the low refractive index layer and the transparent conductive film layer are laminated in this order. The transparent conductive film is characterized in that the high refractive index layer is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 10 to 60% by mass, and the low refractive index layer is composed of The inorganic thin film having a refractive index of 1.30 to 1.60 is formed, and the transparent conductive thin film layer is composed of an inorganic thin film having a refractive index of 1.8 0 to 2.20, and the peak of the spectral transmittance of the transparent conductive thin film is present at 450 to 530 nm. And the total light transmittance is 90% or more, and the color b値 is -2 to 2. 2. The transparent conductive film of claim 1, wherein the high refractive index layer has a tin oxide content of 20 to 60% by mass. 3. The transparent conductive film according to claim 1 or 2, wherein the opposite surface of the surface of the substrate made of the transparent plastic film having the transparent conductive film layer is subjected to a low reflection treatment. A transparent conductive sheet characterized by being bonded by an adhesive agent on the opposite side of the surface of the transparent conductive film of any one of the first to third aspects of the patent application of the transparent conductive film layer Transparent resin sheet 5. A touch panel is a touch panel in which a pair of panels having a transparent conductive film layer are disposed such that a transparent conductive film layer faces each other with a spacer interposed therebetween, and is characterized by at least One of the panels is composed of a transparent conductive film or a transparent conductive sheet according to any one of claims 1 to 4. LSI -39-