WO2007013220A1

WO2007013220A1 - Transparent electrically conductive film, transparent electrically conductive sheet, and touch panel

Info

Publication number: WO2007013220A1
Application number: PCT/JP2006/310847
Authority: WO
Inventors: Hideo Murakami; Toshiyuki Oya; Chikao Morishige
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2005-07-29
Filing date: 2006-05-31
Publication date: 2007-02-01
Also published as: TW200715307A; TWI327736B

Abstract

[PROBLEMS] To provide a transparent electrically conductive film, which, when used in a touch panel, has excellent pen sliding durability near its frame and does not cause breaking of a transparent electrically conductive thin film particularly even after a sliding test under conditions of load 2.5 N and 10000 times with a polyacetal pen, and a transparent electrically conductive sheet and a touch panel using the same. [MEANS FOR SOLVING PROBLEMS] A transparent electrically conductive film comprising a transparent plastic film (a base material) and a transparent electrically conductive thin film comprising a metal oxide as a constituent stacked through a cured product layer onto the base material. The transparent electrically conductive film is characterized in that the transparent electrically conductive thin film is amorphous and the concentration of carbon in the transparent electrically conductive thin film is 1 × 1020 to 1 × 1022 (atoms/cm3). A transparent electrically conductive sheet comprising a transparent resin sheet applied through a pressure-sensitive adhesive to the transparent electrically conductive film on its side remote from the transparent electrically conductive thin film face. A touch panel comprising panel plates at least one of which is the transparent electrically conductive film or transparent electrically conductive sheet.

Description

Specification

Transparent conductive film, transparent conductive sheet, and touch panel

Technical field

[0001] The present invention relates to a transparent conductive film, a transparent conductive sheet, and a touch panel in which a transparent conductive thin film is laminated on a base material having a transparent plastic film force via a cured product layer, and particularly in the vicinity of a frame of the touch panel. The present invention relates to a transparent conductive film, a transparent conductive sheet, and a touch panel excellent in pen sliding durability.

Background art

A transparent conductive film in which a transparent thin film with low resistance is laminated on a substrate that also has a transparent plastic film force is used for applications that use the conductivity, such as a liquid crystal display or an electoluminescence (EL) display. It is widely used in electrical and electronic fields such as flat panel displays and transparent electrodes for touch panels.

[0003] In recent years, with the miniaturization of portable information terminals, digital video cameras, digital cameras, etc., the number of cases in which a touch panel is mounted on a display in order to omit operation keys has increased. However, these recording media are desired to have a smaller screen and a larger display display. For this reason, the housing area (frame) surrounding the display is becoming narrower, and a narrower frame is required for a touch panel. Furthermore, the vicinity of the frame is not in the case and is on the display area.

[0004] When pen input is performed on the touch panel, the transparent conductive thin film on the fixed electrode side and the transparent conductive thin film on the movable electrode (film electrode) side come into contact with each other, but in particular near the frame, the transparent conductive thin film on the movable electrode side A strong bending stress due to a pen load is applied to the thin film. Therefore, even if strong bending stress due to pen load is applied, the transparent conductive thin film does not break, such as cracking or peeling! / !, Transparent conductive film with excellent pen sliding durability near the frame is desired It has been. However, the conventional transparent conductive film has the following problems.

[0005] There has been proposed a transparent conductive film in which a transparent conductive thin film is formed on a substrate having a thickness of 120 μm or less and a transparent conductive film is bonded to another transparent substrate with an adhesive layer ( For example, see Patent Document 1). Transparent conductive film having such an adhesive layer Although the touch panel using a pad satisfies the pen sliding durability near the frame of the touch panel, which will be described later, the pen input load (hereinafter referred to as the ON load) when used as a touch panel is heavy, so pen input is possible. It is difficult to recognize whether or not you have power. Furthermore, when this technique is used, foreign matters are mixed in the manufacturing process, particularly the bonding process, and the yield of the product is reduced, resulting in an increase in manufacturing cost. For this reason, the touch panel described above cannot satisfy the low cost of touch panels in recent years and the requirements of the plant.

Patent Document 1: Japanese Patent Application Laid-Open No. 2-66809

[0006] Further, a transparent conductive film in which a base layer formed by hydrolysis of an organic silicon compound is provided on a substrate that also has a transparent plastic film force, and a crystalline transparent conductive thin film is further laminated. It has been proposed (see, for example, Patent Documents 2 to 7).

Patent Document 2: JP-A-60-131711

Patent Document 3: Japanese Patent Application Laid-Open No. 61-79647

Patent Document 4: Japanese Patent Laid-Open No. 61-183809

Patent Document 5: Japanese Patent Laid-Open No. 2-194943

Patent Document 6: Japanese Patent Laid-Open No. 2-276630

Patent Document 7: JP-A-8-64034

[0007] However, these transparent conductive films are very brittle. After the pen sliding durability test in the vicinity of the touch panel frame described later, there was a problem that cracks occurred in the transparent conductive thin film.

On the other hand, a transparent conductive film has been proposed in which an amorphous transparent conductive thin film is provided on a base material having a transparent plastic film force via a cured product layer (see, for example, Patent Document 8). ). However, in order to improve the adhesion between the cured product layer and the transparent conductive thin film, a touch panel using a transparent conductive film produced by surface-treating the cured product layer with an acid or alkaline aqueous solution is used at the center of the touch panel. The pen writing characteristics were improved, but the pen sliding characteristics near the frame were insufficient.

Patent Document 8: Japanese Patent Laid-Open No. 11-224539

Disclosure of the invention

Problems to be solved by the invention That is, in view of the above-described conventional problems, the object of the present invention is excellent in pen sliding durability (edge durability) in the vicinity of the frame when used in a touch panel, and in particular, a polyacetal pen is used. The object is to provide a transparent conductive film, a transparent conductive sheet, and a touch panel in which the transparent conductive thin film is not destroyed even after 10,000 sliding tests at a load of 2.5 N in the vicinity of the frame of the touch panel. .

Means for solving the problem

[0010] The present invention has been made in view of the situation as described above, and the transparent conductive film, the transparent conductive sheet, and the touch panel that have solved the above-described problems are as follows. is there.

[0011] That is, the first invention in the present invention is a transparent conductive film in which a transparent conductive thin film containing a metal oxide as a constituent component is laminated on a base material having a transparent plastic film force via a cured product layer. The transparent conductive thin film is amorphous, and the carbon concentration contained in the transparent conductive thin film is 1 × 10 ^2G to 1 × 10 ²² (atoms / cm ³ ). It is a transparent conductive film.

[0012] A second invention is characterized in that the metal oxide is an indium tin oxide complex, and the ratio of the content of tin to indium is 15 to 60% by mass. It is a transparent conductive film as described in this invention.

[0013] A third invention is characterized in that at least two layers having different refractive indexes are provided between the transparent conductive thin film and the cured product layer, and the transparent conductive film according to the first invention is provided. It is a sex film.

[0014] The fourth invention is characterized in that the cured product layer contains particles, and the center line average roughness (Ra) of the transparent conductive thin film surface is 0.1 to 0.5 m. The transparent conductive film described in the invention.

[0015] A fifth invention is the transparent conductive film according to the first invention, characterized in that a hard coat layer is laminated on the surface opposite to the transparent conductive thin film surface.

[0016] A sixth invention is the transparent conductive film according to the fifth invention, wherein the hard coat layer has an antiglare property.

[0017] A seventh invention is characterized in that the hard coat layer is subjected to a low reflection treatment. It is a transparent conductive film described in the light.

[0018] The eighth invention is characterized in that a transparent resin sheet is bonded to the surface of the transparent conductive film described in the first invention opposite to the transparent conductive thin film surface via an adhesive. It is a transparent conductive sheet.

[0019] A ninth invention is a touch panel in which a pair of panel plates having the transparent conductive thin film are arranged via a spacer so that the transparent conductive thin film faces each other, and at least one of the panel plates is the first one. A touch panel comprising the transparent conductive film or the transparent conductive sheet according to the first aspect of the invention.

The invention's effect

[0020] The transparent conductive film of the present invention has a configuration in which a transparent conductive thin film containing a metal oxide as a main constituent component is laminated on a base material having a transparent plastic film force via a cured product layer. By using a transparent conductive thin film that is amorphous and has a carbon concentration of 1 × 10 ^2G to 1 × 10 ²² (atoms / cm ³ ) contained in the transparent conductive thin film as the transparent conductive thin film, The adhesive strength with the base material, which is a plastic film, is improved, and the mechanical strength against bending can be improved. For this reason, when a pen sliding test is performed in the vicinity of the touch panel frame, the transparent conductive thin film is less likely to be peeled off and cracked, and the pen sliding durability in the vicinity of the frame can be improved. .

Furthermore, by setting the ratio of tin content to indium in the transparent conductive thin film to 15 to 60% by mass, when the pen sliding test is performed on the transparent conductive thin film, the resistance of the transparent conductive thin film is reduced. Sharpness can be improved. Therefore, pen sliding durability at the center of the touch panel can be improved. In addition, by setting the center line average roughness (Ra) of the transparent conductive thin film surface to 0.1 to 0.5 m, pen sliding durability and prevention of the generation of a single-ton ring when a touch panel is made. Both can be achieved.

Brief Description of Drawings

FIG. 1 is an explanatory view of a touch panel using the transparent conductive film of the present invention.

FIG. 2 is an explanatory diagram of a touch panel using the transparent conductive film of the present invention and not using a glass substrate.

Explanation of symbols [0023] 10: Transparent conductive film

11: Transparent plastic film (base material)

12: Hardened product layer

13: Transparent conductive thin film

14: Node coat layer

20: Beads

30: Glass plate

40: Transparent conductive sheet

41: Adhesive

42: Transparent resin sheet

BEST MODE FOR CARRYING OUT THE INVENTION

[0024] The substrate having a transparent plastic film force used in the present invention is obtained by subjecting an organic polymer to melt extrusion or solution extrusion and, if necessary, stretching, cooling, and heat setting in the longitudinal direction and the Z or width direction. It is a film that has been applied. Organic polymers include polyethylene, polypropylene, polyethylene terephthalate, polyethylene 2,6 naphthalate, polypropylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamideimide, polyethersulfan, polyetheretherketone, Examples include polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polystyrene, syndiotactic polystyrene, and norbornene polymers. It is

[0025] Among these organic polymers, polyethylene terephthalate, polypropylene terephthalate, polyethylene 2,6 naphthalate, syndiotactic polystyrene, nonolebornene-based polymer, polycarbonate, polyarylate and the like are preferable. These organic polymers may be copolymerized with a small amount of other organic polymer monomers, or may be blended with other organic polymers.

[0026] The thickness of the transparent plastic film used in the present invention is preferably in the range of more than 10 μm and 300 μm or less. The upper limit is 260 μm, and the lower limit is 70 μm. m It is particularly preferable. When the thickness of the plastic film is 10 m or less, the mechanical strength is insufficient, especially when it is used for a touch panel, the deformation tends to increase with respect to pen input, and the durability tends to be insufficient. On the other hand, if the thickness exceeds 300 m, it is necessary to increase the pen load for deforming the film when used for touch panels. Therefore, the load applied to the transparent conductive thin film inevitably increases, which is not preferable from the viewpoint of durability of the transparent conductive thin film.

[0027] The substrate having a transparent plastic film force used in the present invention has a corona discharge treatment, a glow discharge treatment, a flame treatment, an ultraviolet irradiation treatment, and an electron beam irradiation treatment as long as the object of the present invention is not impaired. Further, surface activation treatment such as ozone treatment may be performed.

[0028] In the present invention, for the purpose of improving adhesion between the substrate and the transparent conductive layer, imparting pen input durability, chemical resistance, and preventing precipitation of low molecular weight substances such as oligomers, Between the transparent conductive thin film layers, a cured product layer mainly composed of curable resin may be provided.

[0029] The curable resin is not particularly limited as long as it is cured by application of energy such as heating, ultraviolet irradiation, electron beam irradiation, etc. Silicone resin, acrylic resin, methacrylic resin, epoxy Examples include rosin, melamine, polyester and urethane. From the viewpoint of productivity, a curable resin having an ultraviolet curable resin as a main component is preferable.

[0030] Examples of such ultraviolet curable resin include polyfunctional acrylate resin, diisocyanate, polyalcohol such as polyhydric alcohol acrylic acid or methacrylic acid ester, and acrylic acid or methacrylic acid. Examples thereof include polyfunctional urethane acrylate glycols synthesized from hydroxyalkyl esters of acids. If necessary, a monofunctional monomer such as vinyl pyrrolidone, methyl metatalylate, or styrene can be copolymerized with these polyfunctional resins.

[0031] In order to improve the adhesion between the transparent conductive thin film and the cured product layer, it is effective to surface-treat the cured product layer. Specific methods include a discharge treatment method that irradiates a glow or corona discharge, a method that increases carbonyl groups, carboxyl groups, and hydroxyl groups, and a chemical treatment method that uses acids or alkalis to treat amino acids. And a method of increasing the number of polar groups such as a group, a hydroxyl group and a carbonyl group. [0032] The ultraviolet curable resin is usually used by adding a photopolymerization initiator. As the photopolymerization initiator, known compounds that absorb ultraviolet rays to generate radicals can be used without any particular limitation. Examples of such photopolymerization initiators include various benzoins and phenyl ketones. And benzophenones. The addition amount of the photopolymerization initiator is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.

[0033] The concentration of the resin component in the coating solution can be appropriately selected in consideration of the viscosity according to the coating method. For example, the proportion of the total amount of UV curable resin and photopolymerization initiator in the coating solution is usually 20 to 80% by mass. In addition, other known additives such as leveling agents such as silicone surfactants and fluorine surfactants may be added to the coating solution as necessary.

In the present invention, the prepared coating solution is coated on a substrate such as a transparent plastic film cover. As the coating method, a method known in the art such as a bar coating method, a gravure coating method, and a reverse coating method, which are not particularly limited, can be used.

[0035] The thickness of the cured product layer is preferably in the range of 0.1 to 15 µm. The lower limit of the thickness of the cured product layer is more preferably 0.5 m, particularly preferably 1 μm. Further, the upper limit value of the thickness of the cured product layer is more preferably 10 / z m, and particularly preferably 8 m. When the thickness of the cured product layer is less than 0.1 m, it is difficult to form a sufficiently cross-linked structure, so pen input durability tends to decrease chemical resistance, and due to low molecular weight such as oligomers. Decrease in adhesion is also likely to occur. On the other hand, when the thickness of the cured product layer exceeds 15 m, productivity tends to decrease.

In the present invention, the metal oxide constituting the transparent conductive thin film is not particularly limited as long as it is a material having both transparency and conductivity, but indium oxide, tin oxide, zinc oxide. , Indium-tin complex oxide, tin-antimony complex oxide, zinc-aluminum complex oxide, indium zinc complex oxide, silver or silver alloy, copper or copper alloy, gold, etc. Is mentioned. Of these, indium-tin composite oxide is preferred from the viewpoints of environmental stability and circuit processability. The transparent conductive thin film used in the present invention contains a metal oxide as a main component, but contains carbon in a concentration of 1 X 10 ² to 1 X 10 ²² (atomsZcm ³ ) as other components. . Moreover, as long as the effect of the present invention is not impaired. In addition, components other than metal oxide and carbon are contained in an amount of 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

[0037] The layer structure of the transparent conductive thin film may be a single layer structure or a laminated structure of two or more layers.

In the case of a transparent conductive thin film having a laminated structure of two or more layers, the metal oxides constituting each layer may be the same or different.

The film thickness of the transparent conductive thin film is preferably in the range of 4 to: LOOnm, particularly preferably the lower limit is 5 nm and the upper limit is 50 nm. When the film thickness of the transparent conductive thin film is less than nm, it is difficult to obtain a good conductivity that is difficult to form a continuous thin film. On the other hand, when the film thickness of the transparent conductive thin film is thicker than SlOOnm, the transparency tends to decrease and it becomes difficult to obtain a film having mechanical strength that can withstand bending stress near the frame of the touch panel. .

[0039] As a method for forming a transparent conductive thin film in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and depending on the required film thickness, The above methods can be used as appropriate.

[0040] For example, in the case of a sputtering method, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, or means such as ozone addition, plasma irradiation, or ion resist may be used in combination. In addition, a bias such as direct current, alternating current, and high frequency may be applied to the substrate as long as the object of the present invention is not impaired.

[0041] In the present invention, the purpose of using a film having an amorphous force as the transparent conductive thin film is to prevent stress from concentrating on a local area such as a crystal, an amorphous interface, or a crystal interface of the transparent conductive thin film. This is to suppress the occurrence of cracks in the conductive film due to bending stress in the sliding test.

[0042] In order to obtain an amorphous transparent conductive thin film, the following two methods are effective.

(1) Method of lowering the temperature of the film that becomes the substrate during film formation

(2) Method to make it difficult to form a crystal structure by increasing the amount of tin and other dopants relative to indium

First, the above method (1) will be described. In a film-forming atmosphere in which moisture and organic impurities are removed as much as possible when the transparent conductive thin film is formed, migration on the substrate (film) surface is likely to occur because the energy drop of the deposited particles is small. As a result, a transparent conductive film containing crystals in the transparent conductive thin film tends to occur. In order to obtain an amorphous transparent conductive thin film in such a film-forming atmosphere, the temperature of the film as the substrate is lowered, and migration on the surface of the substrate (film) is performed when vapor deposition particles are deposited. There is an effect to make it difficult to occur.

[0044] For example, when a transparent conductive thin film is formed on a film using a roll-up type apparatus by sputtering, contact the back surface of the film (the surface opposite to the surface on which the transparent conductive thin film is formed). By lowering the roll temperature, it is possible to lower the temperature of the film serving as the substrate.

[0045] The temperature at which the transparent conductive thin film is formed on the transparent plastic film as the substrate is preferably -20 to 30 ° C. When the temperature at the time of film formation exceeds 30 ° C, it becomes easy to form crystals in the transparent conductive thin film. On the other hand, when the temperature is lower than -20 ° C, the transparent plastic film becomes brittle.

[0046] In order to control the roll temperature, a water channel is provided in the roll, and a temperature-adjusted heat medium may flow through the water channel. The heating medium is not particularly limited, but simple substances such as water, oil, ethylene glycol, propylene glycol, and mixtures thereof are suitable.

[0047] Furthermore, in order to obtain an amorphous transparent conductive thin film in an atmosphere in which moisture and organic substances in the film forming atmosphere are removed as much as possible, the amount of dopant such as tin is reduced with respect to indium. It is also an effective method to form a crystal structure by increasing it. Specific dopants include Sn, Si, Ti, W, Zr, Hf, and Zn. Among these dopants, tin is preferably used from the viewpoint of improving conductivity and film hardness.

[0048] dopant amount of tin to indium is preferably 15 to 60 mass ^_0/0. 15 mass ^_0/0 improvement of film hardness of an amorphous state if less than is insufficient, pen sliding durability in Tatsuchipaneru central portion in Tatsuchipaneru using such transparent conductive films It becomes insufficient, and the transparent conductive thin film is scraped after the pen sliding test. Also, if it exceeds 60% by mass, the conductivity will be insufficient, and if you try to maintain conductivity that can be used as a touch panel, The film thickness of the transparent conductive thin film must be increased. Therefore, the transparency of the transparent conductive film tends to be lowered. When a touch panel is manufactured using such a transparent conductive film inferior in transparency, the visibility of the touch panel is lowered.

[0049] In the present invention, the purpose of setting the carbon concentration in the transparent conductive thin film to 1 X 10 ² to 1 X 10 ²² (at oms / cm ³ ) In order to obtain a transparent conductive thin film that is less susceptible to peeling and cracking against bending stress near the frame of the touch panel. If the carbon concentration in the transparent conductive thin film is less than 1 × 10 ² ° (at _O msZcm ³ ), the effect of improving the adhesion between the transparent conductive thin film and the substrate is insufficient. On the other hand, it is technically difficult to obtain a transparent conductive thin film exceeding l X 10 ²² (at _O msZcm ³ ).

[0050] For the carbon concentration of the transparent conductive thin film to obtain a ^{_{_{l X 10 2 (a t O}}} msZcm 3) or more transparent conductive thin film, the film formation atmosphere when depositing transparent conductive thin film It is important to introduce a gas component containing carbon with moisture removed as much as possible.

[0051] Examples of the gas component containing carbon include carbon monoxide, carbon dioxide, carbon tetrachloride, and methane. Of these, gases containing only carbon and oxygen such as carbon monoxide and carbon dioxide are preferred.

[0052] For example, in the case of forming a film by sputtering, after evacuating the pressure in the vacuum chamber to a vacuum degree of 0. OOOlPa or less before performing sputtering, an inert gas such as Ar, oxygen, and nitrogen are used. It is preferable to perform sputtering by introducing a reactive gas containing carbon such as acid carbon into a vacuum chamber, generating discharge in a pressure range of 0.01 to 10 Pa. The same applies to other methods such as vapor deposition and CVD.

If moisture remains in the film forming atmosphere, hydrogen is taken into the transparent conductive thin film, and the growth of the network (for example, In—O—) of the transparent conductive thin film may stop. In that case, it becomes difficult for carbon to be taken into the transparent conductive thin film, and a transparent conductive thin film having a specific carbon concentration can be obtained. As a result, the adhesion between the transparent conductive thin film and the substrate made of the film becomes insufficient, and the touch panel using such a transparent conductive film decreases the mechanical strength due to the bending stress of the transparent conductive film, resulting in a frame. Pen sliding durability in the vicinity tends to decrease. [0054] A transparent conductive film in which a transparent conductive thin film having a low carbon concentration in such a transparent conductive thin film is laminated has insufficient adhesion between the transparent conductive thin film and the substrate. When such a transparent conductive film is used for a touch panel, peeling or cracking occurs in the transparent conductive thin film after a linear sliding test of 10,000 times at a load of 2.5 N in the vicinity of the frame.

[0055] In order to reduce the moisture in the film formation atmosphere, it is an effective method to reduce the moisture by exposing the film to a vacuum in a vacuum chamber for performing sputtering or the like. Impurities such as moisture and organic substances in the film formation atmosphere can be further reduced by using a method that raises the temperature of the roll in contact with the film during vacuum exposure or a method that uses film heating with an infrared heater. It becomes possible. The heat treatment temperature at this time is preferably in the range of 100 to 200 ° C. Below 100 ° C, the effect of reducing impurities such as moisture and organic matter becomes insufficient, and at temperatures exceeding 200 ° C, it tends to be difficult to maintain the flatness of the film.

[0056] Furthermore, it is also an effective method to provide a cryocoil in the deposition chamber in order to remove moisture in the deposition atmosphere.

[0057] In this way, by removing moisture in the film formation atmosphere as much as possible and introducing a gas containing carbon as a reactive gas, the carbon concentration in the amorphous conductive thin conductive film is high. A transparent conductive film is obtained. For this reason, when this transparent conductive thin film is used for a touch panel, after a linear sliding test is performed 10,000 times with a load of 2.5 N near the frame using a polyacetal pen (tip shape: 0.8 mmR). However, there is no deterioration of the transparent conductive thin film.

[0058] Further, the carbon concentration in the thickness direction of the transparent conductive thin film may be lowered as it goes toward the inside of the transparent conductive thin film, as long as the conductivity of the transparent conductive thin film is not deteriorated. preferable. More preferably, carbon atoms are localized only within 5 nm from the film substrate. By localizing the carbon concentration in the thickness direction of the transparent conductive thin film in this way, the adhesion between the transparent conductive thin film and the base material is improved, and the same conductivity as when no carbon atom is contained is obtained. A transparent conductive thin film can be obtained. The carbon concentration is controlled by adjusting the flow rate of the gas containing carbon supplied as the reactive gas during film formation. Is possible.

[0059] For the purpose of changing the transmittance, color, and reflectance of the transparent conductive film, it is preferable to provide at least two layers having different refractive indexes between the transparent conductive thin film and the cured product layer. For example, when two layers with different refractive indexes are provided, a layer with a refractive index of 1.60 or more and 2.50 or less and a layer with a refractive index of 1.30 or more and 1.60 or less are laminated from the transparent plastic film side. It is preferable to do.

[0060] A layer having a refractive index of 1.60 or more and 2.50 or less is a layer made of an inorganic substance, a mixture of an organic substance and an inorganic substance. Inorganic, transparent metal oxides such as In O, TiO, and Nb O are common.

2 3 2 2 5

Used for.

[0061] The layer composed of a mixture of an organic substance and an inorganic substance includes a cured resin and metal oxide by ionizing radiation, and has a refractive index in the range of 1.60 to L80 (hereinafter, this layer is referred to as a high refractive layer). Called). When the refractive index of the layer is less than 1.60, a transparent conductive film excellent in antireflection performance can be obtained. If the refractive index of the layer exceeds 1.80, it becomes difficult to form the layer. The preferred refractive index has a lower limit of 1.70 and an upper limit of 1.80.

[0062] The metal oxide is not particularly limited as long as a layer having a refractive index of 1.60 to L 80 is obtained, but the transmittance of the transparent conductive film is further improved. Therefore, it is preferable to have excellent adhesion with a layer provided thereon. From this point of view, the metal oxide is not particularly limited as long as it satisfies the above conditions. For example, when the low refractive index layer is a siloxane polymer, antimony monophosphate (tin ( ATO), acid tin and the like can be preferably mentioned. One of these metal oxides can be used alone, or two or more can be used in combination.

[0063] The layer having a refractive index of 1.30 or more and 1.60 or less is also composed of an organic substance, an inorganic substance, or a mixture of an organic substance and an inorganic substance. Generally, inorganic materials are SiO

2, Transparent metal oxides such as Al O are used 2 3

It is done.

[0064] From the viewpoint of adhesion to the transparent conductive thin film, the organic substance includes at least one of a siloxane-based polymer, polyurethane, polyester, and acrylic, and has a refractive index of 1.30 to : L55 is preferable. When the refractive index is out of range In this case, a transparent conductive film excellent in color display is obtained.

[0065] Further, in the case of a touch panel, for the purpose of preventing the occurrence of Yuton ring, particles are added to the cured product layer so that the center line average roughness (Ra) is in the range of 0.1 to 0.5 m. It is preferably contained. When Ra is less than 0.1, it is difficult to prevent the occurrence of Newton rings. On the other hand, when Ra exceeds 0.5 m, the surface of the transparent conductive thin film becomes too rough, and the pen sliding durability tends to deteriorate.

[0066] The particles to be contained in the cured product layer are not particularly limited, but inorganic particles (eg, silica, calcium carbonate, etc.), heat-resistant organic particles (eg, silicon particles, PTFE particles, polyimide particles, etc.) ), Crosslinked polymer particles (crosslinked PS particles, crosslinked acrylic particles, etc.). The average particle size of these particles (by electron microscopy) is preferably 0.5-5 / ζ πι. Further, the content of the particles to be contained in the cured product layer is preferably 0.01 to LO mass%.

[0067] Further, in order to further improve the scratch resistance of the outermost layer (pen input surface) when the touch panel is formed, the surface opposite to the surface on which the transparent conductive thin film of the transparent plastic film is formed (the touch panel and It is preferable to provide a hard coat layer on the outermost pen input surface). The hard coat layer preferably has a pencil hardness of 2 mm or more. When the hardness is less than 2 mm, it is insufficient as a hard coat layer for a transparent conductive film in terms of scratch resistance.

[0068] The thickness of the hard coat layer is preferably 0.5 to 10 µm. If the thickness is less than 0.5 μm, the scratch resistance becomes insufficient, and if it is immediately thicker than 10 m, it is not preferable from the viewpoint of productivity.

[0069] The curable resin composition used in the hard coat layer is preferably a resin having an acrylate functional group. For example, a relatively low molecular weight polyester resin, a polyester resin, an acrylic resin Oligomers or prepolymers such as (meth) acreates of multifunctional compounds such as resin, epoxy resin, urethane resin, alkyd resin, spirocetal resin, polybutadiene resin, polythiolpolyene resin and polyhydric alcohol Etc.

[0070] The reactive diluents include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-butylpyrrolidone, and many others. Functional monomers such as trimethylol propane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl alcohol di (meth) acrylate, etc. can be used

[0071] In the present invention, it is preferable to mix urethane atylate as the oligomer and dipentaerythritol hexa (meth) atallylate as the monomer.

[0072] Further, as the curable resin composition used for the hard coat layer, a mixture of polyester phthalate and polyurethane acrylate is particularly preferable. Polyester acrylate is very hard and suitable as a hard coat layer. However, there is a problem that a coating film of polyester acrylate is low in impact resistance and easily brittle. Therefore, in order to give impact resistance and flexibility to the coating film, it is preferable to use polyurethane acrylate in combination. That is, by using the polyurethane acrylate in combination with the polyester acrylate, the coating film can have functions such as impact resistance and flexibility while maintaining the hardness as the hard coat layer.

[0073] The blending ratio of the two is preferably 30 parts by mass or less of the polyurethane acrylate resin per 100 parts by mass of the polyester acrylate resin. When the blending ratio of polyurethane acrylate resin exceeds 30 parts by mass, the coating film becomes too soft and the impact resistance tends to be insufficient.

[0074] As a method for curing the curable rosin yarn and composition, a normal curing method, that is, a method of curing by heating, electron beam or ultraviolet irradiation can be used. For example, in the case of electron beam curing, it is emitted from various electron beam accelerators such as Cockloft Walton type, handigraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having energy of ˜1000 keV, preferably 100 to 300 keV is used. In the case of ultraviolet curing, ultraviolet rays that emit light, such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal nitride lamp can be used. [0075] Further, in the case of ionizing radiation curing, it is preferable that a photopolymerization initiator or a photosensitizer is contained in the curable resin composition. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoyl benzoate, a-amixy oxime ester, tetramethylthiuram monosulfide, thixanthones, and the like. As the photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine and the like are preferable.

[0076] In order to impart antiglare properties to the hard coat layer, CaCO, SiO, etc.

Effective methods include dispersing the inorganic particles 3 or forming a concavo-convex shape on the surface of the hard coat layer. For example, in order to form irregularities, after applying a coating liquid containing a curable resin composition, a shaped film having a convex shape is laminated on the surface, and ultraviolet rays are irradiated on the shaped film. After curing the curable resin, it is obtained by peeling only the shaped film.

[0077] The shape-imparting film may be a film having a desired convex shape on a base film such as polyethylene terephthalate (hereinafter abbreviated as PET) having releasability, or a base film such as PET. A material having a delicate convex layer can be used. The formation of the convex layer can be obtained, for example, by coating on a base film using a resin composition comprising inorganic particles and a binder resin.

[0078] As the Noinda resin, for example, acrylic polyol cross-linked with polyisocyanate can be used, and as inorganic particles, CaCO, SiO, or the like can be used. Also this

3 2

In addition, use mat-type PET with inorganic particles such as SiO incorporated during PET production.

2

Can do.

[0079] When this shaped film is laminated on a coating film of ultraviolet curable resin and then the coating film is cured by irradiating with ultraviolet rays, when the shaped film is a PET-based film, The short wavelength side is absorbed, and the UV curable resin is insufficiently cured. Therefore, it is necessary to use a moldable film that is laminated on the UV curable resin coating film with a total light transmittance of 20% or more.

[0080] Further, in order to further improve the transmittance of visible light when used in a touch panel, a low reflection treatment may be performed on the hard coat layer. This low reflection treatment A material having a refractive index different from the refractive index is preferably laminated in a single layer or two or more layers.

[0081] In the case of a single-layer structure, it is preferable to use a material having a refractive index smaller than that of the hard coat layer. When a multilayer structure of two or more layers is used, the layer adjacent to the hard coat layer is made of a material having a higher refractive index than that of the hard coat layer, and the upper layer has a lower refractive index. Choose the material you have. The material constituting such a low reflection treatment is not particularly limited as long as the above refractive index relationship is satisfied, whether it is an organic material or an inorganic material. For example, CaF, MgF, NaAlF, SiO, ThF, ZrO, NdO, SnO, Ti

2 2 4 2 4 2 2 3 2

It is preferable to use a dielectric such as 0, CeO 2, ZnS, or In 2 O 3.

2 2 2 3

[0082] The low reflection treatment may be a dry coating process such as a vacuum deposition method, a sputtering method, a CVD method, or an ion plating method, or a wet coating process such as a gravure method, a reverse method, or a die method.

[0083] Further, prior to the lamination of the low reflection treatment layer, as pretreatment, corona discharge treatment, plasma treatment, sputter etching treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, primer treatment, easy adhesion treatment, etc. Apply a known surface treatment to the node coat layer.

[0084] Using the transparent conductive film of the present invention, a transparent conductive thin film is formed, and then laminated with a transparent resin sheet via a surface and an adhesive, whereby the transparent conductive film used for the fixed electrode of the touch panel is used. A laminated resin sheet is obtained. In other words, by changing the glass substrate to the transparent resin sheet as the substrate for the fixed electrode of the touch panel, it is possible to manufacture a touch panel that is light and difficult to break.

[0085] The pressure-sensitive adhesive is not particularly limited as long as it has transparency. For example, an acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and a rubber pressure-sensitive adhesive are suitable. The thickness of the pressure-sensitive adhesive is not particularly limited, but it is usually desirable to set it within a range of 1 to: LOO / zm. When the thickness of the pressure-sensitive adhesive is less than L m, it is difficult to obtain adhesiveness that is practically acceptable, and when it exceeds 100 μm, it is preferable from the viewpoint of productivity.

[0086] The transparent resin sheet to be bonded via the adhesive is used for imparting mechanical strength equivalent to that of glass, and the thickness is preferably in the range of 0.05 to 5 mm. If the thickness of the transparent resin sheet is less than 0.05 mm, the mechanical strength is insufficient compared to glass. one On the other hand, if the thickness exceeds 5 mm, it is too thick to be used for touch panels. The material of the transparent resin sheet can be the same as that of the transparent plastic film.

FIG. 1 shows an example of a touch panel using the transparent conductive film of the present invention. This is because a pair of panel plates having a transparent conductive thin film is placed on a touch panel in which the transparent conductive thin film is disposed through a spacer so that the transparent conductive thin film faces each other. A bright conductive film is used.

[0088] This touch panel detects the position of the pen on the touch panel when the characters are input with the pen and the transparent conductive thin films facing each other come into contact with each other due to the pressing from the pen. can do. By detecting the pen position continuously and accurately, the pen trajectory can also recognize characters. At this time, when the movable electrode on the pen contact side uses the transparent conductive film of the present invention, since the pen sliding durability is excellent, a touch panel that is stable for a long time can be obtained.

[0089] Fig. 2 shows a cross-sectional view of a plastic touch panel obtained using the transparent conductive film and the transparent conductive sheet of the present invention without using a glass substrate. This plastic touch panel does not use glass, so it is very lightweight and will not crack on impact.

Example

[0090] Hereinafter, the present invention will be described in further detail with reference to examples. The present invention is not limited to these examples. The performance of the transparent conductive film, the crystallinity of the transparent conductive thin film, and the pen sliding durability test of the touch panel were measured using the following methods.

[0091] (1) Light transmittance and haze

In accordance with JIS-K7105, light transmittance and haze were measured using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.

[0092] (2) Surface resistivity

Measured by the 4-terminal method in accordance with JIS-K7194. As a measuring machine, Lot est AMCP-T400 manufactured by Mitsubishi Yuka Co., Ltd. was used. [0093] (3) Color (a value, b value)

In accordance with JIS-K7105, color a and b values were measured with standard light CZ2 using a color difference meter (Nippon Denshoku Industries Co., Ltd., ZE-2000).

[0094] (4) Crystallinity of transparent conductive thin film

A transparent conductive film sample piece was cut into a 300 m × 300 m square and fixed to a sample holder of an ultramicrotome with the conductive thin film surface facing forward. Next, a knife was placed at an extremely acute angle with respect to the film surface so that a section having a target observation site of 1 m × 1 μm or more could be obtained, and cutting was performed at a set thickness of 70 nm.

[0095] On the surface side of the conductive thin film of this section and the thin film was not significantly damaged, an observation field of 1 μm X 1 m was secured at the site, and a transmission electron microscope (manufactured by JEOL, JEM — 2010) and photographed at an acceleration voltage of 200 kV and a bright field at an observation magnification of 50,000 times. In the field of view, the electron density is high! Particles with a diameter of 5 nm or more observed as a region are counted as crystal particles, and the average number of particles in 10 fields of view is the number of crystal particles such as metal oxides. The number (number Z m ² ) was used.

[0096] (5) Pen sliding durability test near the frame

Apply a 2.5N load to a polyacetal pen (tip shape: 0.8mmR) at a position 1.5mm away from the inside of the bonding part of the touch panel. Went to the touch panel. The sliding distance at this time was 30 mm, and the sliding speed was 60 mmZ seconds. Furthermore, the gap between the upper and lower substrates of the touch panel was 150 / zm. After this sliding durability test, first, it was visually observed whether the sliding portion was whitened. In addition, the vicinity of the sliding part was observed with a microscope, and observed for occurrence of cracks. Furthermore, the ON resistance (resistance value when the movable electrode (film electrode) and the fixed electrode were in contact) when the sliding part was pressed with a pen load of 1. ON was measured.

[0097] (6) Pen sliding durability test

Polyacetal pen (tip shape: 0.8mmR) scissors 2.5 A load of 5N was applied, and a linear sliding test was performed 100,000 times (50,000 reciprocations) on the touch panel. The sliding distance at this time was 30 mm, and the sliding speed was 60 mmZ seconds. After this sliding durability test, first, it was visually observed whether the sliding portion was whitened. Furthermore, the above sliding part is applied with a pen load of 0.5 N. In this way, we wrote a 20mm φ symbol O and evaluated whether the touch panel could read it correctly. Furthermore, the ON resistance (resistance value when the movable electrode (film electrode) and the fixed electrode were in contact) when the sliding part was pressed with a pen load of 0.5 mm was measured.

[0098] (7) Adhesive force measurement

A 40 μm thick ionomer film was laminated to a 75 m thick polyethylene terephthalate film using a polyester adhesive to produce a laminate for measuring adhesion. The ionomer surface of this laminate for measuring adhesive force and the transparent conductive thin film surface of the transparent conductive film were opposed to each other and heat sealed at 130 ° C. The laminate was peeled from the laminate for measuring adhesive force and the transparent conductive film by a 180 ° peeling method, and this peeling force was defined as the adhesive strength. The peeling speed at this time was set to lOOOmmZ.

[0099] (8) Measurement of carbon concentration in transparent conductive thin film

A 140 m X 224 m detection area was secured on the surface of the conductive thin film, and evaluation was performed with SIMS (PHI, 6650) using primary calo fast voltage lkV and Cs + primary ions. The carbon content in the film was derived by determining the relative sensitivity coefficient with a standard sample ion-implanted with a known carbon concentration. Furthermore, the hydrogen concentration in the transparent conductive thin film is also measured at the same time, and the depth at which the matrix effect (reduction in hydrogen concentration due to changes in the layer constituent materials) is defined is defined as the interface between the transparent conductive thin film and the substrate. The carbon concentration at the depth on the surface side of the 2 nm transparent conductive thin film was defined as the carbon concentration in the transparent conductive thin film.

[0100] (9) Surface roughness

A sample is brought into close contact with a glass plate, and in accordance with JIS B0601, using a two-dimensional surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 300B), cut-off 0.8, measurement length 4mm, stylus load The centerline average roughness (Ra) was measured under the conditions of 4 mN and stylus speed of 0.3 mmZ.

[0101] Example 1

Photopolymerization initiator-containing acrylic resin (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika Beam EXF-01J) A solvent mixture of toluene ZMEK (80Z20: mass ratio) as a solvent and a solid content concentration of 50% by mass The mixture was stirred and dissolved uniformly to prepare a coating solution.

[0102] Biaxially oriented transparent PET film with easy-adhesion layers on both sides (Toyobo Co., Ltd., A4340, thickness 188 m), the prepared coating solution was applied using a Mayer bar so that the coating thickness was 5 μm. After drying at 80 ° C. for 1 minute, the coating film was cured by irradiating with ultraviolet rays (light quantity: 300 mjZcm ² ) using an ultraviolet irradiation device (UB042-5AM-W type, manufactured by I-Graphics). Next, heat treatment was performed at 180 ° C for 1 minute to reduce volatile components.

[0103] Further, in order to expose the biaxially oriented transparent PET film on which the cured product layer was laminated in a vacuum, a rewinding treatment was performed in a vacuum chamber. The pressure at this time was 0.002 Pa, and the exposure time was 20 minutes. The center roll temperature was 40 ° C.

Next, a transparent conductive thin film having an indium-tin composite oxide strength was formed on the cured product layer. At this time, the pressure before sputtering and 0. OOOlPa, indium oxide containing 36 wt% tin oxide as a target (Sumitomo Metal Mining Co., density: 6. 9g / cm ³⁾ used to, DC power 2WZcm ² Was applied. Ar gas 130sccm, O gas 20

2 sccm, CO gas at a flow rate of 20 sccm, DC magnetron spa in 0.4 Pa atmosphere

2

A film was formed using a sputtering method. However, in order to prevent arc discharge that occurs with normal DC, a 5 µs wide pulse was applied at a 50 kHz period using RPG-100 made by Nippon Yanai. The center roll temperature was 10 ° C. and sputtering was performed.

[0105] In addition, while constantly monitoring the oxygen partial pressure of the atmosphere with a sputtering process monitor (manufactured by LEYBOLD INFICON, XPR2), oxygen gas was used so that the acidity in the indium oxide composite oxide thin film was constant. Fed back to the flow meter and DC power supply. As described above, a transparent conductive thin film made of indium monotin complex oxide having a thickness of 22 nm was deposited to produce a transparent conductive film.

[0106] <Production of touch panel>

This transparent conductive film was used as one panel plate, and the other panel plate was an indium-tin composite oxide thin film (thin oxide content: 10% by mass) on a glass substrate with a thickness of 20 nm by plasma CVD. ) Transparent conductive thin film (Nippon Soda Co., Ltd., S500) was used. A touch panel was prepared by placing these two panel plates with 30 m diameter epoxy beads so that the transparent conductive thin film faces each other.

[0107] Example 2 In Example 1, a cryocoil (manufactured by Hakutosha Co., Ltd., polycold) is provided in the film forming chamber, and c

Indium-tin composite as in Example 1 except that the O gas flow rate was 40 sccm.

2

An oxide thin film was formed to produce a transparent conductive film. Further, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1.

[0108] Example 3

In Example 1, a target composed of an indium-tin composite oxide having a tin oxide content of 20% by mass was used, and the amount of oxygen introduced was changed to an amount that minimizes the specific resistance value. A film was formed to produce a transparent conductive film. When this target was used, the content of tin oxide in the indium-tin composite oxide thin film was 19% by mass.

[0109] Example 4

In Example 1, a target composed of an indium-tin composite oxide having a tin oxide content of 60% by mass was used, and the amount of oxygen introduced was set to an amount that minimizes the specific resistance value. A film was formed to produce a transparent conductive film. When this target was used, the content of tin oxide in the indium-tin composite oxide thin film was 59% by mass.

[0110] Example 5

In the same manner as in Example 1, a laminate composed of a base Z cured material layer having a biaxially oriented transparent PET film force was produced. On the surface opposite to the cured product layer surface of this laminate, an ultraviolet curable resin (EXG, manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a mixture of polyester acrylate and polyurethane acrylate, is used as a hard coat layer resin. It was applied by gravure reverse method so that the film thickness after drying was 5 μm, and the solvent was dried. Thereafter, it was passed under a 160 W ultraviolet irradiation device at a speed of 10 mZ to cure the ultraviolet curable resin, thereby forming a hard coat layer. Next, heat treatment was performed at 180 ° C for 1 minute to reduce volatile components.

[0111] This hard coat layer Z Biaxially oriented transparent PET film force Base material Z Hardened material layer force The indium tin oxide composite oxide thin film is formed on the cured material layer of the laminate in the same manner as in Example 1. Then, a transparent conductive film was produced. Sarakuko, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1.

[0112] Example 6

In the same manner as in Example 1, the substrate was made of a Z-cured material layer having a biaxially oriented transparent PET film force. A laminate was prepared. On the surface opposite to the cured product layer surface of this laminate, UV curing type resin (EXG manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a mixture of polyester acrylate and polyurethane acrylate, is dried as a resin for the hard coat layer. The film was applied by the Daravia reverse method so that the subsequent film thickness was 5 μm, and the solvent was dried. After that, a mat-shaped film (X made by Torayen Earth Co., Ltd.) having a PET film with a fine convex shape formed on the surface was laminated so that the mat surface was in contact with the ultraviolet curable resin. The surface shape of this mat shaped film is an average surface roughness of 0.40 ^ m, an average peak interval of 160 / ζ πι, and a maximum surface roughness of 25 m.

[0113] The laminated film was passed under a 160 W ultraviolet irradiation device at a speed of 10 mZ to cure the ultraviolet curable resin. Next, the mat-shaped film was peeled off, and the surface was processed with a concave shape to form a hard coat layer having an antiglare effect. Next, heat treatment was performed at 180 ° C for 1 minute to reduce volatile components.

[0114] This antiglare coating layer, coated layer Z biaxially oriented transparent PET film strength substrate Z cured product layer On the cured product layer of the laminate also having strength, indium-tin composite oxide A transparent thin film was formed as a transparent conductive thin film to produce a transparent conductive film. Further, this transparent conductive film was used as one panel plate, and a touch panel was produced in the same manner as in Example 1.

[0115] Example 7

In the same manner as in Example 5, a laminate comprising an antiglare node coat layer Z, a biaxially oriented transparent PET film, a substrate Z cured product layer, and a Z transparent conductive thin film layer was produced. Next, on this antiglare node coat layer, a TiO thin film layer (refractive index: 2.30, film thickness: 15 nm), SiO thin film successively.

2 2 Film layer (refractive index: 1.46, film thickness: 29nm), TiO thin film layer (refractive index: 2.30, film thickness: 109nm)

2

, SiO thin film layer (refractive index: 1.46, film thickness: 87nm) was laminated to form an antireflection treatment layer

2

. To form a TiO thin film layer, use titanium as a target and a direct current magnetron spa.

2

The vacuum level is set to 0.27 Pa, Ar gas is 500 sccm, and O gas is 80 s.

2

Flowed at a flow rate of ccm. At this time, 7.8 WZcm ² of power was supplied to the target, and the dynamic rate was 23 nm'mZ. In addition, the transparent plastic film was cooled by providing a cooling hole with a surface temperature of 0 ° C on the back of the substrate.

[0116] To form a SiO thin film, a silicon magnet is used as a target and a DC magnetron spas Tulling method, vacuum degree is 0.27Pa, Ar gas is 500sccm, O gas is 80sccm

2

The flow rate was. At this time, 7.8 WZcm ² of power was supplied to the target, and the dynamic rate was 23 nm'mZ. In addition, a 0 ° C cooling roll was provided on the back of the substrate to cool the transparent plastic film. Further, using this transparent conductive film as one panel plate, a touch panel was produced in the same manner as in Example 1.

[0117] Example 8

The transparent conductive film produced in the same manner as in Example 1 was attached to a polycarbonate sheet having a thickness of 1. Omm through an acrylic adhesive to produce a transparent conductive laminate sheet. A touch panel was produced in the same manner as in Example 1 using this transparent conductive laminated sheet as a fixed electrode and the transparent conductive film of Example 6 as a movable electrode.

[0118] Example 9

TiO-containing acrylic hard coat agent QiSR, trade name `` Desolite Z7252D '', solid

2

Form concentration: 45 mass%, TiO: acrylic resin = 75:25 (mass ratio)], solid content concentration is 3 quality

2

A coating solution was prepared by diluting with a mixed solvent of methyl isobutyl ketone and isopropyl alcohol in a mass ratio of 1: 1 so that the amount was%. Next, the hard coating layer Z biaxially stretched PET film prepared in the same manner as in Example 4 Z cured product layer strength on the cured product layer of the laminate, the thickness after the coating solution was completely cured The film was applied to a thickness of 70 nm and dried at 80 ° C for 1 minute. Further, ultraviolet rays were irradiated with a light amount of SOmjZcm ² to be cured in a half-cured state to form a highly refractive layer.

[0119] Further, a fluorine-containing siloxane coating agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-12-12138H", solid content concentration: 3% by mass) with a photopolymerization initiator-containing acrylic resin Fat (Seika Beam EXF-01J, manufactured by Dainichi Seika Kogyo Co., Ltd.) was added so that the total solid content was 6% by mass. This coating solution for forming a low refractive index layer was applied onto the high refractive index layer so that the thickness after the heat treatment was 20 nm, and dried at 80 ° C. for 1 minute. Subsequently, ultraviolet rays were irradiated (light quantity: 300 miZcm ² ) using an ultraviolet ray irradiation device (UB042-5AM-W type, manufactured by Eye Graphics Co., Ltd.). Furthermore, a low refractive index layer having a refractive index of 1.48 was formed by heat treatment at 150 ° C. for 1 minute. Next, a transparent conductive thin film layer was formed in the same manner as in Example 1 to obtain a transparent conductive film. Sarakuko, using this transparent conductive film, the same as Example 1. In this way, a touch panel was produced.

[0120] Example 10

A transparent conductive film was obtained in the same manner as in Example 8 except that the thicknesses of the high refractive layer and the low refractive layer were 90 nm and 45 nm, respectively. Further, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1.

[0121] Example 11

In Example 1, when adjusting with a coating solution for forming a cured product layer, Tospearl 145 having an average particle size of 4.5 μm (manufactured by Toshiba Silicone) was 1 mass per 100 mass parts of acrylic resin. And particles were dispersed in the coating solution. A transparent conductive film is produced in the same manner as in Example 1 except that this coating solution is used as a coating solution for forming a cured product layer, and the coating is applied using a Mayer bar so that the thickness force / zm of the coating film is obtained. did. The center line average roughness (Ra) of the surface of the transparent conductive thin film of the obtained transparent conductive film was 0.24 μm. Further, using this transparent conductive film, a touch panel was prepared in the same manner as in Example 1. In addition, the force to confirm the occurrence of a newton ring while pressing the film against the glass under a three-wavelength fluorescent lamp, no Newton ring was observed.

[0122] Comparative Example 1

In Example 1, a transparent conductive film was produced in the same manner as in Example 1 except that the volatile component reduction process by heat treatment at 180 ° C. for 1 minute and vacuum exposure treatment for 10 minutes was omitted. Further, using this transparent conductive film, a touch panel was prepared in the same manner as in Example 1.

[0123] Comparative Example 2

A transparent conductive film was produced in the same manner as in Example 1 except that the rewinding time was 5 minutes in Example 1. Further, using this transparent conductive film, a touch panel was prepared in the same manner as in Example 1.

[0124] Comparative Example 3

On the cured product layer obtained in the same manner as in Example 1, a transparent conductive thin film made of indium tin composite oxide was formed. At this time, the pressure before sputtering is set to 0. A DC power of ² W / cm ² was applied using indium oxide containing 10% by mass of tin oxide (density: 7.lg / cm ³ ). In addition, Ar gas was flowed at 130 sccm, O gas was flowed at a flow rate of lOsccm, and DC magnetron sputtering was performed in an atmosphere of 0.4 Pa.

2

The film was formed by using the etching method. However, in order to prevent arc discharge that occurs with normal DC, a pulse of 5 μs width was applied at a 50 kHz period using RPG-100 manufactured by Nippon Yanai. The center roll temperature was 50 ° C. and sputtering was performed. The transparent conductive film thus obtained was further heated to 200 ° C. in an oven and held for 5 minutes. Further, using this transparent conductive film, a touch panel was produced in the same manner as in Example 1.

[0125] [Table 1]

[0126] [Table 2]

Pen sliding durability near the frame Pen sliding durability

a¾ i wheat initial ON

Sliding part of sliding part

ON resistance Resistance

Crack whitening

(k Q) (k Q)

Example] None 2 2 None 2 2 Example 2 None 2 2 None 2 2 Example 3 None 2 2 None 2 2 Example 4 None 2 2 None 2 2 Example 5 None 2 2 None 2 2 Example 6 None 2 2 None 2 2 Example 7 None 2 2 None 2 2 Example 8 None 2 2 None 2 2 Example 9 None 2 2 None 2 2 Example 10 None 2 2 None 2 2 Example 1 1 None 2 2 None 2 2 Comparative Example 1 None 2 100 None 2 20 Comparative Example 2 None 2 30 None 2 20 Comparative Example 3 With 2> 1000 None 2 2

[0127] From the results shown in Table 12 above, the touch panel using the transparent conductive film or the transparent conductive sheet described in Example 11 11 satisfying the scope of the present invention is placed near the frame to be polyacetal. Even after a sliding test of 10,000 times with a load of 2.5 N applied to a pen made (tip shape: 0.8 mmR), there was no abnormality in the ON resistance, which did not cause peeling or cracking.

[0128] On the other hand, the conductive films of Comparative Examples 1 and 2 in which the moisture in the film was not sufficiently removed are touch panels using these conductive films in which the carbon concentration in the transparent conductive thin film is low. In the vicinity of the frame, a polyacetal pen (tip shape: 0.8 mmR) was loaded with a load of 2.5 N, and after 10,000 sliding tests, an abnormality occurred in the ON resistance. Furthermore, when the pen sliding portion was evaluated with a microscope, peeling and cracking of the transparent conductive thin film were observed.

In addition, the conductive film of Comparative Example 3 in which the transparent conductive thin film was crystalline had cracks in the transparent conductive thin film after the pen sliding test near the frame of the touch panel, and the ON resistance was abnormal.

Industrial applicability The transparent conductive film or transparent conductive sheet of the present invention has excellent pen sliding durability that does not cause peeling or cracking even near the frame of the touch panel when used in a touch panel for pen input. Because it has excellent position detection accuracy and display quality, it can handle the narrow frame of touch panels, miniaturize recording media used in personal digital assistants, digital video cameras, digital cameras, etc. and increase the display screen. It is particularly suitable as a touch panel that is strongly required.

Claims

The scope of the claims

[1] A transparent conductive film obtained by laminating a transparent conductive thin film containing a metal oxide as a constituent component on a substrate made of a transparent plastic film through a cured product layer, the transparent conductive film A transparent conductive film, wherein the thin film is amorphous, and the carbon concentration contained in the transparent conductive thin film is from 1 X ιο ^{2ΰ to} ι X 10 ²² (atoms / cm ³ ).

[2] The transparent conductive material according to claim 1, wherein the metal oxide is an indium monotin composite oxide, and the ratio of the content of tin to indium is 15 to 60% by mass. Sex Huinolem.

[3] The transparent conductive film according to [1], wherein at least two layers having different refractive indexes are provided between the transparent conductive thin film and the cured product layer.

[4] The cured product layer contains particles, and the center line average roughness (Ra) of the transparent conductive thin film surface is 0.1.

The transparent conductive film according to claim 1, wherein the transparent conductive film has a thickness of ˜0.5 μm.

5. The transparent conductive film according to claim 1, wherein a hard coat layer is laminated on the surface opposite to the transparent conductive thin film surface.

6. The transparent conductive finolem according to claim 5, wherein the hard coat layer has an antiglare property.

7. The transparent conductive film according to claim 5, wherein the hard coat layer is subjected to a low reflection treatment.

[8] A transparent resin sheet, wherein a transparent resin sheet is bonded to the transparent conductive thin film surface of the transparent conductive film according to any one of claims 1 to 7 via an adhesive. Conductive sheet.

[9] The touch panel according to claim 1, wherein a pair of panel plates having the transparent conductive thin film are arranged via a spacer so that the transparent conductive thin film faces each other, and at least one of the panel plates is described in claim 1. A touch panel characterized by comprising a transparent conductive film or a transparent conductive sheet.