WO2015045965A1

WO2015045965A1 - Laminate for touch panels, and touch panel

Info

Publication number: WO2015045965A1
Application number: PCT/JP2014/074440
Authority: WO
Inventors: 直井　憲次; 遠藤　靖; 林　利明; 理士小池; 向井　厚史
Original assignee: 富士フイルム株式会社
Priority date: 2013-09-30
Filing date: 2014-09-16
Publication date: 2015-04-02
Also published as: JP2015069585A

Abstract

The present invention provides: a laminate for touch panels, which provides a touch panel that is not susceptible to malfunctioning if used in the touch panel in combination with a display device, and which is capable of suppressing ion migration between metal thin wires; and a touch panel which comprises this laminate for touch panels. A laminate for touch panels according to the present invention is a laminate for touch panels, which is arranged on the viewing side of a display device. This laminate for touch panels is sequentially provided with a first transparent protective substrate, a first adhesive layer, a conductive film having at least metal thin wires, a second adhesive layer and a second transparent protective substrate in this order. When this laminate for touch panels is arranged on a display device, the second transparent protective substrate is positioned on the display device side, and the second transparent protective substrate is a barrier laminate having at least one organic layer and at least one inorganic layer. The second transparent protective substrate has a water vapor transmission rate of 0.001 g/m²/24h or less (at 40°C at 90% RH), and the amount of metal contained in the metal thin wires per unit area is 0.010-10 g/m².

Description

Laminate for touch panel, touch panel

The present invention relates to a laminate for a touch panel, and more particularly to a laminate for a touch panel including a conductive film having a thin metal wire having a predetermined amount of metal, and a protective substrate having a predetermined water vapor permeability.
Moreover, this invention relates to the touchscreen containing the laminated body for touchscreens.

Conductive films with thin metal wires formed on substrates are widely used in transparent electrodes for various electronic devices such as solar cells, inorganic EL elements, and organic EL elements, electromagnetic wave shields for various display devices, touch panels, and transparent sheet heating elements. It's being used. In particular, the rate of mounting touch panels on mobile phones, portable game devices, and the like is increasing, and for example, capacitive touch panels capable of multipoint detection are attracting attention.
On the other hand, in the touch panel, examples of the metal contained in the thin metal wire in the conductive film functioning as a touch sensor include silver and copper, but these have a problem that ion migration is likely to occur. When such ion migration occurs between the fine metal wires, conduction between the fine metal wires or disconnection of the fine metal wires occurs.
As a method for preventing such ion migration, Patent Document 1 discloses a form in which an adhesive layer containing 5-methyl-1H-benzotriazole is formed on a conductive film.

JP 2012-77281 A

On the other hand, when the present inventors examined the form of Patent Document 1, the malfunction due to the increase in the capacitance value due to the infiltration of water having a high dielectric constant is caused by the use of the pressure-sensitive adhesive layer. However, it cannot always be solved, and another solution is desired.

In view of the above circumstances, an object of the present invention is to provide a laminated body for a touch panel that is unlikely to cause a malfunction of the touch panel when used as a touch panel in combination with a display device, and that can suppress ion migration between thin metal wires.
Another object of the present invention is to provide a touch panel including the laminate for a touch panel.

As a result of diligent investigations on the problems of the prior art, the present inventors are able to obtain a desired effect by using a thin metal wire having a predetermined amount of metal and a protective substrate having a predetermined water vapor permeability. I found.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A laminated body for a touch panel disposed on the viewing side of a display device,
A first transparent protective substrate, a first pressure-sensitive adhesive layer, a conductive film having at least a fine metal wire, a second pressure-sensitive adhesive layer, and a second transparent protective substrate are provided in this order.
When arranged on the display device, the second transparent protective substrate is located on the display device side,
The second transparent protective substrate has at least one or more organic layers and inorganic layers,
The water vapor permeability of the second transparent protective substrate is 0.001 g / m ² · 24 h (40 ° C., 90% RH) or less,
A laminate for a touch panel, wherein the amount of metal per unit area contained in the fine metal wire is 0.010 to 10 g / m ² .
(2) The laminate for a touch panel according to (1), wherein the conductive film has at least a substrate and fine metal wires arranged on both surfaces of the substrate.
(3) The laminate for a touch panel according to (1), wherein the conductive film is formed by bonding together a substrate with a metal fine wire having at least a substrate and a metal fine wire arranged on one side of the substrate via an adhesive layer. .
(4) The touch panel laminate according to any one of (1) to (3), wherein the first transparent protective substrate is a glass substrate.
(5) The second transparent protective substrate has a resin substrate and a barrier layer disposed on the resin substrate,
The laminate for a touch panel according to any one of (1) to (4), wherein the barrier layer has a laminated structure in which at least one inorganic layer and at least one organic layer are alternately laminated.
(6) The laminate for a touch panel according to (5), wherein the number of inorganic layers and the number of organic layers are 1 to 6, respectively.
(7) The laminate for a touch panel according to any one of (1) to (6), wherein the total light transmittance is 80% to 90% and the haze is 0.3% to 3.5%.
(8) The sealing layer is disposed on the surface of the peripheral portion of the first pressure-sensitive adhesive layer, the conductive film, and the second pressure-sensitive adhesive layer exposed from between the first transparent protective substrate and the second transparent protective substrate. The laminate for a touch panel according to any one of (1) to (7).
(9) A touch panel having a display device and the laminate for a touch panel according to any one of (1) to (8).

ADVANTAGE OF THE INVENTION According to this invention, when it uses as a touch panel in combination with a display apparatus, the laminated body for touchscreens which cannot produce the malfunctioning of a touchscreen easily and can also suppress the ion migration between metal fine wires can be provided.
Moreover, according to this invention, the touch panel containing this laminated body for touch panels can also be provided.

It is sectional drawing of one Embodiment of the laminated body for touchscreens of this invention. It is a top view which shows one Embodiment of a conductive film. FIG. 3 is a cross-sectional view taken along a cutting line AA shown in FIG. It is an enlarged plan view of a 1st detection electrode. It is sectional drawing which shows one Embodiment of a touch panel. It is a top view which shows other embodiment of an electroconductive film. It is a top view which shows other embodiment of an electroconductive film. It is sectional drawing of other embodiment of the laminated body for touchscreens of this invention. (A) is the schematic of the formation apparatus of an organic layer, (B) is the schematic of the formation apparatus of an inorganic layer.

Below, the suitable form of the laminated body for touchscreens of this invention is demonstrated. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
First, the feature point compared with the prior art of this invention is explained in full detail.
As described above, one of the features of the present invention is that the amount of metal in the fine metal wires contained in the laminate for a touch panel and the water vapor permeability of the second transparent protective substrate are controlled within a predetermined range. It is done. First, by controlling the water vapor permeability of the second transparent protective substrate, the change in the capacitance value due to the ingress of moisture is suppressed. In general, metal migration proceeds by ionization of metal, but it is presumed that moisture is affected during ionization, and the degree of ionization is controlled by controlling the water vapor permeability of the protective substrate. ing. Furthermore, the present inventor has also found that the control of the amount of metal in the thin metal wire is necessary to suppress the occurrence of migration and malfunction. Specifically, when the amount of metal in the metal wiring is too small, disconnection of the metal wiring is likely to occur, whereas when the amount of metal is too large, suppression of ionization becomes insufficient. Therefore, the amount of metal is controlled so as not to cause the above problem while suppressing the degree of moisture penetration.
Note that one of the reasons for controlling the characteristics of the second transparent protective substrate as described above is that, in the case of a tablet or PC, the outside air is forcibly sent to the vicinity of the liquid crystal module / control circuit and cooled by an air cooling fan. This is because the influence of the characteristics of the second transparent protective substrate has increased, and it has become necessary to consider it in order to detect the touch operation strictly.
In addition, it is conceivable to use a glass substrate or the like that can prevent water permeation itself as the second transparent protective substrate. However, the glass substrate itself is heavy and thick, or it is easy to crack and is easy to handle. It was not a practical solution.

<First Embodiment>
Next, the suitable form of the laminated body for touchscreens of this invention is explained in full detail with reference to drawings.
FIG. 1 shows a cross-sectional view of an embodiment of a laminate for a touch panel. The laminate 1 for a touch panel includes a first transparent protective substrate 2, a first pressure-sensitive adhesive layer 3, and a conductive film 4 having at least a thin metal wire. The second pressure-sensitive adhesive layer 5 and the second transparent protective substrate 6 are provided in this order. In addition, when using it as a touch panel in combination with a display device, the first transparent protective substrate 2 constitutes a touch surface.
Below, each member is explained in full detail. In the following, first, the second transparent protective substrate, which is one of the features of the present invention, will be described in detail.

(Second transparent protective substrate)
A 2nd transparent protective substrate is a board | substrate located most on the display apparatus side, when the laminated body for touchscreens is arrange | positioned on a display apparatus, and is a layer which suppresses the penetration | invasion of moisture. A 2nd transparent protective substrate has a function which prevents the penetration | invasion of the water | moisture content from the contact surface side of a display apparatus and a laminated body for touchscreens, when it is set as a touchscreen combining the laminated body for touchscreens and a display apparatus.
The water vapor permeability of the second transparent protective substrate is 0.001 g / m ² · 24 h (40 ° C., 90% RH) or less, and the malfunction of the touch panel is further suppressed and / or ion migration is further suppressed. (Hereinafter also referred to as “the point where the effect of the present invention is excellent”) is preferably 0.0005 g / m ² · 24 h (40 ° C., 90% RH) or less. When the lower limit is 1 × 10 ⁻⁷ g / m ² · 24 h (40 ° C., 90% RH) or more, a transparent protective substrate having high transparency and high durability can be obtained.
When the water vapor permeability exceeds 0.001 g / m ² · 24 h (40 ° C., 90% RH), the touch panel is likely to malfunction and / or ion migration is likely to occur.
As a method for measuring the water vapor transmission rate, N3 (three times) measurement is performed by the calcium corrosion method (the method described in JP-A-2005-283561), and the water vapor transmission rate is obtained as an average value. More specifically, a metallic calcium thin film is produced on a second transparent protective substrate (particularly an organic layer or an inorganic layer) by a vacuum evaporation method, and this is immediately sealed to produce a test cell. The test cell is stored under predetermined constant temperature and humidity measurement conditions, and the water vapor permeability is measured by calculating the amount of calcium corroded by water vapor. As measurement conditions at that time, the temperature is 40 ° C. and the humidity is 90% RH.

The second transparent protective substrate is optically transparent. Optically transparent means that the total light transmittance is 75% or more, preferably 85% or more, more preferably 90% or more, and even more preferably 100%.
The thickness of the second transparent protective substrate is not particularly limited, but is preferably 5 to 200 μm and more preferably 10 to 100 μm from the viewpoints of handleability and thinning of the touch panel.

The second transparent protective substrate is a barrier laminate having at least one inorganic layer and at least one organic layer.
The inorganic layer preferably contains silicon oxide, silicon nitride, silicon carbide, aluminum oxide, or a mixture thereof as a main component. Here, the main component refers to a component that is contained most in the inorganic layer, for example, that 80% by mass or more of these compounds.
As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, there are physical vapor deposition methods (PVD) such as vapor deposition, sputtering, and ion plating, various chemical vapor deposition (CVD), and liquid phase growth methods such as plating and sol-gel methods.
The smoothness of the inorganic layer is preferably less than 1 nm as an average roughness (Ra value) of 1 μm square, and more preferably 0.5 nm or less. For this reason, it is preferable that the inorganic layer be formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
The thickness of the inorganic layer is not particularly limited, but is usually in the range of 5 to 500 nm, preferably 20 to 200 nm per layer. Two or more inorganic layers may be laminated. When two or more layers are provided, each layer may have the same composition or a different composition.

The organic layer is a layer made of an organic compound (a layer (film) containing an organic compound as a main component) and is basically a monomer and / or oligomer crosslinked (polymerized).
Note that the organic layer preferably contains no halogen. Since the organic layer does not contain halogen, the formation of pinholes in the inorganic layer can be further prevented.
The material for forming the organic layer is not particularly limited, and various known organic compounds (resins / polymer compounds) can be used. In particular, a material containing no halogen is preferable.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetheretherketone, polycarbonate, alicyclic Preferred examples include films of thermoplastic polyolefins such as polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, fluorene ring-modified polyester, and acryloyl compound, or polysiloxane and other organosilicon compounds. Is done.
Among these, an organic layer composed of a radical polymerizable compound and / or a polymer of a cationic polymerizable compound having an ether group as a functional group is preferable from the viewpoint of having a high Tg and excellent strength.
In particular, acrylic resins and methacrylic resins mainly composed of acrylate and / or methacrylate monomers and oligomer polymers are organic in terms of high Tg and strength, low refractive index, and excellent optical properties. Preferably exemplified as a layer.
Among them, in particular, such as trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), and the like in terms of high Tg and excellent etching resistance when forming the inorganic layer. Preferable examples include acrylic resins and methacrylic resins mainly composed of a polymer of acrylate and / or methacrylate monomers or oligomers that are functional or higher.

Although the manufacturing method in particular of an organic layer is not restrict | limited, It is preferable to form with the coating material containing the organic solvent, the organic compound used as an organic layer, and surfactant. In this embodiment, the organic layer contains a surfactant. In this embodiment, the content of the surfactant in the organic layer is not particularly limited, but is preferably 0.01 to 10% by mass. That is, it is preferable to form the organic layer by using a paint containing a surfactant that is 0.01 to 10% by mass in a concentration excluding the organic solvent.
The surfactant used is preferably a surfactant containing no halogen, such as a silicon-based surfactant.
There are no particular limitations on the organic solvent used in the preparation of the paint, and examples of the organic solvent used for forming the organic layer in the organic / inorganic laminated functional film such as methyl ethyl ketone (MEK), cyclohexanone, isopropyl alcohol, and acetone. Various types are available.
Various additives used when forming the organic layer, such as a surfactant, a silane coupling agent, and a photopolymerization initiator, are appropriately added to the coating material forming the organic layer as necessary. May be.

The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 μm square, and more preferably less than 0.5 nm.
The thickness of the organic layer is not particularly limited, but is preferably 50 nm to 2000 nm, and more preferably 200 nm to 1500 nm. If it is in the said range, the uniformity of a film thickness can be acquired and it will be hard to generate | occur | produce a crack by external force.
The surface of the organic layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
It is preferable that the organic layer has a high hardness. It has been found that when the hardness of the organic layer is high, the inorganic layer is formed smoothly and as a result, the barrier ability is improved. The hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.

The lamination of the organic layer and the inorganic layer can be performed by sequentially repeating the organic layer and the inorganic layer according to a desired layer configuration. In particular, when at least one organic layer and at least one inorganic layer are alternately laminated, higher barrier properties can be exhibited. In particular, when the number of organic layers and inorganic layers is 1 to 6 layers (preferably 1 to 4 layers) alternately stacked, higher barrier properties can be exhibited. In the case of the alternate lamination, the number of layers of the organic layer and the inorganic layer may be the same or different.

The barrier laminate described above may include a resin substrate as necessary. That is, the second transparent protective substrate has a resin substrate and a barrier layer having a laminated structure in which at least one inorganic layer and at least one organic layer are alternately laminated, which are disposed on the resin substrate. A configuration is preferred. The preferred embodiment of the laminated structure of the barrier layer is as described above.
The organic layer and the inorganic layer may be provided only on one side of the resin substrate, or may be provided on both sides. Moreover, you may laminate | stack in order of the inorganic layer and the organic layer from the resin substrate side, and may laminate | stack the order of the organic layer and the inorganic layer.

The apparatus for producing the organic layer and the inorganic layer is not particularly limited, but as an apparatus for producing each layer, for example, as shown in FIG. The inorganic film forming apparatus 332 to be formed is exemplified. Hereinafter, these devices will be described in detail.
Both the organic film forming apparatus 330 and the inorganic film forming apparatus 332 send out the film forming material from a roll formed by winding a long film forming material (web-shaped film forming material). Is formed while the film is transported in the longitudinal direction, and the film-formed deposition material is wound again in a roll shape, so-called roll-to-roll (hereinafter also referred to as RtoR), An apparatus for forming a film.

The organic film forming apparatus 330 applies a coating material to be an organic layer while transporting a long support Z (film forming material) in the longitudinal direction, and after drying, an organic compound contained in the coating film by light irradiation. Is an apparatus for forming an organic layer by crosslinking and curing.
As an example, the organic film forming apparatus 330 includes a coating unit 336, a drying unit 338, a light irradiation unit 340, a rotating shaft 342, a winding shaft 346, and transport roller pairs 348 and 350.
In the organic film forming apparatus 330, a support roll ZR formed by winding a long support Z is loaded on the rotary shaft 342. When the support roll ZR is loaded on the rotating shaft 342, the support Z is pulled out of the support roll ZR, passes through the conveying roller pair 348, and passes under the coating means 336, the drying means 338, and the light irradiation means 340. Then, the paper passes through a predetermined conveyance path that passes through the conveyance roller pair 350 and reaches the take-up shaft 346 (paper is passed). In the organic film forming apparatus 330, the feeding of the support Z from the support roll ZR and the winding of the support Zo on which the organic layer is formed on the winding shaft 346 are performed in synchronization. As a result, while the long support Z is transported in the longitudinal direction along a predetermined transport path, the coating material 336 is applied with an organic layer coating material, the drying device 338 is dried, and the light irradiation device 340 is cured. By doing so, an organic layer is formed.

The inorganic film forming apparatus 332 forms (deposits) an inorganic layer on the surface of the support Zo by plasma CVD, and includes a supply chamber 356, a film forming chamber 358, and a take-up chamber 360. Note that the inorganic film forming apparatus 332 in the illustrated example is provided with a vacuum evacuation unit 370 in the supply chamber 356 and a vacuum evacuation unit 376 in the take-up chamber 360 as a preferred embodiment.
The supply chamber 356 includes a rotation shaft 364, a guide roller 368, and a vacuum exhaust unit 370. In the supply chamber 356, a rotating shaft 364 is rotated clockwise in the drawing by a driving source (not shown), the support Zo is fed from the roll ZoR, and a predetermined path is guided by the guide roller 368, so that the partition 372 is formed. From the slit 372a, the film is sent to the film formation chamber 358.

In the film forming chamber 358, an inorganic layer is formed on the surface of the support Zo by plasma CVD.
In the illustrated example, the film forming chamber 358 includes a drum 380, a shower electrode 382, guide

rollers

384 a and 384 b, a high frequency power source 386, a gas supply unit 387, and a vacuum exhaust unit 373.
The support Zo conveyed to the film forming chamber 358 is guided to a predetermined path by the guide roller 384 and is wound around a predetermined position of the drum 380. The support Zo is conveyed in the longitudinal direction while being positioned at a predetermined position by the drum 380, and an inorganic layer is formed by plasma CVD.

As an example, the film formation chamber 358 forms an inorganic layer on the surface of the support Zo by CCP-CVD (capacitive coupling plasma CVD). The drum 380 also functions as a counter electrode in CCP-CVD, and constitutes an electrode pair together with a shower electrode 382 (film formation electrode) described later.
The high frequency power source 386 is a known high frequency power source used for plasma CVD, and supplies plasma excitation power to the shower electrode 382. The gas supply means 387 is also a known film formation gas (raw material gas / process gas) supply means used for plasma CVD, and supplies the film formation gas to the shower electrode 382.

The support Zo on which the inorganic layer is formed by the shower electrode 382 while being supported / conveyed by the drum 380 is guided to a predetermined path by the guide roller 384b, and from the slit 374a formed in the partition wall 374, from the winding chamber 360. To be transported.
The winding chamber 360 includes a guide roller 390, a winding shaft 392, and a vacuum exhaust unit 376. The support conveyed to the take-up chamber 360 is wound into a roll shape by the take-up shaft 392 and collected as the roll 10aR.

A hard coat layer may be disposed on at least one of the front surface and the back surface of the second transparent protective substrate. By arranging the hard coat layer, the occurrence of cracks in the second transparent protective substrate can be further suppressed.
The hardness of the hard coat layer is not particularly limited, but is preferably pencil hardness H or higher, more preferably 2H or higher.
The pencil hardness can be measured by the method described in JIS-K5600.

(First transparent protective substrate)
The first transparent protective substrate is a substrate located on the outermost side when the laminated body for touch panels is arranged on the display device, and serves to protect a conductive film described later from the external environment, and its main surface is a touch surface. Configure.
As the first transparent protective substrate, a plastic substrate, a glass substrate, or the like is used, and a glass substrate is preferable from the viewpoint of strength. It is desirable that the thickness of the first transparent protective substrate is appropriately selected according to each application.
Examples of the raw material for the plastic substrate include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene, and EVA; vinyl resins; Polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), cycloolefin resin (COP), and the like can be used.
The first transparent protective substrate is optically transparent. Optically transparent means that the total light transmittance is 75% or more, preferably 85% or more, more preferably 90% or more, and even more preferably 100%.
The thickness of the first transparent protective substrate is not particularly limited, but is preferably 10 to 1500 μm, and more preferably 100 to 1100 μm from the viewpoints of handleability and thinning of the touch panel.

(First adhesive layer and second adhesive layer)
The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are layers that enhance adhesion between adjacent layers. More specifically, a 1st adhesive layer is arrange | positioned between a conductive film and a 1st transparent protective substrate, and improves both adhesiveness. Moreover, a 2nd adhesive layer is arrange | positioned between a conductive film and a 2nd transparent protective substrate, and improves both adhesiveness.

The kind in particular of the adhesive which comprises a 1st adhesive layer and a 2nd adhesive layer is not restrict | limited, A well-known adhesive can be used.
Specific examples of the pressure-sensitive adhesive include various pressure-sensitive adhesives such as a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive, and an acrylic pressure-sensitive adhesive is preferable.
The acrylic pressure-sensitive adhesive has an acrylic polymer having a main skeleton of an alkyl (meth) acrylate monomer unit as a base polymer. (Meth) acrylate refers to acrylate and / or methacrylate. The average carbon number of the alkyl group of the alkyl (meth) acrylate constituting the main skeleton of the acrylic polymer is preferably about 1 to 12, and specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) ) Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.

The thickness of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 to 500 μm and more preferably 20 to 300 μm from the viewpoint of thinning the touch panel.
The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are preferably optically transparent. More specifically, the total light transmittance of the pressure-sensitive adhesive layer is preferably 80% or more, and more preferably 90% or more.

(Conductive film)
The conductive film uses the change in capacitance that occurs when an external conductor such as a human finger comes into contact (approach) when the touch panel laminate is arranged on the display device to form a touch panel. It functions as a sensor that detects the position of an external conductor such as a human finger. That is, it plays a role as a capacitive touch sensor.
FIG. 2 shows a plan view of one embodiment of the conductive film. FIG. 3 is a cross-sectional view taken along the cutting line AA in FIG. The conductive film 14 includes a substrate 22, a first detection electrode 24 disposed on one main surface (on the front surface) of the substrate 22, a first lead-out wiring 26, and the other main surface (on the back surface) of the substrate 22. The second detection electrode 28, the second lead wiring 30, and the flexible printed wiring board 32 are provided. The region where the first detection electrode 24 and the second detection electrode 28 are provided constitutes an input region E _I (an input region (sensing unit) capable of detecting the contact of an object) that can be input by the user, and input. A first lead wiring 26, a second lead wiring 30 and a flexible printed wiring board 32 are arranged in the outer region E _O located outside the region E _I.
In this embodiment, the metal thin wires 34, which will be described later, and the first lead-out wiring 26 and the second lead-out wiring 30 constituting the first detection electrode 24 and the second detection electrode 28 were controlled to a predetermined metal amount described later. Corresponds to a thin metal wire. Note that the present invention is not limited to this form as long as a thin metal wire having a predetermined metal amount is included. For example, only the first lead wire 26 and the second lead wire 30 are controlled to have a predetermined metal amount. The form comprised by may be sufficient.

The substrate 22 plays a role of supporting the first detection electrode 24 and the second detection electrode 28 in the input region E _I and plays a role of supporting the first lead wiring 26 and the second lead wiring 30 in the outer region E _O. It is a member.
The substrate 22 preferably transmits light appropriately. Specifically, the total light transmittance of the substrate 22 is preferably 85 to 100%.
The substrate 22 preferably has an insulating property (is an insulating substrate). That is, the substrate 22 is a layer for ensuring insulation between the first detection electrode 24 and the second detection electrode 28.

The substrate 22 is preferably a transparent substrate (particularly a transparent insulating substrate). Specific examples thereof include an insulating resin substrate, a ceramic substrate, and a glass substrate. Among these, an insulating resin substrate is preferable because of its excellent toughness.
More specifically, the material constituting the insulating resin substrate is polyethylene terephthalate, polyethersulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyamide, polyarylate, polyolefin, cellulose resin, poly Examples include vinyl chloride and cycloolefin resins. Among these, polyethylene terephthalate, cycloolefin resin, polycarbonate, and triacetyl cellulose resin are preferable because of excellent transparency.

In FIG. 2, the substrate 22 is a single layer, but may be a multilayer of two or more layers.
The thickness of the substrate 22 (when the substrate 22 is a multilayer of two or more layers, the total thickness thereof) is not particularly limited, but is preferably 5 to 350 μm, more preferably 30 to 150 μm. Within the above range, desired visible light transmittance can be obtained, and handling is easy.
Moreover, in FIG. 2, the planar view shape of the board | substrate 22 is substantially rectangular shape, However, It is not restricted to this. For example, it may be circular or polygonal.

The first detection electrode 24 and the second detection electrode 28 are sensing electrodes that sense a change in capacitance, and constitute a sensing unit (sensing unit). That is, when the fingertip is brought into contact with the touch panel, the mutual capacitance between the first detection electrode 24 and the second detection electrode 28 changes, and the position of the fingertip is calculated by the IC circuit based on the change amount.
First detection electrode 24, which has a role to detect the input position in the X direction of the finger of the user in proximity to the input region E _I, has the function of generating an electrostatic capacitance between the finger ing. The first detection electrodes 24 are electrodes that extend in a first direction (X direction) and are arranged at a predetermined interval in a second direction (Y direction) orthogonal to the first direction. Includes patterns.
The second detection electrode 28 has a role of detecting the input position in the Y direction of the user's finger approaching the input area E _I and has a function of generating a capacitance between the second detection electrode 28 and the finger. ing. The second detection electrodes 28 are electrodes that extend in the second direction (Y direction) and are arranged at a predetermined interval in the first direction (X direction), and include a predetermined pattern as will be described later. In FIG. 4, five first detection electrodes 24 and five second detection electrodes 28 are provided, but the number is not particularly limited and may be plural.

In FIG. 2, the first detection electrode 24 and the second detection electrode 28 are composed of thin metal wires. FIG. 4 shows an enlarged plan view of a part of the first detection electrode 24. As shown in FIG. 4, the first detection electrode 24 is composed of fine metal wires 34, and includes a plurality of gratings 36 made of intersecting metal fine wires 34. Note that, similarly to the first detection electrode 24, the second detection electrode 28 also includes a plurality of lattices 36 formed by intersecting metal thin wires 34.

The amount of metal per unit area contained in the fine metal wire 34 is 0.010 to 10 g / m ² . By setting the amount of metal in the above range, it is possible to reduce the film thickness and width of the fine metal wires, meet the demand for high density integration, and suppress ion migration and malfunction of the touch panel. Of these, 0.012 to 8.5 g / m ² is preferable, and 0.015 to 7.0 g / m ² is more preferable in that the effect of the present invention is more excellent.
When the amount of metal is less than 0.010 g / m ² , the fine metal wire is likely to be disconnected, and the touch panel is likely to malfunction. Further, when the amount of metal exceeds 10 g / m ² , the degree of migration is large.

As a method for measuring the amount of metal, the amount of metal in a predetermined volume can be measured by observing a cross-sectional SEM photograph of a thin metal wire and performing elemental analysis by fluorescent X-ray analysis.
Moreover, per unit area of a metal fine wire means per unit area of the contact part with the board | substrate of a metal fine wire. That is, the amount of metal is calculated based only on the area of the contact portion between the fine metal wire and the substrate. In other words, the area of the substrate surface that is not in contact with the fine metal wires (for example, the surface of the substrate that is located between the fine metal wires and is not in contact with the fine metal wires) is taken into consideration in the calculation per unit area of the fine metal wires. Absent. Therefore, the amount of silver contained per unit area of the fine metal wire means the amount of metal contained per unit area (m ² ) at the contact portion between the fine metal wire and the substrate.

The metal thin wire 34 includes a predetermined metal component. For example, a metal such as gold (Au), silver (Ag), copper (Cu), aluminum (Al), or an alloy thereof, ITO (indium oxide-tin) ), Metal oxides such as tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide.
Especially, it is preferable that silver is contained in the metal fine wire 34 from a viewpoint of electroconductivity. Silver may be contained in the form of a silver alloy. When the fine metal wire 34 includes a silver alloy, examples of the metal contained other than silver include tin, palladium, gold, nickel, and chromium.
Moreover, it is also preferable to form the metal thin wire 34 with a metal nanowire made of silver or a silver alloy. The method for producing the metal nanowire is not particularly limited and may be produced by any method, but it is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved. In addition, after forming the metal nanowire, it is preferable to perform a desalting treatment by a conventional method from the viewpoints of dispersibility and stability of the conductive film over time.
In addition, as a method for producing metal nanowires, JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, JP2010-86714A, The method described in JP-T-2009-505358 can be used.

It is preferable that a binder is contained in the fine metal wires 34 from the viewpoint of adhesion between the fine metal wires 34 and the substrate 22.
The binder is preferably a water-soluble polymer because the adhesion between the fine metal wires 34 and the substrate 22 is more excellent. Examples of the binder include gelatin, carrageenan, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polysaccharides such as starch, cellulose and derivatives thereof, polyethylene oxide, polysaccharides, polyvinylamine, chitosan, polylysine, polyacryl. Examples include acid, polyalginic acid, polyhyaluronic acid, carboxycellulose, gum arabic, and sodium alginate. Among these, gelatin is preferable because the adhesion between the fine metal wires 34 and the substrate 22 is more excellent.
In addition to lime-processed gelatin, acid-processed gelatin may be used as gelatin, and gelatin hydrolyzate, gelatin enzyme decomposition product, and other gelatins modified with amino groups and carboxyl groups (phthalated gelatin, acetylated gelatin) Can be used.

The volume ratio (metal volume / binder volume) of the metal and the binder in the thin metal wire 34 is preferably 1.0 or more, and more preferably 1.5 or more. By setting the volume ratio of the metal and the binder to 1.0 or more, the conductivity of the fine metal wire 34 can be further increased. The upper limit is not particularly limited, but is preferably 6.0 or less, more preferably 4.0 or less, and even more preferably 2.5 or less from the viewpoint of productivity.
The volume ratio of the metal and the binder can be calculated from the density of the metal and the binder contained in the fine metal wire 34. For example, when the metal is silver, the density of silver is 10.5 g / cm ³ , and when the binder is gelatin, the density of gelatin is 1.34 g / cm ³ .

The line width of the fine metal wire 34 is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm, further preferably 10 μm, particularly preferably 9 μm or less, and particularly preferably 7 μm or less, from the viewpoint that a low-resistance electrode can be formed relatively easily. Most preferably, 0.5 μm or more is preferable, and 1.0 μm or more is more preferable.
The thickness of the fine metal wire 34 is not particularly limited, but can be selected from 0.00001 mm to 0.2 mm from the viewpoint of conductivity and visibility, but is preferably 30 μm or less, more preferably 20 μm or less, and 0.01 to 9 μm is more preferable, and 0.05 to 5 μm is most preferable.

The lattice 36 includes an opening region surrounded by the thin metal wires 34. The length W of one side of the grating 36 is preferably 800 μm or less, more preferably 600 μm or less, preferably 50 μm or more, and more preferably 400 μm or more.
In the first detection electrode 24 and the second detection electrode 28, the aperture ratio is preferably 85% or more, more preferably 90% or more, and most preferably 95% or more from the viewpoint of visible light transmittance. preferable. The aperture ratio corresponds to the ratio of the transmissive portion excluding the thin metal wires 34 in the first detection electrode 24 or the second detection electrode 28 in the predetermined region.

The lattice 36 has a substantially rhombus shape. However, other polygonal shapes (for example, a triangle, a quadrangle, a hexagon, and a random polygon) may be used. Further, the shape of one side may be a curved shape or a circular arc shape in addition to a linear shape. In the case of the arc shape, for example, the two opposing sides may have an outwardly convex arc shape, and the other two opposing sides may have an inwardly convex arc shape. The shape of each side may be a wavy shape in which an outwardly convex arc and an inwardly convex arc are continuous. Of course, the shape of each side may be a sine curve.
In FIG. 4, the fine metal wires 34 are formed as a mesh pattern, but are not limited to this form, and may be a stripe pattern.

The fine metal wires 34 of the first detection electrode 24 and the second detection electrode 28 may be composed of metal oxide particles, metal paste such as silver paste and copper paste, and metal nanowire particles such as silver nanowire and copper nanowire. Among these, silver nanowires are preferable because they are excellent in conductivity and transparency.
In FIG. 2, the first detection electrode 24 and the second detection electrode 28 are configured by the mesh structure of the metal thin wires 34, but the present invention is not limited to this form. For example, the first detection electrode 24 and the second detection electrode 28 The entire detection electrode 28 may be formed of a metal oxide thin film (transparent metal oxide thin film) such as ITO. Examples of materials that can be used in the above embodiment in addition to ITO include zinc oxide (ZnO), indium zinc oxide (IZO), gallium zinc oxide (GZO), and aluminum zinc oxide (AZO).
The patterning of the electrode can be selected depending on the material of the electrode, and a photolithography method, a resist mask screen printing-etching method, an ink jet method, a printing method, or the like may be used.

The first lead wiring 26 and the second lead wiring 30 are members that play a role in applying a voltage to the first detection electrode 24 and the second detection electrode 28, respectively.
The first lead wiring 26 is disposed on the substrate 22 in the outer region E _O , one end of which is electrically connected to the corresponding first detection electrode 24, and the other end is electrically connected to the flexible printed wiring board 32. The
The second lead wiring 30 is disposed on the substrate 22 in the outer region E _O , one end of which is electrically connected to the corresponding second detection electrode 28, and the other end is electrically connected to the flexible printed wiring board 32. The
In FIG. 2, five first lead wires 26 and five second lead wires 30 are shown, but the number thereof is not particularly limited, and a plurality of them are usually arranged according to the number of detection electrodes. The

The amount of metal per unit area contained in the first lead-out wiring 26 and the second lead-out wiring 30 is 0.010 to 10 g / m ² , similar to the metal thin wire 34 described above. The preferable range of the metal amount is the same as that of the metal thin wire 34 described above.
In addition, the material of the wiring constituting the first lead wiring 26 and the second lead wiring 30 is synonymous with the material constituting the metal thin wire 34 described above. Among these, silver is preferable because of its excellent conductivity. Moreover, you may be comprised with metals and alloy thin films, such as aluminum (Al), molybdenum (Mo), and palladium (Pd). In the case of a metal paste, a screen printing or ink jet printing method is used, and in the case of a metal or alloy thin film, a patterning method such as a photolithography method is suitably used for the sputtered film.
In addition, it is preferable that the binder is contained in the 1st extraction wiring 26 and the 2nd extraction wiring 30 from the point which adhesiveness with the board | substrate 22 is more excellent. The kind of binder is as above-mentioned.

The flexible printed wiring board 32 is a board in which a plurality of wirings and terminals are provided on a substrate, and is connected to the other end of each of the first lead-out wirings 26 and the other end of each of the second lead-out wirings 30, and is a conductive film. 14 and an external device (for example, a display device).

<Method for producing touch panel laminate>
The manufacturing method in particular of the said laminated body for touchscreens is not restrict | limited, A well-known method is employable.
First, as a method for producing a thin metal wire in a conductive film, for example, a subtractive method using an etching process, a semi-additive method using electrolytic plating, a silver paste (for example, a silver nanoparticle or silver nanowire-containing paste) Examples thereof include a method for producing a metal wiring by using a vacuum, a vacuum deposition method, a sputtering film forming method, an ion plating method and the like.

In addition to the above method, a method using silver halide is preferably used. More specifically, first, a step (1) of forming a silver salt emulsion layer containing silver halide on a substrate, a step of forming a fine metal wire by developing after exposing the silver salt emulsion layer ( 2).
Below, each process is demonstrated.

[Step (1): Silver salt emulsion layer forming step]
Step (1) is a step of forming a silver salt emulsion layer on the substrate.
The method for forming the silver salt emulsion layer is not particularly limited. From the viewpoint of productivity, the silver salt emulsion layer-containing composition containing silver halide is brought into contact with the substrate to form the silver salt emulsion layer on the substrate. The method is preferred.
Below, after explaining in full detail about the form of the composition for silver salt emulsion layer formation used by the said method, the procedure of a process is explained in full detail.

The silver salt emulsion layer forming composition contains silver halide.
The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. As the silver halide, for example, silver halides mainly composed of silver chloride, silver bromide and silver iodide are preferably used, and silver halides mainly composed of silver bromide and silver chloride are preferably used.
The silver salt emulsion layer forming composition may contain a resin binder, if necessary. The kind of the resin binder is as described above, and among them, gelatin is preferable.

The composition for forming a silver salt emulsion layer contains a solvent, if necessary.
Examples of the solvent used include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, and the like. Etc.), ionic liquids, or mixed solvents thereof.
The content of the solvent to be used is not particularly limited, but is preferably in the range of 30 to 90% by mass, and more preferably in the range of 50 to 80% by mass with respect to the total mass of the silver halide and the resin binder.

(Process procedure)
The method for bringing the silver salt emulsion layer-forming composition and the substrate into contact with each other is not particularly limited, and a known method can be employed. For example, a method of applying a silver salt emulsion layer forming composition to a substrate, a method of immersing a substrate in a silver salt emulsion layer forming composition, and the like can be mentioned.

[Step (2): Exposure and development step]
Step (2) is a step of forming a fine metal wire by subjecting the silver salt emulsion layer obtained in the above step (1) to exposure treatment and development treatment.
Hereinafter, the exposure process will be described in detail, and then the development process will be described in detail.

(Exposure processing)
By subjecting the silver salt emulsion layer to pattern exposure, the silver halide in the silver salt emulsion layer in the exposed region forms a latent image. In the area where the latent image is formed, fine metal lines are formed by a development process described later. On the other hand, in the unexposed areas that have not been exposed, the silver halide dissolves and flows out of the silver salt emulsion layer during the fixing process described later, and a transparent film is obtained.
The light source used in the exposure is not particularly limited, and examples thereof include light such as visible light and ultraviolet light, and radiation such as X-rays.
The method for performing pattern exposure is not particularly limited. For example, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. The shape of the pattern is not particularly limited, and is appropriately adjusted according to the pattern of fine metal wires to be formed.

(Development processing)
The development processing method is not particularly limited, and a known method can be employed. For example, conventional development processing techniques used for silver salt photographic film, photographic paper, printing plate making film, photomask emulsion mask, and the like can be used.
The type of the developer used in the development process is not particularly limited. For example, PQ developer, MQ developer, MAA developer and the like can be used.
The development process can include a fixing process performed for the purpose of removing and stabilizing the silver salt in the unexposed part. For the fixing process, a technique of fixing process used for silver salt photographic film, photographic paper, printing plate-making film, photomask emulsion mask and the like can be used.
The fixing temperature in the fixing step is preferably 20 to 50 ° C., more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, more preferably 7 to 50 seconds.

Next, as a manufacturing method of a 1st adhesive layer and a 2nd adhesive layer, the composition for adhesive layer formation containing an adhesive is apply | coated on a board | substrate (conductive film) with a metal fine wire, and as needed. Examples thereof include a method of performing a curing treatment to form a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer, and a method of laminating a pressure-sensitive adhesive sheet containing a pressure-sensitive adhesive on a substrate with fine metal wires. The method by the said application | coating is preferable from the point that adjustment of the thickness of a 1st adhesive layer and a 2nd adhesive layer is easy.

The method for applying the adhesive layer forming composition onto the substrate with fine metal wires is not particularly limited, and is a dispensing method, a screen printing method, a curtain coating method, a barcode method, a spin coater method, an ink jet method, a dip dipping method. For example, a known method can be adopted.
Moreover, what is necessary is just to implement heat processing or exposure processing suitably as a hardening process.

Next, a desired laminated body for a touch panel can be manufactured by laminating the first transparent protective substrate and the second transparent protective substrate described above on the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer, respectively.
In addition, in the laminated body for touch panels, the occurrence of migration is further suppressed, and the malfunction of the touch panel is further suppressed, so that the metal wiring in the conductive film is 0.1 cm or more from the end face of the laminated body for touch panels (preferably , 0.3 cm or more).

The total light transmittance of the touch panel laminate produced as described above is not particularly limited, but is preferably 80 to 90% from the viewpoint of application to a touch panel.
Further, the haze of the laminate for a touch panel is not particularly limited, but is preferably 0.3 to 3.5% from the viewpoint of application to a touch panel.
As a method for measuring light transmittance and haze, a measurement method using CM-3600A manufactured by Konica Minolta is adopted.

(Touch panel)
As shown in FIG. 5, the touch panel 10 is manufactured by arranging the above-described laminated body 1 for a touch panel on the viewing side of the display device 11.
In addition, when arrange | positioning the laminated body 1 for touchscreens on a display apparatus, as shown in FIG. 5, it arrange | positions so that the 2nd transparent protective substrate 6 may become the display apparatus 11 side.
The obtained touch panel suppresses the ion migration of the fine metal wire and is unlikely to malfunction.

In addition, the form of the conductive film in the laminated body for touch panels is not limited to the form of FIG. 2, but may be the form shown in FIG.
As shown in FIG. 6, the conductive film 140 is electrically connected to the second substrate 38, the second detection electrode 28 disposed on the second substrate 38, and one end of the second detection electrode 28. A second lead wiring (not shown) disposed on the substrate 38, the adhesive layer 40, the first detection electrode 24, and a first lead wiring electrically connected to one end of the first detection electrode 24. (Not shown), a first substrate 42 adjacent to the first detection electrode 24 and the first lead-out wiring, and a flexible printed wiring board (not shown).
As shown in FIG. 6, the conductive film 140 has the same configuration as that of the conductive film 140 except for the second substrate 38, the first substrate 42, and the adhesive layer 40. Elements are given the same reference numerals, and descriptions thereof are omitted.

The definitions of the second substrate 38 and the first substrate 42 are the same as the definition of the substrate 22 described above.
The pressure-sensitive adhesive layer 40 is a layer for bringing the first detection electrode 24 and the second detection electrode 28 into close contact with each other, and is preferably optically transparent (preferably a transparent pressure-sensitive adhesive layer). As a material constituting the pressure-sensitive adhesive layer 40, a known material is used.
A plurality of the first detection electrodes 24 and the second detection electrodes 28 in FIG. 6 are used as shown in FIG. 2, and both are arranged so as to be orthogonal to each other as shown in FIG.

In the conductive film 140, the first detection electrode 24, the first lead wire electrically connected to one end of the first detection electrode 24, the second detection electrode 28, and one end of the second detection electrode 28 are electrically connected. Similarly to the embodiment shown in FIG. 2, the second lead wiring connected in the manner is composed of a thin metal wire having a metal amount per unit area of 0.010 to 10 g / m ² . In addition, the suitable range and measuring method of metal amount are as above-mentioned.
That is, the conductive film 140 shown in FIG. 6 is prepared by preparing two substrates with fine metal wires having a substrate and fine metal wires (detection electrodes and lead wires) arranged on one side of the substrate so that the fine metal wires face each other. Furthermore, it corresponds to the conductive film obtained by bonding through an adhesive layer.

Furthermore, the form shown in FIG. 7 may be sufficient as the form of the conductive film in the laminated body for touch panels.
In FIG. 7, the conductive film 240 is electrically connected to the second substrate 38, the second detection electrode 28 disposed on the second substrate 38, and one end of the second detection electrode 28. A second lead-out wiring (not shown), an adhesive layer 40, a first substrate 42, a first detection electrode 24 disposed on the first substrate 42, and one end of the first detection electrode 24. And a first lead wiring (not shown) disposed on the first substrate 42 and a flexible printed wiring board (not shown).
The conductive film 240 shown in FIG. 7 has the same layers as those of the conductive film 140 shown in FIG. 6 except that the order of the layers is different. Therefore, the same components are denoted by the same reference numerals. The description is omitted.
Further, a plurality of the first detection electrodes 24 and the second detection electrodes 28 in FIG. 7 are used as shown in FIG. 2, and both are arranged so as to be orthogonal to each other as shown in FIG. .

In the conductive film 240, the first detection electrode 24, the first lead wire electrically connected to one end of the first detection electrode 24, the second detection electrode 28, and one end of the second detection electrode 28 are electrically connected. Similarly to the embodiment shown in FIG. 2, the second lead wiring connected in the manner is composed of a thin metal wire having a metal amount per unit area of 0.010 to 10 g / m ² . In addition, the suitable range and measuring method of metal amount are as above-mentioned.
That is, the conductive film 240 shown in FIG. 7 is prepared by preparing two substrates with fine metal wires each having a substrate and fine metal wires (detection electrodes and lead wires) arranged on one side of the substrate. It corresponds to a conductive film obtained by bonding through an adhesive layer so that the inner substrate and the metal fine wire of the other substrate with metal fine wires face each other.

Second Embodiment
As another form of the laminated body for touch panels, as shown in FIG. 8, at least the first adhesive layer 3 exposed from between the first transparent protective substrate 2 and the second transparent protective substrate 6, the conductive film. 4 and the form by which the sealing layer 12 is arrange | positioned on the surface of the peripheral part of the 2nd adhesive layer 5 is mentioned. By disposing the sealing layer 12, the intrusion of moisture from the end face is suppressed, and the effect of the present invention is more excellent.
In FIG. 8, the first adhesive layer 3, the conductive film 4, and the peripheral portion of the second adhesive layer 5 are the first transparent protective substrate 2, the first adhesive layer 3, the conductive film 4, the second In the laminate in which the pressure-sensitive adhesive layer 5 and the second transparent protective substrate 6 are laminated in this order, the side surfaces of the first pressure-sensitive adhesive layer 3, the conductive film 4, and the second pressure-sensitive adhesive layer 5 exposed to the outside. Intended part.
The sealing layer 12 may be further disposed on the end surfaces and / or main surfaces of the first transparent protective substrate 2 and the second transparent protective substrate 6.

The thickness of the sealing layer is not particularly limited, but is preferably 1.0 μm or more, preferably 2.0 μm or more, more preferably 4.0 μm or more, and even more preferably 10.0 μm or more in terms of more excellent effects of the present invention. . The upper limit is not particularly limited, but is preferably 50 μm or less from the viewpoint that the effect is saturated and the economy is impaired.
In addition, the thickness of a sealing layer is the average value which measured the thickness of 20 places or more places of a sealing layer, and arithmetically averaged them.
The material which comprises a sealing layer in particular is not restrict | limited, A well-known curable resin (thermosetting resin or photocurable resin) and a thermoplastic resin are used.

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Example A>
<Production of sample No. 102>
(Preparation of silver halide emulsion)
To the following 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of each of the following 2 and 3 liquids was simultaneously added over 20 minutes while stirring to form 0.16 μm core particles. Subsequently, the following 4 and 5 solutions were added over 8 minutes, and the remaining 10% of the following 2 and 3 solutions were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the grain formation.

1 liquid:
750 ml of water
9g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
Two liquids:
300 ml of water
150 g silver nitrate
3 liquids:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) 8 ml
Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 10 ml
4 liquids:
100ml water
Silver nitrate 50g
5 liquids:
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first water washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting step. The emulsion after washing with water and desalting was adjusted to pH 6.4 and pAg 7.5, and gelatin 3.9 g, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate 15 mg and chloroauric acid 10 mg were added. Chemical sensitization to obtain optimum sensitivity at 0 ° C., 100 mg of 1,3,3a, 7-tetraazaindene as stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as preservative It was. The finally obtained emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide. It was a silver iodochlorobromide cubic grain emulsion having a coefficient of 9%.

(Preparation of silver salt emulsion layer forming composition)
1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / Mole Ag, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 0.90 g / mole Ag was added, and the pH of the coating solution was adjusted to 5.6 with citric acid, and silver was added. A composition for forming a salt emulsion layer was obtained.

(Silver salt emulsion layer formation process)
After a polyethylene terephthalate (PET) film having a thickness of 100 μm is subjected to corona discharge treatment, a gelatin layer having a thickness of 0.1 μm as an undercoat layer on both sides of the PET film, and an optical density of about 1.0 on the undercoat layer. And an antihalation layer containing a dye which is decolorized by alkali in the developer. On the antihalation layer, the silver salt emulsion layer forming composition was applied, and a gelatin layer having a thickness of 0.15 μm was further provided to obtain a PET film having a silver salt emulsion layer formed on both sides. The obtained film is referred to as film A. The formed silver salt emulsion layer had a silver amount of 6.0 g / m ² and a gelatin amount of 1.0 g / m ² .

(Exposure development process)
The film A was exposed using parallel light using a high-pressure mercury lamp as a light source through a photomask having a comb-shaped pattern with a line and space (L / S) of 50 μm / 50 μm on both surfaces of the film A. After the exposure, development was performed with the following developer, and further development was performed using a fixer (trade name: N3X-R for CN16X, manufactured by Fuji Film). Furthermore, by rinsing with pure water and drying, a PET film in which an electrode pattern composed of Ag fine wires (metal fine wires) and a gelatin layer were formed on both surfaces was obtained. The gelatin layer was formed between Ag fine wires, and the amount of Ag in the Ag fine wires at this time was 5.5 g / m ² from fluorescent X-ray analysis. The obtained film with a comb-shaped wiring pattern is referred to as film B.

(Developer composition)
The following compounds are contained in 1 liter (L) of the developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

(Lamination process)
On the surface where one Ag fine wire of the film B obtained above was present, 3M OCA (# 8146-2: 50 micrometers thick) and the following barrier film 1 were laminated in this order.
Furthermore, a sample in which 3M OCA (# 8146-4: 100 micrometers thickness) and a glass substrate were bonded together in this order on the surface of the film B on which the other Ag fine wire exists was designated as sample No. 101. . At this time, the distance between the Ag fine wire and the end face of the laminate was 1 cm or more.

―Preparation of barrier film 1―
A gas barrier film 10 having an organic layer and a silicon nitride layer on the surface of the support Z was produced as a barrier film.
As the support Z, a long PET film having a width of 1000 mm and a thickness of 100 μm was used.

An organic compound and a surfactant were added to an organic solvent and mixed to prepare a coating material for an organic layer. As the organic compound, TMPTA (manufactured by Daicel-Cytec) was used. MEK was used as the organic solvent. As the surfactant, a silicon-based surfactant (BYK378, manufactured by BYK Japan) was used. The amount added was 1% by weight at a concentration excluding the organic solvent. Furthermore, a photopolymerization initiator (Irg184, manufactured by Ciba Chemicals Co., Ltd.) having a weight of 2% in a concentration excluding the organic solvent was added to the paint (that is, 97% by weight of the organic compound in the solid content). This surfactant and photopolymerization initiator do not contain halogen. The solid content concentration of the paint was 15% by weight.
The support roll ZR formed by winding the support Z is loaded on the rotation shaft 342 of the organic film forming apparatus 330 shown in FIG. 9A, and the prepared paint is applied to the surface of the support Z by the applying means 336. It was coated / dried and crosslinked / cured by light irradiation means 340 to obtain a roll ZoR formed by winding a support Z on which an organic layer was formed. The coating means 336 used a die coater. The coating amount was 20 cc / m ² . The prepared paint has a dry film thickness, that is, an organic layer thickness of 2 μm at this coating amount. The drying means 338 used hot air. As the light irradiation means 340, an ultraviolet irradiation device was used.

Next, the roll ZoR is loaded into the inorganic film forming apparatus 332 shown in FIG. 9B, and a silicon nitride film having a thickness of 50 nm is formed on the surface of the support Zo on which the organic layer is formed by CCP-CVD. A roll 10aR formed by winding a gas barrier film on which a silicon nitride layer was formed was produced.
Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as the film forming gas. The supply amounts were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The film forming pressure was 50 Pa.
The shower electrode 382 was supplied with 3000 W of plasma excitation power at a frequency of 13.5 MHz from a high frequency power source 386. Furthermore, the drum 380 was made of stainless steel, and a bias power of 500 W was supplied from a bias power source (not shown). During film formation, the temperature of the drum 380 was adjusted to −20 ° C.
The water vapor permeability (g / m ² · 24h (40 ° C., 90% RH)) of the produced barrier film 1 was measured by N3 measurement using a calcium corrosion method (a method described in JP-A-2005-283561). The average value was 1 × 10 ⁻⁵ (g / m ² · 24 h (40 ° C., 90% RH)) order.

(Evaluation (migration evaluation))
Sample No. 101 produced by the above method was allowed to stand at 60 ° C./90% RH for 1 hour, a voltage of 5 V was applied for 30 minutes by direct current, and then the state of migration was observed with a microscope, in accordance with the following criteria: evaluated. Table 1 shows the results.
―Evaluation of migration―
5 The occurrence of dendrite etc. cannot be confirmed at all 4 The occurrence of dendrite etc. is almost not seen 3 The occurrence of dendrite etc. is seen, but there is no problem in practical use 2 The occurrence of dendrite etc. is seen, and there is a problem in practical use 1 Occurrence is severe and practically problematic

<Production of sample No. 102>
Instead of the barrier film 1, the organic film / inorganic layer is alternately laminated in the organic film / inorganic layer manufacturing procedure in the above-described barrier film 1 manufacturing procedure (two pairs of organic / inorganic layers + one organic layer) ) Sample No102 was prepared and evaluated according to the same procedure as Sample No101 except that the produced barrier film 2 was used. The results are shown in Table 1. The film obtained had a water vapor permeability of the order of 1 × 10 ⁻⁶ (g / m ² · 24 h (40 ° C., 90% RH)).

<Production of sample No103>
Instead of the barrier film 1, the organic film / inorganic layer is alternately laminated in the production procedure of the above barrier film 1 with organic / inorganic / organic / inorganic / organic / inorganic / organic / inorganic / organic / inorganic / organic layers. Sample No103 was prepared and evaluated according to the same procedure as Sample No101, except that (organic / inorganic 5 pair lamination + organic 1 layer) and the produced barrier film 3 were used. The results are shown in Table 1. Further, the water vapor permeability of the obtained film was less than 1 × 10 ⁻⁶ (g / m ² · 24 h (40 ° C., 90% RH)) order because the change in the state of calcium was very small during the measurement time. Judged that there was.

<Production of sample No. 104>
Instead of the barrier film 1, the sample No. 104 was prepared according to the same procedure as the production of the sample No. 101 except that the barrier film 4 in which the dry film thickness of the organic layer was changed to 0.25 μm was used in the manufacturing procedure of the above barrier film 1. Fabricated and evaluated. The results are shown in Table 1. The film obtained had a water vapor permeability of the order of 1 × 10 ⁻³ (g / m ² · 24 h (40 ° C., 90% RH)).

<Production of sample No. 105>
Sample No105 was produced and evaluated in accordance with the same procedure as that for producing Sample No101 except that Mitsubishi Resin Tech Barrier HX (12 μm thick) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No. 106>
Sample No106 was produced and evaluated in accordance with the same procedure as that for producing Sample No101, except that Mitsubishi Plastics Tech Barrier L (thickness 12 micrometers) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No107>
Sample No107 was produced and evaluated according to the same procedure as that for producing Sample No101, except that Zeonoa Film (40 micrometer thickness) manufactured by Nippon Zeon Co., Ltd. was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of Sample No. 108>
Sample No108 was produced and evaluated in accordance with the same procedure as that for producing Sample No101 except that a hard coat film (G1SBF: 50 μm thickness) manufactured by Kimoto Co. was used instead of the barrier film 1. The results are shown in Table 1.

<Production of sample No. 109>
Sample No109 was prepared and evaluated in accordance with the same procedure as Sample No101 except that JSR Arton Film (40 micrometer thickness) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No110>
Sample No110 was produced and evaluated according to the same procedure as that for producing Sample No101 except that Zeonoa Film (100 micrometer thickness) manufactured by Nippon Zeon Co., Ltd. was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No111>
Instead of film B, except using Ag vapor deposition film produced by vapor deposition of Ag through a metal mask having a comb-shaped pattern with a line and space (L / S) of 50 μm / 50 μm on a PET substrate Sample No111 was prepared and evaluated according to the same procedure as sample No101. The results are shown in Table 1. The amount of Ag was 1.0 g / m ² from fluorescent X-ray analysis.

<Production of sample No112>
Instead of film B, Ag paste (Dotite FA-401CA, manufactured by Fujikura Kasei Co., Ltd.) is screen-printed through a screen mask with a comb-shaped pattern with a line and space (L / S) of 50/50 μm on a PET substrate. And sample No112 was produced and evaluated in accordance with the procedure similar to preparation of sample No101 except having used the film with an Ag paste produced by baking for 30 minutes at 100 degreeC. The results are shown in Table 1. The amount of Ag was 9.3 g / m ² from fluorescent X-ray analysis.

<Production of sample No113>
Sample No113 was produced and evaluated in accordance with the same procedure as that for producing Sample No101 except that the patterned conductive film 1 described later was used instead of the film B. The results are shown in Table 1. The amount of Ag was 0.015 g / m ² from fluorescent X-ray analysis.

(Preparation of aqueous dispersion of silver nanowires)
-Preparation of silver nanowire dispersion (1)-
A silver nitrate solution 101 was prepared by dissolving 60 g of silver nitrate powder in 370 g of propylene glycol. 72.0 g of polyvinylpyrrolidone (molecular weight 55,000) was added to 4.45 kg of propylene glycol, and the temperature was raised to 90 ° C. while venting nitrogen gas through the gas phase portion of the container. This solution was designated as reaction solution 101. 2.50 g of the silver nitrate solution 101 was added to the vigorously stirred reaction solution 101 while maintaining the nitrogen gas flow, and the mixture was heated and stirred for 1 minute. Further, a solution in which 11.8 g of tetrabutylammonium chloride was dissolved in 100 g of propylene glycol was added to this solution to obtain a reaction solution 102.
200 g of the silver nitrate solution 101 was added to the reaction solution 102 which was kept at 90 ° C. and stirred at a stirring speed of 500 rpm at an addition speed of 50 cc / min. The stirring speed was reduced to 100 rpm, the aeration of nitrogen gas was stopped, and heating and stirring were performed for 15 hours. 220 g of the silver nitrate solution 101 was added at an addition speed of 0.5 cc / min to this liquid kept at 90 ° C. and stirred at a stirring speed of 100 rpm, and the heating and stirring were continued for 2 hours after the addition was completed. The stirring was changed to 500 rpm, and after adding 1.0 kg of distilled water, the mixture was cooled to 25 ° C. to prepare a charged solution 101.
Using an ultrafiltration module with a molecular weight cut off of 150,000, ultrafiltration was performed as follows. Addition of a mixed solution of distilled water and 1-propanol (volume ratio of 1: 1) to the charged liquid 101 and concentration of the charged liquid 101 were repeated until the conductivity of the filtrate finally reached 50 μS / cm or less. Concentration was performed to obtain a silver nanowire dispersion liquid (1) having a metal content of 0.45%.
About the silver nanowire of the obtained silver nanowire dispersion liquid (1), the average minor axis length and the average major axis length were measured. As a result, the average minor axis length was 28.5 nm and the average major axis length was 15.2 μm. Hereinafter, the notation “silver nanowire dispersion (1)” indicates the silver nanowire dispersion obtained by the above method.

-Preparation of silver nanowire dispersion (2)-
The following additive solutions A, B, C and D were prepared in advance.
[Additive liquid A]
Stearyltrimethylammonium chloride 55 mg, stearyltrimethylammonium hydroxide 10% aqueous solution 5.5 g, and glucose 1.8 g were dissolved in distilled water 115.0 g to obtain reaction solution A-1. Further, 65 mg of silver nitrate powder was dissolved in 1.8 g of distilled water to obtain an aqueous silver nitrate solution A-1. The reaction solution A-1 was kept at 25 ° C., and the aqueous silver nitrate solution A-1 was added with vigorous stirring. After the addition of the aqueous silver nitrate solution A-1, the mixture was vigorously stirred for 180 minutes to obtain additive solution A.
[Additive liquid B]
42.0 g of silver nitrate powder was dissolved in 958 g of distilled water.
[Additive liquid C]
75 g of 25% aqueous ammonia was mixed with 925 g of distilled water.
[Additive solution D]
400 g of polyvinylpyrrolidone (K30) was dissolved in 1.6 kg of distilled water.

Next, a silver nanowire dispersion liquid (2) was prepared as follows.
1.30 g of stearyltrimethylammonium bromide powder, 33.1 g of sodium bromide powder, 1,000 g of glucose powder and 115.0 g of nitric acid (1N) were dissolved in 12.7 kg of distilled water at 80 ° C. While this liquid was kept at 80 ° C. and stirred at 500 rpm, the additive liquid A was added successively at an addition rate of 250 cc / min, the additive liquid B at 500 cc / min, and the additive liquid C at 500 cc / min. The stirring speed was 200 rpm and heating was performed at 80 ° C. After the stirring speed was set to 200 rpm and heating and stirring were continued for 100 minutes, the mixture was cooled to 25 ° C. The stirring speed was changed to 500 rpm, and additive solution D was added at 500 cc / min. This liquid was used as a charged liquid 201. Next, 1-propanol was vigorously stirred, and the charged solution 201 was added to the mixture at a stretch so that the mixing ratio was 1: 1. Stirring was performed for 3 minutes to obtain a charged solution 202.

Using an ultrafiltration module with a molecular weight cut off of 150,000, ultrafiltration was performed as follows.
After concentrating the feed liquid 202 four times, the addition and concentration of a mixed solution of distilled water and 1-propanol (volume ratio of 1: 1) was repeated until the conductivity of the filtrate finally reached 50 μS / cm or less. It was. Concentration was performed to obtain a silver nanowire dispersion liquid (2) having a metal content of 0.45%.
About the silver nanowire of the obtained silver nanowire dispersion liquid (2), the average minor axis length and the average major axis length were measured. As a result, the average minor axis length was 17.2 nm and the average major axis length was 8.8 μm.

(Preparation of conductive film 1)
The solution of the alkoxide compound having the following composition was stirred at 60 ° C. for 1 hour to confirm that the solution became uniform. When the weight average molecular weight (Mw) of the obtained sol-gel solution was measured by GPC (polystyrene conversion), Mw was 4,400. 2.24 parts of the sol-gel solution and 17.76 parts of the prepared silver nanowire dispersion liquid (1) were mixed and further diluted with distilled water and 1-propanol to obtain a silver nanowire coating liquid (1). The solvent ratio of the obtained coating solution was distilled water: 1-propanol = 60: 40. PET substrate (thickness 125 [mu] m) amount of silver 0.015 g / m ² by a bar coating method on, after the total solid content in the coating solution was coated silver nanowire coating solution (1) so that 0.120 g / m ^2, It dried at 120 degreeC for 1 minute, and the electrically conductive film 1 containing a silver nanowire was formed.

(Alkoxide compound solution)
・ Tetraethoxysilane 5.0 parts (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 1% acetic acid aqueous solution 11.0 parts ・ Distilled water 4.0 parts

(Patterning of conductive film 1)
A photoresist (TMSMR-8900LB: manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the conductive film 1 by spin coating and baked at 90 ° C. for 60 seconds. Next, pattern exposure was performed using a photomask (exposure amount: 12 mW / cm ² , 20 seconds), developed with a developer (NMD-W: Tokyo Sensitivity), washed with water and dried, then at 120 ° C. A patterned photoresist was formed on the conductive film 1 by baking for 60 seconds.
Next, after being immersed in a silver etching solution (SEA-2: manufactured by Kanto Chemical Co., Inc.) for 30 seconds, washed with water and dried, the silver nanowires were etched to form a nonconductive portion in the conductive film 1. Thereafter, the photoresist is stripped using a neutral stripping solution (PK-SFR8120: manufactured by Parker Corporation), then washed with water and dried to be patterned into a comb-shaped electrode pattern (L / S = 50 μm / 50 μm). A conductive film 1 was prepared.

<Production of sample No. 114>
A patterned conductive film 2 was prepared according to the above procedure except that the silver nanowire dispersion liquid (1) was changed to the silver nanowire dispersion liquid (2) in the above (production of conductive film).
Next, sample No. 114 was produced and evaluated according to the same procedure as that for producing sample No. 101 except that the patterned conductive film 2 was used instead of film B. The results are shown in Table 1. The amount of Ag was 0.015 g / m ² from fluorescent X-ray analysis.

<Production of sample No. 115>
Sample No. 115 was produced by applying 8814M9 manufactured by Kyoritsu Chemical Co., Ltd. to the end face of the laminate of sample No. 101, irradiating and curing with 3 J / cm ² of UV light, and sealing the end face of the laminate. In addition, the formed sealing layer was arrange | positioned so that the end surface of an adhesive layer and a conductive film might be covered.

<Production of Sample No. 116>
CR-18CL-CK manufactured by Asahi Chemical Research Laboratories was applied to the end face of the laminate of Sample No. 101, cured in an oven at 130 degrees for 10 minutes, and the end face of the laminate was sealed to prepare Sample 116. In addition, the formed sealing layer was arrange | positioned so that the end surface of an adhesive layer and a conductive film might be covered.

<Production of Sample No. 117>
Sample No. 117 is prepared and evaluated according to the same procedure as Sample No. 101 except that the position of the photomask is adjusted so that the distance between the Ag fine wire and the end face of the laminate is from 1 cm to 0.3 cm. did. The results are shown in Table 1.

<Production of sample No. 118>
Except that the amount of Ag was changed formulation of a silver salt emulsion layer to consist of 5.5 g / m ² to 0.009 g / m ^2, according to the same procedure as preparation of samples No101, to prepare a sample No118, evaluation Carried out. The results are shown in Table 1.

<Production of Sample No. 119>
Sample No. 119 was prepared and evaluated according to the same procedure as Sample No. 101 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 0.03 g / m ^2. Carried out. The results are shown in Table 1.

<Production of sample No120>
Sample No. 120 was prepared according to the same procedure as Sample No. 101 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 9.2 g / m ² , and various evaluations were made. Carried out. The results are shown in Table 1.

<Preparation of sample No121>
Sample No. 121 was prepared according to the same procedure as Sample No. 101 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 12 g / m ² , and various evaluations were performed. did. The results are shown in Table 1.

<Example B>
<Production of sample No. 201>
Sample No. 201 (touch panel) was produced according to the same procedure as the production of sample No. 101 except that (exposure development process) and (bonding process) in the production of sample No. 101 of Example A were changed to the following procedure.

(Exposure development process)
A photomask (hereinafter referred to as photomask) in which detection electrodes (first detection electrode and second detection electrode) and lead wiring portions (first lead wiring and second lead wiring) as shown in FIG. 2 are arranged on both surfaces of the film A. Double-sided simultaneous exposure was performed through the mask X) using parallel light using a high-pressure mercury lamp as a light source. After the exposure, development was performed with the developer used in Example A, and further development processing was performed using a fixing solution (trade name: N3X-R for CN16X, manufactured by FUJIFILM Corporation). Furthermore, by rinsing with pure water and drying, a PET film in which an electrode pattern composed of Ag fine wires (metal fine wires) and a gelatin layer were formed on both surfaces was obtained. The gelatin layer was formed between Ag fine wires, and the amount of Ag in the Ag fine wires at this time was 5.5 g / m ² from fluorescent X-ray analysis. The obtained film with a wiring pattern is referred to as film C.
The first detection electrode arranged on the PET film is an electrode extending in the X direction, the second detection electrode is an electrode extending in the Y direction, 15 X detection electrodes (length: 60 mm), and the Y detection electrodes (Length: 90 mm) was 10.
At this time, the distance between the Ag fine wire and the end face of the laminate was 1 cm or more.

(Lamination process)
OCA (# 8146-2: 50 micrometers thick) manufactured by 3M was bonded to both sides of the film C obtained above. After adjusting the outer shape of the resulting laminate to approximately the same size as a 0.7mm thick soda lime glass with a sensor size, FPC (Flexible Printed Circuit Board) was pressure bonded with Sony Chemicals ACF (CP906AM-25AC) The soda lime glass was pasted on the top side, and the barrier film 1 was pasted on the bottom side.
Next, 3M OCA (# 8146-2: 50 micrometer thick) was bonded onto the barrier film, and further bonded to a liquid crystal display on the OCA to produce Sample No. 201 (touch panel).

(Evaluation (operability of touch panel))
The prepared touch panel was allowed to stand for 240 hours in an environment of 85 ° C. and 85% RH, and the operability of the touch panel was confirmed immediately after being taken out in a room temperature environment. Three samples were prepared for evaluation, and all subjects were checked for movement by 5 subjects. Scores were assigned based on the following evaluation criteria, and the first decimal place of the average score obtained by arithmetically averaging the scores of each person was obtained. The score was rounded down. The results are shown in Table 1.
-Evaluation of touch panel operability-
5 Follow the high-speed flick operation without any problems 4 Follow the high-speed flick operation without any problems 3 There is a slight operational delay near the outer periphery, but there is no practical problem 2 There is a slight operational delay or malfunction in the entire panel There is a problem in practical use such as the occurrence. 1 Malfunction is severe and there is a problem in practical use.

(Evaluation (total light transmittance, measurement of haze))
In sample No. 201 (touch panel), a sample for measuring the total light transmittance and haze was prepared according to the same procedure except that a hard coat film (G1SBF: 50 μm thickness) manufactured by Kimoto was used instead of the liquid crystal display. The total light transmittance and haze were measured. Further, the same measurement was performed for sample Nos. 202 to 221 described later.
The measuring machine used here was CM-3600A manufactured by Konica Minolta.

<Production of sample No. 202>
Sample No. 202 was prepared and evaluated according to the same procedure as Sample No. 201 except that the above barrier film 2 was used instead of the barrier film 1. The results are shown in Table 1.

<Production of sample No. 203>
Sample No. 203 was produced and evaluated according to the same procedure as that for producing sample No. 201 except that the above-described barrier film 3 was used instead of the barrier film 1. The results are shown in Table 1.

<Production of sample No. 204>
Sample No. 204 was produced and evaluated in accordance with the same procedure as that for production of sample No. 201 except that the above-described barrier film 4 was used instead of the barrier film 1. The results are shown in Table 1.

<Production of sample No. 205>
Sample No. 205 was prepared and evaluated in accordance with the same procedure as Sample No. 201 except that Mitsubishi Resin Tech Barrier HX (12 μm thick) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No. 206>
Sample No206 was produced and evaluated in accordance with the same procedure as that for producing Sample No201, except that Mitsubishi Resin Tech Barrier L (thickness: 12 micrometers) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No. 207>
Sample No. 207 was produced and evaluated in accordance with the same procedure as that for producing Sample No. 201 except that Zeonoa Film (40 micrometer thickness) manufactured by Nippon Zeon Co., Ltd. was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No. 208>
Sample No208 was prepared and evaluated in accordance with the same procedure as Sample No201 except that a hard coat film (G1SBF: 50 μm thick) manufactured by Kimoto Co. was used instead of barrier film 1. The results are shown in Table 1.

<Production of sample No. 209>
Sample No. 209 was prepared and evaluated in accordance with the same procedure as Sample No. 201 except that JSR Arton Film (40 micrometer thickness) was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No. 210>
Sample No210 was produced and evaluated according to the same procedure as that for producing Sample No201 except that Zeonoa Film (100 micrometer thickness) manufactured by ZEON Corporation was used instead of Barrier Film 1. The results are shown in Table 1.

<Production of sample No211>
Instead of film B, sample No. 211 is prepared according to the same procedure as sample No. 201 except that an Ag vapor-deposited film prepared by vapor-depositing Ag is deposited on both sides of the PET substrate via the above photomask X. And evaluated. The results are shown in Table 1. The amount of Ag was 1.0 g / m ² from fluorescent X-ray analysis.

<Production of sample No. 212>
Instead of film B, Ag paste (Dotite FA-401CA, manufactured by Fujikura Kasei Co., Ltd.) is screen-printed on both sides of the PET substrate via the above photomask X, and then fired at 100 ° C. for 30 minutes. Sample No. 212 was produced and evaluated according to the same procedure as that for producing sample No. 201 except that the film was used. The results are shown in Table 1. The amount of Ag was 9.3 g / m ² from fluorescent X-ray analysis.

<Production of Sample No. 213>
A sample No. 213 was produced and evaluated according to the same procedure as the production of the sample No. 201 except that the patterned conductive film 3 described later was used instead of the film B. The results are shown in Table 1. The amount of Ag was 0.015 g / m ² from fluorescent X-ray analysis.

(Preparation of conductive film 3)
Silver nanowires coating liquid silver amount bar coating method on both surfaces 0.015 g / m ^2, the total solid content coating amount is prepared in Example A such that 0.120 g / m ² of PET substrate (thickness 125 [mu] m) ( After applying 1), it was dried at 120 ° C. for 1 minute to form a conductive film 3 containing silver nanowires.

(Patterning of conductive film 3)
A photoresist (TMSMR-8900LB: manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the conductive film 1 by spin coating and baked at 90 ° C. for 60 seconds. Next, pattern exposure was performed using the photomask X (exposure amount: 12 mW / cm ² , 20 seconds), development was performed with a developer (NMD-W: Tokyo Sensitivity), water washing and drying, and then 120 ° C. And baked for 60 seconds to form a patterned photoresist on the conductive film 3.
Next, after being immersed in a silver etching solution (SEA-2: manufactured by Kanto Chemical Co., Inc.) for 30 seconds, washed with water and dried, the silver nanowires were etched to form a nonconductive portion in the conductive film 1. Thereafter, the photoresist was stripped using a neutral stripping solution (PK-SFR8120: manufactured by Parker Corporation), and then washed with water and dried to prepare a patterned conductive film 3.

<Production of sample No. 214>
A patterned conductive film 4 was prepared according to the above procedure except that the silver nanowire dispersion liquid (1) was changed to the silver nanowire dispersion liquid (2) in the above (production of the conductive film 3).
Next, sample No. 214 was produced and evaluated according to the same procedure as the production of sample No. 201 except that the patterned conductive film 4 was used instead of film B. The results are shown in Table 1. The amount of Ag was 0.015 g / m ² from fluorescent X-ray analysis.

<Production of sample No. 215>
Sample No. 215 was prepared by applying 8814M9 manufactured by Kyoritsu Chemical Co., Ltd. to the laminate end face of sample No. 201, irradiating it with UV light of ³ J / cm ² and sealing the end face of the laminate.

<Production of sample No. 216>
CR-18CL-CK manufactured by Asahi Chemical Research Laboratories was applied to the end face of the laminate of Sample No. 201, cured in an oven at 130 ° C. for 10 minutes, and the end face of the laminate was sealed to prepare Sample 216.

<Production of sample No. 217>
Sample No. 217 was prepared and evaluated according to the same procedure as Sample No. 201 except that the position of the photomask X was adjusted so that the distance between the Ag fine wire and the end face of the laminate was 1 cm or more to 0.3 cm or more. Carried out. The results are shown in Table 1.

<Production of sample No. 218>
Except that the amount of Ag was changed formulation of a silver salt emulsion layer to consist of 5.5 g / m ² to 0.009 g / m ^2, according to the same procedure as preparation of samples No201, to prepare a sample No218, evaluation Carried out. The results are shown in Table 1.

<Production of Sample No. 219>
Sample No. 219 was prepared and evaluated in accordance with the same procedure as Sample No. 201 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 0.03 g / m ^2. Carried out. The results are shown in Table 1.

<Production of Sample No. 220>
Sample No. 220 was prepared according to the same procedure as Sample No. 201 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 9.2 g / m ² , and various evaluations were made. Carried out. The results are shown in Table 1.

<Production of Sample No. 221>
Sample No. 221 was prepared according to the same procedure as Sample No. 201 except that the formulation of the silver salt emulsion layer was changed so that the Ag amount was changed from 5.5 g / m ² to 12 g / m ² , and various evaluations were performed. did. The results are shown in Table 1.

In Table 1, in the “second transparent protective substrate” column, “alternate lamination” means a barrier laminate having at least one organic layer and inorganic layer.
The “migration” column shows the result of migration evaluation using samples No. 101 to 121, and the “touch panel operability” column shows the result of touch panel operability evaluation using samples No. 201 to 221.
In the “sealing layer” column, a case where the sealing layer is used on the end face of the laminate is indicated as “present”, and a case where the sealing layer is not used is indicated as “−”.
Further, in Table 1, "*" ^{is, 1 × 10 -6 g / m} 2 · 24h (40 ℃, RH 90%) is intended to be less than.

From the results in Table 1, the touch panel laminate of the present invention has reduced migration of water vapor and other gas components, so that the occurrence of migration is suppressed, and further, after being left in a high temperature and high humidity environment for a long time. The operability as a touch panel was confirmed to be very good.
In particular, when the water vapor permeability is 1 × 10 ⁻⁴ g / m ² · 24 h (40 ° C., 90% RH) or less, it was confirmed that the effect is more excellent.
As described above, every time the number of alternating layers is increased, the water vapor permeability is suppressed, and the performance such as migration is improved. However, it was also found that although there is no practical problem, the total light transmittance as a laminate decreases and haze increases.
Moreover, when the sealing layer was provided, it was confirmed that an effect is more excellent.
On the other hand, in Samples Nos. 105 and 205 to Nos. 110 and 210, Samples Nos. 118 and 218, and Samples Nos. 121 and 221 that do not satisfy the predetermined water vapor transmission rate or metal amount, the predetermined effects were not obtained.

<Example C>
Except that the film D in which the first detection electrode and the second detection electrode in the film C used in Example B were formed of an ITO thin film was used instead of the film C, the same procedure as in the preparation of the sample No 201 was followed. Sample No. 301 (touch panel) was produced.
Note that the lead-out wiring portion (first lead-out wiring and second lead-out wiring) connected to the first detection electrode and the second detection electrode in the film D is composed of an Ag fine wire, like the film C.
The obtained sample No. 301 was continuously driven for 100 hours in an environment of 60 ° C. and 90% RH, and after confirming the operation, there was no corrosion of the ITO constituting the first detection electrode and the second detection electrode, and the operation was good. Confirmed to do.
Samples Nos. 202 to 204, 211 to 217, and 219 to 220 described above were prepared by changing the first detection electrode and the second detection electrode to an ITO thin film, and the same evaluation as the sample No. 301 was performed. As a result, it was confirmed that the ITO constituting the first detection electrode and the second detection electrode did not corrode in each sample and operated well.

<Example D>
In sample No. 301 of Example C, the detection electrode portion (first detection electrode and second detection electrode) formed of an ITO thin film on one surface of the substrate, and the extraction wiring (first extraction wiring and Except for preparing two substrates with electrodes having (second lead-out wiring) and using a conductive film obtained by bonding two substrates with electrodes through an adhesive layer so that the detection electrode portions face each other. Sample No. 401 (touch panel) was produced according to the same procedure as sample No. 301, and the same evaluation was performed. In sample No. 401, even after driving for 100 hours in an environment of 60 ° C. and 90% RH, it was confirmed that the ITO constituting the first detection electrode and the second detection electrode did not corrode and operated well.

1, 10, 100 Touch panel laminate 2 First transparent protective substrate 3 First

adhesive layer

4, 14, 140, 240 Conductive film 5 Second adhesive layer 6 Second transparent protective substrate 10 Touch panel 11 Display device 12 Sealing Layer 22 Substrate 24, 24a First detection electrode 26 First extraction wiring 28, 28a Second detection electrode 30 Second extraction wiring 32 Flexible printed wiring board 34 Metal wire 36 Grid 38 Second substrate 40 Adhesive layer 42 First substrate 330 Organic film forming apparatus 332 Inorganic film forming apparatus 336 Application means 338 Drying means 340 Light irradiation means 342 and 364

Rotating shafts

346 and 392

Winding shafts

348 and 350 Conveying roller pair 356 Supply chamber 358 Film forming chamber 360

Winding chambers

368 and 384a , 384b, 390

Guide rollers

370, 373, 376 Vacuum exhaust means 72,374 septum 380 drum 382 showers electrode 386 high-frequency power source 387 gas supply means

Claims

A laminated body for a touch panel arranged on the viewing side of the display device,
A first transparent protective substrate, a first pressure-sensitive adhesive layer, a conductive film having at least a fine metal wire, a second pressure-sensitive adhesive layer, and a second transparent protective substrate are provided in this order.
When disposed on the display device, the second transparent protective substrate is located on the display device side,
The second transparent protective substrate has at least one or more organic layers and inorganic layers,
The water vapor permeability of the second transparent protective substrate is 0.001 g / m 2 · 24 h (40 ° C., 90% RH) or less,
A laminate for a touch panel, wherein an amount of metal per unit area contained in the metal fine wire is 0.010 to 10 g / m 2 .
The laminate for a touch panel according to claim 1, wherein the conductive film includes at least a substrate and fine metal wires disposed on both surfaces of the substrate.
The laminate for a touch panel according to claim 1, wherein the conductive film is formed by bonding substrates with metal wires having at least a substrate and metal wires arranged on one side of the substrate via an adhesive layer.
4. The touch panel laminate according to claim 1, wherein the first transparent protective substrate is a glass substrate.
The second transparent protective substrate has a resin substrate and a barrier layer disposed on the resin substrate,
The touch panel laminate according to any one of claims 1 to 4, wherein the barrier layer has a laminated structure in which at least one inorganic layer and at least one organic layer are alternately laminated.
The laminate for a touch panel according to claim 5, wherein the number of the inorganic layers and the number of the organic layers are 1 to 6, respectively.
7. The touch panel laminate according to claim 1, wherein the total light transmittance is 80% to 90% and the haze is 0.3% to 3.5%.
The first adhesive layer exposed from between the first transparent protective substrate and the second transparent protective substrate, the conductive film, and a sealing layer on the peripheral surface of the second adhesive layer The laminate for a touch panel according to any one of claims 1 to 7, wherein is disposed.
A touch panel having a display device and the laminate for a touch panel according to any one of claims 1 to 8.