JP6615146B2 - Laminated body, touch panel, and display device with touch panel - Google Patents

Description

  The present disclosure relates to a laminate, a touch panel, and a display device with a touch panel.

  Conventionally, indium tin oxide (ITO) films are widely known as transparent electrodes used for touch panel type information terminals and the like. However, it has been pointed out that the ITO film is easily cracked by repeated input operations and is also susceptible to bending. Moreover, since vacuum processes, such as vapor deposition or sputtering required for manufacture of an ITO film | membrane, require a huge installation cost, it is also a barrier at the time of enlarging a film | membrane.

  On the other hand, a transparent electrode using a conductive filler has been proposed as an alternative material for the ITO film, and a touch panel using a transparent conductive sheet provided with a transparent conductive film containing silver nanowires in a binder is known. (For example, refer to Patent Document 1).

  Furthermore, as a technology related to transparent electrodes containing conductive fillers, a plurality of transparent electrode substrates in which conductive nanowires are oriented in one direction are stacked, and conductive nanowires oriented in one direction are in the same direction. A display device in which a transparent electrode substrate is disposed so as to be disposed on the transparent electrode substrate is disclosed, and an example in which a polarizing plate is disposed on the observation surface side of the transparent electrode substrate is also shown (for example, see Patent Document 2). Further, the carbon nanotubes are oriented so that their long axes are aligned along a certain direction, and the conductivity due to the dispersive arrangement of the carbon nanotubes, and the polarization function that transmits light having a vibration direction orthogonal to the certain direction, There is disclosed a conductive polarizing film having (see, for example, Patent Document 3).

JP2015-128036A JP 2013-195969 A JP 2006-285068 A

As described above, the ITO film that has been used conventionally has a problem of poor flexibility. Furthermore, while the ITO film is excellent in transparency, there is also a problem that the electrode pattern is easily visible when used for a touch panel or the like.
Moreover, since the conductive filler proposed as an alternative material for the ITO film easily scatters external light, there is a problem that haze increases.

Problem to be solved by an embodiment of the present invention is to provide a laminate having flexibility, low haze, and improved visibility of an electrode pattern when a film sensor such as a touch panel is manufactured. There is.
The problem to be solved by another embodiment of the present invention is to provide a touch panel and a display device with a touch panel in which the visibility of an electrode pattern is further improved.

In order to bring out the conductive performance of the fibrous filler, the reflectivity when external light is incident, and the mechanical strength, the external light is changed to a linearly polarized component, and the fibrous filler is in one direction perpendicular to the polarization direction. The knowledge that it is desirable to orient the filler has been obtained and achieved based on such knowledge.
The present disclosure has been made in view of the above, and specific means for solving the above-described problems include the following aspects.

  <1> A metal nanowire disposed between a polarizing plate, a λ / 2 plate, a substrate, a polarizing plate and a λ / 2 plate, and oriented in a direction perpendicular to the transmission axis of the polarizing plate, and The first transparent conductive layer containing at least one kind of fibrous conductive particles selected from metal nanotubes, and the fibrous conductive material disposed between the λ / 2 plate and the base material and contained in the first transparent conductive layer And a second transparent conductive layer including at least one kind of fibrous conductive particles selected from metal nanowires and metal nanotubes, which are aligned in a direction orthogonal to the alignment direction of the particles.

A <2> metal nanowire is a laminated body as described in <1> containing a silver nanowire.
<3> A touch panel comprising the laminate according to <1> or <2>.
<4> A touch panel-equipped display device comprising the touch panel according to <3> and a display device.

  <5> A transfer material having at least one type of fibrous conductive particles selected from metal nanowires and metal nanotubes on a temporary support and having a transparent conductive layer in which the fibrous conductive particles are oriented in one direction in the plane. .

According to one embodiment of the present invention, a laminate is provided that has flexibility, low haze, and improved visibility of an electrode pattern when a film sensor such as a touch panel is produced.
According to one embodiment of the present invention, a touch panel and a display device with a touch panel in which the visibility of an electrode pattern is further improved are provided.

It is a disassembled block diagram which decomposes | disassembles and shows an example of a structure of the laminated body of this indication.

  Hereinafter, the laminate, the touch panel, and the display device with a touch panel of the present disclosure will be described in detail.

In the present specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.

  In addition, the term “process” in this specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. included.

In the present specification, the “metal nanowire” is conductive and has a long axis length longer than a diameter (short axis length) and a short axis length (that is, the maximum cross section perpendicular to the long axis direction). This refers to metal particles that have a shape with a nano-order size. In addition, the “metal nanotube” has a conductive and hollow inner tubular shape, the long axis length is longer than the diameter (short axis length), and the short axis length (that is, the long axis) The maximum length of the cross section perpendicular to the direction) is a metal particle having a nano-order size shape.
The “fibrous conductive particles” contained in the laminate of the present disclosure refer to particles selected from metal nanowires and metal nanotubes, and the “fibrous conductive material” in this specification includes metal nanowires and metals. In addition to nanotubes, metallic particles other than metal nanowires and metal nanotubes are also included.
The “fibrous” includes a wire shape, a wire shape, or a rod shape.

  The length of the fibrous conductive particles in the major axis direction refers to the average major axis length, and hereinafter, the length of the fibrous conductive particles is also referred to as “average major axis length”. The length of the fibrous conductive particles in the minor axis direction refers to the average minor axis length, and the length of the fibrous conductive particles is also referred to as “average minor axis length” below.

<Laminate>
The laminate of the present disclosure is disposed between a polarizing plate, a λ / 2 plate (1 / 2λ polarizing plate), a substrate, a polarizing plate, and a λ / 2 plate, and a transmission axis of the polarizing plate A first transparent conductive layer containing at least one type of fibrous conductive particles selected from metal nanowires and metal nanotubes, oriented in an orthogonal direction, and disposed between a λ / 2 plate and a substrate, A second transparent conductive layer containing at least one type of fibrous conductive particles selected from metal nanowires and metal nanotubes, which is oriented in a direction orthogonal to the orientation direction of the fibrous conductive particles contained in one transparent conductive layer; Have.
When the natural light is irradiated from the polarizing plate side, the laminate of the present disclosure transmits a linearly polarized light component orthogonal to the orientation direction of the fibrous conductive particles contained in the second transparent conductive layer.

Conventionally used indium tin oxide (ITO) films are susceptible to cracking due to external forces and have a problem of poor flexibility with respect to bending and the like.
In addition, conductive fillers have been proposed as an alternative material for ITO films, but metal nanowires, which are examples of conductive fillers, have a diameter that is smaller than the visible light wavelength but longer than the visible light wavelength. , It has the property of being easily reflected with respect to light (polarized light) that vibrates parallel to the length direction. Therefore, light incident on the transparent electrode layer containing metal nanowires or the like is reflected by the metal nanowires or the like dispersed in the layer, and light scattering is likely to occur. Light scattering generated in the transparent electrode layer contributes to an increase in haze.

In view of the above, in the laminate of the present disclosure, at least two transparent conductive layers containing a material having a relatively high aspect ratio selected from metal nanowires and metal nanotubes are provided as fibrous conductive particles, and one of the transparent conductive layers ( The first transparent conductive layer is disposed between the polarizing plate and the λ / 2 plate, the orientation direction of the fibrous conductive particles is set to a direction orthogonal to the transmission axis of the polarizing plate, and the other transparent conductive layer ( The second transparent conductive layer) is disposed between the λ / 2 plate and the substrate, and the orientation direction of the fibrous conductive particles is orthogonal to the orientation direction of the fibrous conductive particles contained in the first transparent conductive layer. The direction. That is, the external light incident on the laminate from the polarizing plate side is selectively incident with light that vibrates in the direction of the transmission axis of the polarizing plate, and then the first transparent conductive layer and the second transparent conductive layer located in the lower layer. In each layer, linearly polarized light components that vibrate in a direction orthogonal to the orientation direction of the fibrous conductive particles are selectively transmitted.
Thereby, flexibility is provided to the laminate, and scattering of light derived from the fibrous conductive particles is suppressed, and low haze is achieved. Moreover, when producing film sensors, such as a touch panel, the visibility of an electrode pattern can be reduced more.

[Transparent conductive layer]
First, the transparent conductive layer in the laminate of the present disclosure will be described.
The laminate of the present disclosure has at least two transparent conductive layers. One of the two layers is at least one fiber selected from a metal nanowire and a metal nanotube, which is arranged between a polarizing plate and a λ / 2 plate, which will be described later, and is oriented in a direction perpendicular to the transmission axis of the polarizing plate. It is the 1st transparent conductive layer containing a cylindrical conductive particle. The other of the two layers is disposed between a λ / 2 plate, which will be described later, and the base material, and is oriented in a direction perpendicular to the orientation direction of the fibrous conductive particles contained in the first transparent conductive layer. And a second transparent conductive layer containing at least one fibrous conductive particle selected from metal nanowires and metal nanotubes.

  In this specification, “perpendicular” not only indicates that another direction intersects with a certain direction at an angle of 90 ° (right angle), but the other direction has a direction from 70 ° to 70 °. The case where the angle is in the range of 110 ° is also included. The range of the “orthogonal” angle is preferably in the range of 80 ° to 100 °, more preferably in the range of 85 ° to 95 °, in that light scattering at the interface with the transparent conductive layer or the adjacent layer can be further suppressed. .

In this specification, “transparent” means that the transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, the “transparent conductive layer” refers to a layer having a visible light transmittance of 80% or more at a wavelength of 400 nm to 700 nm. The visible light transmittance of the “transparent conductive layer” is preferably 90% or more.
Moreover, the transmittance | permeability of a transparent conductive layer is a value measured using a spectrophotometer, for example, can be measured using the Hitachi Ltd. spectrophotometer U-3310.

  The first transparent conductive layer and the second transparent conductive layer can be used as, for example, an X-direction electrode or a Y-direction electrode laminated on a sensor film such as a touch panel. Resistance is further reduced, and an effect of improving electrical conductivity can be expected.

  The fibrous conductive particles contained in each of the first transparent conductive layer and the second transparent conductive layer may be the same conductive material or different types of conductive materials.

-First transparent conductive layer-
The first transparent conductive layer is disposed between a polarizing plate, which will be described later, and a λ / 2 plate. For example, as shown in FIG. 1, the polarization hν that vibrates in parallel with the transmission axis 10 is applied by the polarizing plate 14. Incident. The first transparent conductive layer 22 contains at least one kind of fibrous conductive particles selected from metal nanowires and metal nanotubes, and the fibrous conductive particles 12 contained in the layer are orthogonal to the transmission axis 10 of the polarizing plate 14. Therefore, the polarized light from the polarizing plate 14 is hardly scattered by the first transparent conductive layer 22. The transmitted light then enters the lower λ / 2 plate 18.

FIG. 1 is an exploded configuration diagram illustrating an example of a configuration of a laminate according to the present disclosure.
In the laminate 100 shown in FIG. 1, a silver nanowire film (transparent conductive member) 16 in which a first transparent conductive layer 22 is laminated on an isotropic substrate 24 is disposed on a λ / 2 plate 18. When the first transparent conductive layer 22 is patterned, it has an electrode pattern on the isotropic substrate 24.
Although FIG. 1 shows an embodiment in which the isotropic base material 24 is provided between the first transparent conductive layer 22 and the λ / 2 plate 18, the isotropic base material 24 may not be provided in some cases. Good.

(Fibrous conductive particles)
The fibrous conductive particles are those in which a conductive substance is in a fibrous form. There is no restriction | limiting in particular as a metal of the metal nanowire and metal nanotube contained as a fibrous conductive particle, Any metal may be sufficient. Moreover, 2 or more types of metals other than 1 type may be combined, and an alloy may be used.

The metal is preferably at least one metal selected from metals of the fourth period, the fifth period, and the sixth period of the periodic table (IUPAC 1991), and at least one selected from metals of Group 2 to Group 14 More preferably, the group of metals is at least one metal selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14 metals. Further preferred. It is particularly preferable that the metal contains the above metal as a main component. The “main component” means that the ratio to the total amount of metal is 50 mol% or more.
Examples of metals include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, And an alloy containing at least one of them. Among them, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy containing at least one of these is preferable, palladium, copper, silver, gold, platinum, tin, or at least these More preferred is an alloy containing one, and particularly preferred is silver or an alloy containing silver. The silver content in the “silver-containing alloy” is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% or more based on the total amount of the alloy. .

  When the first transparent conductive layer includes metal nanowires and metal nanotubes, the total content ratio of the metal nanowires and metal nanotubes with respect to the total mass of the fibrous conductive material included in the first transparent conductive layer is not particularly limited. The range is preferably 50% by mass or more, and more preferably 80% by mass or more. Furthermore, it is preferable that the total amount of the fibrous conductive material contained in the first transparent conductive layer is substantially silver nanowires. Note that “substantially silver nanowires” means that there may be fibrous conductive materials other than silver nanowires inevitably mixed.

  Further, when other conductive materials described later are further contained, the content ratio of the metal nanowires and the metal nanotubes is a volume with respect to the total amount of the conductive materials including the fibrous conductive particles and the fibrous conductive material. 50% or more is preferable on the basis, 60% or more is more preferable, and 75% or more is still more preferable. When the content ratio of the metal nanowires and the metal nanotubes is 50% or more, a dense network of metal nanowires or the like is formed, and a first transparent conductive layer having excellent conductivity is easily obtained.

The content ratio of the metal nanowire and the metal nanotube is obtained by the following method.
For example, when silver nanowires and metal nanotubes are contained as fibrous conductive particles and silver particles are contained as other conductive materials, an aqueous dispersion containing silver nanowires and metal nanotubes is filtered to obtain silver nanowires and metal nanotubes. Separated from other conductive materials, using an inductively coupled plasma (ICP) emission spectrometer, the amount of silver remaining on the filter paper and the amount of silver that has passed through the filter paper are measured, respectively. The ratio of nanowires and metal nanotubes (fibrous conductive particles) is calculated.

The content of metal nanowires and metal nanotubes contained in the first transparent conductive layer is such that the resistivity, total light transmittance, and haze value of the first transparent conductive layer depend on the types of metal nanowires and metal nanotubes. It is preferable to select appropriately so as to be in a desired range.
The total content of metal nanowires and metal nanotubes in the first transparent conductive layer is preferably 1% by mass to 60% by mass with respect to the total mass of the first transparent conductive layer, and 3% by mass to 50% by mass. Is more preferable, and 5 mass%-40 mass% is still more preferable.
From the viewpoint of controlling the resistivity of the first transparent conductive layer, the amount of metal nanowires and metal nanotubes per unit area of the first transparent conductive ^{layer, 0.020g / m 2 ~2.00g / m} 2 The range of is preferable.

  In addition, the ratio of the total amount of metal nanowires and metal nanotubes to the binder described later (content of metal nanowires and metal nanotubes / content of binder) is preferably in the range of 1/20 to 1/2.

(Metal nanowires)
Examples of the metal nanowires contained as the fibrous conductive particles include silver nanowires, copper nanowires, and copper-nickel nanowires. Among these, silver nanowires are preferable.

The average minor axis length of the metal nanowire is preferably 0.5 nm to 500 nm, more preferably 1 nm to 200 nm, and still more preferably 15 nm to 100 nm. When the average minor axis length of the metal nanowire is 500 nm or less, haze due to light scattering is suppressed, and the transparency is improved. Further, when the average short axis length of the metal nanowire is 0.5 nm or more, the transparency is excellent and the decrease in conductivity due to oxidative degradation is small.
The average major axis length of the metal nanowire is preferably 0.5 μm to 50 μm, more preferably 1 μm to 30 μm, still more preferably 5 μm to 20 μm. When the average major axis length of the metal nanowire is 0.5 μm or more, when the conductor is produced by coating, it is easy to secure a contact between the metals, the conductivity is improved, and the resistance is easily suppressed low. Further, when the average major axis length of the metal nanowire is 50 μm or less, the dispersion stability is further improved.
Among these, it is preferable to contain silver nanowires having an average minor axis length of 15 nm to 100 nm and an average major axis length of 5 μm to 20 μm.

The average minor axis length (average diameter) and average major axis length of the metal nanowire are determined by observing a TEM image or an optical microscope image using a transmission electron microscope (TEM) or an optical microscope.
Specifically, the average minor axis length (average diameter) and the average major axis length of the metal nanowires were 300 randomly selected using a transmission electron microscope (trade name: JEM-2000FX, manufactured by JEOL Ltd.). It is obtained by measuring the short axis length and the long axis length of the metal nanowires and obtaining an average value from each measured value.
In addition, the short-axis length when the short-axis direction cross section of metal nanowire is not circular makes the length of the longest part among the measured values of a short-axis direction short-axis length. In addition, when the metal nanowire is bent, a circle having a bent particle as an arc is assumed, and a value calculated from the radius and the curvature of the circle is a major axis length.

The average aspect ratio of the metal nanowire can be appropriately selected according to the purpose or case, and can be in the range of 1.5 to 1,000,000, and in the range of 10 to 1,000,000. Or in the range of 10 to 1,000. When the average aspect ratio is 1.5 or more, and further 10 or more, a network is formed by the metal nanowires, and the electrical conductivity is easily developed well. Further, when the aspect ratio is 1,000,000 or less, aggregation during the formation of the metal nanowire or subsequent handling is unlikely to occur due to the entanglement of the metal nanowire before film formation.
The average aspect ratio means the ratio of the average major axis length to the average minor axis length of the metal nanowire (ratio of average major axis length / average minor axis length).

The average aspect ratio is measured with a transmission electron microscope.
Specifically, the average aspect ratio of the metal nanowires is to observe the metal nanowires remaining on the filter paper with a transmission electron microscope (TEM), and measure the short axis length and the long axis length of 300 metal nanowires, The average value is obtained, and the ratio of the average major axis length to the average minor axis length of the metal nanowire (average major axis length / average minor axis length ratio) is calculated.
When measuring the average aspect-ratio of metal nanowire with an electron microscope, it should just be able to confirm with one visual field of an electron microscope that the average aspect-ratio of metal nanowire exists in the said range. Moreover, the average aspect ratio of the whole metal nanowire can also be estimated by separately measuring the average major axis length and the average minor axis length of the metal nanowire.

(Metal nanotube)
Examples of the metal nanotubes contained as the fibrous conductive particles include silver nanotubes and copper nanotubes.

The average minor axis length (average diameter) and the average major axis length of the metal nanotube are preferably in the same range as the average minor axis length and the average major axis length of the metal nanowire for the same reason as the metal nanowire described above. .
The average minor axis length and the average major axis length of the metal nanotube are also obtained by observing a TEM image or an optical microscope image using a transmission electron microscope (TEM) and an optical microscope, as in the case of the metal nanowire described above. . Specifically, the average short axis length (average diameter) and the average long axis length of the metal nanotubes are 300 randomly selected using a transmission electron microscope (trade name: JEM-2000FX, manufactured by JEOL Ltd.). It is obtained by measuring the short axis length and the long axis length of each metal nanotube, and obtaining an average value from each measured value.
In addition, the short-axis length when the short-axis direction cross section of the metal nanotube is not circular is the length of the longest portion among the measured values in the short-axis direction. When the metal nanotube is bent, a circle whose arc is a bent particle is assumed, and a value calculated from the radius and the curvature of the circle is a long axis length.

The average aspect ratio of the metal nanotube is also preferably in the same range as the average aspect ratio of the metal nanowire for the same reason as that of the metal nanowire described above.
The average aspect ratio is measured in the same manner as in the metal nanowire described above. However, the outer diameter of the metal nanotube is used as the diameter for calculating the average aspect ratio of the metal nanotube.

~ Method for producing fibrous conductive particles ~
There is no restriction | limiting in particular in the manufacturing method of fibrous electroconductive particle (metal nanowire and metal nanotube), You may produce by what kind of method.
When the fibrous conductive particles are, for example, silver nanowires, it is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved. Moreover, after forming the fibrous conductive particles, it is preferable to perform a desalting treatment by a conventional method from the viewpoints of dispersibility and temporal stability of the first transparent conductive layer.
The manufacturing method of metal nanowires and metal nanotubes is disclosed in JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, JP2010-86714A, and the like. Can be used.

The solvent used for the production of the metal nanowires and the metal nanotubes is preferably a hydrophilic solvent, and examples thereof include water, alcohol solvents, ether solvents, and ketone solvents. A solvent may be used individually by 1 type and may use 2 or more types together.
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and the like.
Examples of ether solvents include dioxane and tetrahydrofuran.
Examples of the ketone solvent include acetone.

When heating at the time of manufacture, the heating temperature is preferably 250 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower, and further preferably 30 ° C. or higher and 180 ° C. or lower. By setting the heating temperature to 20 ° C. or higher, the lengths of the metal nanowires and the metal nanotubes are in a more suitable range for ensuring dispersion stability. In addition, by setting the heating temperature to 250 ° C. or less, it is easy to obtain a smooth outer shape having no sharp protrusion on the outer periphery in the cross section orthogonal to the long axis direction of the fibrous conductive particles, and the surface plasmon of the fibrous conductive particles Coloring due to absorption is suppressed, and the transparency is excellent.
If necessary, the temperature may be changed during the grain formation process. Changing the temperature in the middle can be expected to improve monodispersity by controlling nucleation, suppressing renucleation, and promoting selective growth. .

The heat treatment is preferably performed by adding a reducing agent.
The reducing agent is not particularly limited and can be appropriately selected from those usually used. For example, borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, aromatic Group amines, aralkylamines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like. Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Depending on the reducing agent, there is a compound that functions as a dispersant or a solvent as a function, and can be preferably used in the same manner.

The production of the fibrous conductive particles is preferably performed by adding a dispersant and a halogen compound or metal halide fine particles.
The timing for adding the dispersant and the halogen compound may be before or after the addition of the reducing agent, and may be either before or after the addition of the metal ions or metal halide fine particles. In order to obtain fibrous conductive particles with better monodispersity, it is preferable to add the halogen compound in two or more stages from the viewpoint of controlling nucleation and growth.

The step of adding the dispersant is not particularly limited. Before preparing the fibrous conductive particles, a dispersant may be added in advance, and the fibrous conductive particles may be added in the presence of the dispersant, or the dispersion is performed from the viewpoint of controlling the dispersion state after the preparation of the fibrous conductive particles. An agent may be added.
Examples of the dispersant include amino group-containing compounds, thiol group-containing compounds, sulfide group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides, polysaccharide-derived natural polymers, synthetic polymers, or these. Examples thereof include polymer compounds such as gel.

Examples of the polymer suitably used as the dispersant include gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, partial alkyl esters of acrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone structures, which are protective colloidal polymers. Preferred examples include a copolymer containing, and a polymer having a hydrophilic group such as acrylic acid having an amino group or a thiol group.
In addition, for the structure of the compound that can be used as the dispersant, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.

  The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine, or iodine, and can be appropriately selected according to the purpose. For example, sodium bromide, sodium chloride, sodium iodide, potassium iodide, Compounds that can be used in combination with alkali halides such as potassium bromide and potassium chloride or the following dispersion additives are preferred. Some halogen compounds may function as a dispersion additive, but can be preferably used in the same manner. Further, as a substitute for the halogen compound, silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.

A single substance having both the function of a dispersant and the function of a halogen compound may be used. That is, by using a halogen compound having a function as a dispersant, the functions of both the dispersant and the halogen compound are expressed with one compound.
Examples of the halogen compound having a dispersant function include hexadecyl-trimethylammonium bromide (HTAB) containing an amino group and a bromide ion, hexadecyl-trimethylammonium chloride (HTAC) containing an amino group and a chloride ion, an amino group and a bromide. Dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride, decyl trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dimethyl distearyl ammonium bromide, dimethyl distearyl ammonium chloride, di Lauryldimethylammonium bromide, dilauryldimethylammonium chloride Chloride, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride.

  In the production of the fibrous conductive particles, it is preferable to perform a desalting treatment after the formation of the fibrous conductive particles. The desalting treatment after the formation of the metal nanowires can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation.

  It is preferable that the metal nanowire and the metal nanotube contain as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions.

(binder)
It is preferable that the 1st transparent conductive layer in this indication contains a binder.
By containing the binder, the fibrous conductive particles and the like contained in the first transparent conductive layer can be stably held in a dispersed state, and the adhesion with the adjacent layer can be improved.
It is preferable that the binder does not dissolve in the etching solution described later. This is because when the fibrous conductive particles are removed by etching and the non-conductive region of the first transparent conductive layer having a pattern shape is formed, the light-scattering substance remains in the non-conductive region.

  The binder is not particularly limited as long as it has resistance to the etching solution, and may be appropriately selected according to the purpose. For example, a polymer material such as polyvinyl pyrrolidone (PVP), chitin, polyacrylic acid, acrylic resin, carboxymethyl cellulose, or the like may be used.

There is no restriction | limiting in particular as content of the binder in a 1st transparent conductive layer, What is necessary is just to select suitably according to the objective. The ratio of the fibrous conductive particles to the binder is preferably 1 to 1,000 parts by mass, more preferably 5 to 900 parts by mass, and more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the binder. 800 parts by mass is more preferable.
When the content of the fibrous conductive particles with respect to 100 parts by mass of the binder is 1 part by mass or more, conductivity is easily exhibited. When the content of the fibrous conductive particles with respect to 100 parts by mass of the binder is 1,000 parts by mass or less, the film strength of the first transparent conductive layer, in particular, mechanical properties such as adhesion are increased.

(Other ingredients)
The first transparent conductive layer may contain components other than those described above. There is no restriction | limiting in particular in another component, What is necessary is just to select suitably according to the objective. Examples of other components include surfactants and thickeners.
When the surfactant is contained, the coating uniformity when the first transparent conductive layer is formed by coating can be improved.

  The thickness of the first transparent conductive layer is preferably 1 nm to 20 μm and more preferably 10 nm to 10 μm from the viewpoint of conductivity and transparency.

The haze in the first transparent conductive layer is preferably 3% or less, more preferably 1% to 3%, still more preferably 1.5% to 3%, and particularly preferably 2% to 3%.
Further, from the viewpoint of the visibility of the pattern shape, the ratio of the absolute value of the difference between the haze of the first transparent conductive layer and the haze of the non-conductive region to the haze of the first transparent conductive layer is small. More preferably, it is preferably 50% or less, more preferably 30% or less, and particularly preferably 20% or less.
Haze is a value measured using a haze meter (Haze Guard Plus, manufactured by Gardner).

-Second transparent conductive layer-
The second transparent conductive layer is disposed between a later-described λ / 2 plate and the substrate, and vibrates in parallel with the polarization axis changed by the λ / 2 plate 18, for example, as shown in FIG. Polarized light is incident.
The second transparent conductive layer 26 contains at least one type of fibrous conductive particles 12 selected from at least metal nanowires and metal nanotubes, and the fibrous conductive particles 12 contained in the layer form the first transparent conductive layer 22. Since it is oriented in the direction orthogonal to the orientation direction of the fibrous conductive particles 12 contained, the polarized light from the λ / 2 plate 18 is not easily scattered and reflected by the second transparent conductive layer 26. The transmitted light then enters the lower isotropic substrate 28.

  In the laminate 100 shown in FIG. 1, a silver nanowire film 20 in which a second transparent conductive layer 26 is laminated on an isotropic substrate 28 is disposed, and when the second transparent conductive layer 26 is patterned, etc. An electrode pattern is provided on the isotropic substrate 28.

  The fibrous conductive particles contained in the second transparent conductive layer may contain the same fibrous conductive particles as the first transparent conductive layer and, if necessary, a fibrous conductive material other than the fibrous conductive particles. it can. Further, the fibrous conductive particles contained in the second transparent conductive layer may be of a different type from the fibrous conductive particles contained in the first transparent conductive layer.

  The metal nanowires and metal nanotubes contained as fibrous conductive particles in the second transparent conductive layer are synonymous with the metal nanowires and metal nanotubes contained in the first transparent conductive layer, and the preferred embodiments are also the same.

  In addition, regarding the metal nanowires and metal nanotubes contained in the second transparent conductive layer, the content ratio of the metal nanowires and metal nanotubes relative to the total mass of the fibrous conductive material contained in the second transparent conductive layer, other conductivity described later Content ratio of metal nanowires and metal nanotubes when a conductive material is further contained, method for calculating content ratio of metal nanowires and metal nanotubes, and total content of metal nanowires and metal nanotubes in the second transparent conductive layer Are the same as those in the first transparent conductive layer, and the same applies to the preferred embodiments.

  Similar to the first transparent conductive layer, the second transparent conductive layer can contain a binder and other components. Details and preferred embodiments of the binder and other components that can be contained in the second transparent conductive layer are as described above for the first transparent conductive layer.

  The thickness of the second transparent conductive layer is preferably 1 nm to 20 μm, more preferably 10 nm to 10 μm, from the viewpoints of conductivity and transparency.

The haze in the second transparent conductive layer is preferably 3% or less, more preferably 1% to 3%, still more preferably 1.5% to 3%, and particularly preferably 2% to 3%.
The method for measuring haze is as described above.
Further, from the viewpoint of the visibility of the pattern shape, the ratio of the absolute value of the difference between the haze of the first transparent conductive layer and the haze of the non-conductive region to the haze of the first transparent conductive layer is small. More preferably, it is preferably 50% or less, more preferably 30% or less, and particularly preferably 20% or less.

~ Patterned transparent conductive layer ~
It is preferable that the 1st transparent conductive layer and the 2nd transparent conductive layer in the laminated body of this indication are provided with the pattern shape which consists of an electroconductive area | region and a nonelectroconductive area | region. There is no restriction | limiting in particular about a pattern shape, According to the objective, it can select suitably. The pattern shape is preferably formed by performing an etching process after the first transparent conductive layer or the second transparent conductive layer is provided on the substrate. In addition, the etching treatment brings an etchant that dissolves the fibrous conductive particles contained in the first transparent conductive layer or the second transparent conductive layer into contact with the first transparent conductive layer or the second transparent conductive layer. Preferably, it is implemented.
Details regarding the etching will be described later.

The surface resistance of the conductive region is preferably from 0.1 Ω / □ to less than 5 kΩ / □, and more preferably from 1 Ω / □ to 500 Ω / □.
On the other hand, the surface resistance of the non-conductive region is preferably 5 kΩ / □ or more, more preferably 100 kΩ / □ or more, and further preferably 1 MΩ / □ or more. The upper limit is preferably 109 Ω / □ or less.
Here, the surface resistance is, for example, a value obtained by measuring the transparent conductive layer using a surface resistance meter (Mitsubishi Chemical Corporation, Loresta-GP MCP-T600). “Ω / □” has the same meaning as “Ω / square”.

<Method for producing laminate>
As described above, the laminate of the present disclosure can be manufactured in a structure in which a polarizing plate, a first transparent conductive layer, a λ / 2 plate, a second transparent conductive layer, and a substrate are stacked. The transparent conductive member may be manufactured by any method, and preferably has the following transparent conductive member manufacturing method, and the two manufactured transparent conductive members are connected to each other through a λ / 2 plate. It is manufactured by a method in which the orientation directions of the fibrous conductive particles are laminated so as to be orthogonal to each other, and a polarizing plate is laminated on the upper transparent conductive member of the two transparent conductive members.
In addition, a transparent conductive member points out the laminated body of a base material and a transparent conductive layer (a 1st transparent conductive layer or a 2nd transparent conductive layer).
Here, the first transparent conductive layer and the second transparent conductive layer are collectively referred to simply as “transparent conductive layer”.

The manufacturing method of a transparent conductive member has the following process (a)-process (e).
(A) The process of forming the photoresist layer containing the photosensitive resin composition on a transparent conductive layer (photoresist layer formation process)
(B) Step of pattern exposure of photoresist layer (pattern exposure step)
(C) A step of developing the pattern-exposed photoresist layer, removing the photoresist layer in the pattern-exposed exposed region or non-exposed region, and forming a patterned resist layer on the surface of the transparent conductive layer (developing step) )
(D) A step of forming a non-conductive region by dissolving and removing fibrous conductive particles in a region of the transparent conductive layer not covered with the photoresist layer with an etchant (etching step)
(E) Step of removing the resist layer in the non-exposed region or exposed region remaining after the step (d) with a resist stripping solution (resist stripping step)
Hereinafter, the manufacturing method of a transparent conductive member is demonstrated.

[Formation of transparent conductive layer]
In the method for producing a transparent conductive member, a transparent conductive layer is formed on a substrate.
When forming the transparent conductive layer on the substrate, it is preferable to perform a pretreatment such as a hydrophilic treatment or an uneven treatment on one or both sides of the substrate for the purpose of improving the adhesion and improving the wettability of the coating solution.

−Pretreatment−
Examples of the pretreatment include corona discharge treatment, glow discharge treatment, plasma treatment, atmospheric pressure plasma treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, chromic acid treatment (wet), and saponification treatment (wet). Corona discharge treatment and plasma treatment (vacuum glow discharge and atmospheric pressure glow discharge treatment) are preferable.

(Plasma treatment)
Examples of the plasma treatment include vacuum glow discharge and atmospheric pressure glow discharge, and other methods include flame plasma treatment and the like. For example, the methods described in JP-A-6-123062, JP-A-11-293011, JP-A-11-5857, and the like can be used.
Regarding the plasma treatment, the description in paragraphs 0075 to 0081 of JP2013-200999A can be referred to.

(Corona discharge treatment)
Corona discharge treatment may be performed by a conventionally known method, for example, Japanese Patent Publication No. 48-5043, Japanese Patent Publication No. 47-51905, Japanese Patent Publication No. 47-28067, Japanese Patent Publication No. 49-83767, Japanese Patent Publication No. Sho 51. No. 41770, JP-A No. 51-131576, and the like. Various commercially available corona treatment machines can be used as the treatment machine. For example, a corona treatment machine having a multi-knife electrode manufactured by SOFTAL (Sophthal) is composed of a large number of electrodes, and the film is formed by sending air between the electrodes. This is useful because it can be used to prevent heating and remove small molecules that appear on the film surface. Moreover, in order to avoid the spark between an electrode and a transparent conductive layer with respect to the side in which the transparent conductive layer is not formed of the base material in which the transparent conductive layer was formed in one side, a dielectric covering electrode ( It is desirable to perform a corona treatment using a ceramic roll, a quartz electrode, etc.) and using a metal roll such as stainless steel as a counter electrode.

The corona treatment conditions vary depending on the type of substrate, the type of coating matrix, the type of corona treatment machine, and the like, and above all, the corona treatment is performed in the range of irradiation energy of 0.1 J / m ^{2 to} 10 J / m ^2. surface treatment is preferable, a corona surface treatment performed in the range of 0.5J ^{/ m 2} ~5J ^/ m 2 is more preferable.

  When the surface of the substrate is hydrophilized by performing the above surface treatment, the contact angle of the substrate surface with respect to water is preferably 0 ° to 40 °, more preferably 0 ° to 20 °, and still more preferably. Is in the range of 0 ° to 10 °.

-Formation of transparent conductive layer-
As a method for forming the transparent conductive layer on the substrate, a coating method or a transfer method can be employed.
There is no restriction | limiting in particular in the application method, According to the objective, you may select suitably. Examples of the coating method include a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, and a doctor. Examples include a coating method.

  In addition, when reducing the coating amount of the binder, uneven application of the fibrous conductive particles can be suppressed by using a coating method such as a die coater or a slit coater.

In the transfer method, at least one fibrous form selected from metal nanowires and metal nanotubes formed on a temporary support by applying a coating solution used when applying and forming a transparent conductive layer on the temporary support. The transparent conductive layer may be formed on the substrate by transferring the transparent conductive layer onto the substrate using a transfer material having a transparent conductive layer containing conductive particles and, if necessary, a binder and other components. .
Specifically, for example, a transparent conductive layer can be formed on a substrate by laminating the transfer film on the substrate by bringing the surface of the transparent conductive layer into contact with the substrate and peeling the temporary support. it can.
The transfer material may be used in any form of a film or a sheet.

As a transfer material, on a temporary support, it contains at least one kind of fibrous conductive particles selected from metal nanowires and metal nanotubes, and has a transparent conductive layer in which the fibrous conductive particles are oriented in one direction in the plane, It may have other layers as required.
The transfer film has flexibility and is suitable as a material from which a low-haze transparent film can be obtained. For example, the first transparent conductive layer and the second transparent conductive layer in the laminate of the present disclosure described above are formed. Is preferably used.

-Temporary support-
The material of the temporary support is not particularly limited as long as it has the necessary strength and flexibility when the film is formed. A resin film is preferable from the viewpoint of moldability and cost.
The film used as the temporary support is preferably a film that has flexibility and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heat. More specifically, examples of the temporary support include polyethylene terephthalate (PET) film, cellulose triacetate (TAC) film, polystyrene (PS) film, polycarbonate (PC) film and the like. preferable.
The appearance of the temporary support is not particularly limited, and may be a transparent film or a colored film. Examples of the colored film include resin films containing dyed silicon, alumina sol, chromium salt, zirconium salt and the like.
The temporary support can be imparted with conductivity by the method described in JP-A-2005-221726.

~ Transparent conductive layer ~
The transparent conductive layer is a component used in the first transparent conductive layer and the second transparent conductive layer described above, specifically, at least one fibrous conductive particle selected from metal nanowires and metal nanotubes, and necessary Depending on the binder and other ingredients.
Details of the components contained in the transparent conductive layer are as described above.
The transparent conductive layer can be formed by preparing a preparation solution containing the above components, applying the prepared preparation solution to a temporary support by, for example, coating, and drying.
The above application method can be applied for the application.

  In addition to the transparent conductive layer described above, the transfer material may have any other layer as long as the effect is not impaired.

~ Thermoplastic resin layer ~
The transfer film can be provided with a thermoplastic resin layer between the temporary support and the transparent conductive layer. By providing a thermoplastic resin layer, when a transfer film is transferred to a transfer material to form a laminate, it is preferable because the generation of bubbles in each layer is suppressed and image unevenness due to the bubbles is less likely to occur.
The thermoplastic resin layer preferably contains an alkali-soluble resin. By providing the thermoplastic resin layer, it preferably functions as a cushioning material that absorbs irregularities on the surface of the transfer object, and is preferably a resin layer having a property that can be deformed according to the irregularities of the target surface. .

  The thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component. The Vicat method [specifically, a polymer by American Material Testing Method ASTM D1235] An embodiment containing at least one selected from organic polymer substances having a softening point of about 80 ° C. or less according to the softening point measurement method] is particularly preferable.

  The layer thickness when the thermoplastic resin layer is provided is preferably 3 μm to 30 μm. By making the layer thickness of the thermoplastic resin layer within the above range, the followability at the time of transfer is good, the unevenness of the surface of the transfer object can be absorbed, and drying and development at the time of forming the thermoplastic resin layer are easy. It is preferable because it can be done. The thickness of the thermoplastic resin layer is more preferably 4 μm to 25 μm, and particularly preferably 5 μm to 20 μm.

~ Middle layer ~
In the transfer film, an intermediate layer can be provided between the optionally provided thermoplastic resin layer and the transparent conductive layer. As the intermediate layer, a layer described as “separation layer” in JP-A-5-72724 can be applied.

~Protective film~
The transfer film can be provided with a protective film on the surface of the transparent conductive layer. By providing the protective film, it is possible to protect the surface of the transparent conductive layer which is a surface in close contact with the transfer target in the transfer film.

  As the protective film, protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.

(Middle layer)
An intermediate layer may be provided between the base material and the transparent conductive layer.
By having the intermediate layer, it becomes possible to improve the adhesion between the base material and the transparent conductive layer, the light transmittance of the transparent conductive layer, the haze, and the film strength.

  Examples of the intermediate layer include an adhesive layer for improving the adhesive force between the base material and the transparent conductive layer, and a functional layer for improving functionality by interaction with components contained in the transparent conductive layer. Depending on the situation, it is provided as appropriate. The intermediate layer may be a single layer or may include a plurality of layers.

  For details of the intermediate layer, reference can be made to the descriptions in paragraphs 0089 to 0100 and paragraphs 0101 to 0106 of JP2013-200999A.

  The intermediate layer can be formed by applying a solution in which a compound constituting the intermediate layer is dissolved and dispersed (suspended or emulsified) on a substrate and drying. The coating method may be appropriately selected according to the purpose, for example, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, gravure coating method, curtain coating method. , Spray coating method, doctor coating method and the like.

-Photoresist layer formation process-
In the method for producing a transparent conductive member, first, a photoresist layer containing a photosensitive resin composition is formed on the transparent conductive layer.
The photoresist layer is not particularly limited and can be appropriately selected depending on the purpose, and may be a positive resist layer or a negative resist layer. In the case of a positive resist layer, the patterned exposure region is solubilized, and a patterned resist layer is formed in the unexposed region (unsolubilized region). In the case of a negative resist layer, the exposure region is A cured resist layer is formed, and application of the solution removes the unexposed portion, that is, the uncured portion of the resist layer, thereby forming a patterned resist layer.

The resist layer forming material is not particularly limited, and any of a negative type, a positive type and a dry film type can be used.
For the formation of the resist layer, a commercially available alkali-soluble photoresist may be appropriately selected.

-Pattern exposure process-
In the method for producing a transparent conductive member, the formed photoresist layer is exposed in a pattern (pattern exposure).
The light source used for pattern exposure is selected in relation to the photosensitive wavelength range of the photoresist composition, and generally ultraviolet rays such as g-line, h-line, i-line, and j-line are preferable. Examples of the light source type include a metal halide lamp, a high-pressure mercury lamp, and a light emitting diode (LED).

  The pattern exposure method is not particularly limited, and may be performed by surface exposure using a photomask, or may be performed by scanning exposure using a laser beam or the like. Further, it may be performed by refractive exposure using a lens, or may be performed by reflective exposure using a reflecting mirror. Moreover, you may perform using exposure systems, such as contact exposure, proximity exposure, reduction projection exposure, and reflection projection exposure.

-Development process-
In the manufacturing method of a transparent conductive member, after pattern exposure, the pattern-exposed photoresist layer is developed. Thereby, the photoresist layer in the exposed region or the non-exposed region subjected to the pattern exposure is removed, and a patterned resist layer is formed on the surface of the transparent conductive layer.

In the development process, an alkaline developer is generally used.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Examples include alkaline aqueous solutions containing a quaternary ammonium salt or cyclic amines such as pyrrole and pihelidine.
As the developing method, either a shower method or a dip method may be used.

-Etching process-
In the method for producing a transparent conductive member, fibrous conductive particles in a region of the transparent conductive layer not covered with the photoresist layer are dissolved and removed with an etchant to form a non-conductive region.
Thereby, a patterned conductive region (that is, an electrode pattern) is formed.

As the etching process, known methods include etchant treatment (wet etching) and reactive gas activated plasma discharge under reduced pressure (dry etching). The transparent conductive member according to the present disclosure is known. In manufacturing, an etchant is preferably used.
Examples of the etchant include known etching solutions such as ferric chloride / hydrochloric acid, hydrochloric acid / nitric acid, and hydrobromic acid. When metal nanowires and metal nanotubes containing silver are used as the fibrous conductive particles, it is preferable to contain nitric acid.

Etching may be performed by either a shower method or a dip method.
Further, an etchant may be printed by screen printing or the like on the transparent conductive layer in a region not covered with the photoresist layer.

-Resist stripping process-
In the method for producing the transparent conductive member, finally, the resist layer in the non-exposed region or the exposed region remaining without being etched in the above etching process is removed with a resist stripping solution.
As the resist stripping solution, the developer used in the developing step can be used. Stripping with a resist stripper may be performed by either a shower method or a dip method.

-Polarizing plate-
The laminated body of this indication is equipped with the polarizing plate in the outermost surface in the side into which external light injects.
By placing the polarizing plate, light (polarized light) that vibrates in parallel with a predetermined transmission axis among the external light having various polarization components is selectively transmitted.
By arranging the transmission axis of the polarizing plate and the orientation direction of at least one fibrous conductive particle selected from the first transparent conductive layer metal nanowire and the metal nanotube to be orthogonal, the visibility of the electrode pattern can be improved. , Haze can be lowered.

  A conventionally well-known thing can be arbitrarily selected and used for a polarizing plate. For example, a dichroic polarizing plate containing iodine-based or dye-based polymeric organic matter in the film, a wire grid type polarizing plate in which fine wires such as metal are formed on the substrate at a pitch smaller than the wavelength of light, etc. Can be mentioned.

-Λ / 2 plate-
The laminate of the present disclosure includes a λ / 2 plate between the first transparent conductive layer and the second transparent conductive layer described above. By having the λ / 2 plate, the polarization direction of the light that has passed through the first transparent conductive layer can be rotated by approximately 90 °. By rotating the polarization direction between the first transparent conductive layer and the second transparent conductive layer by approximately 90 °, the first transparent conductive layer and the second transparent conductive layer are moved to the X-direction electrode and Y of the touch panel. When used as a directional electrode, both the low resistance of the transparent conductive layer and the low haze and good visibility of the transparent conductive layer can be achieved.
If the λ / 2 plate used in the present invention is suitable for the purpose of rotating the polarization direction of light by 90 °, even if it is a single-layer λ / 2 plate, a plurality of phase differences are used to expand the wavelength band and viewing angle. The form which laminated | stacked the board may be sufficient. Further, a retardation plate in which the liquid crystal is continuously twisted by 90 ° may be used.

  As the λ / 2 plate, a conventionally known plate can be arbitrarily selected and used. As the λ / 2 plate, a commercially available product can be used. Examples of the commercially available product include a polymer retardation film λ / 2 (manufactured by Edmund Optics Japan) and a λ / 2 quartz wave plate (manufactured by Sigma Kogyo Co., Ltd.). ), HI-RETAX-1 / 2λ wavelength plate (manufactured by Luceo) and the like.

-Base material-
The laminated body of this indication is equipped with the base material.
When the transparent conductive member is produced by forming the first transparent conductive layer and the second transparent conductive layer described above on the base material, the base material is manufactured by manufacturing a laminate using the transparent conductive member. Is obtained.

  There is no restriction | limiting in particular as a base material, From a viewpoint which does not prevent the polarization property of the linearly polarized light component which injected through the polarizing plate, an optically isotropic base material is preferable.

  As the isotropic substrate, an optical film using a cycloolefin polymer, acrylic, tack or the like is preferable, and as an example of a commercially available product on the market, Zeno Film (registered trademark; for example, ZF14, ZF16) of Nippon Zeon Co., Ltd. Is mentioned.

  The thickness of the substrate is preferably 10 μm to 200 μm.

<Touch panel and display device with touch panel>
The touch panel of the present disclosure includes the above-described laminated body of the present disclosure. Moreover, the display apparatus with a touch panel of this indication is equipped with the laminated body of this indication, and is provided with the touch panel and the display apparatus.
Since the touch panel and the display device with a touch panel of the present disclosure include the laminated body of the present disclosure, the visibility of the electrode pattern is further improved.

Examples of the touch panel include a surface capacitive touch panel, a projection capacitive touch panel, and a resistive touch panel.
The touch panel includes a so-called touch sensor and a touch pad.

  Examples of the layer configuration of the touch panel sensor electrode portion in the touch panel include a bonding method in which two transparent electrodes are bonded, a method in which transparent electrodes are provided on both surfaces of a single substrate, and the like.

  The surface capacitive touch panel is described in, for example, JP-T-2007-533044.

  There is no restriction | limiting in particular in the display apparatus in a display apparatus with a touch panel, Any may be sufficient as long as it is an apparatus which can mount a touch panel and can display an image via a touch panel and can operate on a touch panel.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

-Fabrication of silver nanowires-
In the container, 60 g of ethylene glycol and 2.5 g of polyvinyl pyrrolidone (PVP) were added at room temperature (25 ° C.), and the temperature was raised to 135 ° C. over 10 minutes while stirring at 500 rpm (rotation per minute). Thereafter, stirring was continued while maintaining the temperature at 135 ° C. Further, after 10 minutes from the time when the temperature reached 135 ° C., a sodium chloride solution obtained by dissolving 0.006 g (0.1 mmol) of sodium chloride in 0.6 g of ethylene glycol in a separate container in advance was added. Three minutes after the addition of the sodium chloride solution, a silver nitrate solution prepared by previously dissolving 0.85 g (5.0 mmol) of silver nitrate in 7.65 g of ethylene glycol was added in a separate container. After the silver nitrate solution was added, the stirring speed was changed to 100 rpm, the heating was terminated by maintaining at 135 ° C. for 3.0 hours, and the mixture was naturally cooled to room temperature.
After the solution temperature in the container reached room temperature (25 ° C.), the slurry after the reaction was separated into a centrifuge tube, washed with distilled water, and centrifuged at 3000 rpm for 5 minutes. After removing the supernatant after centrifugation, methanol was added to the remaining precipitate to form a slurry, which was centrifuged at 2500 rpm for 5 minutes. After removing the supernatant after centrifugation, methanol was again added to the remaining precipitate to form a slurry, which was then centrifuged at 1500 rpm for 10 minutes. After removing the supernatant after centrifugation, the remaining precipitate was added to water and stirred at 500 rpm for 10 minutes to obtain a silver nanowire dispersion.
The obtained silver nanowire dispersion was mixed with a commercially available magnetic fluid MSG-W11 (FeroTec) to prepare a silver nanowire dispersion A1 containing a magnetic fluid. At this time, the silver nanowire dispersion A1 was prepared by setting the volume concentration of the magnetic particles to the silver nanowire dispersion to 4% and the volume concentration of the silver nanowire to the silver nanowire dispersion to 40%.

When the average major axis length and the average minor axis length of the obtained silver nanowire were measured by the following method, the average major axis length was 10 μm, the average minor axis length (average diameter) was 70 nm, and the average aspect ratio was 140.
<Measurement of average major axis length and average minor axis length of metal nanowires>
Using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.), 300 metal nanowires were randomly selected from the observed metal nanowires, and the major axis length and shortness of the selected metal nanowires were selected. The axial length (diameter) was measured, and the arithmetic average value of each was taken as the average major axis length and the average minor axis length (average diameter) of the metal nanowires.

-Formation of transparent conductive layer-
The above-mentioned silver nanowire dispersion liquid A1 is applied onto Xenore film ZF14 (registered trademark; Zeonor Film ZF14, Nippon Zeon Co., Ltd., thickness: 100 μm), which is an isotropic substrate, and dried at 80 ° C. for 2 minutes. A silver nanowire film B1 (transparent conductive member) having a transparent conductive layer having a thickness of 200 nm containing silver nanowires on the material was produced. Content in the transparent conductive layer of silver nanowire was 40 mass% with respect to the whole quantity of a transparent conductive layer.
Further, when the silver nanowire film B1 was produced, a magnetic field of 100 mT was applied in a direction parallel to the two main planes of the isotropic substrate from the end of the application until the drying for 2 minutes was completed.

<Confirmation of silver nanowire orientation>
The orientation state of the silver nanowires contained in the transparent conductive layer of the silver nanowire film B1 produced as described above was confirmed by the following method. That is,
3.80 parts by mass of binder (A-1) having the following structure (solid content: 40.0% by mass, propylene glycol monomethyl ether acetate (PGMEA) solution), KAYARAD DPHA as a photosensitive compound (hexafunctional monomer; Nippon Kayaku Co., Ltd.) 1.59 parts by mass of IRGACURE 379 (manufactured by Ciba Specialty Chemicals) as a photosensitive compound, 0.150 parts by mass of EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) as a crosslinking agent , Megafac F781F (surfactant; manufactured by DIC Corporation) (0.002 parts by mass) and PGMEA (19.3 parts by mass) were mixed and stirred to prepare a negative resist photosensitive composition C1.
Next, the photosensitive composition C1 for resist was coated on the silver nanowire film B1 so as to have a dry film thickness of 5 μm, and dried in an oven at 100 ° C. for 1 minute to form a photosensitive layer.
Subsequently, a negative pattern (line / space of fine lines: 150 μm / 150 μm, length of fine lines: 5 cm, number of fine lines: 50) is formed on the photosensitive layer on the silver nanowire film B1 through a mask. Then, i-line (365 nm) was irradiated at 60 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp. At this time, the direction of the fine line of the mask and the direction of application of the magnetic field were made parallel.

In addition, the numerical value in the structure of a binder (A-1) shows the molar ratio of each structural unit contained in a binder.
Moreover, the weight average molecular weight (Mw) of a binder (A-1) is 30,000, and molecular weight distribution (Mw / Mn) is 2.21. Mw and Mw / Mn were performed by gel permeation chromatography (GPC) under the following conditions. The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 "," A-1000 ", and" n-propylbenzene ".
<Condition>
GPC: HLC (registered trademark) -8020 GPC (manufactured by Tosoh Corporation)
-Column: TSKgel (registered trademark), Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm)-Eluent: THF (tetrahydrofuran)
Sample concentration: 0.45% by mass
・ Flow rate: 0.35 ml / min
Sample injection volume: 10 μl
・ Measurement temperature: 40 ℃
・ Detector: Differential refractometer (RI)

  After exposure, the silver nanowire film B1 on which the photosensitive layer was formed was subjected to shower development for 60 seconds at a shower pressure of 0.04 MPa using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Then, it rinsed with the shower of pure water, and it was made to dry at 50 degreeC for 1 minute, and produced the silver nanowire film with a resist pattern.

Next, a silver nanowire film with a resist pattern was prepared by adding 1.0% by mass of nitric acid, 1.0% by mass of Fe (III) -EDTA (ethylenediaminetetraacetic acid iron (III) sodium salt trihydrate), 1.0% by mass. After immersing in an etching solution at 30 ° C. made of a mixed aqueous solution containing mass% ammonium thiosulfate for 2 minutes, etching was performed, rinsed with a shower of pure water, and further dried at 50 ° C. for 1 minute.
Thereafter, the resist was peeled off with an aqueous 2.38 mass% tetramethylammonium hydroxide solution, and rinsed with a shower of pure water. Then, it dried at 50 degreeC for 1 minute, and formed the pattern which consists of a 200-nm-thick transparent conductive layer containing silver nanowire on an isotropic base material. The pattern shape had a line / space of 150 μm / 150 μm and a length of 5 cm.
Thereafter, the electrical resistance in the longitudinal direction of the thin wires in the pattern was measured using a four-terminal resistor. As a result, the electric resistance was 20Ω.

Apart from the above, the angle of 0 ° to 90 ° is the same as above except that the angle between the longitudinal direction of the fine line of the mask in the surface direction of the photosensitive layer and the application direction of the magnetic field is changed by 5 °. 18 types of patterns made of a transparent conductive layer having a thickness of 200 nm containing silver nanowires are formed on an isotropic substrate by irradiating with i-line in the range of 1 and developing and the like. Resistance was measured.
As a result, the electrical resistance in the pattern obtained by exposure with the longitudinal direction of the fine wire of the mask parallel to the magnetic field application direction (0 °) is the lowest (20Ω), and the longitudinal direction of the fine wire of the mask and the application of the magnetic field The electric resistance in the pattern obtained by exposing so that the direction forms an angle of 90 ° was the highest (1 kΩ).
From the above results, it was confirmed that in the silver nanowire film B1 produced above, the silver nanowires in the transparent conductive layer were aligned in parallel to the magnetic field application direction.

Example 1
-Formation of patterned silver nanowire film-
The silver nanowire film B1 produced as described above is patterned by the same method as the above “confirmation of silver nanowire orientation”, and an electrode pattern comprising a transparent conductive layer having a thickness of 200 nm containing silver nanowires on an isotropic substrate. A patterned silver nanowire film D1 was formed.
Patterning is performed by applying a longitudinal direction of a fine line of the mask and applying a magnetic field through a mask on which a negative pattern (line / space of fine line: 150 μm / 150 μm, length of fine line: 5 cm, number of fine lines: 50) is formed. This was performed by irradiating the photosensitive layer with i-line in parallel with the direction. The patterned silver nanowire film D1 has a long thin line pattern in a direction parallel to the orientation direction of the silver nanowires.

-Fabrication of laminates-
Subsequently, two patterned silver nanowire films D1 were prepared, and the two patterned silver nanowire films D1 were laminated so that the longitudinal directions of the fine lines formed an angle of 90 ° with each other.
At this time, a λ / 2 plate (polymer retardation film λ / 2 (manufactured by Edmund Optics Japan)) is placed between the two patterned silver nanowire films D1, and the optical axis of the λ / 2 plate and the patterned silver nanowires. The films D1 were sandwiched by being arranged so that the orientation directions of the respective silver nanowires of the film D1 form an angle of 45 °. That is, a λ / 2 plate is laminated on the electrode pattern of the patterned silver nanowire film D1, and another patterned silver nanowire film D1 is laminated on the λ / 2 plate so that the isotropic substrate is in contact with the λ / 2 plate. did.
Subsequently, the polarizing plate is placed on the electrode pattern of the patterned silver nanowire film D1 on the upper layer side, and the orientation direction of the silver nanowires of the patterned silver nanowire film D1 on the upper layer side and the transmission axis of the polarizing plate are 90 ° to each other. And arranged so as to form a layer.
As described above, a laminated body having the laminated structure shown in FIG. 1 was produced. The orientation direction of the silver nanowires in the two patterned silver nanowire films D1 of the produced laminate is in a state of making an angle of 90 ° with each other.

(Examples 2-3)
Example 1 is the same as Example 1 except that the angle formed by the transmission axis of the polarizing plate and the orientation direction of the silver nanowires of the patterned silver nanowire film D1 on the upper layer side is changed to 80 ° or 70 °. Thus, a laminate was produced. At this time, the angle formed by the orientation direction of the silver nanowires of the patterned silver nanowire film on the upper layer side and the orientation direction of the silver nanowires of the patterned silver nanowire film on the lower layer side was 90 °.

(Comparative Example 1)
In Example 1, a laminate was produced in the same manner as in Example 1 except that the polarizing plate was not provided.

(Comparative Example 2)
In Example 1, a laminate was produced in the same manner as in Example 1 except that no magnetic field was applied when producing the silver nanowire film B1.

(Evaluation)
The following evaluation was performed on the laminates produced in Examples 1 to 3 and Comparative Examples 1 and 2. The evaluation results are written and shown in Table 1.

-1. Haze
The haze of the laminate was measured using a haze meter (Haze Guard Plus, manufactured by Gardner) and evaluated according to the following evaluation criteria. Of the evaluation criteria, A is a practically acceptable range.
<Evaluation criteria>
A: Less than 1% B: 1% or more and less than 3% C: 3% or more

-2. Visibility of electrode pattern
Using a transparent adhesive tape (trade name: OCA tape 8171CL, manufactured by 3M Japan Co., Ltd.), a black polyethylene terephthalate (PET) material is pasted on the surface of the isotropic substrate opposite to the side having the polarizing plate of the laminate. It was. The light from the fluorescent lamp was applied to the laminate in the dark room from the side of the polarizing plate, the reflected light from the polarizing plate was visually observed from an oblique direction, and the appearance of the electrode pattern was evaluated according to the following evaluation criteria. Among the evaluation criteria, A, B and C are practically acceptable ranges, A or B is preferable, and A is more preferable.
<Evaluation criteria>
A: The electrode pattern is not visible even when staring from a position 15 cm away from the laminate, and the electrode pattern is not visible even when viewed normally from a position 40 cm away from the laminate.
B: The electrode pattern is slightly visible when staring from a position 15 cm away from the laminate, and the electrode pattern is not visible when viewed normally from a position 40 cm away from the laminate.
C: The electrode pattern is slightly visible when staring from a position 15 cm away from the laminate, and the electrode pattern is also slightly visible when viewed normally from a position 40 cm away from the laminate.
D: The electrode pattern can be clearly seen when staring from a position 15 cm away from the laminate, and the electrode pattern can be seen slightly from the position 40 cm away from the laminate.
E: The electrode pattern is clearly visible when staring from a position 15 cm away from the laminate, and the electrode pattern is also clearly visible when viewed normally from a position 40 cm away from the laminate.

  As shown in Table 1, in the example, polarized light that vibrates in a direction perpendicular to the orientation direction of the silver nanowires was incident, and two transparent conductive layers were disposed via a λ / 2 plate. The visibility of the electrode pattern was remarkably improved and the haze was kept low. In the example, the resistance of the electrode pattern could be reduced more effectively.

  Since the laminate of the present disclosure has improved visibility of the electrode pattern and has low haze and low resistance, for example, a touch panel, a display electrode, an electromagnetic wave shield, an organic EL display electrode, an inorganic EL display electrode, an electronic paper, It is widely applied to various devices such as electrodes for flexible displays, integrated solar cells, liquid crystal display devices, and display devices with touch panel functions. Among these, application to a touch panel is particularly preferable.

10 Transmission axis 12 Fibrous conductive particles (metal nanowires, metal nanotubes)
14 Polarizing plate 16 Silver nanowire film (transparent conductive member)
18 λ / 2 plate 20 Silver nanowire film (transparent conductive member)
22 1st transparent conductive layers 24 and 28 Isotropic base material 26 2nd transparent conductive layer 100 Laminate hν Light

Claims (4)

A polarizing plate;
a λ / 2 plate;
A substrate;
It is disposed between the polarizing plate and the λ / 2 plate, and includes at least one kind of fibrous conductive particles selected from metal nanowires and metal nanotubes, which are oriented in a direction perpendicular to the transmission axis of the polarizing plate. A first transparent conductive layer;
Metal nanowires and metal nanotubes arranged between the λ / 2 plate and the base material and oriented in a direction orthogonal to the orientation direction of the fibrous conductive particles contained in the first transparent conductive layer A second transparent conductive layer containing at least one fibrous conductive particle selected from:
A laminate having   The laminate according to claim 1, wherein the metal nanowire includes a silver nanowire.   A touch panel comprising the laminate according to claim 1. A display device with a touch panel comprising the touch panel according to claim 3 and a display device.