JP2013200953A - Conductive material, polarizer using the same, circular polarization plate, input device and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive material having a small extinction ratio by suppressing orientation and aggregation of a metal nanowire, and to provide a polarizer, a circular polarization plate, an input device and a display device using the same.SOLUTION: The conductive material includes a substrate, and a conductive layer including at least a metal nanowire having an average short axis length of 5-30 nm on the substrate. The dry film thickness of the conductive layer is 0.001-0.1 time of the average long axis length of the metal nanowire. The conductive material is obtained by coating the substrate with a conductive coating liquid, containing at least a metal nanowire having an average short axis length of 5-30 nm and a matrix component, so that the wet film thickness of the conductive layer is 0.2-20 times of the average long axis length of the metal nanowire.

Description

  The present invention relates to a conductive material, a polarizing plate using the conductive material, a circularly polarizing plate, an input device, and a display device.

  ITO glass and ITO films are widely used as conductive materials and electromagnetic wave shielding materials for electrodes used in liquid crystal displays and organic EL displays equipped with touch panels (for example, personal digital assistants and mobile phones), and integrated solar cells. Although it is used, there are few reserves of indium metal, color due to low transmittance in the long wavelength region, high temperature heat treatment is required for low resistance, low bending resistance, etc. Because of the problems, various alternative materials for ITO glass and ITO film have been studied.

  A conductive material using conductive metal nanowires is known as one of alternative materials (for example, Patent Document 1), and metal nanowires are excellent in terms of transparency, low resistance, and reduction in the amount of metal used. For example, Patent Document 2 describes a polarizing plate having a polarizing layer and a conductive layer, and a metal nanowire in the conductive layer. It is described that it has.

  By the way, metal nanowires are known to exhibit reflective polarization when oriented in one direction like a wire grid polarizer (for example, Patent Document 3). The haze value increases as the diameter (short axis length) of the nanowire increases. Especially when the transparent electrode is patterned, the portion with the metal nanowire (conductive region) and the portion without the metal nanowire (nonconductive region) There is a known problem of visibility in which the difference in haze value is large and the electrode pattern is easily visible.

Special table 2009-505358 JP 2009-230130 A JP 2007-298647 A

  In order to reduce the difference in haze value between the conductive region and the non-conductive region, the present inventor has considered that the diameter of the metal nanowire is reduced to make the electrode pattern invisible. However, it has been found that metal nanowires with a small diameter have a problem that orientation and aggregation tend to occur during coating and drying. It has also been found that when the metal nanowires are oriented, the polarizing property is manifested even though it is a substrate that does not necessarily have the polarizing property (increased extinction ratio). Moreover, when aggregation occurs, the problem that the transparency of a base material is impaired (haze value increase) will generate | occur | produce. When a conductive material containing metal nanowires is combined with a polarizing plate or a phase difference plate, there is no polarization property, that is, an extinction ratio of 1.0 is ideal.

  An object of the present invention is to solve the above-mentioned problems, specifically, a conductive material that suppresses the orientation and aggregation of metal nanowires and has a low extinction ratio and a haze, a polarizing plate using the conductive material, a circularly polarizing plate, It is an object to provide an input device and a display device.

  Based on these facts, the present inventor can control the dry film thickness of the conductive layer having a metal nanowire with a small diameter, so that even if the diameter of the metal nanowire is small, the haze value is small and the viewpoint of visibility. Therefore, it has been found that the above problem can be solved because it is suitable and orientation and aggregation are less likely to occur during coating film formation.

  In addition, when the wet film thickness of the conductive layer is less than 0.2 times the average major axis length of the metal nanowire, the inventor generates coating stripes on the coating surface as shown in FIG. 1A as an example. It was also found that the metal nanowires are easily oriented and the extinction ratio is increased. In addition, when the wet film thickness exceeds 20 times the average major axis length of the metal nanowires, as shown in an example in FIG. 1C, it takes time to dry the coating solution, which causes aggregation of the metal nanowires. Also, it has been found that uneven coating occurs because the wet film thickness becomes thick. And even if the diameter of metal nanowire is as thin as 5-30 nm by apply | coating a conductive layer coating liquid so that a wet film thickness may be 0.2-20 times, orientation and aggregation of metal nanowire are suppressed. It has been found that the extinction ratio can be reduced.

The means for solving the problem is the means [1] below, preferably the means [2] to [12] below.
[1] A substrate and a conductive layer containing at least metal nanowires having an average minor axis length of 5 to 30 nm on the substrate, and a dry film thickness of the conductive layer being an average major axis length of the metal nanowires 0.001 to 0.1 times the conductive material.
[2] The conductive layer coating solution for forming the conductive layer includes at least a matrix component and the metal nanowires, and the concentration of metal nanowires in the conductive layer coating solution is 0.01 wt% to 1.0 wt%. The conductive material according to [1], wherein the weight ratio of the matrix component to the metal nanowire is 0.5 to 15.
[3] The conductive material according to [1] or [2], wherein the extinction ratio of the conductive layer alone is 1.5 or less.
[4] The conductive material according to any one of [1] to [3], wherein the metal nanowire includes silver.
[5] The conductive material according to any one of [1] to [4], wherein the substrate is a transparent material having an in-plane retardation Re (550) having a wavelength of 550 nm and high optical isotropy of 40 nm or less.
[6] The conductive material according to any one of [1] to [5], wherein the substrate is a retardation plate.
[7] A conductive layer coating solution containing at least a metal nanowire having an average minor axis length of 5 to 30 nm and a matrix component on a substrate, and a wet film thickness of the conductive layer being an average major axis length of the metal nanowire. A method for producing a conductive material, comprising: applying so as to be 0.2 to 20 times that of the conductive material.
[8] The conductive layer coating solution includes at least a matrix component and the metal nanowires, and the metal nanowire concentration in the conductive layer coating solution is 0.01 wt% to 1.0 wt%, and The manufacturing method of the electrically-conductive material of [7] whose weight ratio with respect to the said metal nanowire of a matrix component is 0.5-15.
[9] A polarizing plate or a circularly polarizing plate comprising the conductive material according to any one of [1] to [6].
[10] A display device or input device comprising the conductive material according to any one of [1] to [6].
[11] A display device or input device having the polarizing plate or circularly polarizing plate of [9].
[12] A touch panel comprising the conductive material according to any one of [1] to [6].

  ADVANTAGE OF THE INVENTION According to this invention, the orientation and aggregation of metal nanowire can be suppressed, and the electrically conductive material with a small extinction ratio, a polarizing plate using the same, a circularly-polarizing plate, an input device, and a display apparatus can be provided.

It is the schematic of an example of the electrically-conductive material of this invention. It is the schematic of another example of the electrically-conductive material of this invention. It is the schematic which showed an example of the relationship between metal nanowire and wet film thickness. It is the schematic of an example of a surface type capacitive touch panel. It is the schematic of another example of a surface-type capacitive touch panel. It is a schematic diagram of an example of a projection type capacitive touch panel. It is the schematic of an example of a resistive film type touch panel. It is the schematic which showed an example of the major axis angle. It is the schematic of the polarizing plate produced in the Example. It is the schematic of the touchscreen produced in the Example. It is the schematic of the PET board | substrate produced in the Example. It is the schematic of the PET board | substrate produced in the Example.

  The present invention will be described in detail below. 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.

  An example of the conductive material of the present invention is shown in FIG. The conductive material of the present invention has a substrate 200 and a conductive layer 100 including at least metal nanowires having an average minor axis length of 5 to 30 nm on the substrate 200. When the conductive layer 100 is formed, By setting the dry film thickness to 0.001 to 0.1 times the average long axis length of the metal nanowires, even if the metal nanowire diameter is as thin as 5 to 30 nm, the orientation and aggregation of the metal nanowires are suppressed. In addition, the extinction ratio can be reduced.

In this specification, the degree of polarization P is measured using VAP-7070 manufactured by JASCO Corporation, and the extinction ratio is defined as calculated using the following conversion formula. When the extinction ratio is 1, it indicates that the metal nanowires are randomly oriented.
Extinction ratio D = (1 + P) / (1-P)

  In the conductive material of the present invention, the extinction ratio of the conductive layer alone is preferably 1.5 or less, more preferably 1.4 or less, and particularly preferably 1.2 or less.

The conductive layer coating solution for forming the conductive layer contains at least a matrix component and metal nanowires, and the weight ratio of the matrix component to the metal nanowires is preferably 0.5 to 15, and preferably 1.0 to 12. Is more preferable, and 2.0 to 10 is particularly preferable. By setting the weight ratio to 0.5 or more, it is possible to improve the adhesion of the metal nanowires to the base material surface and achieve an effect that the film strength is practically durable, and the weight ratio is set to 15 or less. Thus, the increase in the surface resistance value of the conductive layer can be more effectively suppressed.
In addition, a matrix component means all the components except the metal nanowire and solvent which are contained in a conductive layer coating liquid.

  The present invention also relates to a method for producing a conductive material, on a substrate, a conductive layer coating liquid containing at least a metal nanowire having an average minor axis length of 5 to 30 nm and a matrix component, and a wet film thickness of the conductive layer, It coat | covers so that it may become 0.2-20 times the average long axis length of metal nanowire.

The wet film thickness is 0.2 to 20 times the average major axis length of the metal nanowires, preferably 1.0 to 15 times, and more preferably 2.0 to 13 times.
By setting the wet film thickness to 0.2 times or more of the average major axis length of the metal nanowires, it is possible to suppress the occurrence of coating stripes on the coated surface, and the metal nanowires are hardly oriented. When the wet film thickness is less than 10 times the average major axis length of the metal nanowires, the drying time of the coating solution can be shortened, so that aggregation of the metal nanowires can be suppressed and coating unevenness can be suppressed. .

  Hereinafter, various members used in the present invention will be described in detail.

Metal nanowire:
In this specification, the metal nanowire means a metal nanowire having a shape that has conductivity and a length in a major axis direction that is sufficiently longer than a diameter (length in a minor axis direction). It may be a solid fiber or a hollow fiber.

  There is no restriction | limiting in particular as a material of the said metal nanowire, According to the objective, it can select suitably, For example, the group which consists of a 4th period, a 5th period, and a 6th period of a long periodic table (IUPAC1991) At least one metal selected from the group 2, more preferably at least one metal selected from the group 2 to group 14, the group 2, the group 8, the group 9, the group 10, the group 11, At least one metal selected from Group 12, Group 13, and Group 14 is more preferable, and it is particularly preferable that it is included as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, silver and an alloy with silver are particularly preferable in terms of excellent conductivity.
Examples of the metal used in the alloy with silver include platinum, osmium, palladium, iridium, tin, bismuth, and nickel. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a shape of the said metal nanowire, According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and the column shape from which a cross section becomes a polygon. In applications where high transparency is required, a cylindrical shape or a cross-sectional shape with rounded polygonal corners is preferable.
Here, the cross-sectional shape of the metal nanowires can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing a cross-section sliced by a microtome with a transmission electron microscope (TEM).

The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is 5 to 30 nm, preferably 10 to 25 nm, and more preferably 15 to 20 nm.
When the average minor axis length is less than 5 nm, the oxidation resistance may deteriorate and the durability may deteriorate.
The average minor axis length of the metal nanowires was observed using 300 transmission metal microscopes (TEM; JEM-2000FX, JEM-2000FX), and the average value of the metal nanowires was determined from the average value. The average minor axis length was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.

The average major axis length (sometimes referred to as “average length”) of the metal nanowire is preferably 5 μm or more, more preferably 5 μm to 40 μm, and even more preferably 5 μm to 30 μm.
If the average major axis length is less than 5 μm, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
The average major axis length of the metal nanowire is observed, for example, using a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX). The average major axis length was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.

The coefficient of variation of the short axis length of the metal nanowire is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.
The coefficient of variation is obtained by measuring the short axis length (diameter) of 300 nanowires randomly selected from the electron microscope (TEM) image, and calculating the standard deviation and the average value for the 300 nanowires. It was.

The metal nanowire is not particularly limited and may be produced by any method. However, the metal nanowire is preferably produced by reducing metal ions in a solvent in which a halogen compound and a dispersant are dissolved as follows. Moreover, after forming metal nanowire, it is preferable to perform a desalting process by a conventional method from the viewpoint of dispersibility and stability over time of the conductive layer.
Moreover, as a manufacturing method of metal nanowire, Unexamined-Japanese-Patent No. 2009-215594, Unexamined-Japanese-Patent No. 2009-242880, Unexamined-Japanese-Patent No. 2009-299162, Unexamined-Japanese-Patent No. 2010-84173, Unexamined-Japanese-Patent No. 2010-86714 Etc. can be used.

The solvent used for the production of the metal nanowire is preferably a hydrophilic solvent, and examples thereof include water, alcohols, polyhydric alcohols, ethers and ketones, and these may be used alone. In addition, two or more kinds may be used in combination.
Examples of alcohols include methanol, ethanol, normal propanol, isopropanol, butanol and the like. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and the like. Examples of ethers include dioxane and tetrahydrofuran. Examples of ketones include acetone and methyl ethyl ketone. When heating, the heating temperature is preferably 250 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower, further preferably 30 ° C. or higher and 180 ° C. or lower, and 40 ° C. or higher and 170 ° C. as long as the boiling point of the solvent used is not exceeded. The following is particularly preferable, and 50 ° C. or higher and 100 ° C. or lower is most preferable. The boiling point means a temperature at which the vapor pressure of the reaction solvent becomes equal to the pressure in the reaction vessel. It is preferable to set the temperature to 20 ° C. or higher because formation of metal nanowires is promoted and manufacturing process time can be reduced. Moreover, by setting it as 250 degrees C or less, the monodispersity of the short-axis length and long-axis length of metal nanowire improves, and it is suitable from a transparency and electroconductive viewpoint. If necessary, the temperature may be changed during the grain formation process. Changing the temperature during the process has the effect of controlling nucleation, suppressing renucleation, and improving monodispersity by promoting selective growth. There is.

The heating 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 amines, aralkylamines, alcohols, polyhydric alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, glutathione and the like can be mentioned. Among these, reducing sugars, sugar alcohols as derivatives thereof, and polyhydric alcohols 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.

In producing the metal nanowire, it is preferable to add a dispersant and a halogen compound or metal halide fine particles.
The timing of addition of the dispersant may be before, at the same time as, or after the addition of the reducing agent, or may be before, at the same time as, or after the addition of the metal ions or metal halide fine particles. .

The step of adding the dispersant may be added before preparing the particles and may be added in the presence of the dispersed polymer, or may be added for controlling the dispersion state after adjusting the particles. When the addition of the dispersing agent is divided into two or more stages, the amount needs to be changed depending on the length of the short axis and the long axis of the required metal wire. This is because the amount and size of the metal particles that are the core of the metal nanowire are affected by the amount of the dispersant, and the short axis and length of the metal nanowire are determined by the amount and size of the metal particles that are the core of the metal nanowire. This is probably because the length of the shaft is affected.
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. And polymers such as gels. Among these, various polymer compounds used as a dispersant are compounds included in the polymer described later.

Examples of the polymer suitably used as the dispersant include gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylene amine, polyalkylene amine, partially alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone structure, which are protective colloid polymers. A polymer having a hydrophilic group such as a copolymer containing a polyacrylic acid having an amino group or a thiol group is preferable.
The polymer used as the dispersant has a weight average molecular weight (Mw) measured by the GPC method of preferably 3000 or more and 300,000 or less, and more preferably 5000 or more and 100,000 or less.
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 shape of the metal nanowire obtained can be changed depending on the type of the dispersant used.

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, potassium chloride, potassium iodide, and the following dispersants are preferred.
Some halogen compounds may function as a dispersant, but can be preferably used as well.
As an alternative to the halogen compound, silver halide fine particles may be used, or both a halogen compound and silver halide fine particles may be used.

Further, a single substance having both functions may be used as the dispersant and the halogen compound. 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 function as a dispersant include, for example, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium iodide, dodecyltrimethyl containing amino group and bromide ion or chloride ion and iodide ion. Ammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium iodide, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, stearyltrimethylammonium iodide, decyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium iodide, dimethyldistearylammonium Bromide Dimethyl distearyl ammonium chloride, dimethyl distearyl ammonium iodide, dilauryl dimethyl ammonium bromide, dilauryl dimethyl ammonium chloride, dilauryl dimethyl ammonium iodide, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride, dimethyl dipalmityl Ammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium iodide Tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, methyltriethylammonium chloride, methyltriethylammonium bromide, methyltriethylammonium iodide, dimethyldiethylammonium bromide, dimethyldiethylammonium chloride, dimethyldiethylammonium iodide, ethyltrimethyl Ammonium bromide, ethyltrimethylammonium chloride, ethyltrimethylammonium iodide, hexadecyldimethylammonium bromide, hexadecyldimethylammonium chloride, hexadecyldimethylammonium iodide, dodecyldimethylammonium bromide, dodecyldimethylammonium chloride, Examples include dodecyldimethylammonium iodide, stearyldimethylammonium bromide, stearyldimethylammonium chloride, stearyldimethylammonium iodide, decyldimethylammonium bromide, decyldimethylammonium chloride, decyldimethylammonium iodide. These may be used alone or in combination of two or more.

  There are no particular restrictions on the desalting process for removing unnecessary components such as organic substances and inorganic ions other than metal nanowires. Sedimentation of metal nanowires by centrifugation, etc., and subsequent removal of the supernatant, filtrate by ultrafiltration In addition, dialysis, gel filtration, etc. can be used. Moreover, in order to remove unnecessary components, it is possible to add a chemical that promotes elution of unnecessary components and perform desalting treatment. Examples of such an agent that promotes elution of unnecessary components include ammonia for silver halides such as silver chloride, chelating agents for various metal ions, and disodium ethylenediaminetetraacetate.

The metal nanowire preferably contains as little inorganic ions as possible, such as alkali metal ions, alkaline earth metal ions, and halide ions. The electrical conductivity when the metal nanowire is an aqueous dispersion is preferably 1 mS / cm or less, more preferably 0.1 mS / cm or less, and even more preferably 0.05 mS / cm or less.
The viscosity at 20 ° C. when the metal nanowire is an aqueous dispersion is preferably 0.5 mPa · s to 100 mPa · s, and more preferably 1 mPa · s to 50 mPa · s.

The aspect ratio of the metal nanowire is not particularly limited as long as it is 10 or more, and can be appropriately selected according to the purpose, but is preferably 50 or more, more preferably 100 or more, further preferably 5000 or more, More preferred is 10,000 to 100,000. The aspect ratio generally means the ratio between the long side and the short side of a fibrous material (ratio of average major axis length / average minor axis length).
There is no restriction | limiting in particular as a measuring method of the said aspect ratio, According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
When measuring the aspect ratio of the metal nanowire with an electron microscope, it is only necessary to confirm whether the aspect ratio of the metal nanowire is 10 or more with one field of view of the electron microscope. Moreover, the aspect ratio of the whole metal nanowire can be estimated by measuring the average major axis length and the average minor axis length of the metal nanowire separately.
In addition, when the said metal nanowire is tube shape, the outer diameter of this tube is used as a diameter for calculating the said aspect ratio.

The metal nanowire having an aspect ratio of 10 or more is preferably 5% or more, more preferably 50% or more, and particularly preferably 80% or more by volume ratio in the coating solution for all conductive layers. Hereinafter, the ratio of these metal nanowires may be referred to as “the ratio of metal nanowires”.
If the ratio of the metal nanowires is less than 5%, the conductive material that contributes to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration may occur because a dense network cannot be formed. , Durability may be reduced. In addition, particles having a shape other than metal nanowires are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, in the case of metal, transparency may be deteriorated when plasmon absorption such as a spherical shape is strong.

By setting the aspect ratio to 10 or more, a network in which metal nanowires are in contact with each other can be easily formed, and a conductive layer having high conductivity can be easily obtained. Further, by setting the aspect ratio to 100,000 or less, for example, in a coating liquid when a conductive layer is provided on a base material by coating, there is no fear that metal nanowires are entangled and aggregated, and stable. Since a coating liquid is obtained, manufacture becomes easy.
In addition, when the ratio of the metal nanowire is less than 5%, the conductive material that contributes to the conductivity may decrease and the conductivity may decrease. At the same time, a dense network cannot be formed. May occur and durability may be reduced. In addition, particles having a shape other than metal nanowires are not preferable because they do not greatly contribute to conductivity and have absorption. In particular, in the case of metal, transparency may be deteriorated when plasmon absorption such as a spherical shape is strong.

  Here, the ratio of the metal nanowire is, for example, when the metal nanowire is a silver nanowire, the silver nanowire aqueous dispersion is filtered to separate the silver nanowire from the other particles. The ratio of metal nanowires can be determined by measuring the amount of silver remaining on the filter paper and the amount of silver transmitted through the filter paper using an ICP emission analyzer. By observing the metal nanowires remaining on the filter paper with a TEM, observing the average minor axis length of 300 metal nanowires, and examining the distribution thereof, the average minor axis length is 200 nm or less, and the average It confirms that it is a metal nanowire whose major axis length is 1 micrometer or more. The filter paper measures the longest axis of particles other than metal nanowires having an average minor axis length of 200 nm or less and an average major axis length of 1 μm or more in a TEM image, and more than twice the longest axis. In addition, it is preferable to use a metal nanowire having a length equal to or shorter than the shortest length of the major axis.

  Here, the average minor axis length and the average major axis length of the metal nanowire can be obtained by observing a TEM image or an optical microscope image using, for example, a transmission electron microscope (TEM) or an optical microscope. In the present invention, the average minor axis length and the average major axis length of the metal nanowire are obtained by observing 300 metal nanowires with a transmission electron microscope (TEM) and calculating the average value. is there.

The coating amount of the metal nanowires is preferably 0.001 to 0.1 g / cm ^2, more preferably ^{0.005~0.05g / cm 2, 0.005~0.05g / cm} 2 is particularly preferred.

  In addition, the conductive layer may be a patterned conductive layer, and in this aspect, the conductive layer forming composition is preferably a photosensitive composition. The photosensitive composition may be negative or positive. Hereinafter, examples of the photosensitive composition and the sol-gel cured product that can be used for forming the conductive layer will be described, but the present invention is not limited to the following examples.

For the formation of the conductive layer, together with the metal nanowire, as a matrix component, (1) a photosensitive composition containing at least a binder and a photopolymerizable composition, (2) a composition containing at least a sol-gel cured product, (3) A composition containing at least a polymer can be used.
In the present invention, the weight ratio of the matrix component (all components excluding the metal nanowire and the solvent contained in the conductive layer coating solution) to the metal nanowire is 0.5 to 15 (more preferably 1.0 to 12, particularly Preferably it is 2.0-10).
When the weight ratio is less than 0.5, the binder component is small, the adhesion of the metal nanowires to the base material surface is weak, and the film strength may be weakened. The surface resistance value of the layer may increase.
In addition to the metal nanowires and the matrix component that fixes the metal nanowires, the conductive layer may contain an antioxidant, a reducing agent, an ultraviolet absorber, a rust preventive agent, a conductive agent in addition to a dispersant and a surfactant as necessary. May contain functional particles, dyes, pigments, and the like. Moreover, you may provide a protective layer further on the surface of a conductive layer as needed.

binder:
The binder is a linear organic high molecular polymer, and at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) ( For example, it can be appropriately selected from alkali-soluble resins having a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the like.
Among these, those that are soluble in an organic solvent and soluble in an aqueous alkali solution are preferable, and those that have an acid-dissociable group and become alkali-soluble when the acid-dissociable group is dissociated by the action of an acid are particularly preferable. preferable.
Here, the acid dissociable group represents a functional group that can dissociate in the presence of an acid.

  For production of the binder, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and the conditions are determined experimentally. Can be determined.

As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable.
Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial ester, as described in JP-A-59-71048 A maleic acid copolymer, etc., an acidic cellulose derivative having a carboxylic acid in the side chain, a polymer having a hydroxyl group with an acid anhydride added, and a polymer having a (meth) acryloyl group in the side chain Polymers are also preferred.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly preferable.
Furthermore, a high molecular polymer having a (meth) acryloyl group in the side chain and a multi-component copolymer composed of (meth) acrylic acid / glycidyl (meth) acrylate / other monomers are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl described in JP-A-7-140654 Methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Coalescence, etc.

  As specific structural units in the alkali-soluble resin, (meth) acrylic acid and other monomers copolymerizable with the (meth) acrylic acid are suitable.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. In these, the hydrogen atom of the alkyl group and aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylate or aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth). Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meta ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, Polymethyl methacrylate macromonomer, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, CH ₂ = CR ¹ R ² [where R ¹ is a hydrogen atom or a carbon number. Represents an alkyl group of 1 to 5, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ] And the like. These may be used individually by 1 type and may use 2 or more types together.

The weight average molecular weight of the binder is preferably from 1,000 to 500,000, more preferably from 3,000 to 300,000, and even more preferably from 5,000 to 200,000, from the viewpoints of alkali dissolution rate, film physical properties and the like. .
Here, the weight average molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

  The content of the binder is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 85% by mass, based on the total mass of the solid content of the photopolymerizable composition including the metal nanowires. Preferably, 20% by mass to 80% by mass is more preferable. When the content is within the preferable range, both developability and conductivity of the metal nanowire can be achieved.

Photopolymerizable composition:
The photopolymerizable composition means a compound that imparts the function of forming an image by exposure to the conductive layer or gives the trigger thereof. The basic component includes (a) an addition-polymerizable unsaturated compound and (b) a photopolymerization initiator that generates radicals when irradiated with light.

[(A) Addition polymerizable unsaturated compound]
The component (a) addition-polymerizable unsaturated compound (hereinafter also referred to as “polymerizable compound”) is a compound that undergoes an addition-polymerization reaction in the presence of a radical to form a polymer, and usually has a molecular end. A compound having at least one, more preferably two or more, more preferably four or more, still more preferably six or more ethylenically unsaturated double bonds is used.
These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof.
Various kinds of such polymerizable compounds are known, and they can be used as the component (a).
Among these, particularly preferred polymerizable compounds are trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) from the viewpoint of film strength. Acrylate is particularly preferred.

  The content of component (a) is preferably 2.6% by mass or more and 37.5% by mass or less based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires described above. More preferably, it is 0.0 mass% or more and 20.0 mass% or less.

[(B) Photopolymerization initiator]
The photopolymerization initiator of component (b) is a compound that generates radicals when irradiated with light. Examples of such photopolymerization initiators include compounds that generate acid radicals that ultimately become acids upon irradiation with light, and compounds that generate other radicals. Hereinafter, the former is referred to as “photoacid generator”, and the latter is referred to as “photoradical generator”.
-Photoacid generator-
Photoacid generator includes photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecoloring agent for dyes, photochromic agent, irradiation of actinic ray or radiation used for micro resist, etc. Thus, known compounds that generate acid radicals and mixtures thereof can be appropriately selected and used.

There is no restriction | limiting in particular as such a photo-acid generator, According to the objective, it can select suitably, For example, the quinonediazide compound, the triazine which has at least one di- or tri-halomethyl group, or 1,3,4 -Oxadiazole, naphthoquinone-1,2-diazido-4-sulfonyl halide, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, o-nitrobenzyl sulfonate, etc. . Among these, imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid, are particularly preferable.
In addition, a group that generates an acid radical upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin, such as US Pat. No. 3,849,137, German Patent No. 3914407. No., JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853 And compounds described in JP-A 63-146029, etc. can be used.
Furthermore, compounds described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used as an acid radical generator.

  As the triazine compound, for example, compounds described in JP2011-018636A and JP2011-254046A can be used.

  In the present invention, among the photoacid generators, compounds that generate sulfonic acid are preferable, and the following oxime sulfonate compounds are particularly preferable from the viewpoint of high sensitivity.

When a compound having a 1,2-naphthoquinonediazide group is used as the quinonediazide compound, high sensitivity and good developability are obtained.
Among the quinonediazide compounds, those in which D is independently a hydrogen atom or a 1,2-naphthoquinonediazide group in the following compounds are preferred from the viewpoint of high sensitivity.

-Photoradical generator-
The photoradical generator is a compound that has a function of generating radicals by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction. The photo radical generator is preferably one having absorption in a wavelength region of 300 nm to 500 nm.
As such a photo radical generator, many compounds are known. For example, triazine compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, as described in JP-A-2008-268884, Examples thereof include organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and acylphosphine (oxide) compounds. These can be appropriately selected according to the purpose. Among these, benzophenone compounds, acetophenone compounds, hexaarylbiimidazole compounds, oxime ester compounds, and acylphosphine (oxide) compounds are particularly preferable from the viewpoint of exposure sensitivity.

  As the photo radical generator, for example, the photo radical generators described in JP 2011-018636 A and JP 2011-254046 A can be used.

  A photoinitiator may be used individually by 1 type and may use 2 or more types together, The content is based on the total mass of solid content of the photopolymerizable composition containing metal nanowire, It is preferable that it is 0.1 mass%-50 mass%, 0.5 mass%-30 mass% are more preferable, 1 mass%-20 mass% are still more preferable. In such a numerical range, when a pattern including a conductive region and a non-conductive region described later is formed on the conductive layer, good sensitivity and pattern formability can be obtained.

  Other additives other than the above components include, for example, chain transfer agents, crosslinking agents, dispersants, solvents, surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like. Various additives are mentioned.

[Chain transfer agent]
The chain transfer agent is used for improving the exposure sensitivity of the photopolymerizable composition. Examples of such chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzo. Complexes such as imidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Aliphatic polyfunctional mercapto such as mercapto compounds having a ring, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane Compound etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The content of the chain transfer agent is preferably 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass based on the total mass of the solid content of the photopolymerizable composition containing the metal nanowires. % Is more preferable, and 0.5 mass% to 5 mass% is still more preferable.

[Crosslinking agent]
A crosslinking agent is a compound that forms a chemical bond with free radicals or acid and heat to cure the conductive layer, and is, for example, a melamine-based compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Compound, guanamine compound, glycoluril compound, urea compound, phenol compound or phenol ether compound, epoxy compound, oxetane compound, thioepoxy compound, isocyanate compound, azide compound, methacryloyl group or acryloyl group A compound having an ethylenically unsaturated group, and the like. Among these, an epoxy compound, an oxetane compound, and a compound having an ethylenically unsaturated group are particularly preferable in terms of film properties, heat resistance, and solvent resistance.
Moreover, the said oxetane resin can be used individually by 1 type or in mixture with an epoxy resin. In particular, when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.
In addition, when using the compound which has an ethylenically unsaturated double bond group as a crosslinking agent, the said crosslinking agent is also included by the said polymeric compound, The content is content of the polymeric compound in this invention. Should be included.
The content of the crosslinking agent is preferably 1 part by mass to 250 parts by mass, and preferably 3 parts by mass to 200 parts by mass, when the total mass of the solid content of the photopolymerizable composition including the metal nanowires is 100 parts by mass. Is more preferable.

[Dispersant]
A dispersing agent is used in order to disperse | distribute, preventing that the above-mentioned metal nanowire in a photopolymerizable composition aggregates. The dispersant is not particularly limited as long as the metal nanowires can be dispersed, and can be appropriately selected according to the purpose. For example, a commercially available dispersant can be used as a pigment dispersant, and a polymer dispersant having a property of adsorbing to metal nanowires is particularly preferable. Examples of such polymer dispersants include polyvinyl pyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nihon Lubrizol), Ajisper series (manufactured by Ajinomoto Co., Inc.), and the like.
In addition, when a polymer dispersant is added as a dispersant other than that used in the production of the metal nanowires, the polymer dispersant is also included in the binder, and the content thereof is as described above. It should be considered that it is included in the content of the binder.
As content of a dispersing agent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of binders, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are especially preferable. .
By setting the content of the dispersant to 0.1 parts by mass or more, aggregation of metal nanowires in the dispersion is effectively suppressed, and by setting the content to 50 parts by mass or less, a stable liquid film in the coating process Is preferable, and the occurrence of uneven coating is suppressed.

[solvent]
The solvent is a component used to form a coating liquid for forming a composition containing the metal nanowire and the specific alkoxide compound and the photopolymerizable composition on the surface of the substrate in the form of a film. For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol, water, 1-methoxy Examples include 2-propanol, isopropyl acetate, methyl lactate, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate, and the like. This solvent may also serve as at least a part of the solvent of the metal nanowire dispersion described above. These may be used individually by 1 type and may use 2 or more types together.
The solid content concentration of the coating solution containing such a solvent is preferably contained in the range of 0.1% by mass to 20% by mass.

[Metal corrosion inhibitor]
It is preferable to contain the metal nanowire metal corrosion inhibitor. There is no restriction | limiting in particular as such a metal corrosion inhibitor, Although it can select suitably according to the objective, For example, thiols, azoles, etc. are suitable.
By containing a metal corrosion inhibitor, it is possible to exert a rust prevention effect, and it is possible to suppress a decrease in conductivity and transparency of the conductive material over time. The metal corrosion inhibitor is added to the composition for forming the photosensitive layer in a state dissolved in a suitable solvent, or in the form of powder, or after preparing a conductive film with a conductive layer coating solution described later, this is added to the metal corrosion inhibitor. It can be applied by soaking in a bath.
When adding a metal corrosion inhibitor, it is preferable to contain 0.5 mass%-10 mass% with respect to metal nanowire.

  As the other matrix, it is possible to use a polymer compound as a dispersant used in the production of the metal nanowire described above as at least a part of the components constituting the matrix.

  For the formation of the conductive layer, a composition containing at least a sol-gel cured product as a matrix component can be used together with the metal nanowires.

<Sol-gel cured product>
The sol-gel cured product is obtained by hydrolyzing and polycondensing an alkoxide compound of an element selected from the group consisting of Si, Ti, Zr and Al (hereinafter also referred to as “specific alkoxide compound”), and further heating and drying as desired. Is obtained.
[Specific alkoxide compound]
The specific alkoxide compound is preferably a compound represented by the following general formula (I) because it is easily available.
M ¹ (OR ¹ ) _a R ² _4-a (I)
(In general formula (I), M ¹ represents an element selected from Si, Ti and Zr, R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group, and a represents an integer of 2 to 4. Show.)

As each hydrocarbon group of R ¹ and R ² in the general formula (I), an alkyl group or an aryl group is preferable.
Carbon number in the case of showing an alkyl group becomes like this. Preferably it is 1-18, More preferably, it is 1-8, More preferably, it is 1-4. Moreover, when showing an aryl group, a phenyl group is preferable.
The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, an alkylamino group, and a mercapto group.
The compound represented by the general formula (I) is a low molecular compound and preferably has a molecular weight of 1000 or less.

  Specific examples of the compound represented by the general formula (I) are described, for example, in JP-A-2010-064474.

In the present invention, when the sol-gel cured product is used as a matrix of the conductive layer, the ratio of the specific alkoxide compound to the metal nanowire, that is, the mass ratio of the specific alkoxide compound / metal nanowire is 0.25 / 1 to 30 /. Used in the range of 1. When the mass ratio is less than 0.25 / 1, the transparency is inferior, and at the same time, at least one of wear resistance, heat resistance, moist heat resistance and flex resistance is inferior. On the other hand, when the mass ratio is larger than 30/1, the conductive layer is inferior in conductivity and flex resistance.
The mass ratio is more preferably in the range of 0.5 / 1 to 20/1, more preferably in the range of 1/1 to 15/1, and most preferably in the range of 2/1 to 8/1. High conductivity and high transparency It is preferable because it can stably obtain a conductive material having high properties (total light transmittance and haze), excellent wear resistance, heat resistance and moist heat resistance, and excellent flex resistance.

  For the formation of the conductive layer, a composition containing at least a polymer as a matrix component can be used together with the metal nanowires. Synthetic polymers and natural polymers are included as the polymer. Examples of the synthetic polymer include polyester, polyimide, polyacryl, polyvinylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, methacrylic acid resin, fluorine-based resin, and phenol. Examples thereof include resins, melamine resins, silicone resins, synthetic rubbers, and latexes thereof. Examples of the natural polymer include cellulosic resins and natural rubber.

Application method of conductive layer:
An example of a conductive layer coating method (formation method) is as follows, but is not limited to the following example.
First, a conductive layer coating solution is prepared. The coating solution is a metal nanowire having an average minor axis length of 5 to 50 nm and a matrix component (preferably a binder and a photosensitive compound, a sol-gel cured product, or a composition containing at least a polymer, and further if necessary. And other components) can be mixed and prepared by a conventional method.

  Next, the said coating liquid for conductive layers is apply | coated to substrate surfaces, such as a glass plate and a film. The method for applying is not particularly limited and can be appropriately selected depending on the purpose. For example, spray coating method, air brush method, curtain spray method, dip coating method, roller coating method, spin coating method, ink jet method, Examples include an extrusion method.

  As a coating amount, the wet film thickness of the conductive layer is 0.2 to 20 times (preferably 1.0 to 15 times, preferably 2.0 to 13 times) the average major axis length of the metal nanowires. Adjust the coating amount to apply.

Next, the conductive layer coating solution is applied onto the substrate to form a coating layer, and then exposed and cured.
There is no restriction | limiting in particular as said exposure, Although it can select suitably according to a use etc., an ultraviolet irradiation device, an ultraviolet irradiation lamp, etc. are preferable.

You may implement the process of processing the conductive layer after the said exposure (after hardening) with an alkaline solution.
The alkali contained in the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.

  You may add methanol, ethanol, or surfactant to the said alkaline solution as needed. As the surfactant, for example, an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be selected and used. Among these, the addition of nonionic polyoxyethylene alkyl ether is particularly preferable because the resolution becomes high.

The alkali treatment is not particularly limited and may be appropriately selected depending on the intended purpose. For example, any of dip development, paddle development, and shower development can be used.
By performing the alkali treatment, the conductivity of the conductive layer of the three-dimensional curved surface structure can be increased.
There is no restriction | limiting in particular in the immersion time of the said alkaline solution, Although it can select suitably according to the objective, It is preferable that it is 10 seconds-5 minutes.

  Moreover, the process of patterning a conductive layer in a conductive region and a non-conductive region may be included.

The conductive layer of the conductive member is patterned to have a desired pattern composed of a conductive region and a non-conductive region, and the conductive pattern member according to the present invention is manufactured. Examples of such a patterning method include the following methods. In the following description, the conductive layer before patterning is also referred to as “non-patterned conductive layer”.
When the matrix of the conductive layer is non-photosensitive, it is patterned by the following methods (1) to (2).
(1) A photoresist layer is provided on a non-patterned conductive layer, and a desired pattern exposure and development are performed on the photoresist layer to form the patterned resist (etching mask material). Dissolve silver nanowires into silver nanowires in conductive layers in areas that are not protected by resist, either by wet processes where the wires are treated with an etchable etchant or by dry processes such as reactive ion etching A patterning method in which disconnection or disappearance is caused by etching with a liquid. This method is described, for example, in JP-T-2010-507199 (particularly, paragraphs 0212 to 0217).
(2) In a desired region on the non-patterned conductive layer, a photocurable resin is provided on the pattern by an ink jet method or a screen printing method, and the photocurable resin layer is subjected to a desired exposure to form the pattern. After the resist (etching mask material) is formed, the silver nanowires are immersed in an etchable etchant, or the etchant is showered to form a conductive layer in a region not protected by the resist. Patterning method for breaking or disappearing silver nanowires.
In the case of the above method (1) or (2), it is preferable to remove the resist on the conductive layer by a conventional method after the patterning is completed, because a conductive member having excellent transparency can be obtained.

There is no restriction | limiting in particular in the method of providing the said etching mask material, For example, the apply | coating method, the printing method, the inkjet method etc. are mentioned.
The coating method is not particularly limited. For example, 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, Examples thereof include a spray coating method and a doctor coating method.
Examples of the printing method include letterpress (letterpress) printing, stencil (screen) printing, lithographic (offset) printing, and intaglio (gravure) printing.
Note that the resist layer formed in this step 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.
According to this method, in the non-conductive region, both the metal nanowires and the binder contained in the conductive layer are removed, and the base material or the intermediate layer formed on the base material is exposed.

There is no restriction | limiting in particular in the resist layer forming material used for the method of said (1), Any, such as a negative type, a positive type, a dry film type, can be used.
For the formation of the resist layer, commercially available alkali-soluble photoresists can be appropriately selected and used. For example, Fujifilm color mosaic series, FILS series, FIOS series, FMES series, FTENS series, FIES series, for semiconductor processes Each positive type, negative type photoresist series, Fuji Chemical's Fujiresist series, among which FR series, FPPR series, FMR series, FDER series, etc. can be preferably used, and AZ Electronic Materials photoresist series, among others , RFP series, TFP series, SZP series, HKT series, SFP, series, SR series, SOP series, SZC series, CTP series, ANR series, P4000 series , TPM606,40XT, etc. nXT series are preferably mentioned, also including the photoresist JSR Corporation, a high-resolution type, it can be used widely to low resolution type.
As dry film resists, Hitachi Chemical, photosensitive film for printed wiring boards, Asahi Kasei E-materials photosensitive dry film SUNFORT series, DuPont MRC dry film FXG series, FXR series, FX900 series, JSF100 series, SA100 series , LDI series, FRA series, CM series, Fujifilm Transer series, etc., which can be used as appropriate.
What is necessary is just to select these resist layer forming materials suitably according to the resolution etc. of the pattern formed in an electroconductive pattern member.
In the formation of the resist layer, when a dry film type resist layer forming material is used, a photosensitive resist layer of a dry film resist prepared in advance may be transferred to the surface of the formed conductive layer.

The exposure step is a step of performing exposure at an oxygen concentration of 5% or less using an etching mask material containing a photopolymerization initiator.
The exposure is performed in an atmosphere having an oxygen concentration of 5% or less. The oxygen concentration is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.1% or less.
When the exposure is performed in an atmosphere where the oxygen concentration exceeds 5%, metal nanowires are disconnected by reaction with a by-product generated from a photopolymerization initiator contained in the etching mask material, or an oxide such as ozone, Since the resistance value of the conductive part wiring after patterning increases, it is not preferable. The disconnection of metal nanowires in an atmosphere having a high oxygen concentration tends to be particularly noticeable when metal nanowires having a small diameter are used.
Furthermore, it is not preferable to perform the exposure in an atmosphere in which the oxygen concentration exceeds 5%, because the reaction efficiency in curing the etching mask material decreases and the tact time becomes long.

The exposure is preferably performed in an inert gas atmosphere having an oxygen concentration of 5% or less.
The inert gas that can be used is not particularly limited as long as it does not interfere with the UV curing reaction. As the inert gas, nitrogen gas or argon gas is preferable, and nitrogen gas is more preferable because it is easily available and inexpensive.

As the exposure method, surface exposure (solid exposure) not using a photomask, surface exposure using a photomask, or scanning exposure using a laser beam may be performed. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used.
These exposure methods can be appropriately selected as necessary. For example, when the applied etching mask material is applied in a pattern in advance, solid exposure can be performed without using a photomask.
The light source used for the pattern exposure or exposure is selected in relation to the photosensitive wavelength range of the photoresist composition, but in general, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferably used. Moreover, you may use ultraviolet 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. At this time, refractive exposure using a lens or reflection exposure using a reflecting mirror may be used, and exposure methods such as contact exposure, proximity exposure, reduced projection exposure, and reflection projection exposure can be used. Further, the sample film surface temperature at the time of exposure is preferably low, preferably in the range of 0 ° C. to 80 ° C., more preferably 5 ° C. to 70 ° C., still more preferably 10 ° C. to 50 ° C. If the temperature at the time of exposure is lower than 0 ° C., it is difficult to control the temperature, and if it is 80 ° C. or higher, the number of disconnections of the metal nanowires increases and the resistance increase magnification increases.

The solution for dissolving the silver nanowire (referred to as an etching solution) can be appropriately selected according to the silver nanowire. For example, when the silver nanowire is a silver nanowire, in the so-called photographic science industry, bleaching fixer, strong acid, oxidizing agent, peroxidation mainly used for bleaching and fixing process of photographic paper of silver halide color photosensitive material Examples include hydrogen. Of these, bleach-fixing solution, dilute nitric acid, and hydrogen peroxide are particularly preferable. In addition, the dissolution of the silver nanowires by the solution for dissolving the silver nanowires may not completely dissolve the portion of the silver nanowires to which the solution is applied, and partly if the conductivity is lost. It may remain.
The concentration of the diluted nitric acid is preferably 1% by mass to 20% by mass.
The concentration of the hydrogen peroxide is preferably 3% by mass to 30% by mass.

Examples of the bleach-fixing solution include, for example, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper-right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17. The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable.
The bleach-fixing time is preferably 180 seconds or shorter, more preferably 120 seconds or shorter and 1 second or longer, and still more preferably 90 seconds or shorter and 5 seconds or longer. Moreover, the water washing or stabilization time is preferably 180 seconds or shorter, more preferably 120 seconds or shorter and 1 second or longer.
The bleach-fixing solution is not particularly limited as long as it is a photographic bleach-fixing solution, and can be appropriately selected according to the purpose. For example, CP-48S, CP-49E (color paper bleaching) manufactured by Fujifilm Corporation Fixing agent), Kodak Ekta Color RA Bleach Fixer, Dai Nippon Printing Co., Ltd. Bleach Fixer D-J2P-02-P2, D-30P2R-01, D-22P2R-01, and the like. Among these, CP-48S and CP-49E are particularly preferable.

  The development process is a process for removing the etching mask material by applying a solvent. In the case of a positive resist, the development process after the mask exposure and the resist peeling development process after the etching process, and in the case of a negative resist, the etching process. This is a step performed in the resist stripping development step after the step.

As the solvent used in the development step, an alkaline solution is preferable.
The alkali contained in the alkaline solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like.
As the solvent, in addition to the above-mentioned solvents, commercially available photoresist developers can be used.

There is no restriction | limiting in particular as the provision method of the said alkaline solution, According to the objective, it can select suitably, For example, application | coating, immersion, spraying etc. are mentioned. Among these, immersion is particularly preferable.
There is no restriction | limiting in particular in the immersion time of the said alkaline solution, Although it can select suitably according to the objective, It is preferable that it is 10 seconds-5 minutes. Moreover, although the temperature of an alkaline solution can be suitably selected according to the objective, it is preferable that it is 5 to 50 degreeC.

(Other processes)
The patterning step of the method for producing a conductive material in the present invention may further include other steps as necessary in addition to the exposure step and the development step.
Examples of other processes include washing with water after removing the etching mask, and a drying process.

  The conductive layer may be formed on a target substrate by transfer using a transfer material.

  A method for forming the conductive layer on the substrate can be performed by a general coating method, and is not particularly limited and can be appropriately selected according to the purpose. For example, a roll coating method or a bar coating method. Dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and the like.

  Moreover, after forming a conductive layer, you may perform the process for reducing the orientation of the metal nanowire in a layer. Metal nanowires in a conductive layer formed by being applied along one direction tend to be oriented along that direction. Therefore, it is preferable to perform a stretching process (for example, a stretching process with a stretching ratio of 1% or more and less than 5%) along a direction (for example, a direction orthogonal to the direction) different from the direction of application because orientation is reduced. In the case where the stretching process is performed, it is preferable to form a conductive layer on a flexible substrate such as a polymer film and then stretch the conductive layer supported by the substrate together with the substrate.

The surface resistance of the conductive layer is preferably 0.1Ω / □ to 5,000Ω / □, and more preferably 0.1Ω / □ to 500Ω / □.
The surface resistance can be measured by, for example, a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation).

The dry film thickness of the conductive layer is 0.001 to 0.1 times the average major axis length of the metal nanowires, preferably 0.002 to 0.05 times, and more preferably 0.003 to 0.01 times. .
When the dry film thickness exceeds 0.001 times the average major axis length of the metal nanowires, the metal nanowires are difficult to align, and the extinction ratio can be reduced. When the dry film thickness is less than 0.1 times the average major axis length of the metal nanowires, aggregation of the metal nanowires can be prevented.

substrate:
In this invention, it has a board | substrate which supports the said electrically conductive film. The light transmittance of the substrate is preferably 65% or more, and more preferably 70% or more.

  There is no particular limitation on the thickness of the substrate. The average thickness is preferably 0.01 mm to 10 mm, and more preferably 0.02 mm to 1 mm. However, it is not limited to this range.

  The surface of the substrate may be subjected to a surface treatment for improving adhesion with the conductive film. The surface treatment is performed by a physical or chemical method. Examples of the physical method include a method of imparting an anchor effect by roughening the surface of the substrate by a sandblast method or the like. Examples of the chemical method include a method of activating the substrate surface by plasma treatment or corona treatment, a method of chemically increasing adhesion to the conductive film by silane coupling agent treatment, and a method of providing an undercoat layer such as a primer layer. Etc. The undercoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the undercoat layer may be provided with ultraviolet absorbing ability, antioxidant ability, and the like. Among these, plasma processing is particularly preferable in terms of simplicity and processing uniformity.

The substrate may be a substrate having an antistatic layer 100 on a support 200 as shown in an example of FIG. 3 in order to improve optical characteristics such as transmittance and haze.
The antistatic layer preferably has metal oxide fine particles and a binder. The antistatic layer may be provided as an adhesive layer that bonds the support and the conductive layer.
In the present invention, the entire substrate including the support and the layer adjacent to the conductive layer is defined as a substrate. For example, as shown in FIG. 3, when a support and an antistatic layer are provided and the antistatic layer is adjacent to the conductive layer, the substrate including the support and the antistatic layer is defined.

The material for the support is not particularly limited as long as it is a flexible polymer. For example, it can be selected from a polymer (used in the meaning including both a resin and a polymer) film, sheet and molded product.
Examples of usable polymer films include polyethylene terephthalate (PET), polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, polyimide, FRP (fiber reinforced plastic), etc. The film etc. which contain as a main component are included.

  Examples of the metal oxide fine particles include tin oxide, indium oxide, zinc oxide, titanium oxide, magnesium oxide, and antimony oxide. Details of the metal oxide fine particles are described in JP 2010-188604 A.

  In the antistatic layer used in the present invention, the metal oxide fine particles are preferably acicular metal oxide fine particles. By adopting acicular conductive metal oxide fine particles, it is possible to more effectively achieve both of the optical characteristics of transmittance and haze and conductivity.

The needle shape in the conductive acicular metal oxide fine particles has a short axis average particle size of 5 to 500 nm, a long axis average particle size of 50 to 5000 nm, and an aspect ratio of 3 or more. Means things. The minor axis average particle diameter is preferably 5 to 300 nm. The major axis average particle diameter is preferably 100 to 300 nm. The aspect ratio is preferably 5 to 300 nm.
The conductive acicular metal oxide fine particles used in the present invention are preferably oxides containing tin and / or antimony, and more preferably tin oxide doped with antimony. In the case of tin oxide doped with antimony, the content of antimony is preferably 0 to 10 mol%, and more preferably 1 to 5 mol%.
The conductive acicular metal oxide fine particles are preferably contained in an amount of 10 to 100 parts by weight and more preferably 20 to 90 parts by weight with respect to 100 parts by weight of the binder.
Moreover, it is preferable that electroconductive acicular metal oxide microparticles | fine-particles are contained in the ratio of 5-50 weight% with respect to a conductive layer, and it is still more preferable that it is contained in the ratio of 10-45 weight%.

The binder serves as a binder for dispersing the conductive acicular metal oxide. Therefore, as long as this role is fulfilled, the type and the like are not particularly limited. As binders, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyhydroxyethyl acrylate, polyvinyl pyrrolidone, water-soluble polyester, water-soluble polyurethane, water-soluble nylon, water-soluble epoxy resin, gelatin, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose And water-soluble binders such as derivatives thereof; water-dispersed resins such as water-dispersed acrylic resins and water-dispersed polyesters; emulsions such as acrylic resin emulsions, polyvinyl acetate emulsions, and SBR (styrene / butadiene / rubber) emulsions; acrylic resins; An organic solvent-soluble resin such as a polyester resin can be used. Water-soluble binders, water-dispersed resins and emulsions are preferred, and water-soluble binders are more preferred.
The binder preferably has a glass transition temperature of 90 ° C. or higher. By employing such a binder, precipitation of oligomers from the support can be suppressed. Preferred examples of the binder having a glass transition temperature (Tg) of 90 ° C. or higher include polyester and polyurethane.

To these binders, a surfactant may be further added, and a crosslinking agent or the like may be added.
Examples of the surfactant include alkylbenzene imidazole sulfonate, naphthalene sulfonate, carboxylic acid sulfone ester, phosphate ester, heterocyclic amines, ammonium salts, phosphonium salts and betaine-based amphoteric salts. It is preferable that 0.1-20 weight part of surfactant is contained with respect to 100 weight part of binders, and it is more preferable that 1-10 weight part is contained.
Preferred compounds as the crosslinking agent include epoxy compounds, aldehyde compounds, active halogen compounds, active vinyl compounds, N-carbamoylpyridinium salt compounds, N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), carbodiimide compounds. Oxazoline compounds, isocyanate compounds, polymer hardeners (compounds described in JP-A-62-234157, etc.), boric acid and salts thereof, borax, aluminum alum and the like. A crosslinking agent can be suitably determined according to the kind of binder. When a water-soluble binder is used, a carbodiimide compound is preferable. It is preferable that 2-80 weight part is contained with respect to 100 weight part of binders, and it is more preferable that a crosslinking agent is contained 5-50 weight part.

The antistatic layer is formed, for example, by dispersing or dissolving the conductive needle-like metal oxide particles and binder in water or an organic solvent, and coating the obtained coating solution on the substrate surface and heating and drying. can do. The coating can be performed by a known coating method such as an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, or a bar coater.
The coating amount of the antistatic layer is preferably 0.01 to 10 g / m ² by solid content, 0.1-5 g / m ² is more preferable. When the coating amount is 0.01 g / m ² or more, it is preferable from the viewpoint of conductivity.

  The thickness of the antistatic layer is preferably 0.05 to 10 μm, and more preferably 0.1 to 5 μm.

Other layers (functional layers):
The conductive member of the present invention may have other layers (functional layers) in addition to the substrate and the conductive layer.
As the functional layer, for example, an insulating film such as an adhesive layer, protective film, undercoat layer, adhesion layer, cushion layer, overcoat protective layer, protective film layer, antifouling layer, water repellent layer, oil repellent layer, hard coat layer, Examples include an adhesive layer and a barrier layer.
For example, an optical function can be imparted by laminating an antiglare layer, an antireflection layer, a low reflection layer, a λ / 4 layer, a polarizing layer, a retardation layer, and the like. These may be a single layer or a plurality of layers.

  The conductive member of the present invention includes, for example, a polarizing plate, a circular polarizing plate, a touch panel, a display electrode, an electromagnetic wave shield, an organic EL display electrode, an inorganic EL display electrode, an electronic paper, a flexible display electrode, and an integrated solar cell. It is widely applied to display devices, display devices with a touch panel function, and other various devices. Among these, a display device and a touch panel are particularly preferable.

When the conductive member of the present invention is used for a polarizing plate, a circularly polarizing plate, and a liquid crystal display device, the in-plane retardation Re (550) of the substrate having a wavelength of 550 nm is a transparent material having a high optical isotropy of 40 nm or less. Preferably, it is 30 nm or less, more preferably 20 nm or less.
Transparent materials having an in-plane retardation Re (550) with a wavelength of 550 nm of 40 nm or less include, for example, triacetyl cellulose (TAC), polycarbonate, thermoplastic norbornene resin (ZEONEX, ZEONOR, JSR manufactured by Nippon Zeon Co., Ltd.) Arton, Inc.). If the retardation is small, the thickness of the optical member such as a polarizing plate or a circularly polarizing plate and the thickness of a device such as a touch panel can be reduced. Therefore, it is preferable that the substrate to be used is thin.

  Re (λ) is measured with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments Co., Ltd.) by making light of wavelength λ nm incident in the normal direction of the film. In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.

  The substrate may be a retardation plate such as a λ / 4 or λ / 2 plate. Various known λ / 4 and λ / 2 plates can be used as the λ / 4 and λ / 2 plates.

  The conductive member of the present invention includes, for example, a polarizing plate, a circular polarizing plate, a touch panel, a display electrode, an electromagnetic wave shield, an organic EL display electrode, an inorganic EL display electrode, an electronic paper, a flexible display electrode, an integrated solar cell, Widely applied to display devices, display devices with touch panel functions, and other various devices. Among these, a display device and a touch panel are particularly preferable.

Polarizing plate, circular polarizing plate:
The polarizing plate and the circularly polarizing plate of the present invention are not particularly limited except for having the conductive material of the present invention, and can be appropriately selected according to the purpose. A polarizing plate and a circularly-polarizing plate have a conductive material and a polarizing film, and also have a protective film as needed. Preferably, the conductive material is an embodiment in which the conductive material is laminated on the polarizing film or the protective film.

A general linear polarizing film can be used as the polarizing film. The polarizing film may be a stretched film or a layer formed by coating. Examples of the former include a film obtained by dyeing a stretched film of polyvinyl alcohol with iodine or a dichroic dye. Examples of the latter include a layer in which a composition containing a dichroic liquid crystalline dye is applied and fixed in a predetermined alignment state.
As the protective film, it is preferable to use a transparent material having an in-plane retardation Re (550) of a wavelength of 550 nm of 40 nm or less, like the substrate.

Touch panel:
The touch panel is not particularly limited as long as it has the conductive material (transparent conductor) of the present invention, and can be appropriately selected according to the purpose. For example, a surface capacitive touch panel, a projection capacitive system A touch panel, a resistance film type touch panel, etc. are mentioned. The touch panel includes a so-called touch sensor and a touch pad.
The layer structure of the touch panel sensor electrode part in the touch panel is 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, a single-sided jumper or a through-hole method, or a single-area layer method. It is preferable that it is either.

Here, an example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 4, the touch panel 10 has a transparent conductor 12 disposed so as to uniformly cover the surface of the transparent substrate 11 (corresponding to the conductive material of the present invention). An electrode terminal 18 for electrical connection with an external detection circuit (not shown) is formed on the body 12.
In FIG. 4, 13 indicates a transparent conductor serving as a shield electrode, 14 and 17 indicate protective films, 15 indicates an intermediate protective film, and 16 indicates an antiglare film.
When an arbitrary point on the transparent conductor 12 is touched with a finger, the transparent conductor 12 is grounded through the human body at the touched point, and changes to a resistance value between each electrode terminal 18 and the ground line. Occurs. The change of the resistance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

Another example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 5, the touch panel includes a transparent conductor 22 (corresponding to the conductive material of the present invention), a transparent conductor 23, the transparent conductor 22, and the transparent conductor arranged so as to cover the surface of the transparent substrate 21. And an insulating cover layer 25 that generates capacitance between a contact object such as a finger and the transparent conductor 22 or the transparent conductor 23, and detects the position of the contact object such as a finger. To do. Depending on the configuration, the transparent conductors 22 and 23 may be configured integrally, and the insulating layer 24 or the insulating cover layer 25 may be configured as an air layer.
When the insulating cover layer 25 is touched with a finger or the like, the capacitance value between the finger and the transparent conductor 22 or the transparent conductor 23 changes. This change in capacitance value is detected by the external detection circuit, and the coordinates of the touched point are specified.
6 schematically illustrates the touch panel 20 as a projection capacitive touch panel through an arrangement in which the transparent conductor 22 and the transparent conductor 23 are viewed from the plane.
The touch panel 20 is provided with a plurality of transparent conductors 22 capable of detecting positions in the X-axis direction and a plurality of transparent conductors 23 in the Y-axis direction so as to be connectable to external terminals. The transparent conductor 22 and the transparent conductor 23 are in contact with a plurality of contact objects such as fingertips, and contact information can be input at multiple points.
When an arbitrary point on the touch panel 20 is touched with a finger, the coordinates in the X-axis direction and the Y-axis direction are specified with high positional accuracy.
In addition, as other structures, such as a transparent substrate and a protective layer, the structure of the said surface type capacitive touch panel can be selected suitably, and can be applied. Moreover, although the example of the pattern of the transparent conductor by the some transparent conductor 22 and the some transparent conductor 23 was shown in the touch panel 20, the shape, arrangement | positioning, etc. are not restricted to these.

An example of the resistive touch panel will be described with reference to FIG. In FIG. 7, the touch panel 30 includes a substrate 31 (corresponding to the conductive material of the present invention) on which a transparent conductor 32 is disposed, a plurality of spacers 36 disposed on the transparent conductor 32, and an air layer 34. Thus, the transparent conductor 33 that can contact the transparent conductor 32 and the transparent film 35 disposed on the transparent conductor 33 are supported and configured.
When the touch panel 30 is touched from the transparent film 35 side, the transparent film 35 is pressed, the pressed transparent conductor 32 and the transparent conductor 33 come into contact with each other, and a potential change at this position is not illustrated. By detecting with a circuit, the coordinates of the touched point are specified.

Display device with touch panel function:
The display device with a touch panel function of the present invention is not particularly limited as long as it has the conductive material of the present invention and has a touch panel function, and can be appropriately selected according to the purpose. A liquid crystal display device is preferred.
The liquid crystal display device is the same as the liquid crystal display device of the present invention, and the polarizing plate may be on the liquid crystal panel side or on the air side.
The touch panel function can be appropriately selected from those described above.

  Since the display device of the present invention and the display device with a touch panel function both have the conductive material of the present invention having excellent conductivity, transparency, and flexibility, the number of parts is small. Thus, it can be reduced in weight and thickness, and has display characteristics such as a high viewing angle, high contrast, and high image quality.

Liquid crystal display:
The display device of the present invention may be a liquid crystal display device, and is not particularly limited except that it includes the conductive material of the present invention, and can be appropriately selected according to the purpose.

The liquid crystal display device includes a color filter and a backlight, and further includes other members as necessary.
The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Investigative Research Institute, Inc., 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied, for example, to various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.
There is no particular limitation on the liquid crystal used in the liquid crystal display device, that is, the liquid crystal compound and the liquid crystal composition, and any liquid crystal compound and liquid crystal composition can be used.

  The liquid crystal display device of the present invention includes the conductive material of the present invention, a color filter, a liquid crystal layer, and a TFT substrate.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, “%” and “parts” as the contents are based on mass. In this example, “part” indicating the blending amount indicates “part by mass” unless otherwise specified.

In the following examples, the average minor axis length (average diameter) and average major axis length of the metal nanowires, the coefficient of variation of the minor axis length, and the ratio of silver nanowires having an aspect ratio of 10 or more are as follows. It was measured.
<Average minor axis length (average diameter) of metal nanowires>
Short axis length (diameter) and long axis length of 300 metal nanowires randomly selected from metal nanowires enlarged and observed using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.) Was measured, and the average minor axis length (average diameter) of the metal nanowires was determined from the average value.
<Coefficient of variation of minor axis length (diameter) of metal nanowires>
The short axis length (diameter) of 300 nanowires randomly selected from the electron microscope (TEM) image was measured, and the standard deviation and average value of the 300 nanowires were calculated.
<Ratio of silver nanowires with an aspect ratio of 10 or more>
Using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX), 300 short axis lengths of the silver nanowires were observed, the amount of silver transmitted through the filter paper was measured, and the short axis length was 50 nm. Silver nanowires having a major axis length of 5 μm or more were determined as the ratio (%) of silver nanowires having an aspect ratio of 10 or more.
The silver nanowires were separated when determining the ratio of silver nanowires using a membrane filter (Millipore, FALP 02500, pore size 1.0 μm).

(Preparation Example 1-A)
-Preparation of silver nanowire dispersion (1)-
The following additive solutions A, B, C, and D were prepared in advance.
[Additive liquid A]
Stearyltrimethylammonium chloride 60 mg, stearyltrimethylammonium hydroxide 10% aqueous solution 6.0 g, and glucose 2.0 g were dissolved in distilled water 120.0 g to obtain reaction solution A-1. Furthermore, 70 mg of silver nitrate powder was dissolved in 2.0 g of distilled water to obtain an aqueous silver nitrate solution A-1. The aqueous solution of silver nitrate A-1 was added while vigorously stirring the reaction solution A-1 at 25 ° C. 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]
25.6 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 (1) 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. The stirring was continued for 100 minutes after setting the stirring speed to 200 rpm, and then cooled to 25 ° C. The stirring speed was changed to 500 rpm, and additive solution D was added at 500 cc / min. This solution was used as the charged solution 101. Next, while vigorously stirring 1-propanol, the charged solution 101 was added at once so that the mixing ratio was 1: 1. Stirring was performed for 3 minutes to obtain a charged solution 102.
Using an ultrafiltration module with a molecular weight cut off of 150,000, ultrafiltration was performed as follows. After the feed solution 102 is concentrated four times, the addition and concentration of a mixed solution of distilled water and 1-propanol (volume ratio of 1: 1) is repeated until the conductivity of the filtrate finally becomes 50 μS / cm or less. It was. 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, the average major axis length, the coefficient of variation of the minor axis length of the silver nanowire, and the average aspect ratio were measured as described above.
As a result, the average minor axis length was 18.6 nm, the average major axis length was 5.0 μm, and the coefficient of variation was 15.0%. The average aspect ratio was 440. Hereinafter, when it describes with "silver nanowire aqueous dispersion (1-A)", the silver nanowire aqueous dispersion obtained by the said method is shown.

(Adjustment Example 1-B)
A silver nitrate solution 301 was prepared by dissolving 20 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 used as a reaction solution 301. 2.50 g of the silver nitrate solution 301 was added to the reaction solution 301 that was vigorously stirred while maintaining the aeration of nitrogen gas, and the mixture was heated and stirred for 1 minute. Furthermore, 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 302.
200 g of the silver nitrate solution 301 was added to the reaction solution 302 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 301 was added to this liquid which was kept at 90 ° C. and stirred at a stirring speed of 100 rpm at an addition speed of 0.5 cc / min. 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 301.
Using an ultrafiltration module with a molecular weight cut off of 150,000, ultrafiltration was performed as follows. Addition and concentration of a mixed solution of distilled water and 1-propanol (volume ratio 1: 1) 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 (3) having a metal content of 0.45%.
About the silver nanowire of the obtained silver nanowire dispersion liquid (3), the average minor axis length, the average major axis length, the coefficient of variation of the minor axis length of the silver nanowire, and the average aspect ratio were measured as described above.
As a result, the average minor axis length was 28.5 nm, the average major axis length was 5.2 μm, and the coefficient of variation was 18.6%. The average aspect ratio was 533. Hereinafter, when it describes with "silver nanowire dispersion liquid (1-B)", the silver nanowire dispersion liquid obtained by the said method is shown.

(Preparation Example 2)
-Production of PET substrate 101-
A bonding solution 1 was prepared with the following composition.
[Adhesive solution 1]
・ Takelac WS-4000 5.0 parts (polyurethane for coating, solid content concentration 30%, manufactured by Mitsui Chemicals, Inc.)
・ Surfactant 0.3 part (Narrow Acty HN-100, manufactured by Sanyo Chemical Industries)
・ Surfactant 0.3 part (Sandet BL, solid content concentration 43%, Sanyo Chemical Industries, Ltd.)
・ 94.4 parts of water

  A corona discharge treatment was applied to both surfaces of a 125 μm thick PET film, and the adhesive solution 1 was applied to the surface subjected to the corona discharge treatment and dried at 120 ° C. for 2 minutes to obtain a thickness of 0.11 μm. A first adhesive layer was formed on the PET substrate.

An adhesive solution 2 was prepared with the following composition.
[Adhesive solution 2]
・ Tetraethoxysilane 5.0 parts (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 3.2 parts of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 1.8 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Acetic acid aqueous solution (Acetic acid concentration = 0.05%, pH = 5.2) 10.0 parts ・ Curing agent 0.8 parts (Boric acid, manufactured by Wako Pure Chemical Industries, Ltd.)
Colloidal silica 60.0 parts (Snowtex O, average particle size 10 nm to 20 nm, solid content concentration 20%, pH = 2.6, manufactured by Nissan Chemical Industries, Ltd.)
・ Surfactant 0.2 part (Narrow Acty HN-100, Sanyo Chemical Industries Co., Ltd.)
・ Surfactant 0.2 parts (Sandet BL, solid content concentration 43%, Sanyo Chemical Industries, Ltd.)

  The bonding solution 2 was prepared by the following method. While stirring the aqueous acetic acid solution vigorously, 3-glycidoxypropyltrimethoxysilane was dropped into the aqueous acetic acid solution over 3 minutes. Next, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added to the acetic acid aqueous solution over 3 minutes with vigorous stirring. Next, tetraethoxysilane was added to the acetic acid aqueous solution over 5 minutes with vigorous stirring, and then stirring was continued for 2 hours. Next, colloidal silica, a curing agent, and a surfactant were sequentially added to prepare an adhesive solution 2.

  After the surface of the first adhesive layer formed on both surfaces of the PET substrate is subjected to corona discharge treatment, the adhesive solution 2 is applied to the surface by a bar coating method and heated at 170 ° C. for 1 minute. Then, a second adhesive layer having a thickness of 0.5 μm was formed, and the PET substrate 101 shown in FIG. 11 was obtained.

-Production of PET substrate 102-
After the corona discharge treatment of the surface of the PET substrate (thickness: 125 μm), 0.02% (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane aqueous solution was applied by a bar coating method to a coating amount of 8.8 mg / It was applied to m ² and dried at 100 ° C. for 1 minute to obtain a surface-treated PET substrate 102 (FIG. 12).

-Production of polycarbonate (PC) substrate 103-
After the surface of the polycarbonate substrate (thickness: 75 μm) was subjected to corona discharge treatment, 0.02% (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane aqueous solution was applied at a coating amount of 8.8 mg / bar by the bar coating method. It was applied to m ² and dried at 100 ° C. for 1 minute to obtain a surface-treated polycarbonate substrate 103.

-Fabrication of TAC substrate 104-
After corona discharge treatment of the surface of a TAC (triacetylcellulose: Fujitac) substrate (thickness 100 μm), 0.02% (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane aqueous solution is bar coated. The coating amount was 8.8 mg / m ² by the above method and dried at 100 ° C. for 1 minute to obtain a surface-treated TAC substrate 104.

(Production of Conductive Material T1 (Comparative Example 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 liquid was measured by GPC (polystyrene conversion), Mw was 4,400. 2.24 parts of the sol-gel solution and 17.76 parts of the silver nanowire aqueous dispersion (1-A) obtained in Preparation Example 1 are mixed, and further diluted with distilled water and 1-propanol to obtain a sol-gel coating liquid. It was. The solvent ratio of the obtained coating liquid was distilled water: 1-propanol = 60: 40. Amount of silver 0.015 g / m ² by a bar coating method on the above PET substrate 102 surface, after the total solid content in the coating solution was coated the above sol-gel coating solution so that 0.120 g / m ^2, 1 at 100 ° C. The sol-gel reaction was caused by drying for a minute to form a conductive layer.
<Solution of alkoxide compound>
・ 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

(Preparation of conductive materials T2 to T25 (Comparative Examples 2 to 5, Examples 1 to 23))
It produced similarly to electroconductive material T1 except having changed the board | substrate and the wet coating film thickness similarly to preparation of electroconductive material T1, and obtained electroconductive material T2-T25.

(Preparation of conductive material C2)
In the production of the conductive material 1, a conductive material C1 was obtained in the same manner as the production of the conductive material T1 except that the sol-gel solution was changed to the following solution A. The following solution B is applied onto the conductive material C2 by a bar coating method so that the solid content is 0.18 g / m ^2, and after drying, using an ultra-high pressure mercury lamp i line (365 nm) in a nitrogen atmosphere, It exposed with the exposure amount of 40 mJ / cm < ² >, and obtained the conductive material C2.

<Solution A>
・ Hydroxypropyl cellulose 5.0 parts ・ Distilled water 14.0 parts <Solution B>
Dipentaerythritol hexaacrylate 5.0 parts Photopolymerization initiator: 2,4-bis- (trichloromethyl) -6
[4- [N, N-bis (ethoxycarbonylmethyl) amino] -3-bromophenyl] -s-triazine 0.4 part / methyl ethyl ketone 13.6 parts

(Preparation of conductive material C3)
The conductive material C2 was manufactured in the same manner as the conductive material C2 except that the base material was changed to the TAC substrate 104.

(Preparation of conductive material C4)
The conductive material C2 was manufactured in the same manner as the conductive material C2 except that the base material was changed to the PC substrate 103.

<Patterning>
Patterning of the conductive layers of the conductive materials T1 to T25 and C2 to C4 was performed by a photolithography method using a positive resist.

<Positive resist formulation>
(Synthesis Example 1)
<Synthesis of Binder (A-1)>
Methacrylic acid (MAA) (7.79 g) and benzyl methacrylate (BzMA) (37.21 g) are used as monomer components constituting the copolymer, and AIBN (0.5 g) is used as a radical polymerization initiator. These were polymerized in a solvent PGMEA (55.00 g) to obtain a PGMEA solution (solid content concentration: 45% by mass) of the binder (A-1). The polymerization temperature was adjusted to 60 to 100 ° C.
The molecular weight was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight (Mw) in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2.21.

-Preparation of photosensitive composition (1)-
4.19 parts by mass of binder (A-1) (solid content: 40.0% by mass, PGMEA solution), TAS-200 represented by the following structural formula as a photosensitive compound (esterification rate: 66%, Toyo Gosei Co., Ltd.) 0.95 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.80 parts by mass, and 19.06 parts by mass of PGMEA as a crosslinking agent were added and stirred to prepare a photosensitive composition (1). did.

<< resist patterning process >>
On the conductive layer, the photosensitive composition (1) was applied with a bar to a dry film thickness of 5 μm, dried in an oven at 150 ° C. for 5 minutes, and a high-pressure mercury lamp i-line (365 nm) was applied from the mask to 60 mJ / cm ^2. (Illuminance 20 mW / cm ² ) Exposure was performed. The exposed conductive layer was subjected to shower development for 60 seconds with a 1% sodium hydroxide aqueous solution at 35 ° C. The shower pressure was 0.08 MPa, and the time until the stripe pattern appeared was 30 seconds. After rinsing with a shower of pure water, it was dried at 50 ° C. for 1 minute to produce a conductive layer 1 with a resist pattern.
Further, the exposure mask conforms to a solid exposure / unexposed portion and a comb-shaped electrode pattern (JIS Z 3197), and L / S = 10/10 μm, 15/15 μm, 20/20 μm, 50/50 μm, adjacent. A mask capable of forming an electrode overlap length of 15 mm) was used.

<< Etching process >>
The transparent conductive film 1 with a resist pattern is made to have a mass ratio of 1: 1: 6 of CP-48S-A liquid, CP-48S-B liquid (both manufactured by FUJIFILM Corporation) and pure water. The sample is immersed in an etching solution adjusted to 35 ° C. for 2 minutes to perform etching treatment, rinsed with a shower of pure water, blown off water on the surface of the sample with an air knife, and dried at 60 ° C. for 5 minutes. A patterned transparent conductive layer 1A with a pattern was produced.

<< Resist stripping process >>
The patterned transparent conductive layer 1A with a resist pattern was exposed to 100 mJ / cm ² (illuminance 20 mW / cm ² ) with a high-pressure mercury lamp i-line (365 nm) without masking. The exposed conductive layer was subjected to shower development for 75 seconds with an aqueous 2.38% tetramethylammonium hydroxide solution. The shower pressure was 0.1 MPa. After rinsing with a shower of pure water, water on the sample surface was blown off with an air knife and dried at 60 ° C. for 5 minutes to produce a patterned transparent conductive film 1 having a pattern shape shown in FIGS.

  For each obtained conductive material, in-plane retardation Re at a wavelength of 550 nm of the substrate, wet film thickness / average long axis length of metal nanowire, and matrix component / metal nanowire were evaluated by the method described later, and the results were It is shown in the table below.

<Measurement of in-plane retardation Re at wavelength 550 nm of substrate>
A value at an incident wavelength of 550 nm was measured using KOBRA-WR manufactured by Oji Scientific Instruments.

<Matrix component / Metal nanowire>
The weight ratio was calculated using the components (binder, surfactant, viscosity modifier, dispersant, etc.) excluding the metal nanowires and the solvent contained in the conductive layer coating solution as matrix components.

<Evaluation>
About each obtained conductive material, retardation, surface resistance, an optical characteristic (total light transmittance, haze), and an extinction ratio were evaluated by the method mentioned later, and the result was shown in the following table | surface.

<Surface resistance value>
The surface resistance of the conductive region of the conductive layer was measured using Loresta-GP MCP-T600 manufactured by Mitsubishi Chemical Corporation. The measurement was carried out by measuring the central part of five randomly selected conductive regions of a 10 cm × 10 cm sample to obtain an average value.

<Optical characteristics (total light transmittance)>
The total light transmittance (%) of the portion corresponding to the conductive region of the conductive material and the total light transmittance (%) of the substrate on which the conductive layer is formed are measured using a Gardner Hazeguard Plus, The transmittance of the conductive layer was converted from the ratio. The CIE visibility function y under the C light source was measured at a measurement angle of 0 °, and the average values were obtained by measuring the central portions of five randomly selected conductive regions of a 10 cm × 10 cm sample.

<Optical properties (haze)>
The haze value of the portion corresponding to the conductive region of the conductive material was measured using a haze guard plus manufactured by Gardner. The measurement was carried out by measuring the central part of five randomly selected conductive regions of a 10 cm × 10 cm sample to obtain an average value.

<Extinction ratio>
As for the extinction ratio of the produced conductive layer, the polarization degree P was measured using VAP-7070 manufactured by JASCO Corporation, and the extinction ratio D was calculated using the following conversion formula.
D = (1 + P) / (1-P)

<Orientation degree>
The SEM photograph of the coating film was taken, and the ratio of the number of metal nanowires in which the angle between the coating direction and the silver nanowire major axis falls within the range of −5 to + 5 ° with respect to arbitrary 500 metal nanowires was calculated. The major axis angle of the metal nanowire refers to an angle formed by a straight line connecting both ends of one metal nanowire and the coating direction. For example, FIG. 8a has a major axis angle of 25 ° and FIG. 8b has a major axis angle of 0 °.

  From the table, by setting the dry film thickness of the conductive layer to 0.001 to 0.1 times the average major axis length of the metal nanowires, even if the average minor axis length of the metal nanowires is 5 to 30 nm, the metal It can be seen that the degree of orientation of the nanowire and the extinction ratio are small. On the other hand, it turns out that a comparative example is inferior to an Example in the orientation degree of a metal nanowire, and an extinction ratio compared with an Example.

<Preparation of polarizing plate>
A polarizing plate (conductive material (301)) as shown in FIG. 9 was produced using the conductive member T7.

<Preparation of polarizing layer>
1. A long polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd., 9P75R) is immersed in a dyeing bath (30 ° C.) containing iodine and potassium iodide while being continuously conveyed through a guide roll. After performing 5 times the extending | stretching process, the extending | stretching process and bridge | crosslinking process which are 5 times in total were performed in the acidic bath (60 degreeC) which added boric acid and potassium iodide. The obtained iodine / PVA polarizing film having a thickness of about 30 μm was dried in a dryer at 50 ° C. for 30 minutes. In this manner, an iodine / PVA polarizing film (polarizing layer) was produced.

<Preparation of polarizing plate with conductive layer>
On both sides of the obtained iodine / PVA polarizing film (polarizing layer), an untreated TAC film (75 μm / Fujitac) was produced on one side via an acrylic adhesive layer having a thickness of 20 μm, and the opposite side was produced in Example 4. Bonded with conductive member T7. The polarizing layer adhesion surface was bonded to the opposite surface of the surface coated with the transparent conductive layer to produce a polarizing plate with a conductive layer (301).

<Evaluation of electromagnetic shielding properties>
As a result of measuring the electromagnetic wave shielding property of the polarizing plate with conductive layer (301) by the KEC method, the electromagnetic wave shielding property in the band of 10 MHz to 4 GHz is about 5 dB. It was confirmed that shielding was obtained.

<Manufacture of a display device with a touch panel using a polarizing plate with a conductive layer as an electromagnetic shielding material>
Using the polarizing plate with a conductive layer (301) as an electromagnetic wave shielding material and stacking as shown in FIG. 10, a display device with a touch panel capable of shielding electromagnetic waves from the LCD backlight was produced.

-Fabrication of touch panel 402-
A conductive layer of a conductive material was formed, and a transparent conductive film was formed on the glass substrate. Using the resulting transparent conductive film, "latest touch panel technology" (issued July 6, 2009, Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (December 2004) The touch panel shown in FIG. 8 was produced by the methods described in “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292”, and the like.
When the manufactured touch panel is used, it is excellent in visibility by improving the light transmittance, and for input of characters etc. or screen operation by at least one of bare hands, gloves-fitted hands, pointing tools by improving conductivity It was found that a touch panel with excellent responsiveness can be manufactured.

1 Cover glass 2 OCA
3 Touch Panel 4 Conductive Layer 5 Substrate 6 Polarizing Plate 7 LCD
8 Backlight 100 Conductive layer 200 Support 300 Antistatic layer

Claims (12)

A conductive layer including at least a metal nanowire having an average minor axis length of 5 to 30 nm on the substrate; and a dry film thickness of the conductive layer is about 0. 0 of an average major axis length of the metal nanowire. A conductive material having a ratio of 001 to 0.1. The conductive layer coating solution for forming the conductive layer includes at least a matrix component and the metal nanowires, and the concentration of the metal nanowires in the conductive layer coating solution is 0.01 wt% to 1.0 wt%, The conductive material according to claim 1, wherein a weight ratio of the matrix component to the metal nanowire is 0.5 to 15. The conductive material according to claim 1 or 2, wherein the extinction ratio of the single conductive layer is 1.5 or less. The conductive material according to claim 1, wherein the metal nanowire contains silver. The conductive material according to any one of claims 1 to 4, wherein the substrate is a transparent material having an in-plane retardation Re (550) having a wavelength of 550 nm and a high optical isotropy of 40 nm or less. The conductive material according to claim 1, wherein the substrate is a retardation plate. On a substrate, a conductive layer coating solution containing at least a metal nanowire having an average minor axis length of 5 to 30 nm and a matrix component, the wet film thickness of the conductive layer is 0. 0 of the average major axis length of the metal nanowire. The manufacturing method of the electrically-conductive material including apply | coating so that it may become 2-20 times. The conductive layer coating solution includes at least a matrix component and the metal nanowires, the metal nanowire concentration in the conductive layer coating solution is 0.01 wt% to 1.0 wt%, and the matrix component The method for producing a conductive material according to claim 7, wherein a weight ratio with respect to the metal nanowire is 0.5 to 15. A polarizing plate or a circularly polarizing plate comprising the conductive material according to claim 1. A display device or an input device comprising the conductive material according to claim 1. A display device or an input device comprising the polarizing plate or the circularly polarizing plate according to claim 9. A touch panel comprising the conductive material according to claim 1.

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