JP2012089361A - Conductive material and method for producing the same, and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive material that has a small haze value and an excellent visibility, and is small in view angle dependency of reflectance and reflection, to provide a method for producing a conductive material, and to provide a touch panel.SOLUTION: A conductive material includes a conductive layer at least containing metal nanowires having an average minor axis length of 50 nm or less and an average major axis length of 5 μm or more. The conductive layer contains a specific tetraazaindene compound and a specific mercapto tetrazole compound, and the metal nanowires contain silver and 1×10to 1×10moles of at least one metal selected from nickel, bismuth, tin, beryllium, chromium and rhodium per 1 mole of the silver.

Description

  The present invention relates to a conductive material, a method for manufacturing the conductive material, and a touch panel.

  In recent years, projection capacitive touch panels have been increasingly installed in smartphones, mobile personal computers, and the like. This projected capacitive touch panel can recognize touch points at the same time, so you can use two fingers to enlarge, reduce, and rotate objects on the display, and input chord information by simultaneously touching keyboard objects. Etc., and is more excellent as an input device than a resistive touch panel.

Here, ITO (indium tin oxide) is generally used as the transparent conductive material of the touch panel. However, in the case of a projection type capacitive type, ITO is a comb or diamond having a width of several millimeters. It is necessary to pattern into a shape called a mold. However, since ITO has a higher light reflectance than the substrate (glass or transparent resin), when used as a touch panel on a display, the pattern is visible due to reflection of external light, which deteriorates the visibility of objects on the display. There is a problem of end.
On the other hand, a transparent conductive film in which a silver wire having a thickness of submicron order on a support is formed in a random network (nonwoven fabric) shows transparency equivalent to that of ITO, conductivity (reciprocal of surface resistance), In particular, when formed on a flexible substrate such as polyethylene terephthalate (PET), it is superior in transparency and conductivity to ITO.

  By the way, there are (1) a method of forming a two-dimensional X-direction pattern and a Y-direction pattern on different planes, and (2) a two-dimensional pattern formation method of a projection capacitive touch panel diamond type or the like. There is a method of forming a pattern in the X direction and a pattern in the Y direction on the same plane. In (1), for example, there is a method in which patterns are separately formed on both surfaces of a single substrate, patterns are separately formed on two substrates, and the adhesive layers are sandwiched together. As the method (2), there is a method in which an X-direction pattern and a Y-direction pattern on the same plane are formed without short-circuiting using an insulating layer and a bridge (Patent Document 1, Patent Document 2, and Patent Document 3). reference).

The patterning method (2) for forming the XY pattern on the same plane is easier to align (XY pattern alignment) than the method (1) for forming a pattern on a different plane. When the XY pattern is formed on the same surface using a silver wire, it has been found that operation failure occurs earlier than ITO when the touch panel operation is continued in a high humidity state. It is considered that the cause of this malfunction is silver ion migration.
Therefore, an attempt has been made to add an organic silver adsorbent as a measure against silver ion migration. As a result, although silver ion migration is similar to that of ITO, haze increases and visibility of relatively dark images deteriorates. The current situation is that a new problem arises and a quick solution is desired.

JP 2008-65748 A JP 2010-44453 A JP 2010-33478 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a conductive material, a method for manufacturing the conductive material, and a touch panel that have low haze, low reflectivity and low viewing angle dependency, and excellent visibility.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a projected capacitive touch panel was produced by replacing the transparent conductive film made of metal nanowires (silver nanowires) with ITO. It was found that the external light reflection of the glass was equivalent to that of the substrate and did not hinder the visibility of the object displayed on the display.
In addition, as a result of detailed studies by the present inventors, when prepared by a method of synthesizing silver nanowires in a high temperature organic solvent, due to the thickness of the silver nanowire diameter, the haze is high and the image is relatively dark It was found that the object visibility deteriorated due to the scattering of external light at the silver nanowire pattern portion in the situation where the symbol is displayed, and the reflection is superior to ITO but the scattering is greatly inferior to ITO. On the other hand, when silver nanowires were prepared by a method of synthesizing in an aqueous solution, it was found that the diameter of the silver nanowires was small and the haze was low, so that the scattering of external light was slight and substantially equivalent to ITO.
Furthermore, when organic silver adsorbent is used as a measure against silver ion migration, the results of the present inventors' diligent investigation to solve the problem that haze increases and visibility of relatively dark images deteriorates. By adding at least one metal selected from nickel, bismuth, tin, beryllium, chromium and rhodium to silver, organic silver represented by the following general formula (I) and the following general formula (II) It has been found that even when an adsorbent is used in combination, the haze is restored and the deterioration of visibility can be prevented.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A conductive material having a conductive layer containing at least metal nanowires having an average minor axis length of 50 nm or less and an average major axis length of 5 μm or more,
The conductive layer contains a compound represented by the following general formula (I) and the following general formula (II),
The metal nanowire contains at least one metal selected from silver, nickel, bismuth, tin, beryllium, chromium, and rhodium, from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² per mol of the silver. It is a conductive material characterized by containing a molar amount.
However, in the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an unsubstituted or substituted alkyl group, Any of unsubstituted or substituted aryl group, unsubstituted or substituted amino group, hydroxy group, alkoxy group, alkylthio group, carbamoyl group, halogen atom, cyano group, carboxy group, alkoxycarbonyl group, and heterocyclic residue Represents R ¹ and R ² or R ² and R ³ may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R ¹ and R ³ represents a hydroxy group.
However, in the general formula (II), R ⁵ is substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH, and —NHR ^6. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR. ⁷ or an _-SO 2 ^{R 7.} R ⁷ represents a hydrogen atom, an alkyl group, or an aryl group.
<2> In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, It represents either a phenyl group or a hydroxy group, and at least one of R ¹ and R ³ is a hydroxy group,
In the general formula (II), R ⁵ is phenyl optionally substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —OH, —SO ₃ M, —COOM, and —NHR ^6. Group, or an alkyl group having 1 to 4 carbon atoms that may be substituted by —SO ₃ M, R ⁶ is —COR ⁷ , and R ⁷ is any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. M is the conductive material according to <1>, wherein M is any one of a hydrogen atom and an alkali metal atom.
<3> Any one of <1> to <2>, wherein the total content of the compounds represented by the general formula (I) and the general formula (II) is 0.01% by mass to 10% by mass with respect to silver. It is an electroconductive material as described in.
<4> The mixed mass ratio [general formula (I): general formula (II)] of the compound represented by general formula (I) and the compound represented by general formula (II) is 1:99 to 99: 1. The conductive material according to any one of <1> to <3>.
<5> The conductive material according to any one of <1> to <4>, wherein the conductive layer is patterned, and a distance between the formed patterns is 50 μm or less.
<6> On the base material, a conductive layer forming step of forming a conductive layer by applying a conductive layer composition containing at least metal nanowires;
An application step of applying to the conductive layer a liquid containing a compound represented by the following general formula (I) and
Is a method for producing a conductive material, comprising at least
However, in the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an unsubstituted or substituted alkyl group, Any of unsubstituted or substituted aryl group, unsubstituted or substituted amino group, hydroxy group, alkoxy group, alkylthio group, carbamoyl group, halogen atom, cyano group, carboxy group, alkoxycarbonyl group, and heterocyclic residue Represents R ¹ and R ² or R ² and R ³ may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R ¹ and R ³ represents a hydroxy group.
However, in the general formula (II), R ⁵ is substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH, and —NHR ^6. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR. ⁷ or an _-SO 2 ^{R 7.} R ⁷ represents a hydrogen atom, an alkyl group, or an aryl group.
<7> In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, It represents either a phenyl group or a hydroxy group, and at least one of R ¹ and R ³ is a hydroxy group,
In the general formula (II), R ⁵ is phenyl optionally substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —OH, —SO ₃ M, —COOM, and —NHR ^6. Group, or an alkyl group having 1 to 4 carbon atoms that may be substituted by —SO ₃ M, R ⁶ is —COR ⁷ , and R ⁷ is any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein M is a hydrogen atom or an alkali metal atom. The method for producing a conductive material according to <6>.
<8> The metal nanowire contains at least one metal selected from silver and nickel, bismuth, tin, beryllium, chromium, and rhodium, 1 × 10 ⁻⁴ mol to 1 × 10 6 per mol of the silver. It is a manufacturing method of the electrically-conductive material in any one of said <6> to <7> containing ^-2 mol.
<9> Furthermore, it is a manufacturing method of the electrically-conductive material in any one of said <6> to <8> including the patterning process which pattern-exposes and develops a conductive layer.
<10> A touch panel having a support film and a first sensor electrode array and a second sensor electrode array on the support film,
A first sensor electrode array and a second sensor electrode array are disposed on the same surface of the support film, and the first sensor electrode array and the second sensor electrode array are arranged orthogonally,
The distance between the first sensor electrode array and the second sensor electrode array is 50 μm or less,
The touch panel characterized in that the first sensor electrode array and the second sensor electrode array are formed using the conductive material according to any one of <1> to <5>.
<11> The first sensor electrode array and the second sensor electrode array are composed of a substantially square pad portion and a connecting portion that electrically connects the pad portion,
The touch panel according to <10>, wherein a distance between adjacent sides of the pad portion of the first sensor electrode array and the pad portion of the second sensor electrode array is 50 μm or less.

  According to the present invention, there are provided a conductive material and a method for manufacturing a conductive material, and a touch panel that can solve conventional problems, have low haze, have low reflectance and a low viewing angle dependency, and have excellent visibility. be able to.

FIG. 1 is a schematic cross-sectional view showing an example of a touch panel. FIG. 2 is a schematic view seen from the operation surface side after removing the protective film from the touch panel of FIG. FIG. 3 is a schematic cross-sectional view showing another example of the touch panel. FIG. 4 is a schematic explanatory diagram illustrating still another example of the touch panel. FIG. 5 is a schematic plan view showing an arrangement example of the conductive film in the touch panel shown in FIG. FIG. 6 is a schematic cross-sectional view showing another example of the touch panel.

(Conductive material)
The conductive material of the present invention has a conductive layer containing at least metal nanowires. The conductive material of the present invention may further have other layers such as a substrate, a photosensitive layer, an antifouling layer, a UV cut layer, and an antireflection layer.

The shape, structure, size, and the like of the conductive material are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a film shape and a sheet shape. Examples of the planar shape include a quadrangle and a circle. Examples of the structure include a single-layer structure and a laminated structure. The size can be appropriately selected depending on the application.
The conductive material has flexibility and is preferably transparent, and the transparent includes colorless and transparent, colored transparent, translucent, colored translucent and the like.
The conductive layer in the conductive material may be patterned or unpatterned. Examples of the patterning include patterning performed with an existing ITO transparent conductive film, and examples include a rectangular pattern and a diamond pattern.
When the conductive layer is patterned, the distance between the formed patterns (the distance between adjacent sides of adjacent patterns) is 50 μm or less, widening the effective area of the transparent electrode, This is preferable in terms of improving sensitivity and resolution and improving the visibility of display images.

<Conductive layer>
The conductive layer contains a metal nanowire and a compound represented by the following general formula (I) and the following general formula (II), a polymer, and further contains other components as required.

  In the present invention, it is necessary to use a compound represented by the following general formula (I) and the following general formula (II) in order to suppress silver ion migration, and this effect is represented by the following general formula (I). And it is an effect peculiar to the present invention that the insulating property between the electrodes, which is insufficient when each of the compounds represented by the following general formula (II) is used alone, is insufficient.

<< Compound Represented by Formula (I) (Tetrazaindene Compound) >>
However, in said general formula (I), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > may mutually be the same, may differ, a hydrogen atom, a C1-C20 ring, Unsubstituted or substituted alkyl group which may have a branch, monocyclic or bicyclic unsubstituted or substituted aryl group, unsubstituted or substituted amino group, hydroxy group, total carbon number of 1 to 20 An alkoxy group having 1 to 6 carbon atoms, a carbamoyl group optionally substituted with an aliphatic group or an aromatic group, a halogen atom, a cyano group, a carboxy group, and an alkoxycarbonyl group having 2 to 20 carbon atoms in total. Or a heterocyclic residue containing a 5- or 6-membered ring having a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. R ¹ and R ² or R ² and R ³ may be linked to form a 5-membered or 6-membered ring. However, at least one of R ¹ and R ³ represents a hydroxy group.
Among these, R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a hydroxy group. And at least one of R ¹ and R ³ is preferably a hydroxy group.

  Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-propyl group, an n-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, and a cyclopentylmethyl group. Octyl group, dodecyl group, tridecyl group, heptadecyl group and the like. Examples of the substituent in the substituted alkyl group include a monocyclic or bicyclic aryl group, a hetero residue, a halogen atom, a carboxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 19 or less carbon atoms, and a hydroxy group. Group and the like. Examples of the substituted alkyl group include benzyl group, phenethyl group, chloromethyl group, 2-chloroethyl group, trifluoromethyl group, carboxymethyl group, 2-carboxyethyl group, 2- (methoxycarbonyl) ethyl group, ethoxycarbonylmethyl. Group, 2-methoxyethyl group, hydroxymethyl group, 2-hydroxyethyl group and the like. Examples of the unsubstituted aryl group include a phenyl group and a naphthyl group. Examples of the substituent when the aryl group is substituted include, for example, an alkyl group having 4 or less carbon atoms, a halogen atom, a carboxy group, a cyano group, an alkoxycarbonyl group having 6 or less carbon atoms, a hydroxy group, and 6 or less carbon atoms. An alkoxy group etc. are mentioned. Examples of the substituted aryl group include p-tolyl group, m-tolyl group, p-chlorophenyl group, p-bromophenyl group, o-chlorophenyl group, m-cyanophenyl group, p-carboxyphenyl group, and o-carboxyphenyl. Group, p- (methoxycarbonyl) phenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, m-ethoxyphenyl group and the like. Examples of the substituent of the substituted amino group include an alkyl group (for example, a methyl group, an ethyl group, and a butyl group), an acyl group (for example, an acetyl group, a propionyl group, a benzoyl group, and a methylsulfonyl group). Examples of the group include a dimethylamino group, a diethylamino group, a butylamino group, and an acetylamino group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and a heptadecyloxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, and a hexylthio group. The carbamoyl group may have one or two alkyl groups having 20 or less carbon atoms or aryl groups having 2 or less rings as a substituent. Examples of the substituted carbamoyl group include a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group, and a phenylcarbamoyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. The heterocyclic residue may be a single ring or may have 2 to 3 condensed rings, such as a furyl group, a pyridyl group, a 2- (3-methyl) benzothiazolyl group, and a 1-benzotriazolyl group. Etc.

Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.
Among these, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is particularly preferable from the viewpoint of preventing silver ion migration.

<< Compound Represented by Formula (II) (Mercaptotetrazole Compound) >>
However, in the general formula (II), R ⁵ is substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH, and —NHR ^6. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR. ⁷ or an _-SO 2 ^{R 7.} R ⁷ represents a hydrogen atom, an alkyl group, or an aryl group.

In the general formula (II), R ⁵ represents an organic residue which may be substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH and —NHR ^6. Specifically, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group), and an aryl group having 6 to 14 carbon atoms (for example, a phenyl group and naphthyl group) Group).

Each group represented by R ⁵ in the general formula (II) may be further substituted, and examples of the substituent include the following. Halogen atom (fluorine, chlorine, bromine, iodine), cyano, nitro, ammonio (eg, trimethylammonio, etc.), phosphonio, sulfo (including salt), sulfino (including salt), carboxy (including salt), phosphono (Including salts), hydroxy, mercapto, hydrazino, alkyl (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), alkenyl (eg, allyl, 2-butenyl) , 3-pentenyl), alkynyl (eg, propargyl, 3-pentynyl), aralkyl (eg, benzyl, phenethyl), aryl (eg, phenyl, naphthyl, 4-methylphenyl), heterocycle (eg, pyridyl, furyl, imidazolyl). , Piperidyl, morpholino), alkoxy (Eg, methoxy, ethoxy, butyloxy), aryloxy (eg, phenoxy, 2-naphthyloxy), alkylthio (eg, methylthio, ethylthio), arylthio (eg, phenylthio), amino (eg, unsubstituted amino, methylamino) Dimethylamino, ethylamino, alinino), acyl (eg acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (eg phenoxycarbonyl), carbamoyl (eg none Substituted carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl), acyloxy (eg, acetoxy, benzoyloxy), acylamino ( For example, acetylamino, benzoylamino), alkoxycarbonylamino (eg, methoxycarbonylamino), aryloxycarbonylamino (eg, phenoxycarbonylamino), ureido (eg, unsubstituted ureido, N-methylureido, N-phenylureido) ), Alkylsulfonylamino (eg methylsulfonylamino), arylsulfonylamino (eg phenylsulfonylamino), alkylsulfonyloxy (eg methylsulfonyloxy), arylsulfonyloxy (eg phenylsulfonyloxy), alkylsulfonyl (eg , Mesyl), arylsulfonyl (eg, tosyl), alkoxysulfonyl (eg, methoxysulfonyl), aryloxysulfonyl (eg, phenoxy) Noxysulfonyl), sulfamoyl (eg, unsubstituted sulfamoyl, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), alkylsulfinyl (eg, methylsulfinyl), arylsulfinyl ( For example, phenylsulfinyl), alkoxysulfinyl (for example, methoxysulfinyl), aryloxysulfinyl (for example, phenoxysulfinyl), phosphoric acid amide (for example, N, N-diethylphosphoric acid amide) and the like. These groups may be further substituted. Moreover, when there are two or more substituents, they may be the same or different.

Here, when there are two or more substituents —SO ₃ M, —COOM, —OH and —NHR ⁶ of R ⁵ , they may be the same or different.

In the general formula (II), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR ⁷ , or —SO ₂ R ⁷ , and R ⁷ represents a hydrogen atom, 1 carbon atom. Represents an alkyl group (for example, methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, dodecyl group, octadecyl group) or aryl group (for example, phenyl group, naphthyl group). These groups may be substituted with the substituents exemplified as the substituent for R ⁵ .

  In the general formula (II), M represents a hydrogen atom, an alkali metal atom (for example, lithium, sodium, potassium, etc.), a quaternary ammonium (for example, ammonio, tetramethylammonio, benzyltrimethylammonio, tetrabutylammonio, etc.). Or quaternary phosphonium (eg, tetramethylphosphonio and the like).

In the general formula (II), R ⁵ may be substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —OH, —SO ₃ M, —COOM, and —NHR ^6. A phenyl group, or an alkyl group having 1 to 4 carbon atoms that may be substituted by —SO ₃ M; R ⁶ is —COR ⁷ ; and R ⁷ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. And M is preferably either a hydrogen atom or an alkali metal atom.
More preferably, R ⁵ is a phenyl group substituted with —SO ₃ M, a phenyl group substituted with —COOM, a phenyl group substituted with —NHR ⁶ , or an alkyl group having 1 to 4 carbon atoms substituted with —SO ₃ M. , -COOM is a substituted alkyl group having 1 to 4 carbon atoms, R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -COR ⁷ , and R ⁷ is a hydrogen atom or a hydrophilic group (for example, A C1-C4 alkyl group substituted by a carboxyl group, a sulfo group, or a hydroxy group, and M is a hydrogen atom or a sodium atom. Particularly preferably, R ⁵ is a phenyl group substituted with —SO ₃ M or a phenyl group substituted with —COOM.

Hereinafter, although the specific example of a compound represented with the said general formula (II) is shown, this invention is not limited to these.

  Among these, when 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is used as the first silver ion migration inhibitor, the second silver ion migration is performed from the viewpoint of preventing silver ion migration. As the inhibitor, 1-phenyl-5-mercapto-1H-tetrazole is particularly preferred.

The total content of the compounds represented by the general formula (I) and the general formula (II) is preferably 0.01% by mass to 10% by mass, and 0.02% by mass to 5% by mass with respect to silver. More preferably, 0.05 mass%-1 mass% are still more preferable.
When the total content is less than 0.01% by mass with respect to silver, the silver ion migration effect may be substantially lost. When the total content exceeds 10% by mass with respect to silver, the conductivity decreases. Or may promote silver ion migration.
The mixing mass ratio of the compound represented by the general formula (I) and the compound represented by the general formula (II) [general formula (I): general formula (II)] is 1:99 to 99: 1. It is preferable that it is 10: 90-90: 10.
When the proportion of the compound represented by the general formula (I) is less than 1% by mass, the silver ion migration effect may be substantially lost, and when it exceeds 99% by mass, the conductivity may be lowered. In some cases, silver ion migration may be promoted.

<< Metal nanowires >>
As the material of the metal nanowire, at least one metal selected from silver and nickel, bismuth, tin, beryllium, chromium, and rhodium is used. Among these, nickel is particularly preferable from the viewpoint of visibility.
Said nickel, bismuth, tin, beryllium, chromium, and the content of at least one metal selected from rhodium (metal other than silver), the per mol of silver, 1 × 10 ^-4 mol to 1 × 10 ^{- 2} moles. When the content of the metal other than silver is less than 1 × 10 ⁻⁴ mol per 1 mol of silver, the effect of preventing deterioration of display visibility may be insufficient, and when it exceeds 1 × 10 ⁻² mol. In some cases, metal nanowires may aggregate to deteriorate display visibility.
Here, the content of the metal other than silver can be measured, for example, by atomic absorption, ICP-MS (inductively coupled plasma-mass spectrometry), fluorescent X-ray analysis, or the like.
There is no restriction | limiting in particular as a method of making the said silver contain a metal other than silver, Although it can select suitably according to the objective, For example, (1) Add metal salts other than silver as aqueous solution during metal wire formation (2) A method in which a metal wire-containing layer obtained by coating a metal wire is immersed in an aqueous solution of a metal salt other than silver, and (3) a metal is electrochemically deposited using the metal wire-containing layer as a conductive layer. And the like.

-Shape-
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.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).

−Average minor axis length diameter and average major axis length−
The metal nanowire has an average minor axis length (sometimes referred to as “average minor axis diameter” or “average diameter”) of 50 nm or less, preferably 1 nm to 50 nm, more preferably 10 nm to 40 nm, and more preferably 15 nm. More preferably, ˜35 nm.
When the average minor axis length exceeds 50 nm, scattering due to metal nanowires occurs, and sufficient transparency may not be obtained. When the average minor axis length is less than 1 nm, oxidation resistance deteriorates and durability May get worse.
The average minor axis length of the metal nanowires was observed using 300 transmission metal microscopes (TEM, manufactured by JEOL Ltd., 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.

As the average major axis length of the metal nanowire (sometimes referred to as "average length"),
5 μm or more, preferably 5 μm to 40 μm, more preferably 5 μm to 35 μm, and still 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 nanowires is, for example, observed with 300 metal nanowires using a transmission electron microscope (TEM, manufactured by JEOL Ltd., 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.

-Aspect ratio-
The aspect ratio of the metal nanowire is preferably 10 or more. The aspect ratio generally means the ratio between the long side and the short side of the metal nanowire (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 major axis length and the minor axis length of the metal nanowire separately.

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 to 1,000,000, and preferably 100 to 1,000,000. Is more preferable.
When the aspect ratio is less than 10, network formation by the metal nanowires may not be performed and sufficient conductivity may not be obtained. When the aspect ratio exceeds 1,000,000, the metal nanowires may be formed or handled thereafter. In this case, since the metal nanowires are entangled and aggregate before film formation, a stable liquid may not be obtained.

-Ratio of metal nanowires with an aspect ratio of 10 or more-
The ratio of the metal nanowires having an aspect ratio of 10 or more is preferably 50% or more, more preferably 60% or more, and even more preferably 75% or more in volume ratio in the total conductive composition. 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 50%, the conductive material that contributes to the conductivity may decrease and the conductivity may decrease. At the same time, a voltage concentration occurs 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.

  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 short axis length of 300 metal nanowires and examining their distribution, the short axis length is 200 nm or less and the long axis length It confirms that it is metal nanowire whose length is 1 micrometer or more. The filter paper has a short axis length of 200 nm or less in a TEM image, and the longest axis of particles other than metal nanowires having a long axis length of 1 μm or more is measured and is at least twice the longest axis. And it is preferable to use the thing of the length below the shortest length of the long axis of metal nanowire.

  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.

-Manufacturing method-
There is no restriction | limiting in particular as a manufacturing method of the said metal nanowire, Although it may manufacture by what kind of method, a metal ion is reduce | restored, heating in the solvent which melt | dissolved the halogen compound and the dispersion additive as follows. It is preferable to manufacture by.
Moreover, as a manufacturing method of the said 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, for example. Can be used.

The solvent is preferably a hydrophilic solvent, and examples thereof include water, alcohols, ethers, and ketones. These may be used alone or in combination of two or more.
Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, and ethylene glycol.
Examples of the ethers include dioxane and tetrahydrofuran.
Examples of the ketones include acetone.

As heating temperature at the time of the said heating, 250 degrees C or less is preferable, 20 to 200 degreeC is more preferable, 30 to 180 degreeC is further more preferable, and 40 to 170 degreeC is especially preferable.
If the heating temperature is less than 20 ° C., the lower the heating temperature, the lower the nucleation probability, and the metal nanowires become too long, so the metal nanowires are likely to be entangled, and the dispersion stability may deteriorate. When it exceeds 250 ° C., the corner of the cross section of the metal nanowire becomes steep, and the transmittance in the evaluation of the coating film may be lowered.
If necessary, the temperature may be changed during the formation process of the metal nanowires, and the monodispersity by controlling the nucleation of metal nanowires, suppressing renucleation, and promoting selective growth by changing the temperature during the process. The improvement effect can be improved.

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, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione and the like can be mentioned. Among these, reducing sugars, sugar alcohols as derivatives thereof, and ethylene glycol are particularly preferable.
Examples of the borohydride metal salt include sodium borohydride and potassium borohydride.
Examples of the aluminum hydride salt include lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride.
Examples of the alkanolamine include diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, dimethylaminopropanol, and the like.
Examples of the aliphatic amine include propylamine, butylamine, dipropyleneamine, ethylenediamine, and triethylenepentamine.
Examples of the heterocyclic amine include piperidine, pyrrolidine, N-methylpyrrolidine, and morpholine.
Examples of the aromatic amine include aniline, N-methylaniline, toluidine, anisidine, and phenetidine.
Examples of the aralkylamine include benzylamine, xylenediamine, and N-methylbenzylamine.
As said alcohol, methanol, ethanol, 2-propanol etc. are mentioned, for example.
Examples of the organic acids include citric acid, malic acid, tartaric acid, citric acid, succinic acid, ascorbic acid, and salts thereof.
Examples of the reducing saccharide include glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose and the like.
Examples of the sugar alcohols include sorbitol.

  Depending on the reducing agent, it may function as a dispersion additive or a solvent as a function, and can be preferably used in the same manner.

In the production of the metal nanowire, it is preferable to add a dispersion additive and a halogen compound or metal halide fine particles.
The timing of the addition of the dispersion additive and the halogen compound may be before or after the addition of the reducing agent, and may be before or after the addition of metal ions or metal halide fine particles, but is better in monodispersity. In order to obtain metal nanowires, it is preferable to add the halogen compound in two or more stages.

The dispersion additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an amino group-containing compound, a thiol group-containing compound, a sulfide group-containing compound, an amino acid or a derivative thereof, a peptide compound, and a polysaccharide. Synthetic polymers, gels derived from these, and the like. Among these, gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinyl pyrrolidone, and polyvinyl pyrrolidone copolymer are particularly preferable.
For the structure that can be used as the dispersion additive, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
Moreover, the shape of the metal nanowire obtained can also be changed with the kind of dispersion additive to be 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 Further preferred are alkali halides such as potassium bromide, potassium chloride and potassium iodide, and compounds that can be used in combination with the dispersion additives described below.
Some halogen compounds may function as a dispersion additive, but can be preferably used in the same manner.

  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.

  The dispersant and the halogen compound may be used in the same substance. Examples of the compound in which the dispersant and the halogen compound are used in combination include, for example, HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion, HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion, and an amino group. And bromide or chloride ion containing dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride , Dilauryl dimethyl ammonium bromide, dilauryl dimethyl ammonium Umukurorido, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride, and the like.

  The desalting treatment can be performed by techniques such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming metal nanowires.

<< Polymer >>
As the polymer, both a water-soluble polymer and a water-insoluble polymer can be suitably used.

-Water-soluble polymer-
The water-soluble polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, gelatin, gelatin derivatives, casein, agar, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethylcellulose, hydroxyethylcellulose , Polyvinyl pyrrolidone, dextran, and the like. These may be used individually by 1 type and may use 2 or more types together.
The mass ratio (A / B) of the metal nanowire content (A) and the water-soluble polymer content (B) is preferably 0.2 to 3.0, and preferably 0.5 to 2.5. More preferred.
When the mass ratio (A / B) is less than 0.2, there is a concern that the amount of the polymer is excessive with respect to the metal nanowire, and the resistance increases due to a slight variation in the coating amount. If it exceeds, the film strength may not be practically sufficient due to the small amount of polymer.

-Water-insoluble polymer-
The water-insoluble polymer has a function as a binder, and is a polymer that does not substantially dissolve in water near neutrality. The water-insoluble polymer specifically means a polymer having an SP value (calculated by the Okitsu method) of 18 MPa ^{1/2 to} 30 MPa ^1/2 .

As the SP value ^is preferably 18MPa ^1/2 ~30MPa ^1/2, more preferably 19MPa ^1/2 ~28MPa ^1/2, more preferably 19.5MPa ^1/2 ~27MPa 1/2.
The SP value is less than ^{18 MPa 1/2,} there are cases where to wash the adhered organic stains difficult, exceeds ^{30 MPa 1/2,} the higher the affinity for water, the coating film The conversion efficiency may decrease when a solar cell is manufactured, for example, because the absorption in the infrared region is increased due to the increase in water content.

Here, the SP value is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula. ΔF is a value described in the literature.
SP value (δ) = ΣΔF (Molar Attraction Constants) / V (molar volume)
When using a plurality of water-insoluble polymers, the SP value (σ) and the hydrogen bond term (σh) of the SP value are calculated by the following equations.

However, σn is the hydrogen bond term of the SP value or SP value of the water-insoluble polymer and water, Mn is the molar fraction of the water-insoluble polymer and water in the mixed solution, and Vn is the molar volume of the solvent. , N each represents an integer of 2 or more representing the type of solvent.

The water-insoluble polymer is not particularly limited as long as the SP value is 18 MPa ^{1/2 to} 30 MPa ^1/2 , but is not ethylenic in terms of adhesion of the coating film to the substrate and durability against sliding. Polymers having saturated groups are preferred. Among these, it is preferable that the side chain connected to the main chain contains at least one ethylenically unsaturated bond. A plurality of the ethylenically unsaturated bonds may be contained in the side chain. The ethylenically unsaturated bond may be included in the side chain of the water-insoluble polymer together with the branched and / or alicyclic structure and / or the acidic group.

The ethylenically unsaturated bond is bonded to the main chain of the water-insoluble polymer via at least one ester group (—COO—), and the water-insoluble polymer is composed of only the ethylenically unsaturated bond and the ester group. The side chain may be constituted. Further, it may have a divalent organic linking group between the main chain of the water-insoluble polymer and the ester group and / or between the ester group and the ethylenically unsaturated bond. The saturated bond may constitute a side chain of the water-insoluble polymer as “group having an ethylenically unsaturated bond”.
Examples of the divalent organic linking group include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, etc., (meth) acrylates, vinyl esters, (meth ) Acrylamides are preferred, and (meth) acrylates are particularly preferred.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
The method for introducing a (meth) acryloyl group into the side chain of the water-insoluble polymer is not particularly limited and may be appropriately selected from known methods. For example, an epoxy group may be added to a repeating unit having an acidic group. Of adding (meth) acrylate having a hydroxyl group, adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and adding a (meth) acrylate having a hydroxyl group to a repeating unit having an isocyanate group Etc.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, and can be appropriately selected according to the purpose. For example, it is represented by the following structural formula (1). And a compound represented by the following structural formula (2) are preferred.

However, in the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

In the Structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Among the compounds represented by the structural formula (1) and the structural formula (2), when used as a negative-type or positive-type resist in combination with a photocurable resin, in terms of good developability and film strength, A compound represented by the structural formula (1) is preferred. In the structural formulas (1) and (2), L ¹ and L ² are each independently more preferably an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) and Structural formula (2), For example, the following compounds (1)-(10) are mentioned.

As for mass ratio (A / C) of content (A) of the said metal nanowire, and content (C) of the said water-insoluble polymer, 0.2-3.0 are preferable, 0.5-2.5 Is more preferable.
If the mass ratio (A / C) is less than 0.2, there may be a problem of variation in resistance due to variation in coating amount, or the action of the solution in the present invention may be reduced. If it exceeds 1, practically sufficient strength may not be obtained in the coating film.
The content of the metal nanowires (coating amount) ^{is preferably,} more preferably 0.01g / ^{m 2} ~0.45g / m 2 it is ^{0.005g / m 2 ~0.5g / m 2} , 0 More preferably, it is .015 g / m ^{2 to} 0.4 g / m ² .

-Dispersant-
The dispersant is used to prevent and disperse the metal nanowires. 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 low molecular pigment dispersant or polymer pigment dispersant can be used. In particular, a polymer dispersant having a property of adsorbing to metal nanowires is preferably used. Polyvinylpyrrolidone, BYK series (manufactured by Big Chemie), Solsperse series (manufactured by Nihon Lubrizol), Ajisper series (Ajinomoto Co., Inc.) Company-made).

  As content of the said dispersing agent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of said polymers, 0.5 mass part-40 mass parts are more preferable, and 1 mass part-30 mass parts are. Further preferred. If the content is less than 0.1 parts by mass, metal nanowires may aggregate in the dispersion, and if it exceeds 50 parts by mass, a stable coating film cannot be formed in the coating process. Application unevenness may occur.

-Other ingredients-
Examples of the other components include various additives such as surfactants, antioxidants, sulfurization inhibitors, metal corrosion inhibitors, viscosity modifiers, preservatives, and the like as necessary.

<Base material>
There is no restriction | limiting in particular about the shape, structure, size, etc. of the said base material, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned as said shape. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.

There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, a transparent substrate, a synthetic resin sheet (film), a metal substrate, a ceramic board, a semiconductor substrate which has a photoelectric conversion element, etc. Is mentioned. If necessary, the substrate can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like.
Examples of the transparent glass substrate include white plate glass, blue plate glass, and silica-coated blue plate glass.
Examples of the synthetic resin sheet include a polyethylene terephthalate (PET) sheet, a polycarbonate sheet, a polyethersulfone sheet, a polyester sheet, an acrylic resin sheet, a vinyl chloride resin sheet, an aromatic polyamide resin sheet, a polyamideimide sheet, and a polyimide sheet. Is mentioned.
Examples of the metal substrate include an aluminum plate, a copper plate, a nickel plate, and a stainless plate.

The total visible light transmittance of the substrate is preferably 70% or more, more preferably 85% or more, and still more preferably 90% or more. If the total visible light transmittance is less than 70%, the transmittance may be low and may cause a problem in practical use.
In the present invention, a substrate that is colored to the extent that the object of the present invention is not hindered can also be used.

There is no restriction | limiting in particular as thickness of the said base material, Although it can select suitably according to the objective, 1 micrometer-500 micrometers are preferable, 3 micrometers-400 micrometers are more preferable, and 5 micrometers-300 micrometers are still more preferable.
If the thickness is less than 1 μm, the yield may decrease due to difficulty in handling in the coating process, and if it exceeds 500 μm, the thickness and mass may be a problem in portable applications. is there.

-Other layers-
In this invention, when the said conductive layer does not contain a photosensitive material (a binder, a photosensitive compound), it is preferable to have a photosensitive layer between the said base material and the said conductive layer, or on the said conductive layer.

(Method for producing conductive material)
The method for producing a conductive material of the present invention includes at least a conductive layer forming step, and includes an applying step, a patterning step, and other steps as necessary.

<Conductive layer formation process>
The said conductive layer formation process is a process of apply | coating the conductive layer composition containing a metal nanowire at least on a base material, and forming a conductive layer.
The conductive layer composition contains metal nanowires and a polymer, and further contains other components as necessary.

The substrate, the metal nanowire, and the polymer can be appropriately selected from those described above.
There is no restriction | limiting in particular as the application | coating method of the said conductive layer composition, According to the objective, it can select suitably, For example, a bar coat method, a spin coat method, a roll coat method, a slit coat method etc. are mentioned.

The coating amount of the metal nanowires as (content) is not particularly limited and may be appropriately selected depending on the intended ^purpose, it is preferably ^{0.005g / m 2 ~0.5g / m 2} , 0 more preferably ^{.01g / m 2 ~0.45g / m 2} , 0.015g / m 2 ~0.4g / m 2 is more preferable.
When the coating amount is less than 0.005 g / m ² , there may be a portion where the resistance is locally increased, and the in-plane resistance distribution may be deteriorated, and when it exceeds 0.5 g / m ^2. The haze may deteriorate due to the aggregation of metal nanowires during drying after coating.

There is no restriction | limiting in particular as thickness of the said conductive layer, According to the objective, it can select suitably, 20 nm-5,000 nm are preferable, 25 nm-4,000 nm are more preferable, 30 nm-3,500 nm are still more preferable.
If the thickness is less than 20 nm, the average minor axis length of the metal nanowires is not changed, and the film strength may be reduced. If the thickness exceeds 5,000 nm, the conductive layer is cracked and transmitted. Rate and haze may deteriorate.

<Granting process>
The application step is a step of applying a liquid containing a compound represented by general formula (I) and general formula (II) to the conductive layer.

As the compounds represented by the general formula (I) and the general formula (II), the same materials as the conductive material can be used.
There is no restriction | limiting in particular as a solvent used for melt | dissolving the compound represented by the said general formula (I) and the said general formula (II), According to the objective, it can select suitably, For example, water, methanol, Examples thereof include alcohols such as ethanol, propanol, isopropanol, butanol and ethylene glycol; ethers such as dioxane and tetrahydrofuran; ketones such as acetone.
There is no restriction | limiting in particular as said provision method, According to the objective, it can select suitably, For example, the apply | coating method, the impregnation method, the spray method, the immersion method etc. are mentioned.

<Patterning process>
The patterning step is a step of pattern-exposing and developing the conductive layer.
As the exposure method, surface exposure using a photomask may be performed, 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.

The development is a step of developing the exposed portion or the non-exposed portion of the conductive layer by applying a solvent.
As the solvent, 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.

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. Specifically, a method of immersing the conductive material of the present invention in an alkaline solution, a method of pouring an organic solvent into the conductive material of the present invention using a shower or spray, and an alkaline solution for the conductive material of the present invention. For example, a method of applying with a dipped napkin. Among these, the method of immersing the conductive material of the present invention in an alkaline solution 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.

The surface resistance of the conductive layer in the conductive material of the present invention is preferably 0.1Ω / □ to 5,000Ω / □, and more preferably 0.1Ω / □ to 30Ω / □.
The surface resistance can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation).
The light transmittance of the conductive layer in the conductive material of the present invention is preferably 70% or more, and more preferably 80% or more.
Here, the light transmittance can be measured by, for example, a self-recording spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation).

  The conductive material of the present invention has high permeability, low resistance, improved durability and flexibility, and can be easily patterned. For example, a touch panel, a display electrode, an electromagnetic wave shield, an organic EL display electrode It is widely applied to electrodes for inorganic EL displays, electronic paper, electrodes for flexible displays, integrated solar cells, display elements, and other various devices. Among these, the touch panel described below is particularly preferable.

(Touch panel)
The touch panel of the present invention 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 electrostatic Examples include a capacitive touch panel and a resistive touch panel. 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.

  The touch panel of the present invention is a touch panel having a support film and a first sensor electrode array and a second sensor electrode array on the support film, wherein the first sensor electrode array and the first sensor electrode array The second sensor electrode array is arranged, the first sensor electrode array and the second sensor electrode array are orthogonally arranged, and the distance between the first sensor electrode array and the second sensor electrode array is 50 μm. The first sensor electrode array and the second sensor electrode array are formed using the conductive material of the present invention.

  The first sensor electrode array and the second sensor electrode array are composed of a substantially square pad portion and a connecting portion that electrically connects the pad portion, and the pad portion of the first sensor electrode array The distance between sides adjacent to the pad portion of the second sensor electrode array is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm. When the distance is 50 μm or less, the gap between the sides is inconspicuous, which is preferable in terms of improving the visibility of the display image. The distance between the adjacent sides is preferably 5 μm or more, and more preferably 10 μm or more.

Here, a single area layer type capacitive touch panel will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of the touch panel 110. In the touch panel 110 shown in FIG. 1, a first electrode pattern 112 made of a transparent conductive film and a second electrode pattern 114 made of a transparent conductive film are formed on the same surface on one surface of a transparent transparent substrate 111. Thus, a sensor unit 120 for detecting a change in capacitance is formed. A protective film 115 is laminated on the sensor unit 120.
The first electrode pattern 112 and the second electrode pattern 114 are formed by laminating the conductive material of the present invention on the transparent substrate 111. As a method for forming these electrode patterns, (1) the conductive material of the present invention is applied and dried, and an unnecessary portion is removed by exposing and developing with a mask corresponding to the electrode pattern. There are a method of forming an electrode pattern, and (2) a method of forming an electrode pattern by applying and drying the conductive material of the present invention and applying an etching ink in which metal nanowires are dissolved to the electrode pattern.
The first electrode pattern 112 and the second electrode pattern 114 are formed on the same surface so as to be electrically separated from each other. At this time, since at least one of the electrode patterns is not electrically connected between the pad portion and the pad portion, it is necessary to electrically connect using a metal wiring called a jumper.

FIG. 2 is a schematic view seen from the operation surface side of the touch panel 110 with the protective film 115 removed.
One row of X electrode bodies 112a constituting the first electrode pattern 112 has a rhombus shape and a plurality of X electrodes 112b and X electrodes 112b adjacent to each other in the X direction, which is the horizontal direction of the panel, are connected by an X conduction portion 112c. is there. A plurality of rows of X electrode bodies 112a connected in the horizontal direction are arranged.
A row of Y electrode bodies 114a constituting the second electrode pattern 114 has a rhombus shape and a plurality of Y electrodes 114b arranged in a matrix with the X electrodes, and adjacent to the Y direction which is the vertical direction of the panel. 114b are connected by the Y conduction | electrical_connection part 114c.
A plurality of rows of Y electrode bodies 114a connected in the vertical direction are arranged.
The first electrode pattern 112 and the second electrode pattern 114 are alternately arranged on the panel so that the X electrode 112b and the Y electrode 114b do not overlap, and the X conductive portion 112c and the Y conductive portion 114c are crossed. In addition, the X electrode body 112a and the Y electrode body 114a are arranged in a grid pattern. The first electrode pattern 112 and the second electrode pattern 114 are formed such that the distance between adjacent sides is 50 μm or less. Note that the X conductive portion 112c or the Y conductive portion 114c can be a single-sided transparent conductive film by using a metal wiring called a jumper.

Next, an example of a surface capacitive touch panel will be described with reference to FIG. In FIG. 3, 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), and the transparent conductive material at the end of the transparent substrate 11. An electrode terminal 18 for electrical connection with an external detection circuit (not shown) is formed on the body 12.
In FIG. 3, 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. 4, the touch panel 20 includes a transparent conductor 22 (corresponding to the conductive material of the present invention), a transparent conductor 23, a transparent conductor 22, and a transparent conductor arranged so as to cover the surface of the transparent substrate 21. An insulating layer 24 that insulates the body 23, and an insulating cover layer 25 that generates a capacitance between a contact object such as a finger and the transparent conductor 22 or the transparent conductor 23, and is positioned with respect to the contact object such as a finger Detect. 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.
5 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. 6, 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.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of Binder (A-1)>
7.79 g of methacrylic acid (MAA) and 37.21 g of benzyl methacrylate (BzMA) are used as monomer components constituting the copolymer, and 0.5 g of azobisisobutyronitrile (AIBN) is used as a radical polymerization initiator. And a polymerization reaction in 55.00 g of propylene glycol monomethyl ether acetate (PGMEA) using these as a solvent to obtain a PGMEA solution (solid content concentration: 45% by mass) of the binder (A-1) represented by the following formula: It was. The polymerization temperature was adjusted to 60 to 100 ° C.
As a result of measuring the molecular weight using gel permeation chromatography (GPC), the weight average molecular weight (Mw) in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2.21.

Example 1
<Sample No. Production of 101 conductive material>
-Preparation of silver nanowire dispersion (1)-
The following additive solutions A, G, and H were prepared in advance.
[Additive liquid A]
0.56 g of silver nitrate powder was dissolved in 50 mL of pure water. Then, 1N ammonia water was added until it became transparent. And pure water was added so that the whole quantity might be 100 mL.

[Additive liquid G]
An additive solution G was prepared by dissolving 0.5 g of glucose powder and 0.05 g of hydroxylamine with 140 mL of pure water.

[Additive liquid H]
Additive solution H was prepared by dissolving 0.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 27.5 mL of pure water.

-Preparation of silver nanowire dispersion-
410 mL of pure water was placed in a three-necked flask, and 82.5 mL of the additive solution H and 206 mL of the additive solution G were added through a funnel while stirring at 20 ° C. While stirring this solution at a stirring rotation speed of 800 rpm, 206 mL of the additive solution A was added at a flow rate of 2.0 mL / min. Ten minutes later, 82.5 mL of the additive solution H was added, and an aqueous nickel sulfate hexahydrate solution was added so that the nickel content was 0.01 mol% / Ag. Thereafter, the internal temperature was raised to 78 ° C. at 3 ° C./min. Thus, a silver nanowire dispersion liquid was prepared.

-Preparation of MFG dispersion (Ag-1) of silver nanowires-
Polyvinylpyrrolidone (K-30, manufactured by Wako Pure Chemical Industries, Ltd.) and 1-methoxy-2-propanol (MFG) are added to the silver nanowire dispersion, and after centrifugation, the supernatant water is decanted. It removed, MFG was added, redispersion was performed, and the operation was repeated 3 times, and the MFG dispersion liquid (Ag-1) of silver nanowire was obtained. The final MFG addition amount was adjusted so that the silver content was 1% by mass of silver.

-Preparation of composition for negative conductive layer-
0.241 parts by mass of binder (A-1) of Synthesis Example 1, KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 0.252 parts by mass, IRGACURE 379 (photopolymerization) Initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.0252 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.0237 parts by mass as a crosslinking agent, MegaFuck F781F (produced by DIC Corporation) 0.0003 50 parts by mass, 0.9611 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 44.3 parts by mass of 1-methoxy-2-propanol (MFG), and 54. MFG dispersion (Ag-1) of the silver nanowires. Add 1 part by mass, stir, negative type A composition for a conductive layer was prepared.

-Formation of conductive layer-
The obtained negative conductive layer composition was bar coated on a commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) film having a thickness of 100 μm and dried to form a conductive layer having a thickness of 0.1 μm. .

-Exposure and development-
Next, a pattern in which two squares of 1 cm in length and 1 cm in width were arranged with a gap of 30 μm was exposed, developed, and washed with water.
Here, exposure and development were performed under the following conditions.
The obtained conductive material was uniformly exposed at 100 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp i-line (365 nm), and then a potassium hydroxide developer CDK-1 (Fuji Film Electronics) Materials Development Co., Ltd.) 1.0 mass% developer (CDK-1 1 part by mass, pure water 99 parts by mass diluted solution, 25 ° C.) is subjected to shower development for 30 seconds, and further into ion-exchanged water. After rinsing for 20 seconds, it was dried.

-Immersion treatment (1)-
Next, the produced conductive material was prepared by using 1% by mass of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as the compound represented by the general formula (I) and the general formula (II). ) Was immersed in an aqueous solution containing 1% by mass of 1-phenyl-5-mercapto-1H-tetrazole as a compound represented by the following formula for 30 seconds, washed with water and dried. The total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) was 0.15% by mass with respect to silver (sample No. 101 to sample No. 113). The same). As described above, the sample No. 101 conductive materials were produced.

<Sample No. Production of 102 conductive material>
Sample No. No. 101, except that the nickel sulfate hexahydrate aqueous solution was added so that the nickel content was 0.1 mol% / Ag. In the same manner as in Sample 101, Sample No. 102 conductive materials were produced.

<Sample No. Production of 103 conductive material>
Sample No. 101, except that a bismuth trichloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the bismuth content was 0.05 mol% / Ag. In the same manner as in Sample 101, Sample No. 103 conductive materials were produced.

<Sample No. Production of 104 conductive material>
Sample No. 101, except that a bismuth trichloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the bismuth content was 0.5 mol% / Ag. In the same manner as in Sample 101, Sample No. 104 conductive materials were produced.

<Sample No. Production of 105 conductive material>
Sample No. 101, except that a stannous chloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the tin content was 0.01 mol% / Ag. In the same manner as in Sample 101, Sample No. 105 conductive materials were produced.

<Sample No. Production of 106 conductive material>
Sample No. 101, except that a stannous chloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the tin content was 0.1 mol% / Ag. In the same manner as in Sample 101, Sample No. 106 conductive materials were produced.

<Sample No. Production of 107 conductive material>
Sample No. 101, sample No. 10 was added except that beryllium sulfate aqueous solution was added so that the beryllium content was 0.005 mol% / Ag instead of nickel sulfate hexahydrate aqueous solution. In the same manner as in Sample 101, Sample No. 107 conductive materials were produced.

<Sample No. Production of 108 conductive material>
Sample No. 101, except that a beryllium sulfate aqueous solution was added so that the beryllium content was 0.05 mol% / Ag instead of the nickel sulfate hexahydrate aqueous solution. In the same manner as in Sample 101, Sample No. 108 conductive materials were produced.

<Sample No. Production of 109 conductive material>
Sample No. 101, except that a chromium alum aqueous solution was added instead of the nickel sulfate hexahydrate aqueous solution so that the chromium content was 0.01 mol% / Ag. In the same manner as in Sample 101, Sample No. 109 conductive materials were produced.

<Sample No. Production of 110 conductive material>
Sample No. 101, except that the aqueous solution of chromium alum was added in place of the nickel sulfate hexahydrate aqueous solution so that the chromium content was 0.1 mol% / Ag. In the same manner as in Sample 101, Sample No. 110 conductive materials were produced.

<Sample No. Production of 111 conductive material>
Sample No. No. 101, except that a rhodium chloride trihydrate aqueous solution was added instead of the nickel sulfate hexahydrate aqueous solution so that the rhodium content was 0.02 mol% / Ag. In the same manner as in Sample 101, Sample No. 111 conductive materials were produced.

<Sample No. Production of 112 conductive material>
Sample No. No. 101, except that a rhodium chloride trihydrate aqueous solution was added instead of the nickel sulfate hexahydrate aqueous solution so that the rhodium content was 0.2 mol% / Ag. In the same manner as in Sample 101, Sample No. 112 conductive materials were produced.

<Sample No. Production of 113 conductive material>
Sample No. In sample No. 101, sample no. In the same manner as in Sample 101, Sample No. 113 conductive materials were produced.

<Sample No. Production of 114 conductive material>
Sample No. In sample No. 101, except that nickel sulfate hexahydrate aqueous solution was not added and immersion treatment (1) was not performed. In the same manner as in Sample 101, Sample No. 114 conductive materials were produced.

<Sample No. Production of 115 conductive material>
Sample No. 101, except that the immersion treatment (1) was replaced with the following immersion treatment (2). In the same manner as in Sample 101, Sample No. 115 conductive materials were produced.
-Immersion treatment (2)-
Next, the produced conductive material was immersed in an aqueous solution containing 4% by mass of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as the compound represented by the general formula (I) for 30 seconds. Then, it was washed with water and dried. Content of the compound represented by the said general formula (I) was 0.15 mass% with respect to silver.

<Sample No. Production of 116 conductive material>
Sample No. 101, except that the immersion treatment (1) was replaced with the following immersion treatment (3). In the same manner as in Sample 101, Sample No. 116 conductive materials were produced.
-Immersion treatment (3)-
Next, the produced conductive material was immersed in an aqueous solution containing 0.3% by mass of 1-phenyl-5-mercapto-1H-tetrazole as a compound represented by the general formula (II) for 30 seconds, washed with water, Dried. The content of the compound represented by the general formula (II) was 0.15% by mass with respect to silver.

<Sample No. Production of 117 conductive material>
-Preparation of silver nanowire dispersion (2)-
30 mL of ethylene glycol was placed in a three-necked flask and heated to 160 ° C. Thereafter, 36 mM polyvinylpyrrolidone (PVP K-55, manufactured by Aldrich), 3 μM acetylacetonate iron, 18 μL of 60 μM sodium chloride ethylene glycol solution and 18 mL of 24 mM silver nitrate ethylene glycol solution were added at a rate of 1 mL per minute. . The mixture was heated at 160 ° C. for 60 minutes and then cooled to room temperature. Nickel sulfate hexahydrate aqueous solution was added so that nickel content might be 0.01 mol% / Ag. Thereafter, the internal temperature was raised to 78 ° C. at 3 ° C./min. Add water and centrifuge, purify until the conductivity is 50 μS / cm or less, further centrifuge with propylene glycol monomethyl ether to remove water, finally add propylene glycol monomethyl ether, silver nanowires Dispersion liquid (2) was prepared.

-Preparation of composition for negative conductive layer-
0.241 parts by mass of binder (A-1) of Synthesis Example 1, KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 0.252 parts by mass, IRGACURE 379 (photopolymerization) Initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.0252 parts by mass, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.) 0.0237 parts by mass as a crosslinking agent, MegaFuck F781F (produced by DIC Corporation) 0.0003 Parts by mass, 0.9611 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 44.3 parts by mass of 1-methoxy-2-propanol (MFG), and 54.1 parts by mass of the silver nanowire dispersion (2) , Stirred and composition for negative conductive layer Was prepared.

-Formation of conductive layer-
The obtained negative conductive layer composition was bar-coated on a commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) film (having 0.6%) having a thickness of 0.1 μm. A 1 μm conductive layer was formed.

-Exposure and development-
Next, a pattern in which two squares of 1 cm in length and 1 cm in width were arranged with a gap of 30 μm was exposed, developed, and washed with water.
Here, exposure and development were performed under the following conditions.
The obtained conductive material was uniformly exposed at 45 mJ / cm ² (illuminance 20 mW / cm ² ) using a high-pressure mercury lamp i-line (365 nm), and then a potassium hydroxide developer CDK-1 (Fuji Film Electronics) Materials Development Co., Ltd.) 1.0% by weight developer (CDK-1 1 part by weight, pure water 99 parts by weight diluted solution, 25 ° C.) is subjected to shower development for 30 seconds, and further into ion-exchanged water. After rinsing for 20 seconds, it was dried.

-Immersion treatment (1)-
Next, the produced conductive material was prepared by using 1% by mass of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as the compound represented by the general formula (I) and the general formula (II). ) Was immersed in an aqueous solution containing 1% by mass of 1-phenyl-5-mercapto-1H-tetrazole as a compound represented by the following formula for 30 seconds, washed with water and dried. The total content of the compound represented by the general formula (I) and the compound represented by the general formula (II) was 0.15% by mass with respect to silver (sample No. 117 to sample No. 123). The same). As described above, the sample No. 117 conductive materials were produced.

<Sample No. Production of 118 conductive materials>
Sample No. In Sample No. 117, except that the nickel sulfate hexahydrate aqueous solution was added so that the nickel content was 0.1 mol% / Ag, Sample No. 117, sample No. 118 conductive materials were produced.

<Sample No. Production of 119 conductive material>
Sample No. In Sample 117, sample No. 7 was added except that a bismuth trichloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the bismuth content was 0.02 mol% / Ag. 117, sample No. 119 conductive materials were produced.

<Sample No. Production of 120 conductive materials>
Sample No. 117, except that a bismuth trichloride aqueous solution was added in place of the nickel sulfate hexahydrate aqueous solution so that the bismuth content was 0.2 mol% / Ag. 117, sample No. 120 conductive materials were produced.

<Sample No. Production of 121 conductive material>
Sample No. In Sample 117, except for adding an aqueous rhodium chloride trihydrate solution in place of the nickel sulfate hexahydrate aqueous solution so that the rhodium content was 0.02 mol% / Ag, Sample No. 117, sample No. 121 conductive materials were produced.

<Sample No. Production of 122 conductive material>
Sample No. 117, sample No. 1 was added except that a rhodium chloride trihydrate aqueous solution was added instead of the nickel sulfate hexahydrate aqueous solution so that the rhodium content was 0.2 mol% / Ag. 117, sample No. 122 conductive materials were produced.

<Sample No. Production of 123 conductive material>
Sample No. In Sample No. 117, sample no. 117, sample No. 123 conductive materials were produced.

  Next, sample No. 101-No. About the metal nanowire and electroconductive material produced by 123, various characteristics were evaluated as follows. The results are shown in Table 1.

<Average minor axis length and average major axis length of metal nanowires>
Using a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.), 300 metal nanowires were observed, and the average minor axis length and average major axis length of the metal nanowires were determined from the average values. Asked.

<Coefficient of variation of minor axis length of metal nanowires>
Using a transmission electron microscope (TEM; JEM-2000FX, JEM-2000FX), 300 short-axis lengths of metal nanowires were observed, and the short-axis length of metal nanowires was measured from the average value. The coefficient of variation was obtained by calculating the standard deviation and the average value.

<Ratio of metal nanowires with an aspect ratio of 10 or more>
Each silver nanowire dispersion is filtered to separate silver nanowires and other particles, and the amount of silver remaining on the filter paper using an ICP emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation), The amount of silver that has passed through the filter paper is measured, and the ratio of metal nanowires having a minor axis length of 50 nm or less and a major axis length of 5 μm or more to an aspect ratio of 10 or more (%) As sought.
The metal nanowires were separated when determining the ratio of the metal nanowires using a membrane filter (Millipore, FALP 02500, pore size 1.0 μm).

<Measurement of surface resistance>
About the obtained conductive layer of each conductive material, the surface resistance was measured using a surface resistance meter (manufactured by Mitsubishi Chemical Corporation, Loresta-GP MCP-T600).

<Measurement of haze value>
About each obtained electrically-conductive material, the haze value was measured using the Gardner company make haze guard plus.

<Measurement of time until short circuit>
About each produced conductive material, after measuring haze and surface resistance, a voltage of DC 5V is applied between both electrodes under an atmosphere of 85% RH at 65 ° C., and the time until short-circuiting is measured in units of 1 hour. Measured. Whether or not a short circuit occurred was determined based on the fact that the resistance between the electrodes was 1 × 10 ⁶ Ω or less.

(Example 2)
In Sample 101, instead of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as the compound represented by the general formula (I), the exemplified compound (I-2) or the exemplified compound is used. Each conductive material was produced like the sample 101 except having used the compound (I-3).
About each produced electroconductive material, when it carried out similarly to the sample 101 and measured surface resistance, a haze value, and time to short-circuit, it turned out that all are the same level effects as the sample 101.

(Example 3)
In sample 101, instead of 1-phenyl-5-mercapto-1H-tetrazole as the compound represented by the general formula (II), any one of the exemplified compound (II-12) to the exemplified compound (II-12) Each conductive material was fabricated in the same manner as the sample 101 except that the above was used.
About each produced electroconductive material, when it carried out similarly to the sample 101 and measured surface resistance, a haze value, and time to short-circuit, it turned out that all are the same level effects as the sample 101.

Example 4
-Fabrication of touch panel-
Sample No. Using the 104 transparent conductive film (conductive material), “Latest Touch Panel Technology” (issued July 6, 2009, Techno Times), supervised by Yuji Mitani, “Touch Panel Technology and Development”, CM Publishing (2004) 1), a touch panel similar to that shown in FIG. 1 was produced by a single-sided bridge method described in “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292”, and the like. At this time, the interval between adjacent sides of the substantially square pad portion of the electrode pattern in the X direction and the Y direction was set to 30 μm.
When using the manufactured touch panel, it improves visibility by improving transmittance, and responds to input of characters, etc. or screen operations with at least one of bare hands, hands with gloves, or pointing tools by improving conductivity It was found that a touch panel with excellent performance can be produced. In this embodiment, it was found that no short circuit occurred for a long time and thus no migration occurred, and the electrical characteristics of the touch panel were stable over a long period of time.

(Example 5)
In Example 4, a touch panel was produced in the same manner as in Example 4 except that the distance between adjacent sides of the substantially square pad portion of the electrode pattern in the X direction and the Y direction was 50 μm.
About the produced touch panel of Example 5, when performance was evaluated similarly to Example 4, the same level of performance as Example 4 was obtained.

(Example 6)
In Example 4, a touch panel was produced in the same manner as in Example 4 except that the interval between adjacent sides of the substantially square pad portion of the electrode pattern in the X direction and the Y direction was set to 60 μm.
As for the produced touch panel of Example 6, the pattern of a transparent electrode was visually recognized by visual observation, and it turned out that the pattern space | interval of 60 micrometers or more is an unpreferable aspect.

  The conductive material of the present invention is, for example, a touch panel, antistatic for display, electromagnetic wave shield, electrode for organic EL display, electrode for inorganic EL display, electronic paper, electrode for flexible display, antistatic for flexible display, solar cell, other It can be used widely for various devices.

10, 20, 30, 110 Touch panel 11, 21, 31 Transparent substrate 12, 13, 22, 23, 32, 33 Transparent conductive film 24 Insulating layer 25 Insulating cover layer 14, 17 Protective film 15 Intermediate protective film 16 Antiglare film 18 Electrode terminal 33 Spacer 34 Air layer 35 Transparent film 36 Spacer 111 Transparent substrate 112 First electrode pattern 114 Second electrode pattern 115 Protective film 120 Sensor part

Claims (11)

A conductive material having a conductive layer containing at least metal nanowires having an average minor axis length of 50 nm or less and an average major axis length of 5 μm or more,
The conductive layer contains a compound represented by the following general formula (I) and the following general formula (II),
The metal nanowire contains at least one metal selected from silver, nickel, bismuth, tin, beryllium, chromium, and rhodium, from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² per mol of the silver. A conductive material containing a molar amount.
However, in the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an unsubstituted or substituted alkyl group, Any of unsubstituted or substituted aryl group, unsubstituted or substituted amino group, hydroxy group, alkoxy group, alkylthio group, carbamoyl group, halogen atom, cyano group, carboxy group, alkoxycarbonyl group, and heterocyclic residue Represents R ¹ and R ² or R ² and R ³ may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R ¹ and R ³ represents a hydroxy group.
However, in the general formula (II), R ⁵ is substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH, and —NHR ^6. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR. ⁷ or an _-SO 2 ^{R 7.} R ⁷ represents a hydrogen atom, an alkyl group, or an aryl group. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, And at least one of R ¹ and R ³ is a hydroxy group,
In the general formula (II), R ⁵ is phenyl optionally substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —OH, —SO ₃ M, —COOM, and —NHR ^6. Group, or an alkyl group having 1 to 4 carbon atoms that may be substituted by —SO ₃ M, R ⁶ is —COR ⁷ , and R ⁷ is any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. The conductive material according to claim 1, wherein M is any one of a hydrogen atom and an alkali metal atom.   The conductive material according to claim 1, wherein a total content of the compounds represented by the general formula (I) and the general formula (II) is 0.01% by mass to 10% by mass with respect to silver.   The mixing mass ratio [the general formula (I): the general formula (II)] of the compound represented by the general formula (I) and the compound represented by the general formula (II) is 1:99 to 99: 1 Item 4. The conductive material according to any one of Items 1 to 3.   The conductive material according to claim 1, wherein the conductive layer is patterned, and a distance between the formed patterns is 50 μm or less. On the substrate, a conductive layer forming step of forming a conductive layer by applying a conductive layer composition containing at least metal nanowires;
An application step of applying to the conductive layer a liquid containing a compound represented by the following general formula (I) and
A process for producing a conductive material, comprising at least
However, in the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an unsubstituted or substituted alkyl group, Any of unsubstituted or substituted aryl group, unsubstituted or substituted amino group, hydroxy group, alkoxy group, alkylthio group, carbamoyl group, halogen atom, cyano group, carboxy group, alkoxycarbonyl group, and heterocyclic residue Represents R ¹ and R ² or R ² and R ³ may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R ¹ and R ³ represents a hydroxy group.
However, in the general formula (II), R ⁵ is substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —SO ₃ M, —COOM, —OH, and —NHR ^6. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ⁷ , —COOR. ⁷ or an _-SO 2 ^{R 7.} R ⁷ represents a hydrogen atom, an alkyl group, or an aryl group. In the general formula (I), R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, And at least one of R ¹ and R ³ is a hydroxy group,
In the general formula (II), R ⁵ is phenyl optionally substituted with at least one selected from alkyl groups having 1 to 4 carbon atoms, —OH, —SO ₃ M, —COOM, and —NHR ^6. Group, or an alkyl group having 1 to 4 carbon atoms that may be substituted by —SO ₃ M, R ⁶ is —COR ⁷ , and R ⁷ is any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. The method for producing a conductive material according to claim 6, wherein M is any one of a hydrogen atom and an alkali metal atom. The metal nanowire contains at least one metal selected from silver and nickel, bismuth, tin, beryllium, chromium, and rhodium, from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of the silver. The manufacturing method of the electrically-conductive material in any one of Claim 6 to 7 contained.   Furthermore, the manufacturing method of the electrically-conductive material in any one of Claim 6 to 8 including the patterning process of carrying out pattern exposure and image development of an electrically conductive layer. A touch panel having a support film and a first sensor electrode array and a second sensor electrode array on the support film,
A first sensor electrode array and a second sensor electrode array are disposed on the same surface of the support film, and the first sensor electrode array and the second sensor electrode array are arranged orthogonally,
The distance between the first sensor electrode array and the second sensor electrode array is 50 μm or less,
A touch panel, wherein the first sensor electrode array and the second sensor electrode array are formed using the conductive material according to claim 1. The first sensor electrode array and the second sensor electrode array are composed of a substantially square pad portion and a connecting portion that electrically connects the pad portion,
The touch panel according to claim 10, wherein a distance between adjacent sides of the pad portion of the first sensor electrode array and the pad portion of the second sensor electrode array is 50 μm or less.