JP2017050250A - Manufacturing method of dispersion, transparent conductive film, input unit and organic el substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a dispersion capable of manufacturing a dispersion low in concentration of a colored compound having suppressed aggregate of metal fine particles such as metal nano wires and isolated without absorbing to the metal fine particles with high mass productivity.SOLUTION: There is provided a manufacturing method of a dispersion containing metal fine particles, a colored compound absorbed by the metal fine particles and a solvent and including a process of mixing the metal fine particles, the colored compound and the solvent to obtain a mixed liquid and a process of removing the colored compound isolated by conducting filtration of the mixed liquid to obtain the dispersion, where the filtration is pressure filtration and the pressure is 0.005 to 0.1 MPa.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for producing a dispersion, a transparent conductive film, an input device, and an organic EL substrate, and in particular, a method for producing a dispersion containing metal fine particles such as metal nanowires, a colored compound and a solvent, and the dispersion. The present invention relates to a transparent conductive film using a liquid, an input device, and an organic EL substrate.

  In order to form a transparent conductive film provided on the display surface of a display panel such as a touch panel, it is possible to form a film by coating or printing instead of a conventional metal oxide such as indium tin oxide (ITO). Transparent conductive films using metal nanowires that have high resistance to bending and deflection have been studied. This transparent conductive film can be obtained, for example, by preparing a dispersion containing metal nanowires and a solvent, and forming a film on the substrate using this dispersion.

  Here, when a transparent conductive film using metal nanowires is provided on the display surface side of the display panel, the black light on the display panel is displayed slightly brightly due to diffuse reflection of external light on the surface of the metal nanowires. The so-called black floating phenomenon may occur. The black floating phenomenon is one of the factors that cause deterioration of display characteristics such as a decrease in contrast.

  In order to prevent the occurrence of such a black floating phenomenon, a transparent conductive film using metal nanowires adsorbed with a colored compound such as a dye has been proposed.

  However, transparent conductive films using metal nanowires that adsorb colored compounds are transparent due to the presence of colored compounds (dyes) that are released without adsorbing to metal nanowires in the film. There have been problems such as the possibility of reducing the total light transmittance of the conductive film and the possibility of reducing the effect of preventing the black floating phenomenon.

  Therefore, as a countermeasure to the above problem, for example, in Patent Document 1, a cylindrical filter paper is used to adsorb a colored compound to the metal nanowire in a solvent and to remove the colored compound released in the solvent (cylindrical). The filter paper method) is disclosed. In this method, as a cylindrical filter paper, a container made of a filter that transmits a colored compound and a solvent but does not transmit an aggregate of metal nanowires and a colored compound is used.

JP2015-140467A

However, the above-mentioned cylindrical filter paper method is a method that requires a long time for the treatment in addition to a small amount that can be treated at a time, and thus it is difficult to industrially produce a transparent conductive film from which the liberated colored compounds are removed. There was a problem that there was.
Even when a normal filtration method is adopted, there is a problem that the metal nanowires form a cake layer on the surface of the filter paper, and the aggregation of the metal nanowires occurs at that time. Aggregated metal nanowires may cause a non-uniform structure when a transparent conductive film is formed, and may reduce optical properties and durability.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, according to the present invention, it is possible to produce a dispersion liquid in which the aggregation of metal fine particles such as metal nanowires is suppressed and the colored compound released without adsorbing to the metal fine particles is low in concentration with high productivity. An object of the present invention is to provide a method for producing a dispersion. Moreover, an object of this invention is to provide the transparent conductive film which is excellent in an optical characteristic and durability. Furthermore, an object of this invention is to provide an input device and organic electroluminescent board | substrate provided with the said transparent conductive film.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have suppressed the aggregation and release of metal fine particles such as metal nanowires in a short time by adding a predetermined device during filtration. The inventors have found that a reduction in the concentration of the colored compound can be achieved, and have completed the present invention.

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 method for producing a dispersion, comprising metal fine particles, a colored compound adsorbed on the metal fine particles, and a solvent,
A step of mixing a metal fine particle, a colored compound and a solvent to obtain a mixed solution;
Removing the colored compound liberated by filtering the mixed solution to obtain a dispersion,
The filtration is pressure filtration, and the pressure is 0.005 to 0.1 MPa.
It is the manufacturing method of the dispersion liquid characterized by the above-mentioned.
In the method for producing a dispersion liquid according to <1>, by adopting pressure filtration, it is possible to effectively remove free colored compounds while shortening the time required for filtration. Moreover, by setting the pressure at the pressurizing pressure to 0.005 to 0.1 MPa, filtration can be performed in a short time, and aggregation of metal fine particles can be suppressed.

<2> The filtration is performed while stirring the mixed solution with a stirrer including a rotating shaft and a stirring blade. Here, the number of rotations of the stirrer during stirring is less than 2500 rpm, according to <1>. This is a method for producing a dispersion liquid.

<3> In the filtration, a substantially cylindrical container having a filtration mechanism on the bottom is used, and the blade diameter of the stirring blade is 90% or more of the inner diameter of the container. It is a manufacturing method.

<4> The method for producing a dispersion liquid according to <3>, wherein the stirring blade passes through an upper portion of the entire surface of the filtration mechanism.

<5> The method for producing a dispersion liquid according to any one of <1> to <4>, wherein a cleaning solvent is supplied to the mixed liquid in parallel with the filtration.

<6> The method for producing a dispersion according to any one of <1> to <5>, wherein the filtration is performed until the concentration of the colored compound not adsorbed on the metal fine particles in the mixed solution is 0.5 ppm or less. It is.

<7> The method for producing a dispersion according to any one of <1> to <6>, wherein the solvent contains water as a main component and contains 5 to 30% by mass of a water-soluble alcohol.

<8> The method for producing a dispersion according to any one of <1> to <7>, wherein the colored compound is a phthalocyanine-based complex compound.

前記一般式（１）におけるＭは、Ｃｕ、Ｆｅ、Ｔｉ、Ｖ、Ｎｉ、Ｐｄ、Ｐｔ、Ｐｂ、Ｓｉ、Ｂｉ、Ｃｄ、Ｌａ、Ｔｂ、Ｃｅ、Ｂｅ、Ｍｇ、Ｃｏ、Ｒｕ、Ｍｎ、Ｃｒ、Ｍｏ、Ｓｎ及びＺｎのいずれかであり、存在しても存在しなくてもよく、
前記一般式（１）におけるＲ₁〜Ｒ₄は、フタロシアニン部位に１つ以上存在すればよく、下記一般式群（Ａ）における一般式のいずれかで表されるイオンを含み、それぞれが同じであっても異なっていてもよく、

上記一般式群（Ａ）におけるＲ₅〜Ｒ₇は、水素又は炭化水素基であり、それぞれが同じであっても異なっていてもよく、
前記Ｒ₁〜Ｒ₄は、下記一般式群（Ｂ）における一般式のいずれかで表される対イオンを更に含み、

上記の一般式群（Ｂ）におけるＸは、ＳＯ₃ ^-、ＣＯＯ^-、ＰＯ₃Ｈ^-、ＰＯ₃ ^2-、Ｎ⁺Ｒ₈Ｒ₉Ｒ₁₀、ＰｈＮ⁺Ｒ₈Ｒ₉Ｒ₁₀で表されるイオン、下記一般式（２）で表されるイオン、及び下記構造式（１）で表されるイオンのいずれかであり、

上記の一般式群（Ｂ）、Ｎ⁺Ｒ₈Ｒ₉Ｒ₁₀、ＰｈＮ⁺Ｒ₈Ｒ₉Ｒ₁₀、及び一般式（２）におけるＲ₈〜Ｒ₁₀は、水素又は炭化水素基であり、それぞれが同じであっても異なっていてもよい。 <9> The method for producing a dispersion according to any one of <1> to <8>, wherein the phthalocyanine complex compound is a phthalocyanine complex compound represented by the following general formula (1).

M in the general formula (1) is Cu, Fe, Ti, V, Ni, Pd, Pt, Pb, Si, Bi, Cd, La, Tb, Ce, Be, Mg, Co, Ru, Mn, Cr, Any of Mo, Sn and Zn, which may or may not be present,
R _{1 to} R ₄ in the general formula (1) may be present in one or more at the phthalocyanine site, and include ions represented by any one of the general formulas in the following general formula group (A), each of which is the same Can be different or different,

R _{5 to} R ₇ in the general formula group (A) are hydrogen or a hydrocarbon group, and each may be the same or different,
R _{1 to} R ₄ further include a counter ion represented by any one of the general formulas in the following general formula group (B),

X in the general formula group (B) is represented by SO ₃ ⁻ , COO ⁻ , PO ₃ H ⁻ , PO ₃ ²⁻ , N ⁺ R ₈ R ₉ R ₁₀ , and PhN ⁺ R ₈ R ₉ R _10. An ion, an ion represented by the following general formula (2), and an ion represented by the following structural formula (1),

The above general formula group _{^{(B), N + R 8}} R 9 R 10, PhN + R 8 R 9 R 10 R 8 ~R 10 and in the general formula (2), is hydrogen or a hydrocarbon group, respectively May be the same or different.

<10> The method for producing a dispersion liquid according to <8> or <9>, wherein the filtration is performed until the concentration of the liberated colored compound in the mixed solution becomes 0.3 ppm or less.

<11> A transparent conductive material obtained by applying a dispersion produced by the method for producing a dispersion according to any one of <1> to <10> on a substrate and then drying the dispersion. It is a membrane.

<12> An input device comprising the transparent conductive film according to <11>.

<13> An organic EL substrate comprising the transparent conductive film according to <11>.

According to the present invention, the above-mentioned problems in the prior art are solved, a dispersion liquid in which the aggregation of metal fine particles such as metal nanowires is suppressed and the concentration of the colored compound that has been liberated without adsorbing to the metal fine particles is low. A method for producing a dispersion that can be produced with mass productivity can be provided. Moreover, according to this invention, the transparent conductive film excellent in an optical characteristic and durability can be provided. Furthermore, according to this invention, an input device and an organic electroluminescent board | substrate provided with the said transparent conductive film can be provided.

It is a figure which shows typically the filtration apparatus which concerns on one Embodiment which can be used with the manufacturing method of the dispersion liquid of this invention. It is a figure which shows typically the filtration apparatus which concerns on another embodiment which can be used with the manufacturing method of the dispersion liquid of this invention. It is a figure which shows typically 1st Embodiment of the transparent conductive film of this invention. It is a figure which shows typically 2nd Embodiment of the transparent conductive film of this invention. It is a figure which shows typically 3rd Embodiment of the transparent conductive film of this invention. It is a figure which shows typically 4th Embodiment of the transparent conductive film of this invention. It is a figure which shows typically 5th Embodiment of the transparent conductive film of this invention. It is a figure which shows typically 6th Embodiment of the transparent conductive film of this invention. It is a figure which shows typically one Embodiment of the input device of this invention. It is a figure which shows typically one Embodiment of the organic electroluminescent board | substrate of this invention.

(Dispersion production method)
The method for producing a dispersion according to the present invention relates to a method for producing a dispersion comprising metal fine particles, a colored compound adsorbed on the metal fine particles, and a solvent, and includes at least a mixing step and a filtration step. In addition, other steps are included as necessary.

<Mixing process>
The mixing step is a step of mixing the metal fine particles, the colored compound and the solvent, and further mixing a binder (transparent resin material), a dispersing agent, other components and the like as necessary to obtain a mixed solution.
In the mixing step, for example, metal fine particles, a colored compound, a solvent, and any other components may be mixed at the same time to obtain a mixed solution, or the metal obtained by dispersing metal fine particles in a solvent such as water in advance. The fine particle-containing liquid may be put into a solvent to which a colored compound and any other components are added to obtain a mixed liquid.
The mixing method is not particularly limited, and examples thereof include stirring by a stirrer and shaking.
Further, the mixing ratio of the metal fine particles, the colored compound and the solvent can be appropriately changed.

In the mixing step, it is preferable that the colored compound is adsorbed on the metal fine particles in the mixed solution (surface treatment of the metal fine particles is performed). By adsorbing the colored compound to the metal fine particles, visible light is absorbed by the adsorbed colored compound, and irregular reflection of light on the surface of the metal fine particles can be prevented. Depending on the physical properties of the colored compound, the effect of coating can reduce the influence of conductivity deterioration due to external factors, and the durability of the metal fine particles can be increased.
Here, the method for adsorbing the colored compound on the metal fine particles is not particularly limited, and includes a method of stirring the mixed solution at a predetermined temperature for a predetermined time. The stirring is not particularly limited as long as the fine metal particles and the colored compound can be sufficiently dispersed in the mixed solution.

Here, the adsorption temperature at the time of adsorbing the colored compound to the metal fine particles is not particularly limited as long as the solvent does not boil, and can be appropriately selected according to the purpose. Preferably, 20 ° C to 80 ° C is more preferable.
The adsorption time for adsorbing the colored compound on the metal fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 minute to 120 hours, more preferably 1 minute to 48 hours. 1 hour to 12 hours is particularly preferable.

The amount of the colored compound adsorbed onto the metal fine particles is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.5% by mass to 10% by mass.
When the amount of the colored compound adsorbed on the metal fine particles is 0.5% by mass or more, the effect of suppressing the scattering of external light is brought about, and the visibility of the pattern is improved. By being, it can suppress that the adsorbed colored compound inhibits the contact of metal fine particles, and can maintain high electroconductivity.
The amount of the colored compound adsorbed on the metal fine particles is, for example, analyzed by STEM EDS, specifically, EDS measurement using EM-002B manufactured by Topcon Technohouse and system 6 manufactured by Thermo Fisher Scientific, and ICP. It can be calculated by combining elemental analysis, transmission electron microscope observation (TEM), and the like.

<< Metallic fine particles >>
The metal fine particles are not particularly limited, and can be appropriately selected according to the use of the dispersion liquid and the performance required for the transparent conductive film. Preferably, the fine metal particles have a diameter on the order of nm. Can do. That is, the metal fine particles used in the method for producing a dispersion of the present invention is preferably a metal nanowire.

The constituent element of the metal nanowire is not particularly limited as long as it is a metal element, and can be appropriately selected according to the purpose. For example, Ag, Au, Ni, Cu, Pd, Pt, Rh, Ir, Ru , Os, Fe, Co, Sn, Al, Tl, Zn, Nb, Ti, In, W, Mo, Cr, V, Ta, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, Ag and Au (that is, silver nanowire and gold nanowire) are preferable in terms of high conductivity.

  There is no restriction | limiting in particular as an average short axis diameter of metal nanowire, Although it can select suitably according to the objective, 1 nm-500 nm are preferable. When the average minor axis diameter of the metal nanowire is 1 nm or more, the conductivity of the metal nanowire is hardly deteriorated, and when it is 500 nm or less, the total light transmission of the transparent conductive film including the metal nanowire is achieved. It is possible to prevent the deterioration of the rate and the haze (Haze). From the same viewpoint, the average minor axis diameter of the metal nanowire is more preferably 10 nm to 100 nm, and particularly preferably 10 nm to 29 nm.

  There is no restriction | limiting in particular as an average major axis length of the said metal nanowire, Although it can select suitably according to the objective, 1 micrometer-100 micrometers are preferable. When the average major axis length of the metal nanowires is 1 μm or more, the metal nanowires can be easily connected to each other, and the transparent conductive film including the metal nanowires can function well as a conductive film. By being, it can prevent the deterioration of the total light transmittance of the transparent conductive film containing this metal nanowire, and the deterioration of the dispersibility of the metal nanowire in a dispersion liquid. From the same viewpoint, the average major axis length of the metal nanowire is more preferably 5 μm to 50 μm, further preferably 10 μm to 50 μm, and particularly preferably 10 μm to 30 μm.

The average minor axis diameter and the average major axis length of the metal nanowires are the number average minor axis diameter and the number average major axis length that can be measured with a scanning electron microscope. More specifically, at least 100 metal nanowires are measured, and the projected diameter and projected area of each nanowire are calculated from an electron micrograph using an image analyzer. The projected diameter was the minor axis diameter. Further, the major axis length was calculated based on the following formula.
Long axis length = projected area / projected diameter The average minor axis diameter was an arithmetic average value of minor axis diameters. The average major axis length was the arithmetic average value of the major axis length.
Further, the metal nanowire may have a wire shape in which metal nanoparticles are connected in a bead shape. In this case, the length is not limited.

There is no restriction | limiting in particular as content of the metal nanowire in a dispersion liquid, Although it can select suitably according to the objective, When the mass of a dispersion liquid is 100 mass parts, 0.01 mass part-10.00 Part by mass is preferred.
When the compounding amount of the metal nanowires in the dispersion is 0.01 parts by mass or more, the basis weight of the metal nanowires in the finally obtained transparent conductive film is sufficient (for example, 0.001 g / m ² ˜1.000 g / m ² ), and by setting it to 10.00 parts by mass or less, deterioration of dispersibility of the metal nanowires may be prevented.

<< Colored compounds >>
The colored compound is preferably a substance having absorption in the visible light region. Here, the “visible light region” in this specification is a wavelength band of approximately 360 nm or more and 830 nm or less. Such a colored compound is preferably a compound having a chromophore having absorption in the visible light region and an atomic group having an adsorbing group that adsorbs to a metal constituting the metal fine particle such as a metal nanowire. In particular, the general formula [R—X] (where R is a chromophore having absorption in the visible light region, and X has an adsorbing group that adsorbs to a metal constituting metal fine particles such as metal nanowires. It is preferably a compound represented by:

  The chromophore R is not particularly limited as long as it has absorption in the visible light region, and can be appropriately selected according to the purpose. Examples thereof include phthalocyanine derivatives.

  The atomic group X is not particularly limited as long as it has an adsorbing group that adsorbs to the metal constituting the metal fine particle, and can be appropriately selected according to the purpose. For example, the general formula group (B) described later And counter ions represented by the general formula in FIG. Specific examples of the adsorbing group include, for example, a sulfo group (including a sulfonate), a sulfonyl group, a sulfonamide group, a carboxylate group (including a carboxylate), an aromatic amino group, an amide group, and a phosphate group ( Phosphate, phosphate ester), phosphino group, silanol group, epoxy group, isocyanate group, cyano group, vinyl group, thiol group, sulfide group, carbinol group, ammonium group, pyridinium group, hydroxyl group, metal nanowire Examples thereof include atoms capable of coordinating with the constituent metals (for example, N (nitrogen), S (sulfur), O (oxygen), etc.). These may be used individually by 1 type and may use 2 or more types together. These adsorbing groups may be appropriately selected in consideration of solubility and the like. On the other hand, it is better not to use an alkyl-substituted amino group because it may attack the metal filler. Here, the alkyl-substituted amino group refers to an amino group in which all of the carbon atoms directly bonded to the N atom have an Sp3 hybrid orbital. Moreover, these adsorption groups should just be couple | bonded with the chromophore R as the atomic group X by the covalent bond or the noncovalent bond. Further, the adsorbing group may constitute a part of the chromophore R.

  In particular, the colored compound used in the method for producing a dispersion of the present invention is preferably a phthalocyanine complex compound. By using a phthalocyanine-based complex compound as a colored compound, it is possible to improve the adsorptivity to the metal filler, and further suppress the aggregation of the metal fine particles on which the colored compound is adsorbed in the dispersion. The durability of the used transparent conductive film, suppression of scattering of external light, conductivity, and the like can be improved.

前記一般式（１）におけるＭは、Ｃｕ、Ｆｅ、Ｔｉ、Ｖ、Ｎｉ、Ｐｄ、Ｐｔ、Ｐｂ、Ｓｉ、Ｂｉ、Ｃｄ、Ｌａ、Ｔｂ、Ｃｅ、Ｂｅ、Ｍｇ、Ｃｏ、Ｒｕ、Ｍｎ、Ｃｒ、Ｍｏ、Ｓｎ及びＺｎのいずれかであり、存在しても存在しなくてもよく、
前記一般式（１）におけるＲ₁〜Ｒ₄は、フタロシアニン部位に１つ以上存在すればよく、下記一般式群（Ａ）における一般式のいずれかで表されるイオンを含み、それぞれが同じであっても異なっていてもよく、

上記一般式群（Ａ）におけるＲ₅〜Ｒ₇は、水素又は炭化水素基であり、それぞれが同じであっても異なっていてもよく、
前記Ｒ₁〜Ｒ₄は、下記一般式群（Ｂ）における一般式のいずれかで表される対イオンを更に含み、

上記の一般式群（Ｂ）におけるＸは、ＳＯ₃ ^-、ＣＯＯ^-、ＰＯ₃Ｈ^-、ＰＯ₃ ^2-、Ｎ⁺Ｒ₈Ｒ₉Ｒ₁₀、ＰｈＮ⁺Ｒ₈Ｒ₉Ｒ₁₀で表されるイオン、下記一般式（２）で表されるイオン、及び下記構造式（１）で表されるイオンのいずれかであり、

上記の一般式群（Ｂ）、Ｎ⁺Ｒ₈Ｒ₉Ｒ₁₀、ＰｈＮ⁺Ｒ₈Ｒ₉Ｒ₁₀、及び一般式（２）におけるＲ₈〜Ｒ₁₀は、水素又は炭化水素基であり、それぞれが同じであっても異なっていてもよい。 There is no restriction | limiting in particular as a phthalocyanine type complex compound, Although it can select suitably according to the objective, From a viewpoint which brings the desired effect mentioned above more, the phthalocyanine type complex compound represented by following General formula (1) is used. It is preferable to use it.

M in the general formula (1) is Cu, Fe, Ti, V, Ni, Pd, Pt, Pb, Si, Bi, Cd, La, Tb, Ce, Be, Mg, Co, Ru, Mn, Cr, Any of Mo, Sn and Zn, which may or may not be present,
R _{1 to} R ₄ in the general formula (1) may be present in one or more at the phthalocyanine site, and include ions represented by any one of the general formulas in the following general formula group (A), each of which is the same Can be different or different,

R _{5 to} R ₇ in the general formula group (A) are hydrogen or a hydrocarbon group, and each may be the same or different,
R _{1 to} R ₄ further include a counter ion represented by any one of the general formulas in the following general formula group (B),

X in the general formula group (B) is represented by SO ₃ ⁻ , COO ⁻ , PO ₃ H ⁻ , PO ₃ ²⁻ , N ⁺ R ₈ R ₉ R ₁₀ , and PhN ⁺ R ₈ R ₉ R _10. An ion, an ion represented by the following general formula (2), and an ion represented by the following structural formula (1),

The above general formula group _{^{(B), N + R 8}} R 9 R 10, PhN + R 8 R 9 R 10 R 8 ~R 10 and in the general formula (2), is hydrogen or a hydrocarbon group, respectively May be the same or different.

  Examples of such phthalocyanine-based complex compounds include those represented by the following structural formulas (2) to (9). These may be used individually by 1 type and may use 2 or more types together.

The chromophore R in the phthalocyanine complex compounds represented by the structural formulas (2) to (9) described above is a phthalocyanine moiety (that is, a portion excluding R _{1 to} R ₄ in the general formula (1)). .
In addition, the atomic group X in the phthalocyanine-based complex compound represented by the structural formula (2) to the structural formula (9) is the counter ion in the structural formula (2) to the structural formula (9), or the structural formula (7). SO ₃ ⁻ , COO ⁻ in the structural formula (8), and the like.

  The above phthalocyanine-based complex compound is prepared, for example, by preparing a raw material solution in which a raw material containing a phthalocyanine derivative moiety is dissolved in a solvent and a compound solution in which a compound containing an atomic group X having an adsorbing group that adsorbs to a metal is dissolved in a solvent. It is obtained by precipitating by mixing the raw material solution and the compound solution. Here, “dissolving” includes not only dissolution but also dispersion.

  The raw material containing the phthalocyanine derivative moiety is not particularly limited and can be appropriately selected depending on the purpose. For example, Alcian blue, Alcian blue-tetrakis (methylpyridinium) chloride, tetrasulfonic acid phthalocyanine, monosulfonic acid Phthalocyanine, disulfonic acid phthalocyanine, trisulfonic acid phthalocyanine, tetracarboxylic acid phthalocyanine, monocarboxylic acid phthalocyanine, dicarboxylic acid phthalocyanine, tricarboxylic acid phthalocyanine, copper phthalocyanine-tetrasulfonic acid tetrasodium salt, copper phthalocyanine-monosulfonic acid tetrasodium salt, copper Phthalocyanine-disulfonic acid tetrasodium salt, copper phthalocyanine-trisulfonic acid tetrasodium salt, copper phthalocyanine-tetracarboxylic acid tetrasodium salt, copper Taroshianin - monocarboxylic acid tetrasodium salt, copper phthalocyanine - dicarboxylic acid tetrasodium salt, copper phthalocyanine - tricarboxylic acid tetrasodium salt, and the like.

  The compound containing the atomic group X is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sodium 2-mercapto-1-ethanesulfonate, sodium butanesulfonate, 1,2-ethanedisulfonic acid Disodium, sodium isethionate, potassium 3- (methacryloyloxy) propanesulfonate, 2-aminoethanethiol, sodium 1-octadecanesulfonate, sodium 3-mercapto-1-propanesulfonate, 2-aminoethanol hydrochloride, 2 , 3-Dimercaptopropanesulfonate sodium, 4-[(5-mercapto-1,3,4-thiadiazol-2-yl) thio] -1-butanesulfonate sodium, mercaptoacetate sodium, 2- (5-mercapto -1H-tetrazol-1-yl) sodium acetate , 5-carboxy-1-pentanethiol sodium salt, 7-carboxy-1-heptanethiol sodium salt, 10-carboxy-1-decanethiol sodium salt, 15-carboxy-1-pentadecanethiol sodium salt, carboxy-EG6- And undecanethiol sodium salt, carboxy-EG6-hexadecanethiol sodium salt, and the like.

  There is no restriction | limiting in particular as a solvent used when producing a raw material solution and a compound solution, According to the objective, it can select suitably, For example, water; methanol, ethanol, n-propanol, i-propanol, n-butanol , I-butanol, sec-butanol, tert-butanol and other alcohols; cyclohexanone, cyclopentanone and other anones; N, N-dimethylformamide (DMF) and other amides; dimethyl sulfoxide (DMSO) and other sulfides; It is done. These should just select the optimal thing considering the solubility of a raw material and a product, and may be used individually by 1 type and may use 2 or more types together. Moreover, you may add in the middle. There is no restriction | limiting in particular in the temperature of a solution, What is necessary is just to consider the solubility and reaction rate of a raw material and a product.

There is no restriction | limiting in particular as mixing ratio (raw material solution: compound solution) of a raw material solution and a compound solution, Although it can select suitably according to the objective, 1: 0.1-1: 10 are preferable by mass ratio. .
There is no restriction | limiting in particular as mixing time of a raw material solution and a compound solution, Although it can select suitably according to the objective, 1 minute-48 hours are preferable.

  The method for precipitating the phthalocyanine complex compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method for cooling the solution and a method for adding a poor solvent.

  The number average particle diameter of the colored compound when the colored compound is dispersed or dissolved as a molecule is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 nm to 3 μm, 0 More preferably, the thickness is 5 nm to 1 μm. When the number average particle diameter of the colored compound is 3 μm or less, the possibility of adversely affecting the total light transmittance can be suppressed. The number average particle diameter of the colored compound can be measured by, for example, a laser zeta electrometer “ELS-8000” manufactured by Otsuka Electronics Co., Ltd.

<< Solvent >>
There is no restriction | limiting in particular as a solvent, Although it can select suitably according to the objective, It is preferable that a colored compound can be melt | dissolved in predetermined concentration. Examples of such solvents include water, acetonitrile, 3-methoxypropionitrile, 3,3-dimethoxypropionitrile ethoxypropionitrile, 3-ethoxypropionitrile, 3,3-oxydipropionitrile, 3- Aminopropionitrile, propionitrile, propyl cyanoacetate, 3-methoxypropyl isothiocyanate, 3-phenoxypropionitrile, p-anisidine 3- (phenylmethoxy) propanenitrile, methanol, ethanol, n-propanol, isopropanol, n -Butanol, 2-butanol, isobutanol, t-butanol, ethylene glycol, triethylene glycol, 1-methoxy-ethanol, 1,1-dimethyl-2-methoxyethanol, 3-methoxy-1-propanol, dimethyl Examples include til sulfoxide, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, dichlorobenzene, butyl acetate, ethyl acetate, cyclohexane, cyclohexanone, ethyl methyl ketone, acetone, dimethylformamide, and the like. These may be used individually by 1 type and may use 2 or more types together.
As the solvent, it is preferable to appropriately select a material that can dissolve and / or disperse the colored compound at a predetermined concentration and is compatible with the liquid in which the metal fine particles are dispersed (metal fine particle-containing liquid).

  Among these, the solvent which has water as a main component and contains 5-30 mass% of water-soluble alcohol is preferable. By using such a solvent, the treatment can be performed while maintaining a high dispersibility of the metal fine particles in the filtration step. Here, when the content of the water-soluble alcohol in the solvent is 5% by mass or more, the above-described effect is obtained. On the other hand, when the content is 30% by mass or less, metal fine particles ( In particular, the occurrence of aggregation of metal nanowires can be further suppressed. In the present specification, the “main component” refers to a component having the largest content. Moreover, as water-soluble alcohol, methanol, ethanol, n-propanol, isopropanol etc. are mentioned among the alcohol mentioned above.

<< Binder (transparent resin material) >>
The binder (transparent resin material) can disperse the metal fine particle main body or the metal fine particles on which the colored compound is adsorbed, and can be used as necessary. The binder is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known transparent, natural polymer resins and synthetic polymer resins, and may be thermoplastic resins. Further, it may be a heat (light) curable resin that is cured by heat, light, electron beam, or radiation. These may be used individually by 1 type and may use 2 or more types together.
The thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethyl methacrylate, nitrocellulose, chlorinated polyethylene, chlorinated Examples include polypropylene, vinylidene fluoride, ethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, and the like.
The thermosetting (photo) curable resin is not particularly limited and can be appropriately selected depending on the purpose. For example, melamine acrylate, urethane acrylate, isocyanate, epoxy resin, polyimide resin, silicon resin such as acrylic-modified silicate, And a polymer in which a photosensitive group such as an azide group or a diazirine group is introduced into at least one of the main chain and the side chain.

<< dispersant >>
There is no restriction | limiting in particular as a dispersing agent, According to the objective, it can select suitably, For example, polyvinylpyrrolidone (PVP); a sulfo group (a sulfonate is included), a sulfonyl group, a sulfonamide group, a carboxylic acid group (carboxylic Acid groups), amide groups, phosphate groups (including phosphates and phosphate esters), phosphino groups, silanol groups, epoxy groups, isocyanate groups, cyano groups, vinyl groups, thiol groups, carbinol groups, etc. And compounds that can be adsorbed on metals. These may be used alone or in combination of two or more.
Moreover, you may make a dispersing agent adsorb | suck to the surface of metal nanowire. Thereby, the dispersibility of metal nanowire can be improved.
In addition, when adding a dispersing agent, it is preferable to make it the addition amount of the grade which the electroconductivity of the transparent conductive film finally obtained does not deteriorate.

<< Other ingredients >>
Other components that can be used in the mixing step are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a light stabilizer, an ultraviolet absorber, a light absorbing material, an antistatic agent, a lubricant, and a leveling agent. , Antifoaming agents, flame retardants, infrared absorbers, surfactants, thickeners and other viscosity modifiers, dispersants, curing accelerating catalysts, plasticizers, antioxidants, sulfiding agents, and the like. These may be used individually by 1 type and may use 2 or more types together.

<Filtering process>
A filtration process is a process of filtering the liquid mixture obtained at a mixing process, and obtaining the dispersion liquid from which the liberated colored compound was removed. Here, the filtration in the filtration step is pressure filtration. By adopting pressure filtration, it is possible to effectively remove the colored compounds that are liberated while shortening the time required for filtration. Therefore, metal fine particles caused by the formation of the cake layer, in particular, Aggregation of metal nanowires can be suppressed. Further, the pressure filtration is easy to design in scale-up, and the amount that can be processed at a time can be increased.
In vacuum filtration (suction filtration), the suction side of the filtration mechanism is likely to dry, so the filtration efficiency is poor and the dispersion cannot be produced with high mass productivity.

The pressure at the time of pressure filtration needs to be 0.005 MPa or more. If the pressure during pressure filtration is less than 0.005 MPa, it is difficult or impossible to perform the filtration itself, and even if filtration can be performed, it takes a very long time to obtain a desired dispersion.
Moreover, the pressure at the time of pressure filtration needs to be 0.1 Mpa or less. When the pressure at the time of pressure filtration exceeds 0.1 MPa, metal microparticles will aggregate and the L * value of the transparent conductive film formed using the obtained dispersion will become high.
Here, the pressure filtration can be performed by a batch method. And the pressure at the time of pressure filtration can be suitably adjusted according to the liquid quantity etc. which can be supplied per batch within the range of 0.005-0.1 MPa.
The “pressure during pressure filtration” refers to a differential pressure between the liquid surface of the mixed liquid and the atmosphere during pressure filtration, and can be measured using a known type of pressure gauge.

  Moreover, it does not restrict | limit especially as temperature at the time of filtration, According to the objective, it can select suitably.

  Here, the filtration performed by the method for producing a dispersion according to an embodiment of the present invention will be described in detail with reference to the drawings. A filtration device 1 shown in FIG. 1 includes a cylindrical container 2 and a filtration mechanism (filter) 3 at the bottom thereof. In the filtration step, the mixed solution 4 obtained in the mixing step is supplied into the container 2 of the filtration device 1. And the predetermined pressure P is applied with respect to a liquid mixture, and it filters by the filtration mechanism 3 of a bottom part.

There is no restriction | limiting in particular as a material of the filtration mechanism 3, According to the objective, it can select suitably, For example, a cellulose fiber, polytetrafluoroethylene (PTFE), a polycarbonate, nylon etc. are mentioned. Among these, PTFE is preferable in terms of high solvent resistance.
Moreover, as a hole diameter of the filtration mechanism 3, it is preferable to select a thing smaller than the particle size of metal microparticles (when using metal nanowire, the average major axis length of metal nanowire).

Here, the liquid level of the liquid mixture 4 in the container 2 decreases as filtration is performed. At this time, it is preferable to supply the cleaning solvent to the mixed solution 4 in parallel with the filtration. Specifically, the cleaning solvent can be supplied into the container 2 in a state where most of the mixed liquid 4 in the container 2 is filtered, and the filtration can be continued. Thereby, the density | concentration of the colored compound liberated without adsorb | sucking to a metal microparticle in a dispersion liquid can be reduced effectively. Moreover, drying and agglomeration of metal fine particles can be suppressed by leaving a small amount of liquid on the upper surface of the filtration mechanism 2 without filtering all the mixed liquid.
The supply of the cleaning solvent may be performed all at once until the liquid level reaches a predetermined height when the liquid level of the mixed liquid 4 becomes low to some extent, or the liquid level of the mixed liquid 4 is kept constant. It may be performed continuously or semi-continuously.

There is no restriction | limiting in particular as a washing | cleaning solvent, Although it can select suitably according to the objective, It is preferable that a pure water is included at least. In addition, the cleaning solvent may be used alone or in combination of two or more, and if necessary, a binder, a dispersant, a surfactant, an antifoaming agent, a viscosity modifier. Additives such as these may be mixed.
Further, the cleaning solvent may be the same as or different from the solvent used in the mixing step. In the filtration step, the cleaning solvent can be repeatedly supplied to the mixed solution. However, different types and mixing ratios of cleaning solutions may be used each time the supply is performed.

  And the filtration process can be completed in a state where the liquid level of the mixed liquid 4 in the container 2 is somewhat high, and the mixed liquid 4 in the container 2 at this time can be recovered as a dispersion.

  Here, the filtration in the filtration step is preferably performed until the mixed solution becomes colorless and transparent. Specifically, the filtration in the filtration step is preferably performed until the concentration of the free colored compound in the mixed solution becomes 0.5 ppm or less. If the concentration of the free colored compound in the mixed solution can be 0.5 ppm or less, it is possible to increase the total light transmittance of the transparent conductive film obtained using the recovered dispersion or to prevent the black floating phenomenon. it can.

In particular, when the phthalocyanine-based complex compound described above is used as the colored compound, the filtration in the filtration step is preferably performed until the concentration of the free colored compound in the mixed solution is 0.3 ppm or less, and until 0.15 ppm or less. More preferably. This is because the phthalocyanine complex compound is a substance having a relatively strong color.
Here, the density | concentration of the free colored compound in a liquid mixture does not consider solid content, such as a metal microparticle, but points out the density | concentration of the color compound in the liquid phase of a liquid mixture, for example.
And the density | concentration of the free colored compound in a liquid mixture can be measured by using a filtrate and an absorptiometer, for example.

  Moreover, at the time of filtration in a filtration process, you may perform the ultrasonic vibration to the stirring of a liquid mixture or the filtration mechanism from a viewpoint of suppressing metal particle accumulation (formation of a cake layer) more. Among these, it is preferable to perform stirring from the viewpoint of suppressing damage to the metal fine particles. Specifically, as shown in FIG. 2, a stirring bar 5 provided with a rotating shaft 5a and a stirring blade 5b is installed in a container 2 of the above-described type, and the stirring liquid 5 is rotated, whereby a mixed solution 4 Can be stirred.

The stirrer 5 is preferably installed so that the stirring blade 5b passes over the entire upper surface of the filtration mechanism 3. Specifically, for example, when the filtration mechanism 3 has a circular surface, the rotary shaft 5a is positioned at the center of the filtration mechanism 3, and the blade diameter of the stirring blade 5b (d ₂ in FIG. 2). It is preferable that the diameter of the surface of the filtration mechanism 3 (not shown) is greater than or equal to that shown. Thereby, formation of the cake layer on the filtration mechanism 3 and by extension, aggregation of metal fine particles can be suppressed more effectively.
In FIG. 2, the blade diameter of the stirring blade 5 b is equal to or less than the diameter of the surface of the filtration mechanism 3, that is, a portion where the stirring blade 5 b does not pass through the upper portion exists in the surface of the filtration mechanism 3. In such a case, the above-described preferable configuration can be obtained by “spreading” the part. Here, as a method of applying the eye, for example, a method in which a substantially liquid-impervious film is stacked on the surface of the filtration mechanism, or an adhesive that is insoluble in the solvent to be used is applied to the surface of the filtration mechanism. And a drying method.

  The type of the stirring blade 5b is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a propeller type, a paddle type, and a turbine type. Among these, the paddle type is preferable, and the pitched paddle type as shown in FIG. 2 or the propeller type is more preferable from the viewpoint of effectively suppressing the stacking of metal fine particles by generating a downward flow in the mixed solution. . Here, the stirring bar 5 shown in FIG. 2 can generate a downward flow in the mixed liquid in the container 2 by rotating the rotating shaft 5a in the illustrated direction.

  The number of rotations during stirring of the stirring bar 5 provided with the rotating shaft 5a and the stirring blade 5b is not particularly limited and can be appropriately selected according to the purpose, but is preferably less than 2500 rpm. When the number of rotations of the stirring bar 5 during stirring is less than 2500 rpm, the metal fine particles are sufficiently prevented from being crushed by the shearing force of the stirring blade 5b, and the dispersion liquid is applied when forming the transparent conductive film. Can be easily. From the same viewpoint, the rotation speed of the stirring bar 5 during stirring is more preferably 1000 rpm or less, and particularly preferably 400 rpm or less. Further, the rotational speed of the stirring bar 5 during stirring is preferably 1 rpm or more, more preferably 10 rpm or more, and more preferably 100 rpm or more from the viewpoint of reliably obtaining the effect of suppressing the deposition of metal fine particles. Is particularly preferred.

In addition, when a substantially cylindrical container having a filtration mechanism on the bottom surface is used and stirring is performed using the above-described stirrer, the blade diameter of the stirring blade (indicated by d ₂ in FIG. 2) is the inner diameter of the container ( It is preferably 90% or more of (indicated by d ₁ in FIG. 2). When the blade diameter of the stirring blade is 90% or more of the inner diameter of the container, the stirring efficiency can be made sufficiently high, and formation of a cake layer, and thus aggregation of metal fine particles can be further suppressed. .
From the same viewpoint, the ratio of the blade diameter of the stirring blade to the inner diameter of the container is more preferably 95% or more.

<Other processes>
And as other processes which can be included in the manufacturing method of the dispersion liquid of the present invention, for example, in the dispersion liquid obtained after the filtration process, any solvent, binder (transparent resin material), dispersant, other components, etc. Examples include an addition step of adding components, a stirring step, and the like.
Here, the solvent, binder (transparent resin material), dispersant, and other components in the addition step are the same as those already described in the description of the method for producing the dispersion.

(Transparent conductive film)
The transparent conductive film of the present invention can be formed on a substrate using the dispersion produced by the dispersion production method described above. Specifically, the transparent conductive film can be obtained by applying a dispersion produced by the above-described dispersion production method on a substrate and then drying. The transparent conductive film contains metal nanowires as metal fine particles and a colored compound adsorbed on the metal nanowires, and may further contain a binder, a dispersant, other components, and the like as necessary. Such a transparent conductive film is obtained using the above-described dispersion, and thus has excellent optical characteristics and durability.
Here, the binder, the dispersant, and other components are the same as those already described.

The basis weight of the metal nanowires in the transparent electroconductive film is not particularly limited and may be appropriately selected depending on the intended purpose, preferably ^{0.001g / m 2 ~1.000g / m 2} , 0.003g / m ^{2 to} 0.03 g / m ² is more preferable. When the basis weight of the metal nanowire is less than 0.001 g / m ² , the metal nanowire is not sufficiently present, and the conductivity of the transparent conductive film may be deteriorated, and the basis weight is 1.000 g / m. ^If it exceeds ² , the total light transmittance and haze of the transparent conductive film may deteriorate. On the other hand, when the basis weight of the metal nanowire is within the more preferable range or the particularly preferable range, it is advantageous in that the conductivity of the transparent conductive film is high and the transparency is high.

The transparent conductive film formed on the substrate can be suitably used as a transparent electrode. Here, there is no restriction | limiting in particular as a transparent electrode, According to the objective, it can select suitably, For example, as shown in FIG. 3, only the exposed part from the binder layer of metal nanowire 6 is colored. Compound 7 is adsorbed (the colored compound 7 may be adsorbed to the metal nanowire 6 and may be present in a part of the surface of the binder layer 8 or in the binder layer 8), (ii 4) A binder layer 8 in which metal nanowires 6 on which colored compounds 7 are adsorbed is formed on a substrate 9, as shown in FIG. 4, (iii) a binder as shown in FIG. An overcoat layer 10 is formed on the layer 8, (iv) an anchor layer 11 is formed between the binder layer 8 and the substrate 9 as shown in FIG. 6, (v) As shown in FIG. The binder layer 8 including the adsorbed metal nanowires 6 is formed on both surfaces of the substrate 9, (vi) As shown in FIG. 8, the colored compound 7 is dispersed without dispersing the colored compound 7 in the binder. Examples include those in which the adsorbed metal nanowires 6 are accumulated on the upper portion of the substrate 9, and (vii) those obtained by appropriately combining the above (i) to (vi).
In these, the binder layer 8 corresponds to a transparent conductive film.

<Base material>
There is no restriction | limiting in particular as a base material, Although it can select suitably according to the objective, The transparent base material comprised with the material which has transparency with respect to visible light, such as an inorganic material and a plastic material, is preferable. The transparent substrate has a film thickness required for a transparent electrode having a transparent conductive film. For example, a film (sheet) thinned to such an extent that flexible flexibility can be realized, or an appropriate amount It is assumed that the substrate has a film thickness sufficient to realize flexibility and rigidity.
There is no restriction | limiting in particular as said inorganic material, According to the objective, it can select suitably, For example, quartz, sapphire, glass, etc. are mentioned.
There is no restriction | limiting in particular as a plastic material, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), polyester (TPEE), a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), a polyimide ( PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin And known polymer materials such as urea resin, urethane resin, melamine resin, and cycloolefin polymer (COP). When a transparent base material is configured using such a plastic material, the film thickness of the transparent base material is preferably 5 μm to 500 μm from the viewpoint of productivity, but is not particularly limited to this range.

<Overcoat layer>
It is important that the overcoat layer has a light-transmitting property with respect to visible light, and is composed of a polyacrylic resin, a polyamide resin, a polyester resin, or a cellulose resin, or Consists of hydrolysis, dehydration condensate, etc. of metal alkoxide. Moreover, such an overcoat layer shall be comprised by the film thickness by which the light transmittance with respect to visible light is not inhibited. The overcoat layer may have at least one function selected from a functional group consisting of a hard coat function, an antiglare function, an antireflection function, an anti-Newton ring function, an antiblocking function, and the like.

<Anchor layer>
The anchor layer is not particularly limited as long as it can more firmly bond the base material and the binder layer, and can be appropriately selected according to the purpose.

<Method for producing transparent conductive film>
Below, embodiment of the method of manufacturing a transparent conductive film is described.
As a method for producing a transparent conductive film, for example, a dispersion film forming step, a curing step, a calendering step, an overcoat layer forming step, and a pattern electrode forming step are included. Including methods, and the like.

<< Dispersion film forming process >>
The dispersion film forming step is a step of forming a dispersion film on a base material using a dispersion liquid manufactured according to the above-described dispersion liquid manufacturing method using metal nanowires as metal fine particles. Here, the above-mentioned dispersion liquid preferably contains a binder. This binder may be blended before the filtration step in the above-described method for producing a dispersion, or may be blended after the filtration step.
The method for forming the dispersion film is not particularly limited and may be appropriately selected depending on the intended purpose. However, the wet film formation method is preferable in terms of physical properties, convenience, production cost, and the like.
There is no restriction | limiting in particular as a wet film forming method, According to the objective, it can select suitably, For example, well-known methods, such as the apply | coating method, the spray method, and the printing method, are mentioned.
The coating method is not particularly limited and can be appropriately selected according to the purpose. For example, the micro gravure coating method, the wire bar coating method, the direct gravure coating method, the die coating method, the dip method, and the spray coating method. , Reverse roll coating method, curtain coating method, comma coating method, knife coating method, spin coating method, and the like.
There is no restriction | limiting in particular as a spray method, According to the objective, it can select suitably.
The printing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include letterpress printing, offset printing, gravure printing, intaglio printing, rubber printing, screen printing, and ink jet printing. Can be mentioned.

  As the dispersion, for example, a dispersion subjected to dispersion treatment by stirring, ultrasonic dispersion, bead dispersion, kneading, homogenizer treatment, pressure dispersion treatment, or the like may be used.

<< Curing process >>
A hardening process hardens the dispersion film formed on the base material, and obtains hardened | cured material (The binder layer 8 containing the metal nanowire 6 by which the colored compound 7 was adsorb | sucked to the surface in FIGS. 3-7). It is.
In the curing step, first, the solvent in the dispersion film formed on the substrate is dried and removed. The removal of the solvent by drying may be either natural drying or heat drying. After drying, the uncured binder is cured, and the metal nanowires are dispersed in the cured binder. Here, the curing treatment can be performed by heating and / or irradiation with active energy rays.

<< Calendar process >>
The calendar process is a process of improving the smoothness of the surface or glossing the surface. By performing the calendar process, the sheet resistance value of the obtained transparent conductive film can be lowered.

<< Overcoat layer forming process >>
The overcoat layer forming step is a step of forming an overcoat layer on the cured product after the cured product of the dispersion film is formed.
The overcoat layer can be formed, for example, by applying an overcoat layer-forming coating solution containing a predetermined material on a cured product and curing it.

<< Pattern electrode formation process >>
The pattern electrode forming step is a step of forming a pattern electrode by forming a transparent conductive film on a substrate and then applying a known photolithography process. Thereby, the transparent conductive film of this invention can be applied to the sensor electrode for electrostatic capacitance touch panels. In addition, when the hardening process in a hardening process includes active energy ray irradiation, you may form a pattern electrode by making said hardening process into mask exposure / development. Furthermore, patterning by laser etching may be used.

(Input device)
The input device of the present invention includes the above-described transparent conductive film of the present invention, and further includes other members as necessary. An example of the input device is a touch panel.
FIG. 9 is a schematic view of a touch panel according to an embodiment of the present invention.
In FIG. 9, the touch panel 100 is formed on the image display member 101 having the transparent conductive film of the present invention, the light transmissive cured resin layer 102 formed on the image display member 101, and the light transmissive cured resin layer 102. And a light shielding layer 103 interposed between the light transmissive cured resin layer 102 and the light transmissive cover member 104.

(Organic EL substrate)
The organic EL substrate of the present invention includes the above-described transparent conductive film of the present invention, and further includes other members as necessary.
FIG. 10 is a schematic diagram of an organic EL substrate according to an embodiment of the present invention.
In FIG. 10, an organic EL substrate 200 of the present invention includes a base material 201 made of glass or the like, an anode 202 formed on the surface of the base material 201, and an organic light emitting layer 203 formed on the surface of the anode 202. A cathode 204 formed on the surface of the organic light emitting layer 203, a glass sealing material 205 for sealing these surfaces, a desiccant film 206 formed on the inner surface of the sealing material 205, An adhesive 207 that adheres the base material 201 and the periphery of the sealing material 205 is provided. Here, the anode 202 corresponds to the transparent conductive film of the present invention formed on the substrate 201.

Next, the present invention will be described more specifically with reference examples, examples and comparative examples, but the present invention is not limited to the following examples.
In addition, the analysis of the compound was performed using MALDI-TOF-MS analysis (Shimadzu Corporation AXIMA-CFR Plus).

Example 1
As the metal nanowire, a silver nanowire dispersion liquid [1] (manufactured by Seashell Technology, AgNW-25 (average diameter 25 nm, average length 23 μm)) was used.
The colored compound was prepared by the following procedure.
Alcian blue 8GX (manufactured by ALDRICH) and sodium 2-mercapto-1-ethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in an aqueous solvent at a mass ratio of 1: 2, and the mixture is prepared. Produced. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with water three times and then dried under reduced pressure to produce a colored compound [A]. This colored compound [A] was a phthalocyanine complex compound represented by the structural formula (2) described above.

10 mg of the colored compound [A] was put into 10 g of a solvent of water / ethylene glycol = 1: 1 and dissolved using an ultrasonic cleaner for 60 minutes to prepare a solution. Then, the produced solution was filtered through a PTFE filter having a pore size of 3 μm, and the obtained filtrate was used as a colored compound solution.
Next, 2 g of the silver nanowire dispersion liquid [1] was added to the colored compound solution, and the mixture was stirred at room temperature for 12 hours to obtain a mixed liquid [2] in which the colored compound [A] was adsorbed on the silver nanowires. This mixed solution contained a colored compound (free colored compound) that was not adsorbed on the silver nanowires. Then, pressure filtration of the mixed solution under the condition of 0.005 MPa using a stainless steel holder KST-47 with a tank (cylindrical shape) manufactured by ADVANTEC and a hydrophilic PTFE membrane filter (JCWP04700; pore diameter 10 μm, diameter 47 mm) manufactured by Merck Millipore Went. And the density | concentration of the colored compound in a filtrate is measured every 30 minutes with an absorptiometer, and until the said density | concentration becomes 0.3 ppm or less, to the liquid mixture of the washing solvent of water / ethanol = 95: 5 (mass ratio). The supply of was repeated.
A dispersion liquid was obtained in the above-described step, and this was mixed with other materials in the following composition to prepare a dispersion film forming dispersion liquid.
<Combination>
Dispersion liquid: 0.06 mass% (net silver nanowire mass conversion)
Hydroxypropyl methylcellulose (manufactured by Aldrich): 0.09% by mass
Water: 89.85% by mass
Ethanol: 10% by mass

The prepared dispersion film-forming dispersion was applied onto a transparent substrate with a coil bar of count 10 to form a dispersion film. The basis weight of the silver nanowire was 0.012 g / m ² . As the transparent substrate, PET (Toray Lumirror U34) having a film thickness of 100 μm was used.

  Subsequently, warm air was applied to the coated surface with a drier in the atmosphere to remove the solvent in the dispersion film, and the film was dried at 120 ° C. for 5 minutes to produce a transparent conductive film.

(Example 2)
Alcian blue-tetrakis (methylpyridinium) chloride (ALDRICH) and 1,2-ethanedisulfonic acid disodium (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed in methanol at a mass ratio of 1: 2 to obtain a mixed solution. Was made. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to prepare a colored compound [B]. This colored compound [B] was a phthalocyanine complex compound represented by the structural formula (4) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [B] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [3].

(Example 3)
Alcian blue 8GX (manufactured by ALDRICH) and sodium butanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in methanol at a mass ratio of 1: 2 to prepare a mixed solution. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [C]. This colored compound [C] was a phthalocyanine compound represented by the structural formula (3) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [C] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [4].

Example 4
Alcian blue-tetrakis (methylpyridinium) chloride (manufactured by ALDRICH) and sodium isethionate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in methanol at a mass ratio of 1: 2 to prepare a mixed solution. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [D]. This colored compound [D] was a phthalocyanine complex compound represented by the structural formula (5) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [D] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [5].

(Example 5)
Alcian blue-tetrakis (methylpyridinium) chloride (manufactured by ALDRICH) and potassium 3- (methacryloyloxy) propanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a mass ratio of 1: 2 are mixed in methanol to obtain a mixed solution. Was made. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [E]. This colored compound [E] was a phthalocyanine complex compound represented by the structural formula (6) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [E] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [6].

(Example 6)
Tetrasulfonic acid phthalocyanine hydrate (manufactured by ALDRICH) and 2-aminoethanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in methanol at a mass ratio of 1: 2 to prepare a mixed solution. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [F]. This colored compound [F] was a phthalocyanine complex compound represented by the structural formula (7) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [F] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [7].

(Example 7)
Trimellitic anhydride, urea, ammonium molybdate, and zinc chloride are added to nitrobenzene, stirred, heated to reflux, and the precipitate is recovered. Sodium hydroxide is added to the precipitate for hydrolysis. Decomposition was followed by acidification with hydrochloric acid to obtain zinc phthalocyanine tetracarboxylic acid.
Next, zinc phthalocyanine tetracarboxylic acid and 2-aminoethanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in methanol at a mass ratio of 1: 2 to prepare a mixed solution. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [G]. This colored compound [G] was a phthalocyanine complex compound represented by the structural formula (8) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [G] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [8].

(Example 8)
Alcian blue 8GX (manufactured by ALDRICH) and sodium 1-octadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in methanol at a mass ratio of 1: 4 to prepare a mixed solution. The prepared mixed solution was reacted for 60 minutes using an ultrasonic cleaner, and the reaction solution was filtered with a 3 μm PTFE filter. The obtained solid was washed with methanol three times and then dried under reduced pressure to produce a colored compound [H]. This colored compound [H] was a phthalocyanine complex compound represented by the structural formula (9) described above.
In Example 1, the same procedure as in Example 1 was performed except that the colored compound [H] was used instead of the colored compound [A]. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [9].

Example 9
Lanyl Black BG E / C (manufactured by Taoka Chemical Co., Ltd.) and 2-amine ethanethiol hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in an aqueous solvent at a mass ratio of 4: 1. Produced. The prepared mixed liquid was reacted for 100 minutes using an ultrasonic cleaner, and then allowed to stand for 15 hours. The reaction solution was filtered through a cellulose mixed ester type membrane filter having a pore size of 3 μm, and the obtained solid was washed three times with water and then dried in a vacuum oven at 100 ° C. to produce a colored compound [I]. This colored compound [I] was a colored compound that was not a phthalocyanine complex compound.
In Example 1, instead of using the colored compound [A], the colored compound [I] was used and the supply of the cleaning solvent to the mixed solution until the concentration of the colored compound in the filtrate was 0.5 ppm or less. The procedure was the same as Example 1 except that the above was repeated. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [10].

(Example 10)
In Example 1, instead of using the silver nanowire dispersion [1], the silver nanowire dispersion [11] (manufactured by Kechung, AW-030 (average diameter 30 nm, average length 20 μm)) was used. Except for this, the procedure was the same as in Example 1. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [12].

(Example 11)
In Example 1, instead of using silver nanowire dispersion [1], silver nanowire dispersion [13] (manufactured by ACS Materials, Agnws-40 (average diameter 40 nm, average length 30 μm or more)) is used. Except for this, it was the same as Example 1. Here, the mixed solution after adsorbing the colored compound is referred to as a mixed solution [14].

(Example 12)
100 mg of the colored compound [A] was put into 100 g of a solvent of water / ethylene glycol = 1: 1 and dissolved using an ultrasonic cleaner for 60 minutes to prepare a solution. Then, the produced solution was filtered through a PTFE filter having a pore size of 3 μm, and the obtained filtrate was used as a colored compound solution.
Next, 20 g of the silver nanowire dispersion liquid [1] was added to the colored compound solution and stirred at room temperature for 12 hours to obtain a mixed liquid [2] in which the colored compound [A] was adsorbed on the silver nanowires.
The subsequent operations were the same as in Example 1.

(Example 13)
In Example 12, instead of using ADVANTEC stainless steel holder with tank KST-47 and Merck Millipore hydrophilic PTFE membrane filter (JCWP04700; pore diameter 10 μm, diameter 47 mm), ADVANTEC filtration test equipment TSU-90B and Merck Example 12 was the same as Example 12 except that a Millipore hydrophilic PTFE membrane filter (JCWP09025; pore diameter 10 μm, diameter 90 mm) was used.

(Example 14)
In Example 13, it carried out similarly to Example 13 except performing pressure filtration at 0.001 MPa instead of 0.005 MPa.

(Example 15)
In Example 13, it carried out similarly to Example 13 except performing pressure filtration at 0.1 MPa instead of 0.005 MPa.

(Example 16)
500 mg of the colored compound [A] was added to 500 g of a solvent of water / ethylene glycol = 1: 1 and dissolved using an ultrasonic cleaner for 60 minutes to prepare a solution. Then, the produced solution was filtered through a PTFE filter having a pore size of 3 μm, and the obtained filtrate was used as a colored compound solution.
Next, 100 g of the silver nanowire dispersion liquid [1] was added to the colored compound solution, and the mixture was stirred at room temperature for 12 hours to obtain a mixed liquid [2] in which the colored compound [A] was adsorbed on the silver nanowires.
The subsequent operations were the same as in Example 15.

(Example 17)
In Example 16, it was the same as Example 16 except that the mixed solution was stirred by rotating the stirrer at a rotation speed of 400 rpm during pressure filtration.
The used stirring bar has a pitched paddle type stirring blade and a rotating shaft as shown in FIG. 2. The blade diameter of the stirring blade is 90% of the inner diameter of the tank, and the rotating shaft is a filter. A stir bar was placed so as to be located in the center. And the stirring blade was made to pass through the upper part of the filter whole surface.

(Example 18)
In Example 17, it was the same as that of Example 17 except having changed the rotation speed of the stirring bar into 1000 rpm instead of 400 rpm.

(Example 19)
In Example 17, it was the same as that of Example 17 except having changed the rotation speed of the stirring bar into 1600 rpm instead of 400 rpm.

(Example 20)
In Example 17, the cleaning solvent was the same as Example 17 except that a cleaning solvent of water / ethanol = 100: 0 was used instead of the cleaning solvent of water / ethanol = 95: 5 (mass ratio). .

(Example 21)
In Example 17, the cleaning solvent was the same as Example 17 except that a cleaning solvent of water / ethanol = 70: 30 was used instead of the cleaning solvent of water / ethanol = 95: 5 (mass ratio). .

(Example 22)
In Example 17, the cleaning solvent was the same as Example 17 except that a cleaning solvent of water / ethanol = 50: 50 was used instead of the cleaning solvent of water / ethanol = 95: 5 (mass ratio). .

(Example 23)
In Example 17, it was the same as that of Example 17 except having changed the rotation speed of the stirring element into 2000 rpm instead of 400 rpm.

(Comparative Example 1)
In Example 1, instead of preparing a dispersion for forming a dispersion film by mixing with other materials according to a predetermined composition using the dispersion, mixing in the following composition was used to prepare a dispersion for forming a dispersion film Was the same as in Example 1.
<Combination>
Silver nanowire dispersion [1]: 0.06% by mass (net silver nanowire mass conversion)
Hydroxypropyl methylcellulose (manufactured by Aldrich): 0.09% by mass
Water: 89.85% by mass
Ethanol: 10% by mass

(Comparative Example 2)
In Example 1, instead of performing pressure filtration of the mixed solution under the condition of 0.005 MPa using a stainless steel holder with a tank KST-47 manufactured by ADVANTEC and a hydrophilic PTFE membrane filter manufactured by Merck Millipore, JP 2015-140467 A Referring to the description of the publication No., a fluororesin cylindrical filter paper no. The mixed solution [2] is put into 89, and the concentration of the colored compound in the filtrate is measured every 30 minutes with an absorptiometer, and water / ethanol = 3: 1 until the concentration becomes 0.3 ppm or less. Example 1 was repeated except that the washing was repeated with the above solvent.

(Comparative Example 3)
20 mg of the colored compound [A] was put into 20 g of a solvent of water / ethylene glycol = 1: 1 and dissolved using an ultrasonic cleaner for 60 minutes to prepare a solution. Then, the produced solution was filtered through a PTFE filter having a pore size of 3 μm, and the obtained filtrate was used as a colored compound solution.
Next, 4 g of the silver nanowire dispersion liquid [1] was added to the colored compound solution, and the mixture was stirred at room temperature for 12 hours to obtain a mixed liquid [2] in which the colored compound [A] was adsorbed on the silver nanowires.
The subsequent operations were the same as in Comparative Example 2.

(Comparative Example 4)
100 mg of the colored compound [A] was put into 100 g of a solvent of water / ethylene glycol = 1: 1 and dissolved using an ultrasonic cleaner for 60 minutes to prepare a solution. Then, the produced solution was filtered through a PTFE filter having a pore size of 3 μm, and the obtained filtrate was used as a colored compound solution.
Next, 20 g of the silver nanowire dispersion liquid [1] was added to the colored compound solution and stirred at room temperature for 12 hours to obtain a mixed liquid [2] in which the colored compound [A] was adsorbed on the silver nanowires.
The subsequent operations were the same as in Comparative Example 2.

(Comparative Example 5)
In Example 17, it carried out similarly to Example 17 except performing a pressure filtration at 0.2 MPa instead of 0.005 MPa.

(Comparative Example 6)
Comparative Example 5 was the same as Comparative Example 5 except that the rotation speed of the stirring bar was changed to 1600 rpm instead of 400 rpm.

(Evaluation)
The following evaluation was performed about the transparent conductive film produced by the above Example and the comparative example. These results are shown in Table 1.

<A) Total light transmittance>
The total light transmittance of each transparent conductive film was evaluated according to JIS K7136 using HM-150 (trade name; manufactured by Murakami Color Research Laboratory Co., Ltd.).

<B) Haze value>
The haze value of each transparent conductive film was evaluated according to JIS K7136 using HM-150 (trade name; manufactured by Murakami Color Research Laboratory Co., Ltd.). In addition, as a haze value, the one where a value is small is preferable.

<C) Sheet resistance value>
The sheet resistance value of each transparent conductive film was evaluated using EC-80P (trade name; manufactured by Napson Corporation). The sheet resistance value is preferably 200 [Ω / □] or less.

<D) Δ reflection L * value>
The Δ reflection L * value is obtained by bonding a black vinyl tape (VT-50 manufactured by Nichiban Co., Ltd.) to the silver nanowire layer side, and from the side opposite to the silver nanowire layer side, according to JIS Z8722, manufactured by X-Rite. Evaluation was made using color i5. As a light source, a D65 light source was used, and measurement was performed at three arbitrary locations by the SCE (regular reflection light removal) method, and the average value was taken as a reflection L value.
Here, the Δ reflection L * value can be calculated by the following formula.
(Δ reflection L * value) = (reflection L * value of transparent conductive film including substrate) − (reflection L * value of substrate)
The Δ reflection L * value is preferably smaller.

<E) Change in sheet resistance in 60% humidity 90% environmental test>
The PET film and the slide glass were pasted so that the glass was placed on the surface of the silver nanowire layer using the adhesive film “Product No .: 8146-2 (manufactured by 3M)” on the slide glass “Product No .: S9213 (manufactured by Matsunami Glass Co., Ltd.)”. .
Thereafter, the sheet resistance was placed on a slide glass stand and placed in an oven set at 60 ° C. and a humidity of 90%, and the sheet resistance after 500 hours was evaluated.
The evaluation results are compared based on whether or not the colored compound is adsorbed on the corresponding silver nanowire.
-Evaluation criteria-
◯: The rate of change is smaller for those that are adsorbed than those that are not.
X: The rate of change is greater for the adsorbed material than for the non-adsorbed material.

<F) Change in sheet resistance after Xe lamp irradiation environment test>
The PET film and the slide glass were pasted so that the glass was placed on the surface of the silver nanowire layer using the adhesive film “Product No .: 8146-2 (manufactured by 3M)” on the slide glass “Product No .: S9213 (manufactured by Matsunami Glass Co., Ltd.)”. .
Thereafter, the sheet resistance was put on a slide glass stand, put into the Xe lamp light resistance test, and the sheet resistance after 100 hours was evaluated.
The evaluation results are compared based on whether or not the colored compound is adsorbed on the corresponding silver nanowire.
-Evaluation criteria-
◯: The rate of change is smaller for those that are adsorbed than those that are not.
X: The rate of change is greater for the adsorbed material than for the non-adsorbed material.

<G) Presence or absence of formation of cake layer>
At the end of filtration, whether or not a cake layer was formed on the filter was visually confirmed under the condition that a certain amount of liquid remained on the upper part of the filter. And what was not able to confirm a cake layer was evaluated as (double-circle), what was able to confirm the very thin cake layer was (circle), and what was able to confirm the thick cake layer was evaluated as x.

<H) Filtration time>
In each example, the time required from the start of filtration until the concentration of the colored compound in the filtrate fell below a predetermined value was measured.

First, it can be seen from the comparison between Example 1 and Comparative Example 1 in Table 1 that the Δ reflection L * value is lowered by performing the surface treatment of metal nanowires (adsorption of colored compounds).
Further, from the comparison between Example 1 and Comparative Example 2 in Table 1, by performing pressure filtration, the processing time is significantly shortened while obtaining the same processing effect as the “cylindrical filter paper method” as the prior art. I understand that.
Furthermore, it can be seen from the comparison between Example 12 and Comparative Examples 3 and 4 in Table 1 that the amount of treatment can be increased by performing pressure filtration. In addition, the comparison between Examples 1, 12 and 13 shows that in pressure filtration, it is possible to improve the throughput and the treatment time only by changing the size of the filtration device and the effective filtration area. .
And it turns out that processing time can fully be shortened by making the pressurization pressure at the time of pressurization filtration into the range of 0.005-0.1 MPa from the comparison of Examples 13-15 of Table 1. However, as is clear from Comparative Example 5, it can be seen that when the pressurization pressure is excessively increased, the metal nanowires are not dispersed, and the production of the transparent conductive film becomes difficult.

Moreover, it turns out that formation of a cake layer can be suppressed by performing pressure filtration with a predetermined pressure from the comparison with the Example of Table 1 and a comparative example.
In addition, it turns out that the suppression effect of formation of this cake layer is brought about more by stirring a liquid mixture at the time of filtration so that it may show also from the comparison with Examples 1-16 and Examples 17-23.

  Moreover, from Examples 16-19 and 23 of Table 1, it turns out that processing time can be shortened more by stirring a liquid mixture at the time of filtration. However, as is clear from Comparative Example 6, even when the mixed solution is stirred at the time of filtration, it is understood that the metal nanowires are not dispersed when the pressure is excessively high.

  Moreover, from Examples 1, 10 and 11 in Table 1, it can be seen that even when various metal nanowires are used, the treatment can be completed in a comparable time.

  In particular, the present invention can be suitably used for the production of a transparent conductive film in an input device such as a touch panel, but other uses (for example, an organic EL electrode, a surface electrode of a solar cell, a transparent antenna (cell phone or It can also be suitably used for the manufacture of wireless antennas for charging smartphones and transparent heaters that can be used to prevent condensation.

1 Filtration device 2 Container 3 Filtration mechanism (filter)
4 Mixture 5 Stirrer 5a Rotating shaft 5b Stirring blade 6 Metal nanowire 7 Colored compound 8 Binder layer 9 Base material 10 Overcoat layer 11 Anchor layer 100 Touch panel (input device)
DESCRIPTION OF SYMBOLS 101 Image display member 102 Light transmissive cured resin layer 103 Light shielding layer 104 Light transmissive cover member 200 Organic EL substrate 201 Base material 202 Anode 203 Organic light emitting layer 204 Cathode 205 Sealant 206 Desiccant film 207 Adhesive

Claims (13)

A method for producing a dispersion comprising metal fine particles, a colored compound adsorbed on the metal fine particles, and a solvent,
A step of mixing a metal fine particle, a colored compound and a solvent to obtain a mixed solution;
Removing the colored compound liberated by filtering the mixed solution to obtain a dispersion,
The filtration is pressure filtration, and the pressure is 0.005 to 0.1 MPa.
A method for producing a dispersion liquid.   2. The dispersion according to claim 1, wherein the filtration is performed while stirring the mixed solution with a stirring bar provided with a rotating shaft and a stirring blade, wherein the number of rotations of the stirring bar during stirring is less than 2500 rpm. Manufacturing method.   3. The method for producing a dispersion according to claim 2, wherein the filtration uses a substantially cylindrical container having a filtration mechanism on a bottom surface, and a blade diameter of the stirring blade is 90% or more of an inner diameter of the container.   The said stirring blade is a manufacturing method of the dispersion liquid of Claim 3 which passes the upper part of the whole surface of the said filtration mechanism.   The manufacturing method of the dispersion liquid in any one of Claims 1-4 which supplies a washing | cleaning solvent to the said liquid mixture in parallel with the said filtration.   The manufacturing method of the dispersion liquid in any one of Claims 1-5 which perform the said filtration until the density | concentration of the free colored compound in the said liquid mixture becomes 0.5 ppm or less.   The manufacturing method of the dispersion liquid in any one of Claims 1-6 in which the said solvent has water as a main component and contains 5-30 mass% of water-soluble alcohol.   The manufacturing method of the dispersion liquid in any one of Claims 1-7 whose said colored compound is a phthalocyanine type complex compound. The manufacturing method of the dispersion liquid in any one of Claims 1-8 whose said phthalocyanine type complex compound is a phthalocyanine type complex compound represented by following General formula (1).

M in the general formula (1) is Cu, Fe, Ti, V, Ni, Pd, Pt, Pb, Si, Bi, Cd, La, Tb, Ce, Be, Mg, Co, Ru, Mn, Cr, Any of Mo, Sn and Zn, which may or may not be present,
R _{1 to} R ₄ in the general formula (1) may be present in one or more at the phthalocyanine site, and include ions represented by any one of the general formulas in the following general formula group (A), each of which is the same Can be different or different,

R _{5 to} R ₇ in the general formula group (A) are hydrogen or a hydrocarbon group, and each may be the same or different,
R _{1 to} R ₄ further include a counter ion represented by any one of the general formulas in the following general formula group (B),

X in the general formula group (B) is represented by SO ₃ ⁻ , COO ⁻ , PO ₃ H ⁻ , PO ₃ ²⁻ , N ⁺ R ₈ R ₉ R ₁₀ , and PhN ⁺ R ₈ R ₉ R _10. An ion, an ion represented by the following general formula (2), and an ion represented by the following structural formula (1),

The above general formula group _{^{(B), N + R 8}} R 9 R 10, PhN + R 8 R 9 R 10 R 8 ~R 10 and in the general formula (2), is hydrogen or a hydrocarbon group, respectively May be the same or different.   The method for producing a dispersion according to claim 8 or 9, wherein the filtration is performed until the concentration of the liberated colored compound in the mixed solution becomes 0.3 ppm or less.   A transparent conductive film obtained by applying the dispersion produced by the method for producing a dispersion according to any one of claims 1 to 10 on a substrate and then drying the dispersion.   An input device comprising the transparent conductive film according to claim 11.   An organic EL substrate comprising the transparent conductive film according to claim 11.

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