WO2017159537A1 - ナノワイヤーおよびその製造方法、ナノワイヤー分散液ならびに透明導電膜 - Google Patents

ナノワイヤーおよびその製造方法、ナノワイヤー分散液ならびに透明導電膜 Download PDF

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WO2017159537A1
WO2017159537A1 PCT/JP2017/009484 JP2017009484W WO2017159537A1 WO 2017159537 A1 WO2017159537 A1 WO 2017159537A1 JP 2017009484 W JP2017009484 W JP 2017009484W WO 2017159537 A1 WO2017159537 A1 WO 2017159537A1
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nanowire
nanowires
nickel
value
present
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PCT/JP2017/009484
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English (en)
French (fr)
Japanese (ja)
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裕孝 竹田
由梨 嘉村
稲垣　孝司
大西　早美
吉永　輝政
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ユニチカ株式会社
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Priority to KR1020187022802A priority Critical patent/KR102277621B1/ko
Priority to JP2018504312A priority patent/JP6334076B2/ja
Priority to CN201780008770.2A priority patent/CN108602119B/zh
Publication of WO2017159537A1 publication Critical patent/WO2017159537A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt

Definitions

  • the present invention relates to a nanowire and a manufacturing method thereof, a nanowire dispersion liquid and a transparent conductive film.
  • a transparent conductive film has been widely used as a transparent electrode with the expansion of the solar cell market and the growing demand for touch panels due to the rapid spread of smartphones and tablet terminals.
  • a transparent conductive film is often used from the viewpoint of weight reduction, thinning, and flexibility, and most of them are ITO films using indium tin oxide as a conductive layer.
  • the ITO film has a problem in color tone due to low light transmittance in the long wavelength region.
  • ITO is a semiconductor, there is a limit to achieving high conductivity.
  • ITO has a problem in bendability because the conductive layer has poor bendability. For this reason, there has been a demand for a flexible film having higher transmittance and higher conductivity.
  • carbon nanotubes and conductive polymers are as conductive as semiconductors, and as a result, satisfactory conductivity cannot be obtained as a next-generation transparent conductive film.
  • the transparent conductive film which consists of a metal mesh structure has very high electroconductivity, there existed problems, such as a metal fine wire being visible.
  • transparent conductive films using metal nanowires are attracting attention because they can achieve both conductivity and transparency.
  • Patent Document 1 discloses a nanowire containing at least one metal selected from the group consisting of gold, nickel, and copper having a diameter variation coefficient of 30% or less.
  • Patent Document 2 discloses a copper nanowire having spherical ends.
  • Patent Literature 3 discloses a metal nanowire dispersion liquid including a metal nanowire and a polymer compound layer that the metal nanowire has on the surface.
  • This invention solves the said subject, Comprising: It aims at providing the nanowire which can obtain the nanowire film
  • the present inventors have found that by controlling the nanowire to a specific shape, the conductive loss in the nanowire and the shielding of visible light can be reduced as much as possible, and both high transparency and high conductivity can be achieved.
  • the invention has been reached.
  • the gist of the present invention is as follows.
  • a plurality of nanowires having a particle connection shape in which a plurality of particles are connected one-dimensionally A plurality of nanowires satisfying the following formula (1-1) when the maximum diameter of one nanowire is A (nm) and the minimum value is B (nm). 1.5 ⁇ A / B average value ⁇ 2.5 (1-1)
  • IX The average value of A is 50 to 500 nm
  • the nanowire according to (VII) or (VIII), wherein the average value of B is 10 to 200 nm.
  • (XIV) The plurality of nanowires according to any one of (VII) to (XIII), wherein the plurality of nanowires are metal nanowires.
  • (XV) The plurality of nanowires according to any one of (VII) to (XIV), wherein the plurality of nanowires are made of nickel.
  • (XVI) A method for producing a plurality of nanowires according to (XIV) or (XV), A method for producing a plurality of nanowires, comprising reducing metal ions in a magnetic field.
  • (XVII) A nanowire dispersion liquid in which a plurality of nanowires according to any one of (VII) to (XV) are dispersed.
  • (XVIII) A transparent conductive film comprising a plurality of nanowires according to any one of (VII) to (XV).
  • nanowire of the present invention a nanowire film that can achieve both high transparency and high conductivity can be obtained.
  • FIG. 4 is a TEM image of nickel nanowires produced in Example 1.
  • FIG. The graph of the surface resistance value of the nanowire of Example 1, and the nanowire of Comparative Examples 1 and 2 and the transmittance
  • the present invention provides a single nanowire having a particle connection shape in which a plurality of particles, particularly nanoparticles, are connected one-dimensionally.
  • the particle connection shape is a linear shape as a whole, in which a plurality of particles are connected in series and continuously. Each particle at both ends is connected to one or more adjacent particles, and each other particle is connected to two or more adjacent particles.
  • a concave portion is formed at the connecting portion (particle boundary portion)
  • a convex portion is formed at the particle portion
  • the concave portion and the convex portion are formed in the particle connecting direction (longitudinal direction of the nanowire). Is repeated continuously.
  • a transparent conductive film made of nanowires has higher conductivity as the nanowire is thicker, but the transparency is lowered.
  • the concave portion reduces visible light shielding by suppressing the loss of transparency (light transmittance) by repeatedly having concave and convex portions in the longitudinal direction, and the convex portion is conductive. Reduces sexual loss. As a result, compatibility between high transparency and high conductivity is achieved as a whole.
  • the nanowire of the present invention does not have to have the above-mentioned particle connection shape strictly and clearly, but the concave and convex portions are continuously repeated in the longitudinal direction of the nanowire, and will be described later. What is necessary is just to have such a specific uneven
  • Each particle constituting the nanowire of the present invention has a substantially spherical shape.
  • the substantially spherical shape includes not only a spherical shape having a circular cross section, but also a three-dimensional shape having a cross section of a polygon more than a triangle, an ellipse, or a composite shape thereof.
  • the nanowire of this invention has a specific unevenness
  • the nanowire of the present invention satisfies the following formula (1) when the maximum value of the diameter of one nanowire is A (nm) and the minimum value is B (nm), and is transparent and conductive. From the viewpoint of further improvement, it is preferable to satisfy the following formula (1 ′), and it is more preferable to satisfy the following formula (1 ′′). 1.5 ⁇ A / B ⁇ 2.5 (1) 1.5 ⁇ A / B ⁇ 2 (1 ′) 1.55 ⁇ A / B ⁇ 1.75 (1 ′′)
  • the maximum value A of the diameter is usually 50 to 500 nm, particularly 50 to 400 nm, and preferably 50 to 300 nm, more preferably 50 to 200 nm, from the viewpoint of further improving transparency and conductivity. More preferably, the thickness is 60 to 200 nm, and most preferably 60 to 150 nm.
  • the minimum value B of the diameter is usually 10 to 200 nm, particularly 20 to 200 nm, and preferably 30 to 150 nm, more preferably 30 to 90 nm, from the viewpoint of further improving transparency and conductivity. More preferably, it is 40 to 90 nm.
  • the diameter means a diameter in a cross section perpendicular to the longitudinal direction of the nanowire, and the maximum value and the minimum value of the diameter can be read in a TEM image of the nanowire.
  • the nanowire of the present invention provides a maximum value A of the diameter where it is not an end in one nanowire. The end portion is within 100 nm from the end of the nanowire.
  • a + B is usually 500 nm or less, particularly 80 to 500 nm, and preferably satisfies the following formula (2) from the viewpoint of further improving transparency and conductivity, particularly transparency: It is more preferable to satisfy the following formula (2 ′), and it is more preferable to satisfy the following formula (2 ′′).
  • a + B ⁇ 350nm (2) 80 nm ⁇ A + B ⁇ 350 nm (2 ′) 100 nm ⁇ A + B ⁇ 250 nm (2 ′′)
  • the length of the nanowire affects the conductivity and transparency of the transparent conductive film made from the nanowire. If the nanowire is too short, the number of contacts between the nanowires per unit area increases, and the conductivity of the transparent conductive film decreases. If the nanowires are too long, the dispersibility of the nanowires decreases, so that the produced transparent conductive film tends to be uneven, and uniform transparency and conductivity cannot be obtained. Therefore, in the present invention, the length of the nanowire is preferably 10 ⁇ m or more and 40 ⁇ m or less, more preferably 15 ⁇ m or more and 40 ⁇ m or less, further preferably 15 ⁇ m or more and 30 ⁇ m or less, and most preferably 20 ⁇ m or more and 30 ⁇ m or less.
  • the nanowire of the present invention only needs to be made of a conductive material, and may be, for example, a metal nanowire or a semiconductor or conductive polymer nanowire.
  • the nanowire of the present invention is preferably a metal nanowire from the viewpoint of conductivity.
  • the metal nanowire of this invention is comprised from 1 or more types of metals selected from the group which consists of nickel, cobalt, and iron from the point of a manufacturing method.
  • the nanowire of this invention is comprised from nickel and / or cobalt, especially nickel.
  • the nanowire of the said shape comprised from nickel and / or cobalt, it can obtain the transparent conductive film which has transparency and electroconductivity equivalent to the commercially available silver nanowire, and is excellent in ion migration tolerance. it can.
  • the nanowire is composed of nickel and / or cobalt means that the nanowire is substantially composed only of nickel and / or cobalt, and the nickel and cobalt are analyzed by ICP emission analysis or fluorescent X-ray. Is quantifiable.
  • the nanowire does not have to be strictly composed of only nickel and / or cobalt, and other than nickel and cobalt, as long as the effects of the present invention are not impaired during the synthesis of the nanowire and its raw material. These substances may be included as impurities.
  • the plurality of nanowires of the present invention includes the above-described nanowires. It is practically impossible to grasp the shape and dimensions of the nanowires for all the nanowires in the dispersion or transparent conductive film. In the present invention, any part of the nanowires in the dispersion or the transparent conductive film is evaluated, and if the above conditions are satisfied, it is confirmed that a further improvement effect of transparency and conductivity can be obtained. ing.
  • the plurality of nanowires of the present invention have a particle-connected shape, and when the maximum value of the diameter of one nanowire is A (nm) and the minimum value is B (nm)
  • the following formula (1-1 ′) is preferably satisfied, and the following formula (1-1 ′′) is satisfied. Is more preferable.
  • 1.5 ⁇ A / B average value ⁇ 2.5 (1-1) 1.5 ⁇ A / B average value ⁇ 2 (1-1 ′) 1.55 ⁇ A / B average value ⁇ 1.75 (1-1 ′′)
  • the average value of A / B is the average value of A / B for any 100 nanowires.
  • the average value of the maximum value A of the diameter is usually 50 to 500 nm, particularly 50 to 400 nm, and preferably 50 to 300 nm, from the viewpoint of further improving transparency and conductivity.
  • the thickness is preferably 50 to 200 nm, more preferably 60 to 200 nm, and most preferably 60 to 150 nm.
  • the average value of A is the average value of A for any 100 nanowires.
  • the average value of the minimum value B of the diameter is usually 10 to 200 nm, particularly 20 to 200 nm, and preferably 30 to 150 nm, from the viewpoint of further improving transparency and conductivity.
  • the thickness is preferably 30 to 90 nm, more preferably 40 to 90 nm.
  • the average value of B is the average value of B for any 100 nanowires.
  • the plurality of nanowires of the present invention preferably satisfy the following formulas (1-2) and (1-3) from the viewpoint of further improving transparency and conductivity, and the following formulas (1-2 ′) and ( 1-3 ′) is preferable, and the following formulas (1-2 ′′) and (1-3 ′′) are preferably satisfied.
  • 1.5 ⁇ maximum value of A / B ⁇ 2.5 (1-2) 1.55 ⁇ maximum value of A / B ⁇ 2.2 (1-2 ′) 1.65 ⁇ maximum value of A / B ⁇ 1.85 (1-2 ′′) 1.5 ⁇ A / B minimum value ⁇ 2.5 (1-3) 1.5 ⁇ Minimum value of A / B ⁇ 1.9 (1-3 ′) 1.45 ⁇ minimum value of A / B ⁇ 1.65 (1-3 ′′)
  • the maximum value of A / B is the maximum value of A / B for any 100 nanowires.
  • the minimum value of A / B is the minimum value of A / B for any 100 nanowires.
  • the average value of A + B is usually 500 nm or less, particularly 80 to 500 nm. From the viewpoint of further improving transparency and conductivity, particularly transparency, the following formula (2-1 ) Is more preferable, the following formula (2-1 ′) is more preferable, and the following formula (2-1 ′′) is more preferable. Average value of A + B ⁇ 350 nm (2-1) 80 nm ⁇ A + B average value ⁇ 350 nm (2-1 ′) 100 nm ⁇ A + B average value ⁇ 250 nm (2-1 ′′)
  • the average value of A + B is the average value of A + B for 100 arbitrary nanowires.
  • the plurality of nanowires of the present invention further has a maximum value of A + B of usually 520 or less, particularly 90 to 520 nm, and a minimum value of A + B is usually 480 or less, particularly 70 to 480 nm.
  • the plurality of nanowires of the present invention preferably satisfy the following formulas (2-2) and (2-3) from the viewpoint of further improving transparency and conductivity, and the following formulas (2-2 ′) and ( 2-3 ′) is more preferable, the following formulas (2-2 ′′) and (2-3 ′′) are more preferably satisfied, and the following formulas (2-2 ′ ′′) and (2- More preferably, 3 ′ ′′) is satisfied.
  • the maximum value of A + B is the maximum value of A + B for any 100 nanowires.
  • the minimum value of A + B is the minimum value of A + B for any 100 nanowires.
  • the average diameter is preferably 40 to 300 nm, more preferably 50 to 200 nm, still more preferably 50 to 180 nm, and most preferably 70 to 180 nm from the viewpoint of further improving transparency and conductivity. preferable.
  • the average diameter was measured with a transmission electron microscope at a magnification of 600,000 times for nanowires dried on a grid with a support film, and the average value of nanowire diameters at arbitrary 100 points in 10 fields of view was measured.
  • the average length is preferably 10 ⁇ m or more and 40 ⁇ m or less, more preferably 15 ⁇ m or more and 40 ⁇ m or less, and further preferably 15 ⁇ m or more and 30 ⁇ m or less from the viewpoint of further improving transparency and conductivity. 20 ⁇ m or more and 30 ⁇ m or less is more preferable.
  • the average length is the average length for any 200 nanowires.
  • the plurality of nanowires of the present invention need only be made of the same material as the nanowire described above, and may be, for example, a metal nanowire, or a nanowire of a semiconductor or a conductive polymer. Good.
  • the nanowire of the present invention is preferably a metal nanowire from the viewpoint of conductivity.
  • the metal nanowire of this invention is comprised from 1 or more types of metals selected from the group which consists of nickel, cobalt, and iron from the point of a manufacturing method.
  • the plurality of nanowires of the present invention is preferably composed of nickel and / or cobalt, particularly nickel.
  • the plurality of nanowires of the present invention preferably have a form that can be dispersed in a solvent.
  • a form dispersible in a solvent is a form in which the nanowire is added to a dispersion medium to be described later at a concentration of 0.1 to 2.0% by mass and stirred for 1 minute so that there is no visual aggregate. It is preferable that the nanowire is not cut.
  • the plurality of nanowires of the present invention preferably have substantially no polymer layer.
  • the nanowire has substantially no polymer layer. Even if the nanowire is stained with a phosphotungstic acid staining method and observed with a transmission electron microscope at a magnification of about 600,000 times, the surface of the nanowire This means that no polymer layer is observed.
  • the polymer layer is a form in which the polymer continuously covers the surface of the nanowire in the circumferential direction.
  • the nanowire may have a polymer that does not have such a layer form, but it is preferably not present from the viewpoint of improving dispersibility.
  • the circumferential direction of the nanowire is the circumferential direction of the nanowire in a cross section perpendicular to the longitudinal direction of the nanowire.
  • the manufacturing method of several nanowire is demonstrated, it is clear that one nanowire of this invention can also be manufactured.
  • the nanowire is a plurality of nanowires.
  • the nanowire (especially metal nanowire) of the present invention can be produced, for example, by the following method. Specifically, metal ions, particularly nickel ions are reduced in a magnetic field. The manufacturing method is shown below.
  • the shape (form) of the metal salt may be any form that is soluble in the solvent used and can supply metal ions in a reducible state.
  • the metal salt include metal (especially nickel) chloride, sulfate, nitrate, acetate, and the like. These salts may be hydrates or anhydrides.
  • the concentration of metal ions to be reduced is preferably 1.5 to 20 ⁇ mol / g, more preferably about 1.5 to 15 ⁇ mol / g, based on the total amount of the reaction solution, from the viewpoint of nanowire shape control. Preferably, it is more preferably about 1.5 to 10 ⁇ mol / g.
  • concentration of metal ions is 20 ⁇ mol / g or less, it is possible to suppress the occurrence of three-dimensional aggregation of nanowires (generation of a nonwoven fabric form).
  • concentration of metal ions is 1.5 ⁇ mol / g or more, nanowires satisfying the above shape can be produced.
  • examples of the reducing agent include hydrazine, hydrazine monohydrate, ferrous chloride, hypophosphorous acid, borohydride salts, aminoboranes, lithium aluminum hydride, sulfites, hydroxylamines. (Eg, diethylhydroxylamine), zinc amalgam, diisobutylaluminum hydride, hydroiodic acid, ascorbic acid, oxalic acid, formic acid, ferrous chloride, hypophosphorous acid, borohydride salts, aminoboranes, ascorbic acid, Examples include oxalic acid and formic acid.
  • Preferred reducing agents are hydrazine and hydrazine monohydrate.
  • the concentration of the reducing agent, particularly hydrazine monohydrate, is usually 0.05 to 1.0% by mass with respect to the reaction solution, and 0.1 to 0.00% from the viewpoint of suppressing the formation of the nonwoven fabric form. 5 mass% is preferable.
  • polyols such as ethylene glycol and propylene glycol are preferable.
  • metal salts (particularly nickel salts) and reducing agents can be dissolved, and boiling does not occur even at the reaction temperature, so that the reaction can be performed with good reproducibility.
  • the pH and temperature differ depending on the reducing agent, for example, when the reduction reaction is performed using hydrazine monohydrate in ethylene glycol, the temperature is preferably 70 to 100 ° C. and the pH is preferably 11 to 12. .
  • the central magnetic field of the reaction vessel is preferably about 10 to 200 mT, particularly 80 to 180 mT, from the viewpoint of shape control of the nanowire. Nanowires are not generated when the magnetic field is weak. Moreover, since it is difficult to generate a strong magnetic field, it is not realistic.
  • a nucleating agent and / or a complexing agent may be added to the reaction solution depending on the type of metal ions to be reduced and the reducing agent.
  • nucleating agent examples include salts of noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium and osmium.
  • noble metal salt examples include chloroplatinic acid, chloroauric acid, and palladium chloride.
  • Preferred nucleating agents are platinum salts, especially chloroplatinic acid.
  • the amount of the nucleating agent is not particularly limited as long as the transparency and conductivity improving effect of the present invention is obtained.
  • the number of moles of metal ions to be reduced with respect to 1 mole of noble metal ions of the nucleating agent is preferably 5,000 to 10,000,000, particularly 10,000 to 10,000,000.
  • the reduction time of the reduction reaction is not particularly limited as long as the nanowire of the present invention can be produced, and is, for example, 10 minutes to 1 hour, preferably 10 minutes to 30 minutes, from the viewpoint of shape control of the nanowire.
  • metal nanowire can be obtained by refine
  • the nanowire produced by the above production method is oxidized during production and purification, it is preferable to further perform a reduction treatment.
  • the reduction treatment it may be heated to about 150 ° C. in a polyol solvent such as ethylene glycol. Thereby, a peak derived from a metal simple substance can be confirmed on the nanowire surface by ESCA.
  • the present invention also provides a dispersion in which the nanowires are dispersed.
  • the concentration of nanowires in the dispersion is not particularly limited, and is preferably about 0.01 to 2.0% by mass from the viewpoint of further improving dispersibility.
  • the concentration is a ratio with respect to the total amount of the dispersion.
  • the dispersion medium is not particularly limited, but has a polar group such as a hydroxyl group on the surface of the nanowire. Therefore, alcohols such as ethylene glycol and isopropanol, and polar organic solvents such as acetonitrile, DMSO, and DMF are more preferable. .
  • the nanowire dispersion liquid of the present invention may contain additives such as a binder, an antioxidant, a wetting agent, and a leveling agent as long as the performance is not deteriorated.
  • antioxidant those having no antioxidant or by-product remaining after coating are preferable, and examples thereof include hydrazines and hydroxylamines.
  • concentration of the antioxidant in the dispersion is not particularly limited, but is preferably about 0.01 to 2.0% by mass in order to prevent the dispersibility from being lowered by the antioxidant.
  • the nanowire dispersion of the present invention can be obtained by adding the above nanowires to a dispersion medium containing a desired additive and stirring.
  • a film, a laminate, a wiring, and the like can be formed by applying the nanowire dispersion liquid of the present invention to a substrate and drying it.
  • the substrate include a glass substrate, a polyethylene terephthalate film, a polycarbonate film, a cycloolefin film, a polyimide film, and a polyamide film.
  • the application method is not particularly limited.
  • wire bar coater coating film applicator coating, spray coating, gravure roll coating method, screen printing method, reverse roll coating method, lip coating, air knife coating method, curtain flow coating method, dip coating.
  • Method die coating method, spray method, letterpress printing method, intaglio printing method, and ink jet method.
  • the nanowire film is a nanowire layer that does not contain a binder, and is useful for the use of a transparent conductive film.
  • the nanowire film can be formed by applying the nanowire dispersion of the present invention containing no binder onto a substrate and drying.
  • a photocurable resin or the like is applied on the nanowire film so that the nanowire film is not peeled off from the substrate. be able to.
  • the transparent conductive film usually includes a base material and a nanowire film formed on the base material.
  • the transparent conductive film is also sufficiently excellent in transparency and conductivity.
  • the coating amount of the nanowire dispersion liquid is increased in order to obtain a good surface resistance value in the nanowire film or the transparent conductive film, the transmittance of the film generally decreases significantly.
  • the nanowire dispersion liquid of the present invention is used, even if the coating amount is increased in order to achieve a sufficiently low surface resistance value, the decrease in transmittance is sufficiently suppressed. Therefore, the nanowire and nanowire film
  • the nanowire film achieves a transmittance of 85% or more, preferably 88% or more, more preferably 91% or more when the surface resistance value is 100 ⁇ / ⁇ , for example.
  • the transmittance when the surface resistance value is 100 ⁇ / ⁇ is, for example, the surface resistance value and transmission of five types of nanowire films in which the coating amount is changed so that the surface resistance value of the nanowire film is about 100 ⁇ / ⁇ . It can be obtained by measuring the rate and reading from the graph of surface resistance and transmittance. Detailed measurement methods of the surface resistance value and transmittance of the nanowire film are as shown in the Examples.
  • the basis weight of the nanowire film is usually 1 to 30 mg / m 2 , preferably a 5 ⁇ 20mg / m 2.
  • the obtained nanowire dispersion liquid was applied onto a slide glass with an applicator to obtain five nanowire films having different transmittances (coating amounts).
  • the surface resistance value of the obtained nanowire film was measured with a resistivity meter MCP-T610 manufactured by Mitsubishi Chemical Analytech.
  • permeability the light transmittance in wavelength 550nm was measured for the slide glass as the blank value. Therefore, the transmittance is the transmittance of only the nanowire film.
  • the obtained surface resistance values and the corresponding transmittances are shown in Tables 3 to 8, and are shown in FIGS.
  • the examples and comparative examples described in each table or figure are a combination of examples and comparative examples in which the average diameter and average length of the nanowires are substantially equivalent so that a significant comparison is possible.
  • Example 1 0.25 g (1.05 mmol) of nickel chloride hexahydrate was added to ethylene glycol to make a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride. On the other hand, 0.40 g of sodium hydroxide and 30.7 ⁇ g (59.4 nmol) of chloroplatinic acid hexahydrate were added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide and chloroplatinic acid. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 10 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • a TEM image of the nanowire produced in this example is shown in FIG.
  • Example 2 Nickel chloride hexahydrate 0.20 g (0.84 mmol) was added to ethylene glycol to make a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride. On the other hand, 0.40 g of sodium hydroxide and 30.7 ⁇ g (59.4 nmol) of chloroplatinic acid hexahydrate were added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide and chloroplatinic acid. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 8.4 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the obtained nanowire was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid containing 0.5% by mass of nanowire and 0.5% by mass of hydrazine monohydrate.
  • Example 3 Nickel chloride hexahydrate 0.20 g (0.84 mmol) was added to ethylene glycol to make a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride. On the other hand, 0.40 g of sodium hydroxide was added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 8.4 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Example 4 Nickel chloride hexahydrate 0.20 g (0.84 mmol) and trisodium citrate dihydrate 50 mg (0.17 mmol) were added to ethylene glycol to make a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride. On the other hand, 0.40 g of sodium hydroxide was added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 8.4 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Nickel chloride hexahydrate 0.20 g (0.84 mmol) and trisodium citrate dihydrate 100 mg (0.34 mmol) were added to ethylene glycol to a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride.
  • 0.40 g of sodium hydroxide was added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 8.4 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Example 6 0.25 g (1.05 mmol) of nickel chloride hexahydrate was added to ethylene glycol to make a total amount of 50 g. This solution was heated to 90 ° C. to dissolve nickel chloride. On the other hand, 0.40 g of sodium hydroxide and 30.7 ⁇ g (59.4 nmol) of chloroplatinic acid hexahydrate were added to ethylene glycol to make a total amount of 49.9 g. This solution was heated to 90 ° C. to dissolve sodium hydroxide and chloroplatinic acid. After all the compounds in each solution were dissolved, 0.1 g of hydrazine monohydrate was dissolved in a solution containing sodium hydroxide, and then the two solutions were mixed.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 100 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 10 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Comparative Example 1 The silver nanowire dispersion (Agnws-90) manufactured by AGS Material is added to isopropanol containing hydrazine monohydrate, so that the nanowire concentration is 0.5 mass% and the hydrazine monohydrate concentration is 0.5 mass%. A nanowire dispersion was prepared.
  • Nanowires were produced by reducing metal ions without using a magnetic field by the same method as in Japanese Patent Application Laid-Open No. 2012-238592.
  • the obtained nanowire was mixed with 30 g of ethylene glycol with respect to 50 mg of nanowire, and heated at 150 ° C. for 3 hours. After heating, the nanowires are collected with a magnet, and the obtained nanowires are added to isopropanol contained in hydrazine monohydrate, and the nanowire concentration is 0.5 mass% and the hydrazine monohydrate concentration is 0.5 mass%.
  • a nanowire dispersion was prepared.
  • the mixed solution was immediately put in a magnetic circuit capable of applying a magnetic field of 150 mT at the center, and the magnetic field was applied, and the mixture was allowed to stand for 15 minutes while maintaining at 90 to 95 ° C. to carry out a reduction reaction.
  • the pH was 11.5.
  • the concentration of nickel ions in the reaction solution was 12.6 ⁇ mol / g.
  • the nanowires were collected with a neodymium magnet and purified and recovered.
  • the collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet.
  • the nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Comparative Example 8 A nanowire dispersion was prepared in the same manner as in International Publication No. 2015/163258. Specifically, the following method was used. In ethylene glycol, 0.40 g (1.68 mmol) of nickel chloride hexahydrate and 50 mg (0.17 mmol) of trisodium citrate dihydrate were dissolved. Furthermore, 0.32 g of sodium hydroxide, 3.0 g of dried product of Pitzkol K120L made by Daiichi Kogyo Seiyaku, and 0.92 ml of 0.054M chloroplatinic acid aqueous solution were dissolved in order, and ethylene glycol was added so that the total amount became 75 g. Added.
  • nanowires In order to purify and collect the nanowires from the obtained reaction solution, 100 g of the reaction solution was diluted 10 times with ethylene glycol, and the nanowires were collected and collected with a neodymium magnet and purified and collected. The collected nanowire was mixed with 30 g of ethylene glycol and heated at 150 ° C. for 3 hours. After heating, nickel nanowires were obtained by collecting again with a magnet. The nanowire obtained was added to isopropanol contained in hydrazine monohydrate to prepare a nanowire dispersion liquid having a nanowire concentration of 0.5 mass% and a hydrazine monohydrate concentration of 0.5 mass%.
  • Tables 1 to 9 show the evaluation results of the nanowires obtained in Examples and Comparative Examples and nanowire dispersions. The results of evaluation are shown in Tables 3 to 8 for each combination of Examples and Comparative Examples in which the average diameter and average length of the nanowires are substantially equivalent, and graphs of the surface resistance value and transmittance of the nanowires are shown in FIG. This is shown in FIG. In each figure, “1.E + 01” means “10”, “1.E + 02” means “100”, and “1.E + 03” means “1000”.
  • the transmittance (T) when the surface resistance value was 100 ⁇ / ⁇ was read from each graph, shown in Table 9, and evaluated according to the following ranking.
  • the nanowires of Examples 1 to 6 satisfy the above formula (1-1): average of A / B values, formula (2-1): average of A + B values, and average length of nanowires. Therefore, the nanowire film composed of these nanowires has sufficient surface resistance and transmittance than the conventional nickel nanowire or nanowire film composed of nanowires with similar average length and average diameter. It was excellent.
  • the nanowire film composed of the nanowires of Examples 1 and 4 achieved a higher transmittance even with a lower surface resistance value.
  • Comparative Example 1 is a general silver nanowire. Although the volume resistivity value is lower than that of nickel, silver does not satisfy the shape defined in the present invention. Therefore, the nickel nanowire of Example 1 having the same average diameter and average length has The surface resistance and transmittance were inferior. A graph of the surface resistance value and the transmittance of the nanowire of Example 1 and the nanowire of Comparative Example 1 is shown in FIG.
  • Comparative Examples 2 to 8 are nickel nanowires having an average diameter and an average length corresponding to each example, but do not satisfy the shape defined in the present invention, and therefore each of the examples having the same average diameter and average length.
  • the surface resistance and transmittance were inferior to the nickel nanowires in the examples.
  • 2 to 7 show graphs of the surface resistance value and transmittance of the nanowires of the comparative examples corresponding to the nanowires of the examples.
  • the nanowire of the present invention is useful as a conductive material for a transparent electrode and a transparent conductive film, particularly a flexible transparent conductive film such as a transparent conductive film for a touch panel.

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