WO2009107694A1 - 金属ナノワイヤの製造方法並びに得られた金属ナノワイヤよりなる分散液および透明導電膜 - Google Patents

金属ナノワイヤの製造方法並びに得られた金属ナノワイヤよりなる分散液および透明導電膜 Download PDF

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WO2009107694A1
WO2009107694A1 PCT/JP2009/053489 JP2009053489W WO2009107694A1 WO 2009107694 A1 WO2009107694 A1 WO 2009107694A1 JP 2009053489 W JP2009053489 W JP 2009053489W WO 2009107694 A1 WO2009107694 A1 WO 2009107694A1
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metal
dispersion
metal nanowires
transparent conductive
producing
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PCT/JP2009/053489
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English (en)
French (fr)
Japanese (ja)
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高広 北野
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株式会社クラレ
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Priority to JP2010500727A priority Critical patent/JP5507440B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/10—Cross-flow filtration

Definitions

  • the present invention relates to a method for producing metal nanowires, and more specifically, a method for producing metal nanowires including a step of removing impurities by a cross-flow filtration method.
  • a dispersion liquid in which the obtained metal nanowires are dispersed and a transparent conductive film made of the metal nanowires are dispersed and a transparent conductive film made of the metal nanowires.
  • a transparent conductive film used for a transparent electrode or the like has been mainly dry coating such as sputtering.
  • these methods are batch-type, the manufacturing cost is high, and a manufacturing method capable of continuous production is desired.
  • a high temperature is required at the time of coating, and there is a drawback that a resin substrate such as a plastic film cannot be used.
  • Patent Documents 1 and 2 As a method for solving this problem, wet coating is considered, and a network structure using noble metal fine particles has been proposed as one of material candidates (Patent Documents 1 and 2).
  • Patent Document 1 requires a vapor deposition process in a vacuum system, and it is necessary to pre-treat the substrate before the metal vapor deposition process. is there.
  • Patent Document 2 is an excellent method in which wet coating such as spin coating is possible and can be produced continuously, but there is a problem that a plastic substrate cannot be used because a firing process is essential.
  • Non-Patent Document 1 discloses a method for producing silver nanowires by polyol reduction. Although this method is one of the very effective methods for producing metal nanowires, centrifugation is employed as a method for separating silver fine particles generated as a by-product. The method of recovering metal nanowires as a precipitate by centrifugation is a convenient method for recovery, but in order to produce a transparent conductive film, silver nanowires that have been recovered once in a solid state must be dispersed again in a solvent. .
  • the silver nanowires once collected in a solid state are entangled with each other, and are not easily loosened, making it difficult to produce a dispersion of silver nanowires.
  • an object of the present invention is to provide a method for producing metal nanowires with little entanglement and a transparent conductive film using the same.
  • the present invention that solves the above-mentioned problems is a method for producing metal nanowires that includes a step of cross-flow filtering a dispersion in which crude metal nanowires are dispersed.
  • the metal nanowire is preferably a silver nanowire, and more preferably the silver nanowire is produced by a polyol reduction method.
  • the cross flow filtration method is preferably an internal pressure type circulation filtration method using a hollow fiber membrane, and in particular, the internal pressure type circulation filtration method using a hollow fiber membrane is a hollow fiber membrane having a pore diameter of 0.5 ⁇ m or more. It is more preferable to use Moreover, in the internal pressure type circulation filtration using the hollow fiber membrane, it is more preferable that the flow rate of the dispersion liquid in which the crude metal nanowires are dispersed is 50 mm / second or more and 500 mm / second or less in linear velocity.
  • the dispersion solvent of the dispersion in which the crude metal nanowires are used used in the cross flow filtration method is any one of methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, and 1-butanol.
  • the metal nanowire obtained by the present invention has a short-axis length of 10 nm to 500 nm and a long-axis length of 1 ⁇ m to 100 ⁇ m.
  • the present invention also provides a dispersion obtained by dispersing the metal nanowires obtained by the above-described production method in a dispersion solvent, wherein the solid content concentration is 0.1% by mass or more and 20% by mass or less. It is a dispersion.
  • the dispersion solvent is preferably a single or mixed solvent selected from methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, water, and ethylene glycol.
  • this invention is a transparent conductive film containing the transparent conductive layer which consists of metal nanowire obtained by the manufacturing method of above-described this invention, and the intersection part of several metal nanowire which comprises a transparent conductive layer is especially joined. It is preferable. More preferably, the intersections are joined by pressure bonding or plating.
  • the manufacturing method of the metal nanowire which concerns on this invention can obtain the metal nanowire with few entanglements of metal nanowires. For this reason, there is little loss of metal nanowire and it can manufacture with a high yield. It is also easy to scale up. Moreover, since there are few entanglements of metal nanowires, a dispersion liquid with less entanglement of metal nanowires can be easily produced. For this reason, a highly concentrated dispersion liquid can be made. Further, the solvent of the dispersion can be easily changed. In addition, since a dispersion liquid with less entanglement of metal nanowires can be used, a transparent conductive film with less aggregate and high transmittance can be obtained.
  • FIG. 2 is a result of scanning microscope observation of silver nanowires obtained in Example 1.
  • FIG. 2 is a result of scanning microscope observation of silver nanowires obtained in Example 1.
  • FIG. 3 is a diagram illustrating an example of a pressurizing method performed in Example 1.
  • FIG. It is a scanning microscope observation result of the transparent conductive film obtained in Comparative Example 1. It is the figure which compared the length distribution of the silver nanowire obtained in Example 1 and Comparative Example 1.
  • the present invention is a method for producing metal nanowires that includes a step of removing impurities by a cross-flow filtration method.
  • the material of the metal nanowire used in the present invention is a metal. It does not include ceramics such as metal oxides and nitrides. Specific examples include iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, cadmium, osmium, iridium, platinum, and gold, and copper, silver, platinum, and gold are preferable from the viewpoint of conductivity. Silver is more preferred.
  • the shape of the metal nanowire used in the present invention is not particularly limited as long as the ratio of the length in the minor axis direction to the length in the major axis direction (hereinafter sometimes referred to as aspect ratio) is 10 or more. However, since handling becomes difficult when the aspect ratio is too large, the ratio is preferably 10,000 or less, and more preferably 1,000 or less.
  • a linear metal nanowire is preferable.
  • the straight metal nanowire means that the shape is a rod shape, and does not include a branched shape or a shape in which particles are connected in a bead shape. However, if the metal nanowire has low rigidity and is bent or bent like a banana, it is included in the straight metal nanowire.
  • the length of the metal nanowire in the minor axis direction is preferably 1 nm or more and 1 ⁇ m or less, and more preferably 10 nm or more and 500 nm or less. This is because if the length in the minor axis direction is too large, the transmittance decreases, and if it is too small, synthesis becomes difficult.
  • the length in the major axis direction is preferably 1 ⁇ m or more and 1 mm or less, and more preferably 10 ⁇ m or more and 100 ⁇ m or less. This is because if the length in the major axis direction is too short, the conductivity is lowered, and if it is too long, handling becomes difficult.
  • the shape and size of the metal nanowire can be confirmed with a scanning electron microscope or a transmission electron microscope.
  • the metal nanowire can be synthesized by a known method.
  • a method of reducing silver nitrate in a solution or a method in which an applied voltage or current is applied to the precursor surface from the tip of the probe to pull out the metal nanowire at the tip of the probe and continuously form the metal nanowire (Patent Document) 4) and the like.
  • silver nitrate is reduced in solution by a method of reducing nanofibers composed of metal complexed peptide lipids (Patent Document 5) or a method called polyol reduction, while heating in ethylene glycol.
  • Examples include a method of reducing (Patent Document 6), a method of reducing in sodium citrate (Non-Patent Document 1), and the like.
  • the method of reducing with heating in ethylene glycol is preferable because metal nanowires with high crystallinity can be obtained most easily.
  • the cross-flow filtration method in the present invention represents a filtration method in which a supply liquid flows along a membrane surface, and a permeate passing through the membrane flows in a direction perpendicular to the supply liquid.
  • Specific examples include a flat membrane method and a hollow fiber membrane method, but a hollow fiber membrane method is preferable from the viewpoint of scale-up and ease of handling.
  • the pore size of the filtration membrane used in the present invention varies depending on the particle size of impurities contained in the liquid to be filtered, but is preferably 0.1 ⁇ m or more and 1 ⁇ m or less, preferably 0.2 ⁇ m or more and 1 ⁇ m or less, and preferably 0.2 ⁇ m or more and 1 ⁇ m or less. And more preferably 0.5 ⁇ m or more and 1 ⁇ m or less.
  • the linear velocity is preferably 10 mm / second or more and 1000 mm / second, and more preferably 50 mm / second or more and 500 mm / second or less.
  • the linear velocity represents the supply amount of the supply liquid with respect to the long fiber direction of the hollow fiber membrane.
  • the linear velocity of 10 mm / second represents the supply amount of 10 mm per second with respect to the long fiber direction of the hollow fiber membrane.
  • the linear velocity is too high, the metal nanowire may be damaged, and if it is too low, the efficiency may be lowered.
  • washing solvent used in the crossflow filtration method
  • methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1- Butanol, water, or a mixed solvent thereof is preferable. It is also possible to change the solvent during filtration.
  • the present invention also provides a dispersion of metal nanowires obtained by the above production method.
  • a process of taking out the metal nanowires once in a solid state is necessary, and therefore, a process of redispersion is necessary or the metal nanowires are damaged at the time of redispersion.
  • the method for producing metal nanowires according to the present invention solves these problems, and in principle there is no decrease in yield in this step.
  • the solid concentration of the metal nanowire dispersion according to the present invention is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less. preferable. If the solid content concentration is too small, the number of times of coating until the desired resistance value is increased, and if the solid content concentration is too large, the metal nanowires may be damaged during handling.
  • the solvent of the dispersion of the metal nanowires according to the present invention is not particularly limited, but methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol from the viewpoint of workability during coating and preferred solvent types in the crossflow filtration step. More preferably, it is a single or mixed solvent selected from 1-butanol, water, and ethylene glycol.
  • the present invention also provides a transparent conductive film containing metal nanowires obtained by the above production method.
  • the transparent conductive film according to the present invention is not particularly limited as long as the transparent conductive layer containing at least the metal nanowire is laminated on the base material, but in a range not impairing the effects of the present invention, a protective layer, an undercoat layer, There may be a hard coat layer, an antistatic layer, an antiglare layer, an antireflection layer, a color filter layer, a retardation film layer and the like.
  • a specific layer structure a layer structure in which a protective layer and an antireflection layer are laminated on a transparent conductive layer as shown in FIGS. 1 and 2, and a transparent conductive film is formed on a hard coat layer as shown in FIG. And a layer configuration in which an antiglare layer is provided on the side opposite to the transparent conductive layer as shown in FIG.
  • a protective layer on the transparent conductive layer.
  • thermoplastic resins such as polyester resin, cellulose resin, vinyl alcohol resin, vinyl resin, cycloolefin resin, polycarbonate resin, acrylic resin, ABS resin, photocurable resin, and heat
  • a known coating material such as a curable resin can be used.
  • the material of the protective layer is preferably the same material as the base material from the viewpoint of adhesion.
  • the base material is a polyester resin
  • the protective layer is preferably a polyester resin.
  • the thickness of the protective layer is too thick, the contact resistance of the transparent conductive layer increases, and if it is too thin, the effect as a protective layer cannot be obtained, and is preferably 1 nm or more and 1 ⁇ m or less, and preferably 10 nm or more and 100 nm or less.
  • the substrate is not particularly limited as long as it is in the form of a sheet or film.
  • ceramics such as glass and alumina, metals such as iron, aluminum and copper, polyester resins, cellulose resins, vinyl alcohol resins, and chlorides.
  • vinyl resins cycloolefin resins, polycarbonate resins, acrylic resins, ABS resins, and other thermoplastic resins, photo-curing resins, thermosetting resins, etc., and emphasizing transparency when using the transparent conductive film according to the present invention.
  • the total light transmittance of the said base material is 80% or more, Specifically, glass, a polyester resin, a polycarbonate resin, an acrylic resin, a cellulose resin etc. are mentioned.
  • the preferable range of the thickness of the base material varies depending on the use, but is preferably 500 ⁇ m or more and 10 mm or less in the case of a sheet, and preferably 10 ⁇ m or more and 500 ⁇ m or less in the case of a film.
  • components other than metal nanowires can be added to the transparent conductive layer as long as the effects of the present invention are not impaired.
  • Photocurable resin, binder components such as epoxy-based, melamine-based, and silicon-based thermosetting resins, surfactants, pigments, and the like.
  • the blending ratio of other components such as metal nanowire and binder can be arbitrarily changed according to the application, but if the blending ratio of metal nanowire is too small, there is a risk that the conductivity will decrease, so the transparent conductive layer
  • the weight ratio of the metal nanowires in the whole is preferably 10% by mass or more and 100% by mass or less, and more preferably 30% by mass or more and 60% by mass or less.
  • the intersections of the metal nanowires are joined. This is because the contact resistance between the linear metal nanowires is lowered by joining the intersections, and as a result, the surface resistance value of the transparent conductive layer is lowered.
  • the intersection portion between the linear metal nanowires is a portion where the linear metal nanowires appear to overlap each other when the transparent conductive layer in which the linear metal nanowires are dispersed in a network is viewed from directly above. It is preferable that the intersections are joined by pressure bonding or plating. Being crimped represents a state in which the intersection portion is deformed and the contact areas of the linear metal nanowires are increased.
  • being plated refers to a state in which the intersection portion of the linear metal nanowires is thicker than before plating and the contact area is increased. In the present invention, it is not necessary that all the intersections are joined, and may be a part. This is because even if it is a part, the effect of lowering the surface resistance value of the transparent conductive layer can be obtained. Whether or not the intersection part of the linear metal nanowires is pressure-bonded or plated can be confirmed by the presence or absence of deformation of the intersection part with a scanning electron microscope or a transmission electron microscope.
  • the surface resistance value of the transparent conductive film according to the present invention is preferably 0.1 ⁇ / ⁇ or more and 100000 ⁇ / ⁇ or less, and more preferably 1 ⁇ / ⁇ or more and 1000 ⁇ / ⁇ or less. This is because if the surface resistance value is too high, the possibility of being used as an electrode is lowered, and if the surface resistance value is too low, the transmittance is lowered in exchange and the possibility of being unavailable as an optical member is increased.
  • the total light transmittance of the transparent conductive film used in the present invention varies depending on the substrate to be used, the total light transmittance is preferably 60% or more and 99% or less, and more preferably 70% or more and 90% or less.
  • the total light transmittance of a transparent conductive film here refers to the total light transmittance as a transparent conductive film including a substrate, not the total light transmittance of only the transparent conductive layer. This is because if the total light transmittance is too high, the surface resistance value becomes too high in exchange and the possibility of being used as an electrode is reduced, and if the total light transmittance is too low, the possibility of being usable as an optical member is reduced. .
  • Example 1 In a 1 L three-necked flask, 333.9 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 48 ng of sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 41 ng of tris (2,4-pentanedionate) iron (III) (manufactured by Aldrich) was heated to 160 ° C.
  • the resulting crude silver nanowire dispersion was subjected to pressure-type hollow fiber membrane filtration (trade name Midi cross crossflow module membrane area 80 cm 2 pore size 0.5 ⁇ m hollow fiber diameter 0.5mm Spectrum Co.).
  • the cleaning solvent is 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the linear velocity is 150 mm / sec.
  • the filtration was concentrated to obtain 20 g of a 2-propanol dispersion of purified silver nanowires.
  • 2-propanol is added to the obtained dispersion of purified silver nanowires to obtain a solid content concentration of 3.0% by mass, and then a PET film (product name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) is 18 ⁇ m in wet film thickness. Bar coated on top. The laminate was dried at 80 ° C. for 3 minutes.
  • a PET film with a release layer (trade name: Cosmo Shine K1572 manufactured by Toyobo Co., Ltd.) is stacked on the laminated film so that the release layer is in contact with the transparent conductive layer, and as shown in FIG. The surface was rubbed with a pestle to apply pressure to the transparent conductive layer surface. The results are shown in Table 1.
  • Example 2 A diameter of the hollow fiber is 1mm as internal pressure type hollow fiber membrane using a (trade name Midi cross crossflow module membrane area 60cm 2 pore size 0.5 ⁇ m Spectrum Co.), is carried out except that the linear velocity 500 mm / sec The same operation as in Example 1 was performed. The results are shown in Table 1.
  • Example 3 2-propanol is added to the resulting purified silver nanowire dispersion to adjust the solid concentration to 0.1% by mass, and then a PET film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) is 18 ⁇ m in wet film thickness. Bar coated on top.
  • a PET film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) is 18 ⁇ m in wet film thickness. Bar coated on top.
  • Example 4 2-propanol is added to the resulting purified silver nanowire dispersion to adjust the solid concentration to 0.1% by mass, and then a PET film (trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.) is 18 ⁇ m in wet film thickness. Bar coated on top.
  • a PET film trade name: Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.
  • Example 5 A polyester resin (trade name Byron UR-4800, manufactured by Toyobo Co., Ltd.) was spray-coated on the transparent conductive film obtained in Example 1 so that the film thickness was 10 nm. When the obtained film was subjected to a cross-cut test (JIS K5400), it was 100/100 and no peeling was observed. Table 1 shows the results of the surface resistance and the total light transmittance of the transparent conductive film obtained.
  • Example 6 A butyral resin (trade name: MOWITAL B60H, manufactured by KSE) was added to the 3% by mass silver nanowire dispersion obtained in Example 1 so that the concentration of the silver nanowires relative to the solid content was 37.5% by mass, and PET film (Product name: Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) was applied with a wet film thickness of 30 ⁇ m and dried at 80 ° C. for 3 minutes to obtain a laminated film. A pressure was applied to the surface of the transparent conductive layer in the same manner as in Example 1 for the obtained laminated film. When the obtained film was subjected to a cross-cut test (JIS K5400), it was 100/100 and no peeling was observed. The results are shown in Table 1.
  • the obtained silver nanowire dispersion was bar-coated on a PET film (trade name: Cosmo Shine A4100, total light transmittance 92%, manufactured by Toyobo Co., Ltd.) so as to have a wet film thickness of 3 ⁇ m.
  • the laminate film was obtained by drying at 80 ° C. for 3 minutes.
  • pressure was applied to the transparent conductive layer surface. The results are shown in Table 1.
  • FIG. 1 shows a method for producing metal nanowires according to the method of the present invention
  • FIG. 8 shows a method for producing metal nanowires according to the prior art.
  • Example 1 and Comparative Example 1 when Example 1 and Comparative Example 1 are compared, the yields of metal nanowires are 59% and 4%, respectively. Therefore, it is clear that the method for producing metal nanowires by the method of the present invention has a higher yield than the conventional method.
  • the surface resistance value (device name: manufactured by Loresta EP Dia Instruments Co., Ltd.), total light transmittance, and haze value (device name direct reading haze computer, manufactured by Suga Test Instruments Co., Ltd.) of the obtained transparent conductive film were measured. The results are shown in Table 1.
  • FIG. 9 shows the length distribution of the silver nanowires obtained in Example 1 and Comparative Example 1. From the above results, it can be seen that the mode value of Example 1 is 6 ⁇ m to 8 ⁇ m, and the mode value of Comparative Example 1 is 2 ⁇ m to 4 ⁇ m. That is, it can be seen that the production method of the present invention can selectively produce long metal nanowires compared to the conventional method.

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PCT/JP2009/053489 2008-02-27 2009-02-26 金属ナノワイヤの製造方法並びに得られた金属ナノワイヤよりなる分散液および透明導電膜 WO2009107694A1 (ja)

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WO2010150619A1 (ja) * 2009-06-24 2010-12-29 コニカミノルタホールディングス株式会社 透明電極、該透明電極に用いられる導電性繊維の精製方法、及び有機エレクトロルミネッセンス素子
US20120088656A1 (en) * 2010-10-06 2012-04-12 The Research Foundation Of State University Of New York Nanostructures having enhanced catalytic performance and method for preparing same
US20130008690A1 (en) * 2009-12-07 2013-01-10 Duke University Compositions and methods for growing copper nanowires
WO2013025312A1 (en) * 2011-08-12 2013-02-21 Carestream Health, Inc. Nanowire purification methods, compositions, and articles
WO2013047197A1 (ja) * 2011-09-29 2013-04-04 富士フイルム株式会社 透明導電性塗布膜、透明導電性インク、及びそれらを用いたタッチパネル
JP2013199690A (ja) * 2012-03-26 2013-10-03 Fujifilm Corp 金属ナノワイヤ分散液の製造方法、金属ナノワイヤ分散液、金属ナノワイヤ分散液を用いて形成された導電性部材、及びその導電性部材を用いたタッチパネル、及び太陽電池
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JP2014507553A (ja) * 2010-12-09 2014-03-27 ケアストリーム ヘルス インク ナノワイヤ調製方法、組成物、および物品
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JP2014523047A (ja) * 2011-07-12 2014-09-08 エルジー イノテック カンパニー リミテッド タッチパネル及び電極製造方法
CN104700927A (zh) * 2013-12-04 2015-06-10 三星Sdi株式会社 透明导体、制备其的方法以及包括其的光学显示器
WO2015083421A1 (ja) 2013-12-02 2015-06-11 住友理工株式会社 導電性材料およびそれを用いたトランスデューサ
WO2015115630A1 (ja) * 2014-02-03 2015-08-06 デクセリアルズ株式会社 透明導電膜及びその製造方法、情報入力装置、並びに、電子機器
JP2016066590A (ja) * 2014-06-09 2016-04-28 日立化成株式会社 導電フィルム、感光性導電フィルム、導電膜の形成方法、導電パターンの形成方法及び導電膜基材
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WO2017098207A1 (en) * 2015-12-08 2017-06-15 Quantum Chemical Technologies (Singapore) Pte. Ltd. Methods of purifying nanostructures
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61127198A (ja) * 1984-11-26 1986-06-14 日本精線株式会社 導電性複合体
JPH11504638A (ja) * 1995-05-08 1999-04-27 ノバルティス・アクチエンゲゼルシャフト 低溶解性の薬剤の経口投与のためのナノ粒子
JP2001225406A (ja) * 2000-02-17 2001-08-21 Nippon Telegr & Teleph Corp <Ntt> 分子導線と金属電極の接続方法および基板
WO2003068674A1 (fr) * 2002-02-15 2003-08-21 Japan Science And Technology Agency Structure de fils nanometriques en metal noble et leur procede de production
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
JP2005524635A (ja) * 2002-02-08 2005-08-18 アボット ゲーエムベーハー ウント カンパニー カーゲー 難溶性化合物から水分散性の乾燥粉末を生成するための製法
WO2006113207A2 (en) * 2005-04-13 2006-10-26 Nanosys, Inc. Nanowire dispersion compositions and uses thereof
JP2007215542A (ja) * 2006-01-20 2007-08-30 Ezaki Glico Co Ltd 水溶性キシランによる、難溶性または不溶性の物質の溶媒への親和性向上

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007320828A (ja) * 2006-06-02 2007-12-13 Horiba Ltd カーボンナノチューブ含有物質の作成方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61127198A (ja) * 1984-11-26 1986-06-14 日本精線株式会社 導電性複合体
JPH11504638A (ja) * 1995-05-08 1999-04-27 ノバルティス・アクチエンゲゼルシャフト 低溶解性の薬剤の経口投与のためのナノ粒子
JP2001225406A (ja) * 2000-02-17 2001-08-21 Nippon Telegr & Teleph Corp <Ntt> 分子導線と金属電極の接続方法および基板
JP2005524635A (ja) * 2002-02-08 2005-08-18 アボット ゲーエムベーハー ウント カンパニー カーゲー 難溶性化合物から水分散性の乾燥粉末を生成するための製法
WO2003068674A1 (fr) * 2002-02-15 2003-08-21 Japan Science And Technology Agency Structure de fils nanometriques en metal noble et leur procede de production
US20050056118A1 (en) * 2002-12-09 2005-03-17 Younan Xia Methods of nanostructure formation and shape selection
WO2006113207A2 (en) * 2005-04-13 2006-10-26 Nanosys, Inc. Nanowire dispersion compositions and uses thereof
JP2007215542A (ja) * 2006-01-20 2007-08-30 Ezaki Glico Co Ltd 水溶性キシランによる、難溶性または不溶性の物質の溶媒への親和性向上

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WO2010150619A1 (ja) * 2009-06-24 2010-12-29 コニカミノルタホールディングス株式会社 透明電極、該透明電極に用いられる導電性繊維の精製方法、及び有機エレクトロルミネッセンス素子
US20130008690A1 (en) * 2009-12-07 2013-01-10 Duke University Compositions and methods for growing copper nanowires
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US20120088656A1 (en) * 2010-10-06 2012-04-12 The Research Foundation Of State University Of New York Nanostructures having enhanced catalytic performance and method for preparing same
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US9528168B2 (en) 2010-12-14 2016-12-27 Lg Innotek Co., Ltd. Nano wire and method for manufacturing the same
JP2014505787A (ja) * 2010-12-14 2014-03-06 エルジー イノテック カンパニー リミテッド ナノワイヤー及びその製造方法
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WO2013025312A1 (en) * 2011-08-12 2013-02-21 Carestream Health, Inc. Nanowire purification methods, compositions, and articles
JP2013084571A (ja) * 2011-09-29 2013-05-09 Fujifilm Corp 透明導電性塗布膜、透明導電性インク、及びそれらを用いたタッチパネル
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WO2013047197A1 (ja) * 2011-09-29 2013-04-04 富士フイルム株式会社 透明導電性塗布膜、透明導電性インク、及びそれらを用いたタッチパネル
JP2013199690A (ja) * 2012-03-26 2013-10-03 Fujifilm Corp 金属ナノワイヤ分散液の製造方法、金属ナノワイヤ分散液、金属ナノワイヤ分散液を用いて形成された導電性部材、及びその導電性部材を用いたタッチパネル、及び太陽電池
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