WO2020175255A1 - Nanofils d'argent, leur procédé de production, solution réactionnelle contenant des nanofils d'argent et dispersion de nanofils d'argent - Google Patents

Nanofils d'argent, leur procédé de production, solution réactionnelle contenant des nanofils d'argent et dispersion de nanofils d'argent Download PDF

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WO2020175255A1
WO2020175255A1 PCT/JP2020/006397 JP2020006397W WO2020175255A1 WO 2020175255 A1 WO2020175255 A1 WO 2020175255A1 JP 2020006397 W JP2020006397 W JP 2020006397W WO 2020175255 A1 WO2020175255 A1 WO 2020175255A1
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silver
silver nanowire
alcohol
vinylpyrrolidone
solution
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Japanese (ja)
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崇 樋之津
王高 佐藤
健介 柳田
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Ｄｏｗａエレクトロニクス株式会社
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Definitions

  • Silver nanowires production method thereof, reaction liquid containing silver nanowires, and silver nanowire dispersion liquid
  • the present invention provides a silver nanowire having a small diameter and a small variation in diameter distribution, which is useful as a conductive material (filler) for a transparent conductive film, a method for producing the same, and a reaction used for the reduction deposition reaction of the silver nanowire. Regarding the reaction solution after completion.
  • the present invention also relates to a silver nanowire dispersion liquid containing the silver nanowire.
  • nanowire a fine metal wire having a thickness of about 200 n or less is referred to as "nanowire”. ()”.
  • Silver nanowires are regarded as promising as a conductive material for imparting conductivity to a transparent base material.
  • Glass coating solution containing silver nanowires After being applied to a transparent substrate such as (polyethylene terephthalate) or ⁇ (polycarbonate), the liquid components are removed by evaporation, etc., and the silver nanowires form a conductive network by contacting each other on the substrate. It is possible to realize a transparent conductive film.
  • a transparent conductive film used for a touch panel or the like of an electronic device is required to have good conductivity and clear visibility with less haze.
  • the average diameter of the wire is simply thin, it is difficult to sufficiently support the further improvement in quality of the transparent conductive film. Even if the average diameter is small, if a large amount of thick wires are mixed, those thick wires will hinder the haze reduction effect.
  • the diameter of each individual wire should be as uniform as possible. ⁇ 2020/175 255 2 (: 170? 2020 /006397
  • the dispersion of the diameter distribution is small. Further, in order to accurately control the sheet resistance of the transparent conductive film within a predetermined range based on the silver concentration in the coating silver nanowire dispersion liquid, it is advantageous that the variation in the diameter distribution is small.
  • Patent Document 1 shows an example in which thin silver nanowires having an average short axis diameter of 15.1 nm or 16.4 nm are synthesized (Samples 8 and 10 in Fig. 1).
  • an aqueous solvent is used in the seed particle synthesis step (Preparation Examples 8 and 1) and the growth step (Preparation Examples 16 and 17).
  • Silver nanowires synthesized in an aqueous medium are easy to aggregate. Therefore, it is difficult to increase the silver concentration in the reaction solution. It is also necessary to take measures to prevent coagulation, such as adding a large amount of hydrophilic polymer. In fact, in Preparation Examples 16 and 17 above, a large amount of (polyvinylpyrrolidone) is added.
  • Patent Document 2 discloses an invention whose object is to synthesize a fine metal nanowire having an average diameter of about 10 to 50 n (paragraph 007).
  • the synthesis method uses a polyol solvent having 2 to 6 carbon atoms in the alcohol solvent reduction method. List of various polyols that can be used ⁇ 2020/175 255 3 (: 170? 2020 /006397
  • 1,2-butanediol there is also a description of 1,2-butanediol in it (paragraph 0 0 4 1).
  • the synthetic method specifically shown in the examples is a method of reducing and precipitating silver at 150°C using propylene glycol, and the average diameter of the obtained silver nanowires is the smallest. 3 2 .0 (Example 8).
  • Patent Documents 3 and 4 also describe synthesizing metal nanowires by an alcohol solvent reduction method using a polyol.
  • 1,2-butanediol is also described.
  • the synthetic methods concretely shown as examples in these documents are also methods for reducing and precipitating silver using propylene glycol at a temperature of about 150 ° C., and the diameter of the obtained silver nanowire is Both are over 30.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2 0 1 3 _ 1 9 9 6 9 1
  • Patent Document 2 International Publication No. 2 0 1 7/0 5 7 3 2 6
  • Patent Document 3 Japanese Patent Laid-Open No. 20 17-1 4 6 21
  • Patent Document 4 Japanese Patent Laid-Open No. 20 17-6 6 4 7 1 Summary of Invention
  • the present invention is to provide a silver nanowire having an extremely small average diameter, which is advantageous in improving the haze of a transparent conductive film using a silver nanowire as a conductive material. ⁇ 0 2020/175 255 4 (: 17 2020 /006397
  • the above object can be realized by a silver nanowire having an average diameter smaller than 2 0.0 n 01 and a very small variation in diameter.
  • Such silver nanowires can be reduced by silver in an alcohol solvent reduction method using a 1,2-alkanediol having a carbon number of 4 or more and 6 or less as a solvent at a temperature of 50°C or more and 90°C or less. It was found that it can be produced by proceeding with precipitation.
  • the following inventions are disclosed in this specification.
  • [0012] [1] 0 average diameter 2.0 less than n, the following (1) Average aspect ratio A M defined by equation 1 0 0 or more, variation coefficient ⁇ diameter 1 5.0% The following is a silver nanowire having a polymer having a vinylpyrrolidone structural unit attached to the surface.
  • L M is a value in which the average length of the silver nanowire is expressed in units of n
  • D M is a value in which the above average diameter is expressed in units of 001.
  • the polymer having the vinylpyrrolidone structural unit is a copolymer of vinylpyrrolidone and diallyldimethylammonium ( ⁇ ⁇ ⁇ ⁇ ⁇ 1 ⁇ 111 6 1: 11 7 ⁇ 3 111 1X1 0 ⁇ 01) salt monomer.
  • a reaction liquid used for the reduction deposition reaction of silver nanowires wherein the silver nanowires according to any one of [1] to [3] are dispersed in an alcohol-based liquid medium.
  • the polymer having the vinylpyrrolidone structural unit is a copolymer of vinylpyrrolidone and diallyldimethylammonium ( ⁇ So ⁇ ⁇ 1 ⁇ 1116 1:11 7 ⁇ 3111111 ⁇ Li01) salt monomer.
  • Mass ratio of the amount of the polymer having the vinylpyrrolidone structural unit to be present in the alcoholic solvent and the total amount of silver used for the reduction precipitation “polymer/silver mass ratio” is set to 0.5 to 5.0.
  • a silver nanowire dispersion liquid in which the silver nanowire according to any one of [1] to [3] is dispersed in a liquid medium.
  • the silver nanowire according to any one of the above [1] to [3] has a liquid medium in which the mass ratio of alcohol is 95% or more, and the total mass ratio of alcohol and water is 95%.
  • the "alcohol-based" relating to the liquid medium constituting the reaction liquid of the above [4] is a term meaning that it is not "water-based". That is, the “alcoholic liquid medium” means a liquid medium in which the mass ratio of alcohol in the liquid medium is larger than that of water.
  • the average length, average diameter, and coefficient of variation of diameter ⁇ 3 V of silver nanowires follow the definitions below.
  • the trace length from one end to the other end of a silver nanowire is defined as the length of the wire.
  • the average length of the individual silver nanowires present on the microscope image is defined as the average length. In order to calculate the average length, the total number of wires to be measured shall be 100 or more.
  • the distance between the contours on one side in the thickness direction of one silver nanowire is defined as the diameter of the wire.
  • Each wire can be considered to have a substantially uniform thickness over its entire length. Therefore, the thickness can be measured by selecting the part that does not overlap with other wires.
  • the Ding 1//1 image showing one field of view all of the silver nanowires observed in that image, except for the wires that completely overlap with other wires and whose diameters are difficult to measure.
  • the operation of measuring the diameter is performed for multiple randomly selected fields of view, the diameters of a total of 100 or more different silver nanowires are calculated, and the average value of the diameters of the individual silver nanowires is calculated. Is defined as the average diameter.
  • the coefficient of variation of diameter ⁇ 3 (%) is calculated by calculating the standard deviation for the diameter value (1 ⁇ 01) of the total of 100 or more individual wires used in the calculation of the above average diameter. Calculated by
  • the silver nanowire according to the present invention has an extremely small average diameter of less than 20 n and has a very small variation in diameter. Since the average diameter is extremely thin as described above, it is advantageous in achieving a high level of both conductivity and visibility balance (conductivity-haze balance) in a transparent conductive film using silver nanowires as a conductive material. Also, the fact that the variation in the average diameter of the wires is extremely small means that the amount of wires that are considerably thicker than the average diameter is small. Mixed thick wire ⁇ 2020/175 255 7 ⁇ (: 170? 2020 /006397
  • the silver nanowire according to the present invention is extremely useful for highly improving the haze of a transparent conductive film. Furthermore, in the alcohol solvent reduction method of the present invention, it is possible to significantly reduce the amount of polymer used to secure the dispersibility of the synthesized wire, as compared with the synthesis method using an aqueous solvent. Therefore, industrial implementation is easy in terms of cost. The amount of polymer attached to the synthesized wire is also reduced, which is also advantageous for improving the conductivity of the transparent conductive film.
  • the reaction solution obtained by the alcohol-solvent reduction method has much less aggregation of the synthesized wires than the reaction solution using an aqueous solvent. It will be advantageous to rationally produce.
  • FIG. 1 Structural formula of vinylpyrrolidone structural unit.
  • FIG. 6 Graph showing the relationship between synthesis temperature and average diameter.
  • the silver nanowire is preferably as thin and long as possible from the viewpoint of forming a transparent conductive coating film having excellent conductivity and visibility.
  • it has been found that it is extremely advantageous to improve the visibility (reduce haze) that the average diameter is very small and the amount of thick wires mixed is small.
  • the haze reduction effect is high, so that the conductivity-haze balance of the transparent conductive film can be adjusted. It became easier and it was found that increasing the average wire length to improve conductivity becomes less important. That is, the average of the wires during synthesis ⁇ 2020/175 255 8 boxes (: 170? 2020 /006397
  • a silver nanowire having such a size and shape can be produced by a conventionally known alcohol solvent reduction method and has an average diameter of about 25 n, or 30 nm. It is more effective in improving the conductivity-haze balance of the transparent conductive film than those having a small degree.
  • L M is a value in which the average length of the silver nanowire is expressed in units of n
  • D M is a value in which the above average diameter is expressed in units of 001.
  • Average diameter is 18.0 n It is more preferably not more than 16.0 n, still more preferably not more than 16.0 n.
  • the variation coefficient ⁇ of the diameter is more preferably 12.0% or less, further preferably 10.0% or less.
  • the value of the average diameter + 3 7 is more preferably 2 2.0 n or less, and further preferably 2 0.0 n or less.
  • the average diameter should be in the range of 10 and 01.
  • the average aspect ratio is preferably 100 or more and 100 or less. If the average aspect ratio of silver nanowires is too small, the probability of contact between the wires in the transparent conductive film becomes low, and the contribution to conductivity becomes insufficient. If the average aspect ratio is too large, the wires are likely to be arranged in a bundle when the silver nanowire dispersion liquid is applied, which may be an obstacle to obtaining a high-quality transparent conductive film.
  • the polymer of the organic protective agent used during the reaction adheres to the surface of the synthesized silver nanowires, ensuring dispersibility in the liquid.
  • an organic protective agent one having a vinylpyrrolidone structural unit can be applied.
  • Figure 1 shows the vinylpyrrolidone structural unit. Specifically, copolymers of vinylpyrrolidone and other monomers can be used.
  • the dispersibility in an aqueous solvent containing alcohol can be improved more than V. It is important that such a cobolimer has a structural unit of a hydrophilic monomer.
  • the hydrophilic monomer means a monomer having a property of dissolving 19 or more in 100 0 0 9 of water of 25 ° .
  • acrylate-based or methacrylate-based monomer examples include ethyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate.
  • maleimide-based monomer 4-hydroxybutyl acrylate, 1 ⁇ 1 _ methyl maleide, 1 ⁇ 1 _ ethyl maleide, 1 ⁇ 1 _ propyl maleide, 1 ⁇ 1-I 6 "I-butyl maleide Is mentioned.
  • the “alcohol solvent reduction method” is known as a method for synthesizing silver nanowires, in which silver is reduced and deposited in a wire shape in an alcohol solvent in which an organic protective agent is dissolved.
  • the inventors have found that in an alcohol solvent reduction method using a polymer having a vinylpyrrolidone structural unit as an organic protective agent,
  • the alcohol solvent use an alcohol solvent containing at least 40% by mass of one or more 1,2-alkanediols having 4 to 6 carbon atoms in one molecule, ⁇ 2020/175 255 10 units (: 170? 2020 /006397
  • the polymer molecules of the organic protective agent are selectively adsorbed on the ⁇ 100 ⁇ face of the silver nucleus crystal to suppress the growth of the ⁇ 100 ⁇ face, and the silver crystal It is considered that the linear structure of metallic silver is formed by preferential growth of the ⁇ 1 1 1 ⁇ plane, which is the closest surface. It is not clear at this time why the above-mentioned reduction conditions of I) and (I) satisfy the reduction condition to enable stable synthesis of silver nanowires with extremely small average diameter and very small diameter variation. Absent.
  • the temperature at the time of reduction and precipitation is more preferably 85°° or less, and further preferably 60°° or less.
  • the temperature during reduction precipitation is set to 50 ° C or higher. From the viewpoint of reaction time, it is more preferable to set it to 53° or more. From the viewpoint of stably synthesizing silver nanowires with a particularly small diameter and a particularly small O value, for example, one molecule ⁇ 2020/175 255 1 1 ⁇ (: 170? 2020 /006397
  • the average diameter is less than 20.0 n and the variation coefficient of diameter 0 V is 15.0% or less. It is difficult to stably synthesize silver nanowires with a very small variation in. Even with alkane diols having 4 to 6 carbon atoms, the reducing power of only alkane diols having a hydroxy group other than the 1 and 2 positions such as 1,3-butane diol and 1,4-butane diol can be obtained. It is difficult to synthesize thin silver nanowires using the synthesis method. On the other hand, 1,2-alkanediols having 7 or more carbon atoms are often solid at around room temperature, and are poor in handleability as an alcohol solvent for industrially producing silver nanowires.
  • 1,2-alkanediol having 4 to 6 carbon atoms specifically, 1,2-butanediol (having 4 carbon atoms), 1,2-pentanediol (having 5 carbon atoms), 1, 2- Hexanediol (6 carbon atoms) can be mentioned.
  • a mixed alcohol solvent of 1,2-alkanediol having 4 to 6 carbon atoms and another alcohol can be used, but the mass ratio of the solvent to the alcohol component is 4 to 6 carbon atoms. It is necessary to use an alcohol solvent containing at least 40% of a total of one or more of the following 1,2-alkanediols.
  • the mass ratio of the solvent to the alcohol component is controlled. Good.
  • examples of other alcohols include 1,2-propanediol (having 3 carbon atoms).
  • the above-mentioned polymer having a vinylpyrrolidone structural unit which is an organic protective agent is applied.
  • the mass ratio “polymer/silver mass ratio” between the amount of the polymer having the above formula and the total amount of silver used for the reduction precipitation is preferably in the range of 0.5 to 5.0.
  • the use of an alcohol solvent in which too much polymer is present results in an excessive amount of polymer attached to the surface of the synthesized silver nanowires. If silver nanowires with an excessive amount of attached polymer are applied to the transparent conductive film, the contact resistance between the wires increases, which is disadvantageous in obtaining a transparent conductive film with high conductivity.
  • a silver compound soluble in an alcohol solvent is used as a silver source used for the synthesis of silver nanowires.
  • a silver compound soluble in an alcohol solvent is used.
  • a silver compound, chloride, bromide, aluminum salt, etc. may be added to the reaction vessel in the form of a solution.
  • a solvent for preparing a solution of each substance it is suitable to use a solvent having a high polarity and a high solubility among alcohol solvents.
  • 1,2-propanediol propylene glycol
  • the total amount of silver used with respect to the total amount of alcohol solvent used is preferably in the range of 0.01 to 0.1 mol of silver per 1!
  • the total amount of bromide used in relation to the total amount of alcohol solvent used is 1/_ of alcohol solvent as the amount of 0.0000 01 (1 X 10-6) to ⁇ . ⁇ ⁇ 1 (1 X 10-3).
  • the total amount of metal hydroxide used is the amount of hydroxide per 1!_ alcohol solvent.
  • the total amount of aluminum salt used relative to the total amount of alcohol solvent used is 8 I amount per 1 solvent of [0.0 0 0 0 1 (1 X 1 0 _ 5 ) to 0.0 0 0 1 (1 X 1 0 -3 ) It is preferable to set it in the molar range.
  • Acetic acid ester or water may be contained as a solvent component in a range of 2% or less based on the total mass of the solvent.
  • the “liquid medium” is the liquid portion that constitutes the silver nanowire dispersion liquid, and when another substance is dissolved in the solvent substance, that substance is also a constituent component of the liquid medium.
  • a silver nanowire dispersion liquid (this is sometimes referred to as “silver nanowire ink”) in which a thickening component, a binder component, etc. are added as needed to adjust the properties to be particularly suitable for coating.
  • the thickening component and binder component dissolved in the solvent also constitute the liquid medium.
  • a solvent of water solvent, water and alcohol is used as the solvent used for the silver nanowire dispersion liquid for coating or the silver nanowire dispersion liquid which is an intermediate product for producing the silver nanowire dispersion liquid for coating. It is common to use either a mixed solvent or an alcohol solvent.
  • the presence of water is advantageous for ensuring the dispersibility of the silver nanowires in the liquid, and the presence of alcohol for ensuring the wettability of the silver nanowire dispersion on the transparent resin substrate such as Ningyo (polyethylene terephthalate). To be advantageous.
  • Suitable alcohols used as a solvent for the silver nanowire dispersion liquid include monohydric alcohols having 1 to 4 carbon atoms. Specifically, methanol, ethanol, 2-propanol (isopropyl alcohol), 2-methyl-1-propanol, ⁇ 2020/175 255 14 ⁇ (: 170? 2020 /006397
  • Alcohols such as butanol are good candidates. These have moderately high boiling points and are easy to use for coating to form a transparent conductive film.
  • one or more monohydric alcohols having 1 to 4 carbon atoms be 50% or more with respect to the total mass of the alcohol used.
  • a silver nanowire dispersion liquid having a good balance between the liquid dispersion properties of the silver nanowires and the wettability with a base material such as a knife
  • a mixed solvent of water and alcohol it is effective to use a mixed solvent of water and alcohol.
  • the mass ratio of water to alcohol is preferably adjusted such that water:alcohol is in the range of, for example, 95:5 to 70:30.
  • water: alcohol is 0:
  • the liquid medium constituting the silver nanowire dispersion liquid may contain a thickening component, a binder component, a surfactant component and the like in addition to the solvent component.
  • the mass ratio of the solvent component in the liquid medium is preferably 95% or more.
  • a liquid medium in which the mass ratio of alcohol is 95% or more a liquid medium in which the total mass ratio of alcohol and water is 95% or more, It is preferable to apply any of the liquid media in which the mass ratio of water is 95% or more.
  • the mass ratio of the silver nanowires to the total mass of the dispersion liquid is preferably adjusted in the range of, for example, 0.03 to 1.50% in terms of metallic silver.
  • 1,2-butanediol manufactured by Wako Pure Chemical Industries, Ltd., special grade 8 1 7.69 contains 10% by mass of lithium chloride (manufactured by Aldrich) 1, 2 ⁇ 2020/175 255 15 units (: 170? 2020 /006397
  • nt “36” copolymer (vinylpyrrolidone 99% by mass, diaryldimethylammonium nitrate 1% by mass to prepare a copolymer, weight average molecular weight: 75,000) 8.399 was added and dissolved to prepare solution 8.
  • Silver nitrate 6.809 was added to a mixed solvent of alcohol and water consisting of 1,2-propanediol, 9.579 % pure water, 0.809, and the mixture was stirred at 35 ° and dissolved to form a solution.
  • the reduction precipitation reaction of silver was allowed to proceed under the synthesis conditions of a synthesis temperature of 85° and a reaction time of 24 hours.
  • the above solution was put into a 1!_ beaker, which was a reaction vessel, and the temperature was raised from room temperature to 85° while stirring, and then the whole amount of the solution was added to the solution over 1 minute.
  • the vessel and line used to add the solution basin were co-washed with 49 1,2-propanediol.
  • the liquid in the reaction container was stirred and held at 85° for 24 hours and then cooled to room temperature to obtain a reaction liquid containing silver nanowires.
  • the alcohol solvent used in this example was prepared by mixing 1,2-butanediol existing in the above-mentioned solution and 1,2-propanediol (propylene glycol) of a small child supplied from the above-mentioned solution Contains as an ingredient.
  • Alcohol component The mass ratio of each alcohol to the total is 1,2-butanediol 98.2%
  • the average diameter of the obtained silver nanowires was determined as follows. Transfer the above dispersion liquid to a grid with a supporting film for a transmission electron microscope (Cu 150 mesh manufactured by JEOL Ltd.), and use a transmission electron microscope (JEOL Ltd.; J EM-1 01 1). , The accelerating voltage is 100 kV, and the bright field image is observed at a magnification of 40,000 times to collect the observed image, and the original image taken to measure the diameter accurately is enlarged to double the size.
  • Software M otic I mage P
  • Example 1 An experiment was performed under the same conditions as in Example 1 except that the synthesis temperature was changed to 75° and the reaction time was changed to 72 hours in Example 1. The results are shown in Table 1.
  • the average diameter is An extremely fine silver nanowire with a diameter variation coefficient ⁇ 3 V of 1 3.5% and very small diameter variation was synthesized.
  • Example 2 An experiment was conducted under the same conditions as in Example 1 except that the synthesis temperature was changed to 65° and the reaction time was changed to 84 hours in Example 1. The results are shown in Table 1.
  • the average diameter is An extremely fine silver nanowire with a diameter variation coefficient ⁇ 3 V of 14.6% and very small diameter variation was synthesized.
  • Figure 2 shows an example of a 1:1 (transmission electron microscope) photograph of the silver nanowire obtained in this example.
  • Example 1 An experiment was conducted under the same conditions as in Example 1 except that the synthesis temperature was changed to 55 ° and the reaction time was changed to 130 hours in Example 1. The results are shown in Table 1.
  • the average diameter is An extremely fine silver nanowire with a diameter variation coefficient ⁇ 3 V of 8.6% and very small diameter variation was synthesized.
  • lithium chloride (Aldrich) content is 1 0 wt% 1, 2 - propanediol (Propylene glycol) solution 0.3999, potassium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) 1,2-propanediol solution 0.476 9 with a content of 1 mass%, lithium hydroxide (manufactured by Aldrich) 0.07 1 19
  • Silver nitrate 6.809 was added to a mixed solvent of water, and the mixture was stirred and dissolved at 35 ° C to form a solution.
  • the reduction precipitation reaction of silver was allowed to proceed under the synthesis conditions of a synthesis temperature of 65° and a reaction time of 72 hours as follows.
  • the above solution was placed in a 1!_ beaker, which was a reaction vessel, and the temperature was raised from room temperature to 65° while stirring, and then the whole amount of the solution was added to the solution over 1 minute.
  • the vessel and the conduit used for the addition of the solution basin were co-washed with 49 1,2-propanediol. Then, the liquid in the reaction vessel was stirred and held at 65° for 72 hours and then cooled to room temperature to obtain a reaction liquid containing silver nanowires.
  • the alcohol solvent used in this example is composed of 1,2-pentanediol present in the above solution and 1,2-propanediol (propylene glycol) of a small child supplied from the above solution as an alcohol component. Contained as.
  • the mass ratio of each alcohol in the total alcohol components is 1,2-pentanediol 98.2% and 1,2-propanediol 1.8%.
  • the mass ratio “polymer/silver mass ratio” with the total amount of silver used for reduction precipitation is 1.94.
  • the diameter and length of the obtained silver nanowire were measured in the same manner as in Example 1. The results are shown in Table 1. In this example, an average diameter of 1 6.7 n m, coefficient of variation of diameter ⁇ 3 is 1 3.2%, very narrow diameter variation is very small again silver nanowires were synthesized.
  • Example 2 An experiment was conducted under the same conditions as in Example 1, except that the synthesis temperature was changed to 55 ° and the reaction time was changed to 130 hours in Example 5. The results are shown in Table 1.
  • the average diameter is An extremely fine silver nanowire with a diameter variation coefficient ⁇ 3 V of 8.6% and very small diameter variation was synthesized.
  • 1,2-butanediol 81 1 6.39 has a lithium chloride content of 10% by mass 1,2-propanediol (propylene glycol) solution 3.9869, potassium bromide 0.04769, lithium hydroxide ⁇ .7 ⁇ ⁇ 9.
  • Copolymer (vinylpyrrolidone 99% by mass, diallyldimethylammonium nitrate 1% by mass to prepare a cobolimer, weight average molecular weight of 75,00) 83.8759 was added and dissolved to prepare a solution 8.
  • Silver nitrate 67.969 was added to a mixed solvent of alcohol and water consisting of 1,2-propanediol 95.709 and pure water 8.009, and the mixture was stirred at 35 ° and dissolved to form a solution.
  • the reduction precipitation reaction of silver proceeded under the synthesis conditions of a synthesis temperature of 65° and a reaction time of 84 hours as follows. Put the above solution into the reaction vessel, which is a 10 !_ beaker, and raise the temperature from room temperature to 65° ⁇ while stirring at a rotation speed of 225 ′′, and then add the total amount of the solution to the solution. After completion of the addition of the solution, the container and the pipe used for the addition of the solution were washed together with 1,092-propanediol of 1009. After that, the liquid in the reaction vessel was stirred. While stirring, the mixture was kept at 65 ° for 84 hours and then cooled to room temperature to obtain a reaction solution containing silver nanowires.
  • the alcohol solvent used in this example was prepared by mixing 1,2-butanediol existing in the above-mentioned solution and 1,2-propanediol (propylene glycol) of the young child supplied from the above-mentioned solution Contains as an ingredient. Mass ratio of each alcohol to all alcohol components is 1,2-butanediol 97.6%
  • the diameter and length of the obtained silver nanowire were measured in the same manner as in Example 1. The results are shown in Table 1. In this example, the average diameter is the same as in Example 3. ⁇ 2020/175 255 20 units (: 170? 2020 /006397
  • Copolymer was prepared with 99% by mass and 1% by mass diallyldimethylammonium nitrate, and the weight average molecular weight was 75,000) 8.399 was added and dissolved to prepare a solution 8.
  • Silver nitrate 6.809 was added to a mixed solvent of alcohol and water consisting of 1,2-propanediol, 9.579 % pure water, 0.809, and the mixture was stirred at 35 ° and dissolved to form a solution.
  • the alcohol solvent used in this example is the 1-, 2-hexene present in the above solution.
  • the weight ratio of each alcohol to all the alcohol components is 1,2-hexanediol 49.1% and 1,2-propandiol 50.9%.
  • the mass ratio “polymer/silver ratio” to the total amount of silver used for reduction precipitation is 1.94.
  • the diameter and length of the obtained silver nanowire were measured by the same method as in Example 1. The results are shown in Table 1. In this example, an extremely fine silver nanowire with an average diameter of 15.9 nm and a coefficient of variation CV of 13.8% was synthesized.
  • Silver was synthesized under the following synthesis conditions at a synthesis temperature of 65 °C and a reaction time of 84 hours as follows.
  • the reduction precipitation reaction of was allowed to proceed.
  • the above solution A was placed in a 1 L beaker which was a reaction vessel, the temperature was raised from room temperature to 65°C with stirring, and then the entire amount of solution B was added to solution A over 1 minute. After the addition of solution B was complete, the vessel and conduit used to add solution B were co-washed with 4 g of 1,2-propanediol. Then, the liquid in the reaction vessel was stirred and held at 65°C for 84 hours and then cooled to room temperature to obtain a reaction liquid containing silver nanowires.
  • the alcohol solvent used in this example was 1,2-butanediol and 1,2-hexanediol present in the solution A, and 1,2- Contains propanediol (propylene glycol) as an alcohol component.
  • the weight ratio of each alcohol in the total alcohol components is 1,2-butanediol 24.5%, 1,2-hexanediol 73.7%, and 1,2-propanediol 1.8%.
  • the mass ratio “polymer/silver mass ratio” with the total amount of silver used for reduction precipitation is 1.94.
  • the diameter and the length of the obtained silver nanowire were measured by the same method as in Example 1. The results are shown in Table 1. In this example, an extremely thin silver nanowire with an average diameter of 18.4 nm and a coefficient of variation CV of 14.4% was synthesized.
  • Copolymer was prepared with 99% by mass and 1% by mass diallyldimethylammonium nitrate, and the weight average molecular weight was 75,000) 8.399 was added and dissolved to prepare a solution 8.
  • Silver nitrate 6.809 was added to a mixed solvent of alcohol and water consisting of 1,2-propanediol, 9.579 % pure water, 0.809, and the mixture was stirred at 35 ° and dissolved to form a solution.
  • the reduction precipitation reaction of silver was allowed to proceed under the synthesis conditions of a synthesis temperature of 65° and a reaction time of 84 hours as follows.
  • the above solution was placed in a 1!_ beaker, which was a reaction vessel, and the temperature was raised from room temperature to 65° while stirring, and then the whole amount of the solution was added to the solution over 1 minute.
  • the vessel and the conduit used for the addition of the solution basin were co-washed with 49 1,2-propanediol. Then, the liquid in the reaction vessel was stirred and held at 65° for 84 hours and then cooled to room temperature to obtain a reaction liquid containing silver nanowires.
  • the alcohol solvent used in this example was 1,2-butanediol and 1,2-hexanediol present in the above solution, and 1,2-propane of a small child supplied from the above solution. Contains diol (propylene glycol) as an alcohol component.
  • the weight ratio of each alcohol to the total alcohol components is 1,2-butanediol 73.7%, 1,2-hexanediol 24.5%, and 1,2-propanediol 1.8%.
  • the mass ratio “polymer/silver mass ratio” with the total amount of silver used for reduction precipitation is 1.94.
  • the diameter and length of the obtained silver nanowire were measured by the same method as in Example 1. The results are shown in Table 1. In this example, an extremely fine silver nanowire with an average diameter of 17.3 nm and a coefficient of variation of ⁇ 3 of 14.7% was synthesized.
  • Example 1 The experiment was performed under the same conditions as in Example 1 except that the amount of potassium bromide added when preparing the solution in Example 7 was changed from 0.04769 to 0.07149. The results are shown in Table 1. In this example, an average diameter of 1 7.7 n m, diameter variations ⁇ 2020/175 255 24 ⁇ (: 170? 2020 /006397
  • Example 1 An experiment was carried out under the same conditions as in Example 1 except that the amount of potassium bromide added when preparing the solution in Example 7 was changed from 0.04769 to 0.09529. The results are shown in Table 1. In this example, an average diameter of 1 7. 1 n m, is 1 4.6% variation coefficient ⁇ diameter, very thin diameter variation is very small Gin'na Nowaiya were synthesized.
  • Example 2 An experiment was conducted under the same conditions as in Example 1 except that the synthesis temperature was changed to 95 ° in Example 1. The results are shown in Table 2.
  • silver nanowires with an average diameter of 22.7 n were synthesized.
  • the diameter variation coefficient ⁇ is as small as 11.9%, but due to the high synthesis temperature, extremely thin wires with an average diameter of less than 20 n could not be obtained.
  • Example 2 An experiment was conducted under the same conditions as in Example 1 except that the synthesis temperature in Example 1 was changed to 105 ° . The results are shown in Table 2.
  • silver nanowires with an average diameter of 24.7 n were synthesized.
  • the coefficient of variation of diameter ⁇ 3 was small at 1 3.4%, but due to the high synthesis temperature, extremely thin wires with an average diameter of less than 20 n could not be obtained.
  • Example 2 An experiment was conducted under the same conditions as in Example 1 except that the synthesis temperature was changed to 115 ° in Example 1. The results are shown in Table 2.
  • silver nanowires with an average diameter of 24.7 n were synthesized.
  • the coefficient of variation of diameter ⁇ 3 was small at 1 3.4%, but due to the high synthesis temperature, extremely thin wires with an average diameter of less than 20 n could not be obtained.
  • 1,2-propanediol 81 1 6.39 contains lithium chloride. ⁇ 2020/175 255 25 units (: 170? 2020 /006397
  • Silver nitrate 67.969 was added to a mixed solvent of alcohol and water consisting of 1,2-propanediol 95.709 and pure water 8.009, and the mixture was stirred at 35 ° and dissolved to form a solution.
  • the reduction and precipitation reaction of silver was allowed to proceed under the synthesis conditions of a synthesis temperature of 85° and a reaction time of 24 hours.
  • the reaction vessel which is a 10 !_ beaker, and raise the temperature from room temperature to 65° ⁇ while stirring at a rotation speed of 225 ′′, and then add the total amount of the solution to the solution.
  • the container and the pipe used for the addition of the solution were co-washed with 1,092-propanediol of 1009. After that, the liquid in the reaction vessel was stirred.
  • the alcohol solvent used in this example was 1,2-propandiol (propylene glycol) present in the above solution, and 1,2-propanediol (propylene glycol) of the young child supplied from the above solution mitsubo. And are included as alcohol components. That is, all of the alcohol component consists of 1,2-propanediol (propylene glycol).
  • the diameter and length of the obtained silver nanowire were measured by the same method as in Example 1. The results are shown in Table 2.
  • a silver nanowire having an average diameter of 25.4 n and a coefficient of variation of the diameter ⁇ of 15.6% was synthesized.
  • Conventional ⁇ 2020/175 255 26 ⁇ (: 170? 2020 /006397
  • 1,2-Propanediol an alcohol solvent for the synthesis of various silver nanowires, has an average diameter of less than 20 n and a coefficient of variation of diameter even when the synthesis temperature is lowered to 90 ° It was not possible to synthesize a silver nanowire with an extremely small diameter of 0 V of 15% or less and a very small diameter/rack.
  • the alcohol solvent used in this example was prepared by mixing 1,4-butanediol present in the above-mentioned solution and 1,2-propanediol (propylene glycol) of a small child supplied from the above-mentioned solution Contains as an ingredient. Mass ratio of each alcohol to all alcohol components is 1, 4-butanediol 98.2%
  • 1,2-propanediol is 1.8%.
  • the alcohol solvent used in this example was prepared by mixing 1,3-butanediol present in the above solution and 1,2-propanediol (propylene glycol) of a small child supplied from the above-mentioned solution Nomi. Contains as an ingredient.
  • the weight ratio of each alcohol to all alcohol components is 1,3-butanediol 98.2%
  • 1,2-propanediol is 1.8%.
  • Figure 6 shows the relationship between synthesis temperature and average diameter
  • Figure 7 shows the relationship between synthesis temperature and diameter variation coefficient ⁇ 3 V.
  • Example 7 using the silver nanowires synthesized in Example 7 and Comparative Example 4, a transparent conductive film was prepared as follows, and haze was measured.
  • Example 7 the silver nanowire obtained in Example 7 was used, and an experiment was conducted in the following procedure.
  • Example 7 To the reaction mixture obtained in Example 7 described above (those was cooled to room temperature) 84009, and stirred for 1 0 minutes by adding pure water 1 890 9. Next, acetone 75809 was added and stirred for 10 minutes. Next, xylene 88209 was added and the mixture was stirred for 10 minutes. Then, it was left to stand for 3 hours. Since the concentrate and the supernatant were observed after standing, the supernatant was removed and the concentrate containing silver nanowires was recovered.
  • the above-mentioned polymer-containing aqueous solution (having the above-mentioned cobolimer concentration of 1% by mass) was added, and the mixture was stirred with a stirrer at a rotation speed of 100 "for 12 hours, A silver nanowire dispersion liquid after the washing process was obtained.
  • the third washing step to the sixth washing step were performed, and a silver nanowire dispersion liquid after the sixth washing step was obtained.
  • the turbidity of the supernatant was reduced each time the washing process was repeated.
  • the silver concentration was measured with a ⁇ ⁇ ⁇ emission spectroscopic method (apparatus: Agilent Technology Co., Ltd. ⁇ ⁇ emission spectrophotometer 7 2 0—Mimi 3), and the concentration of silver nanowires was calculated in terms of metallic silver 2. It was 4 74% by mass.
  • a thickener As a thickener, a methoxy group 21.5 mass%, a hydroxypropoxy group 30.
  • Disk turbine blades were used.
  • the above-mentioned thickener 1509 treated with hot water was added to pure water 9850 9 heated to 95 ° ⁇ , cooled to 40 ° ⁇ while stirring at 475 ⁇ , and then cooled by a chiller in the jacket of the tank.
  • the resulting mixture was cooled by flowing cooling water and stirred for 12 hours The temperature at the end of stirring was 5° ⁇ In this way, the thickener was dissolved in water to obtain a thickener aqueous solution.
  • the resulting thickener aqueous solution was pressure filtered at a set pressure of 0.21 ⁇ /1 3 to remove insoluble components.Pressure filtration was performed with a depth pleated filter (manufactured by Roki Techno Co., Ltd.) with filter filtration accuracy (opening) 1. ; Type) was used. Thickener component in the thickener aqueous solution after this filtration was 1.24% by mass.
  • Silver nanowire dispersion liquid 3 1 3 9 after the 7th washing step, pure water 19209, and thickener aqueous solution 3479 after the filtration are put in one container, and 6 blades with a diameter of 1700 are used. And stirred for 2 hours at 1 50". After that, 17209 was added a 50% aqueous solution of 2-propanol,
  • the mixture was stirred to obtain a silver nanowire dispersion for coating in which the solvent components in the liquid medium were water and alcohol.
  • the metallic silver concentration of this silver nanowire dispersion liquid was measured by an optical emission spectroscopy analysis method, the silver nanowire content was 0.180 mass% in terms of metallic silver.
  • a Mingo film base material (Cosmoshine (registered trademark) 4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 001 and a size of 1 0001111X 150 51111 was prepared. Paint above ⁇ 2020/175 255 34
  • the silver nanowire dispersion liquid for use in d was applied to the bare surface of the above-mentioned Mingo film base material with a bar coater having a count of 1 ⁇ 10.6 (manufactured by Tester Sangyo Co., Ltd., 3_203) to form a coating film.
  • the area of the coating film formed on the base material is 8 0 1 0 1 1 2 Met.
  • the coating film was dried in air at 120 ° for 1 minute to obtain a transparent conductive film.
  • the haze value of the base material to the transparent conductive film is the haze value (%) of the object made of the base material film and the transparent conductive film formed thereon, and the "haze value of the base material only” is It is the haze value (%) of the base film before forming the conductive film. It is evaluated that the smaller the value of haze evaluation index 1 to 1, which is the difference between the two, is, the smaller the amount of haze generated due to the transparent conductive film is.
  • the haze evaluation index ! ⁇ 1 of the transparent conductive film obtained in this example was 0.40.
  • the results are shown in Table 3.
  • Example 7 the silver nanowire obtained in Example 7 was used.
  • the above-described sixth washing step was performed under the same conditions as in Example 7 to obtain a silver nanowire dispersion liquid after the sixth washing step. This was subjected to the following steps.
  • This alcohol silver nanowire dispersion liquid was dissolved in 60% nitric acid and analyzed by Agilent Technologies Co., Ltd. ⁇ 10mi 3720 by high frequency inductively coupled plasma ( ⁇ 09) emission spectroscopy, and the above alcohol silver The silver concentration in the nanowire dispersion was calculated. Based on this silver concentration value, the above-mentioned alcohol silver nanowire dispersion liquid was diluted with a predetermined amount of 2-propanol to obtain a coating silver nanowire dispersion liquid with a silver concentration of 0.2% by mass. ..
  • a Mingo film base material (Cosmoshine (registered trademark) 4100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 001 and a size of 1 0001111X 150 51111 was prepared.
  • the above alcohol-based silver nanowire dispersion for coating was applied to the bare surface of the above-mentioned Mingo film base material using a bar coater with a count of 1 ⁇ 10.6 (manufactured by Tess Yuichi Sangyo Co., Ltd., 381203).
  • a coating film was formed. The area of the coating film formed on the substrate was 80 120. This coating film was dried in the air at 80 ° for 1 minute to obtain a transparent conductive film.
  • the haze evaluation index !! was obtained in the same manner as in Example 7.
  • the haze evaluation index !! of the transparent conductive film obtained in this example was 0.38.
  • the results are shown in Table 3.
  • Example 7 an experiment was performed under the same conditions as in Example 7 except that the silver nanowire obtained in Comparative Example 4 was used and the precipitation step was performed under the following conditions.

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Abstract

Le problème décrit par la présente invention est de fournir des nanofils d'argent présentant un diamètre moyen extrêmement réduit et qui sont utiles pour réduire le trouble dans un film conducteur transparent à l'aide de nanofils d'argent en tant que matériau conducteur. La solution selon l'invention porte sur des nanofils d'argent dont le diamètre moyen est inférieur à 20,0 nm, le rapport d'aspect moyen AM défini par la formule (1) est supérieur ou égal à 100, le coefficient de variation CV du diamètre est inférieur ou égal à 15,0 %, et un polymère ayant un motif structural vinyl pyrrolidone est collé sur lesdits nanofils d'argent. AM=LM/DM … (1). LM est une valeur représentant la longueur moyenne des nanofils d'argent dans les motifs nm, et DM est une valeur représentant le diamètre moyen dans les motifs nm. Ces nanofils d'argent peuvent être obtenus à l'aide d'un solvant alcoolique contenant au moins 40 % au total d'une ou de plusieurs espèces parmi les 1,2-alcanediols ayant entre 4 et 6 atomes de carbone inclus et favorisant la précipitation réductrice à une température comprise entre 50 °C et 90 °C inclus.
PCT/JP2020/006397 2019-02-26 2020-02-19 Nanofils d'argent, leur procédé de production, solution réactionnelle contenant des nanofils d'argent et dispersion de nanofils d'argent WO2020175255A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013146509A1 (fr) * 2012-03-26 2013-10-03 富士フイルム株式会社 Procédé pour produire un liquide dispersé dans des nanofils métalliques, liquide dispersé dans des nanofils métalliques, élément conducteur qui est formé en utilisant un liquide dispersé dans des nanofils métalliques, panneau tactile utilisant un élément conducteur qui est formé en utilisant un liquide dispersé dans des nanofils métalliques, et cellule solaire
JP2013199691A (ja) * 2012-03-26 2013-10-03 Fujifilm Corp 金属ナノワイヤの製造方法、及び金属ナノワイヤ、並びに、金属ナノワイヤを用いたインク組成物、及び導電性部材、導電性部材を用いたタッチパネル、及び太陽電池
JP2015180772A (ja) * 2014-03-07 2015-10-15 Ｄｏｗａホールディングス株式会社 銀ナノワイヤの製造方法並びに銀ナノワイヤおよびそれを用いたインク
JP2017515983A (ja) * 2014-04-11 2017-06-15 シーエーエム ホールディング コーポレーション 塗布液および銀ナノワイヤーの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013146509A1 (fr) * 2012-03-26 2013-10-03 富士フイルム株式会社 Procédé pour produire un liquide dispersé dans des nanofils métalliques, liquide dispersé dans des nanofils métalliques, élément conducteur qui est formé en utilisant un liquide dispersé dans des nanofils métalliques, panneau tactile utilisant un élément conducteur qui est formé en utilisant un liquide dispersé dans des nanofils métalliques, et cellule solaire
JP2013199691A (ja) * 2012-03-26 2013-10-03 Fujifilm Corp 金属ナノワイヤの製造方法、及び金属ナノワイヤ、並びに、金属ナノワイヤを用いたインク組成物、及び導電性部材、導電性部材を用いたタッチパネル、及び太陽電池
JP2015180772A (ja) * 2014-03-07 2015-10-15 Ｄｏｗａホールディングス株式会社 銀ナノワイヤの製造方法並びに銀ナノワイヤおよびそれを用いたインク
JP2017515983A (ja) * 2014-04-11 2017-06-15 シーエーエム ホールディング コーポレーション 塗布液および銀ナノワイヤーの製造方法

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