WO2022137886A1 - Procédé de production de nanofil d'argent - Google Patents

Procédé de production de nanofil d'argent Download PDF

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WO2022137886A1
WO2022137886A1 PCT/JP2021/041880 JP2021041880W WO2022137886A1 WO 2022137886 A1 WO2022137886 A1 WO 2022137886A1 JP 2021041880 W JP2021041880 W JP 2021041880W WO 2022137886 A1 WO2022137886 A1 WO 2022137886A1
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reaction
silver nanowires
temperature
silver
cooling
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PCT/JP2021/041880
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Japanese (ja)
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葵 長谷川
真尚 原
正彦 鳥羽
智之 野口
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昭和電工株式会社
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Priority to JP2022571955A priority Critical patent/JP7424516B2/ja
Priority to CN202180077031.5A priority patent/CN116529000A/zh
Priority to KR1020237012150A priority patent/KR20230066423A/ko
Publication of WO2022137886A1 publication Critical patent/WO2022137886A1/fr

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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • 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
    • 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
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold

Definitions

  • the present invention relates to a method for manufacturing silver nanowires.
  • silver nanowires have been attracting attention as a raw material for highly transparent and highly conductive thin films that can replace the ITO (indium tin oxide) film used for transparent electrodes such as touch panels.
  • Such silver nanowires are generally produced by a so-called polyol reduction method in which a silver compound is heated in the presence of a polyol such as polyvinylpyrrolidone and ethylene glycol (Patent Document 1, Non-Patent Document 1).
  • High transparency is required for the transparent conductive film used for touch panels and the like.
  • the so-called polyol reduction method used in the production of silver nanowires is generally performed under heating.
  • the reaction is carried out at a high temperature of around 150 ° C., the reaction is completed relatively quickly (Patent Document 2).
  • the reaction temperature is high, it is possible that the silver source remaining in the reaction system further reacts with residual heat during cooling from the reaction temperature to room temperature, and the diameter of the silver nanowire may increase.
  • the cooling rate is expected to be even slower, and the effect of residual heat during cooling is expected to be large.
  • an object of the present invention is to provide a method for producing silver nanowires, which is highly productive and can suppress an increase in diameter during cooling of the reaction solution after the reaction is completed.
  • the present invention includes the following embodiments.
  • a method for producing silver nanowires which comprises a step of cooling at a cooling rate of a minute or more.
  • a solvent having a boiling point of 40 ° C. or lower and a boiling point equal to or higher than the reaction temperature at the time of synthesizing silver nanowires is added to the reaction solution over 30 minutes to cool the reaction.
  • the method for manufacturing silver nanowires according to any one.
  • the present invention it is possible to suppress an increase in diameter due to residual heat after synthesizing silver nanowires and to produce a desired fine silver nanowire.
  • embodiments for carrying out the present invention (hereinafter referred to as embodiments) will be described.
  • the method for producing silver nanowires according to the present embodiment is a step of synthesizing silver nanowires at a temperature of 120 to 170 ° C. by a polyol reduction method, and a reaction solution temperature after completion of silver nanowire synthesis from the temperature at the end of reaction. It is characterized by comprising a step of cooling to 80 ° C. at an average cooling rate of ⁇ 0.50 ° C./min or more.
  • "at the end of the reaction” means that silver nanowires are synthesized by a polyol reduction method under a predetermined temperature condition and heated at a predetermined temperature of a heat source at the time of synthesis (in the examples described later, an oil bath is predetermined).
  • the cooling rate of "average ⁇ 0.50 ° C./min or more" means that the absolute value of the cooling rate (speed of temperature decrease [° C./min]) is 0.50 or more on average.
  • the reaction solution the reaction solvent used for the synthesis and the liquid containing the generated silver nanowires, etc.
  • the silver source remaining in the reaction solution due to the residual heat during cooling can suppress the increase in the diameter of silver nanowires.
  • the present inventor has found that the diameter of the silver nanowires hardly increases when the reaction solution temperature drops to 80 ° C. Therefore, it is possible to suppress an increase in the diameter of the silver nanowires by increasing the cooling rate until the reaction solution temperature is set to 80 ° C.
  • This cooling rate has an average of ⁇ 0.50 ° C./min or higher, preferably ⁇ 0.60 ° C./min or higher, and more preferably ⁇ 0.70 ° C./min or higher. If the cooling rate is smaller than ⁇ 0.50 ° C./min on average, the diameter of the silver nanowires will greatly increase due to the residual heat during cooling even after the reaction is completed. Even when the cooling rate up to 80 ° C. is not constant, if the average cooling rate is within the above range, the effect of suppressing the increase in diameter is recognized. If the increase in the average diameter of the silver nanowires after cooling the reaction solution temperature to 80 ° C.
  • the cooling rate is preferably less than -10.00 ° C / min, more preferably less than ⁇ 8.00 ° C / min.
  • the reaction liquid cooling method after the reaction is not particularly limited as long as it is a cooling method having a cooling rate higher than the above.
  • a method of cooling the reaction vessel with a gas at the time of cooling a method of cooling by contacting with a liquid refrigerant, a method of blowing air toward the reaction vessel to be air-cooled, and the like can be mentioned.
  • the temperature of the liquid refrigerant and the temperature of the blown air are preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and even more preferably 30 ° C. or lower. If the temperature exceeds 40 ° C, the effect of increasing the cooling rate becomes small.
  • a cooling method having a cooling rate higher than the above there is also a method of adding a solvent having a temperature of 40 ° C. or lower into the reaction solution after the reaction is completed.
  • the boiling point of the solvent is set to be equal to or higher than the reaction temperature at the time of synthesizing silver nanowires so as not to suddenly boil at the temperature at the time of charging. Specifically, it is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, and even more preferably 180 ° C. or higher.
  • the solvent is preferably added to the liquid over 30 minutes, more preferably 40 minutes or more, still more preferably 50 minutes or more.
  • the amount of the solvent to be added is suppressed to about 1/5 of the reaction liquid amount at most.
  • adding a large amount of solvent at once puts a load on the synthetic container due to a sudden temperature change. It is not preferable because it may cause problems such as the presence of. Further, if the amount of the solvent added at one time is small, the cooling effect becomes insufficient.
  • the solvent may be, for example, 2-octanol (boiling point: 179 ° C.), 2-ethylhexanol (boiling point: 187 ° C.), 2-butoxyethanol (boiling point: 171 ° C.), benzyl alcohol (boiling point: 200 ° C.), acetphenone (boiling point: 187 ° C.).
  • 1,3-propanediol (boiling point: 214 °C), diethylene glycol (boiling point: 245 °C), triethylene glycol (boiling point: 288 °C), dipropylene glycol (boiling point: 232 °C), 1,2-butanediol (Boiling point: 194 ° C), 1,3-butanediol (boiling point: 207 ° C), 1,4-butanediol (boiling point: 228 ° C), 2-methyl-1,3-propanediol (boiling point: 214 ° C), Examples thereof include polyols such as glycerin (boiling point: 290 ° C.).
  • the solvent is preferably at least one selected from the group consisting of these.
  • Polyols are preferable from the viewpoint of compatibility with polyols used as a reaction solvent and a reducing agent, and dihydric alcohols are more preferable from the viewpoint of not having a high viscosity, and among them, ethylene glycol and propylene glycol are economical. More preferred.
  • the liquid heat medium (oil bath in the examples described later) used at the time of synthesis after the completion of silver nanowire synthesis (reaction) has a high thermal conductivity, for example, 100 W / m ⁇ K or more.
  • a method of throwing a metal plate (aluminum, copper, duralumin, etc.) that is partly in contact with air and blowing air at 40 ° C or lower toward the part of the metal plate that is in contact with air. ..
  • the cooling rate of the liquid heat medium is improved by using a metal having high thermal conductivity.
  • the metal used for the metal plate is not particularly limited, but aluminum is particularly preferable from the viewpoint of workability and economy.
  • cooling methods may be implemented in combination. Especially in the reaction vessel for mass production machines, it is considered that the cooling effect is limited by only one method due to the increase in the internal capacity. It is preferable to combine two or three of the above cooling methods as needed.
  • air at room temperature (40 ° C.) or lower is blown toward the reaction vessel and / or at room temperature (40 ° C.) or lower.
  • examples thereof include a method of dropping the polyol until the reaction liquid temperature becomes a predetermined temperature (for example, 80 ° C.) or less.
  • the reaction solution temperature during the production (synthesis) of silver nanowires is 120 ° C to 170 ° C, preferably 130 to 165 ° C, more preferably 140 to 160 ° C. If the temperature is lower than 120 ° C, it takes a long time to complete the growth process of silver nanowires, and the productivity is poor. If the temperature exceeds 170 ° C, the heat medium that can be used during manufacturing is limited and the versatility is lowered.
  • silver nanowires of the present invention As the method for producing silver nanowires of the present invention, a known polyol (Poly-ol) reduction method is used. Silver nanowires can be synthesized by reducing silver nitrate in the presence of poly-N-vinylpyrrolidone (see Chem. Matter., 2002, 14, 4736).
  • the production method previously disclosed by the applicant in WO2017 / 057326 that is, a first solution containing an ionic derivative (containing a polyol as a solvent) is kept at the above temperature and is added to the first solution.
  • the molar ratio with and (the number of moles of the metal atom of the metal salt supplied per minute / the total number of moles of the halogen atom of the ionic derivative) is preferably less than 10, preferably 1 or less, more preferably 0.22.
  • the molar ratio of the total number of moles of halogen atoms of the ionic derivative in the first solution to the number of moles of metal atoms of the metal salt (number of moles of metal atoms of the metal salt / ionic derivative) is as follows.
  • a (co) polymer containing a monomer unit derived from N-vinylpyrrolidone as a structure-determining agent is supplied in the first solution or the second solution. You can apply the method of putting it in at least one of them.
  • the reaction pressure is normal pressure (atmospheric pressure).
  • the reaction solvent used in the above-mentioned polyol reduction method is polyols used as reducing agents, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1 , 2-Butanediol, 1,3-Butanediol, 1,4-Butanediol, 2-Methyl-1,3-Propylenediol, glycerin, etc., and be at least one selected from the group consisting of these. Is preferable.
  • the reaction solution after the synthesis reaction contains silver nanoparticles produced as a by-product in addition to the ionic derivative used for the synthesis, the structure-defining agent, and the reaction solvent together with the target silver nanowire.
  • the silver nanowire obtained by synthesis is metallic silver having a diameter on the order of nanometers, and is a conductive material having a linear shape (including silver nanotubes in the shape of a hollow tube). Further, it is preferable that the metallic silver of the silver nanowire does not contain a metal oxide in terms of conductive performance, but if air oxidation is unavoidable, a silver oxide may be contained in a part (at least a part of the surface). ..
  • the length (diameter) of the silver nanowire in the minor axis direction is preferably 5 nm or more and 90 nm or less on average, more preferably 10 nm or more and 85 nm or less on average, and the length in the major axis direction is preferably 1 ⁇ m or more and 100 ⁇ m or less on average, more preferably. Is 5 ⁇ m or more and 95 ⁇ m or less on average.
  • the term "silver nanowire” means that the aspect ratio represented by a / b exceeds 5 when the length in the major axis direction is a and the length (diameter) in the minor axis direction is b. It means, and it is preferable that it is 10 or more.
  • the “silver nanoparticles” means particles having an aspect ratio of 5 or less, which are by-produced by synthesis, excluding the above-mentioned “silver nanoparticles”.
  • the above-mentioned ionic derivative is a component that contributes to the growth of metal wires, and can be applied as long as it is a compound that can be dissolved in a solvent to dissociate halogen ions, and quaternary ammonium salt halides and metal halides are suitable. ..
  • the halogen ion is preferably at least one of chlorine ion, bromine ion and iodine ion, and more preferably contains a compound capable of dissociating chlorine ion.
  • a quaternary alkylammonium salt having a total number of carbon atoms in the molecule of 4 to 20 (four alkyl groups are bonded to the nitrogen atom of the quaternary ammonium salt, and each alkyl group is
  • the same or different halides are preferred, for example quaternary ammonium such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, octyltrimethylammonium chloride, hexadecyltrimethylammonium chloride.
  • Examples thereof include chlorides and quaternary ammonium bromides such as tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, octyltrimethylammonium bromide and hexadecyltrimethylammonium bromide. Any one of these may be used alone or in combination of two or more. Further, a quaternary ammonium hydroxide reacted with hydrogen chloride, hydrogen bromide or hydrogen iodide to form an ammonium salt can be used.
  • hydrogen chloride hydrogen bromide, hydrogen iodide
  • they may be neutralized using their aqueous solution in a polyol solvent, and water or excess water or excess can be obtained by heating after neutralization. Hydrogen halide can also be distilled off.
  • a halide of a quaternary alkylammonium salt having a total molecular weight of 4 to 16 carbon atoms is more preferable in terms of solubility and usage efficiency, and the longest alkyl chain attached to a nitrogen atom has a carbon atom number.
  • a halide of a quaternary alkylammonium salt having a molecular weight of 12 or less, more preferably 8 or less, is more preferable in terms of efficiency of use because the molecular weight is not so large.
  • tetramethylammonium chloride tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, Octyltrimethylammonium chloride and octyltrimethylammonium bromide are particularly preferred.
  • metal halogen compound examples include alkali metal halides, alkaline earth metal halides, and metal halides of Groups 3 to 12 of the Long Periodic Table.
  • alkali metal halides include alkali metal chlorides such as lithium chloride, sodium chloride and potassium chloride, alkali metal bromides such as lithium bromide, sodium bromide and potassium bromide, lithium iodide, sodium iodide and potassium iodide. Examples thereof include alkali metal iodide.
  • alkaline earth metal halide include magnesium chloride, magnesium bromide, and calcium chloride.
  • Group 3 to Group 12 metal halides in the Long Periodic Table include ferric chloride, ferric chloride, ferric bromide, and ferric bromide. Any one of these may be used alone or in combination of two or more.
  • a compound that dissociates chloride ions for wire formation.
  • a compound that dissociates chloride ions in order to obtain a wire having a small diameter, it is preferable to use a compound that dissociates chloride ions, and at least one of a compound that dissociates bromine ions and a compound that dissociates iodine ions in combination.
  • the molar ratio of A) / (B) is preferably 2 to 8, more preferably 3 to 6.
  • the structure-defining agent used for synthesis is a compound having a function of one-dimensionally defining the growth direction of metal particles at the time of synthesis, and the ratio of metal nanowires formed in the particle forming step by using the structure-defining agent. Can be enhanced.
  • the structure-determining agent preferentially or selectively adsorbs to a specific crystal plane of the target particle and controls the growth direction by suppressing the growth of the adsorption plane. This growth direction can be controlled by adding a structure-defining agent to the polyols and adsorbing them on the surface of the silver nanowires to be produced.
  • the structure-determining agent a structure-determining agent having a weight average molecular weight of more than 1000 is preferable, a structure-determining agent having a weight average molecular weight of 2000 or more is more preferable, and a structure-determining agent having a weight average molecular weight of 10,000 or more is further preferable.
  • the weight average molecular weight of the structural regulator is preferably 1.5 million or less, more preferably 1 million or less, and even more preferably 500,000 or less.
  • the type of the structural regulator include poly-N-vinylpyrrolidone (PVP), a 1: 1 copolymer of N-vinylpyrrolidone and vinyl acetate, and the like.
  • the structure-defining agent has the effect of controlling the wire-like growth of silver nanowires during the synthesis of silver nanowires and preventing the aggregated silver nanowires produced.
  • the by-produced silver nanoparticles are contained in addition to the ionic derivative, the structure-defining agent, and the solvent used for the synthesis together with the target silver nanowire. It is possible to prepare a conductive ink containing silver nanowires by performing a known purification step of silver nanowires according to the above.
  • Synthesis Example 1 Production of silver nanowires 667 g of propylene glycol (manufactured by AGC Co., Ltd.) is weighed in a 1 L plastic container, and 22.5 g (0.13 mol) of silver nitrate (manufactured by Toyo Kagaku Kogyo Co., Ltd.) is added as a metal salt to block light at room temperature. A silver nitrate solution (second solution) was prepared by stirring underneath for 2 hours.
  • Sokalan (registered trademark) K90) was charged and completely dissolved by stirring at 150 ° C. for 1 hour using an oil bath as a heat medium at a rotation speed of 200 rpm to obtain a first solution.
  • the silver nitrate solution (second solution) prepared above was connected to a metering pump and dropped onto the first solution at a temperature of 150 ° C. over 2.5 hours to synthesize silver nanowires. After the dropping was completed, heating and stirring were continued for another 30 minutes to complete the reaction. At the end of the reaction, heating of the heat source (heating of the oil bath) was stopped.
  • Example 1 After the reaction of Synthesis Example 1 was completed, silver nanowires were produced in the same manner as in Synthesis Example 1 except that the flask was taken out from the oil bath and cooled (air-cooled). Similar to Synthesis Example 1, the solution (reaction solution) immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. .. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The average cooling rate is the difference (T-80) ° C. between the temperature T (° C.) at the end of the reaction and 80 ° C. divided by the time t (minutes) required from immediately after the end of the reaction to 80 ° C. ((T-80). / T) Calculated by. The same applies to the other examples and comparative examples. The results are shown in Table 2.
  • Example 2 After the reaction of Synthesis Example 1 was completed, the flask was taken out from the oil bath, and was further cooled by blowing air toward the flask with a small fan (Yamazen Corporation, 15 cm mini desktop fan DS-A151). Similarly, a silver nanowire was manufactured. As in Synthesis Example 1, the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Example 3 After the reaction of Synthesis Example 1 was completed, the flask was immersed in an oil bath in which heating was stopped, and 500 g of propylene glycol at 25 ° C. was added dropwise at a rate of 9.0 g / min to cool the flask, which was the same as the method of Synthesis Example 1.
  • Manufactured silver nanowires As in Synthesis Example 1, the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Example 4 After the reaction of Synthesis Example 1 was completed, silver nanowires were produced in the same manner as in Synthesis Example 1 except that the solution in the flask was transferred to another 2L SUS container and cooled at room temperature. As in Synthesis Example 1, the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Example 5 Silver nanowires were produced in the same manner as in Example 1 except that the temperature at which the first solution was prepared and the temperature at which the silver nitrate solution (second solution) was dropped into the first solution was changed to 170 ° C.
  • the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Example 6 Silver nanowires were produced in the same manner as in Example 2 except that the temperature at which the first solution was prepared and the temperature at which the silver nitrate solution (second solution) was dropped into the first solution was changed to 170 ° C.
  • the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Example 7 After the reaction of Synthesis Example 1 is completed, the flask is immersed in an oil bath with an aluminum heat sink (length 300 mm ⁇ width 40 mm ⁇ thickness 8 mm metal plate) immersed in the oil bath while being immersed in the oil bath in which heating is stopped. In the oil bath between the flask and the installation position of the fan, immerse the two heat sinks in the oil bath by a vertical length of 150 mm so that the surfaces of the two heat sinks face the fan (150 mm is exposed from the oil surface).
  • an aluminum heat sink length 300 mm ⁇ width 40 mm ⁇ thickness 8 mm metal plate
  • a silver nanowire was produced in the same manner as in the method of Synthesis Example 1 except that the oil was cooled.
  • the solution immediately after the reaction was completed and cooled to 80 ° C. was sampled, the dimensions (diameter) of any 100 silver nanowires obtained were measured, and the arithmetic mean value was obtained. Further, the average cooling rate of the reaction solution from immediately after the completion of the reaction to 80 ° C. was determined. The results are shown in Table 2.
  • Examples 1 to 7 having an average cooling rate of ⁇ 0.50 ° C./min or more it was confirmed that the difference in the diameter of the silver nanowires immediately after the reaction was completed and after cooling to 80 ° C. was 1 nm or less, and the diameter hardly increased. rice field.
  • Comparative Examples 1 to 3 having an average cooling rate of less than ⁇ 0.50 ° C./min the difference in the diameter of the silver nanowires immediately after the reaction was completed and after cooling to 80 ° C. was larger than 1 nm, and the cooling rate was particularly slow in Comparative Example 1. The diameter increased by 2 nm or more, and the correlation between the cooling rate and the increase in diameter was confirmed.
  • Example 8 evaluation of transparent conductive film
  • transparent conductive films were prepared and evaluated using the silver nanowires of Example 4 and Comparative Example 1. The following purification operations were performed on the silver nanowire reaction solutions of Example 4 and Comparative Example 1, respectively.
  • PFA perfluoroalkoxyethylene-tetrafluoroethylene copolymer
  • the opening and closing of the permeation valve was adjusted so that the permeation rate of the filtrate was about 10 g / min, and 100 g of ion-exchanged water was added to the system by backwashing every 100 g of the filtrate (solvent retention rate 95%). Backwash pressure 0.15 MPa).
  • the solvent added to the system by backwashing was changed from ion-exchanged water to ethanol, and cross-flow filtration (second filtration) was continued at a filtration differential pressure of 0.03 MPa.
  • Cross-flow filtration was terminated when an additional 2800 g of filtrate was obtained.
  • the silver concentration is determined using the Forhardt method. Weigh about 1 g of the sample into a beaker and add 4 mL of nitric acid (1 + 1) and 20 mL of pure water. Cover the beaker with a watch glass and heat it to 150 ° C. on a hot plate to dissolve the solids. After confirming the dissolution, stop heating and allow to cool, then wash the inner surface of the watch glass and the wall surface of the beaker with pure water to make the liquid volume about 50 mL.
  • the silver concentration is determined according to the following formula.
  • Silver concentration (mass%) ⁇ (V ⁇ c) ⁇ 107.9 / 1000 ⁇ / m m: Sample weight (g) V: Amount of ammonium thiocyanate aqueous solution consumed for titration to the end point (mL) c: Concentration of aqueous solution of ammonium thiocyanate (0.01 mol / L)
  • ammonium iron sulfate (III) 3% nitric acid acidity
  • a mixture of 5.17 g of ammonium iron sulfate (III), 170 g of pure water and 2.00 g of nitric acid was used.
  • As the 0.01 mol / L ammonium thiocyanate aqueous solution pure water was added to 38.06 mg of ammonium thiocyanate to prepare a total volume of 50 mL.
  • PNVA poly-N-vinylacetamide
  • GE191-103 manufactured by Showa Denko KK, homopolymer (10% by mass aqueous solution of weight average molecular weight 900,000 (catalog value))
  • PNVA poly-N-vinylacetamide
  • GE191-103 manufactured by Showa Denko KK, homopolymer (10% by mass aqueous solution of weight average molecular weight 900,000 (catalog value)
  • the mixing amount was adjusted so as to be a dispersion medium), and each ink was obtained.
  • Each of the above silver nanowire inks was used as a supporting base material plasma-treated at a printing speed of 500 mm / sec using a coating machine 70F0 manufactured by Imoto Seisakusho Co., Ltd. and a bar coater having a wet film thickness of about 15 ⁇ m. It was applied to a COP (cycloolefin polymer) supporting substrate (film substrate, ZF-14 manufactured by Zeon Corporation) having a size of 21 cm ⁇ 30 cm. Then, it was dried at 80 ° C. for 1 minute with a hot air dryer (ETAC HS350 manufactured by Kusumoto Kasei Co., Ltd.) to form a transparent conductive film having a transparent conductive layer.
  • COP cycloolefin polymer
  • ⁇ Plasma treatment of supporting substrate (film substrate)> The plasma treatment as the surface treatment of the film substrate was carried out for 20 seconds at an output of 1 kW under a nitrogen gas atmosphere using a plasma treatment device (AP-T03 manufactured by Sekisui Chemical Co., Ltd.).
  • the sheet resistance (surface resistivity) of the obtained transparent conductive film was measured by Loresta-GP manufactured by Mitsubishi Chemical Analytech. Further, as the optical characteristics of the transparent conductive film, the total light transmittance, haze and b * were measured by a spectroscopic color / haze meter COH7700 manufactured by Nippon Denshoku Kogyo Co., Ltd. The reference for measuring the optical characteristics was measured using air. The results are shown in Table 3.
  • the transparent conductive film using the silver nanowires synthesized in Example 4 has a low haze despite having the same surface resistivity. , High transparency was confirmed.

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Abstract

La présente invention vise à fournir un procédé de production de nanofil d'argent ayant une grande capacité de production et permettant la suppression d'une augmentation de diamètre pendant un refroidissement qui suit un achèvement de réaction. À cet effet, l'invention concerne un procédé de production de nanofil d'argent qui est caractérisé par le fait qu'il comprend l'étape consistant à synthétiser un nanofil d'argent à une température de 120 à 170 °C par le procédé de réduction de polyol, et l'étape consistant à refroidir, après la fin de la synthèse de nanofil d'argent, la température de solution de réaction, de la température au moment de la fin de la réaction jusqu'à 80 °C, à une vitesse de refroidissement de -0,50 °C/minute ou plus rapide en moyenne.
PCT/JP2021/041880 2020-12-24 2021-11-15 Procédé de production de nanofil d'argent WO2022137886A1 (fr)

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CN202180077031.5A CN116529000A (zh) 2020-12-24 2021-11-15 银纳米线的制造方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080210052A1 (en) * 2006-06-21 2008-09-04 Cambrios Technologies Corporation Methods of controlling nanostructure formations and shapes
CN105086630A (zh) * 2015-08-18 2015-11-25 Tcl集团股份有限公司 导电油墨用银纳米线和银纳米线电极的制备方法
JP2016166402A (ja) * 2014-10-28 2016-09-15 ダウ グローバル テクノロジーズ エルエルシー 銀ナノワイヤを製造する方法
WO2017057326A1 (fr) * 2015-09-30 2017-04-06 昭和電工株式会社 Procédé de production d'un nanofil métallique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7585349B2 (en) 2002-12-09 2009-09-08 The University Of Washington Methods of nanostructure formation and shape selection
KR101283984B1 (ko) * 2011-05-20 2013-07-09 한국화학연구원 돌기를 가진 은 나노선 및 이의 제조 방법
JP2020033603A (ja) 2018-08-30 2020-03-05 Ｄｏｗａエレクトロニクス株式会社 銀ナノワイヤの集合体、銀ナノワイヤ分散液、銀ナノワイヤインク、及びそれらの製造方法
JP7239297B2 (ja) 2018-10-22 2023-03-14 トヨタ自動車株式会社 銀ナノワイヤの製造方法
CN110315091B (zh) * 2019-06-26 2022-07-01 中山大学 一种快速制备纳米银线的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080210052A1 (en) * 2006-06-21 2008-09-04 Cambrios Technologies Corporation Methods of controlling nanostructure formations and shapes
JP2016166402A (ja) * 2014-10-28 2016-09-15 ダウ グローバル テクノロジーズ エルエルシー 銀ナノワイヤを製造する方法
CN105086630A (zh) * 2015-08-18 2015-11-25 Tcl集团股份有限公司 导电油墨用银纳米线和银纳米线电极的制备方法
WO2017057326A1 (fr) * 2015-09-30 2017-04-06 昭和電工株式会社 Procédé de production d'un nanofil métallique

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