WO2016104359A1 - Procédé de production de nanofils d'argent, nanofils d'argent obtenus à l'aide dudit procédé, et encre contenant lesdits nanofils d'argent - Google Patents

Procédé de production de nanofils d'argent, nanofils d'argent obtenus à l'aide dudit procédé, et encre contenant lesdits nanofils d'argent Download PDF

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WO2016104359A1
WO2016104359A1 PCT/JP2015/085481 JP2015085481W WO2016104359A1 WO 2016104359 A1 WO2016104359 A1 WO 2016104359A1 JP 2015085481 W JP2015085481 W JP 2015085481W WO 2016104359 A1 WO2016104359 A1 WO 2016104359A1
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silver
silver nanowires
producing
nanowires
compound
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Japanese (ja)
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内田　博
真尚 原
菅原　篤
守 橘川
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昭和電工株式会社
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Priority to JP2016566193A priority Critical patent/JP6636949B2/ja
Priority to CN201580063555.3A priority patent/CN107000065B/zh
Priority to KR1020177012753A priority patent/KR101990346B1/ko
Publication of WO2016104359A1 publication Critical patent/WO2016104359A1/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
    • 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
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • 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 producing silver nanowires, a silver nanowire obtained by the method, and an ink containing the silver nanowire.
  • silver nanowires have attracted attention as raw materials for highly transparent and highly conductive thin films that can be substituted for ITO (indium tin oxide) films used for transparent electrodes such as touch panels.
  • Such silver nanowires are generally produced by heating a silver compound in the presence of a polyol such as polyvinylpyrrolidone and ethylene glycol (Patent Document 1, Non-Patent Document 1).
  • Patent Document 2 Although polyvinylpyrrolidone has solubility in glycol and water, in the above reaction, in order to control the wire diameter of silver nanowires, chloride salts and other inorganic salts often coexist (Patent Document 2). When these are present, the solubility of polyvinyl pyrrolidone in glycol and water decreases. For this reason, it has been difficult to deposit after the reaction so that polyvinylpyrrolidone adheres to the surface of the silver nanowire grown in the presence of these, and to remove it by washing.
  • the subject of this invention is providing the silver nanowire manufacturing method with which the washing
  • one embodiment of the present invention is a method for producing a silver nanowire, wherein R-CONHR ′ (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ′ is In the presence of a polymer having a weight average molecular weight of 100,000 to 280000 and a reducing agent containing a secondary amide compound represented by a alkenyl group having a carbon-carbon double bond and having 2 or 3 carbon atoms in the monomer unit. And a step of heating the silver compound.
  • R-CONHR ′ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ′ is In the presence of a polymer having a weight average molecular weight of 100,000 to 280000 and a reducing agent containing a secondary amide compound represented by a alkenyl group having a carbon-carbon double bond and having 2 or 3 carbon atoms in the monomer unit.
  • the polymer of the above compound is preferably at least one polymer selected from poly (N-vinylformamide), poly (N-vinylacetamide) or poly (N-vinylpropionamide).
  • the silver compounds are silver nitrate, hexafluorophosphate silver, silver borofluoride, silver perchlorate, silver chlorate, silver chloride, silver bromide, silver fluoride, silver carbonate, silver sulfate, silver acetate, trifluoro. It is preferably any of silver acetate.
  • polyol is preferably a divalent to hexavalent alcohol compound having 2 to 6 carbon atoms.
  • the method for producing the silver nanowire it is preferable to use 10,000 to 100,000 parts by weight of polyol with respect to 100 parts by weight of the silver compound.
  • the method for producing the silver nanowire further adds a quaternary ammonium salt.
  • the method for producing silver nanowires further includes a step of removing a polymer attached to the surface of the obtained silver nanowires.
  • another embodiment of the present invention is a silver nanowire, which is obtained by any one of the above-described silver nanowire manufacturing methods.
  • Still another embodiment of the present invention is an ink, characterized in that it contains the silver nanowire.
  • the cleaning process during the production of silver nanowires can be greatly simplified.
  • FIG. 3 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of the silver nanowires obtained in Example 1.
  • FIG. 6 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of silver nanowires obtained in Example 2.
  • FIG. 6 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of the silver nanowires obtained in Example 3.
  • FIG. 6 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of silver nanowires obtained in Example 4.
  • FIG. 6 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of the silver nanowires obtained in Example 5.
  • FIG. 6 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of the silver nanowires obtained in Example 6.
  • FIG. 10 is a diagram showing a field emission scanning electron microscope (FE-SEM) image of the silver nanowires obtained in Example 7.
  • FIG. 10 is a diagram showing a field emission scanning electron microscope (FE-
  • the method for producing a silver nanowire according to the present embodiment includes R-CONHR ′ (R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ′ represents the number of carbon atoms having a carbon-carbon double bond. And a step of heating the silver compound in the presence of a polymer containing a secondary amide compound represented by 2 or 3 alkenyl group) as a monomer unit and a reducing agent.
  • Silver nanowires refer to silver nanofibers with a diameter on the order of nanometers.
  • Examples of the silver compound include silver salts, which may be used singly or in combination of two or more.
  • reaction can be performed homogeneously by using a silver compound soluble in the solvent which melt
  • the above silver salts are roughly classified into inorganic salts and organic salts, but inorganic salts are preferred from the viewpoint of industrial availability.
  • silver compound silver nitrate (AgNO 3), hexafluorophosphate silver (AgPF 6), ⁇ halide (AgBF 4), silver perchlorate (AgClO 4), silver perchlorate (AgClO 3), chloride Silver (AgCl), silver bromide (AgBr), silver fluoride (AgF), silver carbonate (Ag 2 CO 3 ), silver sulfate (Ag 2 SO 4 ), silver acetate (AgO 2 CCH 3 ), silver trifluoroacetate (AgO 2 CCF 3 ), and from the viewpoint of obtaining the production efficiency of the silver nanowire and the shape of the target silver nanowire, silver nitrate, silver perchlorate, silver chlorate, silver fluoride, hexafluorophosphate silver, Silver borofluoride and silver trifluoroacetate are preferred, and silver nitrate, hexafluorophosphate silver, silver borofluoride and silver trifluoroa
  • the silver concentration in the reaction solution is preferably in the range of 0.05 to 2% by mass as metal silver, more preferably in the range of 0.06 to 1% by mass, and in the range of 0.07 to 0.5% by mass. It is particularly preferable for obtaining a silver nanowire having a diameter.
  • the polymer (polymer) containing the secondary amide compound in the monomer unit used in the present embodiment acts as a capping agent in the silver nanowire synthesis stage.
  • the capping agent is a substance (ion, surfactant, etc.) adsorbed on a specific surface of the generated nucleus, and controls the shape of the generated particles by suppressing the growth rate of the surface.
  • thin and long nanowires can be obtained by selecting those that adsorb to the side portions of the nanowires.
  • the capping agent is outlined in the following non-patent literature, for example. Xia, et al. Acc. Chem. Res. 2007, 40, 1067. ⁇ Nobuyuki Korezu, Journal of Japanese Society for Crystal Growth, 2010, 37, No. 4, 281
  • Examples of the capping agent include R-CONHR ′ (R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ′ represents an alkenyl group having 2 or 3 carbon atoms having a carbon-carbon double bond. And a polymer having a monomer unit of the secondary amide compound which is a derivative of formic acid, acetic acid, propionic acid and butyric acid, which is a carboxylic acid having a relatively hydrophilic carbon atom number of 3 or less.
  • R ′ include a vinyl group, an isopropenyl group, and an allyl group.
  • the capping agent examples include poly (N-vinylformamide), poly (N-vinylacetamide), and poly (N-vinylpropionamide).
  • the capping agent can be easily washed from the produced silver nanowire by heating the silver compound in the presence of one or more polymers selected from such polymers and a reducing agent. it can.
  • the polymer is not only a single polymer selected from poly (N-vinylformamide), poly (N-vinylacetamide) or poly (N-vinylpropionamide) or a mixture as a polymer, but also the secondary amide.
  • Copolymers with other polymerizable monomers containing the compound in monomer units can also be used.
  • examples of other polymerizable monomers include acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, acrylamide, N, N-dimethylacrylamide and the like. It is done.
  • the secondary amide monomer unit in the copolymer is preferably in the range of 20 to 95 mol%, more preferably 30 to 90 mol%.
  • these polymers have a hydrogen atom bonded to the nitrogen atom constituting the amide group, and have a high affinity with the (hydrophilic) reaction solvent described later, so the protective colloid properties are low.
  • the range of molecular weights of the polymers that can be used to obtain them.
  • the total amount of the polymer used is not particularly limited, but is usually about 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 1 part by mass of the silver compound. If it is lower than 0.5 parts by mass, it cannot be effectively adsorbed, and if it exceeds 20 parts by mass, the viscosity of the reaction solution becomes too high, which is not preferable.
  • the heating of the silver compound in the presence of the polymer can be performed in the presence of an alkali metal inorganic acid salt together with the polymer.
  • the alkali metal inorganic acid salt is preferably an alkali metal nitrate or alkali metal nitrite, more preferably an alkali metal nitrate.
  • potassium nitrate sodium nitrate
  • potassium nitrite sodium nitrite and the like, and any of these may be used alone or in combination.
  • the total amount of the alkali metal inorganic acid salt used is not particularly limited, but is usually about 0.05 to 2 molar equivalents, preferably 0.1 to 1 molar equivalents, per 1 mol of the silver compound.
  • an alkali metal halide may be used together with this.
  • alkali metal halides include alkali metal chlorides such as sodium chloride and potassium chloride; alkali metal bromides such as sodium bromide and potassium bromide; alkali metal iodides such as sodium iodide and potassium iodide. Any of these may be used alone or in combination.
  • the total amount of the alkali metal halide used is not particularly limited, but is usually about 1 ⁇ 10 ⁇ 7 to 3 ⁇ 10 ⁇ 1 molar equivalent, preferably 1 ⁇ 10 ⁇ 6 to 1 ⁇ , per 1 mol of the silver compound. 10 -2 molar equivalents.
  • the total amount of alkali metal halide used is less than 1 ⁇ 10 ⁇ 7 molar equivalent, selective growth into a silver nanowire shape is not promoted and the yield of the wire is extremely reduced.
  • the total amount of alkali metal halide used exceeds 3 ⁇ 10 ⁇ 1 molar equivalent, the yield of coarse silver particles increases and the yield decreases extremely.
  • a quaternary ammonium salt may be used together with the polymer.
  • Such quaternary ammonium salts include quaternary ammonium chlorides such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, hexadecyltrimethylammonium chloride, tetramethylammonium bromide, bromide bromide.
  • Quaternary ammonium bromides such as tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, hexadecyltrimethylammonium bromide and the like can be mentioned, and any of these may be used alone or in combination. .
  • tetrabutylammonium chloride and tetrabutylammonium bromide are preferable from the viewpoint of the obtained wire shape.
  • the total amount of the quaternary ammonium salt used is not particularly limited, but is usually about 0 to 1 molar equivalent, preferably 0 to 0.5 molar equivalent, relative to 1 mol of the silver compound.
  • the above heating is performed in the presence of a reducing agent.
  • the silver compound is reduced by the reducing agent, and metallic silver is deposited.
  • the reducing agent those having a known reducing action, for example, hydrogen gas, hydrazine, sodium borohydride, lithium aluminum hydride and the like can be used, but those that can also be used as a solvent described later may be used. From the viewpoint of safety and economy.
  • the above heating needs to be performed in the presence of a solvent in a state where the silver compound is dissolved or dispersed.
  • a solvent examples include polyol, water, monohydric alcohol, and the like. From the viewpoint of obtaining a reducing action, a solvent containing a polyol is preferable.
  • polyol examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2- Dihydric alcohols such as butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol; trihydric alcohols such as glycerin; pentaerythritol, diglycerin, ditrile Examples include tetravalent alcohols such as methylolpropane and hexavalent alcohols such as sorbitol, and any of these may be used alone or in combination.
  • a bivalent to hexavalent alcohol compound having 2 to 6 carbon atoms is more preferable in terms of a high boiling point and a high temperature at normal pressure, and a reducing property.
  • the use of a polyol as a solvent eliminates the need for a separate reducing agent.
  • dihydric alcohols are more preferable from the viewpoint of not having high viscosity, and ethylene glycol and propylene glycol are particularly preferable from the viewpoint of economy.
  • the total amount of the polyol used is not particularly limited, but is usually about 10,000 to 100,000 parts by weight, preferably 15,000 to 60,000 parts by weight with respect to 100 parts by weight of the silver compound. If the amount is less than this, the reduction rate becomes slow, and if it is more, the productivity tends to deteriorate.
  • the total amount of the solvent containing or not containing the polyol as a solvent is not particularly limited, but is usually about 10,000 to 100,000 parts by weight, preferably 15,000 to 60,000 parts by weight with respect to 100 parts by weight of the silver compound. .
  • the total amount of the solvent used is less than 10000 parts by mass, the silver concentration in the reaction solution is too high, and side reactions such as spherical powder formation may occur and the yield of the wire may decrease.
  • the total amount of the solvent used exceeds 100000 parts by mass, the silver concentration in the reaction solution is too low, the reaction rate is lowered, and the productivity is lowered.
  • the heating temperature of the silver compound is not particularly limited, but is usually 60 to 300 ° C., preferably 100 to 200 ° C.
  • the heating time is usually 0.1 to 48 hours, preferably 0.2 to 24 hours.
  • the silver nanowire produced by the heating step is purified by centrifugation, crossflow filtration, etc. to remove the capping agent attached to the surface, but the capping agent used in this embodiment is compared with polyvinylpyrrolidone. Because of its high water solubility, it can be removed with a simple washing process. Solvents that can be used for washing include water, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, sec-butanol, etc. Among them, methanol, ethanol, isopropyl alcohol are industrial. It is preferable in terms of availability and easiness of solvent exchange in a subsequent process.
  • the silver nanowires obtained by the production method described above have very little residue derived from the capping agent, the resistance after the ink is prepared and applied is easily reduced, and the dispersibility in an aqueous solvent is particularly improved. .
  • the diameter of the obtained silver nanowire is about 20 to 250 nm, and the length is about 1 to 50 ⁇ m.
  • the diameter and length of silver nanowire according to the method as described in the Example mentioned later.
  • the ink according to this embodiment contains silver nanowires obtained by the above production method.
  • the content of silver nanowires in the ink is preferably large from the viewpoint of improving the conductivity of the pattern formed by the ink, but has an upper limit from the viewpoint of suppressing optical properties and aggregation, and is 0.05 to 60. % By mass is preferable, and 0.1 to 30% by mass is more preferable.
  • it is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in consideration of light transmittance.
  • the solvent contained in the ink of the present embodiment is not particularly limited.
  • water alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone; alkylene glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol, and 1,3-propanediol; hydrocarbon solvents such as alkyl ethers of alkylene glycol, terpineol, toluene, and hexane It is done. These may be used individually by 1 type and may use 2 or more types together.
  • poly (N-vinylformamide), poly (N-vinylacetamide) or poly (N-vinylpropionamide) is used.
  • organic solvents more hydrophobic
  • the amount of these added is not particularly limited, but is usually about 0.01 to 10 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of silver nanowires.
  • binder resin polyurethane resin, cellulose resin, polyacetal resin, polyalkylene glycol resin, etc.
  • binder resin components polyurethane resin, cellulose resin, polyacetal resin, polyalkylene glycol resin, etc.
  • the ink of the present embodiment includes various additives other than those described above (for example, surfactants, polymerizable compounds, polymers, antioxidants, corrosion inhibitors, viscosity modifiers, antiseptics, etc.) Agent).
  • additives for example, surfactants, polymerizable compounds, polymers, antioxidants, corrosion inhibitors, viscosity modifiers, antiseptics, etc.
  • the substrate on which the ink of the present embodiment is printed is not particularly limited, and examples thereof include insulating materials such as resin, glass, ceramic, and paper, semiconductor materials, and conductors such as metal.
  • the resin substrate include a polyethylene terephthalate substrate, a triacetyl cellulose substrate, a polyethylene naphthalate substrate, a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, and a polyacryl substrate.
  • GPC gel permeation chromatography
  • Measuring apparatus HPLC manufactured by Shodex Eluent: Distilled water Detector: shodex RI-201I Pump: SHIMADZU LC-20AD Column oven: SHODEX AO-30C Analysis device: SHIMAZU SIC 480II Data Station Pump flow rate: 0.7 mL / min Column: 2 Shodex GPC SB-806 HQ Column temperature: 40 ° C Sample concentration: 0.2% by mass Injection volume: 200 ⁇ L
  • the shape (length / diameter) of the silver nanowires was determined by observing the diameter of 100 nanowires using an ultra high resolution field emission scanning electron microscope SU8020 (acceleration voltage 3 to 10 kV) manufactured by Hitachi High-Technologies Corporation.
  • Thermogravimetric analysis of the purified sample was performed using TG / DTA manufactured by NETZSCH.
  • Synthesis Example 1 Synthesis of poly (N-vinylformamide) N-vinylformamide (Tokyo Chemical Industry Co., Ltd., 100 g, 1.41 mol) and 400 g of pure water were added to a 1 L three-necked flask and completely dissolved. The liquid phase was replaced with nitrogen gas for 2 hours (nitrogen gas flow for the gas phase and nitrogen gas bubbling for the liquid phase). Only the substitution of nitrogen gas in the liquid phase was stopped, and the temperature was raised to 60 ° C. with the gas phase flowing in the nitrogen gas flow.
  • V-50 manufactured by Wako Pure Chemical Industries, Ltd., 0.9 g, 3.32 mmol
  • 10 g of pure water was added to the system using a syringe.
  • the reaction solution is put into a vat and placed in an oven.
  • the temperature is slowly raised to 120 ° C while watching the drying condition at normal pressure, and finally transferred to a vacuum oven.
  • 77 g of poly (N-vinylformamide) was obtained as a white solid.
  • Mw was 160000.
  • Example 1 Production of Silver Nanowire
  • a reaction vessel for personal organic synthesizer PPS-CTRL1 manufactured by Tokyo Rika Kikai Co., Ltd. 20 g of propylene glycol and 0.68 g of poly (N-vinylformamide) synthesized in Synthesis Example 1 (9 .6 mmol) was added and stirred at 60 ° C. for 1 hour for complete dissolution.
  • a vial 0.3 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 4 g of propylene glycol were added and completely dissolved by stirring at room temperature.
  • a dropping funnel was installed at the top of the reaction vessel and the silver nitrate solution prepared earlier was added. did. Nitrogen gas was passed through the branch pipe at a flow rate of 300 mL / min for 5 minutes to replace the system with nitrogen gas. The nitrogen gas in the branch pipe was stopped, a thermometer was installed, and the temperature was raised until the internal temperature reached 130 ° C. The contents of the dropping funnel were dropped over 6 minutes at an internal temperature of 130 ° C., and the reaction was further continued at 130 ° C. for 1 hour.
  • AROS tetrabutylammonium chloride
  • the reaction mixture was diluted 5-fold with ethanol, and silver nanowires were precipitated by treating with a centrifuge at a rotation speed of 6000 rpm for 5 minutes.
  • the operation of adding 50 g of ethanol and treating at 6000 rpm for 5 minutes was further performed twice to wash the poly (N-vinylformamide) and the solvent remaining in the system.
  • the shape of the obtained wire was measured using a field emission scanning electron microscope (FE-SEM).
  • the shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • Example 2 Production of Silver Nanowire Instead of 0.68 g (9.6 mmol) of poly (N-vinylformamide) synthesized in Synthesis Example 1, poly (N-vinylacetamide) (hereinafter abbreviated as PNVA)
  • PNVA poly (N-vinylacetamide)
  • a silver nanowire was obtained under the same conditions as in Example 1 except that GP191-405 (Mw: 130000, 0.817 g, 9.6 mmol) was used and the reaction time at 130 ° C. was changed from 1 hour to 20 minutes. Then, the shape of the wire was measured.
  • the shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • FE-SEM field emission scanning electron microscope
  • Example 3 A silver nanowire was obtained under the same conditions as in Example 2 except that GP191-405 (Mw: 260000) was used as PNVA, and the shape of the wire was measured.
  • the shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • Example 4 A silver nanowire was obtained under the same conditions as in Example 2 except that GE191-205 (Mw: 180000) was used as PNVA, and the shape of the wire was measured. The shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • GE191-205 Mw: 180000
  • FE-SEM field emission scanning electron microscope
  • Example 5 9-to-1 copolymer of N-vinylacetamide and acrylonitrile instead of 0.68 g (9.6 mmol) of poly (N-vinylformamide) synthesized in Synthesis Example 1 (hereinafter referred to as NVA / AN)
  • NVA / AN poly (N-vinylformamide) synthesized in Synthesis Example 1
  • Silver nanowires were obtained under the same conditions as in Example 1 except that 0.82 g (9.6 mmol) was used, and the shape of the wires was measured.
  • the shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • FE-SEM field emission scanning electron microscope
  • Example 6 instead of 0.68 g (9.6 mmol) of poly (N-vinylformamide) synthesized in Synthesis Example 1, a 9-to-1 copolymer of N-vinylacetamide and methyl methacrylate (hereinafter referred to as NVA / MMA) Silver nanowires were obtained under the same conditions as in Example 1 except that 0.82 g (9.6 mmol) manufactured by Mw: 150,000) was used, and the shape of the wires was measured. The shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • NVA / MMA 9-to-1 copolymer of N-vinylacetamide and methyl methacrylate
  • Example 7 Propylene glycol 20 g and PNVA GP191-405 (Mw: 130000) 0.54 g (6.4 mmol) were placed in a reaction vessel for the personal organic synthesizer PPS-CTRL1 manufactured by Tokyo Rika Kikai Co., Ltd., and stirred at 60 ° C. for 1 hour. To completely dissolve. 0.075 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 g of propylene glycol were placed in a vial and stirred completely at room temperature for complete dissolution.
  • PPS-CTRL1 personal organic synthesizer
  • a dropping funnel was installed at the top of the reaction vessel and the silver nitrate solution prepared earlier was added. did. Nitrogen gas was supplied from the branch pipe at a flow rate of 300 mL / min to replace the system with nitrogen gas, and the temperature was increased until the internal temperature reached 130 ° C. The contents of the dropping funnel were added dropwise at an internal temperature of 130 ° C. over 1 minute, and the reaction was further continued at 130 ° C. for 1 hour.
  • AROS tetrabutylammonium chloride
  • the reaction mixture was diluted 5-fold with ethanol, and silver nanowires were precipitated by treating with a centrifuge at a rotation speed of 6000 rpm for 5 minutes.
  • the operation of adding 50 g of ethanol and treating at 6000 rpm for 5 minutes was further performed twice to wash away PNVA and the solvent remaining in the system.
  • the shape of the wire was measured using a field emission scanning electron microscope (FE-SEM).
  • the shape of the obtained silver nanowire is shown in Table 1, and a field emission scanning electron microscope (FE-SEM) image is shown in FIG.
  • Example 8 A 1 L four-necked flask (mechanical stirrer, dropping funnel, reflux tube, thermometer) was charged with 200 g of propylene glycol and PNVA GP191-405 (Mw: 130000, 8.17 g, 96 mmol) and stirred at 60 ° C. for 1 hour. It was completely dissolved. In a beaker, 3 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 40 g of propylene glycol were placed and stirred at room temperature for complete dissolution.
  • PNVA GP191-405 Mw: 130000, 8.17 g, 96 mmol
  • the reaction mixture was diluted 4 times with methanol, and washed using a cross flow filtration apparatus (NGK Filtech Corp., Selfif tabletop tester, pore size 2 ⁇ m). Table 2 shows the washing conditions and the analysis results by TG / DTA.
  • Comparative Example 1 A silver nanowire manufacturing process was performed under the same conditions as in Example 2 except that GE191-104 (Mw: 300,000) was used as PNVA. The shape of the product is shown in Table 1.
  • the shape of the product in this comparative example was spherical, and silver nanowires could not be produced. This is probably because the weight average molecular weight Mw of PNVA was as high as 300000.
  • Comparative Example 2 A silver nanowire manufacturing process was performed under the same conditions as in Example 2 except that GE191-405P (Mw: 80000) was used as PNVA. The shape of the product is shown in Table 1.
  • the shape of the product in this comparative example was fine, and silver nanowires could not be produced. This is probably because the weight average molecular weight Mw of PNVA was as low as 80000.
  • Comparative Example 3 1 L four-necked flask (mechanical stirrer, dropping funnel, reflux tube, thermometer) with propylene glycol 200 g, polyvinylpyrrolidone K-90 (hereinafter abbreviated as PVP K-90, manufactured by Wako Pure Chemical Industries, Ltd.) 10.7 g ( 96 mmol) was added and stirred at 60 ° C. for 1 hour for complete dissolution. 3 g of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 80 g of propylene glycol were placed in a beaker and stirred at room temperature for complete dissolution.
  • PVP K-90 polyvinylpyrrolidone K-90
  • the reaction mixture was diluted 4 times with methanol, and washed using a cross flow filtration apparatus (NGK Filtech Corp., Selfif tabletop tester, pore size 2 ⁇ m). Table 2 shows the washing conditions and the analysis results by TG / DTA.
  • Example 8 using PNVA After the filtration washing process by cross flow filtration was repeated 6 times, in Example 8 using PNVA, the residual amount of resin was 0.05% by mass, whereas in Comparative Example 3 using PVP, 0.29% by mass. It can be seen that a large amount of resin cannot be cleaned.

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Abstract

La présente invention concerne : un procédé de production de nanofils d'argent, les nanofils d'argent produits étant aptes à être facilement nettoyés ; des nanofils d'argent qui sont obtenus par ce procédé ; et une encre qui contient les nanofils d'argent. Les nanofils d'argent selon la présente invention sont produits par chauffage d'un composé d'argent en présence d'un agent réducteur et d'un polymère qui possède une masse moléculaire moyenne en poids comprise entre 100 000 et 280 000, et qui contient, en tant qu'unité monomère, un composé d'amide secondaire qui est représenté par la formule R-CONHR' (dans laquelle R représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 3 atomes de carbone ; et R' représente un groupe alcényle ayant 2 ou 3 atomes de carbone et une double liaison carbone-carbone). Le polymère du composé est au moins un polymère choisi parmi le poly(N-vinyl-formaldéhyde), le poly(N-vinylacétamide) et le poly(N-vinyl-propionamide).
PCT/JP2015/085481 2014-12-26 2015-12-18 Procédé de production de nanofils d'argent, nanofils d'argent obtenus à l'aide dudit procédé, et encre contenant lesdits nanofils d'argent WO2016104359A1 (fr)

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CN201580063555.3A CN107000065B (zh) 2014-12-26 2015-12-18 银纳米线的制造方法、通过该方法得到的银纳米线及含有该银纳米线的墨
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WO2021132095A1 (fr) * 2019-12-27 2021-07-01 昭和電工株式会社 Procédé de production pour dispersion de nanofils d'argent
CN112331410B (zh) * 2020-09-07 2021-11-26 湖南大学 一种银纳米线的制备及其在透明导电膜中的应用

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