WO2016104359A1 - Method for producing silver nanowires, silver nanowires obtained by said method, and ink containing said silver nanowires - Google Patents
Method for producing silver nanowires, silver nanowires obtained by said method, and ink containing said silver nanowires Download PDFInfo
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- 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
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- 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
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- 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.
Abstract
Description
・Xia, et al. Acc. Chem. Res. 2007, 40, 1067.
・是津信行, 日本結晶成長学会誌, 2010, 37, No. 4, 281 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. In the case of silver nanowires, 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
重量平均分子量Mwの測定にはゲルパーミエーションクロマトグラフィー(以下GPCと省略する)を用い、プルラン(標準試料)に換算した値で求めた。なおGPCの測定条件は以下のとおりである。 <Molecular weight measurement>
For the measurement of the weight average molecular weight Mw, gel permeation chromatography (hereinafter abbreviated as GPC) was used, and it was obtained as a value converted to pullulan (standard sample). The measurement conditions for GPC are as follows.
溶離液 :蒸留水
検出器 :shodex RI-201I
ポンプ :SHIMADZU LC-20AD
カラムオーブン :SHODEX AO-30C
解析装置 :SHIMAZU SIC 480II Deta Station
ポンプ流速 :0.7mL/min
カラム :Shodex GPC SB-806 HQ 2本
カラム温度 :40℃
試料濃度 :0.2質量%
注入量 :200μL 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 μL
銀ナノワイヤーの形状(長さ・直径)は、株式会社日立ハイテクノロジーズ製超高分解能電界放出形走査電子顕微鏡SU8020(加速電圧3~10kV)を用いて100本のナノワイヤーの径を観測した。 <Observation of silver nanowire shape>
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.
精製サンプルの熱重量分析はNETZSCH社製TG/DTAを用いて行った。 <Thermogravimetric analysis>
Thermogravimetric analysis of the purified sample was performed using TG / DTA manufactured by NETZSCH.
1L三口フラスコにN-ビニルホルムアミド(東京化成工業(株)製、100g、1.41mol)および純水400gを加え完全に溶解させた後、気相と液相を窒素ガスで2時間置換(気相は窒素ガスフロー、液相は窒素ガスバブリング)した。液相の窒素ガス置換のみを止め、気相を窒素ガスフローさせたまま60℃まで昇温した。重合開始剤としてV-50(和光純薬工業(株)製、0.9g、3.32mmol)を純水10gに溶解させ、シリンジを用いて系中に加えた。60℃で6時間反応を継続した後、反応液をバットにあけオーブンに入れて、常圧で乾燥具合を見ながら突沸しないように120℃までゆっくり昇温し、最終的に真空オーブンに移して24時間減圧乾燥させることでポリ(N-ビニルホルムアミド)を白色固体として77g得た。GPCによる分子量測定の結果、Mwは160000であった。 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. As a polymerization initiator, V-50 (manufactured by Wako Pure Chemical Industries, Ltd., 0.9 g, 3.32 mmol) was dissolved in 10 g of pure water and added to the system using a syringe. After the reaction is continued for 6 hours at 60 ° C, 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. By drying under reduced pressure for 24 hours, 77 g of poly (N-vinylformamide) was obtained as a white solid. As a result of molecular weight measurement by GPC, Mw was 160000.
東京理化機械(株)製のパーソナル有機合成装置PPS-CTRL1用反応容器に、プロピレングリコール20g、合成例1で合成したポリ(N-ビニルホルムアミド)0.68g(9.6mmol)を仕込み、60℃で1時間撹拌することで完全に溶解させた。バイアル瓶に硝酸銀(和光純薬工業(株)製)0.3g、プロピレングリコール4gを入れ室温で撹拌することで完全に溶解させた。塩化テトラブチルアンモニウム(ACROS社製)の1質量%プロピレングリコール溶液0.738g(26.6μmol)を反応容器に添加した後、反応容器上部に滴下漏斗を設置して先に調製した硝酸銀溶液を投入した。枝管より窒素ガスを300mL/minの流量で5分間流して系を窒素ガス置換した。枝管の窒素ガスを止め温度計を設置し、内温が130℃となるまで昇温した。内温130℃にて6分間かけて滴下漏斗の内容物を滴下し、さらに130℃で1時間反応を継続した。反応混合物をエタノールで5倍に希釈し、遠心分離機を用いて6000rpmの回転数で5分間処理することで銀ナノワイヤーを沈降させた。エタノール50gを添加し6000rpmで5分間処理する操作をさらに2回行い系中に残存するポリ(N-ビニルホルムアミド)及び溶媒を洗浄した。得られたワイヤーについて電界放出形走査電子顕微鏡(FE-SEM)を用いてワイヤーの形状を測定し。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図1に示す。 Example 1 Production of Silver Nanowire In 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. In 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. After adding 0.738 g (26.6 μmol) of a 1% by mass propylene glycol solution of tetrabutylammonium chloride (ACROS) to the reaction vessel, 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. 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.
合成例1で合成したポリ(N-ビニルホルムアミド)0.68g(9.6mmol)の代わりにポリ(N-ビニルアセトアミド)(以下PNVAと略する昭和電工(株)製)GP191-405(Mw:130000、0.817g、9.6mmol)を用い、130℃での反応時間を1時間から20分間に変更した以外は実施例1同様の条件により銀ナノワイヤーを得て、ワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図2に示す。 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) 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.
PNVAとしてGP191-405(Mw:260000)を用いた以外は実施例2と同様の条件により銀ナノワイヤーを得て、ワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図3に示す。 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.
PNVAとしてGE191-205(Mw:180000)を用いた以外は実施例2と同様の条件により銀ナノワイヤーを得て、ワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図4に示す。 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.
合成例1で合成したポリ(N-ビニルホルムアミド)0.68g(9.6mmol)の代わりにN-ビニルアセトアミドとアクリロニトリルの9対1共重合体(以下NVA/ANと略する昭和電工(株)製、Mw:150000)0.82g(9.6mmol)を用いた以外は実施例1同様の条件により銀ナノワイヤーを得て、ワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図5に示す。 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) 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.
合成例1で合成したポリ(N-ビニルホルムアミド)0.68g(9.6mmol)の代わりにN-ビニルアセトアミドとメタクリル酸メチルの9対1共重合体(以下NVA/MMAと略する昭和電工(株)製、Mw:150000)0.82g(9.6mmol)を用いた以外は実施例1同様の条件により銀ナノワイヤーを得て、ワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図6に示す。 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.
東京理化機械(株)製のパーソナル有機合成装置PPS-CTRL1用反応容器に、プロピレングリコール20g、PNVA GP191-405(Mw:130000)0.54g(6.4mmol)を仕込み、60℃で1時間撹拌することで完全に溶解させた。バイアル瓶に硝酸銀(和光純薬工業(株)製)0.075g、プロピレングリコール1gを入れ室温で撹拌することで完全に溶解させた。塩化テトラブチルアンモニウム(ACROS社製)の1質量%プロピレングリコール溶液0.738g(26.6μmol)を反応容器に添加した後、反応容器上部に滴下漏斗を設置して先に調製した硝酸銀溶液を投入した。枝管より窒素ガスを300mL/minの流量で流して系を窒素ガス置換しつつ、内温が130℃となるまで昇温した。内温130℃にて1分間かけて滴下漏斗の内容物を滴下し、さらに130℃で1時間反応を継続した。反応混合物をエタノールで5倍に希釈し、遠心分離機を用いて6000rpmの回転数で5分間処理することで銀ナノワイヤーを沈降させた。エタノール50gを添加し6000rpmで5分間処理する操作をさらに2回行い系中に残存するPNVA及び溶媒を洗浄した。得られたワイヤーについて電界放出形走査電子顕微鏡(FE-SEM)を用いてワイヤーの形状を測定した。得られた銀ナノワイヤーの形状を表1に、電界放出形走査電子顕微鏡(FE-SEM)画像を図7に示す。 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. After adding 0.738 g (26.6 μmol) of a 1% by mass propylene glycol solution of tetrabutylammonium chloride (ACROS) to the reaction vessel, 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. 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.
1L四つ口フラスコ(メカニカルスターラー、滴下漏斗、還流管、温度計)にプロピレングリコール200g、PNVA GP191-405(Mw:130000、8.17g、96mmol)を仕込み、60℃で1時間撹拌することで完全に溶解させた。ビーカーに硝酸銀(和光純薬工業(株)製)3g、プロピレングリコール40gを入れ室温で撹拌することで完全に溶解させた。塩化テトラブチルアンモニウム(ACROS社製)の1質量%プロピレングリコール溶液7.38g(0.27mmol)をフラスコに添加した後、滴下漏斗へ先に作製した硝酸銀溶液を投入した。滴下漏斗上部より窒素ガスを300mL/minの流量で20分間流して系を窒素ガス置換した。枝管の窒素ガスを止め、内温が130℃となるまで昇温した。内温130℃にて30分間かけて滴下漏斗の内容物を滴下し、さらに130℃で60分反応を継続した。 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. After adding 7.38 g (0.27 mmol) of a 1% by mass propylene glycol solution of tetrabutylammonium chloride (manufactured by ACROS) to the flask, the previously prepared silver nitrate solution was charged into the dropping funnel. Nitrogen gas was supplied from the upper part of the dropping funnel at a flow rate of 300 mL / min for 20 minutes to replace the system with nitrogen gas. The nitrogen gas in the branch pipe was stopped and the temperature was raised until the internal temperature reached 130 ° C. The contents of the dropping funnel were added dropwise at an internal temperature of 130 ° C. over 30 minutes, and the reaction was further continued at 130 ° C. for 60 minutes.
PNVAとしてGE191-104(Mw:300000)を用いた以外は実施例2と同様の条件により銀ナノワイヤーの製造工程を実施した。生成物の形状を表1に示す。 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.
PNVAとしてGE191-405P(Mw:80000)を用いた以外は実施例2と同条件にて銀ナノワイヤーの製造工程を実施した。生成物の形状を表1に示す。 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.
1L四つ口フラスコ(メカニカルスターラー、滴下漏斗、還流管、温度計)にプロピレングリコール200g、ポリビニルピロリドン K-90(以下PVP K-90と省略する和光純薬工業(株)製)10.7g(96mmol)を仕込み、60℃で1時間撹拌することで完全に溶解させた。ビーカーに硝酸銀(和光純薬工業(株)製)3g、プロピレングリコール80gを入れ室温で撹拌することで完全に溶解させた。塩化テトラブチルアンモニウム(ACROS社製)の1質量%プロピレングリコール溶液7.38g(0.27mmol)をフラスコに添加した後、滴下漏斗へ先に作製した硝酸銀溶液を投入した。滴下漏斗上部より窒素ガスを300mL/minの流量で20分間流して系を窒素ガス置換した。枝管の窒素ガスを止め、内温が160℃となるまで昇温した。内温160℃にて30分間かけて滴下漏斗の内容物を滴下し、さらに160℃で60分反応を継続した。 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. After adding 7.38 g (0.27 mmol) of a 1% by mass propylene glycol solution of tetrabutylammonium chloride (manufactured by ACROS) to the flask, the previously prepared silver nitrate solution was charged into the dropping funnel. Nitrogen gas was supplied from the upper part of the dropping funnel at a flow rate of 300 mL / min for 20 minutes to replace the system with nitrogen gas. The nitrogen gas in the branch pipe was stopped and the temperature was raised until the internal temperature reached 160 ° C. The contents of the dropping funnel were added dropwise at an internal temperature of 160 ° C. over 30 minutes, and the reaction was further continued at 160 ° C. for 60 minutes.
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.
Claims (10)
- R-CONHR’(Rは水素原子または炭素原子数が1~3のアルキル基、R’は炭素-炭素二重結合を有する炭素原子数が2または3のアルケニル基)で表される第二級アミド化合物をモノマー単位に含む重量平均分子量が100000~280000の重合体および還元剤の存在下で、銀化合物を加熱する工程を含む銀ナノワイヤーの製造方法。 A secondary group represented by R—CONHR ′ (wherein R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ′ is an alkenyl group having 2 or 3 carbon atoms having a carbon-carbon double bond) A method for producing silver nanowires, comprising a step of heating a silver compound in the presence of a polymer containing an amide compound in a monomer unit and having a weight average molecular weight of 100,000 to 280000 and a reducing agent.
- 前記重合体が、ポリ(N-ビニルホルムアミド)、ポリ(N-ビニルアセトアミド)またはポリ(N-ビニルプロピオンアミド)から選ばれる1種以上の重合体である、請求項1に記載の銀ナノワイヤーの製造方法。 The silver nanowire according to claim 1, wherein the polymer is at least one polymer selected from poly (N-vinylformamide), poly (N-vinylacetamide), or poly (N-vinylpropionamide). Manufacturing method.
- 前記銀化合物が、硝酸銀、ヘキサフルオロホスフェート銀、硼弗化銀、過塩素酸銀、塩素酸銀、塩化銀、臭化銀、フッ化銀、炭酸銀、硫酸銀、酢酸銀、トリフルオロ酢酸銀のいずれかである請求項1または2に記載の銀ナノワイヤーの製造方法。 The silver compound is silver nitrate, hexafluorophosphate silver, silver borofluoride, silver perchlorate, silver chlorate, silver chloride, silver bromide, silver fluoride, silver carbonate, silver sulfate, silver acetate, silver trifluoroacetate The method for producing silver nanowires according to claim 1 or 2, wherein the silver nanowires are any one of the above.
- ポリオールを前記還元剤および/または溶媒として含む、請求項1~3のいずれか一項に記載の銀ナノワイヤーの製造方法。 The method for producing silver nanowires according to any one of claims 1 to 3, comprising a polyol as the reducing agent and / or solvent.
- 前記ポリオールが、炭素原子数2~6であり、2~6価のアルコール化合物である請求項4に記載の銀ナノワイヤーの製造方法。 The method for producing silver nanowires according to claim 4, wherein the polyol is a divalent to hexavalent alcohol compound having 2 to 6 carbon atoms.
- 前記銀化合物100質量部に対して前記ポリオールを10000~100000質量部用いる、請求項4または5に記載の銀ナノワイヤーの製造方法。 The method for producing silver nanowires according to claim 4 or 5, wherein 10,000 to 100,000 parts by mass of the polyol is used with respect to 100 parts by mass of the silver compound.
- 4級アンモニウム塩をさらに加える、請求項1~6のいずれか一項に記載の銀ナノワイヤーの製造方法。 The method for producing a silver nanowire according to any one of claims 1 to 6, wherein a quaternary ammonium salt is further added.
- 請求項1~7のいずれか一項に記載の銀ナノワイヤーの製造方法で得られた銀ナノワイヤーの表面に付着した前記重合体を除去する工程をさらに含む銀ナノワイヤーの製造方法。 A method for producing silver nanowires, further comprising a step of removing the polymer attached to the surface of the silver nanowires obtained by the method for producing silver nanowires according to any one of claims 1 to 7.
- 請求項1~8のいずれか一項に記載の銀ナノワイヤーの製造方法で得られた銀ナノワイヤー。 A silver nanowire obtained by the method for producing a silver nanowire according to any one of claims 1 to 8.
- 請求項9に記載の銀ナノワイヤーを含有するインク。
An ink containing the silver nanowire according to claim 9.
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