WO2019082997A1 - Solution d'éther de cellulose soluble dans l'eau, modificateur de viscosité et procédé de production d'encre à nanofils d'argent - Google Patents

Solution d'éther de cellulose soluble dans l'eau, modificateur de viscosité et procédé de production d'encre à nanofils d'argent

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Publication number
WO2019082997A1
WO2019082997A1 PCT/JP2018/039787 JP2018039787W WO2019082997A1 WO 2019082997 A1 WO2019082997 A1 WO 2019082997A1 JP 2018039787 W JP2018039787 W JP 2018039787W WO 2019082997 A1 WO2019082997 A1 WO 2019082997A1
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Prior art keywords
water
cellulose ether
soluble cellulose
solution
filtration
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PCT/JP2018/039787
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English (en)
Japanese (ja)
Inventor
宏敏 齋藤
王高 佐藤
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Ｄｏｗａエレクトロニクス株式会社
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Priority to CN201880052763.7A priority Critical patent/CN110997786A/zh
Publication of WO2019082997A1 publication Critical patent/WO2019082997A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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

Definitions

  • the present invention relates to a water-soluble cellulose ether solution having a small content of coarse gel particles, which is useful as a viscosity modifier of a conductive paint, and a viscosity modifier using the same.
  • the present invention also relates to a method of producing a silver nanowires ink using the viscosity modifier.
  • a fine metal wire having a thickness of about 200 nm or less is referred to as “nanowire (s).”
  • the processing solution is called “conductive paint.”
  • a conductive paint containing silver nanowires as a conductive filler, or a silver nanowire dispersion in which the dispersibility and silver concentration of silver nanowires are adjusted to produce the conductive paint The operation of obtaining a silver nanowire ink having a predetermined property by adding a binder component, a viscosity modifier, and the like to a solution in which silver nanowires are dispersed is referred to as “inking”.
  • Silver nanowires are considered promising as a conductive filler to form a transparent conductive film.
  • a transparent substrate such as glass, PET (polyethylene terephthalate), PC (polycarbonate), etc.
  • the liquid component is removed by evaporation or the like, and the silver nanowires become the substrate
  • a transparent conductive film can be realized because the conductive network is formed by contacting each other on top.
  • a viscosity modifier suitable for the application is added to the paint.
  • water-soluble cellulose ether can be mentioned as one of the representative substances for viscosity adjustment.
  • silver nanowire inks using HPMC hydroxypropyl methyl cellulose
  • HPMC hydroxypropyl methyl cellulose
  • the conductive paint contains a conductive filler such as metal particles or metal nanowires.
  • the conductive filler is ideally uniformly distributed in the paint.
  • part of the conductive filler An event occurs in which the particles aggregate to form an aggregate (hereinafter referred to as "conductive filler aggregate").
  • conductive filler aggregate coarse ones cause a short circuit in the circuit of the transparent conductive coating film, and cause deterioration of the appearance as white spot-like foreign matter.
  • the filler when the filler is a nanowire, it is easy to form a bundle-like aggregate, and the above-mentioned problems due to coarse foreign substances are likely to be manifested. In order to avoid such a foreign matter problem, it is desirable to construct a conductive paint (ink) in which a coarse conductive filler aggregate is not easily formed.
  • the present invention provides a solution using a water-soluble cellulose ether which is useful as a viscosity regulator such as a conductive paint, which is unlikely to cause formation of a coarse conductive filler aggregate at the time of preparation or coating of the conductive paint. With the goal.
  • a water-soluble solvent contains water-soluble cellulose ether at a content of 0.05% by mass or more, and the amount of particles with a particle diameter of 10 ⁇ m or more measured by a liquid shielding particle counter is 20 / Water-soluble cellulose ether solution which is less than mL.
  • a method for producing a silver nanowires ink comprising a step of mixing a viscosity modifier with a silver nanowire dispersion using an aqueous solvent, wherein the viscosity modifier as described in any one of the above [1] to [5]
  • a method for producing a silver nanowires ink wherein a water-soluble cellulose ether solution is used to adjust the water-soluble cellulose ether content in the ink in the range of 0.01 to 1.0 mass.
  • the aqueous solvent solution of the water-soluble cellulose ether according to the present invention has a very small amount of coarse gel-like particles.
  • this water-soluble cellulose ether solution is used for preparation of a conductive paint, it is possible to remarkably suppress the formation of a coarse "conductive filler aggregate" starting from the gel-like particles while exhibiting an appropriate thickening action. it can. Therefore, the water-soluble cellulose ether solution according to the present invention is extremely useful for construction of a transparent conductive circuit free from shorts between adjacent wires and excellent in surface appearance.
  • the water-soluble cellulose ether is one that is rendered water-soluble by substituting many of the hydrogen atoms of OH groups possessed by cellulose with a substituent. For example, substitution of a hydrogen atom of an OH group with a methyl group (-CH 3 ) forms a methoxy group (-OCH 3 ), and substitution with a hydroxypropyl group (-CH 2 CHOHCH 3 ) results in a hydroxypropoxy group (-OCH 2 CHOHCH 3 ) is formed and substituted with a hydroxyethyl group (-CH 2 CH 2 OH) to form a hydroxyethoxy group (-OCH 2 CH 2 OH).
  • MC methylcellulose
  • HEC hydroxyethylcellulose
  • HPMC, HEMC, MC, HEC, etc. are usually supplied to the market as industrial materials in the form of dried powder. When applied to silver nanowire ink applications, it is more preferable to use, for example, HPMC or HEMC having a weight average molecular weight of 200,000 to 1,500,000. Those having a weight average molecular weight of 300,000 to 1,400,000 are more preferable.
  • the water-soluble cellulose ether tends to form gel-like particles when the powder product is dissolved in an aqueous solvent. Only some of the particles constituting the powder are wetted with the aqueous solvent in the surface layer portion, and remain in the form of gel particles while leaving undissolved portions in the particles.
  • fine particles of hot water mixed with powder for example, water of 85 to 100 ° C., preferably 90 to 99 ° C.
  • the slurry can be uniformly dissolved by a method of cooling the slurry.
  • the water-soluble cellulose ether solution according to the present invention with very few coarse gel particles utilizes the technique of dissolving the powder in the aqueous solvent as uniformly as possible and filtering through a filter, as exemplified in the following examples. Can be obtained.
  • aqueous solvent refers to a solvent comprising water or a mixed solution of water and a water-soluble substance, wherein the proportion of water is at least 30% by mass.
  • Water-soluble cellulose ether represented by HPMC and HEMC dissolves well in water, and in the case of a mixed solvent of water and alcohol, it can usually be industrially implemented if the mixing ratio of water is in the range of 30% by mass or more It exhibits solubility. Therefore, a solvent in which the mixing ratio of water is 30 to 100% by mass here is applied as the "aqueous solvent”. You may manage so that the mixing
  • a water-soluble cellulose ether solution using an aqueous solvent can be used as a viscosity modifier for producing a conductive paint (ink) using an aqueous solvent.
  • the solvent of the water-soluble cellulose ether solution to be added at the time of ink formation also has the same water solubility as the above. It is preferable to use a mixed solution using a substance.
  • the wettability to a substrate such as PET can be improved by making the solvent of the conductive paint "a mixed solvent of water and alcohol".
  • the “mixed solvent of water and alcohol” using the same alcohol as the conductive paint may be applied to the solvent of the water-soluble cellulose ether solution used for the preparation of the conductive paint.
  • a mixed solvent of water and alcohol as the alcohol, one having a polarity of solubility parameter (SP value) of 10 or more is preferable.
  • SP value solubility parameter
  • low boiling point alcohols such as methanol, ethanol and 2-propanol (isopropyl alcohol) can be suitably used.
  • SP value is water: 23.4, methanol: 14.5, ethanol: 12.7, and 2-propanol is 11.5.
  • an ink whose alcohol content in the ink is adjusted in the range of 1.0 to 25.0% by mass.
  • the SP values described here are the values defined by the regular solution theory introduced by Hildebrand.
  • the present invention is directed to a water-soluble cellulose ether solution having a water-soluble cellulose ether content of 0.05% by mass or more in an aqueous solvent.
  • a water-soluble cellulose ether content of 0.05% by mass or more in an aqueous solvent.
  • the content of the water-soluble cellulose ether is too low, it is difficult to obtain a sufficient viscosity control effect at the time of ink formation. It is more preferable to set it as 0.1 mass% or more, and it is more preferable to set it as 0.5 mass% or more.
  • the water-soluble cellulose ether content is excessive, the amount of gel-like particles tends to be large.
  • the number of gel-like particles having a particle diameter of 10 ⁇ m or more can be easily suppressed as described later.
  • the water-soluble cellulose ether content is more preferably 5.0% by mass or less, and still more preferably 2.5% by mass or less. You may manage to 2.0 mass% or less or 1.5 mass% or less.
  • the water-soluble cellulose ether content is the total of the water-soluble cellulose ether dissolved in the solvent and the water-soluble cellulose ether present as gel-like particles. It can be grasped by measuring the amount of water-soluble cellulose ether.
  • the amount of particles having a particle diameter of 10 ⁇ m or more measured by a liquid shielding particle counter is 20 particles / mL or less Is desirable, and 10 or less is more desirable.
  • the light shielding type liquid particle counter it is possible to detect the presence of translucent gel-like particles, and to obtain the particle size distribution thereof.
  • the water-soluble cellulose ether solution according to the present invention can be prepared using a technique of dissolving the powder in the aqueous solvent as uniformly as possible and then filtering it with a filter.
  • a technique of dissolving the powder in the aqueous solvent as uniformly as possible and then filtering it with a filter.
  • Such gel-like particles tend to slip through the filter by deformation. It is possible to obtain high capturing power by applying a filter with a small opening. However, in this case, once some particles are trapped, clogging occurs and premature filtration becomes impossible.
  • filters for example, SCP type shown in the below-mentioned example etc.
  • a water-soluble cellulose ether solution viscosity modifier
  • a conductive paint in the generation inhibiting performance of the conductive filler aggregate
  • I can not get it.
  • the particle size distribution of gel-like particles in the solution after filtration may be variously changed depending on conditions such as pressure, viscosity of the solution to be subjected to filtration, and amount of gel-like particles present in the solution to be filtered. It can be mentioned.
  • the inventors reduced the number of gel-like particles having a particle diameter of 10 ⁇ m or more in order to suppress the formation of a coarse “conductive filler assembly” that adversely affects formation of a transparent conductive circuit.
  • the number of gel particles having a particle diameter of 10 ⁇ m or more is controlled in a water-soluble cellulose ether solution (viscosity modifier). Therefore, an aqueous solvent solution of a water-soluble cellulose ether adjusted to the present form of gel-like particles as specified in the present invention has not been realized until now.
  • the inventors satisfy all the following conditions (i) to (iii) as a water-soluble cellulose ether solution (hereinafter sometimes referred to as "solution before filtration") to be subjected to filtration.
  • solution before filtration a water-soluble cellulose ether solution
  • the amount of particles having a particle diameter of 10 ⁇ m or more measured by a light shielding type liquid particle counter is 20 using a filter selected from among commercially available products. It has been found that it is possible to industrially relatively efficiently produce the above-mentioned predetermined water-soluble cellulose ether solution which is less than 10 / mL.
  • the solvent is water or a solvent comprising a mixed solution of water and a water-soluble substance, and the blending ratio of water is 30% by mass or more.
  • the content of the water-soluble cellulose ether (including the water-soluble cellulose ether present as gel-like particles) in the solvent is more than 0.05% by mass.
  • the amount of particles having a particle diameter of 10 ⁇ m or more measured by a light shielding type liquid particle counter should be 3000 particles / mL or less.
  • pre-filtration is performed with a metal mesh filter having a large opening to obtain gel-like particles having a large particle diameter. It is necessary to apply techniques such as removing parts.
  • the viscosity of the solution before filtration is adjusted in the range of 0.005 to 100 Pa ⁇ s at 25 ° C. and a shear rate of 3.1 (1 / s). If the viscosity of the solution before filtration is too low, it will be difficult to produce a silver nanowires ink having a viscosity suitable for coating. If the viscosity of the solution before filtration is too high, filtration for trapping gelled particles becomes difficult.
  • Example of conductive paint A silver nanowire ink is illustrated below as a preferable example of the conductive paint prepared using the above-mentioned water-soluble cellulose ether solution.
  • the silver nanowire used in the silver nanowire ink is preferably as thin as possible in a long shape.
  • the average diameter is 50 nm or less and the average length is 10 ⁇ m or more. It is more preferable to use one having an average diameter of 30 nm or less and an average length of 10 ⁇ m or more.
  • the average aspect ratio is preferably 200 or more, and more preferably 450 or more.
  • the average length, the average diameter, the average ask and the ratio of the silver nanowires follow the following definitions.
  • Average length L M The trace length from one end of one silver nanowire to the other end of a silver nanowire is defined as the length of the wire on an image observed by a field emission scanning electron microscope (FE-SEM). A value obtained by averaging the lengths of the individual silver nanowires present on the microscopic image is defined as an average length L M. In order to calculate the average length, the total number of wires to be measured is set to 100 or more.
  • the operation is performed on a plurality of randomly selected fields of view, the diameters of a total of 100 or more different silver nanowires are determined, the average value of the diameters of the individual silver nanowires is calculated, and the value is defined as the average diameter D M.
  • the average aspect ratio AM is calculated by substituting the above average diameter D M and the average length L M into the following equation (1). However, it is assumed that D M and L M to be substituted into the equation (1) are both values expressed in nm.
  • a M L M / D M (1)
  • Such thin and long silver nanowires can be obtained by a known method (alcohol solvent reduction method) in which silver is deposited on a wire by using the reducing power of alcohol which is a solvent in an alcohol solvent in the presence of an organic protective agent.
  • an organic protective agent PVP or a copolymer of vinyl pyrrolidone and another monomer can be used.
  • the organic protective agent used at the time of synthesis adheres to the surface of the silver nanowire, and the organic protective agent is responsible for the in-liquid dispersibility.
  • the dispersibility in an aqueous solvent to which alcohol is added can be improved more than PVP.
  • the copolymer has a structural unit of a hydrophilic monomer.
  • the hydrophilic monomer means a monomer having a property of dissolving 1 g or more in 1000 g of water at 25 ° C.
  • diallyldimethylammonium salt monomers acrylate or methacrylate monomers
  • maleimide monomers include ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate.
  • the maleimide-based monomer 4-hydroxybutyl acrylate, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-tert-butyl maleimide may be mentioned.
  • the silver nanowire ink targeted here contains the water-soluble cellulose ether supplied from the water-soluble cellulose ether solution according to the present invention in the liquid medium constituting the ink, and is adjusted to a desired viscosity.
  • Water-soluble cellulose ethers such as HEMC (hydroxyethyl methylcellulose) and HPMC (hydroxypropyl methyl cellulose) do not have a ligand that coordinates to silver, such as a carboxyl group.
  • HEMC hydroxyethyl methylcellulose
  • HPMC hydroxypropyl methyl cellulose
  • the surface activity of a fluorine-based, nonionic-based, cationic-based, etc. is compared with the case of combining the silver nanowires with “h, vi” and “viscosity modifiers based on HEMC and HPMC”.
  • the dispersibility of silver nanowires in the applied conductive coating can be improved without resorting to the addition of agents.
  • the liquid medium (portion other than the solid substance) constituting the silver nanowire ink includes the component of the aqueous solvent and the water-soluble cellulose ether.
  • the organic substance also becomes a component of the liquid medium.
  • the proportion of the liquid medium in the silver nanowires ink is preferably 95% by mass or more, and may be controlled to 98% by mass or more.
  • the water-soluble cellulose ether content (content ratio of water-soluble cellulose ether to the total mass of the ink including silver nanowires) in the ink is, for example, in the range of 0.01 to 1.0% by mass according to the desired viscosity. You can adjust it.
  • the weight average molecular weight of the water-soluble cellulose ether to be used can be, for example, in the range of 200,000 to 1,500,000. It may be managed in the range of 300,000 to 1,400,000. The weight average molecular weight can be confirmed, for example, by the GPC-MALS method.
  • Comparative Example 1 (Dissolution operation) A powder product of HEMC (hydroxyethyl methyl cellulose) having a weight average molecular weight of 910,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. The solvent was placed in a reaction vessel with a capacity of 20 L provided with a baffle and was kept in a state of being vigorously stirred at 500 rpm by turbine blades while maintaining at 95 ° C. An amount of the above-mentioned water-soluble cellulose ether powder to be 1.50% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring.
  • HEMC hydroxyethyl methyl cellulose
  • the "water-soluble cellulose ether solution” in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained.
  • the solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • the mass ratio of the water-soluble cellulose ether (including the portion present as gel-like particles) in the solution in the total mass of the solution is referred to as the “in-liquid content” of the water-soluble cellulose ether.
  • the content of the water-soluble cellulose ether in the solution obtained in the present example is 1.50% by mass.
  • solution which has not yet been subjected to the filtration operation at the stage where this dissolution operation has been completed is referred to as "solution before filtration".
  • Viscosity of solution before filtration The viscosity of the aqueous solution of cellulose ether (solution before filtration) was determined with a rheometer (viscoelasticity measuring device) (HAAKE RheoStress 600 manufactured by Thermo, cone diameter 35 mm, cone angle 2 ° cone angle). As a result, the viscosity at 25 ° C. and shear rate 3.1 (1 / s) was 9.85 (Pa ⁇ s).
  • the solution A was placed in a reaction vessel, and the temperature was raised while stirring from normal temperature to 90 ° C., and then the whole solution B was added to the solution A over 1 minute. After the addition of solution B was completed, stirring was further maintained and maintained at 90 ° C. for 24 hours. Thereafter, the reaction solution was cooled to room temperature.
  • the synthesis method alcohol solvent reduction method
  • the reaction liquid (liquid containing the synthesized silver nanowire) cooled to normal temperature was separated into 1 L, transferred to a PFA bottle with a capacity of 35 L, and then 20 kg of acetone was added and stirred for 15 minutes. Then left to stand for 24 hours. After standing, a concentrate and a supernatant were observed, so the supernatant portion was removed to obtain a concentrate. An appropriate amount of 1% by mass PVP aqueous solution was added to the obtained concentrate, and the mixture was stirred for 3 hours to confirm that the silver nanowires were redispersed. After stirring, 2 kg of acetone was added and stirred for 10 minutes and then allowed to stand.
  • the silver nanowire dispersion obtained by the above washing was diluted with pure water to a silver nanowire concentration of 0.07% by mass to make the solution volume 52 L, and subjected to cross flow filtration using a tube of a porous ceramic filter.
  • Cross-flow filtration was performed in a circulating system in which the liquid in the tank was returned to the tank via a pump and a filter.
  • the material of the filter is SiC (silicon carbide), and the size of the tube is 12 mm in outer diameter, 9 mm in inner diameter, and 500 mm in length.
  • the average pore diameter (median diameter) by mercury porosimetry using a mercury porosimeter manufactured by Micromeritics was 5.9 ⁇ m.
  • the flow rate was set to 150 L / min, and circulation was performed for 12 hours while supplying pure water equivalent to the amount of liquid discharged as filtrate to the tank. After that, cross flow filtration was continued for 12 hours in a state in which the supply of pure water was stopped, and concentration of the silver nanowires dispersion was performed using the fact that the amount of liquid decreased due to discharge of the filtrate.
  • the silver nanowire dispersion obtained by the above cross flow filtration (the medium is water), the above water soluble cellulose ether solution, the above water soluble acrylic-urethane copolymer resin emulsion, and isopropyl alcohol
  • the container was stirred and mixed in a manner of shaking the container up and down 100 times.
  • 0.30 mass% of water-soluble cellulose ether component, 0.15 mass% of water-soluble acrylic-urethane copolymer resin component, silver with respect to the total weight of all mixtures, 80/20 of water / isopropyl alcohol
  • the mixing amount of each substance was adjusted so as to be 0.15 mass% of metallic silver of the nanowires.
  • a silver nanowire ink was obtained.
  • a conductive coating was produced as follows.
  • the surface of a PET film substrate (Lumirror U48, manufactured by Toray Industries, Inc., with a thickness of 100 ⁇ m and a size of 150 mm ⁇ 200 mm, using a silver coater) using a die coater (Dymon Co., New platform die S-100)
  • a coating of 100 mm ⁇ 100 mm in area was formed.
  • the coating conditions were: wet thickness: 11 ⁇ m, gap: 21 ⁇ m, speed: 10 mm / s, timer: 2.2 s, coating length: 100 mm. After coating, it was dried at 120 ° C. for 1 minute to obtain a transparent conductive coating.
  • the size of the wire aggregate is large or the number is large, they are accumulated more often to form a coarse wire aggregate.
  • a coarse wire assembly causes a short circuit in the circuit of the transparent conductive coating film and causes deterioration of the appearance as a white spot-like foreign matter. Then, the performance regarding the conductive filler aggregation property of silver nanowire ink was evaluated by how large a coarse wire aggregate is formed in the said conductive coating film formed by die-coater coating.
  • the above conductive coating is observed by a scanning electron microscope (SEM), and both a major axis and a minor axis are 10 ⁇ m or more in a region of 1 mm 2 or more in total of randomly selected fields of view.
  • SEM scanning electron microscope
  • longest axis the longest line segment among line segments connecting any two points on the outline of the wire assembly on the image.
  • minor axis is defined as the length of the longest part of the wire assembly measured in the direction perpendicular to the long axis on the image.
  • the ink evaluated as ⁇ by this observation method is a conductive filler It can be determined that the aggregate generation suppression performance is excellent. Therefore, as evaluation of silver nanowire ink, ⁇ evaluation was accepted, and ⁇ evaluation was rejected.
  • Tables 1A and 1B show the experimental results together with each example described later.
  • the ink evaluation was a failure ( ⁇ evaluation).
  • the SEM photograph of the part in which the coarse wire aggregate was observed is illustrated in FIG. 1 about the electrically conductive coating film produced by the comparative example 1.
  • FIG. What appears white is a wire aggregate, and the portion formed by bringing together the above wire aggregates with a portion appearing dark as a core is a coarse wire aggregate.
  • the portion of the core is considered to be mainly attributable to the gel-like particles of the thickening substance. Two coarse wire aggregates can be seen in this image.
  • Comparative Example 2 The following filtration operation was performed on the water-soluble cellulose ether solution (solution before filtration) produced in Comparative Example 1.
  • the solution before filtration is put into a pressure filtration device, and a pressure filtration force of 0.2 MPa is applied with nitrogen gas using a 25 ⁇ m thread-wound filter (Roki Techno Co .; DIAII) with a filter filtration accuracy (aperture), and pressure filtration is performed. went.
  • the water-soluble cellulose ether solution recovered after filtration is referred to as "solution after filtration" (same in each of the following examples).
  • a conductive coating was prepared under the same conditions as Comparative Example 1 except that the solution after filtration of the water-soluble cellulose ether obtained above was used as a thickener for silver nanowire ink, and the above-mentioned coarse wire was observed by SEM observation. The presence of the aggregates was examined to evaluate the silver nanowire ink.
  • the evaluation method is also the same as in Comparative Example 1. As a result, in the above-mentioned filtration, the removal of gel-like particles having a particle diameter of 10 ⁇ m or more was insufficient, and the ink evaluation was rejection ( ⁇ evaluation).
  • Comparative Example 3 In the filtration operation, an experiment was conducted under the same conditions as in Comparative Example 2 except that pressure filtration was carried out at a pressure of 0.2 MPa using a 10 ⁇ m filter wound filter (Roki Techno Co .; DIAII) with a filter filtration accuracy (aperture). Did.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.33% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 134 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink, and a conductive coating film was prepared, and the presence of coarse wire aggregates was examined by SEM observation. As a result, the ink evaluation failed ( X).
  • Comparative Example 4 In the filtration operation, an experiment was conducted under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.05 MPa using a 10- ⁇ m filter-wound filter (Roki Techno; DIAII) with a filter filtration accuracy (aperture). Did.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.40% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 38 particles / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink, and a conductive coating film was prepared, and the presence of coarse wire aggregates was examined by SEM observation. As a result, the ink evaluation failed ( X).
  • Comparative Example 5 In the filtration operation, an experiment was conducted under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a 5 ⁇ m filter wound filter (Roki Techno Co .; DIAII) with a filter filtration accuracy (aperture). Did.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.34% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 140 particles / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink, and a conductive coating film was prepared, and the presence of coarse wire aggregates was examined by SEM observation. As a result, the ink evaluation failed ( X).
  • Example 1 In the filtration operation, the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co .; SCP type) with a filter filtration accuracy (aperture) of 3 ⁇ m.
  • the experiment was conducted at The obtained solution after filtration had a water-soluble cellulose ether content of 1.19% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 6 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 2 In the filtration operation, the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SCP type) with a filter filtration accuracy (aperture) of 1 ⁇ m.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.07% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 4 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 3 In the filtration operation, the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SCP type) with a filter filtration accuracy (aperture) of 5 ⁇ m. The experiment was conducted at As for the solution after filtration obtained, the content of the water-soluble cellulose ether in the solution was 0.80% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 3 / mL. The solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 4 The same conditions as in Comparative Example 2 except that, in the filtration operation, pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 15 ⁇ m.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.36% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 3 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 5 The same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) having a filter filtration accuracy (aperture) of 10 ⁇ m in the filtration operation.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.31% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 2 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 6 The same conditions as in Comparative Example 2 except that in the filtration operation, pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 5 ⁇ m.
  • the experiment was conducted at The obtained solution after filtration had a water-soluble cellulose ether content of 1.18% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 3 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 7 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Roki Techno Co., Ltd .; MPX type) with a filter filtration accuracy (aperture) of 15 ⁇ m. I did an experiment.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.36% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 2 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 8 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Roki Techno Co., Ltd .; MPX type) with a filter filtration accuracy (aperture) of 10 ⁇ m. I did an experiment.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.31% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 5 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 9 In the filtration operation, it is the same as Comparative Example 2 except that pressure filtration is performed at a pressure of 0.2 MPa using a pleated filter (Roki Techno Co., Ltd .; MPX type) having a filter filtration accuracy (aperture) of 4.5 ⁇ m.
  • the experiment was conducted under the conditions.
  • the resultant solution after filtration had a water-soluble cellulose ether content of 0.66% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 6 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 10 The same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Roki Techno Co., Ltd .; L1P type) having a filter filtration accuracy (aperture) of 10 ⁇ m in the filtration operation.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.33% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 4 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 11 The same conditions as in Comparative Example 2 except that, in the filtration operation, pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (manufactured by Roki Techno; L1P type) with a filter filtration accuracy (aperture) of 5 ⁇ m.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.31% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 4 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 12 The same conditions as in Comparative Example 2 except that in the filtration operation, pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (manufactured by Roki Techno; L1P type) with a filter filtration accuracy (aperture) of 3 ⁇ m.
  • the experiment was conducted at The resultant solution after filtration had a water-soluble cellulose ether content of 1.44% by mass, and the presence of particles having a particle diameter of 10 ⁇ m or more was not observed.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 13 In the filtration operation, the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (Asahi Kasei Co., Ltd .; KNA type) having a filter filtration accuracy (aperture) of 2 ⁇ m. The experiment was conducted at The obtained solution after filtration had a water-soluble cellulose ether content of 0.69% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 8 / mL. The solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 14 In the filtration operation, the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a depth pleated filter (manufactured by Asahi Kasei Corporation; KNA type) having a filter filtration accuracy (aperture) of 1 ⁇ m.
  • the experiment was conducted at As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 0.53% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 5 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 15 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Asahi Kasei Corporation; KNP type) with a filter filtration accuracy (aperture) of 5 ⁇ m. I did an experiment.
  • the solution after filtration the content of the water-soluble cellulose ether in the solution was 1.35% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 2 / mL.
  • the solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 16 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Asahi Kasei Co., Ltd .; KNP type) with a filter filtration accuracy (aperture) of 3 ⁇ m. I did an experiment. The resulting solution after filtration had a water-soluble cellulose ether content of 1.35% by mass, and the presence of particles having a particle diameter of 10 ⁇ m or more was not observed. The solution after filtration of this water-soluble cellulose ether was used as a thickener for silver nanowire ink to prepare a conductive coating film, and the presence of a coarse wire aggregate was examined by SEM observation. As a result, the ink evaluation passed ( ⁇ Evaluation).
  • Example 17 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Asahi Kasei Co., Ltd .; KMZ type) with a filter filtration accuracy (aperture) of 5 ⁇ m. I did an experiment. As for the solution after filtration obtained, the content of the water-soluble cellulose ether in the solution was 1.28% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 1 / mL.
  • a pleated filter As for the solution after filtration obtained, the content of the water-soluble cellulose ether in the solution was 1.28% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 1 / mL.
  • Example 18 In the filtration operation, under the same conditions as in Comparative Example 2 except that pressure filtration was performed at a pressure of 0.2 MPa using a pleated filter (Asahi Kasei Co., Ltd .; KMZ type) with a filter filtration accuracy (aperture) of 3 ⁇ m. I did an experiment.
  • the content of the water-soluble cellulose ether in the solution was 1.26% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 2 / mL.
  • Comparative Example 6 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 350,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. An amount of the above-mentioned water-soluble cellulose ether powder to be 1.50% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of water-soluble cellulose ether in the liquid was 1.50% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 364 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 0.91 (Pa ⁇ s).
  • Example 19 The water-soluble cellulose ether solution prepared in Comparative Example 6 was used as the solution before filtration, and in the filtration operation, using a pleated filter (Roki Techno Co., Ltd .; MPX type) with a filter filtration accuracy (aperture) of 10 ⁇ m, no pressure was applied. The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 2 MPa. As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 1.33% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 6 / mL.
  • Example 20 A dissolution operation is performed in the same manner as Comparative Example 6 except that a powder product of HPMC (hydroxypropyl methyl cellulose) having a weight average molecular weight of 660,000 is used as a water soluble cellulose ether, and a water soluble cellulose ether solution (before filtration Solution) was prepared.
  • HPMC hydroxypropyl methyl cellulose
  • a water soluble cellulose ether solution before filtration Solution
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1.
  • the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 4.96 (Pa ⁇ s).
  • Comparative Example 7 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 840,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. An amount of the above-mentioned water-soluble cellulose ether powder to be 2.25% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of water-soluble cellulose ether in the solution was 2.25% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 1505 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 63.27 (Pa ⁇ s).
  • Example 21 The water-soluble cellulose ether solution prepared in Comparative Example 7 was used as the solution before filtration, and in the filtration operation, using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 0.35 MPa. As for the solution after filtration obtained, the content of the water-soluble cellulose ether in the solution was 2.03% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 9 / mL.
  • Comparative Example 8 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 840,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. An amount of the above-mentioned water-soluble cellulose ether powder to be 2.75% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of the water-soluble cellulose ether in the liquid was 2.75% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 5509 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 107.30 (Pa ⁇ s).
  • Comparative Example 9 The water-soluble cellulose ether solution prepared in Comparative Example 8 as a solution before filtration was subjected to pressure filtration at a pressure of 0.40 MPa using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m. I tried. However, because of the high viscosity of the water-soluble cellulose ether solution (solution before filtration), filtration under the above conditions was impossible. Therefore, the subsequent experiments were discontinued.
  • Comparative Example 10 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 660,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. An amount of the above-mentioned water-soluble cellulose ether powder to be 2.50% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of the water-soluble cellulose ether in the liquid was 2.50% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 2804 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 34.38 (Pa ⁇ s).
  • Example 22 The water-soluble cellulose ether solution prepared in Comparative Example 10 was used as the solution before filtration, and in the filtration operation, using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 0.35 MPa. The resultant solution after filtration had a water-soluble cellulose ether content of 2.34% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 7 / mL.
  • a depth pleated filter Rosin Techno Co., Ltd .; SHP type
  • Comparative Example 11 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 840,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. A portion of the water-soluble cellulose ether powder in an amount of 0.60% by mass was charged into this solution, and strong stirring was continued at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of water-soluble cellulose ether in the solution was 0.60% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 1029 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 2.00 (Pa ⁇ s).
  • Example 23 The water-soluble cellulose ether solution prepared in Comparative Example 11 was used as the solution before filtration, and in the filtration operation, using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 0.20 MPa. As for the solution after filtration, the content of the water-soluble cellulose ether in the solution was 0.56% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 5 / mL.
  • Comparative Example 12 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 840,000 was prepared as a water-soluble cellulose ether.
  • HPMC hydroxypropyl methylcellulose
  • IPA 2-propanol
  • An amount of the above-mentioned water-soluble cellulose ether powder to be 1.25% by mass was charged into this solution, and strong stirring was continued at 75 ° C. for 1 hour. Then, it cooled to 10 degreeC, continuing strong stirring.
  • the "water-soluble cellulose ether solution” in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained.
  • the solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of water-soluble cellulose ether in the solution was 1.25% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 745 particles / mL.
  • the viscosity of the solution before filtration was measured by the same method as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 11.08 (Pa ⁇ s).
  • Example 24 The water-soluble cellulose ether solution prepared in Comparative Example 12 was used as the solution before filtration, and in the filtration operation, using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 0.20 MPa. The resultant solution after filtration had a water-soluble cellulose ether content of 1.10% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 3 / mL.
  • Comparative Example 13 (Dissolution operation) A powder product of HPMC (hydroxypropyl methylcellulose) having a weight average molecular weight of 350,000 was prepared as a water-soluble cellulose ether. Pure water was prepared as a solvent. It was set as the state currently stirred strongly by the method similar to the comparative example 1, maintaining the said solvent at 95 degreeC. An amount of the above-mentioned water-soluble cellulose ether powder to be 4.50% by mass was charged into this solution, and strong stirring was continued as it is at 95 ° C. for 24 hours. Then, it cooled to 10 degreeC, continuing strong stirring. Thus, the "water-soluble cellulose ether solution" in which the water-soluble cellulose ether is dissolved in the aqueous solvent was obtained. The solution contains gel-like particles of a water-soluble cellulose ether which is not completely dissolved and remains as a solid.
  • HPMC hydroxypropyl methylcellulose
  • the experiment was conducted under the same conditions as in Comparative Example 1 except that the "solution before filtration" obtained by the above-described dissolution operation was used.
  • the content of water-soluble cellulose ether in the solution was 4.50% by mass, and the amount of particles having a particle diameter of 10 ⁇ m or more was 1408 particles / mL.
  • the viscosity of the solution before filtration was measured in the same manner as in Comparative Example 1. As a result, the viscosity at a shear rate of 3.1 (1 / s) at 25 ° C. was 56.75 (Pa ⁇ s).
  • Example 25 The water-soluble cellulose ether solution prepared in Comparative Example 13 was used as the solution before filtration, and in the filtration operation, using a depth pleated filter (Roki Techno Co., Ltd .; SHP type) with a filter filtration accuracy (aperture) of 10 ⁇ m The experiment was performed under the same conditions as Comparative Example 2 except that pressure filtration was performed at 0.35 MPa. The resultant solution after filtration had a water-soluble cellulose ether content of 4.19% by mass, and the amount of particles with a particle diameter of 10 ⁇ m or more was 9 / mL.
  • a silver nanowire ink using a water-soluble cellulose ether solution having a very small amount of particles with a particle diameter of 10 ⁇ m or more measured by a light shielding type liquid particle counter as a thickener are extremely useful for preventing the formation of coarse wire aggregates in the conductive coating.

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Abstract

La présente invention vise à fournir une solution d'éther de cellulose soluble dans l'eau qui n'est pas susceptible de former des agrégats de charge électroconductrice grossiers lorsqu'un matériau de revêtement électroconducteur est préparé ou revêtu. L'invention concerne par conséquent une solution d'éther de cellulose soluble dans l'eau qui contient un éther de cellulose soluble dans l'eau à une teneur de 0,05 % en masse ou plus dans un milieu aqueux, et dans lequel le nombre de particules ayant des diamètres de 10 µm ou plus, tel que mesuré à l'aide d'un compteur de particules dans un liquide de type de protection contre la lumière, est de 20 particules/ml ou moins. Des exemples de l'éther de cellulose soluble dans l'eau comprennent l'HEMC (hydroxyéthylméthyl cellulose) et l'HPMC (hydroxypropylméthyl cellulose).
PCT/JP2018/039787 2017-10-27 2018-10-25 Solution d'éther de cellulose soluble dans l'eau, modificateur de viscosité et procédé de production d'encre à nanofils d'argent WO2019082997A1 (fr)

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Citations (4)

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JP2007042581A (ja) * 2005-07-07 2007-02-15 Fujifilm Holdings Corp 固体電解質ドープの製造方法、固体電解質フィルム及びその製造方法、電極膜複合体、燃料電池
JP2011505428A (ja) * 2007-01-24 2011-02-24 ダウ グローバル テクノロジーズ インコーポレイティド アルカリセルロースまたはセルロース誘導体の製造方法
JP2012226865A (ja) * 2011-04-15 2012-11-15 Sumitomo Metal Mining Co Ltd 導電性ペースト組成物
JP2014118490A (ja) * 2012-12-17 2014-06-30 Fujimi Inc セルロース誘導体組成物、当該セルロース誘導体組成物を用いた研磨用組成物、当該研磨用組成物の製造方法、および当該研磨用組成物を用いた基板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007042581A (ja) * 2005-07-07 2007-02-15 Fujifilm Holdings Corp 固体電解質ドープの製造方法、固体電解質フィルム及びその製造方法、電極膜複合体、燃料電池
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JP2012226865A (ja) * 2011-04-15 2012-11-15 Sumitomo Metal Mining Co Ltd 導電性ペースト組成物
JP2014118490A (ja) * 2012-12-17 2014-06-30 Fujimi Inc セルロース誘導体組成物、当該セルロース誘導体組成物を用いた研磨用組成物、当該研磨用組成物の製造方法、および当該研磨用組成物を用いた基板の製造方法

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