WO2012133355A1 - Processus et dispositif de production d'une couche contenant des nanoparticules et processus et dispositif de production d'une structure électroconductrice - Google Patents

Processus et dispositif de production d'une couche contenant des nanoparticules et processus et dispositif de production d'une structure électroconductrice Download PDF

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WO2012133355A1
WO2012133355A1 PCT/JP2012/057841 JP2012057841W WO2012133355A1 WO 2012133355 A1 WO2012133355 A1 WO 2012133355A1 JP 2012057841 W JP2012057841 W JP 2012057841W WO 2012133355 A1 WO2012133355 A1 WO 2012133355A1
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coating film
nanoparticle
nanoparticles
conductive
dispersant
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PCT/JP2012/057841
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English (en)
Japanese (ja)
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朋成 小川
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富士フイルム株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

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  • the present invention relates to a method of manufacturing a nanoparticle-containing layer and a manufacturing apparatus thereof, and a method of manufacturing a conductive structure and a manufacturing apparatus thereof.
  • a technique for forming a nanoparticle-containing layer by applying a coating solution containing nanoparticles on a substrate to form a coating film and drying the coating film is used in the manufacture of various electronic materials such as conductive materials and inks. Used in fields such as fields.
  • a coating solution containing nanoparticles Used in fields such as fields.
  • efforts have been made to increase the dispersibility of the nanoparticles in the coating solution.
  • it has become essential to add a dispersant to the coating solution.
  • the nanoparticle-containing layer is formed by drying the coating solution
  • the dispersion effect by the dispersant is obtained by adsorbing the dispersant to the nanoparticles, so that the contact between the nanoparticles is inhibited. is there. Therefore, when it is desired to increase the number of contacts between nanoparticles after drying, there may be a disadvantage.
  • the nanoparticle is a conductive nanoparticle and a conductive layer is produced, a network of conductive nanoparticles is formed by increasing the number of contacts between the conductive nanoparticles, thereby obtaining suitable conductivity. be able to.
  • the contact between the conductive nanoparticles is inhibited by the dispersant, there is a problem that the conductivity is lowered.
  • an aqueous dispersion of fine metal particles adsorbed with an organic protective agent is mixed with a polymer solution in which a conductive polymer compound is dissolved in an organic solvent that is not compatible with water and has a specific gravity smaller than that of water.
  • a separation solution separated into an aqueous phase and an organic phase is formed, and a solution for dissolving the organic protective agent is added thereto to form an aggregate of metal fine particles at the liquid-liquid interface of the separation solution.
  • the polymer contained in the organic phase is formed into a film by volatilizing the solvent, the metal fine particle aggregates at the liquid-liquid interface are taken into the film, and the metal fine particle aggregates are contained in the surface layer portion of the liquid-liquid interface of the film
  • Patent Document 1 A method for producing a polymer film has been proposed (see Patent Document 1).
  • Patent Document 1 it is necessary to add a surfactant to the separation solution, or to make the film into the substrate after film formation, and the operation is complicated.
  • a container for storing the liquid is necessary, which is unsuitable for producing a large-sized film and lacks mass productivity.
  • a particle dispersion in which particles are dispersed in a first solvent such as water is applied to the substrate, In a liquid-liquid interface between the first solvent and the second solvent, disposed in a second solvent such as an organic solvent that can be phase-separated with the solvent, formed on the surface of the substrate, the first solvent A method has been proposed in which particles are accumulated at the liquid-liquid interface using the diffusion of one solvent into the second solvent (see Patent Document 2).
  • the proposed method can separate the first solvent and the particles and arrange the particles densely, in a system including the dispersant in the first solvent, the dispersant bonded to the particles is not used. This is a problem in that it cannot be separated from the particles.
  • the dispersant adsorbed on the nanoparticles is separated in the coating film. It is possible to reduce dispersibility, increase the contact point between nanoparticles, make it possible to make close contact between nanoparticles in the nanoparticle-containing layer after drying, and a method for producing a nanoparticle-containing layer that is simple and efficient in production And its manufacturing apparatus, and the nanoparticles are conductive nanoparticles, and a network of conductive nanoparticles is formed by increasing the number of contacts between the conductive nanoparticles, and the conductivity is excellent in conductivity and transparency. At present, it is required to provide a structure manufacturing method and a manufacturing apparatus therefor.
  • the present invention is a uniform coating film containing a nanoparticle and a dispersant and formed using a coating solution having good dispersibility of the nanoparticle.
  • the agent can be separated to reduce dispersibility, increase the number of contacts between the nanoparticles, and the nanoparticles can be in close contact with each other in the nanoparticle-containing layer after drying.
  • Layer manufacturing method and manufacturing apparatus thereof, and the nanoparticles are conductive nanoparticles. By increasing the number of contacts between the conductive nanoparticles, a network of conductive nanoparticles is formed. It aims at providing the manufacturing method of the electroconductive structure excellent in property, and its manufacturing apparatus.
  • the method for producing a nanoparticle-containing layer of the present invention forms a coating film by applying a nanoparticle-containing coating solution containing at least nanoparticles and a dispersant for dispersing the nanoparticles to a substrate.
  • the nanoparticles are agglomerated in the coating film by at least one of a coating film forming step, a process of applying sonic vibration to the coating film, and a process of applying a poor solvent for the dispersant to the coating film.
  • Nanoparticle aggregation step is a coating film forming step, a process of applying sonic vibration to the coating film, and a process of applying a poor solvent for the dispersant to the coating film.
  • the dispersant adsorbed on the nanoparticles is separated in the coating.
  • the dispersibility can be lowered, the contacts between the nanoparticles can be increased, and the nanoparticles can be in close contact with each other in the nanoparticle-containing layer after drying.
  • a nanoparticle-containing layer that is simple and has high production efficiency can be produced, and that when the nanoparticle is a conductive nanoparticle, a conductive structure having excellent conductivity and transparency can be produced.
  • the invention has been completed.
  • a nanoparticle aggregating step for aggregating the nanoparticles in the coating film by at least one of a process for imparting a poor solvent for the dispersant to the coating film It is a manufacturing method of a nanoparticle content layer.
  • the process of applying sonic vibration to the coating film is a process of applying sonic vibration to the coating film from the front surface side of the coating film via air. More preferably, in the process of applying sonic vibration to the coating film via air, the frequency of the sonic vibration is 100 Hz or more. More preferably, the treatment for imparting sonic vibration to the coating film is a treatment for imparting sonic vibration to the coating film from at least one of the substrate and the liquid from the substrate side of the coating film. More preferably, in the treatment for applying the sonic vibration to the coating film via at least one of the base material and the liquid, the sonic vibration includes an ultrasonic component.
  • the treatment of applying a poor solvent for the dispersant to the coating film is a treatment of spraying a mist containing the poor solvent onto the coating film, and the coating film is disposed in a region filled with the mist containing the poor solvent. It is one of the processes. More preferably, the method further includes a drying step of drying the coating film that has undergone the aggregation step after the nanoparticle aggregation step. More preferably, the viscosity of the coating film at 25 ° C. is 10 mPa ⁇ s or less.
  • the method for producing a conductive structure comprises applying a conductive nanoparticle-containing coating solution containing at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles to a substrate, and then coating the substrate.
  • the conductive nanoparticles are agglomerated in the coating film by at least any one of a coating film forming step for forming a coating, a process for imparting sonic vibration to the coating film, and a process for imparting a poor solvent for the dispersant to the coating film.
  • the method includes a conductive nanoparticle aggregation step and a drying step of drying a coating film in which the conductive nanoparticles are aggregated to form a conductive layer.
  • the conductive nanoparticles have an aspect ratio of 10 to 10,000. More preferably, the surface resistance value of the conductive layer is 0.1 ⁇ / ⁇ to 10 3 ⁇ / ⁇ . More preferably, the conductive nanoparticles are metal nanoparticles or carbon nanoparticles. More preferably, the metal nanoparticle is at least one of a metal nanotube, a metal nanorod, a metal nanohorn, and a metal nanowire, and the carbon nanoparticle is at least one of a carbon nanotube, a carbon nanorod, a carbon nanohorn, and a carbon nanowire. is there.
  • the apparatus for producing a nanoparticle-containing layer according to the present invention is a coating film forming method in which a nanoparticle-containing coating solution containing at least nanoparticles and a dispersant for dispersing the nanoparticles is applied to a substrate to form a coating film.
  • Nanoparticle aggregation in which the nanoparticles are aggregated in the coating film by at least one of means, a sonic vibration imparting body that imparts sonic vibration to the coating film, and a poor solvent imparting body that imparts a poor solvent for the dispersant to the coating film
  • the sound wave vibration imparting body is either a speaker or an ultrasonic wave transmitter.
  • An apparatus for producing a conductive structure according to the present invention includes a conductive nanoparticle-containing coating liquid that includes at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles.
  • Conductive nano-particles in the coating film by at least one of a coating film forming means for forming sonic vibration imparting body that imparts sonic vibration to the coating film, and a poor solvent imparting body that imparts a poor solvent for the dispersant to the coating film
  • the present invention includes a method for producing a nanoparticle-containing layer whose base material has elasticity. Moreover, the manufacturing method of the nanoparticle content layer in which a base material has a light transmittance is included by this invention.
  • “Ohm per square ( ⁇ / sq)”, which is a unit representing the surface resistance value, may be expressed as “ ⁇ / ⁇ ”.
  • the dispersion adsorbed to the nanoparticles in the coating film can be separated to reduce dispersibility, increase the contact between the nanoparticles, and the nanoparticles can be in close contact with each other in the nanoparticle-containing layer after drying.
  • the manufacturing method of the electroconductive structure excellent in electroconductivity and transparency and its manufacturing apparatus can be provided. Therefore, according to the present invention, the conventional problems can be solved and the object can be achieved.
  • FIG. 1A is a schematic explanatory view schematically showing an example of a top view on the front surface side of a coating film containing conductive nanowires.
  • 1B is an enlarged cross-sectional view of the inside of the broken line part of FIG. 1A as seen from the direction of the arrow in FIG. 1A, and is a schematic explanatory view schematically showing an example of a state after the coating film forming process and before the conductive nanoparticle aggregation process. is there.
  • FIG. 1C is a schematic explanatory view schematically showing an example of a state after conducting the conductive nanoparticle aggregation step from the state shown in FIG. 1B.
  • FIG. 1A is a schematic explanatory view schematically showing an example of a top view on the front surface side of a coating film containing conductive nanowires.
  • 1B is an enlarged cross-sectional view of the inside of the broken line part of FIG. 1A as seen from the direction of the arrow in FIG. 1A, and is
  • FIG. 2 is a schematic diagram illustrating an example of a method for manufacturing a conductive structure and a manufacturing apparatus thereof according to the present invention, and a manufacturing line to which the method for manufacturing a nanoparticle-containing layer and the manufacturing apparatus according to the present invention are applied.
  • FIG. 3 is a schematic view showing another example of the manufacturing method and the manufacturing apparatus for the conductive structure of the present invention, and the manufacturing line to which the manufacturing method and the manufacturing apparatus for the nanoparticle-containing layer of the present invention are applied. is there.
  • FIG. 4A is a diagram illustrating the arrangement of the speakers in Example 1, and is a schematic top view of the speakers and the coating film viewed from the front surface side of the coating film.
  • FIG. 4B is a diagram illustrating the arrangement of the speakers in Example 1, and is a cross-sectional view in the width direction of the coating film and in the thickness direction of the coating film indicated by A-A ′ in FIG. 4A.
  • the method for producing a nanoparticle-containing layer of the present invention preferably includes at least a coating film forming step and a nanoparticle aggregation step, and further includes a drying step, and further includes other steps as necessary.
  • the apparatus for producing a nanoparticle-containing layer of the present invention has at least a coating film forming unit and a nanoparticle aggregation unit, and preferably further includes a drying unit, and further includes other units as necessary. .
  • the coating film forming step can be suitably performed by the coating film forming unit, and the nanoparticle aggregating step can be suitably performed by the nanoparticle aggregating unit.
  • the method for producing a conductive structure of the present invention includes at least a coating film forming step, a conductive nanoparticle aggregation step, and a drying step, and further includes other steps as necessary.
  • the apparatus for producing a conductive structure of the present invention includes at least a coating film forming unit, a conductive nanoparticle aggregation unit, and a drying unit, and further includes other units as necessary.
  • the coating film forming step can be suitably performed by the coating film forming unit
  • the conductive nanoparticle aggregation step can be suitably performed by the conductive nanoparticle aggregation unit
  • the drying step can be It can be suitably performed by a drying means.
  • the production apparatus for the nanoparticle-containing layer of the present invention will be described in detail together with the description of the method for producing the nanoparticle-containing layer of the present invention.
  • the method for producing a nanoparticle-containing layer and the apparatus for producing a nanoparticle-containing layer according to the present invention when the nanoparticle is a conductive nanoparticle, the method for producing the conductive structure according to the present invention and the Corresponds to manufacturing equipment for conductive structures. Therefore, together with the description of the method for producing the nanoparticle-containing layer and the device for producing the nanoparticle-containing layer, the method for producing the conductive structure of the present invention and the device for producing the conductive structure of the present invention are also included. This will be described in detail.
  • the coating film forming step is a step of forming a coating film by applying a nanoparticle-containing coating solution containing at least nanoparticles and a dispersant for dispersing the nanoparticles to a substrate.
  • the said coating-film formation process is suitably performed by the said coating-film formation means.
  • Nanoparticle-containing coating solution contains at least nanoparticles, a dispersant for dispersing the nanoparticles, and a solvent, and further contains other components as necessary.
  • nanoparticles There is no restriction
  • an inorganic nanoparticle, an organic nanoparticle, etc. are mentioned. These may be used alone or in combination of two or more.
  • inorganic nanoparticles-- There is no restriction
  • a metal, a metal oxide, an inorganic oxide, a semiconductor, etc. are mentioned.
  • the inorganic nanoparticles may be composed of particles of one material alone, or may be multilayer particles formed by laminating these materials in layers.
  • the metal is not particularly limited and may be appropriately selected depending on the purpose.
  • the said metal may be used individually by 1 type, and may use 2 or more types together. Further, it can be used as an alloy, and a metal compound may be used.
  • the metal is preferably at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the Long Periodic Table (IUPAC 1991), and at least one selected from Groups 2 to 14 More preferably, at least one metal selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, Group 14 is more preferable, It is particularly preferable that these metals are contained as a main component.
  • the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, Examples thereof include antimony, lead, and alloys thereof.
  • copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof are preferable, palladium, copper, silver, gold, platinum, tin, or alloys thereof are more preferable, Silver or an alloy containing silver is particularly preferred.
  • the metal oxide is not particularly limited and may be appropriately selected depending on the purpose.
  • the oxide of the said metal is mentioned.
  • Group IV semiconductors such as Si, Ge and SiC
  • Group I-VII semiconductors such as CuCl
  • Group II-VI semiconductors such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe
  • III-V semiconductors such as AlP, AlAs, AlSb, InP, InAs, and InSb.
  • the semiconductor includes CdS core-CdSe shell, CdSe core-CdS shell, CdS core-ZnS shell, CdSe core-ZnS shell, CdSe nanocrystals core-ZnS shell, CdSe
  • a semiconductor having a core-shell structure in which the nanocrystal is a core-ZnSe shell and Si is a core-SiO 2 shell may be used.
  • organic pigments organic dye pigments, polymer compound pigments such as carbon, graphite, fullerene, polydiacetylene, and polyimide
  • aromatic hydrocarbon pigments for example, polycyclic aromatic pigments
  • aliphatic hydrocarbon pigments for example, Aromatic hydrocarbons or aliphatic hydrocarbons having orientation, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimation properties
  • monomers such as (meth) acrylic, fluorine-substituted (meth) acrylic-styrene, or (co) polymers.
  • organic nanoparticles for example, those described in JP-A-2006-308880, JP-A-2009-242687 and the like can be used.
  • nanowire means a solid nanoparticle.
  • Nanotube means hollow nanoparticles.
  • Nanorod means a rod-shaped nanoparticle having a long axis longer than a short axis.
  • the nanohorn means a horn-shaped nanoparticle in which one end of the nanotube is closed.
  • the particle diameter of the nanoparticles is not particularly limited and can be appropriately selected depending on the shape of the nanoparticles.
  • the material of the conductive nanoparticles is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose, but is preferably at least one of the metal and carbon.
  • the conductive nanoparticles include metal nanoparticles (more preferably, metal nanotubes, metal nanorods, metal nanohorns, metal nanowires) and carbon nanoparticles (more preferably, carbon nanotubes, carbon nanorods, carbon nanohorns, carbon nanowires). ) Is preferably at least one selected from the group consisting of, and among these, at least one of metal nanowires, metal nanotubes, and carbon nanotubes is particularly preferable.
  • the metal nanowires are solid conductive nanoparticles made of the metal or metal compound.
  • a shape of the said metal nanowire According to the objective, it can select suitably, For example, it can take arbitrary shapes, such as a column shape, a rectangular parallelepiped shape, and the column shape from which a cross section becomes a polygon. In applications where high transparency is required, a cylindrical shape or a cross-sectional shape with rounded polygonal corners is preferable.
  • the cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the corner of the cross section of the metal nanowire refers to an apex of a virtual polygon that extends along a substantially straight side and is surrounded by the extended straight line in the cross section of the metal nanowire. . If the corner is sharp, the transparency of the nanoparticle-containing layer (conductive layer) may be deteriorated, for example, a yellowish color may remain. This is presumed to be because electrons are localized at the corners of the cross section of the metal nanowire and plasmon absorption increases.
  • the average minor axis length (average diameter) of the metal nanowire is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 nm or less, more preferably 35 nm or less, and particularly preferably 20 nm or less. . Note that if the average minor axis length is too small, the oxidation resistance deteriorates and the durability may deteriorate, so the average minor axis length is preferably 5 nm or more. If the average minor axis length exceeds 50 nm, sufficient transparency may not be obtained because of scattering caused by metal nanowires.
  • the average major axis length (average length) of the metal nanowire is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and particularly preferably 30 ⁇ m or more. preferable.
  • the average major axis length of the metal nanowire is too long, it may be entangled during the production of the metal nanowire, or aggregates may be generated in the production process. Therefore, the average major axis length is 1 mm or less. It is preferable that If the average major axis length is less than 5 ⁇ m, it may be difficult to form a dense network, or sufficient conductivity may not be obtained.
  • the average minor axis length and the average major axis length of the metal nanowire can be obtained by observing a TEM image or an optical microscope image using, for example, a transmission electron microscope (TEM) or an optical microscope. it can.
  • the average minor axis length and the average major axis length of the metal nanowires are obtained by observing 300 metal nanowires with a transmission electron microscope (TEM) and calculating the average value.
  • TEM transmission electron microscope
  • the metal nanotube is a hollow conductive nanoparticle made of the metal or metal compound.
  • the metal nanotube may be a single wall or a multilayer, but a single wall is preferable in terms of excellent conductivity.
  • the average thickness (difference between the outer diameter and the inner diameter) of the metal nanotube is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 10 nm or less. preferable.
  • the average thickness is preferably 3 nm or more. When the average thickness exceeds 80 nm, scattering due to metal nanotubes may occur.
  • the hollow ratio of the metal nanotube is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30% to 500%, more preferably 50% to 300%, and particularly preferably 80% to 200%. preferable.
  • the average minor axis length and average major axis length of the metal nanotube can be measured by the same method as the average minor axis length and average major axis length of the metal nanowire.
  • the carbon nanotube is a conductive nanoparticle in which a graphite-like carbon atomic surface (graphene sheet) is a single-layer or multilayer coaxial tube.
  • Single-walled CNTs are called single-wall nanotubes (SWNT)
  • multi-walled CNTs are called multi-walled nanotubes (MWNT)
  • DWNT double-walled nanotubes
  • the CNT may be a single layer or a multilayer, but a single layer is preferable in terms of excellent conductivity.
  • the single-walled CNT theoretically includes 1/3 metallic CNT and 2/3 semiconducting CNT, but only metallic CNT can be separated.
  • the single-walled CNTs it is more preferable to use only separated metal CNTs from the viewpoints of transparency and conductivity.
  • separating the said metallic CNT According to the objective, it can select suitably.
  • known methods such as agarose gel method, decomposition with hydrogen peroxide, and the like can be mentioned.
  • the aspect ratio of the nanoparticles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 to 10,000, more preferably 20 to 2,000, and particularly preferably 50 to 1,000. preferable. When the aspect ratio is less than 10, the contacts between the nanoparticles cannot be increased, and when the nanoparticles are conductive nanoparticles, the conductive nanoparticles do not form a network. Is not preferable in that it cannot be sufficiently removed. In addition, when the aspect ratio exceeds 10,000, nanoparticles are entangled and aggregated before film formation in the formation and application of nanoparticles, and subsequent handling, and therefore, a stable nanoparticle-containing coating solution is obtained. It may not be obtained.
  • the aspect ratio is a ratio between a long side and a short side of a fibrous substance (for example, a wire, a tube, etc.) (major axis length / minor axis length ratio).
  • a fibrous substance for example, a wire, a tube, etc.
  • major axis length / minor axis length ratio there is no restriction
  • the method of measuring with an electron microscope etc. is mentioned.
  • the aspect ratio of the nanoparticles is high, it is difficult to accurately measure the aspect ratio of each nanoparticle. It only has to be confirmed in the field of view.
  • the aspect ratio of the whole nanoparticles can be estimated.
  • the outer diameter of the tube is used as the short axis length for calculating the aspect ratio.
  • the content of the nanoparticles in the nanoparticle-containing coating solution is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 90% by mass, and 3% by mass to 70% by mass. Is more preferable. When the content is less than 1% by mass, the load in the drying step described later may be large. When the content exceeds 90% by mass, the nanoparticles are aggregated in the nanoparticle-containing coating solution before coating. May be more likely to occur.
  • the dispersant is not particularly limited as long as it can disperse the nanoparticles, and can be appropriately selected from known dispersants according to the purpose.
  • the description of “Encyclopedia of Pigments” edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.
  • dispersant examples include amino group-containing compounds, thiol group-containing compounds, sulfide group-containing compounds, amino acids or derivatives thereof, peptide compounds, polysaccharides, polymer compounds, halogen compounds, and gels derived therefrom. . These may be used alone or in combination of two or more.
  • amino group-containing compound examples include alkylamines such as oleylamine, dibutylamine, tripropylamine, dicyclohexylamine, piperidine, ethylamine, ethanolamine, diethanolamine, polyallylamine, polyalkyleneamine; pyridine, aniline, benzylamine, and the like. And amines having the following aromatic groups.
  • thiol group-containing compound examples include alkyl thiols such as ⁇ -thioglycerol, methyl mercaptan, and ethyl mercaptan; and aryl thiols such as thiophenol, thionaphthol, and benzyl mercaptan.
  • amino acid examples include aspartic acid, glutamic acid, cysteic acid and the like.
  • amino acid derivatives include amino acid polymers.
  • peptide compound examples include a dipeptide compound containing a cysteine residue, a tripeptide compound, a tetrapeptide compound, an oligopeptide compound containing 5 or more amino acid residues; a globular protein having metallothionein or cysteine residues arranged on the surface, etc. Is mentioned.
  • polysaccharide examples include methyl cellulose, hydroxypropyl cellulose, gelatin, carrageenan, polyvinyl pyrrolidone (PVP), and starch.
  • polymer compound examples include polyacrylate, polymethacrylate (for example, poly (methyl methacrylate)), polyacrylic acid, polyacrylonitrile, polyvinyl alcohol, polyester (for example, polyethylene terephthalate (PET), polyester naphthalate, polycarbonate).
  • polyacrylate for example, poly (methyl methacrylate)
  • polymethacrylate for example, poly (methyl methacrylate)
  • polyacrylic acid for example, poly (methyl methacrylate)
  • polyacrylonitrile for example, polyvinyl alcohol
  • polyester for example, polyethylene terephthalate (PET), polyester naphthalate, polycarbonate.
  • phenol-formaldehyde or cresol-formaldehyde for example, Novolacs (registered trademark), etc.
  • polymers having high aromaticity polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide, polyamide, polyamide imide, polyether amide, Polysulfide, polysulfone, polyphenylene, polyphenyl ether, polyurethane (PU), epoxy, polyolefin (eg poly Propylene, polymethylpentene, cyclic olefins, etc.), acrylonitrile-butadiene-styrene copolymer (ABS), cellulose and its derivatives, silicon and other silicon-containing polymers (eg polysilsesquioxane and polysilane), polyvinyl chloride (PVC) , Polyacetate, polynorbornene, synthetic rubber (eg, EPR, SBR, EPDM, etc.), and fluorbornene
  • the halogen compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound containing at least one of bromine, chlorine and iodine is preferable. Examples thereof include alkali halides such as sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide, potassium chloride and potassium iodide.
  • metal halide fine particles may be used as an alternative to the halogen compound, or both the halogen compound and the metal halide fine particles may be used.
  • Examples of the compound used in combination with the dispersant include HTAB (hexadecyl-trimethylammonium bromide) containing an amino group and a bromide ion; HTAC (hexadecyl-trimethylammonium chloride) containing an amino group and a chloride ion; Contains chloride ion, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride, dilauryl Dimethylammonium bromide, dilauryldimethylammonium chloride, Methyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride.
  • gelatin polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinylpyrrolidone, polyvinylpyrrolidone copolymer, and HTAB are particularly preferable as the dispersant.
  • the content of the dispersant in the nanoparticle coating liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 80% by mass, and 0.3% by mass More preferable is 50 mass%. If the content of the dispersant is less than 0.1% by mass, the nanoparticle coating solution may be poorly dispersed and may cause aggregation of metal nanowires in the nanoparticle coating solution, and exceeds 80% by mass. In some cases, the functions of the original nanoparticles may not be expressed.
  • solvent there is no restriction
  • water, alcohol solvents, ether solvents, ester solvents, ketone solvents, amide solvents, nitrile solvents and the like can be mentioned.
  • Examples of the alcohol solvent include methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, glycerin, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2- Examples include butanediol, 1,4-butanediol, 1,5-pentanediol, 1-ethoxy-2-propanol, ethanolamine, diethanolamine, 2- (2-aminoethoxy) ethanol, 2-dimethylaminoisopropanol, and the like.
  • Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like.
  • ester solvent examples include ethyl acetate and butyl acetate.
  • ketone solvent examples include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like.
  • amide solvent examples include dimethylformamide and dimethylacetamide.
  • nitrile solvent examples include acetonitrile and butyronitrile.
  • solvents may be used alone or in combination of two or more.
  • a solvent is compatible, without phase-separating.
  • a hydrophilic solvent is mainly used as a solvent used for the said electroconductive nanoparticle containing coating liquid, and water is especially preferable.
  • a solvent miscible with water is preferably used in a proportion of 80% by volume or less with respect to water.
  • an organic solvent having a boiling point of 50 ° C. to 250 ° C. is preferable, and an alcohol solvent having a boiling point of 55 ° C. to 200 ° C. is more preferable.
  • the alcohol solvent is particularly preferably ethanol or ethylene glycol.
  • the other components in the nanoparticle-containing coating liquid are not particularly limited and may be appropriately selected depending on the intended purpose, but preferably include a corrosion inhibitor, and include a surfactant, a polymerizable compound, and an antioxidant.
  • various additives such as a sulfidation inhibitor, a viscosity modifier, and a preservative may be included.
  • an azole type compound is preferable.
  • An azole type compound is preferable.
  • limiting in particular as said azole type compound According to the objective, it can select suitably.
  • benzotriazole, tolyltriazole, mercaptobenzothiazole, mercaptobenzotriazole, mercaptobenzotetrazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, and alkali metal salts thereof examples thereof include at least one selected from ammonium salts and amine salts. These may be used alone or in combination of two or more.
  • the corrosion inhibitor may be added directly to the nanoparticle-containing coating solution, may be added in a state dissolved in a suitable solvent, or in a powder state, and the nanoparticle-containing layer or the conductive structure. After the product is formed, it may be applied by immersing it in a corrosion inhibitor bath.
  • the conductive nanoparticle-containing coating solution preferably contains as little inorganic ions as possible such as alkali metal ions, alkaline earth metal ions, and halide ions.
  • the mass ratio (X / Y) with the content Y of nanoparticles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 to 3, more preferably 0.1 to 1. preferable.
  • the mass ratio (X / Y) is less than 0.05, the deterioration of optical properties such as conductivity and transmittance due to aggregation of the conductive nanoparticles, the mechanical strength of the conductive layer, and the adhesion to the substrate Problems such as degradation, particularly degradation of the quality of the pattern obtained by patterning using photolithography (faithful reproducibility of the exposure pattern) may occur.
  • the mass ratio (X / Y) exceeds 3
  • the viscosity of the coating film is preferably 10 mPa ⁇ s or less, more preferably 1 mPa ⁇ s to 5 mPa ⁇ s. If the viscosity exceeds 10 mPa ⁇ s, it may be difficult to cause aggregation of nanoparticles in the coated film after coating. If it is less than 1 mPa ⁇ s, fluctuations in film thickness due to drying unevenness may occur.
  • the nanoparticle-containing layer may not perform its original function.
  • the method for adjusting the viscosity is not particularly limited and may be appropriately selected depending on the purpose. However, preliminary drying is performed between the coating film forming step and the nanoparticle aggregation step, and the preliminary drying time is appropriately set. For example, a method of adjusting the solid content concentration in the coating film can be mentioned. Since it is difficult to directly measure the viscosity of the coating film, in the present invention, in the nanoparticle aggregation step, the coating film is scraped with a scraper or the like to determine the solid content concentration in the coating film. The viscosity of the coating film is determined by measuring the viscosity using a liquid separately adjusted to the solid content concentration. The viscosity can be measured with a rotary viscometer (Bismetron VDA-2, manufactured by Shibaura System) or the like.
  • the electrical conductivity of the conductive nanoparticle-containing coating solution is not particularly limited and can be appropriately selected depending on the purpose.
  • nanoparticles are metal nanowires, metal nanotubes, or carbon nanotubes, they can be prepared by the following method.
  • Metal nanowires-- The method for preparing the metal nanowire is not particularly limited and may be appropriately selected according to the purpose. However, there is a method in which a metal complex solution is added to a solvent containing the dispersant and heated. preferable. Examples of methods for preparing metal nanowires include, for example, JP2009-215594A, JP2009-242880A, JP2009-299162A, JP2010-84173A, and JP2010-86714A. It is also possible to use the method described in the Japanese Patent Gazette.
  • a dispersant may be added to a solvent in advance, and metal particles that become the core of the metal nanowire may be added in the presence of the dispersant, or after the metal particles are prepared in the solvent, the dispersion state
  • the dispersant may be added.
  • the addition of the dispersing agent is divided into two or more steps, the amount needs to be changed depending on the length of the metal nanowire required. This is considered to be due to the length of the metal nanowires by controlling the amount of metal particles as a nucleus.
  • the shape of the metal nanowire obtained can also be changed with the kind of dispersing agent to be used.
  • a silver complex is especially preferable.
  • the ligand of the silver complex include CN—, SCN—, SO 3 2 —, thiourea, ammonia, and the like. For these, see “The Theory of the Photographic Process 4th Edition”, Macmillan Publishing, T .; H. Reference can be made to the description by James. Among these, a silver ammonia complex is particularly preferable.
  • the step of adding the metal complex is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably added after the dispersant. By adding in this order, it is possible to form a wire nucleus with a high probability, or the ratio at which metal nanowires with an appropriate diameter and length can be formed can be increased.
  • the heating temperature at the time of heating is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 150 ° C. or lower, more preferably 20 ° C. to 130 ° C., further preferably 30 ° C. to 100 ° C., 40 ° C. to 90 ° C. is particularly preferable.
  • the lower the heating temperature the lower the probability that a wire nucleus can be formed, and the metal nanowire becomes too long. If the heating temperature is less than 20 ° C., the metal nanowire is easily entangled and the dispersion stability is deteriorated. Sometimes.
  • corner of the cross section of metal nanowire may become steep, and the transmittance
  • a reducing agent during the heating.
  • the step of adding the reducing agent may be before or after the addition of the dispersant.
  • limiting in particular as said reducing agent It can select suitably from what is normally used.
  • borohydride metal salt, aluminum hydride salt, alkanolamine, aliphatic amine, heterocyclic amine, aromatic amine, aralkylamine, alcohol, organic acid, reducing sugar, sugar alcohol, sodium sulfite, hydrazine compound examples include dextrin, hydroquinone, hydroxylamine, citric acid or a salt thereof, succinic acid or a salt thereof, ascorbic acid or a salt thereof, ethylene glycol, and glutathione.
  • Examples of the borohydride metal salt include sodium borohydride and potassium borohydride.
  • Examples of the aluminum hydride salt include lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, magnesium aluminum hydride, and calcium aluminum hydride.
  • Examples of the alkanolamine include diethylaminoethanol, ethanolamine, propanolamine, triethanolamine, dimethylaminopropanol, and the like.
  • Examples of the aliphatic amine include propylamine, butylamine, dipropyleneamine, ethylenediamine, and triethylenepentamine.
  • Examples of the heterocyclic amine include piperidine, pyrrolidine, N-methylpyrrolidine, and morpholine.
  • Examples of the aromatic amine include aniline, N-methylaniline, toluidine, anisidine, phenetidine and the like.
  • Examples of the aralkylamine include benzylamine, xylenediamine, N-methylbenzylamine and the like.
  • Examples of the alcohol include methanol, ethanol, 2-propanol and the like.
  • Examples of the organic acids include citric acid, malic acid, tartaric acid, citric acid, succinic acid, ascorbic acid, and salts thereof.
  • Examples of the reducing saccharide include glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose and the like.
  • Examples of the sugar alcohols include sorbitol.
  • reducing sugars and sugar alcohols are preferable, and glucose is particularly preferable.
  • the reducing agent may function as a dispersant or a solvent as a function, and can be preferably used as a dispersant or a solvent.
  • a desalting treatment after forming the metal nanowires.
  • a desalting process There is no restriction
  • Metal nanotubes-- There is no restriction
  • a coating film can be formed by apply
  • coating method of the said nanoparticle containing coating liquid According to the objective, it can select suitably. Examples thereof include spin coating, casting, roll coating, flow coating, printing, dip coating, casting film formation, bar coating, gravure printing, and die coating.
  • Base material There is no restriction
  • examples of the shape include a film shape, a sheet shape, a disk shape, and a card shape.
  • examples of the structure include a single layer structure and a laminated structure.
  • the size can be appropriately selected according to the application.
  • the wiring portion may have pores and fine grooves having an aspect ratio of 1 or more, and in these, the nanoparticle-containing coating solution may be formed by an inkjet printer or a dispenser. Can also be discharged.
  • the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having elasticity and light transmittance are preferred, and specifically described in (1) to (3) below. And so on.
  • Acrylic resin for example, polycarbonate, polymethyl methacrylate, etc.
  • vinyl chloride resin for example, poly Vinyl chloride, vinyl chloride copolymer, etc.
  • polyarylate polysulfone, polyethersulfone, polyimide, polyethylene terephthalate (PET), polyethernitrile (PEN), triacetylcellulose (TAC), fluororesin, phenoxy resin, polyolefin
  • Thermoplastic resins such as epoxy resins, nylon, styrene resins, ABS resins
  • Thermosetting resins such as epoxy resins Among these, the base material is suitable for manufacturing, lightweight, flexible, optical (polarization) (P
  • the light transmittance of the said base material there is no restriction
  • the transmittance can be measured using, for example, an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation).
  • the thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the average thickness is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 400 ⁇ m, and particularly preferably 5 ⁇ m to 300 ⁇ m.
  • the average thickness is less than 1 ⁇ m, the yield may decrease due to the difficulty in handling in the coating film forming process.
  • the average thickness exceeds 500 ⁇ m, in portable devices such as mobile phones and tablet PCs. In some cases, thickness and mass may be a problem.
  • the average thickness of the substrate is, for example, observed with a scanning electron microscope (SEM) after taking out a cross section of the nanoparticle-containing layer or the conductive structure by a microtome cutting method, or containing the nanoparticles After embedding a layer or a conductive structure with an epoxy resin, a section prepared with a microtome can be measured by observing with a transmission electron microscope (TEM).
  • the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said nanoparticle content layer or a conductive structure.
  • the base material is preferably one having a hydrophilic treatment applied to the surface and coated with a hydrophilic polymer.
  • the hydrophilic treatment is not particularly limited and may be appropriately selected depending on the purpose.
  • chemical treatment such as a silane coupling agent, mechanical surface roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, glow discharge treatment, active plasma treatment, laser treatment and the like can be mentioned.
  • the surface tension of the surface of the base material is 30 dyne / cm or more by these hydrophilization treatments.
  • the hydrophilic polymer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include gelatin, gelatin derivatives, gazein, agar, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, dextran and the like.
  • the thickness of the hydrophilic polymer layer when dried is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the average thickness is preferably 0.001 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 20 ⁇ m.
  • the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said base material, and can be measured by the method similar to the thickness of the said base material.
  • a hardener to the hydrophilic polymer layer.
  • a hardener there is no restriction
  • aldehyde compounds such as formaldehyde and glutaraldehyde
  • ketone compounds such as diacetyl and cyclopentanedione
  • vinylsulfone compounds such as divinylsulfone
  • triazine compounds such as 2-hydroxy-4,6-dichloro-1,3,5-triazine Isocyanate compounds described in U.S. Pat. No. 3,103,437 and the like.
  • the hydrophilic polymer layer is prepared by dissolving or dispersing the compound contained in the hydrophilic polymer layer in a solvent such as water to prepare a coating solution, and the resulting coating solution is subjected to spin coating, dip coating, or extrusion. It can be formed by applying to a hydrophilic surface of a base material using a coating method such as a coating method, a bar coating method, or a die coating method, and drying.
  • the drying temperature at the time of drying is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 120 ° C. or lower, more preferably 30 ° C. to 100 ° C., and particularly preferably 40 ° C. to 80 ° C. .
  • an undercoat layer may be formed between the base material and the hydrophilic polymer layer as necessary for the purpose of improving adhesion.
  • nanoparticle aggregation means The nanoparticle aggregating step is performed by at least one of a process of imparting sonic vibration to the coating film formed in the coating film forming process and a process of imparting a poor solvent for the dispersant to the coating film. It is a step of aggregating the nanoparticles in the coating film.
  • the nanoparticle aggregation step is suitably performed by the nanoparticle aggregation means.
  • the nanoparticle aggregation means preferably includes at least one of a sonic vibration imparting body and a poor solvent imparting body, and further includes other members as necessary.
  • the treatment for imparting sonic vibration to the coating film can be suitably performed by the sonic vibration imparting body, and the treatment for imparting a poor solvent for the dispersant to the coating film is suitably performed by the poor solvent imparting body. be able to.
  • “aggregation” means that the nanoparticles are directly bonded to each other.
  • the dispersing agent adsorbed on the nanoparticles is separated to reduce the dispersibility of the nanoparticles in the coating film, the contact between the nanoparticles is increased, and in the nanoparticle-containing layer after drying
  • the mechanism for forming a good network will be described.
  • the coating film formed in the coating film forming step stably maintains a state in which the nanoparticles are uniformly dispersed.
  • the dispersing agent in the coating film influences to inhibit the aggregation of the nanoparticles and increase the contact between the nanoparticles.
  • the nanoparticles are conductive nanoparticles, there is a problem in that sufficient conductivity and transparency cannot be obtained. there were.
  • sucked to the nanoparticle in the coating film can be isolate
  • the nanoparticles are conductive nanoparticles, the obtained conductive structure is advantageous in that high conductivity and transparency can be obtained.
  • FIG. 1A to 1C are schematic explanatory views schematically showing the state of conductive nanowires and a dispersant, taking as an example the case where the nanoparticles are conductive nanowires.
  • FIG. 1A is a top view on the front surface side of a coating film including conductive nanowires
  • FIGS. 1B and 1C are enlarged cross-sectional views of a portion surrounded by a broken line in FIG. .
  • the conductive nanowires 30 seem to form a network at first glance, but the intersection of one conductive nanowire 30a that appears to overlap with another conductive nanowire 30b (FIG. 1A).
  • FIG. 1B When the portion surrounded by the broken line is enlarged, it is as shown in FIG. 1B.
  • FIG. 1A the portion surrounded by the broken line is enlarged, it is as shown in FIG. 1B.
  • the metal nanowire 30a is a cross-sectional view in the long axis length direction
  • the metal nanowire 30b is a cross-sectional view in the short axis length direction, to which the dispersant 31 is bonded.
  • the dispersant 31 is adsorbed around each of the metal nanowires 30a and 30b, and the metal nanowires are wrapped with the dispersant. Therefore, the metal nanowire 30a and the metal nanowire 30b are not in direct contact.
  • the conductive nanoparticle aggregation step is performed on the coating film in this state by the conductive nanoparticle aggregation means, the dispersant spreads by migration, and as shown in FIG.
  • the dispersant 31 becomes the metal nanowire 30a and the metal nanoparticle. Separating from the wire 30b, the metal nanowire 30a and the metal nanowire 30b can come into contact with each other, and a network of conductive nanowires can be formed.
  • the treatment for imparting sonic vibration (hereinafter sometimes referred to as “sonic vibration imparting treatment”) is a treatment for aggregating the nanoparticles in the coating film by applying sonic vibration to the coating film. . This process is preferably performed by the sonic vibration imparting body.
  • the dispersing agent adsorbed on the nanoparticles is separated by the vibrations of the nanoparticles and the dispersing agent due to the sonic vibrations, and as a result, the contacts between the nanoparticles can be increased.
  • the sound wave vibration applying treatment can apply sound wave vibration to the coating film via a medium, and the medium is not particularly limited and can be appropriately selected according to the purpose.
  • the medium is not particularly limited and can be appropriately selected according to the purpose.
  • air for example, air, liquid , Solids and the like.
  • the surface for applying the sonic vibration in the coating film is not particularly limited and may be appropriately selected depending on the purpose. It is preferable to apply sonic vibration from the surface (the surface opposite to the side in contact with the substrate of the coating film).
  • the traveling direction of the sonic vibration is not particularly limited and can be appropriately selected according to the purpose, but the front surface of the coating film is used as a reference surface.
  • the reference plane (the direction parallel to the front surface of the coating film) is 0 °, it is preferably greater than 0 ° and not more than 90 ° from the reference plane, more preferably 60 ° to 90 °, and 90 ° (coating film).
  • the direction perpendicular to the front surface is particularly preferred.
  • the frequency of the sonic vibration in the treatment of applying the sonic vibration to the coating film via the air is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 100 Hz or more, preferably 100 Hz to 10 000 Hz is more preferable.
  • the frequency is less than 100 Hz, sufficient sonic vibration cannot be imparted to the coating film, so the number of contacts between the nanoparticles cannot be increased, and the nanoparticles are conductive nanoparticles. The conductivity of the conductive structure may be lowered.
  • the frequency exceeds 10,000 Hz the efficiency of imparting vibration to the coating film is adversely affected and the effect may be reduced.
  • the time for applying the sound wave vibration in the process of applying the sound wave vibration to the coating film via the air is not particularly limited and can be appropriately selected according to the purpose, but preferably 3 seconds or more, More preferably, it is 3 seconds to 10 seconds. If the time for applying the sonic vibration is less than 3 seconds, the contact between the nanoparticles cannot be increased because sufficient sonic vibration cannot be applied to the coating film, and the nanoparticles are conductive. When it is a nanoparticle, the electroconductivity of the said electroconductive structure may become low. In addition, if the time for applying the sonic vibration exceeds 10 seconds, it may take a long time for production or the equipment cost may increase.
  • the sonic vibration imparting body in the process of imparting the sonic vibration to the coating film via the air in the nanoparticle-containing layer production apparatus is not particularly limited as long as the sonic vibration can be imparted to the coating film. And can be appropriately selected according to the purpose. For example, a speaker etc. are mentioned. Specifically, 230SM (manufactured by BOSE) or the like can be used as the speaker.
  • the surface of the coating film to which the sonic vibration is applied is not particularly limited and may be appropriately selected depending on the purpose. It is preferable that the sonic vibration is applied to the coating film from at least one of the substrate and the liquid from the substrate side of the coating film (the side in contact with the substrate of the coating film).
  • the frequency of the sonic vibration in the process of applying the sonic vibration to the coating film via the liquid is not particularly limited and may be appropriately selected depending on the purpose, but preferably includes an ultrasonic component.
  • the ultrasonic wave including the ultrasonic component generally refers to 16 kHz or higher, preferably 28 kHz or higher, and more preferably 28 kHz to 40 kHz.
  • the frequency is less than 16 kHz, sufficient sonic vibration cannot be imparted to the coating film, so the number of contacts between the nanoparticles cannot be increased, and the nanoparticles are conductive nanoparticles. May have low conductivity.
  • time to provide the said sonic vibration to the said coating film in the process which provides the said sonic vibration to the said coating film through the said liquid is no restriction
  • 3 second The above is preferable, and 3 to 10 seconds is more preferable. If the time for applying the sonic vibration to the coating film is less than 3 seconds, sufficient sonic vibration cannot be applied to the coating film, so that the contact points between the nanoparticles cannot be increased. When the particles are conductive nanoparticles, the conductivity may be low. In addition, if the time for applying the sonic vibration to the coating film exceeds 10 seconds, it may take a long time for production or increase the equipment cost.
  • an ultrasonic transmitter is used.
  • the ultrasonic transmitter include NL series such as NL-300, NL-600, NL-900, NL-1200, NK-1800, NL-2400, vibrator units (hereinafter referred to as Nippon Alex). Etc.) can be used.
  • a method of applying the sonic vibration to the coating film from at least one of the base material and the liquid from the substrate side of the coating film As, for example, by installing a sonic vibration imparting body such as an ultrasonic transmitter on the bottom surface inside the water tank, filling the water tank with a liquid, the water surface, and the base material side of the base material having the coating film (more Specifically, there is a method in which at least a part of the surface of the base material on the side where the coating film is not formed is brought into contact, and a potential is applied to the sonic vibration imparting body.
  • a sonic vibration imparting body such as an ultrasonic transmitter
  • the coating film When the nanoparticle-containing coating solution is not compatible with the liquid in the water tank, the coating film is immersed in the liquid together with the base material, and the sound wave is transmitted from the base material side through the base material. Simultaneously with applying vibration to the coating film, the sonic vibration can be applied to the coating film via a liquid in contact with the coating film.
  • the solvent etc. in the said nanoparticle containing coating liquid it can select suitably.
  • water, an organic solvent, etc. are mentioned.
  • the liquid in the water tank is in contact with the coating film, or when the coating film itself is immersed in the liquid in the water tank, the coating film is mainly formed of a water-soluble solvent.
  • the liquid in the water tank is preferably an organic solvent that is phase-separated from the water-soluble solvent.
  • the arrangement and number of the sonic vibration imparting bodies in the nanoparticle aggregating step are not particularly limited and may be appropriately selected depending on the size of the coating film. It is preferable that the number and arrangement be such that vibration can be applied.
  • the manufacturing apparatus of the said nanoparticle content layer or the manufacturing apparatus of the said conductive structure has a belt which can convey the said coating film at a fixed speed
  • the width direction (perpendicular to a conveyance direction) of a coating film
  • One or a plurality of sonic vibration imparting bodies may be disposed in the direction), and the sonic vibration may be sequentially applied to the longitudinal direction of the coating film while conveying the coating film (the same direction as the conveying direction).
  • a plurality of the sound wave vibration imparting bodies may be arranged in the transport direction.
  • the treatment for imparting a poor solvent for the dispersant to the coating film (hereinafter sometimes referred to as “poor solvent imparting treatment”) is performed by imparting the poor solvent for the dispersant to the coating film. In the process, the nanoparticles are aggregated. This treatment is preferably performed with the poor solvent-imparting body.
  • the poor solvent for the dispersant (hereinafter sometimes simply referred to as “poor solvent”) means a solvent having low solubility in the dispersant.
  • the coating film made of the nanoparticle-containing coating solution and the poor solvent for the dispersant in the coating film are mixed, and the poor solvent and the dispersant in the coating film are in contact with each other. Since the dispersant is separated from the poor solvent, it is presumed that the dispersant adsorbed on the nanoparticles is separated from the nanoparticles, and as a result, the contacts between the nanoparticles are increased.
  • the solubility is not particularly limited and may be appropriately selected depending on the type of the dispersant.
  • the solubility of the dispersant in 100 mL of the poor solvent is preferably 30% by mass or less at 25 ° C. The following is more preferable. When the solubility exceeds 30% by mass, the metal nanowires may not sufficiently aggregate in the coating film.
  • the poor solvent include alcohol solvents, aromatic hydrocarbon solvents, paraffin solvents, chlorinated paraffin solvents, chlorinated olefin solvents, chlorinated aromatic hydrocarbon solvents, linear ether solvents, cyclic Examples include ether solvents, ketone solvents, ester solvents, nitrogen-containing compounds, and the like. These may be used alone or in combination of two or more.
  • Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.
  • Examples of the aromatic hydrocarbon solvent include benzene, toluene, mesitylene, tetralin, and xylene.
  • Examples of the paraffinic solvent include cyclohexane, heptane, hexane, ligroin, pentane, ethylcyclopentane, petroleum ether, isooctane, isohexane, isoheptane, isopentane, decalin, decane, dodecane, octane, and nonane.
  • chlorinated paraffinic solvent examples include carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, methylene chloride, ethyl chloride, butyl chloride, propyl chloride and the like.
  • chlorinated aromatic hydrocarbon solvent examples include 1-chloronaphthalene, o-dichlorobenzene, m-dichlorobenzene and the like.
  • linear ether solvent examples include diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dimethoxymethane, ethyl methyl ether, dibenzyl ether, diphenyl ether, and triglyme.
  • Examples of the cyclic ether solvent include dioxane and tetrahydrofuran.
  • Examples of the olefin chloride solvent include tetrachloroethylene, trichloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, and the like.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, acetal, acetaldehyde, cyclohexanone, methyl isobutyl ketone, dimethyl sulfoxide, and the like.
  • ester solvent examples include ethyl acetate, ethyl formate, methyl acetate, methyl formate, butyl formate, propyl formate, isopropyl formate, propyl acetate, ethyl propionate, methyl propionate, ethyl butyrate, and methyl butyrate.
  • nitrogen-containing compound examples include acetamide, acetonitrile, diethylamine, diisopropylamine, ethylamine, ethylenediamine, hydrazine, nitromethane, piperidine, propylamine, pyridine, N, N, N ′, N′-tetramethylethylenediamine, triethylamine, acrylonitrile.
  • the poor solvent is preferably an ether organic solvent, a ketone organic solvent, an alcohol organic solvent or the like.
  • the state of the poor solvent when applying the poor solvent is not particularly limited and may be appropriately selected depending on the purpose.
  • a liquid form, a mist form, a dip form, etc. are mentioned.
  • a mist shape is preferable.
  • the anti-solvent application treatment is not particularly limited as long as the anti-solvent can be applied to the coating film, and can be appropriately selected depending on the purpose, but the mist containing the anti-solvent is sprayed on the coating film.
  • Treatment hereinafter sometimes referred to as “mist spraying treatment”
  • treatment for disposing the coating film in a region filled with the mist containing the poor solvent hereinafter referred to as “mist filling treatment”. Any one of the treatments is preferred.
  • the mist spraying process is a process of spraying the mist containing the poor solvent onto the coating film.
  • the spraying direction for spraying the mist is not particularly limited and may be appropriately selected according to the purpose.
  • the front surface of the coating film is used as a reference surface, and the reference surface ( When 0 ° is defined as the coating surface (horizontal with the front surface), it is preferably more than 0 ° and 90 ° or less from the reference surface, more preferably 60 ° to 90 °, 90 ° (on the coating surface)
  • the direction perpendicular to the above is particularly preferred.
  • the amount of mist applied in the mist spraying process is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 g / min to 100 g / min, more preferably 50 g / min to 80 g / min. preferable.
  • the application amount is less than 20 g / min, a sufficient amount of poor solvent cannot be applied to the coating film, and therefore, the contact between the nanoparticles cannot be increased, and the nanoparticles are conductive nano particles. In the case of particles, the conductivity may be lowered.
  • the said application amount exceeds 100 g / min, since the aggregation effect of metal nanowire does not increase any more, it may become disadvantageous in cost.
  • the wind speed on the front surface of the coating film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.2 m / sec to 10 m / sec, preferably 0.5 m. / Second to 5 m / second is more preferable. If the wind speed is less than 0.2 m / sec, the contact between the nanoparticles cannot be increased, and if the nanoparticles are conductive nanoparticles, the conductivity may be low. If it exceeds 10 m / second, the front surface of the coating film may be rough and the original function may be deteriorated.
  • the spraying time for spraying the mist in the mist spraying process is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 seconds or more, and more preferably 5 seconds to 10 seconds. If the spraying time is less than 5 seconds, a sufficient amount of poor solvent cannot be applied to the coating film, so the number of contacts between the nanoparticles cannot be increased, and the nanoparticles are not conductive. In the case of nanoparticles, the conductivity may be lowered. In addition, if the spraying time exceeds 10 seconds, it may take a long time for production or the equipment cost may increase.
  • the poor solvent-imparting body in the mist spraying treatment is not particularly limited as long as mist containing a poor solvent can be sprayed onto the coating film, and can be appropriately selected according to the purpose.
  • a spray, a nozzle, etc. are mentioned.
  • the said mist filling process is a process which arrange
  • the region filled with the mist containing the poor solvent is formed by the poor solvent imparting body.
  • the poor solvent-imparting body in the mist filling process is not particularly limited as long as it can be filled with the mist containing the poor solvent, and can be appropriately selected according to the purpose.
  • the said coating film can be arrange
  • the filling rate of the mist containing the poor solvent in the poor solvent-imparted body is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20% by volume or more at 60 ° C. and 40% by volume to 80%. Volume% is more preferable. If the filling rate is less than 20% by volume, a sufficient amount of poor solvent cannot be applied to the coating film, so that the number of contacts between the nanoparticles cannot be increased, and the nanoparticles are electrically conductive. In the case of nanoparticles, the conductivity may be lowered. Even if the filling rate exceeds 80% by volume, the aggregation effect of the metal nanowires does not increase any more, which may be disadvantageous in cost.
  • the temperature at which the poor solvent application treatment is performed is not particularly limited and may be appropriately selected depending on the type of the poor solvent, but is preferably 20 ° C. to 80 ° C., more preferably 30 ° C. to 70 ° C. . When the temperature is less than 20 ° C., the poor solvent may not be able to maintain a mist state. When the temperature is higher than 80 ° C., the concentration of the poor solvent may be reduced and the effect may be reduced.
  • the number of the poor solvent-imparting body in the nanoparticle aggregation step is not particularly limited and can be appropriately selected according to the size of the coating film. It is preferable that the number and arrangement be such that they can be given.
  • the manufacturing apparatus of the said nanoparticle content layer or the manufacturing apparatus of the said conductive structure has a belt which can convey the said coating film at a fixed speed
  • the width direction (perpendicular to a conveyance direction) of a coating film may be disposed in the direction), and sonic vibration may be sequentially applied to the longitudinal direction of the coating film (the same direction as the transport direction) while transporting the coating film.
  • a plurality of the poor solvent imparting bodies may be arranged in the transport direction.
  • the said sound wave vibration provision process and the said poor solvent provision process may perform one process independently, and may use two processes together, but performing two processes together, This is preferable in that the number of contacts between nanoparticles increases.
  • each process may be performed separately and may be performed simultaneously. In the case where the two processes are performed separately, the order of the processes is not particularly limited.
  • the drying step is a step of drying the coating film that has undergone the aggregation step after the nanoparticle aggregation step.
  • the drying step is preferably performed by the drying means.
  • an air drying means, a heat drying means, a hot air drying means, a spray drying means, an indirect heat drying means, a vacuum reduced pressure drying means and the like can be mentioned.
  • natural drying may be sufficient.
  • the temperature and time for drying by heating are not particularly limited as long as the coating film can be dried, and can be appropriately selected according to the purpose.
  • the coating film forming step, the nanoparticle forming step, the drying step and the like are preferably performed in this order.
  • Each step may be performed only once, may be performed a plurality of times, only the nanoparticle aggregation step may be performed a plurality of times, or a laminate may be formed by performing a cycle of each step a plurality of times. .
  • the sound wave vibration applying treatment (the process of applying the sound wave vibration to the coating film through the air and / or the sound wave vibration to the coating film through the liquid)
  • the order, combination and number of times of the poor solvent application process (the mist spraying process and / or the mist filling process) are not particularly limited and can be appropriately selected according to the purpose.
  • the conductive structure manufactured by the manufacturing method of the conductive structure and / or the manufacturing apparatus thereof has at least a conductive layer containing the conductive nanoparticles and a base material, and if necessary. Furthermore, it has a hydrophilic polymer layer, an undercoat layer, and other layers.
  • the conductive layer is a layer containing the conductive nanoparticles.
  • the average thickness of the conductive layer after drying is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 ⁇ m to 30 ⁇ m, more preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 5 ⁇ m. Particularly preferred. When the average thickness is less than 0.1 ⁇ m, the in-plane distribution of conductivity may be nonuniform, and when it exceeds 30 ⁇ m, the transmittance may be lowered and transparency may be impaired.
  • the average thickness can be adjusted by changing the coating amount of the conductive nanoparticle-containing coating solution when the conductive nanoparticle-containing coating solution is applied to a substrate.
  • the average thickness is observed, for example, with a scanning electron microscope (SEM) after the cross section of the conductive structure is taken out by a microtome cutting method, or the conductive structure is embedded with an epoxy resin. Then, it can measure by observing the section
  • TEM transmission electron microscope
  • the said average thickness means the average value of the thickness measured in arbitrary 10 places or more in the said electroconductive structure.
  • the content of the conductive nanoparticles of the conductive layer is not particularly limited, as appropriate may be selected, 0.01g / m 2 ⁇ 30g / m 2 are preferred according to the purpose, 0.01 g / M 2 to 10 g / m 2 is more preferable, and 0.02 g / m 2 to 2 g / m 2 is particularly preferable. If the content of the conductive nanoparticles is less than 0.01 g / m 2 , the conductive material that contributes to conductivity may decrease and conductivity may decrease, and at the same time a dense network cannot be formed. In some cases, voltage concentration occurs, resulting in a decrease in durability and an increase in surface resistance.
  • the said component when the component which does not contribute largely to electroconductivity other than metal nanowire is included, the said component may have absorption of the light of a specific wavelength, and is unpreferable.
  • the component other than the metal nanowire is a metal and the plasmon absorption such as a spherical shape is strong, the transparency may be deteriorated.
  • the content of the conductive nanoparticles exceeds 30 g / m 2 , the transmittance may be lowered.
  • the content of the conductive nanoparticles in the conductive layer can be measured by, for example, a fluorescent X-ray analyzer (ICP emission analyzer).
  • the surface resistance value of the conductive layer is not particularly limited and may be appropriately selected according to the purpose. However, when used for a transparent electrode or the like, 0.1 ⁇ / ⁇ to 10 3 ⁇ / ⁇ is preferable. 1 ⁇ / ⁇ to 200 ⁇ / ⁇ is more preferable. When used for antistatic purposes, 10 6 ⁇ / ⁇ to 10 9 ⁇ / ⁇ are often used.
  • the surface resistance can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600; manufactured by Mitsubishi Chemical Corporation).
  • the thickness of the nanoparticle-containing layer, the content of nanoparticles in the nanoparticle-containing layer, and the like in the nanoparticle-containing layer produced by the method for producing the nanoparticle-containing layer and / or the production apparatus thereof are also particularly limited.
  • the thickness and content are the same as those of the conductive layer.
  • FIG. 2 is a schematic view showing an example of the method for manufacturing the nanoparticle-containing layer and the manufacturing apparatus thereof according to the present invention, and the manufacturing line to which the method for manufacturing the conductive structure and the manufacturing apparatus according to the present invention are applied. is there.
  • the production of the nanoparticle-containing layer is shown as an example, but the conductive structure can be produced in the same manner.
  • the 2 includes a coating film forming unit 12, a speaker 1a, a nanoparticle aggregation unit having an ultrasonic transmitter 1b, a drying unit 76, and the like.
  • the speaker 1a and the ultrasonic transmitter 1b are the sound wave vibration imparting bodies.
  • the base material W is sent out from the delivery machine 66.
  • the substrate W preferably has a hydrophilic polymer layer and an undercoat layer.
  • the substrate W is guided by the guide roller 68 and sent to the dust remover 74, and the dust attached to the surface of the substrate W is removed.
  • a coating film forming means 12 is provided downstream of the dust remover 74, and the coating solution is formed by applying the nanoparticle-containing coating solution to the substrate W wound around the backup roller 11.
  • a speaker 1a is provided downstream of the coating film forming means 12, and an electric potential is applied to the speaker 1a from an applying means (not shown), and sound wave vibration (indicated by a broken arrow) is applied to the front surface side of the coating film. Is done.
  • a potential is applied from an application means (not shown) to the ultrasonic wave transmitter 1b provided in the water tank 2 filled with the liquid, and ultrasonic waves are applied to the coating film from the substrate side of the coating film through the substrate W. Vibration (indicated by dashed arrows) is applied. Thereby, the nanoparticle and dispersing agent in a coating film isolate
  • the coating film is dried by the drying means 76 to form a nanoparticle-containing layer. And the base material W in which the nanoparticle content layer was formed is wound up by the winder 82 provided downstream.
  • a guide roller 68 is provided over substantially the entire production line 10 of the nanoparticle-containing layer so as to wrap and support the substrate W and to enable the conveyance of the substrate W.
  • the guide roller 68 is a rotatable roller member, and preferably has a width substantially the same as the width of the substrate W.
  • FIG. 3 is a schematic view showing another example of a production line for a nanoparticle-containing layer to which the method and apparatus for producing a nanoparticle-containing layer of the present invention are applied.
  • the nanoparticle-containing layer production line 20 in FIG. 3 is changed from the nanoparticle aggregation means in FIG. 2 to the nozzle 3a and the poor solvent filling box 3b filled with the poor solvent for the dispersant in the nanoparticle-containing coating liquid. Except for this, it is the same as the production line 10 of the nanoparticle-containing layer in FIG.
  • the nozzle 3 a provided downstream of the coating film forming means 12 is used to enter the nanoparticle-containing coating liquid.
  • a mist containing a poor solvent for the dispersant (shown by a broken arrow) is sprayed on the coating film, and the mist containing the poor solvent is applied to the front surface side of the coating film (mist spraying treatment).
  • the coating film passes through a poor solvent filling box 3b filled with a mist containing a poor solvent for the dispersant in the nanoparticle-containing coating solution, and the mist containing the poor solvent further passes through the front surface of the coating film.
  • the said coating film is dried by the drying means 76, and the base material W in which the nanoparticle content layer was formed is wound up similarly to the production line 10 of the nanoparticle content layer of FIG.
  • the example in which the speaker 1a and the ultrasonic transmitter 1b are used together as the nanoparticle aggregating means and in the example in FIG. 3, the nozzle 3a and the poor solvent filling box 3b are used in combination as the nanoparticle aggregating means.
  • these nanoparticle aggregation means may be used individually by 1 type, and may use 2 or more together.
  • the order, number, and combination of these nanoparticle aggregating means are not particularly limited and can be appropriately selected according to the purpose.
  • the method and apparatus for producing the nanoparticle-containing layer of the present invention includes a nanoparticle and a dispersant, and the nanoparticle is formed in a uniform coating film formed using a coating solution having good dispersibility of the nanoparticle.
  • the dispersant adsorbed on the particles can be separated in the coating film to reduce the dispersibility, increase the contact between the nanoparticles, and the nanoparticles are in close contact with each other in the nanoparticle-containing layer after drying.
  • the said nanoparticle is the said electroconductive nanoparticle, the electroconductive structure excellent in electroconductivity and transparency can be manufactured by this.
  • the nanoparticle-containing layer produced by the method for producing a nanoparticle-containing layer and / or the production apparatus thereof of the present invention and the conductive method produced by the method for producing a conductive structure and / or the production apparatus thereof of the present invention.
  • the structural structure can be suitably used for various applications.
  • transparent conductor as an alternative to ITO, touch panel, electronic paper, antistatic material, antistatic for display, antistatic for flexible display, electromagnetic wave shield, electromagnetic wave shielding film for plasma display panel, electromagnetic wave shielding film for liquid crystal television, optical filter Circuit materials such as conductive pastes, conductive paints, conductive coatings, wiring materials, electrodes for organic or inorganic EL displays, electrodes for flexible displays, electrodes for solar cells, and various electronic materials for various conductive substrate applications Others: Catalysts, Colorants, Inkjet inks, Color materials for color filters, Filters, Cosmetics, Near-infrared absorbers, Anti-counterfeiting inks, Electromagnetic wave shielding films, Surface-enhanced fluorescence sensors, Surface-enhanced Raman scattering sensors, Biological use Marker, recording material, drag Delivery for a drug carrier, biosensors, DNA chips, are widely applied to such test agents.
  • optical filter Circuit materials such as conductive pastes, conductive paints, conductive coatings, wiring materials,
  • Example 1 ⁇ Preparation of additive solution>
  • the additive liquid A, additive liquid G, and additive liquid H were prepared in advance by the method described below.
  • the said additive liquid G and the said additive liquid H are the dispersing agents in the silver nanowire containing coating liquid mentioned later.
  • -Preparation of additive solution A 1.53 g of silver nitrate powder was dissolved in 150 mL of pure water. Thereafter, 1N ammonia water was added thereto until it became transparent. And the pure water was further added so that the whole quantity might be 300 mL, and the addition liquid A was prepared.
  • additive solution G was prepared by dissolving 1.0 g of glucose powder with 280 mL of pure water.
  • additive liquid H An additive solution H was prepared by dissolving 1.5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 82.5 mL of pure water.
  • HTAB hexadecyl-trimethylammonium bromide
  • an ultrafiltration module (SIP1013, manufactured by Asahi Kasei Co., Ltd., molecular weight cut-off 6,000), a magnet pump, and a stainless steel cup were connected with a silicon tube to produce an ultrafiltration device. After cooling the obtained silver nanowire ammonia dispersion liquid, it put into the stainless steel cup of this ultrafiltration apparatus, the ultrafiltration was performed by operating a pump. When the filtrate from the module reached 50 mL, 950 mL of distilled water was added to the stainless steel cup for washing. After repeating said washing
  • the average minor axis length and average major axis length of silver nanowires in the obtained silver nanowire aqueous dispersion were measured by the following method, the average minor axis length was 17.6 nm and the average major axis length was The thickness was 36.7 ⁇ m.
  • ⁇ Hydrophilic treatment and preparation of undercoat layer A commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) film (thickness: 100 ⁇ m, width: 60 cm) is subjected to a corona discharge treatment at 8 W / m 2 ⁇ min and subjected to a hydrophilization treatment. The pulling layer was coated so that the dry thickness was 0.8 ⁇ m.
  • PET polyethylene terephthalate
  • Composition of undercoat layer A copolymer latex of butyl acrylate (40% by mass), styrene (20% by mass), and glycidyl acrylate (40% by mass) contained 0.5% by mass of hexamethylene-1,6-bis (ethylene urea).
  • ⁇ Preparation of hydrophilic polymer layer> The surface of the undercoat layer was subjected to a corona discharge treatment of 8 W / m 2 ⁇ min, and hydroxyethyl cellulose was coated as a hydrophilic polymer layer so that the dry thickness was 0.2 ⁇ m.
  • the viscosity of the coating film was determined by first scraping the coating film with a scraper and measuring the solid content concentration in the coating film. Separately, using a solution adjusted to the same solid content concentration as the coating film, the viscosity was measured with a rotary viscometer (Bismetron VDA-2, manufactured by Shibaura System Co., Ltd.) at 25 ° C. It was set as the viscosity of the film.
  • FIG. 4A is a schematic top view of the speaker and the coating film as viewed from the reference surface side.
  • 4B is a cross-sectional view in the width direction of the coating film and in the thickness direction of the coating film indicated by AA ′ in FIG. 4A.
  • the speaker surface S is separated by 50 cm from the front surface (reference surface O) of the coating film 35 on the substrate 36 in the thickness direction of the coating film 35 (direction of 90 ° from the reference surface).
  • the sound wave was moved so that the traveling direction V of the sound wave was opposed to the front surface of the coating film 35 (see FIG. 4B).
  • the transport direction (longitudinal direction of the coating film) L of the coating film 35 and the direction D (the width direction of the coating film) D perpendicular to the transport direction L are set, the plurality of speakers 1a have a distance between centers of the speakers 1a.
  • each is 30 cm apart, and the center-to-center distance is equal, and the coating film longitudinal direction is alternately arranged in the longitudinal direction of the coating film.
  • a total of 10 rows were installed in 4 rows (see FIG. 4A).
  • a function generator (AFG3011 type, manufactured by Tektronix, Inc.)
  • the input to the speaker is adjusted to about 20 W, a sound wave vibration with a frequency of 100 Hz is generated, and the coating film is conveyed at 5 m / min. Sonic vibration was applied to the coating film via air for 10 seconds.
  • this method may be referred to as a “speaker system”.
  • Example 2 In Example 1, instead of conducting the conductive nanoparticle aggregation process when the viscosity of the coating film was 5 mPa ⁇ s, a silver nanowire aqueous dispersion (viscosity 5 mPa ⁇ s) was applied in the coating film forming process. Thereafter, the conductive layer was preliminarily dried before the conductive nanoparticle aggregation step, and the conductive layer was formed in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed when the viscosity of the coating film was 8 mPa ⁇ s. Produced.
  • Example 3 In Example 1, instead of conducting the conductive nanoparticle aggregation process when the viscosity of the coating film was 5 mPa ⁇ s, a silver nanowire aqueous dispersion (viscosity 5 mPa ⁇ s) was applied in the coating film forming process. Thereafter, the conductive layer was preliminarily dried before the conductive nanoparticle aggregation step, and the conductive layer was formed in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed when the viscosity of the coating film was 10 mPa ⁇ s. Produced.
  • Example 4 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the frequency in the conductive nanoparticle aggregation step was changed to 100 Hz to 500 Hz.
  • Example 5 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the frequency in the conductive nanoparticle aggregation step was changed to 100 Hz to 1,000 Hz.
  • Example 6 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the frequency in the conductive nanoparticle aggregation step was changed to 100 Hz to 10,000 Hz.
  • Example 7 a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • An ultrasonic transmitter (NL300, manufactured by Nippon Alex Co., Ltd.) with a width of 60 cm was installed on the bottom of a water tank (depth: 40 cm, width: 70 cm, length: 50 cm). Water is accumulated in this water tank to a depth of 40 cm, and this water surface is brought into contact with the substrate side of the substrate having the coating film (at least a part of the substrate surface on which the coating film is not formed). It was. That is, the distance between the ultrasonic wave transmitter and the base material (base material surface) was 25 cm. In addition, the water tank is always replenished with a small amount of water.
  • Overflowing water is collected by providing a tub around it, and water droplets adhering to the base material can be air blowed as necessary. Scraped and dried.
  • An ultrasonic vibration of 28 kHz was generated from the ultrasonic wave transmitter, and ultrasonic vibration was applied to the coating film through water and a substrate for 6 seconds while the coating film was conveyed at 5 m / min.
  • this method may be referred to as “ultrasonic method”.
  • Example 7 In Example 7, instead of applying ultrasonic vibration for 6 seconds, a conductive layer was produced in the same manner as in Example 7 except that it was applied for 3 seconds.
  • Example 1 a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was not performed.
  • Comparative Example 2 In Comparative Example 1, the amount of coated silver in the coating film forming step was changed to 0.02 g / m 2 , 0.08 g / m 2, and the viscosity of the coating film was 5 mPa ⁇ s. A conductive layer was produced in the same manner as in Example 1 except that the pressure was changed to 10 mPa ⁇ s.
  • the transmittance of the film at 400 nm to 800 nm was measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation), and evaluated based on the following evaluation criteria.
  • evaluation criteria A: The transmittance is 90% or more, which is a practically acceptable level.
  • ⁇ Surface resistance (conductive)> The surface resistance of the film was measured using a low resistivity meter (Loresta-GP MCP-T600, manufactured by Mitsubishi Chemical Corporation), and evaluated based on the following evaluation criteria.
  • a low surface resistance value indicates high conductivity.
  • evaluation criteria A: The surface resistance value is less than 100 ⁇ / ⁇ , which is a level that is not problematic in practice.
  • C The surface resistance value is less than 1,000 ⁇ / ⁇ , which is a level that causes no problem in practical use.
  • D The surface resistance value is 1,000 ⁇ / ⁇ or more, which is a practically problematic level.
  • Example 9 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • a two-fluid conical spray nozzle (manufactured by Miri no Ikeuchi) has a discharge direction from the nozzle so that the front surface of the coating film (the surface opposite to the side in contact with the substrate of the coating film)
  • the reference plane the direction parallel to the front surface of the coating film
  • 90 ° the direction perpendicular to the front surface of the coating film, (Position in the thickness direction)
  • nozzles are longitudinal in the width direction of the coating film at intervals of 20 cm in the transport direction of the coating film (longitudinal direction of the coating film) and in the direction perpendicular to the transporting direction (width direction of the coating film).
  • a total of 16 lines were installed in 4 rows.
  • Applying IPA (isopropyl alcohol), which is a poor solvent for the dispersant (glucose and HTAB) in the coating film at 25 ° C. from the nozzle to the reference surface while transporting the coating film at 5 m / min.
  • the amount was sprayed for 5 seconds at an amount of 20 g / minute and a wind speed of 5 m / second.
  • the time for applying the poor solvent may be referred to as “poor solvent application time”.
  • Example 10 a conductive layer was produced in the same manner as in Example 9 except that the poor solvent application time in the conductive nanoparticle aggregation step was changed to 5 seconds to 10 seconds.
  • Example 11 In Example 9, the conductive layer was formed in the same manner as in Example 9 except that the amount of poor solvent applied in the conductive nanoparticle aggregation step was changed to 20 g / min and changed to 50 g / min. Was made.
  • Example 12 In Example 9, the application amount of the poor solvent in the conductive nanoparticle aggregation step was changed to that performed at 20 g / min, and was performed at 50 g / min, and the application time of the poor solvent was changed to 5 seconds and changed to 10 seconds. A conductive layer was produced in the same manner as in Example 9 except that.
  • Example 13 In Example 9, a conductive layer was produced in the same manner as in Example 9 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • -Conductive nanoparticle aggregation process The temperature in a poor solvent-filled box (height: 50 cm, width: 70 cm, length: 50 cm) was set to 60 ° C., and IPA (isopropyl) as a poor solvent for the dispersant (glucose and HTAB) was placed in the box. Alcohol) was filled in the form of a mist. The coating film was allowed to pass through the box while being conveyed at 5 m / min, and the poor solvent was applied to the coating film under conditions of an application amount of the poor solvent of 50 g / min and a poor solvent application time of 10 seconds.
  • IPA isopropyl
  • Alcohol was filled in the form of a mist.
  • Example 14 In Example 13, the amount of the poor solvent applied in the conductive nanoparticle aggregation step was changed to 50 g / min, and was changed to 100 g / min. Was made.
  • Example 15 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • Example 9 A speaker was installed in the same manner as in Example 1.
  • a two-fluid conical spray nozzle was installed in the same manner as in Example 9. While conveying the coating film at 5 m / min, a sound wave vibration having a frequency of 10,000 Hz was applied through air for 10 seconds by the same speaker method as in Example 1, and in the same manner as in Example 9, An application amount of IPA (isopropyl alcohol), which is a poor solvent, was sprayed for 10 seconds at a wind speed of 5 m / second with respect to the dispersant (glucose and HTAB) in the coating film.
  • IPA isopropyl alcohol
  • Example 16 In Example 1, a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • Example 13 A speaker was installed in the same manner as in Example 1. At the same time, a poor solvent filling box was installed in the same manner as in Example 13. While conveying the coating film at 5 m / min, a sound wave vibration having a frequency of 10,000 Hz was applied through air for 10 seconds by the same speaker method as in Example 1, and in the same manner as in Example 13, IPA (isopropyl alcohol), which is a poor solvent, was applied to the dispersant (glucose and HTAB) in the coating film for 10 seconds at an application amount of 100 g / min.
  • IPA isopropyl alcohol
  • Example 17 a conductive layer was produced in the same manner as in Example 7 except that the conductive nanoparticle aggregation step was performed by the method described below.
  • Example 7 In the same manner as in Example 7, an ultrasonic transmitter was installed on the bottom surface of the water tank. At the same time, a two-fluid conical spray nozzle was installed in the same manner as in Example 9. While conveying the coating film at 5 m / min, 28 kHz ultrasonic vibration was applied for 10 seconds through water and a substrate by the same ultrasonic method as in Example 7, and Example In the same manner as in No. 9, IPA (isopropyl alcohol), which is a poor solvent, was sprayed on the dispersant (glucose and HTAB) in the coating film for 10 seconds at an application rate of 50 g / min and a wind speed of 5 m / sec.
  • IPA isopropyl alcohol
  • Example 9 Using the film having a conductive layer containing silver nanowires produced in Examples 9 to 17, the transmittance and the surface resistance value were measured in the same manner as in Example 1. For the films of Examples 9 to 17, 10 samples were prepared, and evaluation was performed based on the average value of these samples. The conditions of Examples 9 to 17 are shown in Table 2 below, and the results are shown in Table 3 below.
  • the method for manufacturing a conductive structure and the apparatus for manufacturing the same according to the present invention have high conductivity and transparency. Therefore, the conductive structure manufactured by the conductive structure manufacturing method and / or the manufacturing apparatus thereof according to the present invention is, for example, a transparent conductor, touch panel, electronic paper, antistatic material, and display charging as a substitute for ITO.

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Abstract

La présente invention concerne un processus de production facile et efficace d'une couche contenant des nanoparticules, un fluide de revêtement contenant des nanoparticules et un dispersant et les nanoparticules présentant une dispersibilité suffisante, ladite couche étant utilisée pour former un film de revêtement régulier, et le dispersant adsorbé sur les nanoparticules en étant séparé dans le film de revêtement pour réduire la dispersibilité. Ainsi, le nombre de points de contact entre nanoparticules peut être augmenté et, dans la couche contenant des nanoparticules obtenue par séchage, les nanoparticules peuvent être en contact dense les unes avec les autres. L'invention concerne également un dispositif de production de la couche contenant des nanoparticules. Ce processus de production d'une couche contenant des nanoparticules est caractérisé par le fait qu'il comprend une étape de formation de film de revêtement au cours de laquelle un fluide de revêtement contenant des nanoparticules et contenant au moins des nanoparticules et un dispersant destiné à disperser les nanoparticules est appliqué sur un substrat pour former un film de revêtement et une étape d'agrégation de nanoparticules au cours de laquelle les nanoparticules sont agrégées dans le film de revêtement au moyen d'un traitement au cours duquel une vibration sonore est amenée à se propager vers le film de revêtement et/ou d'un traitement au cours duquel un solvant lent pour le dispersant est ajouté au film de revêtement.
PCT/JP2012/057841 2011-03-31 2012-03-27 Processus et dispositif de production d'une couche contenant des nanoparticules et processus et dispositif de production d'une structure électroconductrice WO2012133355A1 (fr)

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US20180338396A1 (en) * 2017-05-16 2018-11-22 Murata Manufacturing Co., Ltd. Electronic component having electromagnetic shielding and method for producing the same
CN111511476B (zh) 2017-12-22 2022-05-03 富士胶片株式会社 成膜方法

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