JP2012216411A - Method of manufacturing nanoparticle-containing layer and device of manufacturing the same, method of manufacturing conductive structure and device of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple and efficient method of manufacturing a nanoparticle-containing layer and a device of manufacturing the same by which a dispersant adsorbed to nanoparticles is separated to reduce the dispersibility and increase contact points of the nanoparticles in a uniform coating film formed by using a coating liquid containing the nanoparticles and the dispersant and having a good dispersibility of the nanoparticles, and make the nanoparticles be contacted tightly with each other in a nanoparticle-containing layer after drying, and to provide a method of manufacturing a conductive structure having excellent conductivity and transparency and a device of manufacturing the same by which the contact points of nanoparticles having conductivity are increased to form a network of the conductive nanoparticles.SOLUTION: A method of manufacturing a nanoparticle-containing layer includes: a coating film formation step of coating nanoparticle-containing coating liquid at least containing nanoparticles 30a and 30b and a dispersant 31 for dispersing the nanoparticles to a base material to form a coating film; and a nanoparticle aggregation step of aggregating the nanoparticles in the coating film by at least any one of processing for giving the coating film sonic vibration and processing for giving the coating film poor solvent for the dispersant.

Description

  The present invention relates to a method for manufacturing a nanoparticle-containing layer and an apparatus for manufacturing the same, and a method for manufacturing an electroconductive structure and an apparatus for manufacturing the same.

  The technology 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. It is used in various fields such as fields. In order to uniformly apply the nanoparticles, efforts have been made to increase the dispersibility of the nanoparticles in the coating solution. In recent years, a dispersant has been added to the coating solution as a method to increase the dispersibility of the nanoparticles in the coating solution. It has become essential.

However, when 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.
For example, when 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. Therefore, when the contact between the conductive nanoparticles is inhibited by the dispersant, there is a problem that the conductivity is lowered.

To solve this problem, 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 A method for producing a polymer film has been proposed (see Patent Document 1).
However, in this proposed method, 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. Furthermore, in order to form an aggregate of metal fine particles in the liquid, a container for storing the liquid is necessary, which is unsuitable for producing a large-sized film and has a problem of lack of mass productivity.

Further, as a method for directly producing an aggregate of particles on a substrate, 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).
However, although 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.

  Therefore, in a uniform coating film containing a nanoparticle and a dispersant and formed using a coating solution with good dispersibility of the nanoparticles, 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.

JP 2011-16953 A JP 2006-159166 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a uniform coating film formed using a coating solution containing nanoparticles and a dispersant and having good dispersibility of the nanoparticles. 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, forming a network of conductive nanoparticles by increasing the number of contacts between the conductive nanoparticles, conductivity and transparency An object of the present invention is to provide a method for manufacturing a conductive structure and an apparatus for manufacturing the same.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, 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. Including a nanoparticle aggregation step, in a uniform coating film containing a nanoparticle and a dispersant, and formed using a coating solution having good dispersibility of the nanoparticles. Separation of the dispersant adsorbed on the particles can lower the 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. A good nanoparticle-containing layer Rukoto, and when the nanoparticles are conducting nanoparticles, and knowledge to be able to produce a conductive structure which is excellent in conductivity and transparency, and have completed the present invention.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A coating film forming step of forming a coating film by applying a nanoparticle-containing coating solution containing at least nanoparticles and a dispersing agent for dispersing the nanoparticles to a substrate, and applying a sonic wave to the coating film And a nanoparticle aggregation step of aggregating the nanoparticles in the coating film by at least one of a treatment for imparting vibration and a treatment for imparting a poor solvent for the dispersant to the coating film. This is a method for producing a nanoparticle-containing layer.
<2> The method for producing a nanoparticle-containing layer according to <1>, wherein the treatment for imparting sonic vibration is a treatment for imparting the sonic vibration to the coating film via air from the coating surface side of the coating film. It is.
<3> The method for producing a nanoparticle-containing layer according to <2>, wherein the frequency of the sound wave vibration is 100 Hz or more in the treatment of applying sound wave vibration to the coating film via air.
<4> The process according to <1>, wherein the treatment for imparting sonic vibration is a treatment for imparting the sonic vibration to the coating film via at least one of the substrate and liquid from the substrate side of the coating film. This is a method for producing a nanoparticle-containing layer.
<5> The method for producing a nanoparticle-containing layer according to <4>, wherein the ultrasonic vibration includes an ultrasonic component in the treatment of applying the ultrasonic vibration to the coating film through at least one of the base material and the liquid. .
<6> A process of imparting a poor solvent to the dispersant is a process of spraying a mist containing the poor solvent on a coating film, and a process of arranging the coating film in a region filled with the mist containing the poor solvent. The method for producing a nanoparticle-containing layer according to <1>, which is any treatment.
<7> The method for producing a nanoparticle-containing layer according to any one of <1> to <6>, further including a drying step of drying the coating film after the nanoparticle aggregation step.
<8> The method for producing a nanoparticle-containing layer according to any one of <1> to <7>, wherein the viscosity of the coating film at 25 ° C. of the nanoparticle-containing coating solution is 10 mPa · s or less.
<9> A coating film forming step of forming a coating film by applying a conductive nanoparticle-containing coating liquid containing at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles to a substrate. Conductive nanoparticle that agglomerates the conductive nanoparticles in the coating film by at least any one of 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. A method for producing a conductive structure comprising: a particle aggregating step; and a drying step of drying a coating film obtained by aggregating the conductive nanoparticles to form a conductive layer.
<10> The method for producing a conductive structure according to <9>, wherein the conductive nanoparticles have an aspect ratio of 10 to 10,000.
<11> The method for producing a conductive structure according to any one of <9> to <10>, wherein the surface resistance value of the conductive layer is 0.1Ω / □ to 10 ³ Ω / □.
<12> The conductive structure according to any one of <9> to <11>, wherein the conductive nanoparticle is at least one of a metal, a carbon, and a nanoparticle, a nanotube, a nanorod, and a nanohorn. It is a manufacturing method of a thing.
<13> A coating-film forming means for forming a coating film by applying a nanoparticle-containing coating liquid containing at least nanoparticles and a dispersant for dispersing the nanoparticles to a substrate, and sonication on the coating film A nanoparticle aggregating means for aggregating the nanoparticles in the coating film by at least one of a sound wave vibration imparting body that imparts vibration, and a poor solvent imparting body that imparts a poor solvent for the dispersant to the coating film; It is a manufacturing apparatus of the nanoparticle content layer characterized by having.
<14> The apparatus for producing a nanoparticle-containing layer according to <13>, wherein the sound wave vibration imparting body is either a speaker or an ultrasonic transmitter.
<15> A coating film forming means for forming a coating film by applying a conductive nanoparticle-containing coating solution containing at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles to a substrate. The conductive nanoparticles are agglomerated in the coating film by at least one of 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. An apparatus for producing a conductive structure, comprising: a conductive nanoparticle aggregating means for drying; and a drying means for drying the coating film on which the conductive nanoparticles are agglomerated to form a conductive layer.

<16> The method for producing a nanoparticle-containing layer according to any one of <1> to <8>, wherein the substrate has elasticity.
<17> The method for producing a nanoparticle-containing layer according to any one of <1> to <8> and <16>, wherein the substrate has light transmittance.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and a coating liquid containing nanoparticles and a dispersant and having good dispersibility of the nanoparticles is used. In a uniform coating film, the dispersing agent adsorbed on the nanoparticles can be separated in the coating film to reduce the dispersibility and increase the contact between the nanoparticles. In the nanoparticle-containing layer after drying, Nanoparticle-containing layer production method and production apparatus for nanoparticle-containing layer that can be intimately contacted with each other, and its production efficiency, and the nanoparticles are conductive nanoparticles, and increase the number of contacts between the conductive nanoparticles By forming a network of conductive nanoparticles, a method for manufacturing a conductive structure and a manufacturing apparatus therefor can be provided that are excellent in conductivity and transparency.

FIG. 1A is a schematic explanatory view schematically showing an example of a top view of an application surface 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 diagram schematically showing an example of a state after conducting the conductive nanoparticle aggregation step in FIG. 1B. 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 coating 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.

(Method for producing nanoparticle-containing layer, device for producing nanoparticle-containing layer, method for producing conductive structure, and device for producing conductive structure)
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 layer of the present invention includes 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, and the drying step can be It can be suitably performed by a drying means.

Hereinafter, 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.
In 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.

<Coating film forming process, coating film forming means>
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 >>
The 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 | limiting in particular as said nanoparticle, According to the objective, it can select suitably, For example, 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 | limiting in particular as an inorganic material which comprises the said inorganic nanoparticle, According to the objective, it can select suitably, For example, 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.

  There is no restriction | limiting in particular as said metal, According to the objective, it can select suitably. 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 2-14 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 to include it as a main component.

Specific examples of 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.
Among these, 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.

  There is no restriction | limiting in particular as said metal oxide, According to the objective, it can select suitably, For example, the said metal oxide etc. are mentioned.

The inorganic oxide is not particularly limited and may be appropriately selected depending on the purpose, for _{example, SiO 2, SnO 2, ZnO} , MgO, CaO, SrO, BaO, Al 2 O 3, ZrO 2, Nb ₂ O ₅ , V ₂ O ₅ , TiO ₂ , Sc ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , Ta ₂ O ₅ , HfO, Fe ₂ O ₃ , Fe ₃ O ₄ , Sn ₂ doped In ₂ O ₃ (ITO), Sb doped SnO ₂ (ATO), Zn doped In ₂ O ₃ (IZO), MgIn ₂ O ₄ , CuAlO ₂ , AgInO ₂ , Group 13 element ZnO doped with (B, Al, Ga, In, Tl), ZnO doped with a group 17 element (F, Cl, Br, I), doped with a group 1 element (Li, Na, K, Rb, Cs) Zn , Group 15 elements (N, P, As, Sb, Bi), such as doped ZnO can be cited a.

There is no restriction | limiting in particular as said semiconductor, According to the objective, it can select suitably, For example, IV group semiconductors, such as Si, Ge, SiC, I-VII group semiconductors, such as CuCl, CdS, CdSe, CdTe, ZnS II-VI group semiconductors such as ZnSe and ZnTe, and III-V group semiconductors such as GaN, GaP, GaAs, GaSb, AlN, 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. core nanocrystals core -ZnSe shell, the Si to the core -SiO ₂ shell of - may be a semiconductor having a shell structure.

--Organic nanoparticles--
The organic material constituting the organic nanoparticles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic pigments, organic pigments, carbon, graphite, fullerene, polydiacetylene, polyimide, and the like. Molecular compound pigments; aromatic hydrocarbon pigments (for example, polycyclic aromatic pigments); aliphatic hydrocarbon pigments (for example, aromatic hydrocarbons or aliphatic hydrocarbons having orientation, or aromatic carbonization having sublimation properties) (Meth) acrylic, styrene, (meth) acryl-styrene, fluorine-substituted (meth) acrylic, fluorine-substituted (meth) acryl-styrene-based monomers or ) Polymers.

  As these organic nanoparticles, for example, those described in JP 2006-308880 A, JP 2009-242687 A, and the like can be used.

The shape of the nanoparticles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sphere, a wire, a tube, a rod, a horn, a plate, a thin piece, a torus, a hollow body, a cube, a radial body, etc. Is mentioned. Moreover, the secondary particle which 2 or more of these at least 1 type aggregated may be sufficient. Among these, at least one of a wire, a tube, a rod, and a horn is preferable.
Here, in this invention, 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.

  There is no restriction | limiting in particular as a particle diameter of the said nanoparticle, According to the shape of a nanoparticle, etc., it can select suitably.

-Conductive 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.
Among these, the conductive nanoparticles are particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

--- Metal nanowires--
The metal nanowires are solid conductive nanoparticles made of the metal or metal compound.
There is no restriction | limiting in particular as 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).
The corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, each side of the cross section means a straight line connecting these adjacent corners. In this case, the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners. The sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at the corners, and plasmon absorption may increase, or the transparency may deteriorate due to yellowing or the like.

  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 due to 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 μm or more, more preferably 10 μm or more, and particularly preferably 30 μm or more. preferable. In addition, if 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. Preferably there is. If the average major axis length is less than 5 μm, it may be difficult to form a dense network, or sufficient conductivity may not be obtained.

  Here, 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. In the present invention, 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.

--- Metal nanotubes--
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.
In addition, when the average thickness of the metal nanotube is too thin, the oxidation resistance is deteriorated and the durability may be deteriorated. Therefore, the average thickness is preferably 3 nm or more. When the average thickness exceeds 80 nm, scattering due to metal nanotubes may occur.

There is no restriction | limiting in particular as an average major axis length (average length) of the said metal nanotube, Although it can select suitably according to the objective, 2 micrometers or more are preferable.
There is no restriction | limiting in particular as a hollow rate of the said metal nanotube, Although it can select suitably according to the objective, 30%-500% are preferable, 50%-300% are more preferable, 80%-200% are especially preferable.

  The average minor axis length and the average major axis length of the metal nanotube can be measured by the same method as the average minor axis length and the average major axis length of the metal nanowire.

--Carbon nanotube--
The carbon nanotube (CNT) 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), and in particular, double-walled CNTs are also called double-walled nanotubes (DWNT). In the conductive nanoparticles of the present invention, 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. As the single-layer CTN, it is more preferable to use only separated metal CNTs in terms of transparency and conductivity.
There is no restriction | limiting in particular as a method to isolate | separate said metallic CNT, According to the objective, it can select suitably, For example, known methods, such as agarose gel method and decomposition | disassembly by hydrogen peroxide, etc. are mentioned.

-Aspect ratio-
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. 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.

In the present invention, 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).
There is no restriction | limiting in particular as a measuring method of the said aspect ratio, According to the objective, it can select suitably, For example, the method etc. which measure with an electron microscope etc. are mentioned.
When measuring the aspect ratio of the nanoparticles with an electron microscope, if 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. Further, by measuring the major axis length and minor axis length of the nanoparticles separately, the aspect ratio of the whole nanoparticles can be estimated.
When the nanoparticles are tube-shaped, the outer diameter of the tube is used as the short axis length for calculating the aspect ratio.

  There is no restriction | limiting in particular as content of the said nanoparticle in the said nanoparticle containing coating liquid, Although it can select suitably according to the objective, 1 mass%-90 mass% are preferable, and 3 mass%-70 mass% are preferable. 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.

-Dispersant-
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. For the structure that can be used as the dispersant, for example, the description of “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000) can be referred to.

  Examples of the dispersant 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.

  Examples of the amino group-containing compound 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.

  Examples of the thiol group-containing compound include alkyl thiols such as α-thioglycerol, methyl mercaptan, and ethyl mercaptan; and aryl thiols such as thiophenol, thionaphthol, and benzyl mercaptan.

  Examples of the amino acid include aspartic acid, glutamic acid, cysteic acid, and the like. Examples of the amino acid derivatives include amino acid polymers.

  Examples of the peptide compound 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.

  Examples of the polysaccharide include methyl cellulose, hydroxypropyl cellulose, gelatin, carrageenan, polyvinyl pyrrolidone (PVP), and starch.

  Examples of the polymer compound include polyacrylate, polymethacrylate (for example, poly (methyl methacrylate)), polyacrylic acid, polyacrylonitrile, polyvinyl alcohol, polyester (for example, polyethylene terephthalate (PET), polyester naphthalate, polycarbonate). Etc.), 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 (for example, polypropylene) Pyrene, 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 fluoropolymer (eg, polyvinylidene fluoride, polytetrafluoroethylene (TFE), polyhexafluoropropylene, etc.), fluoro-olefin, Copolymers of hydrocarbon olefins (for example, Lumiflon (registered trademark), etc.), amorphous fluorocarbon polymers or copolymers (for example, CYTOP (registered trademark) manufactured by Asahi Glass Co., Ltd., Teflon manufactured by DuPont) (Registered trademark) AF, etc.), polyethylene oxide, polysaccharides, polyvinyl amine, chitosan, polylysine, polyalginic acid, polyhyaluronic acid, carboxymethyl cellulose, and the like copolymers thereof.

  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. For example, sodium bromide, sodium chloride, iodine Examples thereof include alkali halides such as sodium iodide, potassium iodide, potassium bromide, potassium chloride and potassium iodide.

  Further, 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 using these dispersants in combination 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, an amino group and a bromide. Containing ions or chloride ions, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, stearyltrimethylammonium bromide, stearyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium chloride, dimethyldistearylammonium bromide, dimethyldistearylammonium chloride, Dilauryl dimethyl ammonium bromide, dilauryl dimethyl ammonium chloride De, dimethyl dipalmityl ammonium bromide, dimethyl dipalmityl ammonium chloride.

  Among these, gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, polyalkyleneamine, partial alkyl ester of polyacrylic acid, polyvinylpyrrolidone, polyvinylpyrrolidone copolymer, and HTAB are particularly preferable as the dispersant.

  There is no restriction | limiting in particular as content of the said dispersing agent in the said nanoparticle coating liquid, Although it can select suitably according to the objective, 0.1 mass%-80 mass% are preferable, 0.3 mass% -50 mass% is more preferable. 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-
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water, alcohol solvents, ether solvents, ester solvents, ketone solvents, amide solvents, and nitrile solvents. 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.
Examples of the ester solvent include ethyl acetate and butyl acetate.
Examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N-methyl-2-pyrrolidone, and the like.
Examples of the amide solvent include dimethylformamide and dimethylacetamide.
Examples of the nitrile solvent include acetonitrile and butyronitrile.

These solvents may be used alone or in combination of two or more. In addition, when using 2 or more types together in the said nanoparticle containing coating liquid, it is preferable that a solvent is compatible, without phase-separating.
Moreover, when the said nanoparticle is an electroconductive nanoparticle, it is preferable that a hydrophilic solvent is mainly used as a solvent used for this electroconductive nanoparticle containing coating liquid, and water is especially preferable. When a solvent other than water is contained, it is preferable to use a solvent miscible with water at a ratio of 80% by volume or less with respect to water.

  As the solvent used in combination with 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. By using such an alcohol solvent in combination, it is possible to improve the coating in the coating film forming step and reduce the drying load in the drying step described later. Among these, the alcohol solvent is particularly preferably ethanol or ethylene glycol.

-Other ingredients-
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. In addition, various additives such as a sulfidation inhibitor, a viscosity modifier, and a preservative may be included.

There is no restriction | limiting in particular as said corrosion inhibitor, Although it can select suitably according to the objective, An azole type compound is preferable.
The azole compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, benzotriazole, tolyltriazole, mercaptobenzothiazole, mercaptobenzotriazole, mercaptobenzotetrazole, (2-benzothiazolylthio) ) Acetic acid, 3- (2-benzothiazolylthio) propionic acid, and at least one selected from alkali metal salts, ammonium salts, and amine salts. These may be used alone or in combination of two or more.
When the nanoparticle-containing coating solution contains the corrosion inhibitor, a further excellent rust prevention effect can be exhibited. The corrosion inhibitor may be added directly to the nanoparticle-containing coating solution, or 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 forming, it may be applied by immersing it in a corrosion inhibitor bath.

  In addition, when the said nanoparticle is the said electroconductive nanoparticle, it is preferable that the said electroconductive nanoparticle containing coating liquid does not contain inorganic ions, such as an alkali metal ion, an alkaline-earth metal ion, and a halide ion, as much as possible.

  When the nanoparticles are the conductive nanoparticles, the total content X of components other than the conductive nanoparticles in the conductive layer after the drying step (in the case of only one kind, a single content) and the conductivity There is no restriction | limiting in particular as mass ratio (X / Y) with content Y of a nanoparticle, Although it can select suitably according to the objective, 0.05-3 are preferable and 0.1-1 are more. preferable. When 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. On the other hand, if the mass ratio (X / Y) exceeds 3, there may be a decrease in conductivity due to a decrease in the number of contact points between the conductive nanoparticles, and a deterioration in optical characteristics such as light transmittance.

-Viscosity-
There is no restriction | limiting in particular as a viscosity of the coating film in 25 degreeC after apply | coating the said nanoparticle containing coating liquid to a base material, Although it can select suitably according to the objective, In the case of the said nanoparticle aggregation process The viscosity of the coating film is preferably 10 mPa · s or less, and 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 intended 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.

  When the nanoparticles are the conductive nanoparticles, the electrical conductivity of the conductive nanoparticle-containing coating solution is not particularly limited and can be appropriately selected depending on the purpose.

-Preparation method of nanoparticle-containing coating solution-
There is no restriction | limiting in particular as a preparation method of the said nanoparticle containing coating liquid, According to the material, shape, etc. of a nanoparticle, it can select suitably. For example, when the 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.
Moreover, as a preparation method of metal nanowire, Unexamined-Japanese-Patent No. 2009-215594, Unexamined-Japanese-Patent No. 2009-242880, Unexamined-Japanese-Patent No. 2009-299162, Unexamined-Japanese-Patent No. 2010-84173, Unexamined-Japanese-Patent No. 2010-86714, for example. It is also possible to use the method described in the Japanese Patent Gazette.

The step of adding the dispersant is not particularly limited and may be appropriately selected depending on the purpose. For example, the dispersant is added to a solvent in advance, and the metal nanowire is added in the presence of the dispersant. The metal particles serving as the core of the above may be added, or after preparing the metal particles in a solvent, the dispersant may be added for controlling the dispersion state.
When 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.
Moreover, the shape of the metal nanowire obtained can also be changed with the kind of dispersing agent to be used.

There is no restriction | limiting in particular as said metal complex, Although it can select suitably according to the objective, A silver complex is especially preferable. Examples of the ligand of the silver complex include CN—, SCN—, SO ₃ ² —, thiourea, and ammonia. 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.

  There is no restriction | limiting in particular as a step which adds the said metal complex, Although it can select suitably according to the objective, It is preferable to add after the said dispersing agent. By adding in this order, there is an effect of increasing the proportion of metal nanowires having appropriate diameters and lengths, probably because wire nuclei can be formed with high probability.

There is no restriction | limiting in particular as heating temperature at the time of the said heating, Although it can select suitably according to the objective, 150 degrees C or less is preferable, 20 to 130 degreeC is more preferable, 30 to 100 degreeC is still more preferable, 40 to 90 degreeC is especially preferable. The lower the heating temperature, the lower the nucleation probability and the longer the metal nanowires. If the heating temperature is less than 20 ° C., the metal nanowires are likely to be entangled and the dispersion stability may deteriorate. Moreover, when the said heating temperature exceeds 150 degreeC, the angle | corner of the cross section of metal nanowire may become steep, and the transmittance | permeability by coating-film evaluation may become low.
As needed, you may change temperature suitably in the formation process of metal nanowire. By changing the temperature during the formation process of the metal nanowires, it is possible to improve the monodispersity improvement effect by controlling the nucleation of metal nanowires, suppressing renucleation, and promoting selective growth.

It is preferable to add a reducing agent during the heating. The step of adding the reducing agent may be before or after the addition of the dispersant.
The reducing agent is not particularly limited and can be appropriately selected from those usually used. For example, 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, dextrin, hydroquinone, hydroxylamine, citric acid or salt thereof, succinic acid or salt thereof, ascorbic acid or salt thereof, Examples include 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, and phenetidine.
Examples of the aralkylamine include benzylamine, xylenediamine, and N-methylbenzylamine.
As said alcohol, methanol, ethanol, 2-propanol etc. are mentioned, for example.
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.

Among these, reducing sugars and sugar alcohols are preferable, and glucose is particularly preferable.
Depending on the type of the reducing agent, it may function as a dispersant or a solvent as a function, and can be preferably used as a dispersant or a solvent.

  After forming the metal nanowires, it is preferable to further perform a desalting treatment. The desalting treatment is not particularly limited and can be appropriately selected from known methods according to the purpose. Examples thereof include ultrafiltration, dialysis, gel filtration, decantation, and centrifugation. .

--- Metal nanotubes--
There is no restriction | limiting in particular as a preparation method of the said metal nanotube, You may manufacture by what kind of method, For example, well-known methods, such as US application publication 2005/0056118, etc. can be used.

--Carbon nanotube--
The method for preparing the carbon nanotube is not particularly limited and may be appropriately selected depending on the purpose. For example, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, thermal CVD method, plasma CVD method, Known means such as a vapor phase growth method and a HiPco method in which carbon monoxide is reacted with an iron catalyst at a high temperature and high pressure to grow in a vapor phase can be used.
In addition, the carbon nanotubes obtained by these methods have been highly purified to remove residues such as by-products and catalytic metals by methods such as washing, centrifugal molecules, filtration, oxidation, and chromatography. It is preferable at the point which can obtain a carbon nanotube.

-Application method-
A coating film can be formed by apply | coating the said nanoparticle containing coating liquid on a base material.
The method for applying the nanoparticle-containing coating solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include spin coating, casting, roll coating, flow coating, printing, dip coating. Method, casting film forming method, bar coating method, gravure printing method, die coating method and the like.

<< Base material >>
The shape, structure, size, etc. of the substrate are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a film shape, a sheet shape, a disk shape, and a card shape. It is done. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.
Further, when printed wiring is performed on the substrate, the wiring portion may have pores and fine grooves having an aspect ratio of 1 or more, and the nanoparticle-containing coating solution may be included in these by an inkjet printer or a dispenser. Can also be discharged.

There is no restriction | limiting in particular as said base material, Although it can select suitably according to the objective, What has elasticity and a light transmittance is preferable, Specifically, it describes in following (1)-(3). And so on.
(1) Quartz glass, alkali-free glass, crystallized transparent glass, Pyrex (registered trademark) glass, glass such as sapphire (2) 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 (3) Thermosetting resins such as epoxy resins Among these, the base material is suitable for manufacturing, lightweight, flexible, optical (polarization) (Positive properties) Mer films are preferred, PET film, TAC film, PEN film is particularly preferred.

There is no restriction | limiting in particular as the light transmittance of the said base material, Although it can select suitably according to the objective, 80% or more is preferable, 85% or more is more preferable, and 90% or more is especially preferable. If the light transmittance is less than 80%, the transmittance may be low and may cause a problem in practice.
In the present invention, a substrate that is colored to the extent that the object of the present invention is not hindered can also be used.
The transmittance can be measured using, for example, an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation).

There is no restriction | limiting in particular as thickness of the said base material, Although it can select suitably according to the objective, 1 micrometers-500 micrometers are preferable at an average thickness, 3 micrometers-400 micrometers are more preferable, and 5 micrometers-300 micrometers are especially preferable. When the average thickness is less than 1 μm, the yield may decrease due to the difficulty of handling in the coating film forming process. When the average thickness exceeds 500 μm, the thickness and mass are problematic in portable applications. It may become.
Here, the average thickness of the base material is, for example, observed with a scanning electron microscope (SEM) after the section of the nanoparticle-containing layer or the conductive structure is taken out by microtome cutting, or the nanoparticle-containing layer Or after embedding a conductive structure with an epoxy resin, it can measure by observing the section | slice produced with the microtome with a transmission electron microscope (TEM).
In addition, 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 substrate preferably has a surface subjected to a hydrophilic treatment and is coated with a hydrophilic polymer. Thereby, the applicability | paintability to the said base material of the said nanoparticle containing coating liquid and adhesiveness improve.

  The hydrophilic treatment is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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. It is preferable that the surface tension of the surface of the base material is 30 dyne / cm or more by these hydrophilic treatments.

  The hydrophilic polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include gelatin, gelatin derivatives, casein, agar, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, hydroxy Examples include ethyl cellulose, polyvinyl pyrrolidone, and dextran.

There is no restriction | limiting in particular as thickness at the time of drying of the said hydrophilic polymer layer, Although it can select suitably according to the objective, 0.001 micrometer-100 micrometers are preferable at an average thickness, and 0.01 micrometer-20 micrometers are more preferable. .
In addition, 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.

  It is preferable to increase the film strength by adding a hardener to the hydrophilic polymer layer. The hardener is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aldehyde compounds such as formaldehyde and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; vinyl sulfones such as divinyl sulfone. Compounds; triazine compounds such as 2-hydroxy-4,6-dichloro-1,3,5-triazine; isocyanate compounds described in US 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.
There is no restriction | limiting in particular as drying temperature at the time of the said drying, Although it can select suitably according to the objective, 120 degrees C or less is preferable, 30 to 100 degreeC is more preferable, and 40 to 80 degreeC is especially preferable. .
Further, 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 process, nanoparticle aggregation means>
The nanoparticle aggregation step is performed by at least one of a treatment for imparting sonic vibration to the coating film formed in the coating film formation step and a treatment for imparting a poor solvent for the dispersant to the coating film. In this step, the nanoparticles are aggregated 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.
In the present invention, “aggregation” means that the nanoparticles are directly bonded to each other.

<< Mechanism >>
Here, in the present invention, 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. In the conventional method for producing a nanoparticle-containing layer or the like, when the coating film is dried, the dispersing agent in the coating film influences to inhibit the aggregation of the nanoparticles and increase the contact between the nanoparticles. Therefore, it is difficult to form a good network of nanoparticles after drying, and when the nanoparticles are conductive nanoparticles, there is a problem in that sufficient conductivity and transparency cannot be obtained. there were.
On the other hand, in the method for producing a nanoparticle-containing layer of the present invention, by including the nanoparticle aggregation step, the dispersant adsorbed to the nanoparticle in the coating film can be separated, thereby increasing the contact between the nanoparticles, When this is dried, a network of nanoparticles can be suitably formed. Therefore, when the nanoparticles are conductive nanoparticles, the obtained conductive structure is advantageous in that high conductivity and transparency can be obtained.

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 of a coating surface of a coating film, and FIGS. 1B and 1C are enlarged cross-sectional views of a portion surrounded by a broken line in FIG.
In FIG. 1A, 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). When the portion surrounded by the broken line is enlarged, it is as shown in FIG. 1B. In FIG. 1B, the metal nanowire 30a is a cross-sectional view in the long axis length direction, and the metal nanowire 30b is a cross-sectional view in the short axis length direction, to which the dispersant 31 is bonded. As shown in FIG. 1B, normally, in the coating film before drying, 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.
When 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. 1C, 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.

<< Process for imparting sonic vibration, sonic vibration imparting body >>
The treatment for imparting sonic vibration (hereinafter sometimes referred to as “sonic vibration provision treatment”) is a treatment for agglomerating the nanoparticles in the coating film by imparting sonic vibration to the coating film. . This process is preferably performed by the sonic vibration imparting body.
In the sonic vibration applying treatment, the dispersing agent adsorbed on the nanoparticles is separated by the vibrations of the nanoparticles and the dispersing agent due to the sonic vibration, 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. For example, air, liquid , Solids and the like.

-Treatment for applying sonic vibration through air-
In the treatment for applying sonic vibration through the air, the surface for applying sonic vibration in the coating film is not particularly limited and may be appropriately selected according to the purpose. It is preferable to apply sonic vibration from the coated surface of the coating solution (the surface opposite to the side in contact with the substrate of the coating film).

  In the process of applying the sonic vibration through the air, the traveling direction of the sonic vibration is not particularly limited and can be appropriately selected according to the purpose. When (degree of application and horizontal direction) is 0 °, it is preferably more than 0 ° and not more than 90 ° from the application surface, more preferably 60 ° to 90 °, and particularly 90 ° (direction perpendicular to the application surface). preferable.

  There is no restriction | limiting in particular as the frequency of the said sonic vibration in the process which provides sonic vibration via the said air, Although it can select suitably according to the objective, 100 Hz or more is preferable and 100 Hz-10,000 Hz are more preferable. . When the frequency is less than 100 Hz, sufficient sonic vibration cannot be applied to the coating film, so that the contacts between the nanoparticles cannot be increased, and the nanoparticles are conductive nanoparticles. The conductivity of the conductive structure may be lowered. On the other hand, when the frequency exceeds 10,000 Hz, the efficiency of imparting vibration to the coating film is adversely affected and the effect may be reduced.

  There is no restriction | limiting in particular as time to provide the sound wave vibration in the process which provides sound wave vibration through the air, Although it can select suitably according to the objective, 3 seconds or more are preferable and 3 seconds-10 seconds Is more preferable. When the time for applying the sonic vibration is less than 3 seconds, sufficient sonic vibration cannot be applied to the coating film, so the number of contacts between the nanoparticles cannot be increased, 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 sonic vibration via the air in the nanoparticle-containing layer production apparatus is not particularly limited as long as sonic vibration can be imparted to the coating film, depending on the purpose. For example, a speaker etc. are mentioned. Specifically, 230SM (manufactured by BOSE) or the like can be used as the speaker.

-Treatment of applying sonic vibration through liquid-
In the treatment for applying the sonic vibration through the liquid, the surface for applying the sonic vibration in the coating film is not particularly limited and may be appropriately selected depending on the purpose. Therefore, it is preferable to apply the sonic vibration through at least one of the base material and the liquid.

  There is no restriction | limiting in particular as the frequency of the said sonic vibration in the process which provides a sonic vibration through the said liquid, Although it can select suitably according to the objective, It is preferable that an ultrasonic component is included. The ultrasonic wave generally refers to 16 kHz or more, preferably 28 kHz or more, and more preferably 28 kHz to 40 kHz. When the frequency is less than 16 kHz, sufficient vibration cannot be imparted to the coating film, so that the contact points between the nanoparticles cannot be increased, and the nanoparticles are conductive nanoparticles. , Conductivity may be low.

  There is no restriction | limiting in particular as time to provide the said sonic vibration in the process which provides a sonic vibration through the said liquid, Although it can select suitably according to the objective, 3 seconds or more are preferable and 3 seconds-10 seconds Is more preferable. If the time for applying the sonic vibration is less than 3 seconds, sufficient vibration cannot be applied to the coating film, so that the contacts between the nanoparticles cannot be increased, and the nanoparticles are not conductive nano-particles. In the case of particles, the conductivity may be lowered. 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 sonic vibration via the liquid is not particularly limited as long as it can impart sonic vibration to the coating film, and can be appropriately selected according to the purpose. And an ultrasonic transmitter. Specific examples of the ultrasonic transmitter include NL series such as NL-300, NL-600, NL-900, NL-1200, NK-1800, NL-2400, and transducer units (hereinafter referred to as Nippon Alex). Etc.) can be used.

In the process of applying sonic vibration through the liquid, as a method of applying sonic vibration through at least one of the base material and the liquid from the base material side of the coating film, for example, a super Install a sound wave vibration imparting body such as a sound wave transmitter, fill the water tank with liquid, and contact the water surface with the substrate side of the substrate having the coating film (the side in contact with the substrate of the coating film) And a method of applying a potential to the sonic vibration applicator. When the nanoparticle-containing coating solution is incompatible with the liquid in the water tank, the coating film is immersed in the liquid together with the substrate, and sonic vibration is applied from the substrate side through the substrate. At the same time, sonic vibration can be applied to the coating film via the liquid in contact with the coating film.
There is no restriction | limiting in particular as said liquid, According to the solvent etc. in the said nanoparticle containing coating liquid, it can select suitably, For example, water, an organic solvent, etc. are mentioned. For example, when the coating film itself is immersed in a liquid in a water tank, and the coating film is mainly formed of a water-soluble solvent, the liquid in the water tank is phase-separated from the water-soluble solvent. Such organic solvents are preferred.

  The arrangement and number of the sonic vibration imparting bodies in the nanoparticle aggregating step are 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 vibration can be applied.

  Moreover, when 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, it is the width direction (it is perpendicular | vertical with respect to a conveyance direction) of a coating film. One or a plurality of sonic vibration imparting bodies may be arranged in the direction), and sonic vibration may be sequentially imparted to the longitudinal direction of the coating film while transporting the coating film (the same direction as the transport direction). At this time, a plurality of the sound wave vibration imparting bodies may be arranged in the transport direction.

<< Process for imparting poor solvent, poor solvent imparting substance >>
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.
In the present invention, the poor solvent for the dispersant (hereinafter sometimes simply referred to as “poor solvent”) means a solvent having low solubility in the dispersant.
In the poor solvent application treatment, the coating film made of the nanoparticle-containing coating liquid and the poor solvent for the dispersant in the coating film are mixed together, and the poor solvent and the dispersant in the coating film are in contact with each other. Since the agent leaves 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.

  Specific examples of 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, nonane and the like.
Examples of the chlorinated paraffinic solvent include carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, methylene chloride, ethyl chloride, butyl chloride, and propyl chloride.
Examples of the chlorinated aromatic hydrocarbon solvent include 1-chloronaphthalene, o-dichlorobenzene, m-dichlorobenzene, and the like.
Examples of the linear ether solvent 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 chloroolefin 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.
Examples of the ester solvent 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. .
Examples of the nitrogen-containing compound include acetamide, acetonitrile, diethylamine, diisopropylamine, ethylamine, ethylenediamine, hydrazine, nitromethane, piperidine, propylamine, pyridine, N, N, N ′, N′-tetramethylethylenediamine, triethylamine, acrylonitrile. Aniline, diisopropylethylamine, dimethylacetamide, dimethylaniline, N, N-dimethylformamide, formamide, N-methylpyrrolidone, morpholine, nitrobenzene, quinoline and the like.

  When the dispersant is, for example, hexadecyl-trimethylammonium bromide (HTAB), glucose or the like, the poor solvent is preferably an ether organic solvent, a ketone organic solvent, an alcohol organic solvent or the like.

  There is no restriction | limiting in particular as a state of this poor solvent at the time of providing the said poor solvent, According to the objective, it can select suitably, For example, liquid form, mist form, dip form etc. are mentioned. Among these, 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”), and treatment for disposing the coating film in an area filled with the mist containing the poor solvent (hereinafter referred to as “mist filling treatment”). Any one of the treatments is preferred.

-Mist spraying process-
The mist spraying process is a process of spraying the mist containing the poor solvent onto the coating film.
In the mist spraying process, the spraying direction for spraying the mist is not particularly limited and can be appropriately selected according to the purpose. The application surface is a reference surface, and the reference surface (horizontal with the application surface) is used. When the direction is 0 °, it is preferably greater than 0 ° and 90 ° or less from the coated surface, more preferably 60 ° to 90 °, and particularly preferably 90 ° (direction perpendicular to the coated surface).

  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. If the applied amount is less than 20 g / min, a sufficient amount of poor solvent cannot be applied to the coating film, so that the contacts between the nanoparticles cannot be increased, and the nanoparticles are not conductive nano-particles. In the case of particles, the conductivity may be lowered. Moreover, even if 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.

  In the mist spraying process, the wind speed on the coated surface 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 / sec to 5 m / sec 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 / sec, the coated surface may be rough and the original function may be reduced.

  There is no restriction | limiting in particular as spraying time which sprays the said mist in the said mist spraying process, Although it can select suitably according to the objective, 5 seconds or more are preferable and 5 seconds-10 seconds are more preferable. When the spraying time is less than 5 seconds, a sufficient amount of poor solvent cannot be applied to the coating film, so that the contact 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 the mist containing the poor solvent can be sprayed onto the coating film, and can be appropriately selected according to the purpose. For example, spray, nozzle, etc. Is mentioned.

-Mist filling process-
The said mist filling process is a process which arrange | positions the said coating film in the area | region where the mist containing the said poor solvent is filled. 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. For example, the coating film is disposed. And a box-shaped container that can be filled with a certain amount of a mist of a poor solvent for a certain period of time.

  There is no restriction | limiting in particular as a filling rate of the mist containing the said poor solvent in the said poor solvent provision body, Although it can select suitably according to the objective, 20 volume% or more is preferable at 60 degreeC, and 40 volume%-80 Volume% is more preferable. When the filling rate is less than 20% by volume, a sufficient amount of poor solvent cannot be imparted to the coating film, so 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.

  There is no restriction | limiting in particular as time to provide the said poor solvent to the said coating film, According to the filling rate of the said poor solvent, the number of the said poor solvent provision bodies, the conveyance speed of the said coating film, etc., it can select suitably. Is preferably 5 seconds or more, and more preferably 5 seconds to 10 seconds.

  There is no restriction | limiting in particular as temperature at the time of performing the said poor solvent provision process, Although it can select suitably according to the kind etc. of a poor solvent, 20 to 80 degreeC is preferable and 30 to 70 degreeC is more preferable. . 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.

  Moreover, when 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, it is the width direction (it is perpendicular | vertical with respect to a conveyance direction) of a coating film. The poor solvent-imparting body may be disposed in the direction), and the sonic vibration may be sequentially applied to the longitudinal direction (the same direction as the transport direction) of the coating film while transporting the coating film. At this time, a plurality of the poor solvent imparting bodies may be arranged in the transport direction.

  In addition, 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. In addition, when using two processes together, each process may be performed separately and may be performed simultaneously.

<Drying process, drying means>
The drying step is a step of drying the coating film after the nanoparticle aggregation step. The drying step is preferably performed by the drying means.
The drying means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include air drying means, heat drying means, hot air drying means, spray drying means, indirect heat drying means, and vacuum reduced pressure drying means. Is mentioned. Moreover, 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.

In the method for producing a nanoparticle-containing layer of the present invention, 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. .
When performing the nanoparticle aggregation step a plurality of times, a sound wave vibration applying process (a process for applying sound wave vibration via air and / or a process for applying sound wave vibration via liquid) and a poor solvent applying process (mist spraying) There is no restriction | limiting in particular also as an order, a combination, and frequency | count of a process and / or a mist filling process), According to the objective, it can select suitably.

<< Conductive structure >>
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.
There is no restriction | limiting in particular as average thickness after drying of the said conductive layer, Although it can select suitably according to the objective, 0.1 micrometer-30 micrometers are preferable, 0.5 micrometer-10 micrometers are more preferable, 1 micrometer-5 micrometers are Particularly preferred. When the average thickness is less than 0.1 μm, the in-plane distribution of conductivity may be nonuniform, and when it exceeds 30 μm, 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 the substrate.
Here, the average thickness is obtained, for example, by observing with a scanning electron microscope (SEM) after embedding a cross section of the conductive structure by microtome cutting or embedding the conductive structure with an epoxy resin. It can be measured by observing a section prepared with a microtome with a transmission electron microscope (TEM).
In addition, 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. Furthermore, when the component which does not contribute largely to electroconductivity other than metal nanowire is included, since this component has absorption, it is not preferable. In particular, when 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.
Moreover, the transmittance | permeability may fall when content of electroconductive nanoparticle exceeds 30 g / m < ² >.
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, 0.1Ω / □ to 10 ³ Ω / □ is preferable. 1Ω / □ to 200Ω / □ is more preferable. In the case of using for antistatic or the like, 10 ⁶ Ω / □ to 10 ⁹ Ω / □ is often used.
The surface resistance can be measured using, for example, a surface resistance meter (Loresta-GP MCP-T600; manufactured by Mitsubishi Chemical Corporation).

  In addition, the thickness of the nanoparticle-containing layer and the content of nanoparticles in the nanoparticle-containing layer in the nanoparticle-containing layer produced by the method and / or the production apparatus for the nanoparticle-containing layer are also particularly limited. However, the thickness and content are the same as those of the conductive layer.

Next, the method for manufacturing the nanoparticle-containing layer of the present invention and the apparatus for manufacturing the same, and the method for manufacturing the conductive structure of the present invention and the apparatus for manufacturing the same will be described in detail with reference to the drawings. It is not limited to this.
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.
Here, the production of the nanoparticle-containing layer is shown as an example, but the conductive structure can be produced in the same manner.

  2 includes a coating film forming unit 12, a speaker 1a, a nanoparticle aggregating unit having an ultrasonic transmitter 1b, a drying unit 76, and the like. The peaker 1a and the ultrasonic wave transmitter 1b are the sound wave vibration imparting body.

In the production line 10 of the nanoparticle-containing layer, 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 unit 12 is provided downstream of the dust remover 74, and a coating film is formed on the base material 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 sonic vibration (indicated by a broken line arrow) is applied to the coating surface of the coating film. . Next, 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 | separate, and the contact of nanoparticles will increase. Next, the coating film is dried by a 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.
Further, a guide roller 68 is provided over almost the entire production line 10 of the nanoparticle-containing layer so as to wrap and support the substrate W and to allow the substrate W to be conveyed. The guide roller 68 is a rotatable roller member, and preferably has a length 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.

  In the same manner as in FIG. 2, after the coating film on which the nanoparticle-containing coating liquid is applied is formed on the substrate W, 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 line arrow) is sprayed on the coating film, and the mist containing the poor solvent is applied to the coating surface of the coating film (mist spraying treatment). Next, the coating film passes through the 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 is further applied from the coating surface side of the coating film. It is given (mist filling process). Thereby, the nanoparticle and dispersing agent in a coating film isolate | separate, and the contact of nanoparticles will increase. Next, the coating film is dried by the drying means 76, and the substrate W on which the nanoparticle-containing layer is formed is wound up in the same manner as in the nanoparticle-containing layer production line 10 of FIG.

  In the example of FIG. 2, 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. Although the example to do was demonstrated, 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.

<Application>
The method for producing the nanoparticle-containing layer and the apparatus for producing the same according to the present invention include a nanoparticle and a dispersant, and in a uniform coating film formed using a coating solution having good dispersibility of the nanoparticle, In the coating film, the dispersant adsorbed on the nanoparticles can be separated to reduce the dispersibility, increase the contact between the nanoparticles, and intimate contact between the nanoparticles in the nanoparticle-containing layer after drying Thus, a network of nanoparticles can be formed. When the said nanoparticle is the said electroconductive nanoparticle, the electroconductive structure excellent in electroconductivity and transparency can be manufactured by this.
Therefore, 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. For example, 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 absorbing materials, Anti-counterfeiting inks, Electromagnetic wave shielding films, Surface-enhanced fluorescence sensors, Surface-enhanced Raman scattering sensors Marker, recording material, drag Delivery for a drug carrier, biosensors, DNA chips, are widely applied to such test agents.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1
<Preparation of additive>
Additive A, additive G, and additive H were prepared in advance by the method shown below. In addition, the said additive G and the said additive H are 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. Then, 1N ammonia water was added until it became transparent. And pure water was added so that the whole quantity might be 300 mL.

-Preparation of additive solution G-
An additive solution G was prepared by dissolving 1.0 g of glucose powder with 280 mL of pure water.

-Preparation of 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.

<Preparation of silver nanowire aqueous dispersion>
410 mL of pure water was placed in a three-necked flask, and 82.5 mL of additive solution H and 206 mL of additive solution G were added through a funnel while stirring at 20 ° C. (first stage). Next, a total of 206 mL of the additive solution A was added to this solution under the conditions of a flow rate of 2.0 mL / min and a stirring rotation speed of 800 rpm (second stage). After the additive A was added dropwise, the mixture was stirred for 10 minutes, and 82.5 mL of additive H was further added. Next, the temperature was increased to 75 ° C. at 3 ° C./minute, and the stirring rotation speed was heated at 200 rpm for 5 hours to obtain a silver nanowire ammonia dispersion.
Next, 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 obtain 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 | cleaning 10 times, it concentrated until the quantity of mother liquor became 50 mL.

  When 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 μm.

<< Measurement of average minor axis length and average major axis length of silver nanowires >>
The silver nanowires in the silver nanowire aqueous dispersion were observed with a transmission electron microscope (TEM) (JEM-2000FX, manufactured by JEOL Ltd.), and the minor axis length and major axis length were measured. The minor axis length of 300 silver nanowires was the average minor axis length of silver nanowires, and the major axis length of 300 silver nanowires was the average major axis length of silver nanowires.

<Hydrophilic treatment and preparation of undercoat layer>
A commercially available biaxially stretched heat-fixed polyethylene terephthalate (PET) film (thickness: 100 μm, 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 μm.
[Composition of undercoat layer]
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 μm.

<Production of conductive structure>
-Coating film formation process-
The concentrated silver nanowire aqueous dispersion was diluted by adding water to prepare a silver nanowire-containing coating solution. The viscosity which measured the silver nanowire containing coating liquid at this time with the rotary viscometer (Bismetron VDA-2, Shibaura System Co., Ltd.) at 25 degreeC was 5 mPa * s.
The coating amount was adjusted so that the coating silver amount was 0.02 g / m ^2, and applied on the hydrophilic polymer layer by a die coating method.
Moreover, the viscosity of the coating film after apply | coating the silver nanowire containing coating liquid was 5 mPa * s.
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 liquid 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.

-Conductive nanoparticle aggregation process-
For a full range speaker (230SM, manufactured by BOSE), the traveling direction of the sonic vibration from the speaker is the coating surface of the coating film (the surface opposite to the side in contact with the coating film substrate) as the reference surface. When the reference plane (applied surface and horizontal direction) was set to 0 °, it was installed at a position of 90 ° (perpendicular to the applied surface, coating thickness direction) from the applied surface. 4A and 4B are schematic explanatory views of the speaker arrangement. FIG. 4A is a schematic top view of the speaker and the coating film as viewed from the coating surface side of the coating film. FIG. 4B is a cross-sectional view in the width direction of the coating film indicated by AA ′ in FIG. 4A and in the thickness direction of the coating film.
The speaker 1a is arranged at a distance of 50 cm away from the speaker surface S in the thickness direction of the coating film 35 (90 ° direction from the reference surface) from the coating surface (reference surface O) of the coating film 35 on the substrate 36. It was installed such that the direction V of vibration was opposed to the application surface (see FIG. 4B). When the coating direction of the coating film 35 (longitudinal direction of the coating film) L and the direction D (the width direction of the coating film) D perpendicular to the conveyance direction L are set, the distance between the centers of the speakers 1a In the longitudinal direction L of the film and in the width direction D of the coating film, the coating is carried out in a staggered arrangement such that the intervals are 30 cm, the center-to-center distance is equal, and the coating film is alternately arranged in the longitudinal direction. A total of four rows in the longitudinal direction of the membrane were installed (see FIG. 4A).
With a function generator (AFG3011 type, manufactured by Tektronix), 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. Hereinafter, this method may be referred to as a “speaker system”.

-Drying process-
The coating film after the application of vibration was dried at 60 ° C. for 3 minutes to produce a conductive layer.

(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. Subsequently, a conductive layer was produced in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was pre-dried and the conductive nanoparticle aggregation step was performed when the viscosity of the coating film was 8 mPa · s. did.

(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, a conductive layer was prepared in the same manner as in Example 1 except that the conductive nanoparticle aggregation step was pre-dried and the conductive nanoparticle aggregation step was performed when the viscosity of the coating film was 10 mPa · s. did.

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)
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.

-Conductive nanoparticle aggregation process-
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 was accumulated in this water tank to a depth of 40 cm, and this water surface was brought into contact with the base material surface of the coating film (side in contact with the base material of the coating film). That is, the distance between the ultrasonic transmitter and the substrate 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.
Ultrasonic vibration of 28 kHz was generated from the ultrasonic wave transmitter, and ultrasonic vibration was applied to the coating film through water and the substrate for 6 seconds while the coating film was conveyed at 5 m / min. Hereinafter, this method may be referred to as “ultrasonic method”.

(Example 8)
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.

(Comparative Example 1)
In 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 | permeability and surface resistance value were measured with the following method using the film which has the electroconductive layer containing the silver nanowire produced in Examples 1-8 and Comparative Examples 1-2. In addition, 10 samples of each of the films of Examples and Comparative Examples were prepared, and evaluation was performed based on an average value of these samples. The results are shown in Table 1 below.

<Transmissivity>
The transmittance | permeability of 400 nm-800 nm of a film was measured using the ultraviolet visible spectrophotometer (UV-2550, Shimadzu Corporation make), and evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: The transmittance is 90% or more, which is a level with no practical problem.
A: The transmittance is 80% or more and less than 90%, which is a level that is not problematic in practice.
Δ: The transmittance is 75% or more and less than 80%, which is a level that is not problematic in practice.

<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 100Ω / □, which is a practically acceptable level.
◯: The surface resistance value is less than 750Ω / □, which is a level with no practical problem.
(Triangle | delta): A surface resistance value is a level which is satisfactory practically less than 1,000 ohms / square.
X: The surface resistance value is 1,000Ω / □ 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.

-Conductive nanoparticle aggregation process-
A two-fluid conical spray nozzle (manufactured by Miri no Ikeuchi) is used as the reference surface when the discharge direction from the nozzle is the coating surface of the coating film (the surface opposite to the side in contact with the coating film substrate) And when the reference plane (the coated surface and the horizontal direction) is 0 °, the coating surface is 90 ° (the direction perpendicular to the coated surface, the thickness direction of the coated film). It was installed at a distance of 30 cm from the coating surface. At this time, four nozzles are provided 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 transport direction (width direction of the coating film). A total of 16 pieces were installed in 4 rows in the longitudinal direction.
While transporting the coating film at 5 m / min, IPA (isopropyl alcohol), which is a poor solvent for the dispersant (glucose and HTAB) in the coating film, is applied to the coating surface of the coating film from the nozzle at 25 ° C. Then, it was sprayed for 5 seconds at an application rate of 20 g / min and a wind speed of 5 m / sec. Hereinafter, the time for applying the poor solvent may be referred to as “poor solvent application time”.

(Example 10)
In Example 9, 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 the poor solvent-filled box (height: 50 cm, width: 70 cm, length: 50 cm) is set to 60 ° C., and IPA which is a poor solvent for the dispersants (glucose and HTAB) is contained in the box (Isopropyl alcohol) was filled in a mist form. The coating film was passed through this box while being conveyed at 5 m / min, and the poor solvent was applied to the coating film under the conditions of an application amount of the poor solvent of 50 g / min and a poor solvent application time of 10 seconds.

(Example 14)
In Example 13, the application amount of the poor solvent in the conductive nanoparticle aggregation step was changed to 50 g / min, 100 g / min, and the poor solvent application time was changed to 5 seconds, and 10 seconds. A conductive layer was produced in the same manner as in Example 13 except that.

(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.

-Conductive nanoparticle aggregation process-
A speaker was installed in the same manner as in Example 1. 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, in the same manner as in Example 9, while applying sound wave vibration with a frequency of 10,000 Hz through air for 10 seconds in the same speaker system as in Example 1. The application amount of IPA (isopropyl alcohol), which is a poor solvent, to the dispersants (glucose and HTAB) in the coating film was sprayed for 10 seconds at a wind speed of 5 m / sec.

(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.

-Conductive nanoparticle aggregation process-
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, using the same speaker method as in Example 1, applying sonic vibration with a frequency of 10,000 Hz for 10 seconds via air, and simultaneously using the same method as in Example 13. IPA (isopropyl alcohol), which is a poor solvent, was applied to the dispersant (glucose and HTAB) in the coating film at an applied amount of 100 g / min for 10 seconds.

(Example 17)
In Example 7, 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.

-Conductive nanoparticle aggregation process-
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, in the same ultrasonic method as in Example 7, while applying ultrasonic vibration of 28 kHz through water and a substrate for 10 seconds, simultaneously with Example In the same manner as in No. 9, IPA (isopropyl alcohol), which is a poor solvent, was sprayed for 10 seconds at an application rate of 50 g / min and a wind speed of 5 m / sec against the dispersant (glucose and HTAB) in the coating film.

  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. In addition, 10 samples of each of the films of Examples 9 to 17 were prepared, and evaluation was performed based on an 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 manufacturing method and the manufacturing apparatus for the conductive structure of 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. Prevention, antistatic for flexible display, electromagnetic wave shield, electromagnetic wave shield film for plasma display panel, electromagnetic wave shield film for liquid crystal television, optical filter, conductive paste, conductive paint, conductive coating film, circuit material such as wiring material, organic Or electrodes for inorganic EL displays, electrodes for flexible displays, electrodes for solar cells, various electronic materials such as various conductive substrates, catalysts, colorants, inks for inkjet, color materials for color filters, filters, cosmetics , Near infrared absorbing material, anti-counterfeit ink, Wave shielding film, surface-enhanced fluorescence sensor, a surface-enhanced Raman scattering sensor, biological marker, recording materials, drug delivery for drug carriers, biosensors, DNA chips, it is widely applied to such test agents.
Moreover, since the manufacturing method of the said nanoparticle content layer of this invention and its manufacturing apparatus can distribute a nanoparticle in a uniform state in this nanoparticle content layer, it uses suitably for various uses using a nanoparticle. Is possible.

DESCRIPTION OF SYMBOLS 1a Speaker 1b Ultrasonic transmitter 2 Water tank 3a Nozzle 3b Poor solvent filling box 10 Conductive layer production line 11 Backup roller 12 Coating film forming means 20 Conductive layer production line 30 Conductive nanowire 30a Conductive nanowire 30b Conductive nano Wire 31 Dispersant 35 Coating film 36 Substrate 66 Feeder 68 Guide roller 74 Dust remover 76 Drying means 82 Winding machine W Substrate L Transport direction D Width of coating film V Progression direction of sound wave vibration O Reference plane S Speaker surface

Claims (15)

A coating film forming step of forming a coating film by applying a nanoparticle-containing coating liquid containing at least nanoparticles and a dispersant for dispersing the nanoparticles to a substrate;
A nanoparticle aggregating step of aggregating the nanoparticles in the coating film by at least one of a process of imparting sonic vibration to the coating film and a process of imparting a poor solvent for the dispersant to the coating film; The manufacturing method of the nanoparticle content layer characterized by including.   The method for producing a nanoparticle-containing layer according to claim 1, wherein the treatment for imparting sonic vibration is a treatment for imparting the sonic vibration to the coating film via air from the coating surface side of the coating film.   3. The method for producing a nanoparticle-containing layer according to claim 2, wherein in the treatment of applying sonic vibration to the coating film via air, the frequency of the sonic vibration is 100 Hz or more.   2. The nanoparticle-containing composition according to claim 1, wherein the process of imparting sonic vibration is a process of imparting the sonic vibration to the coating film via at least one of the substrate and liquid from the substrate side of the coating film. Layer manufacturing method.   5. The method for producing a nanoparticle-containing layer according to claim 4, wherein in the treatment of applying sonic vibration to the coating film via at least one of the base material and the liquid, the sonic vibration includes an ultrasonic component.   Any of the process which provides the poor solvent with respect to a dispersing agent, the process which sprays the mist containing the said poor solvent on a coating film, and the process which arrange | positions the said coating film in the area | region with which the mist containing the said poor solvent is filled. The method for producing a nanoparticle-containing layer according to claim 1, which is a treatment.   The method for producing a nanoparticle-containing layer according to any one of claims 1 to 6, further comprising a drying step of drying the coating film after the nanoparticle aggregation step.   The method for producing a nanoparticle-containing layer according to any one of claims 1 to 7, wherein the viscosity of the coating film at 25 ° C of the nanoparticle-containing coating solution is 10 mPa · s or less. A coating film forming step of forming a coating film by applying a conductive nanoparticle-containing coating solution containing at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles to a substrate;
Conductive nanoparticles for aggregating the conductive nanoparticles in the coating film by at least one of 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 An aggregation process;
A drying step of drying the coating film in which the conductive nanoparticles are aggregated to form a conductive layer, and a method for producing a conductive structure.   The method for producing a conductive structure according to claim 9, wherein the conductive nanoparticles have an aspect ratio of 10 to 10,000. The method for producing a conductive structure according to claim 9, wherein the conductive layer has a surface resistance value of 0.1Ω / □ to 10 ³ Ω / □.   The method for producing a conductive structure according to any one of claims 9 to 11, wherein the conductive nanoparticles are at least one of metal, carbon, and at least one of nanoparticles, nanotubes, nanorods, and nanohorns. A coating film forming means for forming a coating film by applying a nanoparticle-containing coating liquid containing at least nanoparticles and a dispersant for dispersing the nanoparticles to a substrate;
Nanoparticles that aggregate the nanoparticles in the coating film by at least one of 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. An apparatus for producing a nanoparticle-containing layer.   The apparatus for producing a nanoparticle-containing layer according to claim 13, wherein the ultrasonic vibration imparting body is one of a speaker and an ultrasonic transmitter. A coating film forming means for forming a coating film by applying a conductive nanoparticle-containing coating liquid containing at least conductive nanoparticles and a dispersant for dispersing the conductive nanoparticles to a substrate;
The conductive nanoparticles are aggregated in the coating film by at least one of 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. Conductive nanoparticle aggregation means;
And a drying means for drying the coating film in which the conductive nanoparticles are aggregated to form a conductive layer.