JP5894228B2 - Continuous production method of metal fine particles, conductive curable composition, and electronic device - Google Patents

Description

The present invention uses a method for continuously producing metal fine particles having a plurality of radially projecting conical protrusions, a conductive curable composition comprising the metal fine particles and a curable organic resin, and the conductive curable composition. The present invention relates to an electronic device formed by joining electronic components.

The conductive paste made by dispersing silver powder as the conductive particles in the thermosetting resin composition is cured by heating to form a conductive film or a conductive layer. Formation; Formation of electrodes for various electronic components such as resistors and capacitors; Formation of electrodes for various display elements; Formation of conductive film for electromagnetic wave shielding; Chip components such as capacitors, resistors, diodes, memories, and arithmetic elements (CPUs) Bonding to the substrate; Formation of solar cell electrodes, especially solar cell electrodes that cannot be processed at high temperature using amorphous silicon semiconductors; External of chip-type ceramic electronic components such as multilayer ceramic capacitors, multilayer ceramic inductors, multilayer ceramic actuators Used to form electrodes.

The conventional metal fine particles for conductive paste are all intended to be electrically connected using point contact on the surfaces of adjacent metal fine particles, so the contact area is small and the binder resin is included The problem that the value of the conduction resistance obtained between the connection conductors was large was observed.
Further, conventional metal fine particles generally have a low conductivity of the conductive paste in a state where the binder resin is included. Therefore, in order to obtain a predetermined conduction resistance between the connecting conductors via the conductive paste, A large amount of fine metal particles had to be added. Therefore, the conventional conductive paste has a problem that the viscosity of the conductive paste is increased and the handling is difficult. In addition, in order to improve the handleability of such conductive paste, there is a problem that the amount of metal fine particles added is excessively limited or a large amount of a diluent such as an organic solvent must be used. It was.

In order to solve such a problem, a metal fine particle having a large number of protrusions, a method for producing the same, and a conductive paste containing metal fine particles having a large number of protrusions are disclosed in Japanese Patent No. 3828787 (Patent Document 1) and Japanese Patent No. 4059486 ( Patent Document 2), JP-A 2003-45227 (Patent Document 3), JP-A 2006-228474 (Patent Document 4), JP-A 2009-144196 (Patent Document 5), JP-A 2007-191786 (Patent Document 6), etc. Proposed.

In Japanese Patent No. 3828787 (Patent Document 1), the main component is silver or nickel, and includes convex portions and concave portions extending radially, and the convex portions and the concave portions are adjacent to each other between adjacent conductive powders. There is disclosed a method for producing conductive powder using a liquid phase reduction method in which a conductive path is formed by fitting and connecting to a metal.
This method for producing conductive powder is based on a batch-type reaction in which a reducing agent is dropped into a metal salt aqueous solution in a container for reduction, and there is a problem that production efficiency is low. Further, there is a problem that the particle shape of the manufactured conductive powder is not stable.

Japanese Patent No. 4059486 (Patent Document 2) includes a radially extending convex portion and a concave portion in the gap between the convex portions, and for crystal growth of silver or nickel as a conductive material therein. A conductive powder characterized by containing silver or nickel containing metal-based particles or ceramic-based particles as the core material.
This conductive powder has the problem that it is necessary to prepare metal-based particles or ceramic-based particles that are the core material of the conductive powder, and to grow silver or nickel crystals around the core material, and the manufacturing procedure is complicated. . Further, there is a problem that the particle shape of the manufactured conductive powder is not stable.

JP-A-2003-45227 (Patent Document 3) discloses a conductive paste containing first conductive particles having a plurality of radial protrusions, and dendritic conductive particles and scale-like particles in addition to the first conductive particles. A conductive paste containing one or more second conductive particles selected from the group consisting of conductive particles and spherical conductive particles is disclosed. Since the first conductive particles are made of metal and the radial protrusions are formed on the surface of the raw metal particles by metal growth, there is a problem that the particle shape is not stable. If the shape (particle diameter, protrusion shape) of the particles is not stable, when the conductive paste is used, there is a problem that clogging may occur in a micro discharge test.

In JP-A-2006-228474 (Patent Document 4), the surface of a substrate fine particle is coated with a conductive film, and the conductive film is a conductive fine particle having protrusions raised on the surface, and the conductive fine particle There are disclosed conductive fine particles characterized in that 70 to 90% of the surface area is covered with raised protrusions. This conductive fine particle is a method in which a core substance is attached to the surface of the substrate fine particle, and the conductive film is coated by electroless plating; after the surface of the substrate fine particle is coated by the electroless plating, the core is coated There is a problem in that it is manufactured by a method in which a substance is adhered and a conductive film is coated by electroless plating, and the manufacturing procedure is very complicated. In addition, there is a problem that the core material forming the protrusion easily falls off from the surface of the substrate fine particles, and furthermore, since the protrusion is small, there is a problem that the contact between the protrusions is not sufficient and the conductivity is low.

Japanese Patent Application Laid-Open No. 2009-144196 (Patent Document 5) has a central part and a plurality of protrusions protruding from the central part in a chestnut-like shape, and has a maximum diameter of 100 nm to 3000 nm. Is disclosed.
The metal particles are prepared by preparing a colloidal aqueous solution of spherical or cylindrical gold particles having a maximum diameter of 20 nm or less, and adding an aqueous solution of chloroauric acid, cetyltrimethylammonium bromide, and sodium hydroxide to the colloidal aqueous solution. It is manufactured by a step A of forming a plurality of protrusions protruding like chestnuts around the spherical gold particles, and a step of taking out the gold particles on which the protrusions are formed after the step A. There is a problem that it is complicated. Moreover, there is a problem that the shape of the manufactured metal particles is not stable.

Japanese Patent Laid-Open No. 2007-191786 (Patent Document 6) integrally has a large number of conical projections having a particle diameter of 0.1 μm to 10 μm and a height lower than ¼ of the particle diameter on the outer surface. A composite material in which nickel powder and its manufacturing method and nickel powder are mixed in a matrix resin is disclosed. However, since it is a batch production method, the production efficiency is low, the conical protrusions are small and short, the CV value of nickel powder is around 200%, and the composite material in which the nickel powder is mixed in the matrix resin is conductive. There is a problem that the property is remarkably low.

In Japanese Patent No. 5126862 (Patent Document 7), the first processing surface and the second processing surface, which are arranged to face each other so as to be able to approach and separate from each other and at least one rotates with respect to the other, A fluid to be treated which is a liquid phase is introduced, and a force for moving the second processing surface away from the first processing surface is generated by the pressure of the fluid to be processed. A gap between the working surface and the second processing surface is maintained at a minute interval, and the fluid to be processed passing between the first processing surface and the second processing surface maintained at the minute interval is a thin film. A method for producing metal fine particles is disclosed in which a fluid is formed, and metal ions and a reducing agent react in the thin film fluid to precipitate metal fine particles. International Publication No. 2012/1224046 (Patent Document 8) also discloses. Although the same method for producing fine metal particles has been disclosed, That the fine metal particles are spherical, an unconscious metallic fine particles having a cone-shaped projection, conditions for depositing the fine metal particles having a cone-shaped projection is not described at all.

Japanese Patent No. 3828787 Japanese Patent No. 4059486 JP 2003-45227 A JP 2006-228474 A JP 2009-144196 A JP 2007-191786 A Japanese Patent No. 5126862 International Publication No. 2012/1224046

The present inventors have found a method for producing metal fine particles without the above-mentioned problems, that is, a method for stably and continuously producing metal fine particles having a plurality of radially protruding conical protrusions on the surface, and as a result, It has been found that by mixing the metal fine particles produced by this method and a curable organic resin, it is possible to obtain a conductive curable composition excellent in dischargeability and cured product conductivity, and the present invention has been completed. It was.

An object of the present invention is a method for continuously producing fine metal particles by reducing a metal salt with a reducing agent, and a plurality of radially projecting conical projections having a side shape in a transmission electron micrograph. Having a triangular cone-shaped projection, the apex angle of the triangle is 10 to 40 degrees, and the plurality of cone-shaped projections are in contact with each other, intimately or in close contact with each other, and have an average particle size of Method for producing metal fine particles having a particle size distribution of 0.01 to 10 μm and having a CV value of 100% or less of metal fine particles continuously and stably in one step, and thus produced metal fine particles And a curable organic resin, and a conductive curable composition with excellent dischargeability and cured product conductivity, and a discrete component, a chip component, and a circuit board using the conductive curable composition Connected electronic components It is to provide an electronic apparatus that is.

This object can be achieved by the following [1] to [17].
[1] A fluid to be treated which is a liquid phase is disposed between a first processing surface and a second processing surface, which are disposed so as to be able to approach and separate from each other and at least one of which rotates relative to the other. And a force for moving the second processing surface away from the first processing surface by the pressure of the fluid to be processed is generated, and by this force, the first processing surface and the second processing surface Between the first processing surface and the second processing surface that are maintained at the minute interval, the fluid to be processed forms a thin film fluid, and the thin film fluid A method for continuously producing metal fine particles in which metal ions and a reducing agent react to precipitate metal fine particles,
The fluid to be treated is composed of at least two fluids to be treated, and the first fluid to be treated is an aqueous medium having a pH in the range of 8 to 13 and containing at least a reducing agent and a pH adjuster. The fluid to be treated is an aqueous medium having a pH of 3 to 7 containing at least a metal salt, and the pH of the first fluid to be treated is 1 to 8 larger than the pH of the second fluid to be treated. Each fluid to be treated is introduced between the first processing surface and the second processing surface through a separate introduction path, and the metal ions are reduced in the thin film fluid having a pH of greater than 5 but not greater than 12. Metal fine particles are deposited, and the metal fine particles have a plurality of radially projecting conical protrusions whose conical protrusions have a triangular side surface shape in a transmission electron micrograph, and the apex angle of the triangle is 10 to 10. 40 degrees, and the plurality of conical protrusions are in contact with each other at their roots Closely closely or in contact, the average particle diameter of 0.01 to 10 [mu] m, wherein the CV value of the particle size distribution of the fine metal particles is less than 100%, the continuous production method of fine metal particles.
[1-1] The metal fine particles are characterized by having four or more conical protrusions whose side surface shape is triangular in the transmission electron micrograph is larger than 1/4 of the average particle diameter. [1] The method for continuously producing fine metal particles according to [1].
[1-2] The cone-shaped projection is described in [1] or [1-1], wherein the height of the cone-shaped projection is 1.1 to 5 times the area circle equivalent diameter at the base of the cone-shaped projection. A continuous production method for metal fine particles.
[1-3] The conical protrusions are polygonal pyramid, conical or elliptical conical, characterized in that the continuous metal fine particles according to [1], [1-1] or [1-2] Manufacturing method.
[2] One or both of the first treated fluid and the second treated fluid further contain a boiling point increasing agent and / or a dispersing agent, [1], [1 -1] or [1-2] A continuous production method of metal fine particles.
[3] The fluid to be treated includes three fluids to be treated, which are a first fluid to be treated, a second fluid to be treated, and a third fluid to be treated. The fluid is an aqueous medium having a pH in the range of 8 to 13 containing at least a reducing agent and a pH adjuster, and the second treated fluid is an aqueous medium having a pH of 3 to 7 containing at least a metal salt. The third treated fluid is an aqueous medium containing at least a dispersant, and the first treated fluid, the second treated fluid, and the third treated fluid are separately introduced. [1], [1-1] or [1], wherein the thin film fluid is introduced between the first processing surface and the second processing surface from the path to form a thin film fluid having a pH greater than 5 but not greater than 12. 1-2] The continuous manufacturing method of the metal microparticles.
[4] The metal salt, reducing agent, and pH adjuster in the fluid to be treated are dissolved in water, water-soluble alcohol, or a mixture of water and water-soluble alcohol, [1] or [3] The method for continuously producing fine metal particles according to [3].
[4-1] The boiling point increasing agent and dispersant in the fluid to be treated are dissolved in water, water-soluble alcohol, or a mixture of water and water-soluble alcohol, according to [2] A continuous production method for metal fine particles.
[5] The metal salt is a nickel salt, iron salt, cobalt salt or chromium salt, and the metal fine particles are nickel fine particles, iron fine particles, cobalt fine particles, or chromium fine particles, [1] to [4] A continuous production method of metal fine particles according to any one of [1-1] and [1-2].
[6] The reducing agent is an organic reducing agent, or an inorganic reducing agent and an organic reducing agent, [1] to [4], [1-1], [1-2] A method for continuously producing metal fine particles according to any one of the above.
[7] The pH adjuster is an organic alkali or acid, an inorganic alkali or acid, or an alkaline or acidic salt, [1] to [4], [1-1], [1-2] The method for continuously producing fine metal particles according to any one of the above.
[8] The method for producing fine metal particles according to [2], [4] or [4-1], wherein the boiling point raising agent is a polyhydric alcohol or a polyether.
[9] The continuous production method of metal fine particles according to [2] or [3], wherein the dispersant is a high / intermediate fatty acid salt, a natural polymer dispersant, or a synthetic polymer dispersant.

[9-1] The metal salt is nickel salt, iron salt, cobalt salt or chromium salt, the metal fine particles are nickel fine particles, iron fine particles, cobalt fine particles or chromium fine particles, and the reducing agent is an organic reducing agent, Or an inorganic reducing agent and an organic reducing agent, wherein the pH adjusting agent is an organic alkali or acid, an inorganic alkali or acid, or an alkaline or acidic salt, [1] To [4], [1-1], [1-2], [4-1] The method for continuously producing fine metal particles according to any one of [4-1].
[9-2] The boiling point increasing agent is polyhydric alcohol or polyether, the metal salt is nickel salt, iron salt, cobalt salt or chromium salt, and the metal fine particle is nickel fine particle, iron fine particle, cobalt fine particle or Fine particles of chromium, the reducing agent is an organic reducing agent, or an inorganic reducing agent and an organic reducing agent, and the pH adjusting agent is an organic alkali or acid, an inorganic alkali or acid, or alkaline or The method for continuously producing fine metal particles according to [2], [4] or [4-1], which is an acidic salt.
[9-3] The dispersant is a high / intermediate fatty acid salt, a natural polymer dispersant or a synthetic polymer dispersant, the metal salt is a nickel salt, iron salt, cobalt salt or chromium salt, and the metal fine particles are , Nickel fine particles, iron fine particles, cobalt fine particles or chromium fine particles, the reducing agent is an organic reducing agent, or an inorganic reducing agent and an organic reducing agent, and the pH adjusting agent is an organic alkali or acid, The method for continuously producing fine metal particles according to [2] or [3], which is an inorganic alkali or acid, or an alkaline or acidic salt.

[10] The thin film fluid before the reaction between the metal ions and the reducing agent has a metal salt concentration of 0.02 to 1.1 mol%, and the reducing agent is the same mol to 90 times the mol of the metal salt. %, [1] to [9], [1-1], [1-2], [4-1], [9-1], [9-2], [9- [3] The method for continuously producing fine metal particles according to any one of [3].
[11] The speed at which one of the first processing surface and the second processing surface rotates with respect to the other is 250 rpm to 3000 rpm, and the minute interval is 0.1 μm to 20 μm. ] To [10], [1-1], [1-2], [4-1], [9-1], [9-2], [9-3] Continuous manufacturing method.
[12] The metal according to [1], [1-1], [1-2] or [5], wherein at least a surface of the metal fine particles is melted by irradiation with an electron beam of 10 keV or more. Continuous production method of fine particles.

[13] (A) [1] to [12], [1-1], [1-2], [4-1], [9-1], [9-2], [9-3] A conductive curable composition comprising metal fine particles produced by any one of the continuous production methods and (B) a curable organic resin.
[13-1] The conductive curable composition according to [13], wherein the curable organic resin (B) is a thermosetting resin.
[13-2] The conductive curable composition according to [13-1], wherein the thermosetting organic resin is a thermosetting epoxy resin.
[14] The conductive curable composition according to [13], [13-1] or [13-2], further comprising (C) a curing agent and / or (D) an adhesion promoter.
[15] (A ¹ ) A plurality of radially projecting conical protrusions having conical protrusions whose side shape in the transmission electron micrograph is a triangle, and the apex angle of the triangle is 10 to 40 degrees The plurality of cone-shaped protrusions are in contact with each other, in close contact with each other, in close contact with each other, have an average particle diameter of 0.01 to 10 μm, and a CV value of the particle size distribution of the metal fine particles of 100% or less. A conductive curable composition comprising certain metal fine particles and (B) a curable organic resin.
[15-1] The metal fine particles are characterized by having four or more conical protrusions whose side shape in the transmission electron micrograph is a triangle having a height higher than 1/4 of the average particle diameter. The conductive curable composition according to [15].
[15-2] [15] or [15-1], wherein the cone-shaped protrusion has a height that is 1.1 to 5 times the equivalent diameter of the area circle of the base of the cone-shaped protrusion. Conductive curable composition.
[15-3] The conductive curable composition according to [15], [15-1], or [15-2], wherein the conical protrusion is a polygonal pyramid, a conical shape, or an elliptical conical shape. Composition.
[15-4] The curable organic resin is a thermosetting organic resin, and the metal fine particles (A ¹ ) are nickel fine particles, iron fine particles, cobalt fine particles, or chromium fine particles, [15] , [15-1] or [15-2].
[15-5] The conductive curable composition according to [15-4], wherein the thermosetting organic resin is a thermosetting epoxy resin.
[16] [15], [15-1], [15-2], [15-3], [15], further comprising (C) a curing agent and / or (D) an adhesion promoter -4] or [15-5].

[17] [13] to [16], [13-1], [13-2], [15-1], [15-2], [15-3], [15-4], [15- 5. An electronic device comprising an electronic component selected from a discrete component, a chip component, and a circuit board using the conductive curable composition according to any one of [5].

According to the method for continuously producing fine metal particles of the present invention, a plurality of radially projecting cone-shaped projections having a cone-shaped projection whose side shape in a transmission electron micrograph is a triangle, the apex angle of the triangle 10 to 40 degrees, the plurality of conical protrusions have their visible bases in contact with each other , the average particle diameter is 0.01 to 10 μm, and the CV value of the particle size distribution of the metal fine particles Can be produced continuously and efficiently in a single step.
Since the conductive curable composition and the conductive curable composition according to the production method of the present invention have a CV value of the particle size distribution of the contained metal fine particles of 100% or less, the discharge property is excellent, and The metal fine particles to be formed have a plurality of radially projecting conical projections whose side shape in the transmission electron micrograph is a triangle, and the apex angle of the triangle is 10 to 40 degrees. The plurality of conical protrusions have excellent conductivity because their visible bases are in contact with each other.
Since the electronic device according to the manufacturing method of the present invention uses the conductive curable composition according to the manufacturing method of the present invention to join the electronic component selected from the discrete component, the chip component, and the circuit board, the reliability is high. high.

FIG. 1 is a schematic perspective view of a metal fine particle production apparatus (A) suitable for carrying out the method for continuously producing metal fine particles of the present invention. FIG. 2 is a schematic longitudinal sectional view of the metal fine particle production apparatus (A). FIG. 3 is a schematic plan view of the metal fine particle production apparatus (A). FIG. 4 is a view of the second processing surface of the metal fine particle manufacturing apparatus (A) as viewed from below. The shaded area is a region H that becomes a reaction chamber. FIG. 5 is a plan view of the first processing surface of the metal fine particle production apparatus (A). FIG. 6 is a schematic perspective view of another metal fine particle production apparatus (B) suitable for carrying out the metal fine particle production method of the present invention. FIG. 7 is a schematic longitudinal sectional view of the metal fine particle production apparatus (B). FIG. 8 is a schematic plan view of the metal fine particle production apparatus (B). FIG. 9 is a schematic longitudinal sectional view showing the concept (C) of the embodiment of the fluid treatment apparatus suitable for carrying out the method for producing metal fine particles. FIG. 10 is a view of the second processing surface of the concept (C) of the embodiment of the fluid processing apparatus suitable for carrying out the method for producing metal fine particles as seen from below. The hatched portion is a region HM that becomes a reaction chamber. FIG. 11 is a schematic longitudinal sectional view showing a concept (D) of another embodiment of a fluid treatment apparatus suitable for carrying out a method for continuously producing fine metal particles. FIG. 12 is a schematic longitudinal sectional view showing a concept (E) of another embodiment of a fluid treatment apparatus suitable for carrying out a method for continuously producing metal fine particles. FIG. 13 is a schematic longitudinal sectional view showing the concept (F) of another embodiment of the fluid treatment apparatus suitable for carrying out the method for continuously producing metal fine particles. FIG. 14 is a scanning electron micrograph (magnification: 3,500 times) of the nickel fine particles produced in Example 1 of the present application. The length of the white line below the photo is 1 μm. FIG. 15 is an enlarged photograph (magnification: 35,000 times) of FIG. The length of the white line below the photo is 100 nm. FIG. 16 is a transmission electron micrograph (magnification: 100,000 times) of the nickel fine particles produced in Example 3 of the present application. The length of the black line below the photo is 200 nm. FIG. 17 is a transmission electron micrograph (magnification: 140,000 times) after the fine nickel particles produced in Example 3 of the present application are irradiated with an electron beam. The length of the black line below the photo is 100 nm. FIG. 18 is a scanning electron micrograph (magnification: 70,000 times) of the nickel fine particles produced in Example 3 of the present application. The length of the white line below the photo is 100 nm. " FIG. 19 is a scanning electron micrograph (magnification: 10,000 times) of nickel fine particles continuously produced in Example 7 of the present application. The length of the white line below the photo is 1 μm. FIG. 20 is a transmission electron micrograph (magnification: 15,000 times) of the nickel fine particles continuously produced in Example 7 of the present application. The length of the white line below the photo is 1 μm. FIG. 21 is obtained by adding a parallel line to the root position of the conical protrusion of the nickel fine particle in FIG. FIG. 22 is a diagram in which a triangular outline is added to the cone-shaped projection of the nickel fine particle in FIG. 16 when viewed from the side.

The method for continuously producing fine metal particles according to the present invention is a novel continuous production method for fine metal particles by a wet reduction method, and is a process in which at least one of them rotates relative to the other, being disposed so as to be close to and away from each other. By adjusting the pH in a thin film fluid formed between the working surfaces, metal ions are reduced with a reducing agent to continuously deposit metal fine particles.

The invention according to claim 1 of the present application reduces the metal ion derived from a metal salt in an aqueous medium, that is, the metal ion generated by dissociation of the metal salt with a reducing agent within a specific pH range, More specifically, the present invention relates to a method for continuously producing fine metal particles, and more specifically, a first processing surface and a second treatment surface that are disposed to face each other so as to be able to approach and leave, and at least one of which rotates relative to the other. A fluid to be treated that is in the liquid phase is introduced between the processing surface and a force for moving the second processing surface away from the first processing surface is generated by the pressure of the fluid to be processed. By this force, the space between the first processing surface and the second processing surface is kept at a minute interval, and the space between the first processing surface and the second processing surface kept at the minute interval is maintained. The to-be-processed fluid passing therethrough forms a thin film fluid, A method for continuously producing fine metal particles in which metal ions and a reducing agent react to precipitate fine metal particles, wherein the fluid to be treated is composed of at least two fluids to be treated, and the first fluid to be treated. The body is an aqueous medium having a pH in the range of 8 to 13 containing at least a reducing agent and a pH adjuster, and the second treated fluid is an aqueous medium having a pH in the range of 3 to 7 containing at least a metal salt. Yes, the pH of the first fluid to be treated is 1 to 8 larger than the pH of the second fluid to be treated, and each fluid to be treated is connected to the first treatment surface and the second treatment fluid from different introduction paths. The metal ions are reduced in the thin film fluid having a pH greater than 5 and less than or equal to 12 to precipitate metal fine particles, and the metal fine particles are a plurality of radially projecting conical protrusions. The side shape in the transmission electron micrograph is a triangle. It has Jo projection, a vertex angle of the triangle is 10 to 40 degrees, conical projections of said plurality of in contact with each other is the root which can be the visual, average particle size 0.01~10μm And a CV value of the particle size distribution of the metal fine particles is 100% or less.

A first processing surface, which is used in the continuous production method of metal fine particles according to claim 1 or claim 3 of the present application, is arranged so as to face each other so as to be able to approach and leave, and at least one of which rotates relative to the other. A force that introduces the fluid to be processed that is in the liquid phase between the second processing surface and moves the second processing surface away from the first processing surface by the pressure of the fluid to be processed. By this force, the space between the first processing surface and the second processing surface is kept at a minute interval, and the first processing surface and the second processing surface kept at the minute interval are maintained. The apparatus for producing metal fine particles in which the fluid to be processed that passes between them forms a thin film fluid, and metal ions and a reducing agent react in the thin film fluid to precipitate metal fine particles "is disclosed in Japanese Patent No. 4534098. According to the metal fine particle production apparatus disclosed in the publication.

The continuous production method of the metal fine particles is preferably in accordance with claim 2 of Japanese Patent No. 4534098, a fluid pressure imparting mechanism for imparting pressure to the fluid to be treated, the first treatment part, and the first treatment part. Rotation that relatively rotates at least two processing parts of the second processing part that is relatively close to and away from the processing part, and the first processing part and the second processing part. At least two processing surfaces, the first processing surface and the second processing surface, are provided at positions facing each other in each processing unit, and each processing surface described above. Constitutes a part of a sealed flow path through which the fluid to be treated having the above-mentioned pressure is continuously flowed, and at least a second treatment among the first treatment portion and the second treatment portion. The use part has a pressure receiving surface, and at least a part of the pressure receiving surface. The second processing surface is constituted by the pressure receiving surface in a direction in which the fluid pressure applying mechanism receives the pressure applied to the fluid to be processed and separates the second processing surface from the first processing surface. A fluid to be treated having the above pressure is continuously passed between the first processing surface and the second processing surface that generate a moving force, can be approached and separated, and are relatively rotated. The fluid to be treated forms a thin film fluid, and metal fine particles are continuously deposited in the thin film fluid.

More preferably, according to Claim 3 of Japanese Patent No. 4534098, the continuous production method of the metal fine particles is a kind of the fluid to be treated to which the pressure is applied from the fluid pressure applying mechanism. And a second processing surface, and an independent separate introduction path through which another kind of fluid to be treated different from the kind of fluid to be treated passes. At least one opening to be communicated is provided in at least one of the first processing surface and the second processing surface, and the other type of fluid to be processed is continuously supplied from the separate introduction path to the both processing surfaces. Introducing between the processing surfaces, and mixing the one kind of fluid to be treated and another kind of fluid to be treated in the thin film fluid, thereby continuously depositing the metal fine particles. And

A fluid treatment apparatus suitable for carrying out the above-described continuous production method of metal fine particles is as described in the paragraph [0046] below.
As shown in FIG. 9, the fluid processing apparatus includes a first processing unit 10M, a second processing unit 20M, a contact pressure applying mechanism 4M, a rotation driving unit, a first introduction unit d1M, 2 includes an introduction part d2M, a fluid pressure application mechanism p1M, a fluid pressure application mechanism p2M, and a case 3M. Although the rotation drive unit is connected to the first processing unit 10M, it is not shown. The side wall and bottom of the case 3M are omitted in FIG.
At least one of the first processing unit 10M and the second processing unit 20M can approach and separate from at least one of the other, and the first processing surface 1M and the second processing surface 2M. Can approach and leave.
In a preferred embodiment, the second processing unit 20M approaches and separates from the first processing unit 10M. Conversely, the first processing unit 10M may approach or separate from the second processing unit 20M, and the first processing unit 10M and the second processing unit 20M may approach each other. -It may be separated.

The first processing unit 10M and the second processing unit 20M rotate relative to the other. Preferably, as shown in FIG. 9, the second processing unit 20M is fixed, and the first processing unit 10M rotates. Alternatively, on the contrary, the first processing unit 10M may be fixed, the second processing unit 20M may rotate, or both may rotate in the opposite direction.

The second processing unit 20M is disposed above the first processing unit 10M, the lower surface of the second processing unit 20M is the second processing surface 2M, and the upper surface of the first processing unit 10M. Is the first processing surface 1M.
The first processing surface 1M and the second processing surface 2M are smooth and, for example, mirror-polished. To improve the mixing efficiency, either the first processing surface 1M or the second processing surface 2M is used. Or there may be shallow grooves or depressions in both.

The first processing portion 10M and the second processing portion 20M are exemplified by metal (for example, sintered metal, wear-resistant steel, metal subjected to hardening treatment, plated metal), and ceramic. Since one or both of the first processing unit 10M and the second processing unit 20M rotate, a lightweight material is desirable.

The contact surface pressure applying mechanism 4M applies a force that acts in a direction in which the first processing surface 1M and the second processing surface 2M approach each other to the second processing unit 20M. In a preferred embodiment, the contact pressure application mechanism 4M is provided between the case 3M and the second processing unit 20M or in the second processing unit 20M, and the second processing unit 20M is used as the first processing unit 10M. Energize towards.
The case 3M is disposed outside the outer peripheral surfaces of the first processing unit 10M and the second processing unit 20M, and is generated in the gap between the first processing surface 1M and the second processing surface 2M. The product discharged outside is stored. The case 3M is a liquid-tight container that accommodates the first processing unit 10M and the second processing unit 20M.
The case 3M is provided with a discharge port 32M for discharging the product outside the case 3M. Note that the side wall, bottom, and discharge port 32M of the case 3M are omitted in FIG.

The first introduction part d1M supplies the first fluid to be processed between the first processing surface 1M and the second processing surface 2M.
The fluid pressure applying mechanism p1M is directly or indirectly connected to the first introduction part d1M, and applies fluid pressure to the first fluid to be processed. A pump such as a compressor may be employed for the fluid pressure imparting mechanism p1M.
In a preferred embodiment, the first introduction part d1M is a passage of the first fluid to be treated provided in the central portion of the second processing part 20M, and one end thereof is the second processing surface 2M. Open at the center position. The other end of the first introduction part d1M is connected to the fluid pressure applying mechanism p1M outside the case 3M.

The second introduction part d2M supplies the second processed fluid between the first processing surface 1M and the second processing surface 2M. In a preferred embodiment, the second introduction part d2M is a passage of the second fluid to be processed provided in the second processing part 20M, and one end thereof opens to the second processing surface 2M. The other end of the second introduction part d2M is connected to the fluid pressure applying mechanism p2M outside the case 3M. A pump such as a compressor may be employed for the fluid pressure imparting mechanism p2M.

The first fluid to be treated that is pressurized by the fluid pressure imparting mechanism p1M is introduced between the first treatment surface 1M and the second treatment surface 2M from the first introduction part d1M, and is used for the first treatment. It passes between the surface 1M and the second processing surface 2M and tries to pass outside. At this time, the first processing surface 1M that has received the pressure of the first fluid to be processed moves away from the second processing surface 2M against the urging force of the contact surface pressure applying mechanism 4M, and the first processing surface 1M A minute gap is provided between the processing surface 1M and the second processing surface 2M.
Here, the first processing surface 1M and the second processing surface 2M are preferably adjusted to a minute interval of 0.1 μm to 100 μm, particularly 0.1 μm to 20 μm, thereby realizing a uniform reaction. At the same time, it is possible to produce metal fine particles of several nanometers.

Between the first processing surface 1M and the second processing surface 2M, the second treated fluid is supplied from the second introduction part d2M, merges with the first treated fluid, and is applied to the second processing part 20M. The mixing and reaction are promoted by the rotation of the first processing unit 10M. Between the first processing surface 1M and the second processing surface 2M, the downstream side of the opening m2M of the second introduction portion d2M is a reaction chamber in which the first processed fluid and the second processed fluid react. (FIG. 10).
With respect to the first fluid to be treated introduced between the first processing surface 1 and the second processing surface 2 from the opening m1M of the first introduction part d1M, the second introduction part d2M has the opening m2M to the second. The second fluid to be processed introduced between the first processing surface 1 and the second processing surface 2 is mixed in the region HM serving as the reaction chamber (FIG. 10).

The fluid to be processed, which has been fed by the fluid pressure applying mechanism p1M, tries to move to the outside through a minute gap between the first processing surface 1M and the second processing surface 2M. Since the first processing portion 10M and the first processing surface 1M are rotating, the mixed fluid to be processed is straight from the inside to the outside in the inner and outer directions of the diameter of the processing surface in the reaction region HM. Instead of moving in a plan view, in a state where the processing surface is viewed in plan, the processing surface is moved from the inside to the outside in a spiral shape around the rotation axis of the processing surface. In this way, in the mixed region HM where the reaction is performed, the reaction moves in a spiral shape from the inside to the outside, so that a sufficient reaction can be achieved at a minute interval between the first processing surface 1M and the second processing surface 2M. A necessary section can be secured and a uniform reaction can be promoted.
The reaction product becomes a homogeneous reaction product, and fine metal particles are deposited. The deposited metal fine particles are considered to be further refined by being sheared with the second processing surface 2M by the rotation of the first processing surface 1M.

At least the first processing surface 1M and the second processing surface 1M are balanced by a balance between the pressure applied by the fluid pressure application mechanism p1M, the urging force of the contact surface pressure application mechanism 4M, and the centrifugal force generated by the rotation of the processing surface. The interval between the processing surfaces 2M can be kept at a preferable minute interval. Further, the fluid to be processed that receives the pressure applied by the fluid pressure applying mechanism p1M and the centrifugal force generated by the rotation of the processing surface causes a minute gap between the first processing surface 1M and the second processing surface 2M. The reaction is promoted by moving in a spiral.

The above reaction is forcibly performed by the pressure supplied by the fluid pressure applying mechanism p1M and the rotation of the processing surface. That is, the reaction is forcibly and uniformly mixed between the first processing surface 1M and the second processing surface 2M, which are arranged so as to be able to approach and separate from each other and at least one of which rotates relative to the other. It happens while.
Therefore, the precipitation of the metal fine particles can be controlled by a method that is relatively easy to control, such as adjusting the feed pressure applied by the fluid pressure applying mechanism p1M and adjusting the rotation speed of the processing surface, that is, the rotation speed.

And the reaction product by reaction of both to-be-processed fluids is discharged | emitted from the 1st process surface 1M and the 2nd process surface 2M to the outer side. The reaction product discharged to the outside is finally discharged from the discharge port 32M to the outside of the case 3M.

In the fluid treatment apparatus, a third introduction unit may exist in addition to the first introduction unit and the second introduction unit. The third introduction portion is a passage of the third fluid to be processed provided in the second processing portion 20M, and one end thereof may open to the second processing surface 2M, or the first This is a passage of the third fluid to be processed provided inside the processing portion 10M, and one end thereof may open to the first processing surface 1M.
Furthermore, the 4th introduction part may exist. The fourth introduction portion is a passage of the fourth fluid to be processed provided in the second processing portion 20M, and one end thereof may open to the second processing surface 2M, or the first This is a passage of the fourth fluid to be processed provided in the processing portion 10M, and one end thereof may open to the first processing surface 1M.

In the fluid processing apparatus, as shown in FIG. 11, instead of the first processing unit 10M and the second processing unit 20M, a first holder 11M having a first ring 10RM and a second ring 20RM having a second ring 20RM are provided. It may consist of two holders 21M.
The second holder 21M is disposed above the first holder 11M, the second ring 20RM is fitted or fixed to the lower surface of the second holder 21M, and the first ring 10RM is disposed on the upper surface of the first holder 11M. Are fitted or fixed. The lower surface of the second ring 20RM is the second processing surface 2M, and the upper surface of the first ring 10RM is the first processing surface 1M. The first processing surface 1M and the second processing surface 2M are smooth and are mirror-polished, for example.
The first processing surface 1M protrudes from the upper surface of the first holder 11M, and the second processing surface 2M protrudes from the lower surface of the second holder 21M.

The first holder 11M provided with the first ring 10RM and the second holder 21M provided with the second ring 20RM have at least one of at least one of the first processing unit 10M and the second processing unit 20M. On the other hand, the first processing surface 1M and the second processing surface 2M can approach and separate from each other.
In a preferred embodiment, the second holder 21M having the second ring 20RM approaches and separates from the first holder 11M having the first ring 10RM. On the contrary, the first holder 11M provided with the first ring 10RM may approach or separate from the second holder 21M provided with the second ring 20RM, and the first holder 10M includes the first ring 10RM. The first holder 11M and the second holder 21M provided with the second ring 20RM may approach or separate from each other.

The first holder 11M provided with the first ring 10RM and the second holder 21M provided with the second ring 20RM rotate relative to the other. Preferably, as shown in FIG. 11, the second holder 21M having the second ring M is fixed, and the first holder 11M having the first ring 10RM rotates. Alternatively, on the contrary, the first holder 11M having the first ring 10RM may be fixed and the second holder 21M having the second ring 20RM may rotate, or both may rotate in the opposite direction. Good.

In the fluid treatment apparatus, as shown in FIG. 12, the first holder 11M including the first ring 10RM and the second treatment unit 20M may be used instead of the first treatment unit 10M. Conversely, as shown in FIG. 13, the first processing unit 10M and a second holder 21M including a second ring 20RM instead of the second processing unit 20M may be included.

In the fluid processing apparatus (FIG. 12) including the first holder 11M having the first ring 10RM instead of the first processing part 10M and the second processing part 20M, the first holder 10M having the first ring 10RM is provided. As with the first processing unit 10M and the second processing unit 20M, at least one of the 1 holder 11M and the second processing unit 20M can approach and separate from at least one of the other. The first processing surface 1M and the second processing surface 2M can approach and separate.
In a preferred embodiment, the second processing portion 20M approaches and separates from the first holder 11M having the first ring 10RM. On the contrary, the first holder 11M provided with the first ring 10RM may approach or separate from the second processing unit 20M, and the first holder 11M provided with the first ring 10RM may be used. And the second processing unit 20M may approach and separate from each other.

The first holder 11M provided with the first ring 10RM and the second processing unit 20M rotate relative to the other. Preferably, as shown in FIG. 12, the second processing unit 20M is fixed, and the first holder 11M including the first ring 10RM rotates. Alternatively, on the contrary, the first holder 11M including the first ring 10RM may be fixed, and the second processing unit 20M may rotate, or both may rotate in the opposite direction.

In the fluid processing apparatus (FIG. 13) including the first processing unit 10M and the second holder 21M having the second ring 20RM instead of the second processing unit 20M, the first processing unit 10M and the second processing unit 10M The second holder 21M equipped with the two rings 20RM can be moved toward and away from at least one of the second processing unit 10M and the second processing unit 20M. The first processing surface 1M and the second processing surface 2M can approach and separate.
In a preferred embodiment, the second holder 21M having the second ring 20RM approaches and separates from the first processing portion 10M. On the contrary, the first processing unit 10M may approach or separate from the second holder 21M having the second ring 20RM, and the first processing unit 10M and the second ring 20RM may be connected to each other. The second holder 21M provided may approach or separate from each other.

The first processing unit 10M and the second holder 21M having the second ring 20RM rotate relative to the other. Preferably, as shown in FIG. 13, the second holder 21M having the second ring 20RM is fixed, and the first processing portion 10M rotates. Alternatively, on the contrary, the first processing unit 10M may be fixed, and the second holder 21M including the second ring 20RM may rotate, or both may rotate in the opposite direction.

Hereinafter, an apparatus for producing metal fine particles suitable for carrying out the method for producing metal fine particles of the present invention will be described.

As shown in FIGS. 1 and 2, the metal fine particle manufacturing apparatus includes a first disk 10, a second disk 20, a contact pressure applying mechanism 4, a rotation driving unit, a first introduction unit d 1, 2 includes an introduction part d2, a first fluid pressure application mechanism p1, a second fluid pressure application mechanism p2, and a case 3. The rotation drive unit is connected to the first disk 10 but is not shown.
At least one of the first disk 10 and the second disk 20 can be approached / separated from at least one of the other. The first processing surface 1 and the second processing surface 2 are I can separate.
In the preferred embodiment, the second disk 20 approaches and separates from the first disk 10. On the contrary, the first disk 10 may approach or separate from the second disk 20, or the first disk 10 and the second disk 20 may approach or separate from each other. .

The first disk 10 and the second disk 20 rotate relative to the other. Preferably, as shown in FIGS. 1 and 2, the second disk 20 is fixed and the first disk 10 rotates. Alternatively, on the contrary, the first disk 10 is fixed, the second disk 20 may rotate, and both may rotate in the opposite direction.

The second disk 20 is disposed above the first disk 10, the lower surface of the second disk 20 is the second processing surface 2, and the upper surface of the first disk 10 is the first processing surface. 1.
The first processing surface 1 and the second processing surface 2 are smooth, for example, mirror-polished, but in order to improve mixing efficiency, either the first processing surface 1 or the second processing surface 2 is used. It is preferable that a groove-like recess 5 exists in both or both.

When the first processing surface 1 having the groove-shaped recess 5 rotates, the fluid in the recess 5 advances at a speed toward the tip in the outer circumferential direction of the recess 5, and then the fluid fed to the tip of the recess 5 Furthermore, the pressure from the inner peripheral direction of the recessed part 5 is received, it finally becomes the pressure in the direction which leaves | separates a processing surface, and a fluid is introduce | transduced between processing surfaces simultaneously. Even if it is not rotating, the pressure received by the fluid in the recess 5 provided on the first processing surface 1 finally acts on the second processing surface 2 as a pressure receiving surface that acts on the separation side. .

The same applies to the case where the second processing surface 2 having the groove-like recess 5 is rotated.
About the recessed part 5 provided in the processing surface, corresponding to the physical property of the fluid containing a reactant and a product, the depth, the total area in the horizontal direction with respect to the processing surface, the number of grooves, and the shape Should be set.
The depth of the recess 5 is preferably 1 μm to 50 μm, more preferably 3 μm to 20 μm. The total area in the horizontal direction with respect to the processing surface is 5% to 50%, preferably 15% to 25%, and the number of grooves is 3 to 50, preferably 8 with respect to the entire processing surface. ~ 24. Examples of the shape include those that extend in a curved or spiral shape on the processing surface and those that are bent in an L shape. Furthermore, you may give the gradient to the depth of a recessed part. Fluid from a high viscosity region to a low viscosity region can be stably introduced between processing surfaces.

Examples of the material of the first disk 10 and the second disk 20 include metals (for example, sintered metal, wear-resistant steel, hardened metal, plated metal), and ceramic. Since one or both of the first disk 10 and the second disk 20 rotate, a lightweight material is desirable.

The contact surface pressure imparting mechanism 4 imparts to the second disk 20 a force that causes the first processing surface 1 and the second processing surface 2 to approach each other. In the preferred embodiment, the contact surface pressure applying mechanism 4 is provided between the case 3 and the second disk 20 or in the second disk 20 and biases the second disk 20 toward the first disk 10. Examples of the contact surface pressure imparting mechanism 4 include a spring and pressurized air.
The case 3 is arranged outside the outer peripheral surfaces of the first disk 10 and the second disk 20, and is generated in the gap between the first processing surface 1 and the second processing surface 2 and outside the outer surface. Contains the product to be discharged. The case 3 is a liquid-tight container that houses the first disk 10 and the second disk 20.
The case 3 is provided with a discharge port 32 for discharging the product outside the case 3.

The first introduction part d1 supplies a first fluid to be processed (for example, an aqueous solution of a reducing agent, a boiling point increasing agent, and a pH adjusting agent) between the first processing surface 1 and the second processing surface 2. .
The fluid pressure applying mechanism p1 is directly or indirectly connected to the first introduction part d1, and applies a fluid pressure to the first fluid to be processed. A pump such as a compressor may be employed for the fluid pressure imparting mechanism p1.
In a preferred embodiment, the first introduction part d1 is a passage of the first fluid to be treated provided in the center portion of the second disk 20, and one end thereof is the center of the second processing surface 2 Open at the position. The other end of the first introduction part d1 is connected to the fluid pressure applying mechanism p1 outside the case 3.

The second introduction part d2 supplies a second fluid to be processed (for example, an aqueous solution of a metal salt and a dispersing agent) between the first processing surface 1 and the second processing surface 2. In a preferred embodiment, the second introduction part d2 is a passage of the second fluid to be processed provided in the second disk 20 and one end thereof opens to the second processing surface 2. The other end of the second introduction part d2 is connected to the fluid pressure applying mechanism p2 outside the case 3. A pump such as a compressor may be employed for the fluid pressure imparting mechanism p2.

The first fluid to be processed, which is pressurized by the fluid pressure imparting mechanism p1, is introduced between the first processing surface 1 and the second processing surface 2 from the first introduction part d1, and is used for the first processing. Passing between the surface 1 and the second processing surface 2,
Trying to go outside.
At this time, the second processing surface 2 that has received the pressure of the first fluid to be processed moves away from the first processing surface 1 against the urging force of the contact surface pressure applying mechanism 4, and the first A minute gap is provided between the processing surface 1 and the second processing surface 2.
Here, the first processing surface 1 and the second processing surface 2 are adjusted to a minute interval of 0.1 μm to 100 μm, particularly 1 μm to 20 μm, thereby realizing a uniform reduction reaction and several It is also possible to produce ultrafine metal particles in nm units.

A second processed fluid (for example, an aqueous solution of a metal salt and a dispersant) is supplied from the second introduction part d2 between the first processing surface 1 and the second processing surface 2, and the first processed fluid is supplied. A body (for example, an aqueous solution of a reducing agent, a boiling point increasing agent, and a pH adjusting agent) joins, and the rotation of the first disk 10 relative to the second disk 20 promotes the mixing and reduction reaction. Between the first processing surface 1 and the second processing surface 2, the downstream side of the opening m2 of the second introduction part d2 is the reducing agent in the first processed fluid and the metal in the second processed fluid. It becomes a reaction chamber in which ions react (FIG. 4).
With respect to the first fluid to be treated introduced between the first processing surface 1 and the second processing surface 2 from the first opening m1, the first processing surface 1 and the second processing fluid are introduced from the second opening m2. The second fluid to be processed introduced between the processing surfaces 2 is mixed in the region H serving as the reaction chamber (FIG. 4).
In view of mixing efficiency, the plurality of openings m2 of the second introduction part d2 are preferably plural on an annular one-dot chain line in FIG. 4, and the plural openings m2 are preferably equidistant from each other.

The fluid to be processed that has been fed by the first fluid pressure applying mechanism p1 and the second fluid pressure applying mechanism p2 is mixed from a minute gap between the first processing surface 1 and the second processing surface 2. However, since the first disk 10 and the first processing surface 1 are rotating, the mixed fluid to be processed has a diameter of the processing surface in the reaction region H. Instead of linearly moving from the inner side to the outer side in the inner and outer directions, the processing surface is moved from the inner side to the outer side in a spiral shape around the rotation axis of the processing surface in a state where the processing surface is viewed in plan. In this way, in the region H where the reaction is performed after mixing, sufficient reduction is achieved in the minute gap between the first processing surface 1 and the second processing surface 2 by moving from the inside to the outside in a spiral shape. A section required for the reaction can be secured, and a uniform reduction reaction can be promoted.
The reaction product becomes a homogeneous reaction product, and fine metal particles are deposited. The deposited metal fine particles are considered to be further refined by being sheared with the second processing surface 2 by the rotation of the first processing surface 1.

At least by the balance between the pressure applied by the fluid pressure application mechanism p1 and the second fluid pressure application mechanism p2, the urging force of the contact surface pressure application mechanism 4, and the centrifugal force due to the rotation of the processing surface. The distance between the first processing surface 1 and the second processing surface 2 can be kept at a preferable minute distance. Further, the fluid to be processed which receives the pressure applied by the fluid pressure applying mechanism p1 and the centrifugal force generated by the rotation of the processing surface causes a minute gap between the first processing surface 1 and the second processing surface 2 described above. Is moved in a spiral to promote the reduction reaction.

The above reduction reaction is forcibly performed by the pressure feeding applied by the fluid pressure applying mechanism p1 and the second fluid pressure applying mechanism p2 and the rotation of the processing surface. That is, the reduction reaction is forcibly and uniformly mixed between the first processing surface 1 and the second processing surface 2 that are arranged so as to be able to approach and separate from each other and at least one rotates relative to the other. It happens while.
Therefore, the precipitation of the metal fine particles can be controlled by a method that is relatively easy to control, such as adjusting the feed pressure applied by the fluid pressure applying mechanism p1 and adjusting the rotation speed of the processing surface, that is, the rotation speed. The supply temperature of the first processed fluid and the second processed fluid may be controlled.

Then, the aqueous medium in which the metal fine particles, which are reaction products resulting from the reaction of the two fluids to be processed, are dispersed is discharged from between the first processing surface 1 and the second processing surface 2 to the outside. The reaction product discharged to the outside is finally discharged from the discharge port 32 to the outside of the case 3.

In the metal fine particle manufacturing apparatus, a third introduction unit may exist in addition to the first introduction unit and the second introduction unit. The third introduction part is a passage for a third fluid to be processed (for example, a dispersant or an aqueous medium containing a dispersant and a pH adjuster) provided in the second disk 20, and one end of the third introducer is a second. It may be open to the processing surface 2 or may be a passage of the third fluid to be processed provided inside the first disk 10, and one end of the passage may be open to the first processing surface 1. Good. Furthermore, a fourth introduction part or the like may exist. The fourth introduction part is a passage of the fourth fluid to be processed provided in the second processing part 20, and one end thereof may open to the second processing surface 2, or the first It is a passage of the second fluid to be processed provided inside the disk 10, and one end thereof may be open to the first processing surface 1.

In the metal fine particle manufacturing apparatus, in accordance with the fluid processing apparatus shown in FIG. 11, instead of the first disk 10 and the second disk 20, a first holder 11M and a second ring 20RM each having a first ring 10RM are provided. It may consist of the second holder 21M provided.
The second holder 21M is disposed above the first holder 11M, the second ring 20RM is fitted or fixed to the lower surface of the second holder 21M, and the first ring 10RM is disposed on the upper surface of the first holder 11M. Are fitted or fixed. The lower surface of the second ring 20RM is the second processing surface 2M, and the upper surface of the first ring 10RM is the first processing surface 1M. The first processing surface 1M and the second processing surface 2M are smooth and are mirror-polished, for example.
The first processing surface 1M protrudes from the upper surface of the first holder 11M, and the second processing surface 2M protrudes from the lower surface of the second holder 21M.

As with the first disk 10 and the second disk 20, the first holder 11M having the first ring 10RM and the second holder 21M having the second ring 20RM have at least one of them at least one of the other, The first processing surface 1M and the second processing surface 2M can approach and separate from each other.
In a preferred embodiment, the second holder 21M having the second ring 20RM approaches and separates from the first holder 11M having the first ring 10RM. On the contrary, the first holder 11M provided with the first ring 10RM may approach or separate from the second holder 21M provided with the second ring 20RM, and the first holder 10M includes the first ring 10RM. The first holder 11M and the second holder 21M provided with the second ring 20RM may approach or separate from each other.

The first holder 11M provided with the first ring 10RM and the second holder 21M provided with the second ring 20RM rotate relative to the other. Preferably, according to the fluid treatment apparatus shown in FIG. 11, the second holder 21M having the second ring 20RM is fixed, and the first holder 11M having the first ring 10RM rotates. Alternatively, on the contrary, the first holder 11M having the first ring 10RM may be fixed and the second holder 21M having the second ring 20RM may rotate, or both may rotate in the opposite direction. Good.

According to the fluid processing apparatus shown in FIG. 12, the metal fine particle manufacturing apparatus includes a first holder 11M having a first ring 10RM instead of the first disk 10 and a second processing section 20M. May be. Conversely, according to the fluid processing apparatus shown in FIG. 13, the first processing unit 10 </ b> M and the second holder 21 </ b> M including the second ring 20 </ b> RM instead of the second disk 20 may be included.

In accordance with the fluid processing apparatus shown in FIG. 12, which includes a first holder 11M having a first ring 10RM instead of the first disk 10 and a second processing unit 20M, a first having a first ring 10RM is provided. As with the first disk 10 and the second disk 20, the holder 11M and the second processing part 20M are capable of approaching / separating from at least one of them, and the first processing surface. 1M and the 2nd process surface 2M can approach and separate.
In a preferred embodiment, the second processing portion 20M approaches and separates from the first holder 11M having the first ring 10RM. On the contrary, the first holder 11M provided with the first ring 10RM may approach or separate from the second processing unit 20M, and the first holder 11M provided with the first ring 10RM may be used. And the second processing unit 20M may approach and separate from each other.

The first holder 11M provided with the first ring 10RM and the second processing unit 20M rotate relative to the other. Preferably, according to the fluid processing apparatus shown in FIG. 12, the second processing unit 20M is fixed, and the first holder 11M including the first ring 10RM rotates. Alternatively, on the contrary, the first holder 11M including the first ring 10RM may be fixed, and the second processing unit 20M may rotate, or both may rotate in the opposite direction.

The first processing unit 10M and the second processing unit 10M and the second processing unit 10M are configured according to the fluid processing apparatus shown in FIG. Similar to the first disk 10 and the second disk, the second holder 21M having the ring 20RM can be moved toward and away from at least one of the first disk 10M and the first processing surface 1M. And the second processing surface 2M can approach and separate.
In a preferred embodiment, the second holder 21M having the second ring 20RM approaches and separates from the first processing portion 10M. On the contrary, the first processing unit 10M may approach or separate from the second holder 21M having the second ring 20RM, and the first processing unit 10M and the second ring 20RM may be connected to each other. The second holder 21M provided may approach or separate from each other.

The first processing unit 10M and the second holder 21M having the second ring 20RM rotate relative to the other. Preferably, according to the fluid processing apparatus shown in FIG. 13, the second holder 21M having the second ring 20RM is fixed, and the first processing portion 10M rotates. Alternatively, on the contrary, the first processing unit 10M may be fixed, and the second holder 21M including the second ring 20RM may rotate, or both may rotate in the opposite direction.

Hereinafter, the reduction reaction of metal ions derived from metal salts for metal fine particles, that is, metal ions generated by dissociation of the metal salts will be described in more detail.

This reduction reaction is performed by the first and second processing surfaces 1 and 2 of the metal fine particle manufacturing apparatus shown in FIGS. 1 and 2, which are disposed so as to be able to approach and separate from each other, at least one of which rotates relative to the other. Occurs with uniform mixing between the working surfaces 2 forcibly.

First, an aqueous medium containing at least a reducing agent and a pH adjusting agent as a first fluid is disposed opposite to each other so as to be able to approach and separate from the first introduction part d1 which is one flow path, and at least one of the other is disposed on the other Is introduced between the first processing surface 1 and the second processing surface 2 that rotate relative to each other, thereby forming a thin film fluid composed of the first fluid between the processing surfaces.

Next, an aqueous medium containing at least a metal salt as the second fluid is transferred from the first fluid created between the first processing surface 1 and the second processing surface 2 from the second introduction part d2 which is a separate flow path. Introduce directly into the constructed thin film fluid.
Here, it is necessary that the pH of the first fluid is in the range of 8 to 13 and the pH of the second fluid is in the range of 3 to 7.

In addition, an aqueous medium containing at least a reducing agent and a pH adjusting agent is preferable as the first fluid, and an aqueous medium containing at least a metal salt is preferable as the second fluid, but is not limited thereto. For example, the first fluid is an aqueous medium containing at least a reducing agent and a pH adjuster, the second fluid is an aqueous medium containing at least a metal salt, and either or both of the first fluid and the second fluid are A boiling point increasing agent is contained, and either or both of the first fluid and the second fluid may contain a dispersant.

As described above, between the first processing surface 1 and the second processing surface 2 adjusted to a minute gap by the pressure balance between the fluid supply pressure and the pressure applied between the rotating processing surfaces, The 1st fluid and the 2nd fluid merge and a reduction reaction is performed while mixing uniformly in the thin film. An aqueous medium in which metal ions generated by dissociation of the metal salt are reduced by a reducing agent in the presence of a pH adjuster and in a specific pH range and the generated metal fine particles are dispersed is obtained from the metal fine particle production apparatus. Discharged.

In addition, it is only necessary that the above reduction reaction can be performed between the first processing surface 1 and the second processing surface 2, and conversely, the second fluid is introduced from the first introduction part d1, The first fluid may be introduced from the second introduction part d2.

The particle diameter and particle size distribution of the metal fine particles obtained are the rotational speed of the first processing surface 1 and the second processing surface 2, the distance between the first processing surface 1 and the second processing surface 2, and It can be adjusted by changing the flow rate and raw material concentration of the thin film fluid.
In terms of mixing efficiency and reaction efficiency, the speed at which one of the first processing surface and the second processing surface rotates with respect to the other is 500 rpm to 3000 rpm, and the first processing surface 1 and the second processing surface 2. The distance between them is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 20 μm.

In the reduction reaction, the reaction temperature can be controlled by setting the temperature of the introduced fluid and directly adjusting the temperature of the first processing surface 1 and the second processing surface 2. The reaction temperature is usually not lower than the normal temperature and not higher than the boiling point of the fluid to be treated, but is not limited thereto. The boiling point of the fluid to be treated can be increased by adding a boiling point increasing agent, and the reaction temperature is preferably in the range of 50 ° C to 140 ° C.

As the forced ultrathin film rotary reactor used in the method for producing fine metal particles of the present invention, not only those described in the drawings but also commercially available products can be used. An example of such a commercially available forced ultrathin film rotary reactor is ULREA manufactured by M Technique Co., Ltd. (ULREA is a registered trademark of M Technique Co., Ltd.).

The metal of the metal fine particles is not limited, and examples thereof include nickel, iron, cobalt, chromium, and the like, but nickel is particularly preferable.

The nickel salt used in the method for producing fine metal particles of the present invention is not particularly limited as long as nickel ions dissociated and produced in an aqueous medium are reduced by a reducing agent. Specific examples of nickel salts include nickel sulfate (II) hexahydrate, nickel sulfate (II) ammonium hexahydrate, nickel nitrate (II) hexahydrate, nickel acetate (II) tetrahydrate, hydroxyacetic acid Nickel (II) can be mentioned.

Similarly, in the case of a metal other than nickel, it is not particularly limited as long as the metal ion generated by dissociation in an aqueous medium is reduced by a reducing agent, and iron (II) sulfate heptahydrate, nitric acid Examples include iron (III) nonahydrate, cobalt (II) sulfate heptahydrate, cobalt (II) nitrate hexahydrate, chromium (III) sulfate hydrate, chromium (III) nitrate nonahydrate. The

The fluid to be treated, which is a liquid phase, includes an aqueous medium that dissolves a metal salt, a reducing agent, a pH adjuster, a boiling point increasing agent, and a dispersing agent.
The aqueous medium refers to water or a mixed liquid of water and a water-soluble organic solvent. The water-soluble organic solvent for that purpose is preferably an organic solvent having a solubility in water at 20 ° C. of 50 g / L or more and a boiling point of 30 to 250 ° C. C1-C6 alcohol (for example, ethanol, n-propanol, isopropanol, n-butanol, cyclohexanol, ethylene glycol), C3-C6 ketone (for example, acetone, methyl ethyl ketone, cyclohexanone), C2-C2 6 ethers (for example, tetrahydrofuran, dioxane), alkylene glycol monoethers having 2 to 6 carbon atoms (for example, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether) are preferred, such as ethanol, n-propanol, Isopropanol and tetrahydrofuran are particularly preferred. 50 mass% or less is preferable, as for content of the organic solvent in an aqueous medium, 1-40 mass% is more preferable, and 2-35 mass% is further more preferable. Two or more organic solvents may be used in combination.

In the method for producing fine metal particles of the present invention, water and a water-soluble organic solvent are used from the viewpoint of dissociation of metal salt and solubility and reduction reactivity of metal salt, reducing agent, pH adjuster, boiling point increasing agent and dispersant. Containing water (for example, a mixed solution of water and an alcohol having 1 to 4 carbon atoms) is preferable, and water is particularly preferable.

The reducing agent used in the method for producing fine metal particles of the present invention is not particularly limited as long as the fine metal particles can be precipitated by reducing metal ions generated by dissociation of the metal salt in a liquid phase reaction system. . In the thin film fluid formed between the processing surfaces in which at least one of the metal salt and the reducing agent is disposed to face each other in the presence of a pH adjusting agent described later so as to be capable of approaching and separating, and at least one rotates relative to the other. By reacting, the metal ions generated by dissociation of the metal salt are reduced and metal fine particles are deposited without applying a great amount of heat energy. The deposited metal fine particles are dispersed in an aqueous medium. At this time, the presence of a dispersant in the reaction system is preferable because the dispersibility of the precipitated metal fine particles is improved.

The reducing agent used in the method for producing fine metal particles of the present invention has an action of reducing metal ions generated by dissociation of a metal salt in an aqueous medium to form fine metal particles.
Such reducing agents include inorganic reducing agents and organic reducing agents. Examples of inorganic reducing agents include, for example, borohydride salt reducing agents such as sodium borohydride and ammonium borohydride, phosphorous acid such as phosphorous acid, sodium phosphite, hypophosphorous acid, and sodium hypophosphite. Acidic reducing agents, hydrazine and its hydrates, hydrazine reducing agents such as hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, sulfite reducing agents such as sodium sulfite and sodium bisulfite, sodium thiosulfate, sodium nitrite, Examples thereof include nitrite-based reducing agents such as sodium nitrite and inorganic reducing agents such as transition metal element ions (trivalent titanium ions, divalent cobalt ions, etc.).
Among these, borohydride salt reducing agents such as sodium borohydride and ammonium borohydride and hydrazine and its hydrate, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate and the like in terms of reducing power and solubility. A hydrazine-based reducing agent is preferred.

Examples of organic reducing agents include lower alcohols (methanol, ethanol, 2-propanol, ethylene glycol, etc.), ascorbic acid, lower aldehydes (hydroquinone, formaldehyde, acetaldehyde, propionaldehyde, etc.), glutathione, lower organic carboxylic acids (formic acid). , Oxalic acid, citric acid, sodium citrate, malic acid, tartaric acid, etc.), reducing sugars (glucose, lactose, arabinose, galactose, mannose, fructose, raffinose, stachyose, etc.), sugar alcohols (sorbitol, xylitol, mannitol, etc.) ). Among these, ethylene glycol is preferable in terms of reducing power and solubility in a solvent.
In the case of using a lower alcohol, a reducing saccharide, or a sugar alcohol, it is preferable to use an organic acid or a ketone having a carbonyl group in combination in order to make it stronger.

Examples of the organic reducing agent include amine-based reducing agents. Examples of such amine reducing agents include propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine, triethylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1, Aliphatic amines such as 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, triethylenetetramine, tetraethylenepentamine, piperidine, N-methylpiperidine, piperazine, N, N'-dimethylpiperazine, pyrrolidine, N-methylpyrrolidine, alicyclic amines such as morpholine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine, anisidine, phenetidine and other aromatic amines, benzylamine, N − Chill benzylamine, N, N-dimethylbenzylamine, phenethylamine, xylylenediamine, N, N, N ', an aralkyl amine such as N'- tetramethyl xylylene diamine.

Further, for example, alkanols such as methylaminoethanol, dimethylaminoethanol, triethanolamine, ethanolamine, diethanolamine, methyldiethanolamine, propanolamine, 2- (3-aminopropylamino) ethanol, butanolamine, hexanolamine, dimethylaminopropanol, etc. Mention may also be made of amines. Of these, alkanolamine is preferable, and dimethylethanolamine is more preferable. Furthermore, trimethylamine borane, dimethylamine borane, and tertiary butylamine borane can be mentioned.
Among these, alkanolamine is preferable from the viewpoint of reducing power and solubility in a solvent.

An inorganic reducing agent and an organic reducing agent may be used in combination. Examples of the combination include hydrazine (including hydrate) and ethylene glycol, sodium borohydride, and ethylene glycol.

In the method for continuously producing fine metal particles of the present invention, the reduction reaction of metal ions is performed in a thin film fluid having a pH greater than 5 but not greater than 12. At this time, when the fluids to be treated are the first fluid to be treated and the second fluid to be treated, the pH of the first fluid to be treated is 8 to 13, and the second fluid to be treated. The pH of the first fluid to be treated is 3 to 7, and the pH of the first fluid to be treated is 1 to 8 higher than the pH of the second fluid to be treated.
Thereby, the reduction reaction of metal ions can be performed stably, and a plurality of radially projecting conical projections, the side shape of the transmission electron micrograph is a triangle, and the apex angle of the triangle is 10 Metal fine particles having a particle size distribution of ˜40 degrees, an average particle size of 0.01 to 10 μm, and a CV value of the particle size distribution of 100% or less can be obtained.

As a pH adjuster used in the method for continuously producing fine metal particles of the present invention, an organic alkali or acid, an inorganic alkali or acid, or an alkaline or acidic salt, sodium hydroxide, potassium hydroxide, hydrochloric acid , Sulfuric acid, nitric acid, ammonia, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, potassium hydroxide, sodium hydroxide, phosphate, ammonium acetate, ammonium oxalate, citric acid, sodium citrate, adipic acid, hydrochloric acid The

In the continuous production method of metal fine particles of the present invention, the fluid to be treated, that is, the first fluid to be treated and the second fluid to be treated may contain a boiling point increasing agent. The boiling point raising agent can increase the boiling point of the fluid to be treated, and the metal ion reduction reaction can be performed at a higher temperature. The reaction temperature of the reduction reaction is preferably in the range of room temperature to 150 ° C, more preferably 50 ° C to 140 ° C. For this reason, it is preferable that the temperature of the 1st to-be-processed fluid and the 2nd to-be-processed fluid is the range of normal temperature-150 degreeC.

Examples of such boiling point raising agents include polyhydric alcohols (ethylene glycol, glycerin, etc.), sugar alcohols (sorbitol, xylitol, mannitol, etc.), poval (polyvinyl alcohol), polyethylene glycol, and the like. In addition, such a boiling point raising agent may serve as a dispersing agent and a reducing agent.

The first fluid to be treated is an aqueous medium containing at least a reducing agent and a pH adjusting agent, and is preferably an aqueous solution of a reducing agent, a pH adjusting agent, and a boiling point increasing agent. The pH of the first fluid to be treated is adjusted to a range of 8 to 13 with a pH adjuster, and more preferably in a range of 9 to 12. The first fluid to be treated may further contain a dispersant. The second fluid to be treated is an aqueous medium containing at least a metal salt, and preferably further contains a dispersant or a boiling point raising agent. The pH of the second treated fluid is adjusted to a range of 3 to 7 so that the metal salt becomes a stable metal ion in the aqueous medium. The pH of the first fluid to be treated is 1 to 8 higher than the pH of the second fluid to be treated. When the difference in pH is small, the average particle diameter of the obtained metal fine particles is large, and when the difference in pH is large, the average particle diameter of the obtained metal fine particles is small. The pH of the thin film fluid is substantially the same as the pH of the mixed liquid of the first fluid to be treated and the second fluid to be treated.

When the pH of the thin film fluid produced by mixing the first treated fluid and the second treated fluid is 5 or less, there is a problem that the reducing agent has a reduced reducing power. There is a problem that the amount of the pH adjusting agent in the first fluid to be treated becomes excessive, and the alkalinity is strong and difficult to handle.

The dispersant used in the method for continuously producing fine metal particles of the present invention has a function of better dispersing fine metal particles precipitated by reduction of metal ions generated by the dissociation of metal salts in an aqueous medium in a thin film fluid. is there.
Such a dispersant is not particularly limited as long as it has good solubility in an aqueous medium and can disperse the deposited metal fine particles in a thin film fluid. Various dispersants can be used as the dispersant, and examples thereof include organic acids and salts of these organic acids, particularly high and intermediate fatty acids and salts thereof.

For this purpose, pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12-hydroxyoleic acid) , Monovalent linear saturated fatty acids such as eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (serotic acid), octacosanoic acid (montanoic acid); 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptyldodecanoic acid, isooleic acid Monovalent branched saturated fatty acids such as sorbic acid, maleic acid, palmitoleic acid, oleic acid, isooleic acid, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, gadrenic acid, erucic acid, ceracoleic acid, etc. Saturated fatty acids are exemplified.

In addition, polyvalent acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, oxydiacetic acid (diglycolic acid), glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, diglycolic acid, etc. The aliphatic carboxylic acid is exemplified. Furthermore, polyvalent aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid are exemplified.

Examples of the salt of the high intermediate fatty acid salt include alkali metal salts, particularly sodium and potassium salts, alkaline earth metal salts, amine salts, and ammonium salts.

In addition, natural polymer dispersants such as starch and gelatin, synthetic polymer dispersants, for example, amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, and molecules such as polyacrylamide, polyacrylic acid and carboxymethylcellulose. Hydrocarbon polymer dispersant having carboxylic acid group, poval (polyvinyl alcohol), polyethylene glycol, copolymer having polyethyleneimine part and polyethylene oxide part in molecule, amino group, phosphate group, acidic phosphorus Examples thereof include a polymer dispersant having a polar group such as an acid ester group or a carboxy group. Moreover, it is preferable that the molecular weight is 100,000 or less.

Examples of commercially available synthetic polymer dispersants include, for example, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 41090 (above, manufactured by Avicia Corporation),
DISPERBYK-106, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK- 181, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-190, DISPERBYK-191, DISPERBYK-192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2020, DISPERBYK-2022, DISPERBYK-2025, BYK-9076, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, ANTI-TERRA-250, etc. , Products sold by Big Chemie Japan Co., Ltd.),
Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA -1501, EFKA-1502, EFKA-4540, EFKA-4550 (above, manufactured by EFKA Chemical Co., Ltd.), florene DOPA-158, florene DOPA-22, florene DOPA-17, florene G-700, florene TG-720W, florene -730W, Floren-740W, Floren-745W (manufactured by Kyoeisha Chemical Co., Ltd.), Addispar PA111, Addisper PB711, Addisper PB811, Addispar PB821 AJISPER PW911 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Joncryl 678, Joncryl 679, Joncryl 62 (or more, Johnson made Polymer Co., Ltd.), and the like can be given. These may be used alone or in combination of two or more.

Since this dispersing agent is used to favorably disperse the metal fine particles precipitated in the aqueous medium in the thin film fluid as described above, the first treated fluid and the second treated fluid described above are used. It may be contained in any of them, and may be contained in both the first fluid to be treated and the second fluid to be treated. However, it may be contained in the second fluid to be treated containing a metal salt. Is preferred. Further, a dispersant may be contained in the third processed fluid. In this case, the pH of the third processed fluid is such that the pH of the first processed fluid, the second processed fluid, and the second processed fluid. 3 is prepared by a pH adjuster so that the pH of the thin film fluid formed by introducing the fluid to be processed between the first processing surface and the second processing surface is greater than 5 and 12 or less. Is preferred. Further, the dispersant may be contained in the fourth fluid to be treated.

A complex-forming agent may be used in combination in order to perform the metal salt reduction reaction more stably. The complex forming agent is also called a chelating agent or a complexing agent. The ligand donor atom of the complex-forming agent and the metal ion are combined to form a metal complex compound. Examples of the donor atom include nitrogen, oxygen, and sulfur.

As a complex-forming agent having an oxygen atom as a donor atom, a saturated aliphatic monocarboxylic acid having 1 to 18 carbon atoms, an aliphatic dicarboxylic acid having 1 to 10 carbon atoms (for example, oxalic acid, malonic acid, succinic acid, glutar Acid, adipic acid, fumaric acid, maleic acid), aliphatic hydroxymonocarboxylic acid (eg, glycolic acid, lactic acid, tartronic acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, cerebonic acid), aliphatic Examples include hydroxydicarboxylic acids (eg, malic acid, tartaric acid, citramalic acid), aliphatic hydroxytricarboxylic acids (eg, citric acid, isocitric acid), and alkali metal salts of these carboxylic acids (eg, sodium gluconate, sodium malate) Is done.

As a complex-forming agent having a nitrogen atom as a donor atom, an aliphatic polyamine having 1 to 10 carbon atoms (for example, ethylenediamine, diethylenetriamine, hexamethylenediamine) or an aromatic compound or condensed ring compound having a nitrogen atom as a coordination atom (For example, 2,2′-bipyridine, 4,4′-bipyridine, 1,10-phenanthroline, porphyrin), and a complex-forming agent having an oxygen atom and a nitrogen atom as donor atoms is an aminocarboxylic acid (for example, ethylenediamine). Tetraacetic acid, ethylenediaminediacetic acid (EDDA), ethylenediamine-N, N′-disuccinic acid, nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine, monopropaline) Ruamin, dipropanolamine, tripropanolamine) are exemplified. It is particularly preferably an aliphatic dicarboxylic acid and an aliphatic hydroxycarboxylic acid. Incidentally, complexing agent and pH adjusting agent may be the same.

Here, as described above, in addition to the first introduction part d1 and the second introduction part d2, the third introduction part d3 can be provided in the fluid treatment apparatus. In this case, from each introduction part, for example, In addition, an aqueous solution containing a reducing agent and a pH adjuster, an aqueous solution containing a metal salt, and an aqueous solution containing a dispersant can be separately introduced into the fluid treatment apparatus. If it does so, the density | concentration and pressure of each solution can be managed separately, and reaction which a metal microparticle produces | generates can be controlled more precisely. The same applies to the case where the fourth or more introduction portions are provided, and the fluid to be introduced into the fluid processing apparatus can be subdivided in this way.

As for the reduction reaction of metal ions, in addition to the above, each processing surface is made of a conductive material. By applying a potential difference between the above processing surfaces, electrons are transferred between the processing surfaces. You may use the electrochemical reduction method by giving and receiving.

The thin film fluid before the reaction between the metal ions and the reducing agent preferably has a metal salt concentration of 0.02 to 1.1 mol%, and the reducing agent is the same mol to 90 times mol of the metal salt. More preferably, the concentration of the metal salt is 0.06 to 0.8 mol%, and the reducing agent is the same mol to 50 times mol% of the metal salt.

Although the concentrations of the boiling point increasing agent and the dispersing agent are not limited, in the thin film fluid before the metal ions and the reducing agent react, the concentration of the boiling point increasing agent is 0 to 75% by mass, and the concentration of the dispersing agent is 0. It is preferable that it is -10 mass%.

The generated metal fine particles have an average particle size of 0.01 to 10 μm. If the particle diameter is less than 0.01 μm, the metal fine particles are likely to aggregate and the yield may be reduced. If the particle diameter exceeds 10 μm, many coarse particles are generated and the yield may be decreased.

The fine metal particles produced by the continuous production method of the present invention are characterized by a narrow particle size distribution. Typically, the CV value of the particle size distribution is 100% or less, more typically 70% or less. The CV value is (standard deviation / average particle diameter) × 100. The average particle size, particle size distribution and CV value can be measured by ordinary methods. For example, the particle size distribution can be measured by a laser Doppler particle size distribution measuring device or a laser diffraction particle size distribution measuring device. It is preferable to use a particle size distribution measuring apparatus by a laser Doppler method capable of measurement.

The fine metal particles produced by the continuous production method of the present invention have a plurality of conical protrusions protruding radially, and the conical protrusions whose side shape in the transmission electron micrograph is a triangle. The protuberances have their bases, i.e. roots, in contact with, intimate with or in close contact with each other.
However, the plurality of conical protrusions do not prevent the bases, that is, those having roots close to each other from being mixed.
The side surface shape in the transmission electron micrograph of the metal fine particles is a triangle, that is, the shape when the plane connecting the vertexes of the plurality of conical protrusions and the central point of the root is a cross section is a triangle, The apex angle, that is, the angle with respect to the base that is in contact with or close to the surface of the metal fine particle is 10 to 40 degrees. For example, in FIG. 22, each triangle is an angle with respect to the base that is in contact with or close to the surface of the metal fine particle. In other words, it is an internal angle formed by two sides from the base toward the tip. Note that the roots of the cone-shaped projections can be visually recognized in the transmission electron micrograph, where the adjacent cone-shaped projections are in contact with each other, in close contact with each other, or in close contact with the contact.
As shown in FIG. 16 and FIG. 22, the fine metal particles have a cone-shaped projection whose side shape is a triangle in a transmission electron micrograph and whose height is larger than ¼ of the average particle size per particle. Preferably it is 4 or more, more preferably 6 or more.
For this reason, the contact area between the surfaces of the fine particles is increased, and the conical projections are more easily melted at a lower temperature than the metal fine particle main body, so that the conductivity of the conductive curable composition containing metal fine particles is increased. In addition, among the metal fine particles, magnetic metal (for example, Ni, Fe, Co, Cr) fine particles are characterized by being easily melted by electron beam irradiation, and the metal fine particles are applied to a material having low heat resistance. can do. Specifically, the metal fine particles can be easily melted by irradiation with an electron beam having an electron beam energy of 10 keV or more, preferably 50 keV or more.

The diameter of the conical projection decreases from the root to the tip.
The height is preferably 1.1 to 5 times the area equivalent to the diameter of the base of the conical protrusion, that is, the root. The area circle equivalent diameter is calculated as the diameter of a circle having the same area as the area of the root outline of the conical protrusion. Therefore, the area equivalent circle diameter can be calculated regardless of the shape of the base of the conical protrusion.
The conical protrusions are preferably polygonal, conical or elliptical. In the scanning electron micrograph of the metal fine particles having the conical protrusion, the shape of the root when the conical protrusion is viewed in plan is preferably a polygon, a circle or an ellipse. When the shape of the base of the conical protrusion is a polygon, when the plurality of conical protrusions are in contact with each other, the roots are at least point contact or line contact. When the shape of the roots of the conical protrusions is circular or elliptical, when the plurality of conical protrusions are in contact with each other, the roots are at least point-contacted.
The cone shape is not limited to a pure cone shape, and may be a substantially cone shape or a shape approximating a cone shape.
The polygonal pyramid shape, conical shape, or elliptical cone shape is not limited to a pure polygonal pyramid shape, a conical shape, or an elliptical cone shape. Alternatively, the shape may be approximate to an elliptical cone shape.
Examples of the triangle include an isosceles triangle, an unequal triangle, and an equilateral triangle. However, the triangle is not limited to a pure triangle, and may be a shape that approximates a triangle or a triangle. The sides of the triangle are not limited to a straight line, and may be somewhat curved, bent, or meandered. The vertices of the triangle may be rounded or partially missing.
A plurality of cone-shaped protrusions whose side shapes are triangular are protruding radially from the metal fine particles, but preferably 8 or more, more preferably numerous or innumerable cone-shaped protrusions protrude radially.

The metal fine particles produced | generated by the continuous manufacturing method of this invention are useful as a conductive component in the conductive curable composition of this invention, and are especially useful as a conductive component in a curable conductive adhesive composition.
The conductive curable composition of the present invention comprises metal fine particles (A), a curable organic resin (B) and, if necessary, (C) a curing agent as main components, excellent dischargeability, moisture, and heating. It is characterized by being cured by electron beam irradiation and having excellent conductivity.
Among them, the curable conductive adhesive composition is mainly composed of metal fine particles (A), a curable organic resin (B), and (C) a curing agent and / or (D) an adhesion promoter as necessary. It is characterized by having excellent discharge properties, being cured by moisture, heating, electron beam irradiation, etc., and having excellent conductivity and adhesiveness.

The curable organic resin as the component (B) serves as a binder for the component (A) or (A ¹ ), and may be quickly cured by heating, standing at room temperature, irradiation with a high energy beam (for example, electron beam), etc. In the case of a solid form, it is preferably heat-meltable.
Examples of the curable organic resin include curable epoxy resins, curable phenol resins, curable polyurethane resins, unsaturated polyester resins, alkyd resins, curable acrylic resins, curable silicone resins, and curable polyimide resins. A curable epoxy resin is preferable from the viewpoint of adhesion to the substrate that has been in contact with the curing process, and a thermosetting epoxy resin is preferable from the viewpoint of rapid curing. Next, a curable phenol resin is preferred.

The curing mechanism of the curable organic resin may be any of thermosetting, room temperature curable, high energy ray curable, etc., but thermosetting and high energy ray (eg, electron beam) curable in terms of rapid curing. Is preferred.

The content of the component (A) or (A ¹ ) and the component (B) is such that the component (A) or (A ¹ ) is 30 to 70% by mass of the whole composition, and the component (B) is the whole composition. It is preferable that it is 70-30 mass%.

(C) A hardening | curing agent is required when curable organic resin itself which is a component (B) does not have curability, or when curability is inadequate. The curing agent is an organic crosslinking agent and / or a curing catalyst (curing accelerator).
(C) It is good to use what is used widely according to the kind of curable organic resin as a hardening | curing agent.
(C) The compounding quantity of a hardening | curing agent may be sufficient quantity to harden an electroconductive curable composition. When a hardening | curing agent is an organic type crosslinking agent, it is 5-40 mass% of the whole composition, for example. When a hardening | curing agent is a hardening catalyst (curing accelerator), it is 0.1-5 mass% of the whole composition, for example.

As a curing agent (organic crosslinking agent) for the curable phenol resin, hexamethylenetetramine, paraformaldehyde, trioxane, 1,3-dioxolane, 4-phenyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, Divinylbenzene is exemplified. The compounding ratio of the curing agent is usually 3 to 20 parts by mass, preferably 8 to 17 parts by mass with respect to 100 parts by mass of the curable phenol resin.
Examples of the curing agent (curing catalyst) for the unsaturated polyester resin include benzoyl peroxide and methyl ethyl ketone peroxide. Examples of curing accelerators include tertiary amines and cobalt accelerators.
Examples of alkyd resin curing agents (organic crosslinking agents) include alkyl etherified aminoformaldehyde resins, epoxy compounds and isocyanate compounds.
Examples of the curing agent (organic crosslinking agent) for the curable acrylic resin include polyvalent carboxylic acids, blocked isocyanate compounds, and amino resins. Examples of the curing catalyst include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, or neutralized amines thereof. The curing agent (organic crosslinking agent) is contained in an amount of 5 to 80 parts by mass with respect to 100 parts by mass of the curable acrylic resin, and the curing accelerator is 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable acrylic resin. It is preferable to contain.
Examples of the curing catalyst for the curable silicone resin include alkyl titanates, organotin compounds, and fatty acid metal salts. It is preferable to contain 0.1-5 mass parts with respect to 100 mass parts of curable silicone resin.

(D) It is good to use what is used widely according to the kind of curable organic resin as an adhesion promoter.
Illustrative are organometallic compounds such as silane coupling agents, titanium coupling agents, allyl glycidyl ether, and organic titanium compounds.
(D) The content of the adhesion promoter may be an amount sufficient to adhere to the substrate that the conductive curable composition is in contact with during curing, for example, 0.01 to 5 mass of the entire composition. %.

The conductive curable composition of the present invention preferably exhibits easy-flowing properties such as liquid, paste, and cream at room temperature, but is preferably solid and heat-meltable at room temperature. Further, the volume resistivity of the cured product is preferably 1 × 10 ⁰ Ω · cm or less.

In addition to the component (A) or (A ¹ ), the component (B), the component (C), and the component (D), the conductive curable composition of the present invention includes the curability of the composition and the conductivity of the cured product. As long as the properties are not impaired, a filler, a thixotropic agent, a heat resistance agent, a light resistance agent, a pigment, a solvent, and the like may be contained. The solvent is preferably a non-reactive / volatile organic solvent.

The conductive thermosetting epoxy resin composition comprises a component (A) or (A ¹ ), a thermosetting epoxy resin and a curing agent, and further comprises a curing accelerator and a reactive diluent as necessary. When heated to a temperature of 50 ° C. to 200 ° C., it cures and adheres well to the substrate that was in contact with the curing.

Thermosetting epoxy resins include bisphenol epoxy resins such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol AD diglycidyl ether; polyglycidyl ethers obtained by reaction of phenol novolacs with epichlorohydrin; butanediol diglycidyl Examples include aliphatic epoxy resins such as ether and neopentyl glycol diglycidyl ether; alicyclic epoxy resins such as dicyclopentanediene methanol diglycidyl ether; heterocyclic epoxy resins such as diglycidyl hydantoin; and modified epoxy resins. An epoxy resin may be used independently and may mix and use 2 or more types.
Those which are liquid at room temperature and those which are solid at room temperature and heat-meltable are preferred.
If the curing agent is one that reacts rapidly with the epoxy resin upon heating (for example, about 50 to 200 ° C.) to solidify the epoxy resin and has a long-term storage stability at a temperature below room temperature, It is not limited. Examples of the curing agent include aliphatic polyamines, polyaminoamides, aromatic amines, alicyclic diamines, tertiary amines and other amine compounds; aliphatic aminocarboxylic acids, imidazoles, carboxylic anhydrides, phenols, phenol resins, Examples include hydrazide compounds, dicyandiamide, and Lewis acid complex compounds.

More specifically, epoxy resin curing agents include diethylenetriamine, triethylenetetramine, metaxylenediamine, dimer acid polyamide, 4,4'-diamonodiphenylmethane, metaphenylenediamine, 2,4,6-tris (diamino). Methyl) phenol, ε-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Examples include 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, tetrahydromethyl phthalic anhydride, phenol novolac resin, adipic dihydrazide, isophthalic hydrazide, boron trifluoride / ethylamine complex . These curing agents may be blended alone or in combination.

These curing agents may be those encapsulated in a capsule of a heat-meltable polymer substance or dispersed in particles of a heat-meltable substance, that is, a latent curing agent. The latent curing agent has both long-term storage properties and fast curing properties. These latent hardeners may be blended singly or in combination of a plurality of types.

It is preferable that the conductive thermosetting epoxy resin composition further contains a reactive diluent. Representative examples of reactive diluents include monofunctional glycidyl esters and monofunctional glycidyl ethers. When a reactive diluent such as a monofunctional glycidyl ester and a monofunctional glycidyl ether is contained, the conductive liquid epoxy resin composition can have a low viscosity and a low hardness without greatly impairing the moisture resistance. If the viscosity can be decreased, the content of the conductive particles can be increased to increase the conductivity, and if the hardness can be decreased, flexibility can be provided.

The monofunctional glycidyl ester is exemplified by alkanoic acid glycidyl ester, and the monofunctional glycidyl ether is exemplified by alkyl alcohol monoglycidyl ether.
The content of the monofunctional glycidyl ester and the monofunctional glycidyl ether is preferably 1 to 20% by weight in the thermosetting epoxy resin adhesive, and the monofunctional glycidyl ester and the monofunctional glycidyl ether The weight ratio is preferably 9: 1 to 1: 9.

Conductive curable phenolic resin compositions, the components (A) or (A ^1), consists of a curable phenolic resin as a curing agent, phenol resin, bisphenol A type phenol resin, novolak phenolic resins, ortho-cresol novolac Type resin, bisphenol A novolac type phenol resin, brominated phenol novolac type phenol resin, naphthol novolac type phenol resin, trihydroxyphenylmethane, xylylene type phenol resin, and a reaction product of 4 to 15 carbon dienes and phenol. A hydrocarbon-phenol resin is exemplified.

Conductive curable composition of the invention, the component (A) or (A ^1), by uniformly mixing the component (B), it is possible to easily manufacture. In addition, the component (B) and the component (A) or (A ¹ ) are uniformly mixed, and then the component (C) and / or the component (D) is added and mixed uniformly to produce easily. be able to.
A two-component type or two-component type in which a uniform mixture of component (A) or (A ¹ ) and component (B) and component (C) are stored in separate containers and both components are mixed immediately before the bonding operation. A packaged conductive curable composition may be produced. Further, the conductive curable composition of the present invention may be diluted with a non-reactive / volatile organic solvent to reduce the viscosity.

The conductive curable composition of the present invention is preferably stored in a sealed container until it is used after production. When the sample is subjected to the bonding operation after long-term storage, it is preferable that the storage container is shaken well or the inside of the storage container is thoroughly stirred before the bonding operation. Refrigerated storage may be performed for the purpose of improving storage stability, and the storage temperature is 10 ° C. or lower.

What is necessary is just to apply the electroconductive curable composition of this invention to the location which needs adhesion | attachment by arbitrary methods, such as screen printing, dispensing, dripping, injection | pouring, application | coating. If diluted with a non-reactive / volatile organic solvent, apply it to the place where adhesion is required, and then evaporate the organic solvent by standing at room temperature, spraying with warm air, or gentle heating, and then heat cure It is preferable to make it. In the case of a two-component or two-pack type adhesive, the main agent and the curing agent may be mixed uniformly before use in the bonding operation.

After applying the conductive curable composition of the present invention to a place where adhesion is required, for example, by heating and curing at 50 to 200 ° C., heat sink, resistor, capacitor, coil, crystal resonator, etc. Glue and bond discrete components, diodes, silicon chips, SiC chips, GaAs chips, GaAlAs chips, LSI chips, optical elements, memory elements, power device elements, and other chip parts to substrates, other parts, other members, etc. can do.

Thus, various electronic devices (for example, cellular phones, digital cameras, video cameras, video recorders, navigation systems, personal computers, electronic copying machines, printers, game machines, televisions, etc., home or office electronic devices; engines) It is possible to manufacture automotive electronic devices such as control units, brake systems, inter-vehicle sensors, acceleration sensors, car navigation systems, industrial control devices such as machining centers and robot systems, communication electronic devices, and parts thereof.

Examples and comparative examples of the present invention will be given. In Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”. Metal fine particle production apparatus, pH of first treated fluid (hereinafter referred to as first fluid) and second treated fluid (hereinafter referred to as second fluid), surface shape of metal fine particles, side shape of conical projection And the apex angle of the triangle that is the side surface shape, the height of the cone-shaped projection (magnification with respect to the area equivalent circle diameter of the base of the cone-shaped projection), the average particle size, the particle size distribution, and the CV value measurement method, the component analysis method of the metal fine particles , Measurement method of meltability by electron beam, viscosity of conductive curable composition, micro-discharge property of conductive curable composition, hardness after curing of conductive curable composition, of conductive curable composition The volume resistivity measurement method after curing and the shear bond strength after curing of the conductive curable composition are as follows. In addition, measurement temperature is room temperature (23-25 degreeC), unless there is particular notice.

[Metal fine particle production equipment]
Introducing a fluid to be treated which is a liquid phase between the first processing surface and the second processing surface, which are arranged to face each other so as to be able to approach and leave, and at least one of which rotates relative to the other; A force for moving the second processing surface away from the first processing surface is generated by the pressure of the fluid to be processed, and this force causes a gap between the first processing surface and the second processing surface. The fluid to be processed passing between the first processing surface and the second processing surface maintained at a minute interval and formed between the first processing surface and the second processing surface forms a thin film fluid. ULREA made by M Technique Co., Ltd. (ULREA is a registered trademark of M Technique Co., Ltd.) Used). A schematic diagram of ULREA is shown in FIG. The maximum possible rotation speed of the first processing unit (10M) is 3000 rpm.

[PH of the first fluid and the second fluid]
It measured at normal temperature with the D-51S type | mold made from HORIBA.

[Surface shape of metal fine particles, side shape of cone-shaped projection, and apex angle of triangle that is side shape, height of cone-shaped projection, height, magnification to area circle equivalent diameter of base of cone-shaped projection]
The surface shape of the metal fine particles obtained in the examples and some comparative examples was measured by using a scanning electron microscope JSM-7500F (magnification 3,500 to 70,000 times) and a transmission electron microscope JEM- manufactured by JEOL Ltd. The images were observed at 2100 (magnification 15,000 to 140,000 times) and photographed. The shape of the obtained planar photograph of the transmission electron microscope was the side shape of the conical protrusion. The shape of a large number of metal fine particles in the example is uniform, and the side shape of the cone-shaped projections is mostly triangular, so that 10 triangular cone-shaped projections per particle are selected in descending order. The angle with respect to the base that is in contact with or close to the surface was measured, and the average value was taken as the apex angle. Moreover, the height of the cone-shaped protrusion was measured from these triangles, and the average value was defined as the height of the cone-shaped protrusion. On the other hand, in the obtained plan view of the scanning electron microscope, five conical projections existing in the vicinity of the front surface of the particle are selected, and the base of the conical projection, that is, the outline of the root, is selected for these five conical projections. The area equivalent circle diameter was measured, and the average value was defined as the area equivalent circle diameter. From the height of the cone-shaped projections measured in this way and the area circle equivalent diameter, the height / area circle equivalent diameter is defined as the ratio of the height to the area circle equivalent diameter of the base of the cone-shaped projections. The height of the protrusions (times) was indicated.

[Average particle diameter, particle size distribution and CV value of metal fine particles]
The particle size distribution of the metal fine particles was measured using a particle size distribution measuring apparatus (trade name Microtrac UPA150 manufactured by Nikkiso Co., Ltd.) by a laser Doppler method, and the average particle diameter was calculated.
The average particle diameter is a volume average particle diameter (diameter). The CV value was determined by the following formula.
CV value = (standard deviation / average particle size) × 100

[Component analysis of fine metal particles]
The incident angle and diffraction intensity of the metal fine particles detected by XRD (X-ray diffractometer) were compared with the incident angle and diffraction intensity of each metal reagent.

[Melting properties of fine metal particles by electron beam]
The metal fine particles were set in a transmission electron microscope JEM-2100 manufactured by JEOL Ltd., and irradiated with a 100 keV electron beam for 30 seconds to observe the surface of the metal fine particles.

[Viscosity of conductive curable composition]
A rotor (No. 6) was attached to a rotary viscometer TV-20 manufactured by Toki Sangyo Co., Ltd., and the viscosity was measured at a rotational speed of the rotor of 4 rpm and a temperature of 25 ° C.

[Micro discharge property of conductive curable composition]
A 5 ml syringe (EFD, Inc.) is filled with a conductive curable composition, and a metal needle (made by Musashi Engineering Co., Ltd.) having an inner diameter of 0.14 mm and a length of 15 mm is attached, and at a pressure of 200 kPa at intervals of 1 second. With and without pressurization, the presence or absence of clogging was observed.

[Hardness after curing of conductive curable composition]
In a state where the conductive curable composition is poured into a polytetrafluoroethylene resin mold having a width of 40 mm, a length of 60 mm, and a thickness of 6 mm, and both sides of the mold are sandwiched between plates of polytetrafluoroethylene resin, The conductive curable composition was cured by being sandwiched between an upper plate and a lower plate of a press and heated at 100 ° C. for 1 hour while applying a pressure of 10 MPa. The plate-like cured product thus obtained was measured for hardness with a D-type hardness meter defined in JIS K7215.

[Volume resistivity after curing of conductive curable composition]
In a state where the conductive curable composition is poured into a polytetrafluoroethylene resin mold having a width of 40 mm, a length of 60 mm, and a thickness of 6 mm, and both sides of the mold are sandwiched between plates of polytetrafluoroethylene resin, The conductive curable composition was cured by being sandwiched between an upper plate and a lower plate of a press and heated at 100 ° C. for 1 hour while applying a pressure of 10 MPa. The volume resistivity of the plate-like cured product thus obtained was measured according to JIS K 7194.

[Shear bond strength after curing of conductive curable composition]
A 1 mm thick Teflon mask with an opening of 25 mm width and 12.5 mm length at one end of an aluminum substrate having a width of 25 mm, a length of 100 mm and a thickness of 1 mm (Teflon is a registered trademark) The conductive curable composition is applied to the substrate, and another Teflon mask (Teflon is a registered trademark) is sandwiched between one end of an aluminum substrate having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm. Place the part so that it overlaps, and heat the conductive curable composition by heating at 100 ° C. for 1 hour while fixing the part with a clip, remove the clip to make a test specimen, and shear bond according to JIS K 6850 Strength was measured.

[Reference example]
The liquid thermosetting epoxy resin composition for preparing the conductive curable composition was prepared as follows.
In the mixer, 37.5 parts of Mitsubishi Chemical Corporation bisphenol A type epoxy resin (trade name: jER828, viscosity 14 Pa · s, epoxy equivalent 190 g), ADEKA Corporation epoxy resin (trade name: ED509S, viscosity 20 mPa · s) , Epoxy equivalent 206g) 4.0 parts, 8.5 parts of epoxy resin curing agent (trade name: PN-40) manufactured by Ajinomoto Fine Chemical Co., Ltd. as a curing agent is mixed uniformly to form a liquid thermosetting epoxy resin composition A product was prepared.

[Example 1]
As a first fluid, an aqueous solution containing 10.5% of hydrazine monohydrate as a reducing agent, 43.75% of ethylene glycol as a boiling point increasing agent, and 2% of potassium hydroxide as a pH adjusting agent was prepared. The pH of the aqueous solution was 12.0.
As a second fluid, an aqueous solution containing 12.5% of nickel sulfate (II) sulfate hexahydrate and 2.1% of polyethylene glycol (average molecular weight 600) as a boiling point increasing agent was prepared. The pH of the aqueous solution was 6.5.
Each raw material component content in the first fluid, each raw material component content in the second fluid, each raw material component content in the sum of the first fluid and the second fluid, the flow rate and specific gravity of the first fluid, The flow rate and specific gravity of the two fluids are shown in Table 1. Regarding the content of the reducing agent in the sum of the first fluid and the second fluid, the magnification of the nickel salt content (mol%) is shown in Table 1.
Here, the mol% of the reducing agent and the mol% of the nickel salt in the sum of the first fluid and the second fluid were calculated by the following method.
The specific gravity of the 1st fluid and the 2nd fluid was measured with the buoy meter, and the value was made into each density (g / ml). Next, the mass of the first fluid per unit time is calculated by the product of the density of the first fluid and the flow rate of the first fluid per unit time, and the density of the second fluid and the second fluid per unit time are calculated. The mass of the second fluid per unit time was calculated from the product with the flow rate. Although how to take unit time is arbitrary, it can be made into 1 minute, for example. For all raw material components including nickel salt and reducing agent (all raw material components are nickel salt, reducing agent, boiling point increasing agent, dispersant, pH adjuster, water) Each mass per unit time is calculated from the mass per unit time of the first fluid and the second fluid, and divided by each molecular weight to calculate the number of moles per unit time. The ratio (percentage) of each number of moles in the total number was mol%. The calculated number of moles of each component varies depending on how the unit time is taken, but the ratio (mol%) of each mole number in the total number of moles does not depend on how the unit time is taken. It is constant.
For Examples and Comparative Examples other than Example 1, the mol% of the nickel (metal) salt and the reducing agent was calculated by the same method. Also, each raw material component content in the first fluid, each raw material component content in the second fluid, each raw material component content in the sum of the first fluid and the second fluid, the flow rate and specific gravity of the first fluid The flow rate and specific gravity of the second fluid are listed in each table.

The rotational speed of the forced ultrathin film rotary reactor is 1700 rpm, the gap between the first processing surface and the second processing surface is 10 μm, the first fluid is supplied at a supply pressure of 0.3 MPa / back pressure of 0.02 MPa, and a flow rate of 400 ml. The second fluid was introduced between the processing surface 1 and the processing surface 2 of the apparatus at a flow rate of 50 ml / min at room temperature while feeding at a temperature of 130 ° C./min. The pH of the thin film fluid was 11.4.
Nickel fine particles were discharged from between the processing surface 1 and the processing surface 2 together with an aqueous solution as a reaction residue.

The obtained slurry-like aqueous solution containing nickel fine particles was allowed to stand on a magnet to precipitate the nickel fine particles, and then the separated nickel fine particles were washed with pure water and then with methanol and then vacuum-dried. Measure the surface shape of the obtained nickel fine particles, the side shape of the conical protrusions, the apex angle of the triangular triangle, the height of the conical protrusions, the average particle diameter, the particle size distribution and the CV value, and analyze the components of the nickel fine particles The meltability of nickel fine particles was measured with an electron beam and shown in Table 1. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and the bases of these cone-shaped projections are in contact with each other, in close contact with each other, or in close contact with each other (FIG. 14 to FIG. 14). In many of these conical projections, the side shape in the transmission electron micrograph is a triangle, the apex angle of the triangle is 25 degrees, and the height of the triangle is 1.6 times. The triangular height has conical protrusions larger than 1/4 of the average particle diameter, the average particle diameter is 1.0 μm, the CV value of the particle size distribution is small 61%, and the electron beam irradiation Thus, it was confirmed that the nickel fine particles were melted.

50 parts of the nickel fine particles obtained above and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. . The paste-like conductive thermosetting epoxy resin composition was measured for viscosity, micro-ejection property, hardness after curing, volume resistivity and shear bond strength, and are shown in Table 1. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 2]
A second fluid was prepared in the same manner as in Example 1 except that the nickel salt, nickel (II) sulfate hexahydrate, was 52.1%. The pH of the aqueous solution was 6.1.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.3.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 1. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 29 degrees, the height of the triangle is 1.7 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 0.9 μm, the CV value of the particle size distribution is 76%, and the nickel fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 1 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 3]
A first fluid was prepared in the same manner as in Example 1 except that the reducing agent hydrazine monohydrate was changed to 1.2%. The pH of the aqueous solution was 11.9.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.3.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 1. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface (see FIGS. 16 and 18), and these cone-shaped projections have their roots in contact with each other, closely or in contact with each other. Close to each other (see FIG. 18), and many of these cone-shaped projections are triangular in the side shape in the transmission electron micrograph (see FIGS. 16 and 22), and the apex angle of the triangle is 24 degrees, The height of the triangle is 2.2 times, and the height of the triangle has at least six conical protrusions larger than 1/4 of the average particle diameter (see FIGS. 16 and 22), and the average particle diameter Is 0.6 μm, the CV value of the particle size distribution is small and 65%, and it was confirmed that nickel fine particles were melted by irradiation with an electron beam (see FIG. 17).
In addition, the tip part of the cone-shaped protrusion is missing, and there is a shape in which the shape of the cone-shaped protrusion when viewed from the side is not a triangle (see FIGS. 16 and 22). It is generated by breakage due to force majeure such as unintentional force. The same applies to other embodiments.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 1 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 4]
In Example 1, the same procedure was performed except that the ethylene glycol, which is the boiling point increasing agent of the first fluid, was 0%, and the polyethylene glycol (average molecular weight 600), which was the boiling point increasing agent of the second fluid, was 0%. One fluid was adjusted. The pH of the aqueous solution was 12.0.

In Example 1, the first fluid was introduced between the processing surface 1 and the processing surface 2 except that the supply temperature of the first fluid was set to 60 ° C. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 1. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 30 degrees, the height of the triangle is 1.4 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 2.2 μm, the CV value of the particle size distribution is 85%, and nickel fine particles can be melted by electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 1 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 5]
The same procedure as in Example 1 was carried out except that the first fluid boiling point raising agent, ethylene glycol, was changed to 60%, and the second fluid boiling point raising agent, polyethylene glycol (average molecular weight 600), was changed to 5%. A fluid was prepared. The pH of the aqueous solution was 12.0.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 2. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 24 degrees, the height of the triangle is 1.5 times, and the height of the triangle is the average grain size. It has conical protrusions larger than 1/4 of the diameter, the average particle diameter is 1.8 μm, the CV value of the particle size distribution is small and 88%, and the nickel fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 2 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 6]
In Example 1, a second fluid was prepared in the same manner except that 30% of polyvinyl alcohol (average molecular weight 500) as a dispersant was added to the second fluid. The pH of the aqueous solution was 6.5.

In Example 1, the rotation speed of the forced ultrathin film rotary reactor is 1000 rpm, the gap between the first processing surface and the second processing surface is 3 μm, and the first fluid is supplied at a supply pressure of 0.5 MPa / back pressure of 0 MPa. It was similarly introduced between the processing surface 1 and the processing surface 2 of the apparatus except that the pressure was 0.02 MPa. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 2. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 32 degrees, the height of the triangle is 1.5 times, and the height of the triangle is the average grain size. It has conical protrusions larger than 1/4 of the diameter, the average particle diameter is 1.4 μm, the CV value of the particle size distribution is small 67%, and the nickel fine particles can be melted by electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 2 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 7]
In Example 1, a second fluid was prepared in the same manner except that nickel (II) nitrate hexahydrate was used instead of nickel (II) sulfate hexahydrate, which is a nickel salt. The pH of the aqueous solution was 6.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 2. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface (see FIGS. 19 and 20), and these cone-shaped projections have their roots in contact with each other, in close contact with or in contact with each other. Many of these conical projections have a triangular side shape in a transmission electron micrograph (see FIG. 20), the apex angle of the triangle is 28 degrees, and the height of the triangle is 1. 7 times, and the number of the cone-shaped protrusions is larger than 1/4 of the average particle diameter (see FIG. 20), the average particle diameter is 1.0 μm, and the CV value of the particle size distribution Was 69%, and it was confirmed that the nickel fine particles were melted by the electron beam irradiation.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 2 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 8]
In Example 1, a first fluid was prepared in the same manner except that sodium borohydride was used in place of the reducing agent hydrazine monohydrate. The pH of the aqueous solution was 12.2.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.6.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2, Measures the apex angle of triangles, the height of cone-shaped projections, average particle size, particle size distribution and CV value, and analyzes component of nickel fine particles and measures melting properties of nickel fine particles by electron beam. It was shown in 2. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 29 degrees, the height of the triangle is 1.7 times, and the height of the triangle is the average grain size. It has conical protrusions larger than 1/4 of the diameter, the average particle diameter is 1.1 μm, the CV value of the particle size distribution is small, 76%, and nickel fine particles can be melted by electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 2 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 9]
In Example 1, the first fluid was prepared in the same manner except that 10% of sorbitol was used instead of ethylene glycol which is the boiling point raising agent of the first fluid. The pH of the aqueous solution was 12.0.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the cross-section of the conical protrusions Measure the side shape and the apex angle of the triangle that is the side shape, the height of the conical protrusion, the average particle size, the particle size distribution and the CV value, analyze the component of the nickel fine particles, and measure the meltability of the nickel fine particles with an electron beam The results are shown in Table 3. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions are triangular in the shape of the side surface in the transmission electron micrograph, the apex angle of the triangle is 28 degrees, the height of the triangle is 1.5 times, and the height of the triangle is the average grain size. It has cone-shaped protrusions larger than 1/4 of the diameter, the average particle diameter is 1.0 μm, the CV value of the particle size distribution is small 81%, and the nickel fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 3 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 10]
In Example 1, the second fluid was similarly used except that polyethylene glycol (average molecular weight 600), which is the boiling point raising agent of the second fluid, was not used, and 2.1% polyvinyl alcohol (average molecular weight 500) was used as the dispersant. Was prepared. The pH of the aqueous solution was 6.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, it was discharged together with the reaction residue from between the processing surface 1 and the processing surface 2.
Surface shape of nickel fine particles obtained from a slurry-like aqueous solution containing nickel fine particles coated with polyvinyl alcohol (average molecular weight 2000) as a dispersant, side shape of conical protrusions, and apex angle of triangles and cones which are side shapes Table 3 shows the height, average particle size, particle size distribution, and CV value of the protrusions, and the component analysis of the nickel fine particles and the measurement of the meltability of the nickel fine particles with an electron beam. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 24 degrees, the height of the triangle is 1.6 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 1.0 μm, the CV value of the particle size distribution is 72%, and nickel fine particles can be melted by electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 3 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 11]
In Example 1, the first fluid was prepared in the same manner except that potassium hydroxide, which is the pH adjuster of the first fluid, was changed to 0.1%. The pH of the aqueous solution was 8.3, and the difference from the pH of the second fluid was 1.8.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 8.1.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 3. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 29 degrees, the height of the triangle is 1.2 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle diameter is 8.4 μm, the CV value of the particle size distribution is 84%, and the nickel fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 3 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 12]
A second fluid was prepared in the same manner as in Example 1 except that 0.05% concentrated sulfuric acid (concentration 96%), which is a pH adjuster for the second fluid, was added. The pH of the aqueous solution was 4.5, and the difference from the pH of the first fluid was 7.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.2.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 3. The nickel fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 30 degrees, the height of the triangle is 2.4 times, and the height of the triangle is the average grain size. It has conical protrusions larger than 1/4 of the diameter, the average particle diameter is 0.08 μm, the CV value of the particle size distribution is small and 88%, and the nickel fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 3 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 13]
A second fluid was prepared in the same manner as in Example 1, except that iron (II) sulfate heptahydrate, which is an iron salt, was used instead of nickel (II) sulfate, hexahydrate, which was a nickel salt. . The pH of the aqueous solution was 6.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the iron fine particles obtained from the slurry-like aqueous solution containing the iron fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of conical protrusions, average particle size, particle size distribution and CV value, component analysis of iron fine particles, and measurement of meltability of iron fine particles by electron beam The results are shown in Table 4. This iron fine particle has a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 23 degrees, the height of the triangle is 1.6 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 1.1 μm, the CV value of the particle size distribution is small 61%, and the iron fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained iron fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 4 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of this paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 14]
In Example 1, a second fluid was prepared in the same manner except that cobalt (II) sulfate heptahydrate, which is a cobalt salt, was used instead of nickel (II) sulfate, hexahydrate, which was a nickel salt. . The pH of the aqueous solution was 6.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the cobalt fine particles obtained from the slurry-like aqueous solution containing cobalt fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are the shape and side shape, the height of the cone-shaped projections, the average particle size, the particle size distribution and the CV value, component analysis of the cobalt fine particles, and the measurement of the meltability of the cobalt fine particles by an electron beam The results are shown in Table 4. The cobalt fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, in close contact with each other, or in close contact with each other. Many of the protrusions have a triangular side shape in the transmission electron micrograph, the apex angle of the triangle is 22 degrees, the height of the triangle is 1.7 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 1.0 μm, the CV value of the particle size distribution is 76%, and the cobalt fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained cobalt fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were charged into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 4 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of this paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Example 15]
A second fluid was prepared in the same manner as in Example 1, except that chromium (III) sulfate hydrate, which is a chromium salt, was used instead of nickel (II) sulfate hexahydrate, which is a nickel salt. The pH of the aqueous solution was 6.5.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.4.
In the same manner as in Example 1, the surface shape of the chromium fine particles obtained from the slurry-like aqueous solution containing the chromium fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measure the apex angle of triangles that are the shape and side shape, the height of the cone-shaped projections, the average particle size, the particle size distribution, and the CV value, analyze the components of the chromium fine particles, and measure the melting properties of the chromium fine particles with an electron beam The results are shown in Table 4. These chromium fine particles have a large number of substantially polygonal cone-shaped or substantially cone-shaped projections projecting radially on the surface, and these cone-shaped projections have their roots in contact with each other, intimately, or in close contact with each other. Many of the protrusions are triangular in the side shape in the transmission electron micrograph, the apex angle of the triangle is 24 degrees, the height of the triangle is 1.7 times, and the height of the triangle is the average grain size. It has cone-shaped projections larger than 1/4 of the diameter, the average particle size is 0.9 μm, the CV value of the particle size distribution is small and 65%, and the chromium fine particles can be melted by the electron beam irradiation. It could be confirmed.

50 parts of the obtained chromium fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 4 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of this paste-like conductive thermosetting epoxy resin composition. This paste-like conductive thermosetting epoxy resin composition was confirmed to be excellent in conductivity and adhesiveness. In the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition, no clogging occurred.

[Comparative Example 1]
The first fluid (pH 12.0) used in Example 1 was placed in a glass flask and heated to 100 ° C. in an oil bath. Subsequently, while stirring using an ultrasonic homogenizer (US-150T manufactured by Nippon Seiki Seisakusho Co., Ltd.), the second fluid at normal temperature (pH 6.5) used in Example 1 was dropped with an infusion funnel and dispersed. Nickel fine particles coated with an agent were obtained together with an aqueous solution (pH 11.4) as a reaction residue.

The obtained slurry-like aqueous solution containing nickel fine particles was allowed to stand on a magnet to precipitate the nickel fine particles, and then the separated nickel fine particles were washed with pure water and then with methanol and then vacuum-dried. The surface shape of the obtained nickel fine particles was observed, the average particle size, the particle size distribution, and the CV value were measured. The component analysis of the nickel fine particles and the meltability of the nickel fine particles were measured with an electron beam. . The nickel fine particles had no protrusions on the surface, the average particle size was 13.0 μm, the CV value of the particle size distribution was 330%, and it was confirmed that the nickel fine particles were not melted by electron beam irradiation.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 5 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 2]
As a first fluid, an aqueous solution containing 10.5% of hydrazine monohydrate as a reducing agent, 43.75% of ethylene glycol as a boiling point increasing agent, and 2% of potassium hydroxide as a pH adjusting agent was prepared. The pH of the aqueous solution was 12.0.
As the second fluid, an aqueous solution containing 89% nickel (II) sulfate hexahydrate, which is a nickel salt, and 2.1% polyethylene glycol (average molecular weight 600), which is a boiling point increasing agent, was prepared. The pH of the aqueous solution was 6.1, but nickel (II) sulfate hexahydrate was not completely dissolved and could not be introduced into the forced ultrathin film rotary reactor.

[Comparative Example 3]
A first fluid was prepared in the same manner as in Example 1 except that the reducing agent hydrazine monohydrate was changed to 0.1%. The pH of the aqueous solution was 11.8.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.2.
In the same manner as in Example 1, the aqueous solution discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 contained almost no nickel fine particles. The results are shown in Table 5.
[Comparative Example 4]
A first fluid was prepared in the same manner as in Example 1 except that the reducing agent hydrazine monohydrate was changed to 30.0%. The pH of the aqueous solution was 12.8.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 12.1.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 was observed, and the average particle size was measured. The diameter, particle size distribution, and CV value were measured, and the component analysis of the nickel fine particles and the meltability of the nickel fine particles with an electron beam were measured and shown in Table 5. The nickel fine particles had almost no protrusions on the surface, the average particle size was 1.5 μm, the CV value of the particle size distribution was large 162%, and it was confirmed that the nickel fine particles were not melted by the electron beam irradiation.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 5 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 5]
In Example 1, the first fluid was prepared in the same manner except that concentrated sulfuric acid (concentration 96%) 0.4% was used instead of potassium hydroxide which is the pH adjuster of the first fluid. The pH of the aqueous solution was 6.8, but no nickel fine particles were generated. The results are shown in Table 6.
[Comparative Example 6]
In Example 1, the 2nd fluid was prepared similarly except having added 1% of potassium hydroxide as a pH adjuster to the 2nd fluid. Although the pH of the aqueous solution was 9.0, nickel fine particles were not generated. The results are shown in Table 6.
[Comparative Example 7]
In Example 1, the second fluid was prepared in the same manner except that 0.1% concentrated sulfuric acid (concentration 96%) was added to the second fluid as a pH adjuster. The pH of the aqueous solution was 2.8. The results are shown in Table 6.

In the same manner as in Example 1, the first fluid and the second fluid were introduced between the processing surface 1 and the processing surface 2 by a forced ultrathin film rotary reactor. The pH of the thin film fluid was 11.0.
In the same manner as in Example 1, the surface shape of the nickel fine particles obtained from the slurry-like aqueous solution containing nickel fine particles discharged together with the reaction residue from between the processing surface 1 and the processing surface 2 and the side surfaces of the conical projections Measures the apex angle of triangles that are shapes and side shapes, the height of cone-shaped projections, average particle size, particle size distribution and CV value, component analysis of nickel fine particles, and measurement of meltability of nickel fine particles by electron beam The results are shown in Table 6. The nickel fine particles have a large number of substantially polygonal pyramid or substantially conical protrusions projecting radially on the surface, the average particle diameter is 14.0 μm, and the CV value of the particle size distribution is large, 230%. It was confirmed that the nickel fine particles were melted by the irradiation of the wire.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 6 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of this paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 8]
In Example 1, the rotational speed of the forced ultrathin film rotary reactor is 100 rpm, the gap between the first processing surface and the second processing surface is 30 μm, and the first fluid is supplied at a supply pressure of 0.1 MPa / back pressure of 0 MPa. It was introduced between the processing surface 1 and the processing surface 2 of the apparatus in the same manner except that the pressure was 0.1 MPa. The pH of the thin film fluid was 11.4.
From a slurry-like aqueous solution containing nickel fine particles, in which nickel fine particles coated with polyethylene glycol (average molecular weight 600) as a dispersant are discharged together with an aqueous solution as a reaction residue from between the treatment surface 1 and the treatment surface 2 Measure the surface shape of the obtained nickel fine particles, the side shape of the conical protrusions, the apex angle of the triangular triangle, the height of the conical protrusions, the average particle diameter, the particle size distribution and the CV value, and analyze the components of the nickel fine particles The meltability of nickel fine particles was measured with an electron beam and shown in Table 6. The nickel fine particles have a large number of substantially polygonal pyramid or substantially conical protrusions projecting radially on the surface, the average particle diameter is 17.5 μm, and the CV value of the particle size distribution is large, 295%. It was confirmed that the nickel fine particles were melted by the irradiation of the wire.

50 parts of the obtained nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in Reference Example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 6 shows the viscosity, hardness after curing, volume resistivity, and shear bond strength of this paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 9]
In Example 1, instead of the nickel fine particles obtained in Example 1, the surface shape of the nickel fine particles was observed in the same manner except that the commercially available granular nickel fine particles having an average particle diameter of 2.5 μm were used. The particle size, particle size distribution, and CV value were measured, and the component analysis of the nickel fine particles and the meltability of the nickel fine particles with an electron beam were measured and shown in Table 7. The nickel fine particles had no protrusions on the surface, the average particle size was 2.5 μm, the CV value of the particle size distribution was large, and it was confirmed that the nickel fine particles were not melted by the electron beam irradiation.

50 parts of the nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 7 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 10]
In Example 1, instead of the nickel fine particles obtained in Example 1, flaky nickel fine particles (stearic acid adhesion amount of 0.3%) having a commercially available surface coated with stearic acid and an average particle size of 7.0 μm were used. In the same manner except that it was used, the surface shape of the nickel fine particles was observed, the average particle size, the particle size distribution, and the CV value were measured. It is shown in Table 7. The nickel fine particles had no protrusions on the surface, the average particle size was 7.0 μm, the CV value of the particle size distribution was large, and it was confirmed that the nickel fine particles were not melted by the electron beam irradiation.

50 parts of the nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 7 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 11]
In Example 1, in place of the nickel fine particles obtained in Example 1, nickel fine particles having an average particle diameter of 3.9 μm having needle-like protrusions manufactured by the method described in Example 4 of Japanese Patent No. 3828787 In the same manner, the surface shape of the nickel fine particles, the cross-sectional shape of the protrusions and the apex angle of the triangle, which is the side shape, the height of the conical protrusions, the average particle diameter, the particle size distribution, and the CV value were measured. Table 7 shows the component analysis of the fine particles and the measurement of the meltability of the nickel fine particles with an electron beam. The nickel fine particles had needle-like protrusions on the surface, the average particle size was 3.9 μm, the CV value of the particle size distribution was large, and it was confirmed that the nickel fine particles were not partially melted by electron beam irradiation. .

50 parts of the nickel fine particles and 50 parts of the liquid thermosetting epoxy resin composition prepared in the reference example were put into a mixer and mixed uniformly to prepare a paste-like conductive thermosetting epoxy resin composition. Table 7 shows the viscosity, hardness after curing, volume resistivity and shear bond strength of the paste-like conductive thermosetting epoxy resin composition. The paste-like conductive thermosetting epoxy resin composition has low conductivity, and clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 12]
As described in Example 1 of Japanese Patent Application Laid-Open No. 2007-191786, a base solution containing 50 ml of ion exchange water and 4 g of nickel chloride hexahydrate was prepared. 1 ml of concentrated sulfuric acid was added to this base solution, and NaOH was further added to adjust the solution to about pH 12 with pH test paper. This liquid was kept at a temperature of 60 ° C. in an oil bath, and 3 ml of hydrazine hydrate was added to react. The reaction is completed within 5 hours, and many small conical protrusions on the outer surface have a height lower than 1/4 of the particle diameter (the height of the conical protrusion is 0.7 times the equivalent diameter of the circular area). Obtained nickel powder which grew densely. The average particle diameter of the nickel powder was 1.3 μm, and the CV value was 185%.
50 parts by mass of the above-obtained nickel powder and 50 parts by mass of the liquid thermosetting epoxy resin composition prepared in the reference example are charged into a mixer and mixed uniformly to form a paste-like conductive thermosetting epoxy resin composition. Was prepared. When the volume resistivity of the conductive cured product of the paste-like conductive thermosetting epoxy resin composition was measured, it was 1.1 × 10 ⁺¹ Ω · cm. The volume resistivity of the electroconductive cured product is large, and the electroconductive thermosetting epoxy resin composition in the form of paste has a remarkably low electroconductivity compared to the electroconductive thermosetting epoxy resin composition of the examples of the present application. Was confirmed. Moreover, clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 13]
A base solution containing 25 ml of ion exchange water and 2 g of nickel chloride hexahydrate was prepared as described in Example 4 of JP2007-191786. To this base solution, 1.7 g of sodium carbonate was added. Further NaOH was added to make the pH alkaline. Concentrated nitric acid (2 ml) was added to this solution, NaOH was further added, and the solution was adjusted to a pH of about 12 with pH test paper. This liquid was kept at a temperature of 60 ° C. in an oil bath, and 6 ml of hydrazine hydrate was added and reacted. The reaction is completed within 20 hours, and a large number of small heights on the outer surface are lower than 1/4 of the particle diameter (the height of the cone-shaped protrusion is 0.3 times the equivalent diameter of the circular area). Obtained nickel powder which grew densely. The average particle diameter of the nickel powder was 1.9 μm, and the CV value was 210%.
50 parts by mass of the above-obtained nickel powder and 50 parts by mass of the liquid thermosetting epoxy resin composition prepared in the reference example are charged into a mixer and mixed uniformly to form a paste-like conductive thermosetting epoxy resin composition. Was prepared. When the volume resistivity of the conductive cured product of the paste-like conductive thermosetting epoxy resin composition was measured, it was 1.6 × 10 ⁺¹ Ω · cm. This conductive composition has a large volume resistivity, and the paste-like conductive thermosetting epoxy resin composition has a significantly lower conductivity than the conductive thermosetting epoxy resin composition of the examples of the present application. Was confirmed. Moreover, clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

[Comparative Example 14]
A base solution containing 25 ml of ion exchange water and 2 g of nickel chloride hexahydrate was prepared as described in Example 6 of JP2007-191786. To this base solution, 0.2 g of sodium sulfate, 0.2 g of potassium nitrate, and 1.7 g of sodium carbonate were added, NaOH was further added, and the solution was adjusted to a pH of about 12 with pH test paper. Further, 2 ml of concentrated aqueous ammonia was added.
This liquid was kept at a temperature of 60 ° C. in an oil bath, and 8 ml of hydrazine hydrate was added to react. The reaction is completed within 5 hours, and many small conical protrusions are formed on the outer surface whose height is lower than 1/4 of the particle diameter (the height of the conical protrusion is 0.4 times the equivalent diameter of the circular area). Obtained nickel powder which grew densely. The average particle diameter of the nickel powder was 6.3 μm, and the CV value was 190%.
50 parts by mass of the above-obtained nickel powder and 50 parts by mass of the liquid thermosetting epoxy resin composition prepared in the reference example are charged into a mixer and mixed uniformly to form a paste-like conductive thermosetting epoxy resin composition. Was prepared. When the volume resistivity of the conductive cured product of the paste-like conductive thermosetting epoxy resin composition was measured, it was 4.5 × 10 ⁺¹ Ω · cm. The volume resistivity of the electroconductive cured product is large, and the electroconductive thermosetting epoxy resin composition in the form of paste has a remarkably low electroconductivity compared to the electroconductive thermosetting epoxy resin composition of the examples of the present application. Was confirmed. Moreover, clogging occurred in the micro-discharge test of the paste-like conductive thermosetting epoxy resin composition.

DESCRIPTION OF SYMBOLS 1 1st processing surface 2 2nd processing surface 3 Case 4 Contact surface pressure provision mechanism 5 Groove-shaped recessed part 10 1st disk 20 2nd disk 32 Outlet d1 1st introduction part d2 2nd introduction part d3 3rd introduction Part p1 First fluid pressure applying mechanism p2 Second fluid pressure applying mechanism 50 Rotating shaft 1M First processing surface 2M Second processing surface 3M Case 4M Contact surface pressure applying mechanism 10M First processing unit 10RM First ring 11M First 1 holder 20M second processing part 20RM second ring 21M second holder d1M first introduction part d2M second introduction part p1M fluid pressure application mechanism p2M fluid pressure application mechanism 32M discharge port 41M ring housing part 50M rotating shaft

Claims (17)

Introducing a fluid to be treated which is a liquid phase between the first processing surface and the second processing surface, which are arranged to face each other so as to be able to approach and leave, and at least one of which rotates relative to the other; A force for moving the second processing surface away from the first processing surface is generated by the pressure of the fluid to be processed, and this force causes a gap between the first processing surface and the second processing surface. The fluid to be processed passing between the first processing surface and the second processing surface maintained at a minute interval and formed between the first processing surface and the second processing surface forms a thin film fluid. A continuous production method of metal fine particles in which metal fine particles are precipitated by the reaction of a reducing agent with a reducing agent,
The fluid to be treated is composed of at least two fluids to be treated, and the first fluid to be treated is an aqueous medium having a pH in the range of 8 to 13 and containing at least a reducing agent and a pH adjuster. The fluid to be treated is an aqueous medium having a pH of 3 to 7 containing at least a metal salt, and the pH of the first fluid to be treated is 1 to 8 larger than the pH of the second fluid to be treated. Each fluid to be treated is introduced between the first processing surface and the second processing surface through a separate introduction path, and the metal ions are reduced in the thin film fluid having a pH of greater than 5 but not greater than 12. Metal fine particles are deposited, and the metal fine particles have a plurality of radially projecting conical projections whose conical projections have a triangular side shape in a transmission electron micrograph, and the apex angle of the triangle is 10 to 10. is 40 degrees, conical projections of said plurality of so that the viewing That the roots are in contact with each other, an average particle diameter of 0.01 to 10 [mu] m, wherein the CV value of the particle size distribution of the fine metal particles is less than 100%, the continuous production method of fine metal particles. 2. The metal fine particle according to claim 1, wherein either or both of the first treated fluid and the second treated fluid further contain a boiling point increasing agent and / or a dispersing agent. Continuous manufacturing method. The fluid to be treated includes three fluids to be treated, which are a first fluid to be treated, a second fluid to be treated, and a third fluid to be treated. The aqueous medium having a pH of 8 to 13 containing at least a reducing agent and a pH adjuster, and the second fluid to be treated is an aqueous medium having a pH of 3 to 7 containing at least a metal salt; The third treated fluid is an aqueous medium containing at least a dispersant, and the first treated fluid, the second treated fluid, and the third treated fluid are separated from the separate introduction paths. The method for continuously producing metal fine particles according to claim 1, wherein the thin film fluid is introduced between the first processing surface and the second processing surface to form a thin film fluid having a pH greater than 5 but not greater than 12. The metal salt, the reducing agent, and the pH adjusting agent in the fluid to be treated are dissolved in water, a water-soluble alcohol, or a mixture of water and a water-soluble alcohol. The continuous manufacturing method of the metal microparticle as described in any one of. 5. The metal salt is a nickel salt, an iron salt, a cobalt salt or a chromium salt, and the metal fine particles are nickel fine particles, iron fine particles, cobalt fine particles, or chromium fine particles. The continuous manufacturing method of metal microparticles of any one of these. The method for continuously producing fine metal particles according to any one of claims 1 to 4, wherein the reducing agent is an organic reducing agent, or an inorganic reducing agent and an organic reducing agent. . The metal fine particle according to any one of claims 1 to 4, wherein the pH adjuster is an organic alkali or acid, an inorganic alkali or acid, or an alkaline or acidic salt. Continuous manufacturing method. The method for continuously producing fine metal particles according to claim 2 or 4, wherein the boiling point raising agent is a polyhydric alcohol or a polyether. The method for continuously producing fine metal particles according to claim 2 or 3, wherein the dispersant is a high / intermediate fatty acid salt, a natural polymer dispersant, or a synthetic polymer dispersant. The thin film fluid before the reaction between the metal ions and the reducing agent has a metal salt concentration of 0.02 to 1.1 mol%, and the reducing agent is the same mol to 90 times mol% of the metal salt. The continuous production method of metal fine particles according to any one of claims 1 to 9, wherein The speed at which one of the first processing surface and the second processing surface rotates with respect to the other is 250 rpm to 3000 rpm, and the minute interval is 0.1 μm to 20 μm. Item 11. The method for continuously producing metal fine particles according to any one of Items 10. The method for continuously producing metal fine particles according to claim 1 or 5, wherein at least the surface of the metal fine particles is melted by irradiation with an electron beam of 10 keV or more. (A) A plurality of radially projecting conical protrusions manufactured by the continuous manufacturing method according to any one of claims 1 to 12, wherein the side shape of the transmission electron micrograph is a triangle. The apex angle of the triangle is 10 to 40 degrees, the plurality of cone-shaped protrusions are in contact with each other at their visible bases, and the average particle diameter is 0. A method for producing a conductive curable composition comprising uniformly mixing fine metal particles having a particle size distribution CV value of 100% or less and (B) a curable organic resin. Furthermore, (C) hardening | curing agent and / or (D) adhesion promoter are added and mixed uniformly, The manufacturing method of the conductive curable composition of Claim 13 characterized by the above-mentioned. (A ¹ ) a plurality of radially projecting conical protrusions having conical protrusions whose side shape in a transmission electron micrograph is a triangle, and the apex angle of the triangle is 10 to 40 degrees; The plurality of conical protrusions are in contact with each other at their visible bases , have an average particle size of 0.01 to 10 μm, and a metal fine particle having a CV value of 100% or less of the particle size distribution of the metal fine particle , (B), characterized in that it consists of a curable organic resin, the conductive curable composition.   The conductive curable composition according to claim 15, further comprising (C) a curing agent and / or (D) an adhesion promoter. Characterized by joining the electronic component selected from the discrete components and the chip component and the circuit board using the conductive curable composition according to the manufacturing method according to claim 13 or claim 14, the electronic device Manufacturing method .