JP2014148756A - Colloid of composite metal nanoparticle, composite metal nanoparticle, method for producing colloid of composite metal nanoparticle, method for producing composite metal nanoparticle, and apparatus for producing colloid of composite metal nanoparticle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive, highly pure and highly concentrated colloid of composite metal nanoparticles by a physical producing method.SOLUTION: First metal nanoparticles constituting composite metal nanoparticles have an average particle diameter of 10 nm to 100 nm, At least one metal nanoparticle of each metal nanoparticle composing the encircling nanoparticle arranged around the first metal nanoparticles has an average particle diameter of less than 10 nm. A colloid of composite metal nanoparticle 27 comprises a composite metal nanoparticle and a surfactant without solvents. A metal evaporated in a vacuum is obtained by capturing with a membranous surfactant layer 26 formed on the surface of an inner wall 21a of a vacuum evaporator.

Description

  The present invention relates to a composite metal nanoparticle colloid, a composite metal nanoparticle, a production method thereof, and a composite metal nanoparticle colloid production apparatus, and more specifically, around a first metal nanoparticle that becomes a core nanoparticle. , At least one of a metal type, a particle size, a shape, and an activity of solid-phase reaction is formed by providing a set of a plurality of metal nanoparticles different from the first metal nanoparticles. The present invention relates to a composite metal nanoparticle colloid containing composite nanoparticles as main composite metal nanoparticles, a composite metal nanoparticle, a production method thereof, and a composite metal nanoparticle colloid production apparatus.

  In recent years, attention has been paid to the possibility of using nanoparticles, that is, particles having a particle size of 100 nm or less such as 5 nm (nanometer) or 30 nm. Many improvements are being made, such as attempts to use in catalysts such as fuel cells and exhaust gas purification devices, attempts to use in magnetic media, and attempts to use in semiconductors.

  Several different methods have been proposed for producing metal nanoparticles. They are roughly classified into a chemical method using a chemical reaction in a solution and a physical method in which metal particles are captured in a fine particle state by evaporation or the like in a vacuum.

  As those proposals, there are overwhelmingly many proposals regarding chemical production using reduction reactions, and there are also overwhelmingly many studies on these.

  Metal nanoparticle colloids based on chemical manufacturing methods are complex in many stages, require precise pH control and heat treatment, are expensive and inefficient. The situation is different from metal nanoparticle colloids based on physical manufacturing methods with respect to several important things, such as difficulty in production and the inclusion of compounds in the produced metal nanoparticle colloids.

  It is known that the metal nanoparticles of the present invention are ultrafine particles having a particle size of 100 nm or less, and have properties that are greatly different from, for example, particles having a particle size of 200 nm or more.

  The present invention relates to a composite metal nanoparticle described later, and one of its features is that a physical manufacturing method is used to form a composite nanoparticle constituting the main part of the composite metal nanoparticle of the present invention. However, in order to clarify the present invention, the metal nanoparticle colloid based on the chemical production method with many proposals will be briefly described.

  Patent Document 1 describes a binary metal nanoparticle obtained by polyol reduction of two kinds of metal salts such as a Co salt and a Pd salt at a high temperature in the presence of a thiol compound such as alkanethiol and a production method. .

  Patent Document 2 describes a method of obtaining Fe / Pd composite nanoparticles by a reduction reaction of a metal salt in a solvent.

  Patent Document 3 describes a method for producing composite nanoparticles such as Ag / Pd using a chemical production method of reducing a metal ion-containing liquid.

  Patent Document 5 describes an example of a nanoparticle colloid based on a physical production method. This is because an inorganic material is evaporated in a vacuum using an apparatus similar to the magnetic fluid manufacturing apparatus described in Patent Document 4, and the vapor is combined with the inner wall along the inner wall of a cylindrical rotating vacuum chamber. A rotating surfactant is trapped in a film-like liquid medium dissolved in a solvent, and is produced in a colloidal form.

  In the method for producing nanoparticles described in Patent Documents 1 to 3, since the production process is complicated and goes through a chemical reduction reaction, it is necessary to precisely control the concentration and temperature of the reducing agent and the solvent. It is difficult to obtain a uniform particle size or crystal state.

  In the chemical production of nanoparticles described in Patent Document 1, a thiol compound is indispensable, and there is a problem in the production environment.

  In the method described in Patent Document 1, metal salts are acetylacetonate salts, acetate salts, chlorides, and sulfides, and there are large restrictions on metal salts and noble metal salts. In addition, the alkanethiol has 8 or more carbon atoms, the solvent to be dissolved is limited, and a high boiling point solvent is required.

  As described in paragraph 0014 of Patent Document 1, an anisotropic phase-separated sulfur-containing CoPd nanoparticle (nanoacorn) is obtained as the obtained nanoparticle, which is a nanoparticle made of sulfide.

  The method described in Patent Document 2 is Fe / Pd bimetallic nanoparticles, but since it is produced via a chemical reduction reaction, it is necessary to precisely control the reaction temperature, the concentration of the reactants, and the like. The process is complicated and inefficient. Moreover, an expensive complex raw material must be used, which is disadvantageous in that the production cost from this aspect is high. Furthermore, depending on the type of the reducing agent, it is difficult to efficiently and inexpensively produce nanoparticles having a two-phase separation structure without phase separation.

  Thus, in the production of nanoparticles by this chemical production method, there are significant restrictions on the form of the product and the type of metal, which makes it difficult to control the reaction.

  Patent Documents 6 to 8 describe core / shell nanoparticles produced by a chemical production method.

  Patent Document 6 describes nano-order core / shell nanoparticles composed of an atomic group of two or more atoms.

  Patent Document 7 describes that a core / shell nanoparticle is prepared by mixing a core / shell colloid of two types of particles and a single type of nanoparticle colloid, and the catalyst prepared from this colloid has catalytic activity. It is described that it is extremely high.

  Patent Document 8 describes silver (core) / copper core / shell nanoparticles.

  Each nanoparticle described in Patent Documents 6 to 8 is a nanoparticle produced by a chemical production method. In addition to the above-mentioned major limitations in production, each of the core and shell atoms also undergoes a chemical reaction. There are very big restrictions such as things that cannot be done.

  The nanoparticle described in Patent Document 5 is based on a physical production method. A surfactant polybutenyl succinic acid tetramineimide in which a raw material metal is evaporated in a rotating vacuum chamber and loaded in the vacuum chamber. In this method, 120 g of a 7.1% alkylnaphthalene solution is made by trapping the evaporated metal with a rotating liquid medium in a thin film shape along the inner wall of the rotating vacuum chamber.

  The physical production method is simple because the number of steps is small and separation and concentration after the production of the colloid is sufficient in two steps.

  The method of Patent Document 5 is a manufacturing method based on the idea of diluting and fluidizing a surfactant with a solvent, attaching it to the rotating inner wall of the vacuum chamber, rotating it with the inner wall of the vacuum chamber, and capturing with the surfactant in the solvent. Yes, the surfactant solvent cannot be used in a vacuum.

  As described above, various methods for producing nanoparticles have been proposed, but there are many problems in industrial use.

  For example, when copper nanoparticles are produced by the above physical method, after the copper nanoparticle colloid is taken out from the vacuum into the atmosphere, the copper oxidation phenomenon proceeds strongly, and even if various surfactants are devised, the copper It is impossible to suppress this oxidation phenomenon for 20 days. In addition, copper nanoparticle colloids produced by a chemical method cannot stop the oxidation of copper and are currently used with a reduction step when used.

Japanese Patent Laid-Open No. 2005-240099 JP 2008-138243 A JP 2008-138243 A JP 60-161490 A JP 2008-150630 A JP 2004-263222 A JP 2004-332028 A JP 2008-248298 A

  As described above, the metal nanoparticles having a particle size of 100 nm or less are different from the metal particles having a particle size of 200 nm or more, and there are great expectations for new properties and use thereof. Various methods for producing particle colloids have been proposed. However, metal nanoparticle colloids produced by these methods have many difficult problems.

  In the production of metal nanoparticle colloid by the chemical method, there are problems of compounds and by-products, and further, there are problems such as complicated manufacturing process, difficulty in manufacturing, and high manufacturing cost.

  On the other hand, in the production of metal nanoparticle colloids by the physical method, the above-mentioned problems in the production of metal nanoparticle colloids by the chemical method are not basically, but in reality, there are some solutions. There is a problem.

  For example, the metal nanoparticle colloid produced by the physical method described in Patent Document 5 uses a surfactant diluted with a solvent that can be used in a vacuum as a medium for collecting evaporated metal. When supplying the manufactured metal nanoparticle colloid to the user, in many cases, the solvent of the surfactant is removed to replace the solvent, and the labor and cost become a big problem. Yes.

  Furthermore, since the metal nanoparticle colloid produced by the physical method captures and collects the evaporated metal in a moving membranous liquid medium in which a surfactant is dissolved in a solvent, the membranous liquid medium is collected. The concentration of the metal inside cannot be increased. One of the main reasons is that the surfactant concentration is low because it must be dissolved in a solvent and diluted. That is, the evaporated metal can be collected as a nanocolloid by the surfactant, but the evaporated metal particles cannot be collected by the solvent in which the surfactant is dissolved.

  In the method described in Patent Document 5, when the concentration of the metal particles in the film-like liquid medium exceeds a certain level, the film-like liquid medium containing the metal particles is placed above the inner wall of the rotating vacuum chamber. The fallen object often falls off the inner wall, and the fallen object falls into a crucible containing an evaporation source, forcing the production to be stopped.

  Although the practical application of metal nanoparticles is expected, there are still no multi-component metal nanoparticle colloids produced using metal nanoparticle colloids produced by this physical method.

  In addition, there are problems to be solved for practical use of metal nanoparticles. For example, if the copper nanoparticle colloid produced by the above physical method is taken out from the vacuum chamber to the atmosphere, it will oxidize, and even if the surfactant can be variously devised to slow down the oxidation rate somewhat. It has not been able to hold for 20 days, and how to stop this change has not yet been resolved.

  The present invention has been made as a solution to some of these problems, and one of the objects of the present invention is to provide composite metal nanoparticles capable of exhibiting the physical properties of metal nanoparticles at a mass production level at low cost. There is to provide to. And it exists in providing the improved manufacturing method and manufacturing apparatus for it.

  The present invention has been made in view of the above circumstances, and is intended to provide a high-quality composite metal nanoparticle colloid and a composite metal nanoparticle capable of fully exhibiting the performance as a nanoparticle at a mass production level at low cost. In addition, a manufacturing method and a manufacturing apparatus thereof are also provided.

  Hereinafter, the present invention made to solve the problems will be described more specifically.

  A first invention (hereinafter referred to as invention 1) as an example of the present invention made to solve the problem is a metal fine particle (hereinafter referred to as metal nanoparticle) having a particle size of 100 nm (nanometer) or less in a dispersant. The main composite metal nanoparticles in the composite metal nanoparticle colloid include the first metal nanoparticles having a particle size of less than 100 nm as the core nanoparticles. Around the first metal nanoparticles, a plurality of metal nanoparticles in which at least one of the metal type, particle size, shape, and activity of the solid-phase reaction is different from the first metal nanoparticles are arranged. A composite nanoparticle comprising at least one type of aggregate (hereinafter referred to as a surrounding nanoparticle), wherein the first metal nanoparticle is applied by evaporation or the like in a reduced pressure atmosphere or in a vacuum. It is a nano-particle formed by repeatedly capturing and collecting a metal-movable state in a reduced-pressure atmosphere or in a vacuum with a membrane-like surfactant moving body. It is a composite metal nanoparticle colloid.

  A second invention (hereinafter referred to as invention 2) as an example of the present invention made to solve the problem is a metal fine particle (hereinafter referred to as metal nanoparticle) having a particle size of 100 nm (nanometer) or less in a dispersant. The main composite metal nanoparticles in the composite metal nanoparticle colloid include the first metal nanoparticles having a particle size of less than 100 nm as the core nanoparticles. Around the first metal nanoparticles, a plurality of metal nanoparticles in which at least one of the metal type, particle size, shape, and activity of the solid-phase reaction is different from the first metal nanoparticles are arranged. A composite nanoparticle comprising at least one type of aggregate (hereinafter referred to as a surrounding nanoparticle), wherein at least one type of the surrounding nanoparticle is in a reduced pressure atmosphere or in a vacuum Capturing and collecting the metal in a movable state by evaporation or the like with a movable body of a film-like surfactant that moves in a reduced-pressure atmosphere or vacuum in which the first metal nanoparticles are captured. It is a composite metal nanoparticle colloid characterized in that it is a nanoparticle formed repeatedly.

  A third invention (hereinafter referred to as invention 3) as an example of the present invention developed by developing invention 1 or 2 is the composite metal nanoparticle colloid according to invention 1 or 2, wherein the composite metal nanoparticle is: At least two kinds of surrounding nanoparticles are arranged around the core nanoparticles, and the metal nanoparticles constituting the surrounding nanoparticles closest to the first metal nanoparticles are referred to as second metal nanoparticles. The metal nanoparticles constituting the next surrounding nanoparticles are referred to as third metal nanoparticles (the same applies hereinafter), and the particle diameter of the second metal nanoparticles is the first metal nanoparticles. The composite metal nanoparticle colloid is characterized in that the particle diameter of the third metal nanoparticles is smaller than the particle diameter of the second metal nanoparticles.

  A fourth invention (hereinafter referred to as invention 4) as an example of the present invention developed by developing inventions 1 to 3 is the composite metal nanoparticle colloid according to any one of inventions 1 to 3, in the reduced-pressure atmosphere. Alternatively, the moving body of the membrane-like surfactant moving in vacuum is a composite metal nanoparticle colloid characterized by being a membrane-like surfactant in which the surfactant is fluidized without being dissolved in a solvent. is there.

  A fifth invention (hereinafter referred to as invention 5) as an example of the present invention developed by developing inventions 1 to 4 is the composite metal nanoparticle colloid according to any one of inventions 1 to 4, wherein the composite metal nano The core nanoparticles and surrounding nanoparticles that make up the particles are all collected in a reduced-pressure atmosphere or in a vacuum by making the metal movable by evaporation, etc. This is a composite metal nanoparticle colloid characterized in that it is a nanoparticle formed by repeating this process.

  A sixth invention (hereinafter referred to as invention 6) as an example of the present invention developed by developing inventions 1 to 5 is the composite metal nanoparticle colloid according to any one of inventions 1 to 5, wherein the composite metal nano It is a composite metal nanoparticle colloid characterized in that the core nanoparticles and the surrounding nanoparticles constituting the particles are all nanoparticles produced using the same surfactant.

  A seventh invention (hereinafter referred to as invention 7) as an example of the present invention developed by developing inventions 1 to 6 is the composite metal nanoparticle colloid according to any one of inventions 1 to 6, wherein the composite metal nano A plurality of nanoparticles among the core nanoparticles and the surrounding nanoparticles constituting the particles may be produced by evaporation or the like in a reduced pressure atmosphere or in a vacuum in a continuous process or the same process without breaking the vacuum state. It is a composite metal nanoparticle colloid characterized in that it is a nanoparticle formed by repeatedly capturing and collecting a movable substance in a membrane-like surfactant that has been made movable.

  An eighth invention (hereinafter referred to as invention 8) as an example of the present invention developed by developing inventions 3 to 7 is the composite metal nanoparticle colloid according to any one of inventions 3 to 7, wherein the composite In the metal nanoparticles, the first metal nanoparticles are on the innermost side, and the surrounding nanoparticles composed of the second metal nanoparticles and the third metal nanoparticles on the outside thereof It is a composite metal nanoparticle colloid characterized in that there is a portion where is mixed.

  The ninth invention (hereinafter referred to as invention 9) as an example of the present invention developed by developing inventions 3-8 is the composite metal nanoparticle colloid according to any one of inventions 3-8, wherein the composite In the metal nanoparticles, at least two kinds of surrounding nanoparticles are arranged around the core nanoparticles, the first metal nanoparticles are on the innermost side, and the second metal nanoparticles are formed on the outer side. A composite in which each of the surrounding nanoparticles is arranged and the surrounding nanoparticles composed of the third metal nanoparticles are arranged outside the surrounding nanoparticles composed of the second metal nanoparticles. A composite metal nanoparticle colloid characterized by being a metal nanoparticle.

  The tenth invention (hereinafter referred to as invention 10) as an example of the present invention developed by developing inventions 1 to 9 is the composite metal nanoparticle colloid according to any one of inventions 1 to 9, wherein at least one kind The metal nanoparticles constituting the surrounding nanoparticles are metal nanoparticles having a solid-phase reaction activity lower than that of the first metal nanoparticles, and are composite metal nanoparticle colloids.

  An eleventh invention (hereinafter referred to as invention 11) as an example of the present invention developed by developing inventions 1 to 10 is the composite metal nanoparticle colloid according to any one of inventions 1 to 10, wherein the composite metal nano The average particle diameter of the first metal nanoparticles constituting the particles is 10 nm to 100 nm, and at least of each of the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles An average particle size of one kind of metal nanoparticles is a composite metal nanoparticle colloid characterized by being smaller than 10 nm.

  The twelfth invention (hereinafter referred to as invention 12) as an example of the present invention developed by developing the invention 11 is the composite metal nanoparticle colloid according to the invention 11, wherein the first metal constituting the composite metal nanoparticle is the first invention. The average particle diameter of the metal nanoparticles is 10 nm to 100 nm, and at least one kind of metal nanoparticles among the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles. A composite metal nanoparticle colloid having an average particle size of 5 nm or less.

  A thirteenth invention (hereinafter referred to as invention 13) as an example of the present invention developed by developing inventions 1 to 12 is the composite metal nanoparticle colloid according to any one of inventions 1 to 12, wherein the composite metal nano The metal of the first metal nanoparticles constituting the particles is copper or nickel, and the metal of at least one of the surrounding nanoparticles disposed around the first metal nanoparticles is It is a composite metal nanoparticle colloid characterized by being silver.

  A fourteenth invention (hereinafter referred to as invention 14) as an example of the present invention developed by developing inventions 1 to 13 is the composite metal nanoparticle colloid according to any one of inventions 1 to 13, wherein the surrounding nanoparticles are At least one kind of metal nanoparticles constituting the material is collected by capturing the movable state of the metal-like surfactant in a reduced-pressure atmosphere or under vacuum in a moving state of the moving film-like surfactant. This is a composite metal nanoparticle colloid characterized in that it is a nanoparticle formed by repeating the above.

  A fifteenth invention (hereinafter referred to as invention 15) as an example of the present invention made to solve the problem is an invention of a method for producing a composite metal nanoparticle colloid, wherein the composite metal nanoparticle colloid is the composite metal The main composite metal nanoparticles in the nanoparticle colloid are the first metal nanoparticles with a particle size of less than 100 nm as the core nanoparticles, and the kind, size and shape of the metal around the first metal nanoparticles. At least one of the activities of the solid-phase reaction is a composite nanoparticle comprising at least one kind of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle, The method for producing a composite metal nanoparticle colloid is a method in which the first metal nanoparticle is made into a state in which the metal can be moved by evaporation or the like in a reduced pressure atmosphere or in a vacuum. A process for producing a colloidal metal nanoparticle colloid comprising a step of forming a surrounding nanoparticle by repeatedly capturing and collecting a film-like surfactant moving in an atmosphere or vacuum It is.

  A sixteenth invention (hereinafter referred to as invention 16) as an example of the present invention made to solve the problem is an invention of a method for producing a composite metal nanoparticle colloid, wherein the composite metal nanoparticle colloid is the composite metal The main composite metal nanoparticles in the nanoparticle colloid are the first metal nanoparticles with a particle size of less than 100 nm as the core nanoparticles, and the kind, size and shape of the metal around the first metal nanoparticles. At least one of the activities of the solid-phase reaction is a composite nanoparticle comprising at least one kind of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle, In the method for producing the composite metal nanoparticle colloid, at least one kind of the surrounding nanoparticles is brought into a movable state by evaporation or the like in a reduced-pressure atmosphere or vacuum. A step of forming a surrounding nanoparticle by repeatedly collecting and collecting the first metal nanoparticles by capturing them with a moving body of a surfactant in a reduced pressure atmosphere or in a vacuum in which the first metal nanoparticles are captured It is a manufacturing method of the composite metal nanoparticle colloid characterized by having.

  The seventeenth invention (hereinafter referred to as invention 17) as an example of the present invention developed by developing the invention 15 or 16 is the method for producing a composite metal nanoparticle colloid according to the invention 15 or 16, wherein the composite metal nano At least two kinds of surrounding nanoparticles are arranged around the core nanoparticles, and the second metal nanoparticles have a particle size smaller than that of the first metal nanoparticles, A method for producing a composite metal nanoparticle colloid comprising the step of forming the metal nanoparticles so that the particle size of the metal nanoparticles is smaller than the particle size of the second metal nanoparticles.

  An eighteenth invention (hereinafter referred to as invention 18) as an example of the present invention developed by developing inventions 15 to 17 is the method for producing a composite metal nanoparticle colloid according to any one of inventions 15 to 17, wherein A method for producing a composite metal nanoparticle colloid characterized in that a membrane-like surfactant that moves in a reduced-pressure atmosphere or in a vacuum is used in a fluid state without dissolving the surfactant in a solvent.

  A nineteenth invention as an example of the present invention developed from the inventions 15 to 18 (hereinafter referred to as invention 19) is the method for producing a composite metal nanoparticle colloid according to any one of the inventions 15 to 18, wherein All core nanoparticles and surrounding nanoparticles that make up the composite metal nanoparticles are trapped in a moving membrane-like surfactant that moves the metal in a reduced-pressure atmosphere or in a vacuum by evaporation or the like. It is a manufacturing method of the composite metal nanoparticle colloid characterized by forming by repeating and collecting.

  A twentieth invention (hereinafter referred to as invention 20) as an example of the present invention developed by developing the inventions 15 to 19 is the method for producing a composite metal nanoparticle colloid according to any of the inventions 15 to 19, wherein A method of producing a composite metal nanoparticle colloid, characterized in that the core nanoparticles and surrounding nanoparticles constituting the composite metal nanoparticles are all manufactured using the same type of surfactant.

  A twenty-first invention (hereinafter referred to as invention 21) as an example of the present invention developed by developing inventions 15 to 20 is the method for producing a composite metal nanoparticle colloid according to any one of inventions 15 to 20, wherein Multiple types of nanoparticles among the core nanoparticles and surrounding nanoparticles that make up the composite metal nanoparticles can be used in a reduced pressure atmosphere or in a vacuum in a continuous process or the same process without breaking the vacuum atmosphere or vacuum state. A method for producing a composite metal nanoparticle colloid characterized in that it is formed by repeatedly capturing and collecting a movable substance in the form of a surfactant that moves the metal in a movable state by evaporation or the like. It is.

  A twenty-second invention (hereinafter referred to as invention 22) as an example of the present invention developed by developing inventions 15 to 21 is the method for producing a composite metal nanoparticle colloid according to any one of inventions 15 to 21, wherein Using the same device, multiple types of nanoparticles from the core nanoparticles and surrounding nanoparticles that make up the composite metal nanoparticles were made movable by evaporating them in a reduced-pressure atmosphere or in vacuum. It is a method for producing a composite metal nanoparticle colloid characterized in that it is formed by repeatedly capturing and collecting a moving substance in a membrane-like surfactant that moves the substance.

  A twenty-third invention (hereinafter referred to as invention 23) as an example of the present invention developed by developing the inventions 15 to 22 is the method for producing a composite metal nanoparticle colloid according to any one of the inventions 17 to 22. In the composite metal nanoparticle, the first metal nanoparticle is on the innermost side, and the outer side is composed of the surrounding metal nanoparticle composed of the second metal nanoparticle and the third metal nanoparticle. This is a method for producing a composite metal nanoparticle colloid characterized by forming a portion where surrounding nanoparticles are mixed.

  The twenty-fourth invention (hereinafter referred to as invention 24) as an example of the present invention developed by developing the inventions 15 to 23 is the method for producing a composite metal nanoparticle colloid according to any one of the inventions 17 to 23. The composite metal nanoparticles are arranged such that at least two kinds of surrounding nanoparticles are arranged around the core nanoparticles, the first metal nanoparticles are on the innermost side, and the second metal nanoparticles are on the outer side. Each set is arranged such that the surrounding nanoparticles composed of particles are arranged and the surrounding nanoparticles composed of the third metal nanoparticles are arranged outside the surrounding nanoparticles composed of the second metal nanoparticles. Forming a composite metal nanoparticle to form a composite metal nanoparticle colloid.

  A twenty-fifth invention as an example of the present invention developed by developing the inventions 15 to 24 (hereinafter referred to as invention 25) is the method for producing a composite metal nanoparticle colloid according to any of the inventions 15 to 24, wherein The average particle diameter of the first metal nanoparticles constituting the composite metal nanoparticles is 10 nm to 100 nm, and each of the metal nanoparticles constituting the surrounding nanoparticles disposed around the first metal nanoparticles. It is a method for producing a composite metal nanoparticle colloid characterized in that at least one kind of metal nanoparticles is formed so that the average particle size is smaller than 10 nm.

  A twenty-sixth invention (hereinafter referred to as invention 26) as an example of the present invention developed by developing the invention 25 constitutes the composite metal nanoparticle in the method for producing a composite metal nanoparticle colloid according to the invention 25. The average particle diameter of the first metal nanoparticles is 10 nm to 100 nm, and at least one kind of metal among the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles The composite metal nanoparticle colloid production method is characterized in that the composite nanoparticle is formed so that the average particle diameter of the nanoparticle is 5 nm or less.

  A twenty-seventh invention (hereinafter referred to as invention 27) as an example of the present invention developed by developing inventions 15 to 26 is the method for producing a composite metal nanoparticle colloid according to any one of inventions 15 to 26, wherein The metal of the first metal nanoparticles constituting the composite metal nanoparticles is copper or nickel, and at least one type of the surrounding nanoparticles among the surrounding nanoparticles arranged around the first metal nanoparticles This is a method for producing a composite metal nanoparticle colloid characterized in that the metal is silver.

  A twenty-eighth invention (hereinafter referred to as invention 28) as an example of the present invention developed by developing inventions 15 to 27 is the method for producing a composite metal nanoparticle colloid according to any one of inventions 15 to 27, wherein At least one kind of metal nanoparticles constituting the surrounding nanoparticles is obtained by trapping the movable state of the moving film-like surfactant by moving the metal by sublimation in a reduced-pressure atmosphere or vacuum. It is a method for producing a composite metal nanoparticle colloid characterized in that it is a nanoparticle formed by repeatedly collecting.

  A twenty-ninth invention (hereinafter referred to as invention 29) as an example of the present invention made to solve the problem is an invention of a composite metal nanoparticle manufactured using a composite metal nanoparticle colloid, wherein the composite metal nanoparticle The colloid is the type of metal around the first metal nanoparticle, the main composite metal nanoparticle in the composite metal nanoparticle colloid being the first metal nanoparticle having a particle size smaller than 100 nm as the core nanoparticle. And at least one of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle in at least one of particle size, shape and solid-state reaction activity. The first metal nanoparticle is a composite nanoparticle obtained by allowing the metal to move in a reduced-pressure atmosphere or in a vacuum by evaporation or the like. It is a nanoparticle formed by repeatedly capturing and collecting by a membrane-like surfactant moving body that moves in, and the composite metal nanoparticle is supported on the carrier supporting the composite metal nanoparticle. The composite metal nanoparticle is characterized in that the composite metal nanoparticle is supported in a composite metal nanoparticle colloid.

  A thirtieth invention (hereinafter referred to as invention 30) as an example of the present invention made to solve the problem is an invention of a composite metal nanoparticle manufactured using a composite metal nanoparticle colloid, wherein the composite metal nanoparticle The colloid is the type of metal around the first metal nanoparticle, the main composite metal nanoparticle in the composite metal nanoparticle colloid being the first metal nanoparticle having a particle size smaller than 100 nm as the core nanoparticle. And at least one of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle in at least one of particle size, shape and solid-state reaction activity. The composite nanoparticles, wherein the at least one kind of the surrounding nanoparticles is the one in which the metal can be moved by evaporation or the like in a reduced-pressure atmosphere or vacuum. The nanoparticles are formed by repeatedly capturing and collecting by a membrane-like surfactant moving body moving in a reduced-pressure atmosphere or in a vacuum in which the metal nanoparticles are captured, and the composite metal nanoparticles are The composite metal nanoparticles are characterized in that the composite metal nanoparticles in the composite metal nanoparticle colloid are supported on the carrier supporting the composite metal nanoparticles.

  A thirty-first invention (hereinafter referred to as invention 31) as an example of the present invention developed by developing invention 29 or 30 is the composite metal nanoparticle according to invention 29 or 30, wherein the composite metal nanoparticle is At least two kinds of surrounding nanoparticles are arranged around the core nanoparticle, and the particle size of the second metal nanoparticle is smaller than the particle size of the first metal nanoparticle, and the third metal nanoparticle The composite metal nanoparticles are characterized by having a particle size smaller than that of the second metal nanoparticles.

  A thirty-second invention (hereinafter referred to as invention 32) as an example of the present invention developed by developing inventions 29 to 31 is the composite metal nanoparticle according to any one of inventions 29 to 31, wherein The moving body of the membrane-like surfactant that moves in vacuum is a composite metal nanoparticle that is a membrane-like surfactant that is fluidized without dissolving the surfactant in a solvent.

  A thirty-third invention (hereinafter referred to as invention 33) as an example of the present invention developed by developing the inventions 29 to 32 is the composite metal nanoparticle according to any of the inventions 29 to 32, wherein the composite metal nanoparticle All of the core nanoparticles and surrounding nanoparticles that make up the metal are collected in a reduced-pressure atmosphere or in a vacuum by making the metal movable by evaporation, etc. It is a composite metal nanoparticle characterized by being a nanoparticle formed by repeating.

  A thirty-fourth invention as an example of the present invention developed from the inventions 29 to 33 (hereinafter referred to as invention 34) is the composite metal nanoparticle according to any one of the inventions 29 to 33, wherein the composite metal nanoparticle The composite metal nanoparticles are characterized in that the core nanoparticles and the surrounding nanoparticles are all manufactured using the same kind of surfactant.

  A thirty-fifth invention as an example of the present invention developed by developing the inventions 29 to 34 (hereinafter referred to as invention 35) is the composite metal nanoparticle according to any of the inventions 29 to 34, wherein the composite metal nanoparticle A plurality of types of nanoparticles among the core nanoparticles and the surrounding nanoparticles are formed by the evaporation or the like in a reduced pressure atmosphere or in a vacuum in a continuous process or the same process without breaking the vacuum state. A composite metal nano-particle characterized in that it is a nano-particle formed by repeatedly capturing and collecting a metal-movable surfactant in a moving state in a movable state of the metal.

  A thirty-sixth invention as an example of the present invention developed from the inventions 29 to 35 (hereinafter referred to as invention 36) is the composite metal nanoparticle according to any one of the inventions 31 to 35, wherein the composite metal As for the nanoparticles, the first metal nanoparticles are on the innermost side, and the surrounding nanoparticles composed of the second metal nanoparticles and the surrounding nanoparticles composed of the third metal nanoparticles are outside the nanoparticles. It is a composite metal nanoparticle characterized by having a mixed part.

  The thirty-seventh invention (hereinafter referred to as invention 37) as an example of the present invention developed by developing the inventions 29 to 36 is the composite metal nanoparticle according to any one of the inventions 31 to 36, wherein the composite metal In the nanoparticle, at least two kinds of surrounding nanoparticles are arranged around the core nanoparticle, the first metal nanoparticle is on the innermost side, and the second metal nanoparticle is formed on the outermost side. A composite metal in which the surrounding nanoparticles are arranged and the surrounding nanoparticles composed of the third metal nanoparticles are arranged outside the surrounding nanoparticles composed of the second metal nanoparticles. It is a composite metal nanoparticle characterized by being a nanoparticle.

  A thirty-eighth invention (hereinafter referred to as invention 38) as an example of the present invention developed by developing the inventions 29 to 37 is the composite metal nanoparticle according to any one of the inventions 29 to 37, wherein at least one kind of the above-mentioned The metal nanoparticles constituting the surrounding nanoparticles are composite metal nanoparticles characterized in that the activity of the solid phase reaction is lower than that of the first metal nanoparticles.

  A thirty-ninth invention (hereinafter referred to as invention 39) as an example of the present invention developed by developing the inventions 29 to 38 is the composite metal nanoparticle according to any of the inventions 29 to 38, wherein the composite metal nanoparticle The average particle diameter of the first metal nanoparticles constituting the first metal nanoparticles is 10 nm to 100 nm, and at least one of the metal nanoparticles constituting the surrounding nanoparticles disposed around the first metal nanoparticles. The composite metal nanoparticles are characterized in that the average particle size of the kind of metal nanoparticles is smaller than 10 nm.

  40th invention as an example of the present invention developed from the invention 39 (hereinafter referred to as invention 40) is the composite metal nanoparticle according to the invention 39, wherein the first metal constituting the composite metal nanoparticle The average particle diameter of the metal nanoparticles is 10 nm to 100 nm, and the average of at least one kind of metal nanoparticles among the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles It is a composite metal nanoparticle characterized by having a particle size of 5 nm or less.

  The forty-first invention (hereinafter referred to as invention 41) as an example of the present invention developed by developing the inventions 29 to 40 is the composite metal nanoparticle according to any of the inventions 29 to 40, wherein the composite metal nanoparticle The metal of the first metal nanoparticles constituting the metal is copper or nickel, and the metal of at least one kind of the surrounding nanoparticles arranged around the first metal nanoparticles is silver It is a composite metal nanoparticle characterized by being.

  A forty-second invention (hereinafter referred to as an invention 42) as an example of the present invention developed by developing the inventions 29 to 41 is the composite metal nanoparticle according to any one of the inventions 29 to 41, wherein the surrounding nanoparticles are At least one of the metal nanoparticles constituting the particles is collected by capturing the movable metal-like surfactant in a reduced-pressure atmosphere or in vacuum in a moving state of the moving film-like surfactant. It is a composite metal nanoparticle characterized by being a nanoparticle formed by repeating.

  A forty-third invention (hereinafter referred to as invention 43) as an example of the present invention made to solve the problem is an invention of a method for producing composite metal nanoparticles, wherein the composite metal nanoparticle colloid comprises the composite metal nanoparticle. The main composite metal nanoparticles in the particle colloid are the first metal nanoparticles having a particle size of less than 100 nm as the core nanoparticles, and the type, particle size, shape, and solidity of the metal around the first metal nanoparticles. At least one of the activity of the phase reaction is a composite nanoparticle comprising at least one kind of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle, As a method for producing a composite metal nanoparticle colloid, the first metal nanoparticle obtained by evaporating the metal in a reduced-pressure atmosphere or in a vacuum can be moved in a reduced-pressure atmosphere. A method for forming composite metal nanoparticles, comprising the step of forming nanoparticles by repeatedly capturing and collecting them with a moving body of a film-like surfactant that moves in a vacuum or in a vacuum. In addition, the method further comprises a step of supporting the composite metal nanoparticles in the composite metal nanoparticle colloid on a carrier supporting the composite metal nanoparticles.

  A 44th invention (hereinafter referred to as invention 44) as an example of the present invention made to solve the problem is an invention of a method for producing composite metal nanoparticles, wherein the composite metal nanoparticle colloid is the composite metal nanoparticle. The main composite metal nanoparticles in the particle colloid are the first metal nanoparticles having a particle size of less than 100 nm as the core nanoparticles, and the type, particle size, shape, and solidity of the metal around the first metal nanoparticles. At least one of the activity of the phase reaction is a composite nanoparticle comprising at least one kind of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle, As a method for producing a composite metal nanoparticle colloid, at least one of the surrounding nanoparticles is made movable by evaporation or the like in a reduced-pressure atmosphere or vacuum. There is a nanoparticle formation step in which the first metal nanoparticles are repeatedly captured and collected by a film-like surfactant moving body that moves in a reduced-pressure atmosphere or vacuum. In addition to the above method, the method for producing composite metal nanoparticles further includes a step of supporting the composite metal nanoparticles in the composite metal nanoparticle colloid on a carrier supporting the composite metal nanoparticles. This is a method for producing composite metal nanoparticles.

  A forty-fifth invention (hereinafter referred to as invention 45) as an example of the present invention developed by developing the invention 43 or 44 is the method for producing a composite metal nanoparticle according to the invention 43 or 44, wherein the composite metal nanoparticle Wherein at least two kinds of surrounding nanoparticles are disposed around the core nanoparticles, and the second metal nanoparticles have a particle size smaller than that of the first metal nanoparticles, It is a manufacturing method of the composite metal nanoparticle characterized by having the process formed so that the particle size of a metal nanoparticle may be smaller than the particle size of said 2nd metal nanoparticle.

  Forty-sixth invention (hereinafter referred to as invention 46) as an example of the present invention developed by developing inventions 43 to 45, in the method for producing composite metal nanoparticles according to any one of inventions 43 to 45, the reduced pressure A method for producing composite metal nanoparticles, wherein a film-form surfactant that moves in an atmosphere or vacuum is used in a fluid state without dissolving the surfactant in a solvent.

  Forty-seventh invention (hereinafter referred to as invention 47) as an example of the present invention developed by developing inventions 43 to 46 is the method for producing composite metal nanoparticles according to any of inventions 43 to 46, wherein the composite All of the core nanoparticles and surrounding nanoparticles that make up the metal nanoparticles are captured by the moving body of the membrane-like surfactant that moves the metal in a movable state by evaporation or the like in a reduced-pressure atmosphere or vacuum. It is a manufacturing method of the composite metal nanoparticle characterized by forming by repeating collecting and collecting.

  A forty-eighth invention (hereinafter referred to as invention 48) as an example of the present invention developed by developing inventions 43 to 47 is the method for producing composite metal nanoparticles according to any of inventions 43 to 47, wherein the composite It is a method for producing composite metal nanoparticles, characterized in that all of the core nanoparticles and surrounding nanoparticles constituting the metal nanoparticles are produced using the same type of surfactant.

  A forty-ninth invention (hereinafter referred to as invention 49) as an example of the present invention developed by developing the inventions 43 to 48 is the method for producing composite metal nanoparticles according to any of the inventions 43 to 48, wherein the composite Evaporate multiple types of nanoparticles from the core nanoparticles and surrounding nanoparticles that constitute metal nanoparticles in a reduced pressure atmosphere or in a vacuum in a continuous or the same process without breaking the vacuum atmosphere or vacuum state It is a method for producing composite metal nanoparticles, characterized in that it is formed by repeatedly capturing and collecting a metal-like surfactant moving body that has made the metal movable by, for example, moving it .

  A fifty-th invention as an example of the present invention developed by developing the inventions 43 to 49 (hereinafter referred to as invention 50) is the method for producing composite metal nanoparticles according to any of the inventions 43 to 49, wherein the composite A metal nanoparticle consisting of multiple types of nanoparticles and surrounding nanoparticles, in which the metal is made movable by evaporation, etc. in a reduced-pressure atmosphere or vacuum using the same device It is a method for producing composite metal nanoparticles, characterized in that it is formed by repeatedly capturing and collecting a film-like surfactant in a moving body and collecting it.

  The fifty-first invention as an example of the present invention developed by developing the inventions 45 to 50 (hereinafter referred to as invention 51) is the method for producing composite metal nanoparticles according to any one of the inventions 45 to 50, In the composite metal nanoparticle, the first metal nanoparticle is on the innermost side, and the outer periphery is composed of the second metal nanoparticle and the third metal nanoparticle. This is a method for producing composite metal nanoparticles, wherein a portion where nanoparticles are mixed is formed.

  52nd invention as an example of this invention made | formed by developing invention 45-51 (henceforth invention 52) is the manufacturing method of the composite metal nanoparticle of any one of invention 45-51, The composite metal nanoparticles are arranged such that at least two kinds of surrounding nanoparticles are arranged around the core nanoparticles, the first metal nanoparticles are on the innermost side, and the second metal nanoparticles are on the outer side. The surrounding nanoparticles composed of the third metal nanoparticles are arranged outside the surrounding nanoparticles composed of the second metal nanoparticles, and each set is arranged to dispose the surrounding nanoparticles composed of the third metal nanoparticles. It is the manufacturing method of the composite metal nanoparticle characterized by forming and forming a composite nanoparticle.

  The fifty-third invention (hereinafter referred to as invention 53) as an example of the present invention developed by developing the inventions 43 to 52 is the method for producing metal nanoparticles according to any of the inventions 43 to 52, wherein the composite nano The average particle diameter of the first metal nanoparticles constituting the particles is 10 nm to 100 nm, and at least of each of the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles The metal nanoparticle production method is characterized in that the average particle diameter of one type of metal nanoparticles is smaller than 10 nm.

  A fifty-fourth invention (hereinafter referred to as invention 54) as an example of the present invention developed by developing the invention 53 is the method for producing a composite metal nanoparticle according to the invention 53, wherein the composite metal nanoparticle is constituted as described above. The average particle diameter of the first metal nanoparticles is 10 nm to 100 nm, and at least one kind of metal nanoparticle among the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles It is a method for producing composite metal nanoparticles, wherein the composite nanoparticles are formed so that the average particle diameter of the particles is 5 nm or less.

  A fifty-fifth invention as an example of the present invention made by developing the inventions 43 to 54 (hereinafter referred to as invention 55) is the method for producing composite metal nanoparticles according to any of the inventions 43 to 54, wherein the composite The metal of the first metal nanoparticle constituting the metal nanoparticle is copper or nickel, and at least one of the encircling nanoparticle arranged around the first metal nanoparticle A method for producing composite metal nanoparticles, wherein the metal is silver.

  The 66th invention (hereinafter referred to as invention 66) as an example of the present invention developed by developing the inventions 43 to 55 is the method for producing composite metal nanoparticles according to any of the inventions 43 to 55, wherein At least one kind of metal nanoparticles constituting the nanoparticles is collected by capturing the metal in a movable state by sublimation in a reduced-pressure atmosphere or under vacuum in a moving membrane-like surfactant moving body It is the manufacturing method of the composite metal nanoparticle characterized by being the nanoparticle formed by performing repeatedly.

  A fifty-seventh invention (hereinafter referred to as invention 57) as an example of the present invention made to solve the problem is an invention of an apparatus for producing composite metal nanoparticles for producing a composite metal nanoparticle colloid. The apparatus for producing particles includes a vacuum chamber connected to an evacuation system, at least one crucible (crucible) disposed in the vacuum chamber, and heating means for heating and evaporating a metal placed in the crucible. And a driving means for rotating the outer peripheral wall of the vacuum chamber, a rotation control means for controlling the rotation of the outer peripheral wall of the vacuum chamber, and a part of the outer peripheral wall of the vacuum chamber in which a surfactant can be placed. And a temperature control means for controlling the temperature of the surfactant contained in the surfactant space. Along with the outer peripheral wall of the rotating vacuum chamber as a film-like moving body along the inner wall of the outer peripheral wall of the rotating vacuum chamber in a fluid state without dissolving the surfactant put in the surfactant space in the solvent By repeatedly capturing and collecting the metal fine particles that are moved and flying there, the first metal nanoparticles smaller than 100 nm are used as the core nanoparticles, and the kind of metal around the first metal nanoparticles. And at least one of a set (a surrounding nanoparticle) of a plurality of metal nanoparticles different from the first metal nanoparticle in at least one of particle size, shape and solid-state reaction activity. An apparatus for producing composite metal nanoparticles, comprising producing composite metal nanoparticles.

  A fifty-eighth invention (hereinafter referred to as invention 58) as an example of the present invention developed by developing the invention 57 is the composite metal nanoparticle manufacturing apparatus according to the invention 57, wherein there are a plurality of the crucibles, The crucible differs in at least one of the shape and dimensions of at least two kinds of metal crucibles among the metal for the core nanoparticles and the metal for the surrounding nanoparticles, and the control of the heating means is different for each crucible. It is the manufacturing apparatus of the composite metal nanoparticle characterized by performing under conditions.

A fifty-ninth aspect of the present invention (hereinafter referred to as fifty-ninth invention), which is an example of the present invention developed by developing the invention 57 or 58, is the composite metal nanoparticle manufacturing apparatus according to the invention 57 or 58, wherein a plurality of the vacuum chambers are provided. An apparatus for producing composite metal nanoparticles, characterized by being connected in stages.
In the divisional application of the present application, the following claims have been filed based on the above-described invention and a mode for carrying out the invention described below.
Claim 1 made to solve the problem of the present invention is a composite metal nanoparticle comprising a metal fine particle (hereinafter referred to as metal nanoparticle) having a particle size of 100 nm (nanometer) or less as a main component in a dispersant. In the colloid, the composite metal nanoparticle is characterized in that the main composite metal nanoparticle in the composite metal nanoparticle colloid is a metal fine particle having a particle size of less than 100 nm as a core nanoparticle, and the kind of metal around the core nanoparticle. A set of metal nanoparticles in which at least one of particle size, shape, and activity of solid-phase reaction is different from the core nanoparticles (hereinafter referred to as nano particles surrounding metal nanoparticles arranged around the core nanoparticles). Composite metal nanoparticles comprising at least one kind of particles), wherein the composite metal nanoparticles further include both the core nanoparticles and the surrounding nanoparticles. In a reduced-pressure atmosphere or in a vacuum, the metal can be moved by evaporation or sublimation, so that it is solid at room temperature or is so high that a film-like surfactant layer cannot be formed along the inner wall of the rotating vacuum chamber. The temperature of the surfactant, which is a viscosity, is controlled to a temperature at which the film-like surfactant layer can be formed along the inner wall of the vacuum chamber where it is fluidized and rotated, and the film-like shape moving in the reduced-pressure atmosphere or vacuum The nanoparticle is formed by repeatedly capturing and collecting with a surfactant film-shaped mobile body, which is a surfactant mobile body, and the average particle size of at least one kind of the surrounding nanoparticles is The composite metal nanoparticle colloid composition is smaller than the average particle size of the core nanoparticles, and the composition of the surfactant, the composition of the core nanoparticles and the composition of the core nanoparticles are not included. Be comprised of the composition of the winding nanoparticles are composite metal nanoparticle colloid, wherein.
Claim 2 made by developing Claim 1 is the composite metal nanoparticle colloid according to Claim 1, wherein the surfactant of the core nanoparticle and the surrounding nanoparticle is dissolved in a surfactant solvent. A composite metal nanoparticle colloid characterized in that it is not the same type of surfactant.
Claim 3 made by developing Claim 1 or Claim 2 is the composite metal nanoparticle colloid according to Claim 1 or 2, wherein at least one kind of nanoparticles of the core nanoparticle colloid and the surrounding nanoparticle colloid A colloidal surfactant is a composite metal nanoparticle colloid characterized by having a viscosity of 100 centipoise or less when moving in the reduced-pressure atmosphere or vacuum.
Claim 4 made by expanding claims 1 to 3 is the composite metal nanoparticle colloid according to any one of claims 1 to 3, wherein the film-like interface moves in the reduced-pressure atmosphere or in vacuum. A composite metal nanoparticle colloid wherein the activator is a polyoxyalkyleneamine not dissolved in a surfactant solvent.
Claim 5 made by developing Claims 1 to 4 is the composite metal nanoparticle colloid according to any one of Claims 1 to 4, wherein the core nanoparticles and / or the surrounding nanoparticles are reduced in pressure. Microwaves are applied to nanoparticles formed by a physical method that repeatedly captures and collects them by a membrane-like surfactant moving body that is not dissolved in a surfactant solvent that moves in an atmosphere or vacuum. The composite metal nanoparticle colloid is characterized in that it is a core nanoparticle and / or a surrounding nanoparticle whose particle size is increased by irradiation.
Claim 6 made by developing Claims 1-5 is the composite metal nanoparticle colloid according to any one of Claims 1-5, wherein the composite metal nanoparticle is around the core nanoparticle. At least two kinds of surrounding nanoparticles are arranged, the first metal nanoparticles are arranged on the innermost side, and the surrounding nanoparticles composed of the second metal nanoparticles are arranged on the outer side, and the second metal nanoparticles are arranged. A composite metal nanoparticle comprising a plurality of metal nanoparticles arranged on the outside of the metal nanoparticle to form an assembly of the third metal nanoparticle. Nanoparticle colloid.
Claim 7 made by developing Claims 1 to 6 is a composite metal nanoparticle colloid according to any one of Claims 1 to 6, wherein the metal nanoparticles constituting at least one of the surrounding nanoparticles are: A composite metal nanoparticle colloid characterized in that the activity of a solid-phase reaction is a metal nanoparticle lower than that of the first metal nanoparticle.
Claim 8 made by developing Claim 6 or 7 is the composite metal nanoparticle colloid according to Claim 6 or 7, wherein the average particle diameter of the first metal nanoparticles constituting the composite metal nanoparticles Is between 10 nm and 100 nm, and the average particle size of at least one of the metal nanoparticles constituting the surrounding nanoparticles arranged around the first metal nanoparticles is smaller than 10 nm It is a composite metal nanoparticle colloid characterized by the following.
Claim 9 made by expanding Claim 7 or 8 is the composite metal nanoparticle colloid according to Claim 7 or 8, wherein the average particle diameter of the first metal nanoparticles constituting the composite metal nanoparticles Is 10 nm to 100 nm, and the average particle diameter of at least one kind of metal nanoparticles constituting each of the surrounding nanoparticles arranged around the first metal nanoparticles is 5 nm or less. It is a composite metal nanoparticle colloid characterized by this.
Claim 10 made by developing Claims 1-9 is the composite metal nanoparticle colloid according to any one of Claims 1-9, wherein the composite metal nanoparticle is the first metal nanoparticle. Is the innermost part, and the outer part has a part in which the surrounding nanoparticles composed of the second metal nanoparticles and the surrounding nanoparticles composed of the third metal nanoparticles are mixed. Metal nanoparticle colloid.
Claim 11 made by developing Claims 1 to 10 is the composite metal nanoparticle colloid according to any one of Claims 1 to 10, wherein the first metal nanoparticle constituting the composite metal nanoparticle is formed. A composite metal, wherein the metal of the particles is copper or nickel, and the metal of at least one of the surrounding nanoparticles arranged around the first metal nanoparticles is silver Nanoparticle colloid.
Claim 12 made by developing Claims 1 to 11 is supported by a carrier supporting composite metal nanoparticles in the composite metal nanoparticle colloid according to any one of Claims 1 to 11. It is the featured composite metal nanoparticles.
Claim 13 made by developing Claim 12 is the composite metal nanoparticle according to Claim 12, wherein the composite metal nanoparticle has at least two kinds of surrounding nanoparticles arranged around the core nanoparticle. The metal nanoparticles constituting the surrounding nanoparticles closest to the first metal nanoparticles are referred to as second metal nanoparticles, and then the surrounding nanoparticles close to the first metal nanoparticles. The constituent metal nanoparticles are referred to as third metal nanoparticles (the same applies hereinafter), and the second metal nanoparticles have a particle size smaller than that of the first metal nanoparticles. The composite metal nanoparticles are characterized in that the metal nanoparticles have a particle size smaller than that of the second metal nanoparticles.
Claim 14 made by developing Claim 12 or 13 is a composite metal nanoparticle according to claim 12 or 13, wherein a plurality of core nanoparticles and surrounding nanoparticles constituting the composite metal nanoparticle are used. The type of nano-particles is a film-like interface that moves in a reduced-pressure atmosphere or a vacuum in a continuous process or the same process, and the metal is made movable by evaporation in a reduced-pressure atmosphere or vacuum. A composite metal nano-particle characterized in that it is a nano-particle formed by repeatedly capturing and collecting the active agent in a moving body.
Claim 15 made to solve the problems of the present invention is a composite metal nanoparticle comprising, as a main component, metal fine particles (hereinafter referred to as metal nanoparticles) having a particle size of 100 nm (nanometer) or less in a dispersant. An apparatus for producing a composite metal nanoparticle colloid for producing a colloid, wherein the composite metal nanoparticle colloid production apparatus is a composite metal nanoparticle colloid production apparatus comprising a plurality of vacuum chambers connected, The one-stage vacuum chamber is a vacuum chamber connected to an evacuation system, at least one crucible (crucible) disposed in the vacuum chamber, and evaporates by heating the metal placed in the crucible. Heating means for sublimation, driving means for rotating the outer peripheral wall of the vacuum chamber, and the outer peripheral wall of the vacuum chamber. A rotation control means for controlling rotation, and a space (hereinafter referred to as a surfactant space) provided in a part of the inner peripheral wall of the vacuum chamber in which a surfactant can be placed; The temperature of the surfactant, which is solid at room temperature in the surfactant space or is so viscous that it cannot form a film-like surfactant layer along the inner wall of the rotating vacuum chamber, It has a surfactant temperature control means for controlling it to a temperature at which a film-like surfactant layer can be formed by rotating along the inner wall of a vacuum chamber where it fluidizes and rotates without being dissolved in the solvent, Further, a film-form surfactant in which the surfactant not dissolved in the solvent contained in the surfactant space is rotated along with the rotation of the vacuum chamber along the inner wall of the rotating vacuum chamber. In layers An apparatus for producing composite metal nanoparticles, characterized in that it has a repeated mechanism be collected to capture the fine metal particles flying thereto I.
Claim 16 made to solve the problem of the present invention is a composite metal nanoparticle colloid comprising metal fine particles (ie, metal nanoparticles) whose particle size is 100 nm (nanometer) or less as a main component in a dispersant. In the manufacturing method of
The main composite metal nanoparticles in the composite metal nanoparticle colloid are metal fine particles having a particle size of less than 100 nm as core nanoparticles, and the kind, particle size, shape, and solid phase reaction of the metal around the core nanoparticles. At least one of the activities is provided with at least one type of aggregate of metal nanoparticles different from the core nanoparticles (hereinafter referred to as metal nanoparticles surrounding the core nanoparticles). Composite metal nanoparticles,
The method for producing a composite metal nanoparticle colloid includes a step of preparing a rotary vacuum device capable of evaporating or sublimating a metal nanoparticle raw metal, and an inner wall of a vacuum chamber that is solid at room temperature or rotates. Preparing a surfactant having a viscosity so high that a film-like surfactant layer cannot be formed in the vacuum chamber, and adjusting the temperature of the surfactant in the vacuum chamber without dissolving the surfactant in the solvent. A step of forming a film-like surfactant moving body that moves along the inner wall of the vacuum chamber that rotates in the reduced-pressure atmosphere or in a vacuum controlled above the temperature at which it fluidizes, and the reduced-pressure atmosphere or vacuum The step of making the metal movable by evaporation or sublimation in the inside, and the state of making the metal movable by evaporation or sublimation in the reduced pressure atmosphere or in vacuum are in the reduced pressure atmosphere. Forming a nanoparticle colloidal performed repeatedly be collected to capture the movement of the film-like surfactants that are not dissolved in a solvent to move in a vacuum,
And having a step of forming a plurality of types of nanoparticles among the core nanoparticles and surrounding nanoparticles constituting the composite metal nanoparticles in a continuous process or the same process without breaking a reduced-pressure atmosphere or vacuum state. It is the manufacturing method of the composite metal nanoparticle colloid characterized.

  As described above, according to the present invention, at least one kind of metal nanoparticle among the core nanoparticle and the surrounding nanoparticle, in which the metal is made movable by evaporation or the like in a reduced-pressure atmosphere or vacuum, The colloidal metal nanoparticle colloid prepared by repeatedly capturing and collecting with a moving substance of a film-like surfactant moving in a reduced-pressure atmosphere or in a vacuum can exhibit its physical properties stably.

  For example, the composite metal nanoparticle colloid of the present invention in which copper nanoparticles prepared in a reduced-pressure atmosphere or vacuum are used as core nanoparticles, and silver nanoparticles are arranged as surrounding nanoparticles in a reduced-pressure atmosphere or in vacuum around the atmosphere. It has been found that the oxidation problem does not occur even when stored for more than 3 months.

  In addition, the composite metal nanoparticle colloid of the present invention can capture metal nanoparticles only with a surfactant without diluting the surfactant with a solvent with respect to the surfactant that captures the metal nanoparticles in the production process thereof. Therefore, the composite metal nanoparticle colloid produced only with the surfactant can be used as it is without being dispersed in the solvent, or it can be dispersed in a hydrophilic solvent or a hydrophobic solvent according to the user's request. It becomes possible to provide.

  Furthermore, the composite metal nanoparticles according to a preferred example of the present invention can be used without worrying about the inclusion of compounds such as sulfides, impurities, and by-products in the colloid without using a chemical method using a reduction reaction. It can be mass-produced as a good, high purity, high concentration composite metal nanoparticle colloid and composite metal nanoparticle, and can be provided at low cost.

  The present invention has an unprecedented great effect that it is possible to produce composite metal nanoparticles by combining a kind of metal that cannot be produced by a chemical method, without being limited by chemical reaction. .

  The composite metal nanoparticle colloid and composite metal nanoparticle according to the present invention have a great effect of greatly contributing to industrial development in a wide range of fields such as automobile, battery, electronics, and biotechnology industries.

It is sectional drawing of the principal part of the apparatus which manufactures the metal nanoparticle colloid as an embodiment of this invention. It is a transmission electron micrograph of the nanoparticle colloid as an embodiment of the present invention. FIG. 3 is a transmission electron micrograph of the nanoparticle colloid of FIG. 2 that was heat-treated at 150 ° C. for 2 hours as an embodiment of the present invention. It is a figure explaining the composite nanoparticle as an example of an embodiment of the present invention. It is a figure explaining the example of the surrounding nanoparticle as an embodiment of this invention of two types of composite nanoparticles. It is a figure explaining the example which heat-processed the composite nanoparticle of FIG. 4, and alloyed it. It is a transmission electron micrograph of the composite metal nanoparticle colloid as an embodiment of the present invention. It is a transmission electron micrograph of the composite metal nanoparticle colloid as an embodiment of the present invention. It is sectional drawing of the principal part of the other example of the apparatus which manufactures the composite metal nanoparticle colloid as an embodiment of this invention. It is a schematic diagram explaining a mode that the metal nanoparticle or composite metal nanoparticle is carry | supported by the support | carrier.

  Embodiments of the present invention will be described below with reference to the drawings. The drawings used for the description schematically show the dimensions, shapes, arrangement relationships, and the like of each component to the extent that an example of the present invention can be understood. For convenience of explanation of the present invention, there may be cases where the enlargement ratio is partially changed for illustration, and the drawings used for explanation of the examples of the present invention may not necessarily be similar to the actual objects and descriptions of the embodiments. Moreover, in each figure, about the same component, it attaches and shows the same number, and duplication of description may be avoided.

  As mentioned above, the remarkable feature of the basic idea of the technology used in the present invention is that the composite metal nanoparticle colloid is evaporated or sublimated in a reduced-pressure atmosphere or in a vacuum (hereinafter also referred to as a vacuum). The metal particles are produced by using a method in which the metal particles are trapped by a membrane-like moving body using the surfactant itself fluidized without using the surfactant solvent. By using this production method different from the conventional one, it becomes possible to mass-produce colloidal metal nanoparticle colloids with high purity, high concentration, and extremely highly controlled particle size, which were thought to be impossible. This makes it possible to produce composite metal nanoparticles having a composition that does not depend on chemical reaction restrictions.

  As will be described later, the composite metal nanoparticle colloid of the present invention is produced by rotating the surfactant along the inner wall of a rotating vacuum chamber (vacuum chamber) under reduced pressure in a fluid state or in a vacuum state as the inner wall rotates, evaporating or A sublimated metal (hereinafter, evaporation or sublimation may be referred to as evaporation unless otherwise particularly required) is captured by the surfactant on the inner wall of the vacuum chamber to be in a colloidal state. .

  According to the present invention, it is possible to eliminate the conventional restrictions relating to the solvent of the surfactant, and it is possible to produce the composite metal nanoparticle colloid without using the means of dissolving and diluting the surfactant with the solvent as the diluent. As a result, the production capacity of the composite metal nanoparticle colloid can be increased ten times or more than the conventional one, and the production cost can be greatly reduced from the conventional cost.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention relates to a composite metal nanoparticle colloid, a composite metal nanoparticle, a production method thereof, and an apparatus for producing the same. In order to avoid duplication of explanation, in the following description, for example, production of a composite metal nanoparticle colloid is performed. The description of one form may also serve as an explanation of one of the other forms within the range that does not cause misunderstanding, such as the explanation of the colloidal metal nanoparticle colloid and the composite metal nanoparticle.

  FIG. 1 is a diagram schematically showing a cross section of an essential part of an example of an apparatus for producing a composite metal nanoparticle colloid that is a core nanoparticle, a surrounding nanoparticle, or a composite nanoparticle colloid in the present invention. Reference numeral 21 is a vacuum chamber, 21a is an inner wall of a vacuum chamber (vacuum tank), 21b is an outer wall of the vacuum chamber, 22 is a crucible for evaporating metal, 23 is a source metal for evaporating, 24 is a metal wire bundle evaporating from the crucible, 26 is a surfactant, 27 is a metal nanoparticle colloid, and 28 and 29 are arrows.

  First, in order to clarify the technology that can be used for the main part of the present invention, a case where a single metal metal nanoparticle colloid is produced will be described as an example. This manufacturing method is applied to each of the manufacturing steps in the case where the core nanoparticles constituting the composite metal nanoparticles of the present invention are produced in a vacuum or the surrounding nanoparticles are formed around the core nanoparticles. It can be applied by setting the necessary unique conditions.

  In FIG. 1, an appropriate amount of surfactant 25 is stored in a liquid form below the vacuum chamber 21, and the vacuum chamber 21 is evacuated to a predetermined degree of vacuum suitable for evaporating or sublimating the source metal in the crucible. The vacuum chamber 21 is rotated in the direction of the arrow 28. The liquid surfactant 25 becomes a film-like surfactant 26 on the inner wall 21a of the rotating vacuum chamber 21 and moves in the direction of the arrow 28 along the inner wall 21a of the vacuum chamber in a liquid state. When an electric current is passed through a heat source (not shown) of the crucible 22, the raw metal in the crucible evaporates or sublimates, and the evaporated or sublimated metal flies upward of the vacuum chamber 21 as a metal bundle 24. It reaches the position of the film-like surfactant 26 moving along the inner wall 21a of the vacuum chamber 21, and is captured by the surfactant 26 to be in the state of metal nanoparticle colloid. The film-like surfactant 26 that has captured the metal nanoparticles continues to move in the direction of the arrow 29 as it is, and melts into the liquid surfactant 25 that has accumulated under the vacuum chamber 21.

  The surfactant containing the metal nanoparticle colloid melted into the surfactant 25 becomes a film-like surfactant 26 containing the metal nanoparticle colloid on the inner wall 21a of the rotating vacuum chamber 21, and the inner wall of the vacuum chamber. It moves in the direction of arrow 28 along 21a.

  This operation is continued for a predetermined time, and the moving film-like surfactant 26 continues to capture the evaporated metal, and the concentration of the metal nanoparticles in the metal nanoparticle colloid in the surfactant is increased.

  In the crucible 22, the amount of raw material metal that matches the manufacturing plan is put, and the amount of surfactant that matches the manufacturing plan is put below the vacuum chamber 21, and the above process is performed. Unlike the conventional method, the surfactant is used. When the concentration of the metal nanoparticles in 25 and 26 reaches the upper part of the vacuum chamber 21 in the conventional case, the surfactant diluted with the solvent cannot be attached to the inner wall of the vacuum chamber 21. Even if the concentration is much higher than the concentration at which it may fall (weight concentration of metal nanoparticles relative to the surfactant diluted in the solvent), the method of this application can continue production without dropping. In addition, the concentration of the metal nanoparticles in the metal nanoparticle colloid can be significantly increased as compared with the conventional case.

  Capturing metal nanoparticles with a surfactant without stopping the operation of the device until the amount of raw metal in the crucible reaches a predetermined amount allows the setup process to be completed in a short time, greatly increasing production costs. Can be reduced. The metal nanoparticle colloid produced by this method is a metal nanoparticle colloid with a high concentration and low impurities. When the product is put on the market after production, the metal nanoparticle colloid produced only with a surfactant is dispersed in a solvent. It can be supplied as is, or it can be dispersed in a hydrophobic solvent such as hexane or toluene, or can be dispersed in a hydrophilic solvent such as water or alcohol, depending on the user's request. Can be supplied. This is because the solvent is conventionally limited to a solvent that can be used in a vacuum, and when used in a dispersed state in a solvent that cannot be used in a vacuum depending on the user's usage conditions, it is necessary to remove the solvent used at the time of manufacture. This is a big advantage over what it was.

  The surfactants 25 and 26 are preferably in a liquid state with an appropriate viscosity. As a simple method, a liquid having a temperature that can control the flow state of the surfactant can be used.

  As a particularly preferable example of the surfactant in the above-described embodiment, polyoxyalkyleneamine can be used. The surfactant is a solid or a high-viscosity liquid at normal temperature, but becomes a liquid having an appropriate viscosity by controlling the temperature to a temperature equal to or higher than the temperature at which the flow state of the surfactant can be controlled. By using this method, the surfactant can be made into a low-viscosity liquid, and a predetermined amount of the surfactant can be in a liquid state and accumulated in the lower part of the vacuum chamber 21. When the amount of the liquid surfactant 25 is adjusted to an amount suitable for the metal nanoparticle colloid to be produced and placed in the lower part of the vacuum chamber 21, and the vacuum chamber 21 is rotated at a predetermined speed, a part of the surfactant 25 is vacuumed. It is pulled by the inner wall 21a of the chamber 21 and moves in the vacuum chamber 21 together with the inner wall 21a as a film-like surfactant 26 in the direction of the arrow 28 in FIG.

  There are several ways to make the surfactant polyoxyalkyleneamine into a liquid as described above. An example of an inexpensive and simple method is a bathtub in which at least a part of the outer wall 21b of the vacuum chamber 21 corresponding to a portion containing the surfactant 25 below the vacuum chamber 21 is immersed below the vacuum chamber 21. (Liquid reservoir) is provided, and the temperature of the surfactant can be controlled by applying a liquid having a temperature higher than the temperature at which the surfactant fluidizes from above the outer wall 21 b of the vacuum chamber 21.

  As a result of examination in this embodiment, it has been found that the viscosity of the surfactant in the initial state is preferably set to 100 centipoise or less within a range in which the inner wall of the vacuum chamber 21 can be attached. If the viscosity exceeds this value, the film-like surfactant 26 capturing the evaporated metal is likely to fall from the upper inner wall of the vacuum chamber, and the thickness uniformity of the film-like surfactant 26 is impaired. There is a risk that it will no longer be in a state.

  The metal evaporated from the crucible reaches the position of the liquid film-like surfactant 26 on the upper inner wall of the vacuum chamber 21 and is captured by the surfactant 26. The surfactant 26 captures the evaporated metal while moving, and mixes with the liquid surfactant 25 accumulated under the vacuum chamber 21. By repeating this, it is possible to produce highly uniform and highly concentrated metal nanoparticle colloids having a uniform particle size.

  In one preferable example of the present invention, the amount of the metal nanoparticles trapped by the surfactant is 20% of the nanoparticles having a diameter of 2 to 6 nm with respect to the amount of the dispersant of 100% of the surfactant. Can be obtained. This is not only a good quality of the obtained nanoparticle colloid but also a large reduction in mass production cost at a concentration 10 times higher than that of the production method described in Patent Document 5. .

  In one preferable example of the present invention, the amount of the metal nanoparticles trapped by the surfactant is 20% of the nanoparticles having a diameter of 2 to 6 nm with respect to the amount of the dispersant of 100% of the surfactant. Can be obtained. This is not only a good quality of the obtained nanoparticle colloid but also a large reduction in mass production cost at a concentration 10 times higher than that of the production method described in Patent Document 5. .

  Patent Document 5 describes that when a conventional surfactant diluted with a solvent is used, there is a large variation in particle shape and particle size, and the speed of the vacuum chamber is increased to align the nanoparticle size. ing. In Patent Document 5, when the metal is gold, if the rotation speed of the vacuum chamber is slowed down, the shape of the particles is long and large, and the variation is large. However, if the rotation speed is increased to 81 mm / s (seconds), the particles are linear. Decreases to 5-7 nm and increases to 100 mm / s. When the metal is copper, if the rotational speed is increased to 190 mm / s, the particle size converges to 2 nm. Have been described. In the case of a cylindrical vacuum chamber with an inner diameter of 200 to 300 mm, this rotational speed is considerably high as a vacuum system, shortening the life of parts for maintaining a good vacuum system, and sufficiently suppressing variations in particle size. There are major problems such as being difficult, and mass production is difficult.

  On the other hand, according to the production method using the 100% surfactant of the present invention, the particle size growth phenomenon can be effectively suppressed even if the rotational speed is less than half of the conventional speed, for example, 20 nm. In the following, nanoparticle colloids such as gold and tin whose particle size is very well controlled can be obtained at the mass production level.

  If the production method of the present invention is used, a colloidal nanoparticle colloid having a particle diameter of 2 to 3 nm is stably produced by using polyoxyalkyleneamine as a surfactant for cobalt, nickel and platinum and controlling the above conditions. be able to.

  We produced many metal nanoparticle colloids such as platinum, palladium, iron, cobalt, nickel, copper, gold, silver, germanium, indium, tin, and examined the particle size of metal nanoparticles in each colloid with an electron microscope. It was found that high-concentration metal nanoparticle colloids with a uniform particle size of 2 to 6 nm can be produced at the mass production level.

  The types of nanoparticles that can be produced using the production method of the present invention are not limited to these metals, and nanoparticle colloids of many metals other than the above metals can be produced. In addition to metals, many inorganic nanoparticle colloids that can be evaporated, such as zinc oxide, can be made.

  FIG. 2 is a transmission electron micrograph of an example of a metal nanoparticle colloid produced using a 100% surfactant as an evaporation metal capture medium as an example produced using the production method of the present invention, and the magnification is 30. Million times. In the figure, an index of 5 nm is described, and it can be seen that metal nanoparticles having an extremely uniform particle size of approximately 3 nm or less are uniformly distributed in the surfactant. In this case, the surfactant is polyoxyalkyleneamine and the metal is nickel.

  FIG. 3 is a transmission electron micrograph of the example of the metal nanoparticle colloid of FIG. 2 heat-treated at 150 ° C. for 2 hours as an embodiment of the present invention, and the magnification is 300,000 times. Most of the particles of 10 nm or less are homogeneously distributed.

  In the above, the case where the metal nanoparticle colloid of a single metal was manufactured was demonstrated. Next, the production of the composite metal nanoparticle colloid as the composite nanoparticle colloid of the present invention using this technique will be described.

  FIG. 4 is a diagram for explaining the composite metal nanoparticles.

  FIG. 4 is a diagram for explaining an example of a composite metal nanoparticle in the case where there is one kind of surrounding nanoparticles arranged around the core nanoparticle. Reference numeral 51A denotes a composite metal nanoparticle, 52A denotes a core nanoparticle, and 53A denotes a core nanoparticle. The surrounding nanoparticles are shown.

  FIG. 5 is a diagram for explaining an example of a composite metal nanoparticle having two types of surrounding nanoparticles. Reference numeral 51B denotes a composite metal nanoparticle, 52B denotes a core nanoparticle, 53B denotes a first type of surrounding nanoparticle, and 54B denotes two types. The nanoparticles surrounding the eye are shown.

  FIG. 6 is a diagram for explaining an example in which the composite metal nanoparticles 51A of FIG. 4 are heat-treated and alloyed, and reference numeral 51C indicates the alloyed composite metal nanoparticles.

  First, the composite metal nanoparticles 51A of FIG. 4 will be described. As shown in the figure, the composite metal nanoparticles 51A are arranged so that one kind of surrounding nanoparticles 53A surround the core nanoparticles 52A around the core nanoparticles 52A. The diameter of the surrounding nanoparticles 53A is sufficiently smaller than the diameter of the core nanoparticles 52A.

  Next, a method for producing the composite metal nanoparticles 51A will be described.

  First, core nanoparticles are manufactured using the metal nanoparticle colloid manufacturing apparatus described with reference to FIG. Specifically, as described with reference to FIG. 1, an appropriate amount of polyoxyalkyleneamine is put in the vacuum chamber 21 as a surfactant. At this time, the surfactant is not dissolved in the solvent, and only the surfactant is brought into a fluid state as described above. The crucible 22 is filled with a predetermined amount of copper as a raw material metal 23 to be evaporated, and then the vacuum chamber 21 is closed. While rotating the vacuum chamber 21, the inside of the vacuum chamber 21 is evacuated to a predetermined degree of vacuum.

  The crucible is heated to evaporate the copper in the crucible, and the evaporated copper metal wire bundle 24 becomes a film-like surfactant 26 on the inner wall 21a of the rotating vacuum chamber 21 in a liquid state along the inner wall 21a of the vacuum chamber. Are captured by the surfactant polyoxyalkyleneamine moving in the direction of arrow 28. This is continued until the total amount of the raw metal copper in the crucible (scheduled amount in this example) evaporates to produce a copper nanoparticle colloid.

  A copper nanoparticle colloid having a predetermined size in which the particle diameter of the copper nanoparticles is relatively large is prepared, and then, a predetermined amount of silver as a raw metal 23 is put into an empty crucible according to the production schedule.

  Here, regarding a copper nanoparticle colloid of a predetermined size with a relatively large particle size of the copper nanoparticles, for example, a copper nanoparticle colloid containing copper nanoparticles having an average particle size of 15 nm and a particle size distribution of ± 5 nm. Thus, it is a colloid of conditions suitable for the application.

  When this copper nanoparticle colloid is used as a core nanoparticle, the copper nanoparticle colloid having a predetermined size described with reference to FIG. 1 can be used as it is depending on conditions such as a particle size required for the nanoparticle.

  When a particle size larger than that of the copper nanoparticle colloid having a predetermined size described with reference to FIG. 1 is required, one method is to subject the produced copper nanoparticle colloid to heat treatment. The particle size can be increased in the range of 10 to 100 nm.

  For example, when copper nanoparticles having a large particle size are required as the core nanoparticles, the copper nanoparticle colloid produced above is heated with a heater or microwave to increase the particle size of the copper nanoparticles. . In particular, microwave heating has the advantage that the particle size of the nanoparticles can be increased uniformly.

  Moreover, when multi-metal nanoparticles are required as core nanoparticles, such as nickel-cobalt alloy nanoparticles and multi-metal nanoparticles having an anisotropic phase separation structure, the description has been given with reference to FIG. For example, nickel-cobalt single metal nanoparticle colloids prepared by the same method as copper are mixed and heat-treated, alloy type multi-metal nanoparticle colloids and anisotropic phase-separated multi-metal nanoparticles Colloids can be made.

  In addition, the prepared nanoparticle colloidal surfactant (hereinafter also referred to as a ligand) can be exchanged before use as a nuclear nanoparticle.

  In addition, the copper nanoparticle colloid in the single metal nanoparticle is very strong and easily oxidized as described above. As described above, when various processes are performed by taking out from the vacuum, it is preferable to perform in an inert atmosphere such as in an inert atmosphere.

  The crucible containing silver is sublimated from the crucible containing silver after the exhausted state in the vacuum chamber 21 containing the colloidal copper nanoparticle colloid produced as described above and the rotation state of the vacuum chamber 21 are set to predetermined states. Heat to the temperature to allow. The temperature at which silver is sublimated is lower than the temperature at which silver is evaporated. When the silver sublimated from the crucible becomes a silver metal bundle 24 and reaches the inner wall 21a of the vacuum chamber, the surfactant polyoxyalkylene capturing the copper moving in the direction of arrow 28 along the inner wall 21a of the vacuum chamber. Captured by amines. Continuing to capture and sublimate a predetermined amount of silver, as shown in FIG. 4, a colloid of composite nanoparticles in which copper nanoparticles 52A are used as core nanoparticles, and silver nanoparticles 53A are surrounded by nanoparticles surrounding them. The composite metal nanoparticle colloid as can be prepared.

  The composite metal nanoparticle colloid thus produced is taken out from the vacuum chamber 21 and stored in a predetermined container.

  When the state of the composite metal nanoparticles in the prepared composite metal nanoparticle colloid was examined using an electron microscope or the like, the composite metal nanoparticles were in a state in which silver nanoparticles were arranged around the copper nanoparticles. It was confirmed that the metal nanoparticles were approximately 15 to 20 nm in particle size.

  FIG. 7 is a transmission electron micrograph of the composite metal nanoparticle colloid.

  The particle size of the silver nanoparticles is preferably 10 nm or less, and particularly preferably 5 nm or less. One of the best modes is to produce silver nanoparticles with a uniform particle size of 2 to 3 nm by controlling the conditions to make nanoparticles of copper-silver composite metal nanoparticles colloids with excellent characteristics at a low cost at mass production level. Can do.

  In addition, although the example of the composite metal nanoparticle which arranged the several nanoparticle around the core nanoparticle as a nanoparticle was demonstrated using FIG. 4 and FIG. 5, the structure of the composite metal nanoparticle of this invention is this. The present invention is not limited to a narrow range, and many variations are possible. For example, FIG. 4 illustrates an example in which one kind of surrounding nanoparticles 53A is arranged in a layer so as to cover the core nanoparticles 2A around the core nanoparticles 2A. However, the present invention is not limited thereto, and the core nanoparticles 2A are not limited thereto. One type of surrounding nanoparticles 53A may be arranged in an island shape with a gap between them, and the surrounding nanoparticles 53A of FIG. 4 may alternately arrange two types of layered metal particles. Alternatively, a plurality of types of island-shaped surrounding nanoparticles may be arranged. Variations are also possible for the structure of FIG.

  FIG. 8 shows another example of an embodiment of the present invention, in which composite nano-particles are produced using the same apparatus as that for producing a composite metal nano-particle colloid in which copper is a core nano particle and silver is a surrounding nano particle. 2 is a transmission electron micrograph of particles. As in the case of the copper, the silver nanoparticle as the surrounding nanoparticle was sublimated and moved to the state of movement, and the surfactant polyoxyalkyleneamine trapping nickel (the surfactant was not diluted in a solvent, In the same manner as above and used. In this example, nickel nanoparticles having a particle size of 2 to 3 nm or aggregates of them are used as core nanoparticles, and silver nanoparticles having a particle size of 2 to 3 nm are arranged around the nickel nanoparticles. It is composed.

  It has been found that the composite metal nanoparticle colloid of the present invention exhibits excellent physical properties with extremely high purity that could not be realized so far. For example, as soon as a single copper nanoparticle colloid is taken out from a vacuum state into the atmosphere, it starts to oxidize and discolors, but the composite metal nanoparticle colloid formed with the composite nanoparticles of copper and silver enters the atmosphere from a vacuum state into the atmosphere. It was found that the oxidation phenomenon was not observed even when it was taken out and stored in the atmosphere for 3 months or more, and it can be stored in a stable state for a long period of time without worrying about oxidation as in the past. In addition, when a single nickel nanoparticle colloid is dispersed in alcohol or water, it becomes nickel hydroxide and immediately turns green, but the composite nanoparticle colloid has nickel as the core nanoparticle and silver as the surrounding nanoparticle. Was confirmed not to change color.

  As can be seen from this example, according to the present invention, it can be expected that the use effect of the nanoparticle interface will be greatly improved, such as prevention of oxidation / degeneration of the surface of the metal nanoparticle and remarkable improvement of the catalytic action.

  By subjecting the composite metal nanoparticle colloid to heat treatment, the state of the composite metal nanoparticles contained can be controlled.

  By increasing the heat treatment temperature, the composite metal nanoparticles can be made into an alloy state. FIG. 6 is a view for explaining alloyed metal nanoparticles. Reference numeral 52A0 denotes an interface between the core nanoparticles and the surrounding nanoparticles, and 51C denotes the alloyed metal nanoparticles of the present invention. The heat treatment can be performed by heater heating, but extremely homogeneous alloying can be performed by microwave heating.

  The produced composite metal nanoparticle colloid is subjected to necessary processing as a product, such as particle size control and ligand exchange, in response to user demands.

  FIG. 9 is a diagram schematically showing a cross section of the main part of another example of the apparatus for producing composite metal nanoparticle colloid of the present invention, which is an example of an apparatus for producing composite metal nanoparticle colloid using a plurality of crucibles. is there. Reference numerals 22A and 22B denote crucibles, and 24A and 24B denote metal wire bundles evaporated or sublimated from the crucibles 22A and 22B, respectively.

  By using the manufacturing apparatus of FIG. 9, the core nanoparticles and the surrounding nanoparticles arranged around the core nanoparticles can be manufactured in a continuous manufacturing process without breaking the vacuum.

  A method for producing a composite metal nanoparticle colloid according to the present invention using the production apparatus of FIG. 9 will be described with respect to an example in which the copper nanoparticles are used as core nanoparticles and silver nanoparticles are used as surrounding nanoparticles.

  The crucibles 22A and 22B have lids that can be opened and closed independently from the outside of the apparatus using a control system, so that the evaporated metal or sublimated metal from one crucible does not enter the other crucible. When using one crucible, put the lid on the other crucible.

  The crucible 22A is filled with copper as a raw material metal, and the crucible 22B is filled with a planned amount of silver as a raw metal, and the lid is closed. A planned amount of the same type of surfactant as above is added and the vacuum chamber is closed. While rotating the vacuum chamber, the inside of the vacuum chamber is evacuated to a predetermined degree of vacuum.

  First, the lid of the crucible 22A is opened and heated to evaporate copper, and the film-like surfactant moving on the inner wall of the vacuum chamber rotating in the same manner as described above is captured to capture the copper that has come flying, Make copper nanoparticle colloid. A predetermined amount of copper is evaporated to produce a copper nanoparticle colloid as a core nanoparticle similar to the above, and the power supply of the crucible 22A is turned off. .

  Next, the lid of the crucible 22B is opened, the silver is sublimated by heating, and the silver that has been sublimated to the film-like surfactant containing the colloidal copper nanoparticles moving on the inner wall of the rotating vacuum chamber The copper nanoparticles are captured as core nanoparticles, and silver nanoparticles as nanoparticles are arranged around the copper nanoparticles.

  In this way, the composite metal nanoparticle colloid of the present invention in which copper nanoparticles are used as core nanoparticles and silver nanoparticles having a sufficiently smaller particle diameter than the copper nanoparticles are arranged around the core nanoparticles.

  In the manufacturing apparatus of FIG. 9, the case where the number of crucibles is two is shown, but the number of crucibles can be three or more.

  When the surrounding nanoparticles shown in FIG. 5 produce two types of composite nanoparticles, as a first example, according to the method for producing composite nanoparticles described using the apparatus of FIG. Can produce one kind of composite nanoparticles, put the second kind of surrounding metal nanoparticles into the crucible, and similarly produce two kinds of surrounding nanoparticles. As a second example, a nuclear nanoparticle colloid is first prepared using three crucibles according to the method for manufacturing composite nanoparticles described using the manufacturing apparatus of FIG. 9, and then the first type of surrounding nano-particles. The particles can then be made, then the second type of surrounding nanoparticles can be made and the surrounding nanoparticles can produce two types of composite metal nanoparticles.

  Although not shown, the manufacturing apparatus of FIG. 9 has a function of performing a heat treatment on the nanoparticle colloid in the vacuum chamber. As the heat treatment means, many means such as a heating means using a heater and a heat treatment means using a microwave can be used, but a heat treatment using a microwave is particularly preferable, so that a nanoparticle colloid having a uniform particle size distribution can be easily obtained. The particle size can be reliably controlled. Then, using a heat treatment by microwave, for example, a nanoparticle colloid having excellent characteristics such as effectively preventing oxidation and stabilizing the physical properties of the nanoparticles can be produced.

  The manufacturing apparatus shown in FIG. 9 can be manufactured using, for example, a dedicated vacuum chamber for each nanoparticle of a different source metal by connecting the vacuum chambers in a plurality of stages. It is possible to produce the composite metal nanoparticles and increase the production capacity of the composite metal nanoparticles.

  The method for producing composite metal nanoparticles according to the present invention is not limited to the above example, and many variations are possible.

  In addition, the greatest feature of the present invention is that a surfactant fluidized without dilution in a solvent is used to produce at least one kind of nanoparticle and surrounding nanoparticle constituting the composite metal nanoparticle colloid. In this way, the physical method of capturing the nanoparticles is used. It can be produced. That is, the present invention brings about an extremely great effect that composite metal nanoparticles having a composition that is difficult to produce by a chemical method can also be produced.

  FIG. 10 is a schematic diagram for explaining how metal nanoparticles or composite metal nanoparticles are supported by a carrier. Reference numeral 46 is a carrier in which metal nanoparticles or composite metal nanoparticles are supported, 47 is a carrier, and 48 is a carrier. Metal nanoparticles or composite metal nanoparticles.

  As the carrier, suitable ones can be used depending on the use environment of the metal nanoparticles and the user's request, such as ceramics such as zirconia, alumina, and ceria, iron oxide, carbon, and Teflon (registered trademark).

  The composite metal nanoparticle colloid of the present invention is loaded with a carrier supporting the composite metal nanoparticle, and the composite metal nanoparticle is supported on the carrier, and the carrier is used for, for example, an automobile exhaust gas treatment device to purify exhaust gas by catalytic action. It can be performed.

  As described above, the composite metal nanoparticle colloid of the present invention has been described using a new physical method. However, as is clear from the above description, the present invention is not limited to the above-described embodiment, and many variations are possible. Is possible.

  For example, in the above description, the core nanoparticle and the surrounding nanoparticles arranged around the core nanoparticle are mainly described using a new physical method. However, as the core nanoparticle, the metal nanoparticle manufactured by another method is used. Using the particles, the surrounding nanoparticles can be made using the new physical method. When using metal nanoparticles produced by chemical methods as metal nanoparticles produced by other methods, remove at least undesirable contaminants such as by-products, exchange ligands, and perform necessary treatments. Thereafter, a composite metal nanoparticle colloid can be prepared according to the present invention.

  In addition, the case of copper and nickel as the core nanoparticle has been described by taking the case of silver as an example of the surrounding nanoparticle that brings about a remarkable effect, but as is clear from the purpose of the above explanation, It is not limited to, and many metals can be used.

  According to the present invention, it is possible to provide a high-purity and high-concentration composite metal nanoparticle colloid at a low cost, and to provide a high-quality composite nanoparticle colloid using an inorganic material at a low cost without being limited to a metal. it can.

  The composite metal nanoparticle colloid of the present invention is used in various fields such as automobiles, batteries, wiring / electrode formation, electromagnetic shielding, semiconductor electronics, biosensors, biomarkers, biotechnology, printing, etc. It can bring about great industrial progress.

21: Vacuum chamber 21a: Inner wall of vacuum chamber 22, 22A, 22B: Crucible
23: Raw metal 24, 24A, 24B: Metal bundle 25, 26: Surfactant 27: Metal nanoparticle colloid 28, 29: Arrow 51A, 51B: Composite nanoparticle 52A, 52B: Core nanoparticle 53A, 53B, 54B: Surrounding nanoparticles

Claims (16)

  In a composite metal nanoparticle colloid containing, as a main component, metal fine particles (hereinafter referred to as metal nanoparticles) having a particle size of 100 nm (nanometer) or less in a dispersant, the composite metal nanoparticle is the composite metal nanoparticle colloid. The main composite metal nanoparticle is a metal nanoparticle having a particle size of less than 100 nm as a core nanoparticle, and around the core nanoparticle, at least of the kind of metal, the particle size, the shape, and the activity of the solid phase reaction. One is a composite metal nanoparticle provided with at least one kind of a set of metal nanoparticles different from the core nanoparticle (hereinafter referred to as a metal nanoparticle surrounding the core nanoparticle), The composite metal nanoparticles are further obtained by evaporating or sublimating both the core nanoparticles and the surrounding nanoparticles in a reduced-pressure atmosphere or vacuum. When the metal is in a movable state, it flows at a temperature of the surfactant that is solid at room temperature or is so viscous that a film-like surfactant layer cannot be formed along the inner wall of the rotating vacuum chamber. Of the surfactant in the form of a membrane-like surfactant moving in the reduced-pressure atmosphere or in a vacuum controlled to a temperature at which a membrane-like surfactant layer can be formed along the inner wall of the rotating vacuum chamber. The nanoparticles are formed by repeatedly capturing and collecting by a membrane-like moving body, and the average particle size of at least one of the surrounding nanoparticles is smaller than the average particle size of the core nanoparticles, A composite metal nanoparticle colloid composition comprising the surfactant composition not containing a surfactant solvent, the core nanoparticle composition, and the surrounding nanoparticle composition Genus nanoparticles colloid. 2. The composite metal nanoparticle colloid according to claim 1, wherein the surfactant of the core nanoparticle and the surrounding nanoparticle is the same type of surfactant that is not dissolved in a solvent of the surfactant.
A composite metal nanoparticle colloid characterized by that. The composite metal nanoparticle colloid according to claim 1 or 2, wherein the surfactant of at least one of the core nanoparticle colloid and the surrounding nanoparticle colloid moves in the reduced-pressure atmosphere or in vacuum. A composite metal nanoparticle colloid having a viscosity of 100 centipoise or less. The composite metal nanoparticle colloid according to any one of claims 1 to 3, wherein the film-form surfactant that moves in the reduced-pressure atmosphere or vacuum is not dissolved in a surfactant solvent. A composite metal nanoparticle colloid which is an amine.   The composite metal nanoparticle colloid according to any one of claims 1 to 4, wherein the core nanoparticles and / or surrounding nanoparticles are dissolved in a solvent of a surfactant that moves in the reduced-pressure atmosphere or in a vacuum. Nanoparticles and / or surrounding nano-particles that have been increased in size by irradiating microwaves to the nanoparticles formed by a physical method that repeatedly captures and collects them by a non-film-like surfactant moving body Composite metal nanoparticle colloid characterized by being a particle.   The composite metal nanoparticle colloid according to any one of claims 1 to 5, wherein the composite metal nanoparticle includes at least two kinds of surrounding nanoparticles arranged around the core nanoparticle, The metal nanoparticles of the second metal nanoparticles are arranged on the innermost side, and the second metal nanoparticles are arranged on the outer side, and the first metal nanoparticles are arranged on the outer side of the second metal nanoparticles. A composite metal nanoparticle colloid characterized in that it is a composite metal nanoparticle formed by arranging surrounding nanoparticles composed of three metal nanoparticles to form each set.   The composite metal nanoparticle colloid according to any one of claims 1 to 6, wherein the metal nanoparticles constituting at least one of the surrounding nanoparticles have a solid-phase reaction activity higher than that of the first metal nanoparticles. A composite metal nanoparticle colloid characterized by being a low metal nanoparticle.   The composite metal nanoparticle colloid according to claim 6 or 7, wherein the average particle diameter of the first metal nanoparticles constituting the composite metal nanoparticles is 10 nm to 100 nm, and the periphery of the first metal nanoparticles. A composite metal nanoparticle colloid, wherein an average particle size of at least one metal nanoparticle among the metal nanoparticles constituting the surrounding nanoparticle disposed in a metal nanoparticle is smaller than 10 nm.   The composite metal nanoparticle colloid according to claim 7 or 8, wherein the average particle diameter of the first metal nanoparticles constituting the composite metal nanoparticles is 10 nm to 100 nm, and the periphery of the first metal nanoparticles. The composite metal nanoparticle colloid characterized in that an average particle diameter of at least one metal nanoparticle among the metal nanoparticles constituting the surrounding nanoparticles arranged in 5 is 5 nm or less.   The composite metal nanoparticle colloid according to any one of claims 1 to 9, wherein the composite metal nanoparticle includes the first metal nanoparticle on the innermost side and the second metal nanoparticle on the outermost side. A composite metal nanoparticle colloid characterized in that there is a part in which a surrounding nanoparticle composed of the third metal nanoparticle and a surrounding nanoparticle composed of the third metal nanoparticle are mixed.   11. The composite metal nanoparticle colloid according to claim 1, wherein a metal of the first metal nanoparticle constituting the composite metal nanoparticle is copper or nickel, and the first metal nanoparticle A composite metal nanoparticle colloid characterized in that the metal of at least one of the surrounding nanoparticles arranged around the particle is silver.   A composite metal nanoparticle supported on a carrier that supports the composite metal nanoparticle in the composite metal nanoparticle colloid according to any one of claims 1 to 11.   The composite metal nanoparticle according to claim 12, wherein the composite metal nanoparticle has at least two kinds of surrounding nanoparticles arranged around the core nanoparticle, and is closest to the first metal nanoparticle. The metal nanoparticles constituting the surrounding nanoparticles are referred to as second metal nanoparticles, and then the metal nanoparticles constituting the surrounding nanoparticles close to the first metal nanoparticles are referred to as third metal nanoparticles. (The same applies hereinafter), the second metal nanoparticles have a particle size smaller than that of the first metal nanoparticles, and the third metal nanoparticles have a particle size of the second metal nanoparticles. Composite metal nanoparticles characterized by being smaller than the particle size.   The composite metal nanoparticles according to claim 12 or 13, wherein a plurality of types of nanoparticles among the core nanoparticles and the surrounding nanoparticles constituting the composite metal nanoparticles do not break a vacuum atmosphere or a vacuum state. In a continuous process or in the same process, repeatedly collecting and collecting a film-like surfactant moving body that moves the metal in a reduced-pressure atmosphere or in a vacuum by evaporation, etc. Composite metal nanoparticles, characterized in that they are formed nanoparticles. In the composite metal nanoparticle colloid production apparatus for producing a composite metal nanoparticle colloid containing metal fine particles (hereinafter referred to as metal nanoparticles) having a particle size of 100 nm (nanometer) or less as a main component in a dispersant, the composite The metal nanoparticle colloid production apparatus is a composite metal nanoparticle colloid production apparatus in which a plurality of vacuum chambers are connected to each other, wherein at least one vacuum chamber is connected to a vacuum exhaust system. A chamber, at least one crucible (crucible) disposed in the vacuum chamber, heating means for heating and evaporating or sublimating a metal contained in the crucible, and driving for rotating the outer peripheral wall of the vacuum chamber Means, a rotation control means for controlling the rotation of the outer peripheral wall of the vacuum chamber, and a surfactant. A space provided in a part of the inner peripheral wall of the vacuum chamber (hereinafter referred to as a surfactant space), and is solid at room temperature in the surfactant space, or The temperature of the surfactant, which is so viscous that it cannot form a membrane-like surfactant layer along the inner wall of the rotating vacuum chamber, rotates and rotates without causing the surfactant layer to dissolve in the solvent. It has a surfactant temperature control means that rotates along the inner wall of the vacuum chamber to control the temperature so that a film-like surfactant layer can be formed, and further dissolves in the solvent contained in the surfactant space. Non-surfactant captures and collects the metal fine particles flying there by the film-like surfactant layer that is rotated along with the rotation of the vacuum chamber along the inner wall of the rotating vacuum chamber. Apparatus for producing composite metal nanoparticles, characterized in that it has a repeated mechanism. In a method for producing a composite metal nanoparticle colloid containing metal fine particles (hereinafter referred to as metal nanoparticles) having a particle size of 100 nm (nanometer) or less as a main component in a dispersant,
The main composite metal nanoparticles in the composite metal nanoparticle colloid are metal fine particles having a particle size of less than 100 nm as core nanoparticles, and the kind, particle size, shape, and solid phase reaction of the metal around the core nanoparticles. At least one of the activities is provided with at least one type of aggregate of metal nanoparticles different from the core nanoparticles (hereinafter referred to as metal nanoparticles surrounding the core nanoparticles). Composite metal nanoparticles,
The method for producing a composite metal nanoparticle colloid includes a step of preparing a rotary vacuum device capable of evaporating or sublimating a metal nanoparticle raw metal, and an inner wall of a vacuum chamber that is solid at room temperature or rotates. Preparing a surfactant having a viscosity so high that a film-like surfactant layer cannot be formed in the vacuum chamber, and adjusting the temperature of the surfactant in the vacuum chamber without dissolving the surfactant in the solvent. A step of forming a film-like surfactant moving body that moves along the inner wall of the vacuum chamber that rotates in the reduced-pressure atmosphere or in a vacuum controlled above the temperature at which it fluidizes, and the reduced-pressure atmosphere or vacuum The step of making the metal movable by evaporation or sublimation in the inside, and the state of making the metal movable by evaporation or sublimation in the reduced pressure atmosphere or in vacuum are in the reduced pressure atmosphere. Forming a nanoparticle colloidal performed repeatedly be collected to capture the movement of the film-like surfactants that are not dissolved in a solvent to move in a vacuum,
And having a step of forming a plurality of types of nanoparticles among the core nanoparticles and surrounding nanoparticles constituting the composite metal nanoparticles in a continuous process or the same process without breaking a reduced-pressure atmosphere or vacuum state. A method for producing a composite metal nanoparticle colloid characterized by