WO2013164886A1 - 微粒子の製造方法 - Google Patents
微粒子の製造方法 Download PDFInfo
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- WO2013164886A1 WO2013164886A1 PCT/JP2012/061579 JP2012061579W WO2013164886A1 WO 2013164886 A1 WO2013164886 A1 WO 2013164886A1 JP 2012061579 W JP2012061579 W JP 2012061579W WO 2013164886 A1 WO2013164886 A1 WO 2013164886A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1887—Stationary reactors having moving elements inside forming a thin film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
- B01J2219/00063—Temperature measurement of the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00189—Controlling or regulating processes controlling the stirring velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/084—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid combination of methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0884—Spiral fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0892—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid casting nozzle; controlling metal stream in or after the casting nozzle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B2009/125—Micropellets, microgranules, microparticles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
- B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
Definitions
- the present invention relates to a method for producing fine particles.
- fine particles have been widely used in various fields in industrial fields such as optical materials, magnetic materials, conductive materials, electronic materials, functional ceramics, fluorescent materials, catalytic materials, and chemical materials.
- fine particles such as metals, metal oxides, and composite materials are expected to dramatically improve optical, electromagnetic, and mechanical properties.
- new properties such as ultra-high functionality due to the quantum size effect resulting from micronization and the emergence of new properties.
- the various characteristics described above have a close relationship with the particle size, it is required not only to synthesize fine particles but also to precisely control the particle size of the fine particles.
- the characteristics of the fine particles change depending on the primary particle diameter. However, when a plurality of primary particles are agglomerated, especially when primary particles are united, it is more The characteristics are different.
- Fine particle production methods include a so-called breakdown method in which particles are mainly pulverized using a bead mill, a build-up method in a gas phase method such as CVD or PVD, or a liquid phase method using a device such as a microreactor.
- a build-up method there is a build-up method.
- the breakdown method requires a large amount of energy, it is difficult to produce nano-sized fine particles, and since a strong force acts on the fine particles due to the pulverization process, the characteristics expected as fine particles
- problems such as not actually appearing.
- methods using a gas phase method or a microreactor have problems such as high energy costs, and it has been difficult to produce fine particles stably and in large quantities.
- the generation of the coarse particles described above is due to coalescence of the fine particles, and the particle size distribution of the finally obtained fine particles becomes wide. For this reason, when producing fine particles, the dispersibility of the fine particles is ensured by introducing a modifying group on the surface of the fine particles or using a dispersant to prevent aggregation and coalescence of the fine particles.
- the particle diameter of the fine particles obtained can be controlled by controlling the aggregation and coalescence of the fine particles.
- the aggregation state of primary particles containing a binder resin can be controlled by adding an acrylic acid polymer salt as a dispersant into the diameter. It is described that the particle size and particle size distribution of coalesced particles can be easily controlled.
- JP 2006-184306 A International Publication WO2009 / 008393 Pamphlet International Publication WO2009 / 008390 Pamphlet
- the applicant of the present application is capable of approaching / separating at least two kinds of fluids to be treated, which are a raw material fluid containing a raw material and a treatment fluid containing a material for processing the raw material, facing each other.
- a raw material fluid containing a raw material and a treatment fluid containing a material for processing the raw material, facing each other.
- the inventors have found that by controlling the peripheral speed of the rotation at the portion where the bodies merge (the merging portion), it is possible to control the rate at which the fine particles merge with each other, thereby completing the present invention.
- the present invention uses at least two kinds of fluids to be treated.
- at least one kind of fluid to be treated is a raw material fluid containing at least one kind of raw material.
- At least one kind of fluid to be treated is a treatment fluid containing at least one kind of substance for treating the raw material, and the fluid to be treated is disposed so as to be opposed to and can be separated.
- the raw material fluid and the above Provided is a method for producing fine particles, characterized by controlling the rate at which the fine particles join together by controlling the peripheral speed of the rotation at the confluence where the processing fluid merges That.
- the coalescence of the fine particles means, for example, that when the shape of the fine particles is a sphere, a plurality of spheres are connected to keep a part of the shape of each sphere. It means what is judged to be coalesced, and it does not matter whether the coalescence occurs during the growth process of fine particles or after the growth. Further, the measurement of the particle diameter of the fine particles was performed by measuring the diameter of the combined fine particles as one fine particle. Moreover, this invention can be implemented as said treatment being at least any one selected from precipitation, emulsification, dispersion, reaction, and aggregation.
- any one of the raw fluid and the processing fluid passes between the processing surfaces while forming the thin film fluid, and either of the processing fluids is processed.
- a separate introduction path independent of the flow path through which the fluid flows, and at least one of the at least two processing surfaces includes at least one opening leading to the separate introduction path,
- a fluid to be processed, which is the other of the fluid and the processing fluid, is introduced between the at least two processing surfaces from the opening, and the raw material fluid and the processing fluid are converted into the thin film fluid. It can be implemented as a mixture in.
- the present invention is implemented so as to control the peripheral speed of the rotation in the joining portion where the raw material fluid and the processing fluid are joined within a range of 0.8 to 41.9 m / s. .
- the proportion of the fine particles united is 50% or less, preferably 40% or less. More preferably, it is appropriate to carry out as 30% or less.
- a fluid pressure application mechanism which applies pressure to a fluid to be processed, and a first processing part provided with a first processing surface among the at least two processing surfaces. And a second processing part having a second processing surface among the at least two processing surfaces, and a rotation drive mechanism for relatively rotating these processing parts,
- the surface constitutes a part of a sealed flow path through which the fluid to be processed to which the pressure is applied flows, and at least a first of the first processing portion and the second processing portion.
- the processing portion includes a pressure receiving surface, and at least a part of the pressure receiving surface is constituted by the second processing surface, and the fluid pressure applying mechanism is formed on the pressure receiving surface by the fluid pressure applying mechanism.
- the second processing surface In response to the applied pressure, the second processing surface is moved away from the first processing surface.
- the above pressure is generated between the first processing surface and the second processing surface, which are arranged to face each other and are capable of approaching / separating at least one rotating relative to the other. This is carried out as a method for producing fine particles, in which the fluid to be treated forms the thin film fluid by passing the treated fluid to which the material to be treated is passed. be able to.
- the present invention makes it possible to control the rate at which the fine particles are brought together, which was difficult with the conventional production method, and makes it possible to produce the fine particles easily and continuously. Further, at least two types of flow to be processed between the processing surfaces of at least two processing surfaces arranged opposite to each other and capable of approaching / separating at least one rotating relative to the other. By changing the simple processing conditions that change the peripheral speed of the rotation at the merging part of the body, it becomes possible to control the rate at which the resulting fine particles are united with each other. Thus, it is possible to prepare fine particles according to the purpose, and to provide fine particles stably at low cost.
- FIG. 1 is a schematic cross-sectional view of a fluid processing apparatus according to an embodiment of the present invention.
- (A) is a schematic plan view of a first processing surface of the fluid processing apparatus shown in FIG. 1, and (B) is an enlarged view of a main part of the processing surface of the apparatus.
- (A) is sectional drawing of the 2nd introducing
- (B) is the principal part enlarged view of the processing surface for demonstrating the 2nd introducing
- 4 is a SEM photograph of nickel fine particles produced in Example 2.
- 6 is a SEM photograph of nickel fine particles produced in Example 5.
- 14 is a SEM photograph of silver fine particles produced in Example 13.
- 4 is a SEM photograph of acrylic polymer fine particles produced in Example 16.
- Example 2 is a SEM photograph of acrylic polymer fine particles produced in Example 20.
- 4 is a TEM photograph of amorphous silica fine particles produced in Example 23.
- FIG. The TEM photograph of the amorphous silica fine particles produced in Example 24 is shown.
- the raw material fluid in the present invention contains at least one kind of raw material substance which is a raw material, and it is desirable to mix or dissolve the raw material substance in a solvent to be described later (hereinafter, mixing or dissolution is simply referred to as dissolution).
- the raw material in the present invention is not particularly limited, and examples thereof include organic substances, inorganic substances, organic-inorganic composites, and the like, for example, simple substances of metal elements and nonmetallic elements, and compounds thereof.
- Examples of the compound include salts, oxides, hydroxides, hydroxide oxides, nitrides, carbides, complexes, organic compounds, hydrates and organic solvates thereof. These may be a single raw material or a mixture of two or more.
- the raw material used as the starting material and the processed raw material obtained by mixing with the processing fluid described later may be the same material or different materials before and after the treatment. May be.
- the raw material used as a starting material may be a metal compound, and the processed raw material may be a simple metal constituting the metal compound.
- the raw material used as the starting material is a mixture of a plurality of types of metal compounds, and the processed raw material is a raw material contained in the processing fluid and the plurality of types of metal compounds used as the starting materials.
- a reaction product obtained by reacting a substance for treating the substance may be used.
- the raw material used as a starting material may be a simple metal, and the processed raw material may also be a simple metal.
- the treatment fluid in the present invention contains at least one substance for treating a raw material.
- the treatment is not particularly limited, and examples thereof include precipitation, emulsification, dispersion, reaction, and aggregation.
- a solvent as described later may be used alone, or the following substances may be included in the solvent as a substance for processing the raw material.
- acidic substances such as hydrochloric acid or sulfuric acid, nitric acid or aqua regia, trichloroacetic acid or trifluoroacetic acid, phosphoric acid, citric acid, ascorbic acid, or an inorganic acid
- alkali hydroxides such as sodium hydroxide and potassium hydroxide
- basic substances such as amines such as triethylamine and dimethylaminoethanol
- salts of the above acidic substances and basic substances for example, the reducing agent which can reduce
- the reducing agent is not particularly limited, but hydrazine or hydrazine monohydrate, formaldehyde, sodium sulfoxylate, borohydride metal salt, aluminum hydride metal salt, triethylborohydride metal salt, glucose, citric acid, ascorbic acid, tannic acid, dimethyl formamide, pyrogallol, tetrabutylammonium borohydride, sodium hypophosphite (NaH 2 PO 2 ⁇ H 2 O), Rongalite C (NaHSO 2 ⁇ CH 2 O ⁇ 2H 2 O), a metal compound or their Or a transition metal compound or an ion thereof (iron, titanium, etc.).
- the reducing agents listed above include their hydrates, organic solvates, or anhydrides. These materials for treating the raw material may be used alone or as a mixture in which two or more kinds are mixed. In addition, when the said solvent is used independently as a processing fluid, the said solvent turns into a substance for processing a raw material.
- solvent Although it does not specifically limit as a solvent used for the raw material fluid and process fluid in this invention, Water, such as ion-exchange water, RO water, a pure water, and ultrapure water, Alcohol-type organic solvents, such as methanol and ethanol, Ethylene glycol Polypropylene organic solvents such as propylene glycol, trimethylene glycol, tetraethylene glycol, polyethylene glycol and glycerin, ketone organic solvents such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate Examples thereof include organic solvents, ether organic solvents such as dimethyl ether and dibutyl ether, aromatic organic solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon organic solvents such as hexane and pentane.
- Water such as ion-exchange water, RO water, a pure water, and ultrapure water
- the solvent itself works as a reducing agent.
- the solvent may be used alone or in combination of two or more.
- the solvent can be used alone as the processing fluid. In other words, even if the said solvent is individual, it can become a substance for processing a raw material.
- the raw material fluid and / or processing fluid in the present invention can be carried out even if it contains a solid or crystalline state such as a dispersion or slurry.
- the metal fluid in the present invention is obtained by dissolving at least one kind of metal and / or metal compound as a raw material in the above solvent, and becomes the above raw material fluid.
- the metal in the present invention is not particularly limited. Preferable are all metals on the chemical periodic table. Examples of the metal element include Ti, Fe, W, Pt, Au, Cu, Ag, Pb, Ni, Mn, Co, Ru, V, Zn, Zr, Sn, Ta, Nb, Hf, Cr, Mo, and Re. , In, Ir, Os, Y, Tc, Pd, Rh, Sc, Ga, Al, Bi, Na, Mg, Ca, Ba, La, Ce, Nd, Ho, Eu, and the like.
- non-metallic elements of B, Si, Ge, As, Sb, C, N, O, S, Te, Se, F, Cl, Br, I, and At can be mentioned as metal elements.
- a single element may be sufficient and the substance which contains a nonmetallic element in the alloy which consists of a several metallic element, or a metallic element may be sufficient.
- it can also be implemented as an alloy of a base metal and a noble metal.
- Metal compound In addition to the simple substance of the above metals (including the non-metallic elements listed above), a metal compound which is a compound of these metals dissolved in the above solvent can be used as the metal fluid. Although it does not specifically limit as a metal compound in this invention, for example, a metal salt, an oxide, a hydroxide, a hydroxide oxide, a nitride, a carbide
- the metal salt is not particularly limited, but metal nitrate or nitrite, sulfate or sulfite, formate or acetate, phosphate or phosphite, hypophosphite or chloride, oxy salt or Acetylacetonate salts, hydrates and organic solvates of these metal salts, and examples of organic compounds include metal alkoxides. These metal compounds may be used alone or as a mixture in which two or more kinds are mixed.
- the reducing agent fluid used in the present invention contains at least one reducing agent listed above, and becomes the above-described processing fluid. These reducing agents may be used alone or as a mixture in which two or more kinds are mixed. In addition, it is desirable to use a mixture of the above reducing agent mixed with or dissolved in the above solvent as the reducing agent fluid.
- the metal fluid and / or the reducing agent fluid can be carried out even if it contains a solid or crystalline state such as a dispersion or slurry.
- the mixing of the raw material fluid and the processing fluid is performed in a thin film fluid that is disposed between the processing surfaces that are disposed so as to be able to approach and separate from each other and at least one rotates relative to the other. It is preferable to use a method of stirring and mixing, for example, by mixing using a device of the same principle as the devices disclosed in Patent Documents 2 and 3 by the applicant of the present application. It is preferable to obtain fine particles.
- the fluid processing apparatus shown in FIGS. 1 to 3 processes an object to be processed between processing surfaces in a processing unit in which at least one of approaching and separating can rotate relative to the other,
- the first fluid which is the first fluid to be treated
- the second fluid which is the second fluid to be treated, of the fluids to be treated is introduced between the processing surfaces from another flow path provided with the first fluid and the second fluid between the processing surfaces.
- U indicates the upper side
- S indicates the lower side.
- the upper, lower, front, rear, left and right only indicate a relative positional relationship, and do not specify an absolute position.
- R indicates the direction of rotation.
- C indicates the centrifugal force direction (radial direction).
- This apparatus uses at least two kinds of fluids as a fluid to be treated, and at least one kind of fluid includes at least one kind of an object to be treated and is opposed to each other so as to be able to approach and separate.
- a processing surface at least one of which rotates with respect to the other, and the above-mentioned fluids are merged between these processing surfaces to form a thin film fluid.
- An apparatus for processing an object to be processed As described above, this apparatus can process a plurality of fluids to be processed, but can also process a single fluid to be processed.
- This fluid processing apparatus includes first and second processing units 10 and 20 that face each other, and at least one of the processing units rotates.
- the opposing surfaces of both processing parts 10 and 20 are processing surfaces.
- the first processing unit 10 includes a first processing surface 1
- the second processing unit 20 includes a second processing surface 2.
- Both the processing surfaces 1 and 2 are connected to the flow path of the fluid to be processed and constitute a part of the flow path of the fluid to be processed.
- the distance between the processing surfaces 1 and 2 can be changed as appropriate, but is usually adjusted to 1 mm or less, for example, a minute distance of about 0.1 ⁇ m to 50 ⁇ m.
- the fluid to be processed that passes between the processing surfaces 1 and 2 becomes a forced thin film fluid forced by the processing surfaces 1 and 2.
- the apparatus When a plurality of fluids to be processed are processed using this apparatus, the apparatus is connected to the flow path of the first fluid to be processed and forms a part of the flow path of the first fluid to be processed. At the same time, a part of the flow path of the second fluid to be treated is formed separately from the first fluid to be treated. And this apparatus performs processing of fluid, such as making both flow paths merge and mixing both the to-be-processed fluids between the processing surfaces 1 and 2, and making it react.
- “treatment” is not limited to a form in which the object to be treated reacts, but also includes a form in which only mixing and dispersion are performed without any reaction.
- the first holder 11 that holds the first processing portion 10 the second holder 21 that holds the second processing portion 20, a contact pressure applying mechanism, a rotation drive mechanism, A first introduction part d1, a second introduction part d2, and a fluid pressure imparting mechanism p are provided.
- the first processing portion 10 is an annular body, more specifically, a ring-shaped disk.
- the second processing unit 20 is also a ring-shaped disk.
- the materials of the first and second processing parts 10 and 20 are metal, carbon, ceramic, sintered metal, wear-resistant steel, sapphire, other metals subjected to hardening treatment, hard material lining, It is possible to employ a coating or plating.
- at least a part of the first and second processing surfaces 1 and 2 facing each other is mirror-polished in the processing units 10 and 20.
- the surface roughness of this mirror polishing is not particularly limited, but is preferably Ra 0.01 to 1.0 ⁇ m, more preferably Ra 0.03 to 0.3 ⁇ m.
- At least one of the holders can be rotated relative to the other holder by a rotational drive mechanism (not shown) such as an electric motor.
- Reference numeral 50 in FIG. 1 denotes a rotation shaft of the rotation drive mechanism.
- the first holder 11 attached to the rotation shaft 50 rotates and is used for the first processing supported by the first holder 11.
- the unit 10 rotates with respect to the second processing unit 20.
- the second processing unit 20 may be rotated, or both may be rotated.
- the first and second holders 11 and 21 are fixed, and the first and second processing parts 10 and 20 are rotated with respect to the first and second holders 11 and 21. May be.
- At least one of the first processing unit 10 and the second processing unit 20 can be approached / separated from at least either one, and both processing surfaces 1 and 2 can be approached / separated. .
- the second processing unit 20 approaches and separates from the first processing unit 10, and the second processing unit 20 is disposed in the storage unit 41 provided in the second holder 21. It is housed in a hauntable manner.
- the first processing unit 10 may approach or separate from the second processing unit 20, and both the processing units 10 and 20 may approach or separate from each other. It may be a thing.
- the accommodating portion 41 is a concave portion that mainly accommodates a portion of the second processing portion 20 on the side opposite to the processing surface 2 side, and is a groove that has a circular shape, that is, is formed in an annular shape in plan view. .
- the accommodating portion 41 accommodates the second processing portion 20 with a sufficient clearance that allows the second processing portion 20 to rotate.
- the second processing unit 20 may be arranged so that only the parallel movement is possible in the axial direction, but by increasing the clearance, the second processing unit 20 is
- the center line of the processing part 20 may be tilted and displaced so as to break the relationship parallel to the axial direction of the storage part 41. Furthermore, the center line of the second processing part 20 and the storage part 41 may be displaced.
- the center line may be displaced so as to deviate in the radial direction. As described above, it is desirable to hold the second processing unit 20 by the floating mechanism that holds the three-dimensionally displaceably.
- the above-described fluid to be treated is subjected to both treatment surfaces from the first introduction part d1 and the second introduction part d2 in a state where pressure is applied by a fluid pressure application mechanism p configured by various pumps, potential energy, and the like. It is introduced between 1 and 2.
- the first introduction part d1 is a passage provided in the center of the annular second holder 21, and one end of the first introduction part d1 is formed on both processing surfaces from the inside of the annular processing parts 10, 20. It is introduced between 1 and 2.
- the second introduction part d2 supplies the second processing fluid to be reacted with the first processing fluid to the processing surfaces 1 and 2.
- the second introduction part d ⁇ b> 2 is a passage provided inside the second processing part 20, and one end thereof opens at the second processing surface 2.
- the first fluid to be processed that has been pressurized by the fluid pressure imparting mechanism p is introduced from the first introduction part d1 into the space inside the processing parts 10 and 20, and the first processing surface 1 and the second processing surface 2 are supplied. It passes between the processing surfaces 2 and tries to pass outside the processing portions 10 and 20. Between these processing surfaces 1 and 2, the second fluid to be treated pressurized by the fluid pressure applying mechanism p is supplied from the second introduction part d 2, merged with the first fluid to be treated, and mixed.
- the above-mentioned contact surface pressure applying mechanism applies a force that acts in a direction in which the first processing surface 1 and the second processing surface 2 approach each other to the processing portion.
- the contact pressure applying mechanism is provided in the second holder 21 and biases the second processing portion 20 toward the first processing portion 10.
- the contact surface pressure applying mechanism is a force that pushes in a direction in which the first processing surface 1 of the first processing unit 10 and the second processing surface 2 of the second processing unit 20 approach (hereinafter referred to as contact pressure). It is a mechanism for generating.
- a thin film fluid having a minute film thickness of nm to ⁇ m is generated by the balance between the contact pressure and the force for separating the processing surfaces 1 and 2 such as fluid pressure. In other words, the distance between the processing surfaces 1 and 2 is kept at a predetermined minute distance by the balance of the forces.
- the contact surface pressure applying mechanism is arranged between the accommodating portion 41 and the second processing portion 20.
- a spring 43 that biases the second processing portion 20 in a direction approaching the first processing portion 10 and a biasing fluid introduction portion 44 that introduces a biasing fluid such as air or oil.
- the contact surface pressure is applied by the spring 43 and the fluid pressure of the biasing fluid. Any one of the spring 43 and the fluid pressure of the urging fluid may be applied, and other force such as magnetic force or gravity may be used.
- the second processing unit 20 causes the first treatment by the separation force generated by the pressure or viscosity of the fluid to be treated which is pressurized by the fluid pressure imparting mechanism p against the bias of the contact surface pressure imparting mechanism.
- the first processing surface 1 and the second processing surface 2 are set with an accuracy of ⁇ m by the balance between the contact surface pressure and the separation force, and a minute amount between the processing surfaces 1 and 2 is set. An interval is set.
- the separation force includes the fluid pressure and viscosity of the fluid to be processed, the centrifugal force due to the rotation of the processing part, the negative pressure when the urging fluid introduction part 44 is negatively applied, and the spring 43 is pulled.
- the force of the spring when it is used as a spring can be mentioned.
- This contact surface pressure imparting mechanism may be provided not in the second processing unit 20 but in the first processing unit 10 or in both.
- the second processing unit 20 has the second processing surface 2 and the inside of the second processing surface 2 (that is, the first processing surface 1 and the second processing surface 2).
- a separation adjusting surface 23 is provided adjacent to the second processing surface 2 and located on the entrance side of the fluid to be processed between the processing surface 2 and the processing surface 2.
- the separation adjusting surface 23 is implemented as an inclined surface, but may be a horizontal surface.
- the pressure of the fluid to be processed acts on the separation adjusting surface 23 to generate a force in a direction in which the second processing unit 20 is separated from the first processing unit 10. Accordingly, the pressure receiving surfaces for generating the separation force are the second processing surface 2 and the separation adjusting surface 23.
- the proximity adjustment surface 24 is formed on the second processing portion 20.
- the proximity adjustment surface 24 is a surface opposite to the separation adjustment surface 23 in the axial direction (upper surface in FIG. 1), and the pressure of the fluid to be processed acts on the second processing portion 20. A force is generated in a direction that causes the first processing unit 10 to approach the first processing unit 10.
- the pressure of the fluid to be processed that acts on the second processing surface 2 and the separation adjusting surface 23, that is, the fluid pressure, is understood as a force constituting an opening force in the mechanical seal.
- the projected area A1 of the proximity adjustment surface 24 projected on a virtual plane orthogonal to the approaching / separating direction of the processing surfaces 1 and 2, that is, the protruding and protruding direction (axial direction in FIG. 1) of the second processing unit 20 The area ratio A1 / A2 of the total area A2 of the projected areas of the second processing surface 2 and the separation adjusting surface 23 of the second processing unit 20 projected onto the virtual plane is called a balance ratio K. This is important for the adjustment of the opening force.
- the opening force can be adjusted by the pressure of the fluid to be processed, that is, the fluid pressure, by changing the balance line, that is, the area A1 of the adjustment surface 24 for proximity.
- P1 represents the pressure of the fluid to be treated, that is, the fluid pressure
- K represents the balance ratio
- k represents the opening force coefficient
- Ps represents the spring and back pressure
- the proximity adjustment surface 24 may be implemented with a larger area than the separation adjustment surface 23.
- the fluid to be processed becomes a thin film fluid forced by the two processing surfaces 1 and 2 holding the minute gaps, and tends to move to the outside of the annular processing surfaces 1 and 2.
- the mixed fluid to be processed does not move linearly from the inside to the outside of the two processing surfaces 1 and 2, but instead has an annular radius.
- a combined vector of the movement vector in the direction and the movement vector in the circumferential direction acts on the fluid to be processed and moves in a substantially spiral shape from the inside to the outside.
- the rotating shaft 50 is not limited to what was arrange
- ⁇ ⁇ / ⁇ is the kinematic viscosity
- V the representative speed
- L the representative length
- ⁇ the density
- ⁇ the viscosity
- a acceleration
- m mass
- v velocity
- R represents a radius
- At least one of the first and second processing parts 10 and 20 may be cooled or heated to adjust the temperature.
- the first and second processing parts 10 and 10 are adjusted.
- 20 are provided with temperature control mechanisms (temperature control mechanisms) J1, J2.
- the temperature of the introduced fluid to be treated may be adjusted by cooling or heating. These temperatures can also be used for the deposition of the treated material, and also to generate Benard convection or Marangoni convection in the fluid to be treated between the first and second processing surfaces 1 and 2. May be set.
- a groove-like recess 13 extending from the center side of the first processing portion 10 to the outside, that is, in the radial direction is formed on the first processing surface 1 of the first processing portion 10. May be implemented.
- the planar shape of the recess 13 is curved or spirally extending on the first processing surface 1, or is not shown, but extends straight outward, L It may be bent or curved into a letter shape or the like, continuous, intermittent, or branched.
- the recess 13 can be implemented as one formed on the second processing surface 2, and can also be implemented as one formed on both the first and second processing surfaces 1, 2.
- the base end of the recess 13 reaches the inner periphery of the first processing unit 10.
- the tip of the recess 13 extends toward the outer peripheral surface of the first processing surface 1, and its depth (cross-sectional area) gradually decreases from the base end toward the tip.
- a flat surface 16 without the recess 13 is provided between the tip of the recess 13 and the outer peripheral surface of the first processing surface 1.
- the opening d20 of the second introduction part d2 is provided in the second processing surface 2, it is preferably provided at a position facing the flat surface 16 of the facing first processing surface 1.
- the opening d20 is desirably provided on the downstream side (outside in this example) from the concave portion 13 of the first processing surface 1.
- it is installed at a position facing the flat surface 16 on the outer diameter side from the point where the flow direction when introduced by the micropump effect is converted into a laminar flow direction in a spiral shape formed between the processing surfaces. It is desirable to do.
- the distance n in the radial direction from the outermost position of the recess 13 provided in the first processing surface 1 is preferably about 0.5 mm or more.
- the shape of the opening d20 may be circular as shown in FIGS. 2B and 3B, and although not shown, a concentric circle surrounding the central opening of the processing surface 2 that is a ring-shaped disk.
- An annular shape may be used.
- the annular opening may be continuous or discontinuous.
- the shape of the opening is a concentric ring shape.
- the second introduction part d2 can have directionality.
- the introduction direction from the opening d20 of the second processing surface 2 is inclined with respect to the second processing surface 2 at a predetermined elevation angle ( ⁇ 1).
- the elevation angle ( ⁇ 1) is set to be more than 0 degrees and less than 90 degrees, and in the case of a reaction with a higher reaction rate, it is preferably set at 1 to 45 degrees.
- the introduction direction from the opening d ⁇ b> 20 of the second processing surface 2 has directionality in the plane along the second processing surface 2.
- the introduction direction of the second fluid is a component in the radial direction of the processing surface that is an outward direction away from the center and a component with respect to the rotation direction of the fluid between the rotating processing surfaces. Is forward.
- a line segment in the radial direction passing through the opening d20 and extending outward is defined as a reference line g and has a predetermined angle ( ⁇ 2) from the reference line g to the rotation direction R. This angle ( ⁇ 2) is also preferably set to more than 0 degree and less than 90 degrees.
- This angle ( ⁇ 2) can be changed and implemented in accordance with various conditions such as the type of fluid, reaction speed, viscosity, and rotational speed of the processing surface.
- the second introduction part d2 may not have any directionality.
- the peripheral speed of rotation at the joining portion where at least two kinds of fluids to be treated join together is an opening d20 where the first fluid and the second fluid join as shown in FIG.
- Peripheral speed [m / s] 2 ⁇ ⁇ [m] ⁇ rotational speed [rps] ⁇ ⁇
- ⁇ is the distance from the center of rotation of the first and second processing surfaces 1 and 2 to the nearest point f
- the rotational speed is the rotational speed of the processing surface
- ⁇ is the circumference.
- the merging portion where at least two kinds of fluids to be treated merge means a position closest to the center of rotation of the first and second processing surfaces 1 and 2 in the opening d20. Further, when there are a plurality of merging portions having different distances from the rotation center of the first and second processing surfaces, the point closest to the center of the merging portion where the raw material fluid and the processing fluid merge is the closest point f. And
- the rate at which the fine particles are united can be controlled by controlling the peripheral speed of rotation at the junction.
- the first processing unit 10 of the fluid processing apparatus is rotated with respect to the second processing unit 20, and the first processing surface 1 becomes the second processing surface 2.
- the peripheral speed at the joining portion of the first processing surface 1 is controlled.
- the ratio at which the fine particles are united can be controlled.
- the particle diameter of the fine particles can be controlled by controlling the peripheral speed of rotation at the junction.
- the particle size of the obtained fine particles is also controlled by controlling the proportion of fine particles to coalesce. can do.
- the peripheral speed of rotation at the junction is preferably 0.8 to 41.9 m / s, and more preferably 1.2 to 21.0 m / s.
- the peripheral speed at the joining portion is 1 m / s or less, at least two kinds of fluids to be treated cannot be uniformly mixed and uniform treatment for obtaining fine particles cannot be promoted, so that fine particles can be obtained stably. I can't.
- the fluid to be processed is vaporized due to the temperature rise of the processing surface, thereby increasing the pressure between the processing surfaces 1 and 2.
- TEM transmission electron microscope
- SEM scanning electron microscope
- a ratio represented by the BET method Specific examples include surface area measurement, comparison between specific surface area measurement and electron microscope observation, comparison between specific surface area measurement and particle size distribution measurement.
- the ratio at which the fine particles are united with each other by electron microscope observation was evaluated. Specifically, a TEM photograph or SEM photograph at the same magnification of the produced fine particles is divided into 16 regions, and the coalescence of the produced fine particles is not confirmed in all of the divided 16 regions.
- the proportion of the fine particles united is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
- the number of fluids to be treated and the number of flow paths are two, but may be one, or may be three or more.
- the second fluid is introduced between the processing surfaces 1 and 2 from the second introduction part d2, but this introduction part may be provided in the first processing part 10 or provided in both. Good. Moreover, you may prepare several introduction parts with respect to one type of to-be-processed fluid.
- the shape, size, and number of the opening for introduction provided in each processing portion are not particularly limited, and can be appropriately changed. Further, an opening for introduction may be provided immediately before or between the first and second processing surfaces 1 and 2 or further upstream.
- the second fluid is introduced from the first introduction part d1 and the first fluid is introduced from the second introduction part d2 contrary to the above. May be introduced.
- the expressions “first” and “second” in each fluid have only an implication for identification that they are the nth of a plurality of fluids, and a third or higher fluid may exist.
- treatments such as precipitation / precipitation / emulsification or crystallization are arranged to face each other so as to be able to approach / separate as shown in FIG. 1, and at least one rotates relative to the other. It occurs with forcible uniform mixing between the processing surfaces 1 and 2.
- the particle size and monodispersity of the processed material to be processed are the rotational speed and flow velocity of the processing parts 10 and 20, the distance between the processing surfaces 1 and 2, the raw material concentration of the processed fluid, or the processed fluid. It can be controlled by appropriately adjusting the solvent species and the like.
- a raw material fluid containing at least one kind of raw material and a processing fluid containing at least one kind of material for processing the raw material are mixed to obtain fine particles of the processed raw material.
- the ratio at which the fine particles are united is controlled by controlling the peripheral speed of the rotation at the junction where the raw material fluid and the processing fluid merge.
- the raw material fluid as the first fluid is disposed facing each other so as to be able to approach and separate, and at least one of the processing surfaces 1 rotates with respect to the other.
- the first fluid film which is a thin film fluid composed of the first fluid, is formed between the processing surfaces.
- the processing fluid as the second fluid is directly introduced into the first fluid film formed between the processing surfaces 1 and 2 from the second introduction part d2 which is a separate flow path.
- the first fluid and the second fluid are disposed between the processing surfaces 1 and 2 whose distance is fixed by the pressure balance between the supply pressure of the fluid to be processed and the pressure applied between the rotating processing surfaces. Can be mixed to obtain fine particles of the processed raw material.
- the second fluid is introduced from the first introduction part d1 and the first fluid is introduced from the second introduction part d2 contrary to the above. May be introduced.
- the expressions “first” and “second” in each fluid have only an implication for identification that they are the nth of a plurality of fluids, and a third or higher fluid may exist.
- post-treatment such as heat treatment may be applied to the treated raw material fine particles.
- the third introduction part d3 can be provided in the processing apparatus.
- the first fluid it is possible to introduce the second fluid and the third fluid separately into the processing apparatus. If it does so, the density
- the combination of fluids to be processed (first fluid to third fluid) to be introduced into each introduction portion can be arbitrarily set. The same applies to the case where the fourth or more introduction portions are provided, and the fluid to be introduced into the processing apparatus can be subdivided in this way.
- the temperature of the fluid to be processed such as the first and second fluids is controlled, and the temperature difference between the first fluid and the second fluid (that is, the temperature difference between the supplied fluids to be processed) is controlled.
- the temperature of each processed fluid processing device, more specifically, the temperature immediately before being introduced between the processing surfaces 1 and 2 is measured. It is also possible to add a mechanism for heating or cooling each fluid to be processed introduced between the processing surfaces 1 and 2.
- the pH of the raw material fluid and / or processing fluid in the present invention is not particularly limited. It can be appropriately changed depending on the type and concentration of the raw material used, the material for processing the raw material, the purpose, the target fine particle type, and the like.
- various dispersants and surfactants can be used according to the purpose and necessity. Although it does not specifically limit, As a surfactant and a dispersing agent, various commercially available products generally used, products, or newly synthesized products can be used. Examples include anionic surfactants, cationic surfactants, nonionic surfactants, dispersants such as various polymers, and the like. These may be used alone or in combination of two or more. The above surfactants and dispersants may be included in the raw fluid or processing fluid, or both. Further, the above surfactant and dispersant may be contained in a third fluid different from the raw material fluid and the processing fluid.
- the above surfactants and dispersants may or may not be used.
- the temperature at which the raw material fluid and the processing fluid are mixed is not particularly limited. It can be carried out at an appropriate temperature depending on the raw material to be used and the kind and concentration of the material for processing the raw material, the target fine particle species, the pH of the raw material fluid and the processing fluid, and the like.
- the method for producing fine particles according to the present invention can be used for the production of the following fine particles.
- the present invention is not limited to the following examples, and can be used for the production of fine particles that have been made by conventional batch methods, continuous methods, or microreactors or micromixers.
- a reaction in which an acidic pigment solution prepared by dissolving at least one pigment in a strong acid such as sulfuric acid, nitric acid, and hydrochloric acid is mixed with a solution containing water to obtain pigment particles (acid pasting method).
- a pigment solution prepared by dissolving at least one pigment in an organic solvent is a poor solvent for the pigment, and is a poor solvent compatible with the organic solvent used for the preparation of the solution
- a reaction in which the pigment particles are precipitated by being put in (reprecipitation method).
- the pigment solution in which at least one kind of pigment is dissolved, and the pigment contained in the pigment solution have solubility. Reaction to obtain pigment particles by mixing with a pigment deposition solution that changes the pH of the pigment solution that is not shown or has a lower solubility in the pigment than the solvent contained in the pigment solution.
- Reaction in which metal fine particles are supported on the surface of carbon or carbon black by liquid phase reduction method (as the metal, platinum, palladium, gold, silver, rhodium, iridium, ruthenium, osmium, cobalt, manganese, nickel, iron, chromium, Examples thereof include at least one metal selected from the group consisting of molybdenum and titanium).
- Reaction of producing a crystal composed of fullerene molecules and fullerene nanowhiskers / nanofiber nanotubes by mixing a solution containing a first solvent dissolving fullerene and a second solvent having a solubility of fullerene smaller than that of the first solvent. .
- the ceramic raw materials include Al, Ba, Mg, Ca, La, Fe, Si, Ti, Zr, Pb, Sn, Zn, Cd, As, Ga, Sr, Bi, Ta, Examples include at least one selected from Se, Te, Hf, Ni, Mn, Co, S, Ge, Li, B, and Ce).
- the titanium compound includes tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraiso
- examples include at least one selected from tetraalkoxytitanium such as butoxytitanium and tetra-t-butoxytitanium or derivatives thereof, titanium tetrachloride, titanyl sulfate, titanium citrate, and titanium tetranitrate).
- compound semiconductors include II-VI group compound semiconductors, III-V group compound semiconductors, Examples include group IV compound semiconductors and group I-III-VI compound semiconductors).
- Reaction for reducing semiconductor element to produce semiconductor fine particles is an element selected from the group consisting of silicon (Si), germanium (Ge), carbon (C), and tin (Sn)) .
- Magnetic raw materials include nickel, cobalt, iridium, iron, platinum, gold, silver, manganese, chromium, palladium, yttrium, lanthanides (neodymium, samarium, gadolinium , And terbium).
- a fluid in which at least one biologically ingestible particulate raw material is dissolved in a first solvent with a solvent that can be a second solvent having a lower solubility of the biologically ingestible particulate raw material than the first solvent, Reaction to precipitate.
- a reaction in which a fluid containing at least one kind of an acidic substance or a cationic substance and a fluid containing at least one kind of a basic substance or an anionic substance are mixed and the biologically ingested fine particles are precipitated by a neutralization reaction.
- a water-soluble barium salt solution is used as a raw material fluid
- a water-soluble sulfuric acid compound solution containing sulfuric acid is used as a processing fluid, and both are mixed. Barium sulfate fine particles are precipitated by a neutralization reaction.
- a process for obtaining microemulsion particles by mixing a fluid to be treated containing a fluid to be treated comprising at least an oil-based dispersion solvent.
- at least one of the dispersed phase and the continuous phase contains one or more phospholipids
- the dispersed phase contains a pharmacologically active substance
- the continuous phase is composed of at least an aqueous dispersion solvent, and is continuous with the treated fluid of the dispersed phase. Treatment to obtain liposomes by mixing the fluid to be treated in phase.
- a process in which a fluid obtained by dissolving a resin in a solvent that is soluble and compatible with the resin is mixed with an aqueous solvent to obtain resin fine particles by precipitation or emulsification, an oil phase component such as a resin or oil, and an aqueous phase component.
- Processing to obtain an emulsion by mixing or the process which obtains resin fine particles by mixing the resin melted by heating and solvent (it is not limited about aqueous property and oiliness), and emulsifying and dispersing.
- the resin fine particle dispersion is mixed with a compound solution in which a compound such as a salt is dissolved to aggregate the resin fine particles.
- Friedel-Crafts reaction nitration reaction, addition reaction, elimination reaction, transfer reaction, polymerization reaction, condensation reaction, coupling reaction, acylation, carbonylation, aldehyde synthesis, peptide synthesis, aldol reaction, indole reaction, electrophilic substitution Reaction, nucleophilic substitution reaction, Wittig reaction, Michael addition reaction, enamine synthesis, ester synthesis, enzyme reaction, diazo coupling reaction, oxidation reaction, reduction reaction, multistage reaction, selective addition reaction, Suzuki-Miyaura coupling reaction, Kumada-Corriu reaction, metathesis reaction, isomerization reaction, radical polymerization reaction, anion polymerization reaction, cation polymerization reaction, metal catalyzed polymerization reaction, sequential reaction, polymer synthesis, acetylene coupling reaction, episulfide synthesis, episulfide synthesis, Bamberger rearrangement, Chapman rearrangement, Claisen condensation, quinoline synthesis, Paal-Kn
- a method of obtaining fine particles by precipitating dissolved matter by changing the saturation solubility according to the temperature difference of the fluid For example, when acyclovir (generic name: JAN, INN) [chemical name: 9-[(2-hydroxyethoxy) methyl] guanine], which is an antiviral agent having a purine skeleton, is precipitated, acyclovir containing acyclovir as a fine particle raw material The aqueous solution is mixed with a fluid having a temperature difference with respect to the fluid containing the fine particle raw material, and the fine particles are deposited by utilizing the change in the saturation solubility due to the temperature change of the fluid containing the fine particle raw material.
- JAN, INN chemical name: 9-[(2-hydroxyethoxy) methyl] guanine
- “from the center” means “from the first introduction part d1” of the fluid processing apparatus shown in FIG. 1, and the first fluid is introduced from the first introduction part d1.
- the second fluid to be processed refers to the second fluid to be processed introduced from the second introduction part d2 of the processing apparatus shown in FIG.
- NiNO 3 .6H 2 O nickel nitrate hexahydrate
- TEA triethanolamine
- PAA ammonium polyacrylate
- EG ethylene glycol
- a metal fluid raw material fluid
- a reducing agent fluid processing fluid
- HMH hydrazine monohydrate
- KOH potassium hydroxide
- the liquid supply temperatures of the first fluid and the second fluid are measured immediately before the introduction of the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). Temperature.
- a nickel particle micron dispersion was discharged from between the processing surfaces 1 and 2.
- the nickel fine particles in the discharged nickel fine particle dispersion were filtered, washed with pure water three times, and dried using a vacuum dryer at 25 ° C. and ⁇ 0.1 MPa.
- the particle diameter of the obtained nickel fine particles was confirmed by SEM observation.
- the pH of the first fluid was 6.99, and the pH of the second fluid was 14 or more (measured using a pH test paper).
- Table 1 shows the results obtained by changing the peripheral speed at the junction where the first fluid and the second fluid merge on the first processing surface 1 as Examples 1 to 5. Only the peripheral speed in the confluence
- 4 shows an SEM photograph of the nickel fine particles obtained in Example 2
- FIG. 5 shows an SEM photograph of the nickel fine particles obtained in Example 5.
- the “ratio of fine particles united” in Table 1 means that the SEM photographs of the nickel fine particles obtained in Examples 1 to 5 having the same magnification were divided into 16 regions, and the nickel fine particles were mixed in all regions. "0%” when no coalescence was confirmed, and "100%” when coalescence between nickel fine particles was confirmed in all the regions. The case where one was confirmed was evaluated as “19%”.
- the rate at which the nickel fine particles are united can be controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. It was confirmed. Further, from Table 1, when mixing the first fluid and the second fluid in the thin film fluid, it is possible to control the particle diameter of the nickel fine particles by controlling the peripheral speed at the merging portion of the first processing surface 1. confirmed. About the rate at which the nickel fine particles are united, as shown in Table 1, the rate at which the nickel fine particles unite with each other by controlling the peripheral speed at the junction of the first processing surface 1 is controlled to be high, It was confirmed that the rate at which the nickel fine particles coalesce can be controlled to be low by increasing the peripheral speed at the joining portion of the first processing surface 1.
- Example 3 to 5 it was confirmed that the proportion of nickel fine particles coalescing was low. Further, as shown in Table 1, the particle diameter of the nickel fine particles is controlled so as to increase the particle diameter of the nickel fine particles by slowing the peripheral speed at the joining portion of the first processing surface 1. It was confirmed that the particle diameter of the nickel fine particles can be controlled to be small by increasing the peripheral speed at the joining portion of the surface 1. As shown in FIG. 4, in the region (Examples 1 and 2) where the peripheral speed is relatively low in the joining portion of the first processing surface 1, it was confirmed that the nickel fine particles were poorly separated and united. As shown in FIG.
- Example 5 in the region where the peripheral speed at the joining portion of the first processing surface 1 is faster than that in Example 2 (Examples 3 to 5), it was confirmed that nickel fine particles were well separated. In each example, it was confirmed that the particle diameter of the obtained nickel fine particles could be controlled. From the above, by controlling the peripheral speed at the joining portion of the first processing surface 1, it is possible to control the rate at which the nickel fine particles are united with each other and to control the particle diameter of the nickel fine particles. It was confirmed that it was possible.
- a metal fluid obtained by dissolving copper chloride (CuCl 2 ) in ethylene glycol (EG), hydrazine monohydrate (HMH), and 0.5 mol / L potassium hydroxide (KOH) ethanol solution (0.5 mol / L KOH in EtOH) containing a reducing agent fluid (processing fluid) in a thin film fluid formed between the processing surfaces 1 and 2, Copper fine particles were deposited in the thin film fluid.
- the liquid supply temperatures of the first fluid and the second fluid are measured immediately before the introduction of the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). Temperature.
- a copper fine particle dispersion was discharged from between the processing surfaces 1 and 2.
- the copper fine particles in the discharged copper fine particle dispersion were filtered and washed with methanol five times, and dried using a vacuum dryer at 25 ° C. and ⁇ 0.1 MPa.
- the particle diameter of the obtained copper fine particles was confirmed by SEM observation.
- Table 2 shows results obtained by changing the peripheral speed at the joining portion of the first processing surface 1 where the first fluid and the second fluid join as Examples 6 to 10. Only the peripheral speed in the confluence
- the “ratio of fine particles united” in Table 2 means that the SEM photographs of the copper fine particles obtained in Examples 6 to 10 having the same magnification were divided into 16 regions. “0%” when no coalescence was confirmed, “100%” when coalescence between copper fine particles was confirmed in all regions, and copper fine particles coalescence in three of the 16 regions. The case where one was confirmed was evaluated as “19%”. Moreover, although several copper microparticles exist in one area
- the ratio at which the copper fine particles are united can be controlled by controlling the peripheral speed at the junction of the first processing surface 1. It was confirmed. Further, from Table 2, when mixing the first fluid and the second fluid in the thin film fluid, it is possible to control the particle size of the copper fine particles by controlling the peripheral speed at the confluence of the first processing surface 1. confirmed. About the ratio at which the copper fine particles are united, as shown in Table 2, it is controlled so that the ratio at which the copper fine particles are united is increased by slowing the peripheral speed at the junction of the first processing surface 1. It was confirmed that the rate at which the copper fine particles coalesce can be controlled to be low by increasing the peripheral speed at the confluence of the first processing surface 1.
- the particle diameter of the copper fine particles is controlled so as to increase the particle diameter of the copper fine particles by reducing the peripheral speed at the joining portion of the first processing surface 1. It was confirmed that the particle diameter of the copper fine particles can be controlled to be small by increasing the peripheral speed at the joining portion of the surface 1. Moreover, in the area
- Example 7 to 10 In the region (Examples 7 to 10) where the peripheral speed at the junction is higher than that in Example 6 (see Examples 7 to 10), as shown in Table 2, it was confirmed that the copper fine particles were well separated. It was confirmed that the particle diameter of the obtained copper fine particles could be controlled. From the above, by controlling the peripheral speed at the joining portion of the first processing surface 1, it is possible to control the ratio at which the copper fine particles are joined together and to control the particle diameter of the copper fine particles. It was confirmed that it was possible.
- a metal fluid (raw material fluid) obtained by dissolving silver nitrate in pure water and a reducing agent fluid (processing fluid) containing ascorbic acid are processed surfaces 1 and 2. Mixing in a thin film fluid formed between them, silver fine particles were precipitated in the thin film fluid.
- the first fluid and the second fluid were mixed in the thin film fluid.
- the liquid supply temperatures of the first fluid and the second fluid are measured immediately before the introduction of the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). Temperature.
- a silver fine particle dispersion was discharged between the processing surfaces 1 and 2. Silver fine particles in the discharged silver fine particle dispersion were filtered and washed with pure water three times, and dried using a vacuum dryer at 25 ° C. and ⁇ 0.1 MPa. The particle diameter of the obtained silver fine particles was confirmed by SEM observation.
- Table 3 shows the results obtained by changing the peripheral speed at the junction where the first fluid and the second fluid merge on the first processing surface 1 as Examples 11 to 15. Only the peripheral speed in the confluence
- FIG. 6 shows an SEM photograph of the silver fine particles obtained in Example 13.
- the “ratio of fine particles united” in Table 3 means that the SEM photographs of the same magnification of the silver fine particles obtained in Examples 11 to 15 were divided into 16 regions, and the silver fine particles were separated in all regions. "0%” when no coalescence was confirmed, "100%” when coalescence between silver particles was confirmed in all regions, and silver particles in three of the 16 regions. The case where one was confirmed was evaluated as “19%”.
- a plurality of silver fine particles exist in one region when at least two of the fine particles are combined, it was evaluated that the combination of the silver fine particles was confirmed.
- the rate at which the silver fine particles are united can be controlled by controlling the peripheral speed at the merging portion of the first processing surface 1. It was confirmed. Further, from Table 3, when mixing the first fluid and the second fluid in the thin film fluid, it is possible to control the particle diameter of the silver fine particles by controlling the peripheral speed at the joining portion of the first processing surface 1. confirmed. About the rate at which the silver fine particles are united, as shown in Table 3, it is controlled so that the rate at which the silver fine particles unite with each other is reduced by slowing the peripheral speed at the junction of the first processing surface 1. It was confirmed that the rate at which the silver fine particles coalesce with each other can be increased by increasing the peripheral speed at the joining portion of the first processing surface 1.
- Example 11 it was confirmed that the proportion of silver fine particles coalescing was low. Moreover, about the particle diameter of silver fine particles, it was confirmed that the particle diameter of the silver fine particles obtained changes by changing the peripheral speed in the confluence
- a second fluid a raw material fluid (acrylic monomer containing a polymerization initiator) at 40.4 ° C. is introduced between the processing surfaces 1 and 2 at an introduction rate of 1 ⁇ ml / min, and the first fluid and the second fluid Were mixed in a thin film fluid.
- the liquid supply temperatures of the first fluid and the second fluid are measured immediately before the introduction of the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). Temperature.
- the acrylic monomer fine particle dispersion was discharged from between the processing surfaces 1 and 2.
- the acrylic monomer fine particles in the discharged acrylic monomer fine particle dispersion were heat-treated, and the particle diameter of the acrylic polymer fine particles after the heat treatment was confirmed by SEM observation.
- Table 4 shows the results obtained by changing the peripheral speed at the junction where the first fluid and the second fluid merge on the first processing surface 1 as Examples 16 to 20. Only the peripheral speed in the confluence
- 7 shows an SEM photograph of the acrylic polymer fine particles obtained in Example 16
- FIG. 8 shows an SEM photograph of the acrylic polymer fine particles obtained in Example 20.
- the “ratio of fine particles united” in Table 4 means that SEM photographs of the same magnification of the acrylic polymer fine particles obtained in Examples 16 to 20 were divided into 16 regions, and the acrylic polymer in all regions.
- the ratio at which the acrylic polymer fine particles are united is controlled by controlling the peripheral speed at the merging portion of the first processing surface 1. I confirmed that I can do it. Further, from Table 4, when mixing the first fluid and the second fluid in the thin film fluid, the particle diameter of the acrylic polymer fine particles can be controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. It was confirmed. As shown in Table 4, the ratio at which the acrylic polymer fine particles coalesce is controlled so as to increase the proportion at which the acrylic polymer fine particles coalesce by slowing the peripheral speed at the joining portion of the first processing surface 1.
- the rate at which the acrylic polymer fine particles coalesce can be controlled to be low by increasing the peripheral speed at the joining portion of the first processing surface 1.
- the proportion of acrylic polymer fine particles coalescing was low.
- the particle diameter of the acrylic polymer fine particles is controlled so as to increase the particle diameter of the acrylic polymer fine particles by slowing the peripheral speed at the joining portion of the first processing surface 1. It was confirmed that the particle diameter of the acrylic polymer fine particles can be controlled to be small by increasing the peripheral speed at the merging portion of the processing surface 1.
- the ratio at which the acrylic polymer fine particles are united with each other can be controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. From the above, even in the acrylic polymer fine particles obtained by heat-treating the acrylic monomer fine particles in the acrylic monomer fine particle dispersion discharged from between the processing surfaces 1 and 2, the joining portion of the first processing surface 1 It was confirmed that the ratio of the acrylic polymer fine particles to be united with each other can be controlled by controlling the peripheral speed of the resin, and the particle diameter of the acrylic polymer fine particles can be controlled.
- amorphous silica fine particles Preparation of amorphous silica fine particles
- a fluid raw material fluid
- a processing fluid containing BYK-110 manufactured by BYK Chemie
- BYK-110 manufactured by BYK Chemie
- a processing fluid of 20.0 ° C. 0.5 wt% BYK-110 methanol solution (0.5 wt% BYK-110 in MeOH) was used as the second fluid at the introduction speed of 20 ml / min.
- the first fluid and the second fluid were mixed in the thin film fluid.
- the liquid supply temperatures of the first fluid and the second fluid are measured immediately before the introduction of the processing apparatus (more specifically, immediately before being introduced between the processing surfaces 1 and 2). Temperature.
- An amorphous silica fine particle dispersion was discharged from between the processing surfaces 1 and 2. The particle diameter of the amorphous silica fine particles in the discharged amorphous silica fine particle dispersion was confirmed by TEM observation.
- Table 5 shows the results obtained by changing the peripheral speed at the junction where the first fluid and the second fluid merge on the first processing surface 1 as Examples 21 to 25. Only the peripheral speed in the confluence
- 9 shows a TEM photograph of the amorphous silica fine particles obtained in Example 23
- FIG. 10 shows a TEM photograph of the amorphous silica fine particles obtained in Example 24.
- the “ratio of fine particles united” in Table 4 means that the TEM photographs of the amorphous silica fine particles obtained in Examples 21 to 25 were divided into 16 regions, and the amorphous silica fine particles in all regions “0%” when no coalescence was confirmed, “100%” when coalescence of amorphous silica fine particles was confirmed in all regions, and between amorphous silica fine particles in three of the 16 regions. The case where unity was confirmed was evaluated as “19%”. In addition, although a plurality of amorphous fine particles exist in one region, when at least two of the fine particles are combined, it was evaluated that the combination of the amorphous silica fine particles was confirmed.
- the ratio at which the amorphous silica fine particles coalesce is controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. I confirmed that I can do it. Further, from Table 5, when mixing the first fluid and the second fluid in the thin film fluid, the particle diameter of the amorphous silica fine particles can be controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. It was confirmed. As shown in Table 5, the ratio at which the amorphous silica fine particles coalesce is controlled so as to increase the proportion at which the amorphous silica fine particles coalesce by slowing the peripheral speed at the merging portion of the first processing surface 1.
- the rate at which the amorphous silica fine particles coalesce can be controlled to be low by increasing the peripheral speed at the joining portion of the first processing surface 1.
- the proportion of the amorphous silica fine particles coalesced was low.
- the particle diameter of the amorphous silica fine particles is controlled so as to increase the particle diameter of the amorphous silica fine particles by decreasing the peripheral speed at the joining portion of the first processing surface 1. It was confirmed that the particle diameter of the amorphous silica fine particles can be controlled to be small by increasing the peripheral speed at the merging portion of the processing surface 1.
- the ratio at which the amorphous silica fine particles coalesce can be controlled by controlling the peripheral speed at the joining portion of the first processing surface 1. From the above, by controlling the peripheral speed at the merging portion of the first processing surface 1, it is possible to control the proportion of the amorphous silica fine particles that are joined together and to control the particle diameter of the amorphous silica fine particles. It was confirmed that it was possible.
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Abstract
Description
一方、微粒子同士の凝集や合一を制御することによって、得られる微粒子の粒子径を制御することができる。例えば、特許文献1には、電子写真用トナーの製造方法において、アクリル酸系ポリマー塩を分散剤として径内に添加することにより、結着樹脂を含む一次粒子の凝集状態を制御することができ、合一粒子の粒子径及び粒度分布を容易に制御することができることが記載されている。
本願において、微粒子同士の合一とは、例えば、微粒子の形状を球体とした場合に、複数の球体が結び付いてそれぞれの球体の形状の一部をとどめており、見かけ上、複数の微粒子同士が合体していると判断されるものをいい、その合一が、微粒子の成長過程で生じたものか、成長後に生じたものかは問わない。
また、上記の微粒子の粒子径の測定は、合一した微粒子も一つの微粒子として、その径の測定を行なった。
また、本発明は、上記の処理が、析出、乳化、分散、反応、凝集から選択された少なくとも何れか1種であるものとして実施することができる。
本発明における原料流体は、原料である原料物質を少なくとも1種類含むものであり、原料物質を後述する溶媒に混合または溶解(以下、混合または溶解を単に、溶解と記載する。)することが望ましい。
本発明における原料物質は特に限定されないが、有機物や無機物、有機無機の複合物などが挙げられ、例えば、金属元素や非金属元素の単体、またそれらの化合物などが挙げられる。化合物としては、塩、酸化物、水酸化物、水酸化酸化物、窒化物、炭化物、錯体、有機化合物や、それらの水和物や有機溶媒和物などが挙げられる。これらは単一の原料物質であっても良く、2種類以上が混合された混合物であっても良い。
なお、出発原料として用いられる原料物質と、後述する処理流体との混合によって得られる処理された原料物質とは、処理の前後において、両者が同じ物質であってもよいし、別の物質であってもよい。例えば、金属を例にとると、出発原料として用いられる原料物質が金属化合物であって、処理された原料物質が上記金属化合物を構成する金属単体であってもよい。また、出発原料として用いられる原料物質が複数種の金属化合物の混合物であって、処理された原料物質が、出発原料として用いられる原料物質である複数種の金属化合物と、処理流体に含まれる原料物質を処理するための物質とが反応した反応生成物であってもよい。さらに、出発原料として用いられる原料物質が金属単体であって、処理された原料物質も同じく金属単体であってもよい。
本発明における処理流体は、原料物質を処理するための物質を少なくとも1種類含むものである。そして、上記の処理とは、特に限定されないが、析出、乳化、分散、反応、凝集等が挙げられる。処理流体としては、後述するような溶媒を単独で用いても良く、上記の原料物質を処理するための物質として、下記の物質を上記溶媒中に含むものであっても良い。上記の物質としては特に限定されないが、例えば、塩酸や硫酸、硝酸や王水、トリクロロ酢酸やトリフルオロ酢酸、リン酸やクエン酸、アスコルビン酸などの無機または有機の酸のような酸性物質や、水酸化ナトリウムや水酸化カリウムなどの水酸化アルカリや、トリエチルアミンやジメチルアミノエタノールなどのアミン類などの塩基性物質、上記の酸性物質や塩基性物質の塩などが挙げられる。また、原料物質を還元することができる還元剤、例えば、金属及び/または金属化合物、好ましくは金属イオンを還元することができる還元剤も挙げられる。上記還元剤は特に限定されないが、ヒドラジンまたはヒドラジン一水和物、ホルムアルデヒド、スルホキシル酸ナトリウム、水素化ホウ素金属塩、水素化アルミニウム金属塩、水素化トリエチルホウ素金属塩、グルコース、クエン酸、アスコルビン酸、タンニン酸、ジメチルホルムアミド、ピロガロール、テトラブチルアンモニウムボロヒドリド、次亜リン酸ナトリウム(NaH2PO2・H2O)、ロンガリットC(NaHSO2・CH2O・2H2O)、金属の化合物またはそれらのイオン、好ましくは遷移金属の化合物またはそれらのイオン(鉄、チタンなど)などが挙げられる。上記に挙げた還元剤には、それらの水和物や有機溶媒和物、または無水物などを含まれる。これらの原料物質を処理するための物質は、それぞれ単独で使用しても良く、2種類以上が混合された混合物として使用しても良い。なお、処理流体として上記溶媒を単独で用いる場合には、上記溶媒が、原料物質を処理するための物質となる。
本発明における原料流体や処理流体に用いる溶媒としては特に限定されないが、イオン交換水やRO水、純水や超純水などの水や、メタノールやエタノールのようなアルコール系有機溶媒や、エチレングリコールやプロピレングリコール、トリメチレングリコールやテトラエチレングリコール、またはポリエチレングリコールやグリセリンなどのポリオール(多価アルコール)系有機溶媒、アセトンやメチルエチルケトンのようなケトン系有機溶媒、酢酸エチルや酢酸ブチルのようなエステル系有機溶媒、ジメチルエーテルやジブチルエーテルなどのエーテル系有機溶媒、ベンゼンやトルエン、キシレンなどの芳香族系有機溶媒、ヘキサンや、ペンタンなどの脂肪族炭化水素系有機溶媒などが挙げられる。また上記アルコール系有機溶媒やポリオール系有機溶媒を溶媒として用いた場合には、溶媒そのものが還元剤としても働く利点がある。上記溶媒はそれぞれ単独で使用しても良く、複数以上を混合して使用しても良い。特に、処理流体に関しては、上述の通り、上記溶媒を単独で処理流体として用いることも可能である。言い換えると、上記溶媒は単独であっても原料物質を処理するための物質となりうる。
本発明における金属流体は、原料物質として少なくとも1種類の金属及び/または金属化合物を上記の溶媒に溶解したものであり、上記の原料流体となる。
本発明における金属は、特に限定されない。好ましくは化学周期表上における全ての金属である。金属元素としては、例えば、Ti、Fe、W、Pt、Au、Cu、Ag、Pb、Ni、Mn、Co、Ru、V、Zn、Zr、Sn、Ta、Nb、Hf、Cr、Mo、Re、In、Ir、Os、Y、Tc、Pd、Rh、Sc、Ga、Al、Bi、Na、Mg、Ca、Ba、La、Ce、Nd、Ho、Euなどの金属元素が挙げられる。また、本発明においては、それらの金属元素に加えて、B、Si、Ge、As、Sb、C、N、O、S、Te、Se、F、Cl、Br、I、Atの非金属元素を金属元素として挙げることができる。これらの金属について、単一の元素であっても良く、複数の金属元素からなる合金や金属元素に非金属元素を含む物質であっても良い。当然、卑金属と貴金属の合金としても実施できる。
また、上記の金属(上記に列挙した非金属元素をも含む)の単体に加えて、それら金属の化合物である金属化合物を上記の溶媒に溶解したものを金属流体として用いることができる。本発明における金属化合物としては特に限定されないが、例えば、金属の塩、酸化物、水酸化物、水酸化酸化物、窒化物、炭化物、錯体、有機塩、有機錯体、有機化合物、またはそれら金属化合物の水和物や有機溶媒和物などが挙げられる。金属塩としては、特に限定されないが、金属の硝酸塩や亜硝酸塩、硫酸塩や亜硫酸塩、蟻酸塩や酢酸塩、リン酸塩や亜リン酸塩、次亜リン酸塩や塩化物、オキシ塩やアセチルアセトナート塩、またはそれら金属塩の水和物や有機溶媒和物などや、有機化合物としては金属のアルコキシドなどが挙げられる。これらの金属化合物は単独で使用しても良く、2種類以上が混合された混合物として使用しても良い。
本発明に用いる還元剤流体は、上記に挙げた還元剤を少なくとも1種類含むものであり、上記の処理流体となる。これらの還元剤は、それぞれ単独で使用しても良く、2種類以上が混合された混合物として使用しても良い。また、上記の還元剤を上記の溶媒と混合または溶解したものを還元剤流体として用いることが望ましい。
本発明においては、原料流体と処理流体との混合を、接近・離反可能に互いに対向して配設され、少なくとも一方が他方に対して回転する処理用面の間にできる、薄膜流体中で均一に攪拌・混合する方法を用いて行うことが好ましく、例えば、本願出願人による、特許文献2,3に示される装置と同様の原理の装置を用いて混合する事によって、処理された原料物質の微粒子を得ることが好ましい。
この鏡面研磨の面粗度は、特に限定されないが、好ましくはRa0.01~1.0μm、より好ましくはRa0.03~0.3μmとする。
このように、3次元的に変位可能に保持するフローティング機構によって、第2処理用部20を保持することが望ましい。
P=P1×(K-k)+Ps
なお、図示は省略するが、近接用調整面24を離反用調整面23よりも広い面積を持ったものとして実施することも可能である。
レイノルズ数Re=慣性力/粘性力=ρVL/μ=VL/ν
ここで、ν=μ/ρは動粘度、Vは代表速度、Lは代表長さ、ρは密度、μは粘度を示す。
そして、流体の流れは、臨界レイノルズ数を境界とし、臨界レイノルズ数以下では層流、臨界レイノルズ数以上では乱流となる。
上記流体処理装置の両処理用面1,2間は微小間隔に調整されるため、両処理用面1,2間に保有される流体の量は極めて少ない。そのため、代表長さLが非常に小さくなり、両処理用面1,2間を通過する薄膜流体の遠心力は小さく、薄膜流体中は粘性力の影響が大きくなる。従って、上記のレイノルズ数は小さくなり、薄膜流体は層流となる。
遠心力は、回転運動における慣性力の一種であり、中心から外側に向かう力である。遠心力は、以下の式で表される。
遠心力F=ma=mv2/R
ここで、aは加速度、mは質量、vは速度、Rは半径を示す。
上述の通り、両処理用面1,2間に保有される流体の量は少ないため、流体の質量に対する速度の割合が非常に大きくなり、その質量は無視できるようになる。従って、両処理用面1,2間にできる薄膜流体中においては重力の影響を無視できる。そのため、本来微粒子として得ることが難しい比重差のある2種以上の金属元素を含む合金や複合金属化合物などの微粒子においても、両処理用面1,2間にできる薄膜流体中で得ることができる。
この凹部13の先端と第1処理用面1の外周面との間には、凹部13のない平坦面16が設けられている。
円環形状の開口部d20を処理用面2の中央の開口を取り巻く同心円状に設けると、第2流体を処理用面1,2間に導入する際に円周方向において同一条件で実施することができるため、微粒子を量産したい場合には、開口部の形状を同心円状の円環形状とすることが好ましい。
周速度[m/s]=2×β[m]×回転数[rps]×π
ここで、βは第1、第2の処理用面1,2の回転の中心から最近点fまでの距離、回転数は処理用面の回転数、πは円周率を示す。
つまり、少なくとも2種類の被処理流動体が合流する合流部とは、開口部d20において、上記第1、第2処理用面1,2の回転の中心に最も近い位置を意味する。
また、第1、第2処理用面の回転の中心からの距離が異なる合流部が複数ある場合には、原料流体と処理流体とが合流する、合流部の最も中心に近い点を最近点fとする。
本発明においては、合流部における回転の周速度を制御することによって、微粒子同士が合一する割合を制御することができる。
上述の通り、本実施形態においては、上記流体処理装置の第1処理用部10は第2処理用部20に対して回転しており、第1処理用面1が第2処理用面2に対して回転するため、第1処理用面1の、合流部における周速度を制御することになるが、第1処理用面1と第2処理用面2とがともに回転している場合には、合流部におけるそれらの相対的な周速度を制御することによって、微粒子同士が合一する割合を制御することができる。
また、合流部における回転の周速度を制御することによって、微粒子の粒子径を制御することができる。一般的に、微粒子同士が合一すると粒度分布が広い粗大粒子が発生すると言われるが、本発明においては、微粒子同士が合一する割合を制御することによっても、得られる微粒子の粒子径を制御することができる。
本発明においては、合流部における回転の周速度が、0.8~41.9m/sであることが好ましく、1.2~21.0m/sであることがより好ましい。合流部における周速度が1m/s以下では、少なくとも2種類の被処理流動体を均一に混合し、微粒子を得るための均一な処理を促進することができないため、微粒子を安定して得ることが出来ない。また、合流部における回転の周速度が42m/s以上では、処理用面の温度上昇により被処理流動体が気化し、それによって処理用面1,2間の圧力上昇が見られるため、少なくとも2種類の被処理流動体を安定的に送液できなくなる現象が起こる場合がある。上記の理由より、特定の範囲外では微粒子の製造連続して行うすることが難しくなる。
具体的には、作製された微粒子の同倍率のTEM写真又はSEM写真を16領域に分割し、分割された16の領域のうちの全ての領域において作製された微粒子同士の合一が確認されなかった場合を「0%」、全ての領域において作製された微粒子同士の合一が確認された場合を「100%」、16の領域のうち3つの領域において微粒子同士の合一が確認された場合を「19%」として評価した。また、1つの領域には複数の微粒子が存在するが、そのうちの少なくとも2つの微粒子同士が合一した場合に、微粒子同士の合一が確認されたものと評価した。
本発明においては、上記微粒子同士が合一する割合は50%以下であることが好ましく、より好ましくは40%以下、さらに好ましくは30%以下である。
さらに、第1、第2流体等の被処理流動体の温度を制御したり、第1流体と第2流体等との温度差(即ち、供給する各被処理流動体の温度差)を制御することもできる。供給する各被処理流動体の温度や温度差を制御するために、各被処理流動体の温度(処理装置、より詳しくは、処理用面1,2間に導入される直前の温度)を測定し、処理用面1,2間に導入される各被処理流動体の加熱又は冷却を行う機構を付加して実施することも可能である。
本発明における原料流体及び/または処理流体のpHは特に限定されない。用いる原料物質や原料物質を処理するための物質の種類や濃度、目的や対象となる微粒子種などによって、適宜変更する事が可能である。
また、本発明においては、目的や必要に応じて各種分散剤や界面活性剤を用いる事ができる。特に限定されないが、界面活性剤及び分散剤としては一般的に用いられる様々な市販品や、製品または新規に合成したものなどを使用できる。一例として、陰イオン性界面活性剤、陽イオン性界面活性剤、非イオン性界面活性剤や、各種ポリマーなどの分散剤などを挙げることができる。これらは単独で使用してもよく、2種類以上を併用してもよい。
上記の界面活性剤及び分散剤は、原料流体もしくは処理流体、またはその両方に含まれていてもよい。また、上記の界面活性剤及び分散剤は、原料流体とも処理流体とも異なる第3の流体に含まれていてもよい。
本発明においては、上記の界面活性剤及び分散剤を用いてもよく、また、用いなくてもよい。本発明においては、原料流体と処理流体とが合流する、合流部における前記回転の周速度を制御と、上記の界面活性剤及び分散剤の使用とを併用してもよい。
本発明において、原料流体と処理流体とを混合する際の温度は特に限定されない。用いる原料物質や原料物質を処理するための物質の種類や濃度、対象となる微粒子種、原料流体や処理流体のpHなどによって適切な温度で実施することが可能である。
または、少なくとも1種類の顔料を有機溶媒に溶解し調整された顔料溶液を、前記顔料に対しては貧溶媒であり、かつ前記溶液の調整に使用された有機溶媒には相溶性である貧溶媒中に投入して顔料粒子を沈殿させる反応(再沈法)。
または、酸性またはアルカリ性であるpH調整溶液或いは前記pH調整溶液と有機溶媒との混合溶液のいずれかに、少なくとも1種類の顔料を溶解した顔料溶液と、前記顔料溶液に含まれる顔料に溶解性を示さない、若しくは、前記顔料溶液に含まれる溶媒よりも前記顔料に対する溶解性が小さい、前記顔料溶液のpHを変化させる顔料析出用溶液とを混合して顔料粒子を得る反応。
または、酸性物質もしくは陽イオン性物質を少なくとも1種類含む流体と、塩基性物質もしくは陰イオン性物質を少なくとも1種類含む流体とを混合し、中和反応により生体摂取物微粒子を析出させる反応。例えば、本発明において、造影剤として生体内に摂取される硫酸バリウム微粒子を析出させる場合、水溶性バリウム塩溶液を原料流体とし、硫酸を含む水溶性硫酸化合物溶液を処理流体として両者を混合し、中和反応により硫酸バリウム微粒子を析出させる。
または、分散相もしくは連続相の少なくともどちらか一方に一種類以上のリン脂質を含み、分散相は薬理活性物質を含み、連続相は少なくとも水系分散溶媒よりなり、分散相の被処理流動体と連続相の被処理流動体とを混合することによりリポソームを得る処理。
または、加温して溶融させた樹脂と溶媒(水性及び油性については限定されない)とを混合し、乳化・分散により樹脂微粒子を得る処理。または樹脂微粒子分散液と塩などの化合物を溶解した化合物溶液とを混合して樹脂微粒子を凝集させる処理。
走査型電子顕微鏡(SEM)観察には、電界放射型走査電子顕微鏡(FE-SEM):日本電子製のJSM-7500Fを使用した。観察条件としては、観察倍率を5千倍以上とし、粒子径については、10箇所の平均値を採用した。以下、SEM観察にて確認された微粒子の径を、粒子径とする。
(透過電子顕微鏡)
透過電子顕微鏡(TEM)観察には、エネルギー分散型X線分析装置、透過型電子顕微鏡、JEM-2100(JEOL製)を用いた。観察条件としては、観察倍率を1万倍以上とし、粒子径については、10箇所の平均値を採用した。以下、TEM観察にて確認された微粒子の径についても、粒子径とする。
ニッケル微粒子同士が合一する割合については、表1に示すように、第1処理用面1の合流部における周速度を遅くすることでニッケル微粒子同士が合一する割合が高くなるよう制御し、第1処理用面1の合流部における周速度を速くすることでニッケル微粒子同士が合一する割合が低くなるよう制御できることを確認した。特に、実施例3~5においては、ニッケル微粒子同士が合一する割合が低いことが確認された。
また、ニッケル微粒子の粒子径については、表1に示すように、第1処理用面1の合流部における周速度を遅くすることでニッケル微粒子の粒子径を大きくなるよう制御し、第1処理用面1の合流部における周速度を速くすることでニッケル微粒子の粒子径を小さくなるよう制御できることを確認した。図4に示すように、第1処理用面1の合流部における周速度が比較的遅い領域(実施例1及び2)においては、ニッケル微粒子の分離が悪く合一している様子が確認され、図5に示すように、第1処理用面1の合流部における周速度が実施例2よりも速い領域(実施例3~5)においては、ニッケル微粒子の分離が良い状態が確認されたが、それぞれの実施例において、得られたニッケル微粒子の粒子径を制御できていることを確認した。
以上のことから、第1処理用面1の合流部における周速度を制御することによって、ニッケル微粒子同士が合一する割合を制御することができ、かつ、ニッケル微粒子の粒子径を制御することができることが確認された。
銅微粒子同士が合一する割合については、表2に示すように、第1処理用面1の合流部における周速度を遅くすることで銅微粒子同士が合一する割合が高くなるよう制御し、第1処理用面1の合流部における周速度を速くすることで銅微粒子同士が合一する割合が低くなるよう制御できることを確認した。特に、実施例7~10においては、銅微粒子同士が合一する割合が低いことが確認された。
また、銅微粒子の粒子径については、表2に示すように、第1処理用面1の合流部における周速度を遅くすることで銅微粒子の粒子径を大きくなるよう制御し、第1処理用面1の合流部における周速度を速くすることで銅微粒子の粒子径を小さくなるよう制御できることを確認した。また、第1処理用面1の合流部における周速度が比較的遅い領域(実施例6)においては、銅微粒子の分離が悪く合一している様子が確認され、第1処理用面1の合流部における周速度が実施例6よりも速い領域(実施例7~10)においては、表2に示すように、銅微粒子の分離が良い状態が確認されたが、それぞれの実施例において、得られた銅微粒子の粒子径を制御できていることを確認した。
以上のことから、第1処理用面1の合流部における周速度を制御することによって、銅微粒子同士が合一する割合を制御することができ、かつ、銅微粒子の粒子径を制御することができることが確認された。
銀微粒子同士が合一する割合については、表3に示すように、第1処理用面1の合流部における周速度を遅くすることで銀微粒子同士が合一する割合が低くなるよう制御し、第1処理用面1の合流部における周速度を速くすることで銀微粒子同士が合一する割合が高くなるよう制御できることを確認した。特に、実施例11~13においては、銀微粒子同士が合一する割合が低いことが確認された。
また、銀微粒子の粒子径については、第1処理用面1の合流部における周速度を変化させることによって、得られる銀微粒子の粒子径が変化することが確認された。また、第1処理用面1の合流部における周速度が速い領域(実施例15)においては、銀微粒子の分離が悪く合一している様子が確認され、また、表3に示すように、第1処理用面1の合流部における周速度が遅い領域(実施例11)においては、銀微粒子の分離が良い状態が確認されたが、それぞれの実施例において、得られた銀微粒子の粒子径を制御できていることを確認した。
以上のことから、第1処理用面1の合流部における周速度を制御することによって、銀微粒子同士が合一する割合を制御することができ、かつ、銀微粒子の粒子径を制御することができることが確認された。
次に、図1に示される流体処理装置を用いて、重合開始剤を含むアクリルモノマー(原料流体)と、高分子分散剤としてポリビニルアルコール(PVA)を含む処理流体とを、処理用面1,2間に形成される薄膜流体中で混合し、薄膜流体中で両者を乳化させてアクリルモノマーのエマルションの微粒子を得た。以下、アクリルモノマーのエマルションの微粒子をアクリルモノマー微粒子とする。
アクリルポリマー微粒子同士が合一する割合については、表4に示すように、第1処理用面1の合流部における周速度を遅くすることでアクリルポリマー微粒子同士が合一する割合が高くなるよう制御し、第1処理用面1の合流部における周速度を速くすることでアクリルポリマー微粒子同士が合一する割合が低くなるよう制御できることを確認した。特に、実施例18~20においては、アクリルポリマー微粒子同士が合一する割合が低いことが確認された。
また、アクリルポリマー微粒子の粒子径については、表4に示すように、第1処理用面1の合流部における周速度を遅くすることでアクリルポリマー微粒子の粒子径を大きくなるよう制御し、第1処理用面1の合流部における周速度を速くすることでアクリルポリマー微粒子の粒子径を小さくなるよう制御できることを確認した。また、第1処理用面1の合流部における周速度が比較的遅い領域(実施例16、17)においては、アクリルポリマー微粒子の分離が悪く合一している様子が確認され、第1処理用面1の合流部における周速度が実施例17よりも速い領域(実施例18~20)においては、表4に示すように、アクリルポリマー微粒子の分離が良い状態が確認されたが、それぞれの実施例において、得られたアクリルポリマー微粒子の粒子径を制御できていることを確認した。
さらに、表4から、分散剤を用いた実施例においても、第1処理用面1の合流部における周速度を制御することによって、アクリルポリマー微粒子同士が合一する割合を制御できることを確認した。
以上のことから、処理用面1,2間より吐出させたアクリルモノマー微粒子分散液中のアクリルモノマー微粒子を熱処理して重合させたアクリルポリマー微粒子にあっても、第1処理用面1の合流部における周速度を制御することによって、アクリルポリマー微粒子同士が合一する割合を制御することができ、かつ、アクリルポリマー微粒子の粒子径を制御することができることが確認された。
次に、図1に示される流体処理装置を用いて、ケイ酸ナトリウム(Na2SiO3)を含む流体(原料流体)と、分散剤としてBYK-110(ビックケミー製)を含む処理流体とを、処理用面1,2間に形成される薄膜流体中で混合し、薄膜流体中でアモルファスのシリカ(以下、アモルファスシリカとする。)の微粒子を析出させた。
アモルファスシリカ微粒子同士が合一する割合については、表5に示すように、第1処理用面1の合流部における周速度を遅くすることでアモルファスシリカ微粒子同士が合一する割合が高くなるよう制御し、第1処理用面1の合流部における周速度を速くすることでアモルファスシリカ微粒子同士が合一する割合が低くなるよう制御できることを確認した。特に、実施例23~25においては、アモルファスシリカ微粒子同士が合一する割合が低いことが確認された。
また、アモルファスシリカ微粒子の粒子径については、表5に示すように、第1処理用面1の合流部における周速度を遅くすることでアモルファスシリカ微粒子の粒子径を大きくなるよう制御し、第1処理用面1の合流部における周速度を速くすることでアモルファスシリカ微粒子の粒子径を小さくなるよう制御できることを確認した。また、第1処理用面1の合流部における周速度が比較的遅い領域(実施例21、22)においては、アモルファスシリカ微粒子の分離が悪く合一している様子が確認され、第1処理用面1の合流部における周速度が実施例22よりも速い領域(実施例23~25)においては、表5に示すように、アモルファスシリカ微粒子の分離が良い状態が確認されたが、それぞれの実施例において、得られたアモルファスシリカ微粒子の粒子径を制御できていることを確認した。
さらに、表5から、分散剤を用いた実施例においても、第1処理用面1の合流部における周速度を制御することによって、アモルファスシリカ微粒子同士が合一する割合を制御できることを確認した。
以上のことから、第1処理用面1の合流部における周速度を制御することによって、アモルファスシリカ微粒子同士が合一する割合を制御することができ、かつ、アモルファスシリカ微粒子の粒子径を制御することができることが確認された。
2 第2処理用面
10 第1処理用部
11 第1ホルダ
20 第2処理用部
21 第2ホルダ
d1 第1導入部
d2 第2導入部
d20 開口部
Claims (4)
- 少なくとも2種類の被処理流動体を用いるものであり、
そのうちで少なくとも1種類の被処理流動体は、原料物質を少なくとも1種類含む原料流体であり、
上記以外の被処理流動体で少なくとも1種類の被処理流動体は、上記原料物質を処理するための物質を少なくとも1種類含む処理流体であり、
上記の被処理流動体を、対向して配設された、接近・離反可能な、少なくとも一方が他方に対して相対的に回転を行う少なくとも2つの処理用面間にできる薄膜流体中で混合し、処理された原料物質の微粒子を得る微粒子の製造方法において、
上記原料流体と上記処理流体とが合流する、合流部における前記回転の周速度を制御することによって、上記微粒子同士が合一する割合を制御することを特徴とする微粒子の製造方法。 - 上記原料流体と上記処理流体とのうちの何れか一方の被処理流動体が上記薄膜流体を形成しながら上記両処理用面間を通過し、
上記何れか一方の被処理流動体が流される流路とは独立した別途の導入路を備えており、
上記少なくとも2つの処理用面の少なくとも何れか一方に上記別途の導入路に通じる開口部を少なくとも一つ備え、
上記原料流体と上記処理流体とのうちの何れか他方の被処理流動体を、上記開口部から上記少なくとも2つの処理用面の間に導入して、上記原料流体と上記処理流体とを、上記薄膜流体中で混合することを特徴とする請求項1に記載の微粒子の製造方法。 - 上記原料流体と上記処理流体とが合流する、合流部における前記回転の周速度を0.8~41.9m/sの範囲に制御することを特徴とする請求項1又は2に記載の微粒子の製造方法。
- 上記原料流体と上記処理流体とが合流する、合流部における前記回転の周速度を制御することによって、上記微粒子同士が合一する割合を50%以下とすることを特徴とする請求項1~3の何れかに記載の微粒子の製造方法。
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WO2019088266A1 (ja) * | 2017-11-06 | 2019-05-09 | コニカミノルタ株式会社 | 凝集ナノ粒子および蛍光標識材 |
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CN111495291A (zh) * | 2020-06-11 | 2020-08-07 | 方杰 | 用于纳米材料合成和修饰一体化的连续生产设备及其方法 |
CN112829120B (zh) * | 2021-01-05 | 2022-10-21 | 湖北欣福伟环保科技有限公司 | 一种塑料垃圾袋的清理回收机构 |
CN115321616B (zh) * | 2022-09-23 | 2024-03-29 | 西安稀有金属材料研究院有限公司 | 一种低成本、粒度可控的高比表面积纳米氧化钌制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006184306A (ja) | 2004-12-24 | 2006-07-13 | Kao Corp | 電子写真用トナーの製造方法 |
JP2006341232A (ja) * | 2005-06-10 | 2006-12-21 | Canon Inc | 流体処理装置および流体処理方法 |
WO2009008393A1 (ja) | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | 強制超薄膜回転式処理法を用いたナノ粒子の製造方法 |
WO2009008390A1 (ja) | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | 金属微粒子の製造方法及びその金属微粒子を含む金属コロイド溶液 |
JP2009131831A (ja) * | 2007-11-09 | 2009-06-18 | M Technique Co Ltd | 微粒子の製造方法及びその微粒子 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4842521B2 (ja) | 2004-06-04 | 2011-12-21 | 日東電工株式会社 | ビニル系重合体の多孔質球状粒子の製造方法 |
CA2507897A1 (en) * | 2004-06-07 | 2005-12-07 | Dover Chemical Corporation | High shear process for making metallic esters |
JP2006069880A (ja) * | 2004-09-06 | 2006-03-16 | Fuji Photo Film Co Ltd | 酸化第一銅粒子の製造方法及び酸化第一銅粒子 |
WO2009008391A1 (ja) | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | 生体摂取物微粒子の製造方法、生体摂取物微粒子及びこれを含有する分散体、医薬組成物 |
CN102847538B (zh) | 2007-07-06 | 2016-07-06 | M技术株式会社 | 由球碳形成的结晶的制造方法及制造装置 |
WO2009041274A1 (ja) * | 2007-09-27 | 2009-04-02 | M.Technique Co., Ltd. | 磁性体微粒子の製造方法、これにより得られた磁性体微粒子及び磁性流体、磁性体製品の製造方法 |
-
2012
- 2012-05-01 US US14/398,156 patent/US10166605B2/en active Active
- 2012-05-01 CN CN201280072852.0A patent/CN104284715A/zh active Pending
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- 2012-05-01 EP EP12875972.7A patent/EP2845643A4/en not_active Withdrawn
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006184306A (ja) | 2004-12-24 | 2006-07-13 | Kao Corp | 電子写真用トナーの製造方法 |
JP2006341232A (ja) * | 2005-06-10 | 2006-12-21 | Canon Inc | 流体処理装置および流体処理方法 |
WO2009008393A1 (ja) | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | 強制超薄膜回転式処理法を用いたナノ粒子の製造方法 |
WO2009008390A1 (ja) | 2007-07-06 | 2009-01-15 | M.Technique Co., Ltd. | 金属微粒子の製造方法及びその金属微粒子を含む金属コロイド溶液 |
JP2009082902A (ja) * | 2007-07-06 | 2009-04-23 | M Technique Co Ltd | 強制超薄膜回転式処理法を用いたナノ粒子の製造方法 |
JP2009131831A (ja) * | 2007-11-09 | 2009-06-18 | M Technique Co Ltd | 微粒子の製造方法及びその微粒子 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2845643A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2016098785A1 (ja) * | 2014-12-15 | 2017-09-21 | エム・テクニック株式会社 | 有機物微粒子の製造方法及び有機物微粒子の改質方法 |
JP2020138200A (ja) * | 2014-12-15 | 2020-09-03 | エム・テクニック株式会社 | 有機物微粒子の製造方法及び有機物微粒子の改質方法 |
US11633359B2 (en) | 2014-12-15 | 2023-04-25 | M. Technique Co., Ltd. | Method for producing organic material microparticles, and method for modifying organic material microparticles |
WO2019088266A1 (ja) * | 2017-11-06 | 2019-05-09 | コニカミノルタ株式会社 | 凝集ナノ粒子および蛍光標識材 |
JPWO2019088266A1 (ja) * | 2017-11-06 | 2020-11-26 | コニカミノルタ株式会社 | 凝集ナノ粒子および蛍光標識材 |
JP7192783B2 (ja) | 2017-11-06 | 2022-12-20 | コニカミノルタ株式会社 | 凝集ナノ粒子および蛍光標識材 |
Also Published As
Publication number | Publication date |
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EP2845643A1 (en) | 2015-03-11 |
US10166605B2 (en) | 2019-01-01 |
CN106732226B (zh) | 2020-11-24 |
CN106732226A (zh) | 2017-05-31 |
EP2845643A4 (en) | 2016-04-27 |
JPWO2013164886A1 (ja) | 2015-12-24 |
KR20150013661A (ko) | 2015-02-05 |
US20150114179A1 (en) | 2015-04-30 |
CN104284715A (zh) | 2015-01-14 |
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