JP2012152739A - Method for producing fine particles with regulated particle size - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing fine particles having a regulated particle size in which use is made of a device in which fluids are treated between at least two treatment surfaces which have been approachably and separably disposed face to face, at least one treatment surface rotating relatively to the other.SOLUTION: The device in which fluids are treated in a thin fluid film formed between at least two treatment surfaces 1 and 2 which have been approachably and separably disposed face to face, at least one treatment surface rotating relatively to the other, is used to mix at least two fluids to be treated, i.e., a raw-material solution including a solvent and, dissolved therein, a substance to be precipitated and a precipitation solvent for precipitating the substance to be precipitated, to precipitate fine particles of the substance. The viscosities of the fluids to be treated which are introduced into the space between the treatment surfaces 1 and 2 are regulated to thereby obtain the fine particles having a regulated particle diameter.

Description

  The present invention relates to a method for producing fine particles having a controlled particle size.

  Fine particles, particularly fine particles (nano fine particles) having a particle size of nanometers, exhibit new properties different from those of general-sized materials, and therefore are being researched and developed throughout the industry. Furthermore, since the characteristics of the fine particles change depending on the size (particle diameter), in order to use the fine particles industrially, not only the production method capable of stable and mass production, but also the particle diameter accurately and efficiently. There is a need for a method of producing fine particles that can control the above.

  Fine particle production methods include the so-called breakdown method in which particles are mainly pulverized using a bead mill, the build-up method in a gas phase method such as CVD or PVD, and the liquid phase method using a device such as a microreactor. There is a build-up method. However, although 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 However, there were problems such as not actually appearing. In addition, the gas phase method and the method using a microreactor also have problems such as high energy costs, and it is difficult to stably produce a large amount of fine particles. Further, these methods have a problem that it is very difficult to produce fine particles having a uniformly controlled particle size.

  Fine particles in a thin-film fluid that flows between processing surfaces that are arranged so as to be able to approach and separate from each other and at least one rotates relative to the other as disclosed in Patent Document 1 by the applicant of the present application. In order to precipitate fine particles by introducing and mixing a fine particle raw material solution and a poor solvent between the processing surfaces, as shown in Patent Document 2, There has been provided a method for controlling the particle size of the deposited fine particles by controlling the temperature difference between the fine particle raw material solution and the poor solvent. However, even when such a method is used, it may be difficult to obtain fine particles having a target nano-size or micro-size particle size.

  In view of the above, a method for producing fine particles having a controlled particle size has been appealed.

International Publication WO2009 / 008393 Pamphlet Japanese Patent No. 4446129

  The present invention solves the above-mentioned problems, and an object thereof is to provide a method for producing fine particles having a controlled particle size.

  As a result of intensive studies, the present inventor has made a raw material solution in which a substance to be precipitated is dissolved between processing surfaces that are disposed opposite to each other and are capable of approaching / separating at least one of which is rotated relative to the other. And a fluid containing a deposition solvent for precipitating the substance to be deposited as a fluid to be treated to deposit the substance to be precipitated, The inventors have found that fine particles with a controlled particle size can be obtained by controlling the viscosity of the fluid to be treated, thereby completing the present invention.

  In the first embodiment of the present invention, at least two kinds of fluids are used as the fluid to be treated, and at least one of the fluids is a raw material solution in which a substance to be precipitated is dissolved in a solvent. And at least one kind of fluid is at least one kind of precipitation solvent for precipitating the substance to be deposited, and the substance to be treated is mixed to precipitate the substance to be deposited whose particle diameter is controlled. In the method for producing fine particles to be processed, the above-mentioned object to be processed is provided in a thin film fluid formed between at least two processing surfaces disposed opposite to each other and capable of approaching / separating at least one rotating relative to the other. A fluid is mixed, and by controlling the viscosity of the fluid to be treated introduced between the at least two processing surfaces, a substance to be deposited with a controlled particle diameter is precipitated. To provide a method of manufacturing a fine particle features.

  According to a second aspect of the present invention, the particle diameter of the substance to be deposited is controlled by controlling the viscosity of at least one of the raw material solution and the precipitation solvent. The manufacturing method of the microparticles | fine-particles which concerns on 1 form is provided.

  In the third aspect of the present invention, the viscosity of at least one of the raw material solution and the precipitation solvent is at least one of the viscosity adjusting substances in at least one of the raw material solution and the precipitation solvent. The method for producing fine particles according to the second aspect of the present invention is characterized in that the fine particles are controlled by mixing.

  According to a fourth aspect of the present invention, either one of the fluid containing the raw material solution and the fluid containing the deposition solvent passes between the at least two processing surfaces while forming the thin film fluid, Provided with a separate introduction path independent of the flow path through which any one of the fluids flows, and at least one of the at least two processing surfaces includes at least one opening that communicates with the introduction path. One of the fluid containing the raw material solution and the fluid containing the deposition solvent is introduced between the at least two processing surfaces through the opening, and the fluid containing the raw material solution and the deposition solution are introduced. A method for producing fine particles according to any one of the first to third aspects of the present invention, wherein a fluid containing a solvent is mixed in the thin film fluid.

  The fifth embodiment of the present invention uses at least three kinds of first, second and third fluids to be treated, and the first fluid to be treated has a substance to be precipitated dissolved in a solvent. The second treated fluid is a viscosity adjusting material solution in which at least one viscosity adjusting material is mixed with a solvent, and the third treated fluid is the fluid containing the raw material solution. In a method for producing fine particles, which is a fluid containing at least one kind of precipitation solvent for precipitating a substance to be deposited, and in which the above-described fluid to be treated is mixed to precipitate a substance to be deposited whose particle diameter is controlled. The fluid to be treated is mixed in a thin film fluid formed between at least two treatment surfaces that are arranged in the form of at least two treatment surfaces that can be moved toward and away from each other. The viscosity adjusting substance solution is less Both control the viscosity of the fluid to be processed introduced between two processing surfaces, and any one of the three types of fluids to be processed forms the thin film fluid. However, at least two separate introduction paths that pass between the at least two processing surfaces and are independent of the flow path through which any one of the fluids to be processed flow are provided. The at least two processing surfaces are provided with openings that communicate with each of the at least two separate introduction paths, and the three kinds of fluids to be processed are provided. The remaining two kinds of fluids to be treated are introduced between the at least two treatment surfaces through the separate openings, and the three kinds of fluids to be treated are mixed in the thin film fluid to form particles. Deposition material with controlled diameter To provide a method of manufacturing fine particles, characterized in that to precipitate.

  In the sixth aspect of the present invention, the viscosity of the raw material solution and the solvent for precipitation is made constant and mixed in the thin film fluid to deposit a reference material to be deposited, and the particle size thereof is measured. Particles having a particle size larger than the particle size of the reference substance to be deposited by controlling the viscosity of at least one of the solvent for precipitation and the viscosity when the reference substance to be precipitated is precipitated. By precipitating a material having a diameter, and controlling the viscosity of at least one of the raw material solution and the solvent for precipitation to be lower than the viscosity when the material to be deposited as a reference is deposited. Provided is a method for producing fine particles according to any one of the second to fourth aspects of the present invention, wherein a deposited material having a particle size smaller than that of a standard deposited material is deposited. .

  According to the invention of the present application, it is possible to manufacture fine particles of a precipitated substance with a controlled particle size more easily, at a lower energy, and at a lower cost. Can be provided inexpensively and stably. Further, since the particle size can be easily controlled, fine particles having a particle size suitable for the purpose can be provided.

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 | transducing part of the apparatus, (B) is the principal part enlarged view of the processing surface for demonstrating the 2nd introducing | transducing part.

  Hereinafter, the present invention will be described in detail. However, the technical scope of the present invention is not limited by the following embodiments and examples.

  The substance to be deposited in the present invention is not particularly limited. For example, organic and inorganic substances such as organic and inorganic pigments, biological ingestions such as drugs and resins, metals, non-metals, or salts thereof, oxides, nitrides, borides, carbides, Examples thereof include compounds such as complexes, organic salts, organic complexes, and organic compounds, and organic-inorganic composite materials.

  Examples of the solvent for dissolving the substance to be deposited include water, an organic solvent, or a mixed solvent composed of a plurality of them. Examples of the water include tap water, ion-exchanged water, pure water, ultrapure water, and RO water. Examples of the organic solvent include alcohol compound solvents, amide compound solvents, ketone compound solvents, ether compound solvents, and aromatic compounds. Examples include solvents, carbon disulfide, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, carboxylic acid compounds, and sulfonic acid compounds. Each of the above solvents may be used alone or in combination of two or more.

  In addition, it can be carried out by mixing or dissolving a basic substance or an acidic substance in the solvent. Examples of basic substances include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium isopropoxide, and amine compounds such as triethylamine, 2-diethylaminoethanol and diethylamine. Can be mentioned. Examples of acidic substances include inorganic acids such as aqua regia, hydrochloric acid, nitric acid, fuming nitric acid, sulfuric acid and fuming sulfuric acid, and organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid and trichloroacetic acid. It is done. These basic substances or acidic substances can be carried out by mixing with various solvents as described above, or can be used alone.

  In addition, it can also be carried out by mixing or dissolving an oxidizing agent or a reducing agent in the above solvent. Although it does not specifically limit as an oxidizing agent, Nitrate, hypochlorite, permanganate, and a peroxide are mentioned. Examples of the reducing agent include lithium aluminum hydride, sodium borohydride, hydrazine and hydrazine hydrate, and sulfite.

  The above-mentioned solvent will be described in more detail. Examples of the alcohol compound solvent include linear alcohols such as methanol, ethanol, n-butanol and n-propanol, branched alcohols such as isopropanol, 2-butanol and tert-butanol, and ethylene. And polyhydric alcohols such as glycol and diethylene glycol. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran, propylene glycol monomethyl ether, and the like. Examples of the aromatic compound solvent include nitrobenzene, chlorobenzene, dichlorobenzene, and the like. Examples of the aliphatic compound solvent include hexane. Examples of the nitrile compound solvent include acetonitrile. Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the halogen compound solvent include chloroform, dichloromethane, trichloroethylene, iodoform, and the like. Examples of the ester compound solvent include ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. Examples of the ionic liquid include a salt of 1-butyl-3-methylimidazolium and PF6- (hexafluorophosphate ion). Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, formamide, N-methylformamide, Examples include acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like. Examples of the carboxylic acid compound include 2,2-dichloropropionic acid and squaric acid. Examples of the sulfonic acid compound include methanesulfonic acid, p-toluenesulfonic acid, chlorosulfonic acid, trifluoromethanesulfonic acid, and the like.

  The same solvent as described above can be used as the solvent for precipitation for mixing the raw material solution to precipitate the substance to be deposited whose particle diameter is controlled. A solvent for dissolution and a solvent for precipitation can be selected depending on the target substance to be deposited.

  In the present invention, it is preferable to control the viscosity of at least one of the raw material solution and the precipitation solvent. Thereby, it is possible to control the particle size of the substance to be deposited. The viscosity of the raw material solution and the solvent for precipitation is not particularly limited. It can be carried out by adjusting the viscosity of the raw material solution and / or the solvent for precipitation according to the kind of the substance to be deposited and the target particle size. The viscosity measurement of the raw material solution and the solvent for precipitation is not particularly limited, but can be measured using various viscosity measurements, and examples include a cone plate viscometer and a cylindrical viscometer. . The viscosity can be controlled by the type and temperature of the solvent, but it is preferable that at least one of the raw material solution and the precipitation solvent contains at least one viscosity adjusting substance. Also, a viscosity adjusting substance solution prepared by mixing at least one kind of viscosity adjusting substance in at least one kind of solvent different from the raw material solution and the precipitation solvent is prepared, and the raw material solution and the precipitation solvent are mixed. The viscosity adjusting substance solution may be used immediately before (or in some cases immediately after) to control the viscosity of at least one of the raw material solution and the precipitation solvent. Further, the present invention can also be carried out by preparing a third fluid whose viscosity is controlled by the above-described method, which is different from the raw material solution and the precipitation solvent, and mixing these fluids.

The viscosity-adjusting substance is not particularly limited. However, glycerin, ethylene glycol, polyhydric alcohols such as propylene glycol and diethylene glycol, paraffins such as liquid paraffin, silicone oils such as dimethyl silicone oil, terpineol, or coconut oil. And natural fats and oils such as palm oil or a vegetable oil, and a solvent having a relatively high viscosity compared to other common solvents. Other examples include celluloses such as polyvinyl alcohol, polyvinyl pyrrolidone, and hydroxyalkyl cellulose, and polymers such as xanthan gum. The above solvents or polymers may be used alone or in combination of two or more. By mixing these substances into at least one of the raw material solution and the precipitation solvent, the viscosity of at least one of the raw material solution and the precipitation solvent can be easily controlled. Alternatively, a viscosity adjusting substance solution may be prepared by mixing at least one kind of viscosity adjusting substance with at least one kind of solvent (third solvent) different from the raw material solution and the precipitation solvent. As a 3rd solvent, the thing similar to the solvent for dissolving said to-be-deposited substance can be used. Further, the present invention may be carried out by mixing at least one type of viscosity adjusting substance with two or all of the raw material solution, the solvent for precipitation, and the third solvent. Further, the viscosity adjusting substance may or may not be involved in the chemical reaction with respect to the deposition of the substance to be deposited and the reaction for the deposition itself. In other words, the viscosity-adjusting substance may be active or inactive with respect to the deposition of the substance to be deposited and the reaction for the deposition itself.
As the viscosity adjusting substance, in addition to the above-described viscosity adjusting substances, any substance that can perform a thickening action or a thinning action in the relative relationship with the viscosity of the solution or solvent to which these are added can be used as appropriate. Is.

  In the present invention, mixing of the raw material solution and the solvent for precipitation can be performed between processing surfaces that are disposed so as to face each other so that they can approach and leave, and at least one of which rotates relative to the other. It is preferable to use a method of stirring and mixing uniformly in a thin film fluid. As such a device, for example, a device having the same principle as that described in Patent Document 1 by the applicant of the present application can be used. By using an apparatus of such a principle, it is possible to produce fine particles having a particle diameter uniformly and uniformly controlled. Further, the crystallinity of the fine particles in the present invention is not particularly limited. It may be a crystal. It may be amorphous. Also, there is no particular limitation on the shape, and the shape may be a spherical shape or a shape other than a spherical shape such as a needle shape or a column shape.

  Hereinafter, embodiments of the apparatus will be described with reference to the drawings.

  The fluid processing apparatus shown in FIGS. 1 to 3 is the same as the apparatus described in Patent Document 1, and is provided between processing surfaces in a processing unit in which at least one that can be approached or separated rotates relative to the other. A first fluid that is a first fluid to be treated among the fluids to be treated is introduced between the processing surfaces, and a flow path into which the first fluid is introduced. The second fluid, which is the second fluid to be treated among the fluids to be treated, is introduced between the processing surfaces from another flow path having an opening communicating between the processing surfaces. It is an apparatus that performs processing by mixing and stirring the first fluid and the second fluid between the surfaces. In FIG. 1, U indicates the upper side and S indicates the lower side. However, in the present invention, the upper, lower, front, rear, left and right only indicate a relative positional relationship, and do not specify an absolute position. 2A and 3B, R indicates the direction of rotation. In FIG. 3B, 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. Provided with 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 processing unit 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, and the second processing unit 20 includes a second processing surface 2.

  Both 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 μm to 50 μm. As a result, 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.

  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. Here, “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.

  More specifically, the first holder 11 that holds the first processing part 10, the second holder 21 that holds the second processing part 20, a contact surface pressure applying mechanism, a rotation driving part, A first introduction part d1, a second introduction part d2, and a fluid pressure imparting mechanism p are provided.

As shown in FIG. 2A, in this embodiment, 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 first and second processing parts 10 and 20 are made of metal, ceramic, sintered metal, wear-resistant steel, sapphire, other metals subjected to hardening treatment, hard material lining or coating, It is possible to adopt a material with plating applied. In this embodiment, 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 the mirror polishing is not particularly limited, but is preferably Ra 0.01 to 1.0 μm, more preferably Ra 0.03 to 0.3 μm.

  At least one of the holders can be rotated relative to the other holder by a rotational drive unit (not shown) such as an electric motor. Reference numeral 50 in FIG. 1 denotes a rotation shaft of the rotation drive unit. In this example, 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. Of course, the second processing unit 20 may be rotated, or both may be rotated. In this example, 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. .

  In this embodiment, 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. However, conversely, 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 recess 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. In this embodiment, 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. In this embodiment, 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. Various fluid treatments such as stirring, emulsification, dispersion, reaction, crystallization, crystallization, and precipitation are performed and discharged from both treatment surfaces 1 and 2 to the outside of both treatment portions 10 and 20. In addition, the environment outside both processing parts 10 and 20 can also be made into a negative pressure with a decompression pump.

  The contact surface pressure applying mechanism applies to the processing portion a force that causes the first processing surface 1 and the second processing surface 2 to approach each other. In this embodiment, 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 the first processing surface 1 of the first processing portion 10 and the second processing surface 2 of the second processing portion 20 in the approaching direction (hereinafter referred to as a contact surface). It is a mechanism for generating pressure). A thin film fluid having a minute film thickness of nm to μm 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.

  In the embodiment shown in FIG. 1, the contact surface pressure applying mechanism is arranged between the housing part 41 and the second processing part 20. Specifically, 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. Move away from the use section 10 and leave a small gap between the processing surfaces 1 and 2. As described above, the first processing surface 1 and the second processing surface 2 are set with an accuracy of μm 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 above-described separation force will be described in detail. 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. In this example, 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.

  Further, in the example of FIG. 1, 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 in a direction to approach the first processing unit 10 is generated.

  Note that 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.

The actual pressure P of the sliding surface, that is, the contact pressure due to the fluid pressure is calculated by the following equation.
P = P1 × (K−k) + Ps

  Here, 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, and Ps represents the spring and back pressure.

By adjusting the actual surface pressure P of the sliding surface by adjusting the balance line, a fluid film is formed by the fluid to be processed so that a desired minute gap is formed between the processing surfaces 1 and 2, and the product is processed. The processed object is made fine and a uniform reaction process is performed.
Although not shown, 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 outside the two processing surfaces 1 and 2 which are annular. However, since the first processing unit 10 is rotating, 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 the one arranged vertically, but may be arranged in the horizontal direction or may be arranged inclined. This is because the fluid to be processed is processed at a fine interval between the processing surfaces 1 and 2 and the influence of gravity can be substantially eliminated. Further, this contact surface pressure applying mechanism also functions as a buffer mechanism for fine vibration and rotational alignment when used in combination with a floating mechanism that holds the second processing portion 20 in a displaceable manner.

  At least one of the first and second processing parts 10 and 20 may be cooled or heated to adjust the temperature. In FIG. 1, the first and second processing parts 10 and 10 are adjusted. , 20 are provided with temperature control mechanisms (temperature control mechanisms) J1, J2. Further, 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.

  As shown in FIG. 2, 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. As shown in FIG. 2B, 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. Further, 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. By forming such a recess 13, a micropump effect can be obtained, and there is an effect that the fluid to be processed can be sucked between the first and second processing surfaces 1 and 2.

It is desirable that 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 the 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.

  When the opening d20 of the second introduction portion 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. In particular, 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. Specifically, in FIG. 2B, 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. In particular, when nano-sized fine particles are precipitated from a fluid, it is desirable that mixing of a plurality of fluids to be treated and nano-particle precipitation are performed under laminar flow conditions.

  The second introduction part d2 can have directionality. For example, as shown in FIG. 3A, 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 (θ1). . The elevation angle (θ1) 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.

  Further, as shown in FIG. 3B, 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. In other words, 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 (θ2) from the reference line g to the rotation direction R. This angle (θ2) is also preferably set to more than 0 degree and less than 90 degrees.

  This angle (θ2) can be changed and carried out according to various conditions such as the type of fluid, reaction speed, viscosity, and rotational speed of the processing surface. In addition, the second introduction part d2 may not have any directionality.

  In the example of FIG. 1, the number of fluids to be processed and the number of flow paths are two, but may be one, or may be three or more. In the example of FIG. 1, 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. In addition, 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.

  In the above apparatus, the first fluid in the thin film fluid formed between the processing surfaces 1 and 2 that are disposed so as to be able to approach and separate from each other and at least one rotates relative to the other. And a raw material solution in which at least one kind of substance to be precipitated is dissolved in the solvent as a second fluid, and a fine particle of the substance to be precipitated having a controlled particle diameter is precipitated. In this case, it can be obtained by controlling the viscosity of at least one of the first fluid and the second fluid by a method of including a viscosity adjusting substance in at least one of the first fluid and the second fluid. The particle diameter of the substance to be deposited can be controlled.

  The precipitation reaction of the fine particles is performed while forcibly and uniformly mixing between the processing surfaces 1 and 2 which are disposed so as to be able to approach and separate from each other in the apparatus shown in FIG. Occur.

  First, a process in which a fluid containing a deposition solvent as a first fluid is disposed so as to be able to approach and separate from each other from the first introduction part d1 which is one flow path, and at least one of the fluids rotates with respect to the other. It introduce | transduces between the work surfaces 1 and 2, and makes the thin film fluid comprised from the 1st fluid between this process surface.

  Next, the fluid containing the raw material solution as the second fluid is directly introduced into the thin film fluid composed of the first fluid created between the processing surfaces 1 and 2 from the second introduction part d2 which is another flow path. To do.

  As described above, 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 perform precipitation reaction of fine particles.

  In addition, since it is sufficient that the above reaction can be performed between the processing surfaces 1 and 2, 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. It is also possible to introduce a solution containing. In other words, the expressions “first” and “second” in each fluid have only the meaning of identification that they are the n-th of a plurality of solvents, and third or more fluids may exist.

As described above, in addition to the first introduction part d1 and the second introduction part d2, a third introduction part may be provided in the processing apparatus. In this case, for example, the first introduction part d1 as the first fluid A fluid containing a raw material solution, a fluid containing a solvent for precipitation from the second introduction part d2 as a second fluid, and a viscosity adjustment substance solution in which at least one viscosity adjustment substance is mixed with the solvent as a third fluid from the third introduction part Each can be separately introduced into the processing apparatus. As a result, the concentration and pressure of each solution, the liquid flow rate, etc. can be individually managed, and the precipitation reaction and the stabilization of the particle diameter of the fine particles can be controlled more precisely. In addition, the combination of the to-be-processed derivative | guide_body (1st fluid-3rd fluid) introduce | transduced into each introduction part can be set arbitrarily. Moreover, it is also possible to provide a 4th or more introduction part, By this, the fluid introduced into a processing apparatus can be subdivided. In this case, the third introduction part may be provided inside the processing parts 10 and 20, or may be provided in another passage. When the third introduction part is provided inside the processing parts 10 and 20, the opening part of the third introduction part may be provided either upstream or downstream of the opening part d20 of the second introduction part d2. When the opening of the third introduction part is provided upstream of the opening d20 of the second introduction part d2, the viscosity adjusting substance solution that is the third fluid introduced between the processing surfaces 1 and 2 from the third introduction part The viscosity of the first fluid immediately before mixing with the second fluid can be adjusted. Further, by adopting a structure in which the third introduction part is connected to the first introduction part d1, the first fluid and the third fluid may be merged in the first introduction part d1, and the third introduction part is connected to the second introduction part d1. The second fluid and the third fluid may be joined in the second introduction part d2 by adopting a structure that is connected to the introduction part d2. Then, the first fluid and / or the second fluid and the third fluid are mixed immediately before being introduced between the processing surfaces 1 and 2, and the viscosity of the first fluid and / or the second fluid can be controlled. It is. At this time, the viscosity adjusting substance may be mixed with at least one of the solvent constituting the third fluid, may be mixed with at least one of the first fluid and the second fluid, It does not need to be mixed with both of the second fluids.
Further, the viscosity of the thin film fluid formed between the processing surfaces is adjusted and controlled, and at the same time, the temperature of the fluid to be processed such as the first and second fluids is controlled, or the first fluid and the second fluid are controlled. It is also possible to control the temperature difference from the fluid or the like (that is, the temperature difference between the treated fluids to be supplied). In order to control the temperature and temperature difference of each processed fluid to be supplied, 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.

  EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples.

  In the following embodiments, “from the center” means “from the first introduction part d1” of the processing apparatus shown in FIG. 1 and the first fluid is from the first introduction part d1. The first fluid to be treated is introduced, and the second fluid is the second fluid to be treated introduced from the second introduction part d2 of the treatment apparatus shown in FIG. .

(Viscosity measurement)
A single cylindrical rotary melt viscometer RVDV-II + PRO (manufactured by BROOKFIELD) was used for measuring the viscosity of the fluid.

(Particle size distribution)
The particle size distribution was measured using a nanotrack particle size distribution measuring apparatus UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and D50 value and D90 value were adopted.

(Examples 1-9)
As Examples 1 to 9, as shown in FIG. 1, between processing surfaces 1 and 2, which are disposed facing each other and have processing surfaces that can be approached and separated, and at least one of which rotates relative to the other. In a thin film fluid, a raw material solution and a deposition solvent are mixed using a reactor that uniformly diffuses, agitates, and mixes, and a precipitation reaction is performed in the thin film fluid.

A mixed solvent obtained by mixing pure water and glycerin as the first fluid precipitation solvent from the center under the conditions shown in Table 1 is supplied at a supply pressure / back pressure = 0.50 MPa / 0.04 MPa at a rotation speed of 1000 rpm to 3600 rpm. The raw material solution (polystyrene dissolution concentration 3 wt%) in which polystyrene was dissolved in tetrahydrofuran (THF) was introduced as a second fluid between the processing surfaces at 5 mL / min. The first fluid and the second fluid were mixed in the thin film fluid and discharged from the processing surface as polystyrene fine particles. The viscosity adjusting substance is glycerin. Table 1 shows the results (Examples 1 to 9) of experiments performed by changing the mixing ratio (weight) of pure water and glycerin together with the particle size distribution measurement results of the polystyrene fine particle dispersion. The viscosity measurement result of the first fluid shown in Table 1 is the viscosity obtained under the measurement condition of the rotation speed of 50 rpm using No. 3 as the rotor of the single cylindrical rotary melt viscometer. The viscosity of the second fluid was constant in each example. Specifically, the viscosity of the second fluid was 3.44 [mPa · s] under the same measurement conditions as the first fluid.
The temperature of the first fluid and the second fluid (the temperature immediately before introduction between the processing surfaces) was constant in each example. Specifically, the temperature of the first fluid was 25 ° C., and the temperature of the second fluid was 25 ° C. From Table 1, the particle diameter of the obtained polystyrene fine particles can be controlled by using the solvent for precipitating polystyrene fine particles whose viscosity is controlled by changing the mixing ratio (weight) of pure water and glycerin as the first fluid. I understand that.

(Examples 10 to 12)
As Example 10-12, as shown in FIG. 1, between the processing surfaces 1 and 2 which have the processing surface which can be approached / separated and which is arrange | positioned facing, at least one rotates with respect to the other In a thin film fluid, a raw material solution and a deposition solvent are mixed using a reactor that uniformly diffuses, agitates, and mixes, and a precipitation reaction is performed in the thin film fluid.

As a solvent for precipitation of the first fluid from the center, a solution obtained by dissolving sodium borohydride and thiocalcol 08 (manufactured by Kao) in a mixed solvent obtained by mixing methanol, toluene, and propylene glycol under the conditions shown in Table 2, Supply pressure / back pressure = 0.50MPa / 0.04MPa, sent at a rotation speed of 1000rpm, and a raw material solution in which silver nitrate is dissolved in pure water (silver nitrate dissolution concentration 2wt%) is used as a second fluid for processing at 5mL / min. Introduced between the faces. The first fluid and the second fluid were mixed in a thin film fluid and discharged from the processing surface as a silver fine particle dispersion. The discharged silver fine particles were loosely aggregated and sedimented by centrifugation (× 13000 G). The supernatant liquid after the centrifugation treatment was removed, methanol was added to redisperse the silver fine particles, and then the centrifugal separation was repeated again to wash the silver fine particles. Methanol was added to the finally obtained silver fine particle paste for dispersion treatment. The particle size distribution measurement was performed on the dispersion liquid of the silver fine particles subjected to the dispersion treatment. The viscosity adjusting substance is propylene glycol. Table 2 shows the results (Examples 10 to 12) of experiments conducted by changing the mixing ratio (weight) of methanol, toluene, and propylene glycol together with the particle size distribution measurement results of the silver fine particle dispersion. The viscosity measurement result of the first fluid shown in Table 2 is the viscosity obtained under the measurement condition of the rotation speed of 50 rpm using No. 3 as the rotor of the single cylindrical rotary melt viscometer. The viscosity of the second fluid was constant in each example. Specifically, the viscosity of the second fluid was 2.46 [mPa · s] under the same measurement conditions as the first fluid.
The temperature of the first fluid and the second fluid (the temperature immediately before introduction between the processing surfaces) was constant in each example. Specifically, the temperature of the first fluid was 60 ° C., and the temperature of the second fluid was 30 ° C. From Table 2, the particles of silver fine particles obtained by using as a first fluid a silver fine particle precipitation solvent whose viscosity is controlled by changing the mixing ratio (weight) of methanol, toluene, and propylene glycol. It can be seen that the diameter is controlled.

  As described above, the particle diameter of the obtained fine particles is controlled by controlling the viscosity of the fluid to be treated introduced between the processing surfaces 1 and 2. In particular, the viscosity of the raw material solution and the solvent for precipitation is made constant and mixed in the thin film fluid to precipitate a reference material to be precipitated, and the particle size thereof is measured, and the raw material solution and the solvent for precipitation are measured. By controlling the viscosity of at least any one of the above to be a reference material to be precipitated, the viscosity is larger than the particle size of the reference material to be precipitated. On the contrary, by controlling the viscosity of at least one of the raw material solution and the solvent for precipitation to be lower than the viscosity at the time of depositing the reference material to be precipitated, It was confirmed that the deposited substance having a particle size smaller than that of the deposited substance can be deposited.

DESCRIPTION OF SYMBOLS 1 1st processing surface 2 2nd processing surface 10 1st processing part 11 1st holder 20 2nd processing part 21 2nd holder d1 1st introduction part d2 2nd introduction part d20 Opening part

Claims (6)

At least two kinds of fluids are used as the fluid to be treated.
Among them, at least one type of fluid is a raw material solution in which a deposited substance is dissolved in a solvent,
At least one type of fluid other than the above is at least one type of precipitation solvent for precipitating the substance to be deposited,
In the method for producing fine particles in which the above-described fluid to be treated is mixed and the substance to be deposited with a controlled particle diameter is deposited.
The fluid to be processed is mixed in a thin film fluid formed between at least two processing surfaces which are disposed opposite to each other and can be approached and separated, and at least one of which rotates relative to the other. A method for producing fine particles, characterized in that a substance to be deposited whose particle diameter is controlled is precipitated by controlling the viscosity of the fluid to be treated introduced between the at least two treatment surfaces.   2. The method for producing fine particles according to claim 1, wherein the particle diameter of the substance to be deposited is controlled by controlling the viscosity of at least one of the raw material solution and the precipitation solvent. The viscosity of at least one of the raw material solution and the precipitation solvent is
3. The method for producing fine particles according to claim 2, wherein the method is controlled by mixing at least one kind of viscosity adjusting substance with at least one of the raw material solution and the precipitation solvent. Either one of the fluid containing the raw material solution and the fluid containing the deposition solvent passes between the at least two processing surfaces while forming the thin film fluid,
A separate introduction path independent of the flow path through which any one of the above fluids flows;
At least one of the at least two processing surfaces includes at least one opening that leads to the introduction path,
Either one of the fluid containing the raw material solution and the fluid containing the precipitation solvent is introduced between the at least two processing surfaces from the opening,
The method for producing fine particles according to any one of claims 1 to 3, wherein the fluid containing the raw material solution and the fluid containing the deposition solvent are mixed in the thin film fluid. Using at least three kinds of fluids to be treated, first, second, and third,
The first fluid to be treated is a fluid containing a raw material solution in which a substance to be precipitated is dissolved in a solvent,
The second fluid to be treated is a viscosity adjusting substance solution in which at least one viscosity adjusting substance is mixed with a solvent,
The third fluid to be treated is a fluid containing at least one kind of precipitation solvent for precipitating the substance to be precipitated.
In the method for producing fine particles in which the above-described fluid to be treated is mixed and the substance to be deposited with a controlled particle diameter is deposited.
The fluid to be processed is mixed in a thin film fluid formed between at least two processing surfaces which are disposed opposite to each other and can be approached and separated, and at least one of which rotates relative to the other. Yes,
The viscosity adjusting substance solution controls the viscosity of the fluid to be treated introduced between the at least two processing surfaces.
One of the three types of fluids to be processed passes between the at least two processing surfaces while forming the thin film fluid,
At least two separate introduction paths independent of the flow path through which any one of the fluids to be treated flows;
The at least two separate introduction paths are independent of each other,
At least one of the at least two processing surfaces includes an opening that leads to each of the at least two separate introduction paths,
The remaining two kinds of fluids to be treated among the three kinds of fluids to be treated are introduced between the at least two treatment surfaces through the separate openings,
A method for producing fine particles, wherein the three kinds of fluids to be treated are mixed in the thin film fluid to precipitate a substance to be precipitated with a controlled particle diameter. The viscosity of the raw material solution and the solvent for precipitation is kept constant and mixed in the thin film fluid to precipitate a reference material to be deposited, and its particle diameter is measured.
By controlling the viscosity of at least one of the raw material solution and the precipitation solvent to be higher than the viscosity at the time of depositing the reference deposit material, the particle size of the reference deposit material is controlled. Precipitating substances with larger particle sizes,
By controlling the viscosity of at least one of the raw material solution and the precipitation solvent to be lower than the viscosity at the time of depositing the reference deposit material, the particle diameter of the reference deposit material is controlled. The method for producing fine particles according to any one of claims 2 to 4, wherein a substance to be deposited having a smaller particle diameter is precipitated.

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