JP2011157271A - Aggregate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aggregate of a granular substance by a new shape-control method, which is conventionally impossible, and to provide a method for producing the aggregate. <P>SOLUTION: A solid or hollow aggregate is provided, comprising aggregation of a granular substance of a metal oxide having a particle diameter of less than 0.1 μm, and a method for producing the aggregate is provided. The method includes dispersing the granular substance in a dispersion medium selected from an aqueous solvent, an alcohol- and an ether-based solvent to prepare a mixture liquid containing the granular substance. The granular substance is dispersed in the mixture liquid to obtain an average distance between surfaces of the granular substance satisfying L<SB>DLVO</SB>≥L<SB>Woodcock</SB>in the mixture liquid. The mixture liquid is changed into droplets of less than 100 μm, which are dried by vaporizing the dispersion medium. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a granule using nanoparticles as a raw material, which has a high structure controllability and is excellent in visible light permeability and ultraviolet shielding properties.

  The present invention has been developed from a particle morphology control method (see Patent Documents 1 and 2 and FIGS. 1 and 2) related to the composite particles of the prior application (see FIGS. 3 to 5), and has been previously solidified (crystallized) on the nanometer order. By using particles as the second component (child particles) and the three methods of liquid phase dispersion theory, nanoparticle packing theory, and spraying method (droplet process), solid and hollow granules, reversibly changeable swelling Functional powders and the like are provided.

  The historical factors (technical background) that the present invention was established are the degree of dispersion of the particulate matter in the liquid by the medium stirring type pulverizer (bead mill) and the droplet size distribution by the spray method (particularly 3-4 fluid nozzles). There is rapid progress in fine structure control technology (Figs. 1-3). This was combined with the conventional liquid phase DLVO fine particle dispersion and the theoretical progress to explain the particle packing structure in an integrated manner, which was the beginning of the present invention.

  The technical feature of the present invention resides in the fusion of both. That is, a uniform dispersion method of nanoparticles in a liquid phase combining a liquid phase method (DLVO dispersion theory) and a solid phase method (particle packing theory), a micron-order droplet formation method, and a rapid solidification method of solids As a result of integration as an indispensable technical requirement, the micro force (liquid crosslinking force, hetero-cohesive force, etc.) that governs dispersion and compounding, and the controllability of the primary characteristics of the powder that are adjusted as operating conditions have been greatly improved ( 3-14).

  The feature of the present invention is an ordered mixture, that is, uniform composite and dispersion of different components, etc., and secondary characteristics of the powder such as low cohesiveness of the constituents (in the present invention, morphology and structure control of granules) As a result of improving the controllability of particles, the characteristics of particle aggregates made from particulate materials (visible light transmittance, ultraviolet shielding properties, powders with reversibly changing swelling, powder layer lubricity, thermal conductivity) It is that it can be remarkably improved (FIGS. 11 to 14).

  As a development of the invention, this uniform dispersibility (combination) and low agglomeration are ordered mixtures under realistic concentration conditions (for example, 40 wt (%) or more) in actual production sites called concentrated slurry. And the expansion of the technical field of plate-like granular materials such as granules, hollow particles, and fillers (for example, dispersion of constituent components and crystallization of the second component) Is not possible with a general-purpose process such as an emulsion method that requires simultaneous achievement of

  Plate-like or scale-like powder made from clay mineral, especially called mica, sericite (sericite), mascobite (muscovite), flocovite (phlogopite), or biotite (biotite) Silicate minerals (mica, especially non-swelling clay minerals) are high-performance powders that combine high fluidity (sliding properties) due to powder shape and high transparency. Etc. are often used. In particular, sericite is a kind of mineral and is also referred to as the English name sericite.

Produced as a powdery mass in hydrothermal alteration zones such as volcanic rocks, the Bandai mine in Toei-cho, Kitashirakura-gun, Aichi Prefecture is famous as an international source of sericite. It is sold under the name of “Sanshin Mica”. The chemical composition is approximately “K ₂ Al ₄ Si ₆ Al ₂ O ₂₀ ” and has a monoclinic system close to muscovite (phlogopite). It is mainly used as a cosmetic foundation material. Further, a heat-resistant lubricant, a particle size distribution adjusted or finely pulverized is also used as a filler for reinforcing materials such as plastics, and is an industrially important base material (Patent Document 1). -2, nonpatent literature 1-3).

  Improvement of physical properties, expression of new functions, newness for basic cosmetics (skin care) and finished cosmetics (make-up), as exemplified by new material systems that have penetrated the industry as functional cosmetics (Cosmeticals = Cosmetics + Pharmaceuticals) In addition to pigmentation (makeup) functions such as color rendering (coloration) and finish (soft focus) functions such as transparency and skin feel, texture and concavo-convexity and smoothness and feeling of use such as development of applications There is an increasing demand for functional material raw materials that also have enhanced medicinal functions that promote (UV) shielding ability (SPF value), moisture retention for preventing rough skin, and the like (Non-Patent Documents 5 to 6).

  In addition, sericite (sericite), which is particularly demanded in the above-mentioned luxury cosmetics, may be depleted of resources as a mineral-based raw material, and is a simple basis from the viewpoint of “3R” Reduce (resource saving). Rather than being used as a material, advancement of powder physical properties, development of new functions, development of new applications, etc. are urgent issues (Patent Documents 1 to 6, Non-Patent Documents 1 to 6).

  By covering the technical background of the present invention and the problems of the existing technical group from the viewpoint of [1] extender pigments, and [2] pearl pigments, and manufacturing inventions as [3] particle composite methods. Clarify (see patent conditions map of operating conditions / material structure / material function in FIGS. 1 to 3).

  [1] Body pigment (Body Pigment or Extender Pigment) is a name that has mainly penetrated into the cosmetics industry. It is colorless or white (that is, low refractive index and low hiding property), and has a high degree of freedom in coloring and high lubrication. Refers to plate-like or scale-like silicate mineral (mica-based, especially non-swelling clay mineral) powders that have high function, high touch and feeling of use as material functions. It is a raw material powder base material for cosmetics (a product having a foundation composition blended with a molded product, oil, or the like).

Mainly clay minerals such as mica, that is, surface treatment such as hydrophilicity / hydrophobization of surface hydroxyl groups, titanium oxide (titanium dioxide TiO ₂ called titania, black low-order titanium oxide TiOX For example, the following is a list of representative examples that have become the starting point for further development of single-function particulate materials that have not been combined with other oxide-based materials. Patent Documents 1 to 6, Non-Patent Documents 1 to 16).

(1) Purification of natural product-derived raw material powder (adjusted particle size distribution), low purity (including talc), Yamaguchi Mica Co., Ltd., Asada Flour Milling Co., Ltd. (2) Purification of natural product-derived raw material powder (Particle size distribution adjustment), high purity, sericite (mica)
(3) Surface treatment of raw material powders derived from natural products (wet / dry method, hydrophilic / hydrophobic base material surface), Kakuhachi Fish Foil Co., Ltd. “Eight Pearl”, Miyoshi Kasei Co., Ltd., Daito Kasei (4) Synthetic mica (fluorine substitution of hydroxyl groups of phlogopite and hydrothermal treatment of natural minerals), Topy Industries, Ltd., Corp Chemical Co., Ltd., etc.

The current technical problems are extracted from the group of representative past technologies of extender pigments as follows.
(1) Control of the shape and structure of the powder and powder operation are often simple (particle size distribution adjustment level by refining, etc.).
(2) Since the present system is a material system specialized in a single function (pigment function≈color rendering property and lubricity), it is difficult to add an artificial operation compared to a synthetic material, or it is economically disadvantageous.
(3) (Therefore) There are many techniques for improving pigment functions (color rendering properties, lubricity, etc.), and there are few intellectual properties for the purpose of medicinal functions (such as ultraviolet shielding).
(4) The more raw material powders derived from natural products and the higher the performance of powders, the greater the problems such as depletion of the raw materials themselves (so-called “3R” reduction from the viewpoint of resource saving) is essential. ).
(5) The existing technology group is a method developed inductively (experience or trial and error / individual correspondence / local optimization), and is not in a direction to search (appropriately) heterogeneous technologies.

  Especially the last subject mentioned above is a big problem in functional cosmetics. The basic physical properties of extender pigments, which are base materials for functional cosmetics, are primary characteristics that affect composite powder and foundation characteristics in the subsequent process. Therefore, even if the characteristics are improved locally, other characteristics may deteriorate. For example, the essence of the technology will not be dealt with unless it is based on the understanding of powder engineering phenomena related to particle dispersion theory and nanoparticle packing theory in the liquid phase.

  Applying the understanding of academic phenomena related to dispersion theory in liquid phase and nanoparticle packing theory that have been elucidated in powder engineering, deduction (which is an important element as an invention) (overview or hypothesis verification, theoretical design, Although it is essential to make a structure in terms of overall adjustment, it has not been realized at this time. As a result, only local effects that improve only basic physical properties such as fluidity (sliding property) of extender pigments can be achieved, and the urgent essential requirement (inventive step of the invention) of synergy of multiple functions of functional cosmetics. Essentially no means to solve it.

[2] The pearl pigments (Pearl Pigments) in the past technology group are the names that have mainly penetrated into the cosmetics industry, especially composite particles that aim at multiple reflection, scattering and interference light (so-called pearly luster). Say. It is a raw material powder additive for cosmetics. As a group of mother particles, mica and talc silicate minerals as well as borosilicate metal oxides are used. As child particle groups, titania, zinc oxide ZnO (zinc white), iron oxide (iron tetroxide magnetite Fe ₃ O ₄ and iron sesquioxide hematite Fe ₂ O ₃ (so-called dial)), barium sulfate BaSO ₄ , cerium oxide Spherical or plate-like metal oxide particles such as CeO ₂ and calcium carbonate CaCO ₃ (limestone) are used.

  In addition, as examples of the structure and shape (morphology) of the child particles, the particles are attached in a granular form (multiple components may be multi-layered), rod-like, film-like (multi-layered in two or more layers), or porous. -It includes a wide variety of morphologies, such as coated structures (from weak electrostatic contact to strong bonds with chemical reactions and material transformations).

As a material invention, when focusing on the technical components of pearl pigments, it is partially the same as the present invention as the mother particles / child particles (type of material) having the same (or partially the same) configuration as the reference invention described later. There are several existing technical groups using the operation method (production method). That is, the above-mentioned extender pigment is used as a base particle, and spherical particles (or thin film) such as titania, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and zirconia (ZrO ₂ ) are added as a second component (child particle). The basic representative examples that have become the basis for the subsequent development are listed below (Patent Documents 7 to 21, Non-Patent Documents 12 to 31).

(1) Basic patent on composite particles of clay minerals such as mica and titania, DuPont.
(2) Multilayer / composite, alumina and silicon-based surface treatments in addition to titania, Catalyst Chemical Co., Ltd. “Coverleaf”, Merck Co., Ltd., etc.
(3) Child particles are in special form, cup-shaped aluminum hydroxide Al (OH) with a lid, ₃ granular coating, Miyoshi Kasei Co., Ltd. Shiseido Co., Ltd. “Excel Mica”.
(4) The child particles have a special form, feather-shaped zinc oxide, Shiseido Co., Ltd.

(5) Barium sulfate-based, Shiseido Co., Ltd., a child particle having a special form, a reflex plate or a butterfly shape.
(6) Child particles have a special form, titania prismatic shape (including spindle shape and nanotube), Osaka City Institute of Technology (ammonium peroxotitanate method), etc.
(7) The child particles have a special form, hollow pearl pigment, Kao Corporation.

(8) The child particles have a special form, granule (diatom) -like pearl pigment, Teika Co., Ltd.
(9) Child particles are polymer, PMMA (polymethyl methacrylate, polymethyl methacrylate, acrylic resin), L'Oreal Co., Ltd. “Aero Powder”, Noevir Co., Ltd., Shiseido Co., Ltd., etc.
(10) Skin color enhancement for Asians, Bengala (petal) iron oxide (Fe ₃ O ₄ and Fe ₂ O ₃ ), BASF Corp. (former Engelhard Corp.), Merck Corp. (the world's two largest manufacturers) .
(11) Skin color enhancement for Asians, Fe-substituted mica (synthetic product), Topy Industries, Ltd.

  In addition, in the patent map analysis of operating conditions, material structure, and material function, typical examples in which the material function is cited as a claim are listed as follows (Patent Documents 7 to 30, Non-Patent Documents 32- 59).

(1) Cerium oxide (suntan long wavelength UVA (400 to 315 nm) ultraviolet shielding), Kose Corporation, Tohoku University, Osaka University.
(2) Titanium oxide (sunburn short wavelength UVB (315 to 280 nm) ultraviolet shielding) and zinc oxide (UVA ultraviolet shielding) optimum blend, Showa Denko K.K.
(3) Natural color development (soft focus = transmittance VS reflectivity) evaluation, Nippon Koken Co., Ltd.
(4) Feeling of use / psychological evaluation (tactile test, sensory evaluation), Sankyo Piotech Co., Ltd. “Tribo Station”, etc., and adjustment of blending of Nippon Menard Cosmetics Co., Ltd.
(5) Nanoseed Co., Ltd., including powder layer shear test (fracture envelope evaluation) and evaluation of adhesion (atomic force microscope, etc.) between powders (one particle for a molded body) and wall surfaces etc.

The current technical issues are extracted from the representative group of existing pearl pigment technologies as follows.
(1) Scientifically limited to simple compounding methods, simple powder shape and structure control and powder manipulation (multi-layer / composite by increasing process, non-artificial morphogenesis of material types) It is often a special form coating that depends on
(2) Currently, the material system is mainly intended for a single function (particularly pigment function ≒ color rendering and lubricity), so that it is difficult to add man-made operations compared to synthetic materials, or it is economically disadvantageous. .
(3) The more raw material powders derived from natural products and the higher the performance of powders, the greater the problems such as depletion of the raw materials themselves (required countermeasures from the viewpoint of “3R” Reduce). .
(4) The synergy of pigment function (color rendering property, lubricity, etc.) and medicinal function (UV shielding, etc.) essential for functional cosmetics is not achieved.

(5) The existing technology group is in a form of applying a methodology developed inductively (experience or trial and error, individual correspondence, local optimization).
(6) Among them, the improvement and evaluation of lubricity and feeling of use (especially quantification of psychological and qualitative evaluation) are undeveloped. Most of them are pigment functions (color rendering, etc.) and medicinal functions (ultraviolet ray shielding). Etc.), the lubricity decreased, and the evaluation was filed in a qualitative (non-quantitative) questionnaire format. There are no applications filed in a form that can be compared to each other technically, and they remain at a separate, independent study level at the laboratory scale, which is not easily conceived by technical experts.

  In particular, the latter half of the above-mentioned problems should be overcome in order to further enhance the functionality of functional cosmetics. For example, the basic physical properties of the pearl pigment, which is an additive for functional cosmetics, are primary properties that affect the foundation properties of the subsequent process. Therefore, even if the properties are improved locally, other properties may deteriorate. For example, the essence of the technology will not be dealt with unless it is based on the understanding of powder engineering phenomena related to particle dispersion theory and nanoparticle packing theory in the liquid phase.

  Applying the understanding of academic phenomena related to dispersion theory in liquid phase and nanoparticle packing theory that have been elucidated in powder engineering, deduction (which is an important element as an invention) (overview or hypothesis verification, theoretical design, What is structured in terms of overall coordination is not at least as of now. As a result, only the basic physical properties such as the fluidity (smoothness) of extender pigments can be improved, and the essential requirement (inventive inventive step) of synergy of multiple functions of functional cosmetics is essentially solved. I have not been able to play the means.

  [3] The technique of the existing technology group (particle composite method) is a composite structure, porous body, granule, porous material in which a granular material whose shape or structure is controlled is formed from at least two substances It refers to a method for producing a granular substance having a controlled shape or structure, characterized in that it is a porous granule, a composite structured granule, an aggregate, or a hollow body.

  When paying attention to technical components as a manufacturing method invention, mother particles / child particles (type of material) having the same (or partially the same) configuration as the reference invention described later, and partially the same operating method as the present invention ( There are several existing technology groups using the manufacturing method. That is, among the substances, manufacturing methods, and functions, the following is a list of basic representative examples that have become the starting point of subsequent development mainly in methods and processes (production methods) (Patent Documents 22 to 29, non-patent documents). References 38-45).

(1) Including methods typified by solid-phase methods, mechanical compounding methods (such as ball mill and bead mill methods), and dry molding processes.
(2) Techniques categorized as liquid phase method, wet surface treatment, silane coupling, titanyl sulfate hydrolysis method, sol-gel method, difference of electrostatic repulsion force calculated from DLVO theory and van der Waals attraction Dispersed in liquid.
(3) Methods typified by vapor phase methods, dry surface treatment, various spray processes (freeze drying method, spray drying method, spray pyrolysis method, chemical flame method, etc.), chemical vapor deposition (deposition) CVD method, Physical vapor deposition (vapor deposition) PVD method, granule production, particle composite, etc.
(4) Including methods typified by high energy production methods, production methods of new materials such as carbon nanotubes, such as plasma method and supercritical fluid method.

The current technical problems are extracted from the representative group of existing technology of particle composite method as follows.
(1) When analyzed as operating conditions (uniqueness of the invention), uniform dispersion of particles / powder (Breaking Down) and dense filling / forming (Building Up) are not controlled at the same time. As a result, when child particles that can cover the surface of the mother particles are added in a stoichiometric composition as a material (powder) structure, formation of aggregates of the mother particles and the child particles cannot be avoided. In order to avoid agglomeration, it is possible to add only child particles that are excessively smaller than the stoichiometric ratio (FIGS. 1 and 2). Therefore, there was a limit to the material functions that can be reached (→ For example, as described below, synergy of pigment functions (color rendering and lubricity, etc.) essential for functional cosmetics and medicinal functions (such as UV shielding) has been achieved. Absent).

(2) History of achievement (or purpose) of synergy between pigment function (color rendering property, lubricity, etc.) and medicinal function (ultraviolet ray shielding, etc.) essential for functional cosmetics when analyzed as inventive step There is no technical group (Figs. 1 and 2).
(3) If it is limited to actual material systems (systems that are practically used and have a large particle size distribution range, such as a wide range, etc., there are many control problems) The main method is a method using a specific shape change limited to a species (for example, acicularization of zinc oxide) (and therefore not versatile). Compared with past cases of synthetic materials and laboratory scales, it is difficult to perform an artificial operation or it is economically disadvantageous.
(4) The existing technology group is in a form of applying a methodology developed inductively (experience or trial and error, individual correspondence, local optimization).

  Specifically, in the preparation of mixed substances, it is difficult to be restricted by the composition of the target material, the hydrophilicity / new oiliness of the powder surface, and mechanical (a kind of solid-phase method) for controlling the shape and structure of the powder. There is a compounding method. Above all, the method using shearing between multiple elliptical shapes and grinding media rotating in opposite directions has relatively low shearing force among mechanical compounding methods, and can be combined without destroying cosmetics and drugs. (For example, Patent Document 3), for example, control of the release characteristics of enzymes from yeast is being studied (Non-Patent Document 2). However, this method is also a typical batch process (a batch processing method performed in a non-continuous manner divided into unit operations), which is disadvantageous in terms of productivity, industrialization, and cost, and special capital investment is essential. It seems that it is not so popular at present.

  In the preparation of mixed substances, there is no limitation on the material, and when considering the manufacturing method to achieve high functionality by controlling the shape and structure of the powder, hydrolysis reaction and humidification of metal alkoxide and particle surface hydroxyl group Local hydrolysis method using water film formed on particle surface in atmosphere, heteroaggregation method using charge sign difference of ζ (zeta) potential of electric double layer proposed by Harding (1972) et al., Suspension weight There are legal methods, sol-gel methods and emulsion methods. These so-called “liquid phase processes” are methods that are relatively common in the cosmetics and pharmaceutical fields to which powders made from clay minerals, especially plate-like or scale-like powders, are applied (microcapsule production). It is also a typical liquid phase method relating to the control of the shape and structure of the powder.

  The manufacturing principle uses uniform dispersion of constituent components resulting from the repulsion of the aqueous phase and the oil phase, and composite using a surfactant. It is exemplified as a method with relatively high controllability of the particle structure. However, these methods require that the dispersion of the constituent components and the crystallization of the second component be achieved simultaneously in time, and a typical batch process (= discontinuous multiple steps) that is difficult to control is essential. In addition to disadvantages in terms of productivity, industrialization, and cost, there is no generalized raw material in current technology, and it is necessary to search for the composition, powder characteristics, and preparation method depending on the target material , Etc. are problems. As a result, successful examples are classified into laboratory-scale manufacturing methods that are often found in material systems that are easy to synthesize, such as silica, and that have a positive and negative ζ potential in the liquid and that have a function of electrostatic attraction. It is unsuitable for a realistic concentration condition (for example, 40 wt (wt)% or more) in an actual manufacturing site called a concentrated slurry of interest (for example, Non-Patent Documents 3 to 5).

  In the preparation of mixed substances, previous cases with intermediate technical characteristics of liquid phase to gas phase processes (especially competing with the present invention) are analyzed. An example of an apparatus configuration assumed when the conversion process of liquid substance → particulate substance is embodied is illustrated. Considering mass productivity and continuous productivity, the gas phase synthesis method (gas phase method) is relatively superior when a production method for controlling the shape and structure of the powder is examined. Above all, the “droplet process” centered on the “spray method” such as spray drying method, spray pyrolysis method, freeze drying method, supercritical method, etc. is a typical example of success in industrializing lactose and inhalation preparations. It is a phase method.

  However, the current droplet process is solidified in as short a time as possible by keeping the uniform distribution of the raw material dissolved (or dispersed) in the liquid material by a relatively fast drying process compared to the liquid phase method. The main point is to create a uniform distribution of a plurality of granular materials. For example, in the case of solid powder, agglomerated powder, granules, and composite powder, keratin and pigment composite powder (Patent Document 3), lactose and sodium alginate composite powder (Non-Patent Document 5), inhalation The novelty as a patent, such as a granule of a pharmaceutical powder (Non-patent Document 6), is often attributed to the uniform distribution of a plurality of granular substances. Therefore, as with mica-based powders, clay mineral powders, and emulsion methods, new powders (for example, composite-structured powders, porous powders, In order to produce a granule, a microcapsule, etc.), it is necessary to search for a composition, powder characteristics, and a preparation method depending on the target material.

  The same applies to the case of a porous powder or a hollow powder in a droplet process, and simple control and the like due to a uniform distribution state of a plurality of particulate substances are mainly used. Porous powder or hollow powder can be used for adjusting the operating conditions of the droplet process, such as the heat treatment temperature of the droplet or the moving speed of the droplet, adding foaming components typical of glass fillers, or burning the core material Manufactured in a “bubble process” with acid dissolution removal. This method mainly includes a batch processing (non-continuous processing) manufacturing method (for example, Patent Document 6) in an electric furnace similar to a glass-based material to which a foaming component such as an inorganic material is added. A continuous production method in the gas phase combined with (for example, Patent Document 7), a production method using an organic substance having a decomposition starting temperature having a boiling point lower than that of an inorganic substance such as an azo substance (for example, Patent Document 8), A method of continuous production in the gas phase using a flammable liquid substance such as gasoline as a solvent or a dispersion medium and utilizing foaming from the solvent (for example, Patent Document 9), a method in which the core material is burned out or dissolved and removed with an acid ( For example, there is Patent Document 10).

  However, since these conventional technologies are indiscriminately dispersed gaseous substances (so-called carpet bombing), foaming outside the droplets (so-called false explosions) occurs with considerable probability, and the inside of the droplets of gaseous substances Explosion (foaming) at was expected with probability. Therefore, the limitations of achieving uniformity and high controllability of the porous or hollow structure are not essentially solved, and since the droplet size distribution is wide, the porosity and the pore size are non-uniform, almost certainly. Many problems such as the generation of ruptured particles have not been solved.

  Furthermore, the problems as a manufacturing method are clarified by analyzing individual past cases. In particular, in Patent Document 27, the main purpose is to eliminate the aggregation of mother particles and child particles, and plate-like particles such as 500 μm talc are used as a second stirring medium (zirconia beads), and the particles (crystallized in advance) are used. The aim is to improve the dispersibility of nanometer fine particles by a method using a medium stirring mill method of several hundreds of μm of zirconia beads and an organic solvent using fine particles such as titania of several tens of nm as a second component (child particles), It is disclosed.

  As an example of a cosmetic composition, there is disclosed a method for producing a powder cosmetic comprising the above components using a medium stirring mill method or a Henschel mixer method of an organic solvent and a rotary disk type spray drying method as methodologies ( Patent Document 25).

  Using fine particles such as titania with a diameter of several tens of nanometers that have been preliminarily granulated (crystallized), the methodology is a medium stirring mill method of several mm of zirconia beads and an organic solvent and a two-fluid nozzle type spray drying method (combined use) Powders for cosmetics (so-called granules) and the like prepared by the above (Patent Document 26).

  As a past example of equipment engineering, a child particle on the surface of the mother particle was designed with the method of designing and proposing the nozzle of the two-fluid nozzle type / spray drying method for the purpose of avoiding aggregation of the mother particle / child particle of micron order or less. A compounding method is disclosed (Patent Document 28).

  As a patent that uses both a mathematical model and a spraying process, a polymer material is used for the mother particles, and the weight ratio of the child particles per unit surface area that adheres to the mother particle surface is determined by using an equatorial surface effect / mathematical model. A particle composite method is disclosed (Patent Document 29).

  However, the above-mentioned avoidance of the aggregation of the mother particles and the child particles and the combination of the child particles on the surface of the mother particles are simultaneously based on the understanding of the powder engineering phenomenon related to the particle dispersion theory in the liquid phase and the nanoparticle packing theory. Otherwise, you will not deal with the essence of technology. Applying the understanding of academic phenomena related to dispersion theory in liquid phase and nanoparticle packing theory that have been elucidated in powder engineering, deduction (which is an important element as an invention) (overview or hypothesis verification, theoretical design, What is structured in terms of overall coordination is not at least as of now. As a result, the improvement of single function such as fluidity (smoothness) as extender pigment and color rendering as pearl pigment is essential, and the essential requirement (inventive step of invention) of synergy of multiple functions of functional cosmetics is essential. It has not been possible to solve the problem.

  One reason for the above analysis of the current situation is that, for example, all the existing technical groups using plate-like particles (= harder to eliminate aggregation than spherical particles) as the mother particles are all organic solvents (= in many cases, hydrophilic surfaces are removed). In the case of an aqueous dispersion medium, both the mother particles and the child particles remain spherical particles. Point up.

  As summarized in the above technical problem (3), when focusing on the technical components as the manufacturing process patents, if the new operating conditions (uniqueness of the invention) are not added, the intended inventive step is achieved. It proves the position of the present invention that cannot be achieved.

  As described above, regarding the control method of the external form and internal structure of one particle and / or particle group (including a powder layer, a particle packed layer, a molded body, a green compact, and the like), its granular substance, and a control device ( From the three viewpoints, 1) extender pigments, (2) pearl pigments, (3) particle compounding methods, the problems of technical components as patents are summarized as follows.

(1) A configuration in which particle / powder uniform dispersion (Breaking Down) and dense filling / molding (Building Up) are simultaneously controlled is impossible.
(2) It is not possible to extract technical items by formulating the powder engineering theory related to the particle dispersion theory in the liquid phase and the nanoparticle packing theory simultaneously as control conditions.
(3) The synergy of pigment function (color rendering property, lubricity, etc.) and medicinal function (ultraviolet ray shielding, etc.) essential for functional cosmetics is impossible.

  As a result, in the composite particles in which the plate-like particles are the mother particles and the nanometer order particles previously solidified (crystallized) are the child particles, the mother particles and the child particles are free from aggregation and the child particles are fine on the surface of the mother particles. It has not been possible at present to satisfy all of the following requirements for uniformly composite particles.

(1) The subtraction (difference) of the transmittance at an optical wavelength of 800 nm and the transmittance at 400 nm of the aggregate (including a powder layer, a particle packed layer, a molded body, a green compact, etc.) of the particulate matter is visible. When each index is defined by subtracting (difference) between light transmittance and transmittance at an optical wavelength of 400 nm by transmittance at 290 nm as UV shielding rate, visible light transmittance is 20% or less and UV shielding rate is 40. %more than,
(2) The internal friction angle of the aggregate of the granular materials is 15 ° or less,
(3) Operation conditions that do not require high-cost artificial operation and are economically satisfactory (improvement of the process),
(4) In particular, a hydrous aluminum potassium silicate having an average particle diameter of 15 μm or less and an aspect ratio (= average particle diameter ÷ average particle thickness) of 100 or less, or a layered silicate, mica, or a plate made of clay mineral A technical component as an invention suitable for a granular material raw material and an additive material made of a metal oxide that has been pre-solidified (crystallized) with an average particle diameter of 0.1 μm or less is required.

  Therefore, in the existing technology, it is related to the particulate matter such as an ordered mixture (uniform composite + aggregation-free) manufacturing method under a realistic concentration condition (for example, 40 wt (% by weight) or more) called a concentrated slurry. We were unable to meet the urgent demands for high-control technology for fine structures.

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  In view of the above-described analysis of the present situation, the present inventors have aimed to develop a form control method for particulate matter, and the particulate matter and control device that can drastically solve the technical problems of the existing technology group. As a result of earnest research, we focused on the progress of understanding of powder engineering and academic phenomena related to particle dispersion theory in liquid phase and nanoparticle packing theory.

  The micro force acting on the particle is composed of van der Waals (or London-van der Waals) attractive force, intermolecular force, electrostatic force, liquid bridging force (capillary condensing force), etc., and handled atmosphere (humidity, vacuum, constituent gas) Composition) and powder characteristics (particle diameter, morphology (external shape, internal structure, etc.), macroscopic flatness, microscopic surface roughness, and hydrophilic (oil repellent) to hydrophobic (water repellent) based on material These are influenced by the properties and the like, and are appropriately selected and controlled in each material system.

  Among them, the present inventors have many electrostatic homo-repulsive forces, electrostatic hetero-cohesive forces, Van der Waals cohesive forces, and liquid-crosslinking cohesive forces in the atmosphere (= water is essentially present) as well as many We paid attention to the fact that it is the dominant factor of the adhesion force acting on the particles in the atmosphere, and is considered to have the greatest influence among the adhesion forces of the particles in the liquid phase.

  In the particle dispersion theory, the liquid phase process is a methodology that is relatively easy to match the controllability of particles / powder and the economics of the process. In the case of uniform dispersion of particles / powder (Breaking Down) But it is also used (Fig. 1). On the other hand, with regard to dense filling / molding (Building Up), various examples of applying a mathematical model such as hexagonal close-packing to an actual material system are mainly performed as a dry (solid phase) process in the tableting process of a preparation. Yes.

  Combining both, electrostatic “repulsive force” is used to uniformly disperse the same kind of mother and child particles, and the child particles that can cover the surface of the mother particles are combined in a stoichiometric composition, while the mother particles and child particles are simultaneously It is possible that a so-called ordered mixture (ordered mixture = homogeneous complex + aggregation-free) that avoids the formation of agglomerates is given.

  However, at present, in the particle dispersion theory, when the child particles capable of covering the surface of the mother particles are added in a stoichiometric composition, although there is a possibility that physical contact between the particles may occur, “(限界) is limited in dispersion. The particle packing theory is not taken into account at all, as if it was “not (= can be infinitely dispersed)”.

  In particular, under the realistic concentration conditions (for example, 40 wt (weight)% or more) of an actual manufacturing site called a concentrated slurry, the calculation formula assumed to be “infinitely dispersible” in this way, the aggregation of the child particles Cannot be avoided. As a result, at present, the formation of agglomeration of the mother particles and the child particles has not been avoided, or if trying to avoid agglomeration, it is a very serious problem that only child particles that are excessively smaller than the stoichiometric ratio can be added. It remains (Figure 2).

  Furthermore, in recent years, there has been a change in the situation that so-called nanometer-sized (submicron or smaller) fine particles (nanoparticles) have been put into practical use. At the academic level (laboratory scale) such as powder engineering, attempts to synergize the particle dispersion theory in the liquid phase with the nanoparticle / packing theory are being carried out from a mathematical approach.

  However, the inventors of the present invention, as their practical application and verification (examples), remain within a model range based on mathematical calculations or a small amount of samples at a laboratory level. There are no precedents that succeeded in verifying material properties on a scale and extracting technically essential items. However, the present inventors, because these are the results obtained by accumulating knowledge based on empirical rules in the past technology group, that the "essential limiting element" of the phenomenon has not been clarified, We thought that the idea of combining knowledge from different fields was rare, and that it was not the limit of industrial technology.

  An object of the present invention is to provide an aggregate of granular materials by a novel form control method that is impossible at present and a method for producing the same.

In order to solve the above problems, the reference invention is a plate-like, rod-like, metal oxide having a particle diameter of less than 30 μm and an aspect ratio (division of particle diameter by particle thickness (quotient)) of 100 or less. In a method for producing a composite particle comprising a spindle-shaped or scale-like granular material (mother particles) and a metal oxide granular material (child particles) having a particle diameter of less than 0.1 μm, , Dispersed in a liquid substance (dispersion medium) selected from aqueous solvents, alcohols or ether solvents, to produce a liquid substance (mixed liquid) containing a particulate substance, and the degree of dispersion of the granular substance and the liquid substance in the mixed liquid The liquid mixture is determined by the interaction between van der Waals attractive force acting in the mixed liquid and the electrostatic repulsion force based on the overlap of the interfacial electric double layer. Grain inside To calculate the average surface distance of substance (L _DLVO), at the same time, the solid concentration of particulate matter contained in the liquid mixture, determined by the particle diameter and the average surface distance of the particulate matter in the mixed liquid (L _(Woodcock ) is calculated separately, and the particulate matter in the mixed liquid is controlled to be highly dispersed so that the average distance between the surfaces of the particulate matter in the mixed liquid becomes “L _DLVO ≧ L _Woodcock ”. By making the mixed liquid a liquid substance (droplet) of less than 100 μm and controlling the speed of drying of the liquid substance so that the control temperature of the droplet becomes −100 to 10000 ° C., the mother particle and the child particle The composite particles having the form, shape, or structure in which the child particles are coated in a uniform state or a locally controlled non-uniform state on the surface of the mother particles without agglomerating alone. Method for producing a composite particle according to symptom is.
The first invention is a method for producing a solid or hollow aggregate obtained by agglomerating a particulate material of a metal oxide having a particle diameter of less than 0.1 μm.
Dispersing the particulate material in a dispersion medium selected from an aqueous solvent, alcohol or ether solvent to produce a mixed liquid containing the particulate material,
The average inter-surface distance of the particulate matter in the mixed liquid determined by the interaction between both micro forces of the van der Waals attractive force acting in the mixed liquid and the electrostatic repulsive force based on the overlap of the interfacial electric double layer ( L _DLVO ) and calculating the average inter-surface distance (L _Woodcock ) of the particulate material in the mixed liquid determined by the solid content concentration and particle size of the particulate material contained in the mixed liquid,
Dispersing the particulate material in the mixed liquid so that the average inter-surface distance of the particulate material in the mixed liquid is “L _DLVO ≧ L _Woodcock ”;
In the method for producing an aggregate, the mixed liquid is made into droplets of less than 100 μm, and the dispersion medium is evaporated from the droplets and dried.

In addition, the reference invention is a metal oxide plate-like, rod-like, bell-like or scale-like granular material (mother particle) produced by the above production method and having a particle diameter of less than 30 μm and an aspect ratio of 100 or less. ) And a particulate material (child particle) of metal oxide having a particle diameter of less than 0.1 μm, and the surface of the mother particle without agglomeration of the mother particle and the child particle alone The composite particles are characterized by having a shape, shape, or structure in which the child particles are coated in a uniform state or a locally controlled non-uniform state.
Moreover, 2nd invention exists in the aggregate manufactured by the manufacturing method of the said 1st invention.

  In addition, in the material characteristics of the aggregate using the above granular material as a raw material, the visible light transmittance and the ultraviolet shielding property are selected as evaluation indexes, and the subtraction (difference) of the transmittance at the optical wavelength of 800 nm by the transmittance at 400 nm is calculated. The visible light transmittance, the subtraction (difference) of the transmittance at the optical wavelength of 400 nm by the transmittance of 290 nm is defined as the ultraviolet shielding rate, each index is defined, and the visible light transmittance is 20% or less, and / or It is preferable that the ultraviolet shielding rate is 40% or more.

Further, the reference invention is an apparatus for use in the above-described method for producing a granular substance / group, and is a plate, rod, spindle made of metal oxide having a particle diameter of less than 30 μm and an aspect ratio of 100 or less. A granular substance / group composed of a granular or scale-like granular substance (mother particle) and a metal oxide granular substance (child particle) having a particle diameter of less than 0.1 μm, an aqueous solvent, alcohol or ether Means for producing a liquid substance (mixed liquid) that is dispersed in a liquid substance (dispersion medium) selected from a system solvent and containing all the granular substance groups, and the average distance between the surface of the granular substances in the mixed liquid is _expressed as “L _DLVO ≧ "L _Woodcock " means to highly disperse the particulate material in the mixed liquid, at the same time, means to make the mixed liquid a liquid material (droplet) of less than 100 μm, the temperature of the droplet is -100 to 10000 ° C So that the liquid Means to accelerate the drying of the particulate material, and the mother particles are coated on the surface of the mother particles in a uniform state or in a locally controlled non-uniform state without agglomeration of the mother particles and the child particles alone. An apparatus for producing a granular substance / group, characterized in that it is a device for producing a granular substance / group having a form, shape or structure.

Next, the present invention and the reference invention will be described in more detail.
As a result of intensive studies to achieve the above idea, the present inventors specifically combined the following five points [A] to [E] simultaneously, continuously, or intermittently. And embodied the invention;

1) [A] A plate-like particle having a high aspect ratio of micron order and an additive substance made of a metal oxide that has been solidified (crystallized) with an average particle diameter of 0.1 μm or less, Means [A] for producing a liquid substance (hereinafter referred to as a mixed substance) dispersed in a liquid substance (hereinafter referred to as a dispersion medium) and containing all particulate substances

2) [B] In a mixed substance, which is determined by the interaction between both micro forces of van der Waals attractive force acting on the second component in the mixed substance and electrostatic repulsive force based on the overlap of the interface electric double layer Means for calculating the average inter-surface distance (hereinafter referred to as L _DLVO ) between the second components of [B]

3) [C] Means for calculating the average surface distance between the second components in the mixed material (hereinafter referred to as L _Woodcock ) based on the solid content concentration of the second component contained in the mixed material and the diameter of the second component [C]
4) [D] Means in which the average surface-to-surface distance between the second components in the mixed material is L _DLVO ≧ L _Woodcock [D]
5) [E] Means for converting the mixed material into droplets of less than 100 μm and moving the droplets to a device that provides a heat treatment temperature in the range of −100 to 10000 ° C. [E]

With regard to the means [A], that is, the target material group and the dispersion method in the liquid substance, the present technology level and the applicability to the particle composite technology were reviewed in terms of equipment engineering.
As a result, from the viewpoint of the development of new materials such as cosmetics, pharmaceuticals, and industrial fillers, (a) sericite (sericite), (b) dispersion media, (c) additive substances, and (d) water-based liquid substances. We focused on four types of dispersion.

(A) Sericite (sericite) is an outdoor name for micaceous clay minerals, collectively called sericite, muscovite, and phlogopite. Hydrothermal activity, action in metamorphic rocks, and diagenesis of sedimentary rocks. A substance characterized by having a pearly luster and slipperiness due to the production of Hydrous potassium aluminum silicate comprising sericite from turfgrass (composition of SiO ₂ 60.0% or less and Al ₂ O ₃ 0.0% or more, and K ₂ O 6.0% or more and an average particle size of 15 μm or less), Alternatively, a layered silicate, mica, or clay mineral is suitable, but if it is an oxide having a layered crystal structure mainly composed of silicon oxide (silicic acid, etc.) and aluminum oxide (alumina, etc.), Substances with different amounts of trace components may be used.

  Further, mica and clay mineral are oxides having a layered crystal structure mainly composed of silicon oxide (silicic acid or the like) and aluminum oxide (alumina or the like), and are not particularly limited. Further, the solubility is not limited, and even if it is a water-insoluble mica-based powder, even if it is a substance having the above composition, even if it is a substance that is easily soluble in any solvent, it is not a problem. Absent.

  (I) Aqueous liquid material (hereinafter referred to as dispersion medium) refers to ion-exchanged water, distilled water, etc., and the raw material granular material (sericite) and additive material are dissolved in an ionic state, or in granular or colloidal form. Examples of the dispersed solution or slurry are not particularly limited.

  (C) The particulate material, liquid material or gaseous material (hereinafter referred to as additive material) for controlling the shape or structure of sericite powder is, for example, the state of the material (solid, liquid or gas, etc.), material (metal or There are no particular restrictions on the polymer, oxide, non-oxide, etc.), size, amount added, etc., metal such as gold, silver, copper, platinum, iron, titanium, titanium compound, boron compound, zinc Various functional imparting / accelerating agents such as polyethylene compounds, various polymer additives such as polyethylene glycol, polyvinyl alcohol, and gum arabic, various surfactants, various binders, and particulates that have the property of generating gaseous substances when decomposed by heating Examples thereof include substances, liquid substances, gaseous substances (foaming agents such as azo substances), sericite, and clay mineral-based plate-like powders other than sericite.

  (D) Dispersion in a water-based liquid substance is a grinding-type wet-stirring ball mill, that is, a stator having a vertically-oriented cylindrical shape and having a jacket through which cooling water is passed and filled with beads. A shaft disposed on the stator shaft and rotatably supported on the upper portion of the stator, the shaft having an upper shaft center as a hollow discharge passage, a separator that rotates integrally with the shaft, and a shaft below the separator A pin or disk-shaped rotor that protrudes in the radial direction, a shaft that is fixed to a shaft that protrudes upward from the stator, a pulley that is belted with a motor pulley, and a shaft bottom end of the stator facing the shaft shaft end. The material slurry supply port with a screen for separating beads and a rotary joint attached to the opening end of the upper end of the shaft protruding from the stator The rotor is composed of a pair of disks fixed at a certain interval in the axial direction of the shaft and a blade connecting the two disks to form an impeller. The centrifugal force is applied to the beads, and the beads are separated by the difference in specific gravity, that is, beads having a relatively large specific gravity are blown outward in the radial direction, while a slurry having a relatively small specific gravity is opened between the disks to open the shaft in the radial direction. A medium agitation type pulverizing apparatus that discharges upward through the discharge passage from the outlet hole formed in is suitable, but there is no particular limitation.

  For example, pulverizers such as jaw crushers, ball mills, jet mills, vibration mills, planetary mills, horizontal cylindrical types and V types as shown in JIS-Z8840, etc. Blade-type kneaders and extrusion molding machines, fluidized beds (including medium and vibration types), rotating drum / pan / spray type granulators / dryers, cake / centrifugal type classification / filtration / sedimentation / Examples include solid-liquid separators such as dehydrators, sieving / dust collectors such as cyclones and bag filters, and the like.

  By various theoretical and experimental studies, the present inventors have obtained high-aspect-ratio micron-order sericite (sericite) and pre-solid (crystallized) titania nanoparticles having an average particle size of 0.1 μm or less. A system in which the medium stirring type pulverizer is applied to distilled water as a dispersion (disintegration) apparatus is suitable as a method, but the material type and method are not particularly limited.

Regarding the means [B], that is, the particle dispersion theory of the liquid phase process, the current technical level and the applicability to the particle composite technology were reviewed in terms of equipment engineering.
As a result, from the viewpoint of developing new materials such as cosmetics, drugs, and industrial fillers, we examined the micro forces (intermolecular force, electrostatic force, liquid crosslinking force, capillary condensing force, etc.) that act on the particles. der Waals attractive force, (a) electrostatic repulsive force based on the overlap of the interfacial electric double layer, (c) the average inter-surface distance between the second components in the mixed material determined by the interaction between both micro forces (hereinafter referred to as L _DLVO) We focused on three types.

(A) Van der Waals (or London-van der Waals) attractive force is a general term for cohesive force that works between neutral atoms and molecules that do not have an electric charge. Van der Waals attractive potential VA is calculated by the following theoretical calculation. formula,
V _A = −A × d ÷ 24 ÷ H
However,
A is the Hammer constant of the substance (10-20J)
d is the average particle size (m)
H is the average inter-surface distance (m) between particles on which attractive force is acting
Calculate from the above formula.

(B) Electrostatic repulsive force based on the overlap of interfacial electric double layer is the change in ion concentration caused by the formation of an interfacial electric double layer on the surface of particles dispersed in a liquid substance and the overlapping of the electric double layers of particles. The electrostatic repulsion potential VR is a repulsive force acting to lower (osmotic pressure generation), and is expressed by the following theoretical formula:
V _R = π × d × εr × ε0 × Ψ0 ² × ln {1 + exp (−κH)}
However,
εr is the dielectric constant of particles placed in air (10 ⁻²⁰ J)
ε0 is the dielectric constant of vacuum (F / m)
Ψ0 is the electric double layer thickness (Debye Length), and usually ζ potential is used. Κ is the inverse of the electric double layer thickness (Debye Length).
Calculate from the above formula.

(C) Mean surface distance (L _DLVO ) between the second components in the mixed material determined by the interaction between both micro forces ((a) van der Waals attraction and (b) electrostatic repulsion) The van der Waals attractive potential VA and the electrostatic repulsion potential VR are sums (however, since the sign is the opposite sign, it is actually a difference), that is, the potential barrier VT is expressed by the following empirical formula:
V _A + V _R <(10-20) × σ × T
However,
σ is Stefan-Boltmann constant T is absolute temperature (K)
The average inter-surface distance H between particles (hereinafter, L _DLVO ) is calculated so that the peak value (V _Tmax ) of the potential barrier VT satisfies the above formula.

  In general, the smaller the particle size, the smaller the potential barrier even at the same surface potential due to electrostatic repulsion required by DLVO (Derjaguin, Landau, Verwey and Overbek) theory, and dispersion stabilization due to electrostatic repulsion becomes more difficult. Therefore, as a theoretical calculation example, FIG. 6 shows a calculation example of a potential curve in consideration of van der Waals attraction and electrostatic repulsion calculated from the DLVO theory with the same surface potential and counter ion concentration (nanometer). 20 nm as an example, 300 nm as a submicron example, and 100 nm as an intermediate size).

That is, for particles of submicron or larger, the peak value V _Tmax of the potential barrier necessary for particle dispersion is 10 to 20 times the product of the Boltzmann constant and the absolute temperature, and it is sufficiently dispersible under this surface potential condition. is there. On the other hand, nanoparticles having an average particle diameter of 20 nm or the like have a very low potential barrier, and aggregation occurs under these conditions. Dispersion of nanoparticles requires a high surface potential of hundreds of mV or more, but such a high surface potential cannot be obtained by ordinary methods.

  Therefore, at present, in the particle dispersion theory, if the child particles that can cover the surface of the mother particles are added in a stoichiometric composition, there is no limit to the dispersion even though physical contact between the particles may occur. Thus, the particle packing theory is not considered at all. As a result, at present, it has not been possible to avoid the formation of agglomeration of each of the mother particles and the child particles, or if it is attempted to avoid the aggregation, only a small amount of child particles can be added in excess of the stoichiometric ratio. This theoretical calculation result is shown in FIG.

Note that the average inter-surface distance L _DLVO between the second components in the mixed material, which is determined by the interaction between the two micro forces of the van der Waals attraction and the electrostatic repulsion based on the overlap of the interfacial electric double layer, Although the method calculated | required by the DLVO theory was illustrated, it does not restrict | limit in particular, The simple calculation on the realistic concentration conditions (for example, 40 wt (weight)% or more) of the actual manufacturing site called the target concentrated slurry As long as it can provide the method, it is not limited thereto.

Regarding the particle packing theory in the means [C], that is, in the solid phase process (dry molding) (and in the liquid phase to which it is applied), regarding the current technical level and applicability to the particle composite technology, Reexamined. As a result, from the viewpoint of developing new materials such as cosmetics, pharmaceuticals, and industrial fillers, the average surface distance H between particles and the average particle diameter d, and the concentration F of particles charged (filled) into the dispersion system are 3 It was found that the geometric relationship (mathematical model) of the kind should be considered.
Specifically, for example, the following theoretical calculation formula by general-purpose hexagonal close packing,
H = d × {(π ÷ 3 ÷ √2 ÷ F) ^ (1/3) −1}
Or the calculation formula proposed by Woodcock et al.
H = d × {√ (1 ÷ 3 ÷ π ÷ F + 5/6) −1}
The average inter-surface distance of the particles is calculated from the above formula.

FIG. 7 shows an example of theoretical calculation of the average particle surface distance (hereinafter referred to as L _Woodcock ) according to the Woodcock equation (similar to FIG. 8, it is set to 20, 100, and 300 nm). That is, for particles of submicron or more, it is necessary for the dispersion of the particles required by the DLVO theory shown in FIG. 6 unless the particle concentration F is 50 vol (volume)% or more under common-sense operating conditions of the surface potential. It can be seen that the peak value of the potential barrier is not reached. On the other hand, in the case of nanoparticles having an average particle size of 20 nm or the like, the allowable particle concentration F is several tens vol%, compared with the actual concentration conditions (for example, 40 wt (weight)% or more) at the actual manufacturing site called concentrated slurry. It is expected to be very insane (so-called “dilute” slurry) values.

Note that the average inter-surface distance L _Woodcock between the second components in the mixed substance is determined by the hexagonal close packing model and the Woodcock equation according to the solid content concentration of the second component contained in the mixed substance and the diameter of the second component. Although the method to obtain | require was illustrated, it does not restrict | limit in particular, The simple calculation method on the realistic concentration conditions (for example, 40 wt (weight)% or more) of the actual manufacturing site called the target concentrated slurry is provided. If it can be obtained, it is not limited thereto.

Regarding the means [D], that is, the average distance between the surfaces of the second components in the mixed material, the present technology level and applicability to the particle composite technology were reviewed in terms of equipment engineering. As a result, from the viewpoint of developing new materials such as cosmetics, drugs, and industrial fillers, paying attention to the second component in the mixed material (that is, the constituent component on the fine side in the dispersion), the mutual average inter-surface distance Has been found to satisfy the following conditions.
L _DLVO ≧ L _Woodcock

Figures 8 and 9 show the results of calculation of the target nanometer-order particle L _DLVO at two surface potentials, L _Woodcock as the nanometer and submicron, and the hexagonal close-packed model of the nanometer order particle for comparison. It illustrates together. In FIGS. 8 and 9, a line with a representative value of 15 is indicated by a dotted line as an example of a product of the Stefan = Boltzmann constant, which is a dispersible threshold according to the DLVO theory, and an absolute temperature.

  That is, in the case of nanometer order particles, the average inter-surface distance between the second components reaches the level of several nanometers at the dispersion limit under common-sense operating conditions of the surface potential. Under such conditions, the allowable particle concentration F is several tens vol% (several vol% @ Woodcock equation to 30 vol% @ hexagonal close packing model), which is an acceptable limit.

However, the inventors pay attention to the constituent component on the fine side in the dispersion system, achieve the above means [D] (L _DLVO ≧ L _Woodcock ) for the second component (child particles), and disperse In the main component (mother particles) in the system (and also in the mixed material to which the child particles are added), the actual concentration conditions (for example, 40 wt (wt)% or more) at the actual manufacturing site called the target concentrated slurry ) Was found.

Here, the conversion method of volume% and weight% of the mixed liquid is exemplified by a titania-mica (sericite) composite system:
* Titania weight% = 20 wt% (example: 30 ÷ (30 + 120) g)
* Solid content% by weight = 30 wt% ((30 + 120) ÷ (30 + 120 + 350) g)
* Titania: Average true density of mica 2.4 g / cm ³ (4 g / cm ³ × 20 wt% + 2 g / cm ³ × 80 wt%)
* Solid content volume% = 15 vol% (divide by 2.4)

As described above, as shown in FIG. 8 (and FIGS. 12 and 13), if L _{DLVO to} L _Woodcock are used and the second component (child particle) mobility is suppressed, locally controlled particle complexation, hollow granules and controlled Sinking granules can be produced (eg, coarsening of the particle diameter, electrical neutralization by silica surface treatment, improving the degree of aggregation, etc.).

As shown in FIG. 9 (and FIGS. 12 and 13), if L _DLVO > L _Woodcock and the second component (child particle) mobility is increased, uniform particle composition and solid granules can be produced (example: For example, the particle size is refined and the surface is electrically polarized by alumina treatment to suppress the degree of aggregation. The present invention is embodied based on such device engineering knowledge.

  Regarding the means [E], that is, the “liquid substance → particulate substance” conversion process, the current technical level and applicability to the particle composite technique were reviewed in terms of equipment engineering. As a result, from the viewpoint of developing new materials such as cosmetics, pharmaceuticals, and industrial fillers, (a) mixed substances → droplet-like substance conversion process, (b) liquid-like substance heat treatment process, (c) liquid substance → We paid attention to three types of conversion process of particulate matter.

  (A) Examples of the conversion process of the mixed substance → droplet-like substance include various spraying methods such as a rotating disk method, a gas nozzle method such as a two-fluid method, an ultrasonic atomization method, an electrostatic spraying method, and the like. Among them, the three-fluid or four-fluid nozzle method, that is, a method capable of producing a few to several tens of μm droplets that can theoretically contain only one target micron-order mother particle with high productivity, When a liquid is supplied to an inclined surface, the supplied liquid is thinly stretched with an air flow that flows at high speed along the inclined surface to form a thin film flow, and when the thin film flow is injected (sprayed) into the gas from the tip of the inclined surface, a sharp point is obtained. Two or more different liquids are supplied in the middle of two or more inclined surfaces provided on both sides with an edge as a boundary, and the thin film is stretched thinly with an air flow that causes the liquid supplied to the inclined surfaces to flow at high speed. The method is characterized in that a thin film flow is jetted (sprayed) into the gas from the edge of the tip of the inclined surface.

  This spraying method includes a three-fluid nozzle method in which a concentric thin film flow is flown on a conical (pencil-shaped) cone surface, and a four-fluid nozzle in which two or more kinds of linear liquids are flowed on a triangular prism (knife-shaped) slope. There is a law. However, any method may be used as long as it is a method capable of realizing a realistic concentration condition (for example, 40 wt (wt)% or more) of an actual manufacturing site called a target concentrated slurry.

  In the preparation of mixed substances, the hydrolysis reaction between the metal alkoxide and the particle surface hydroxyl group is not limited to the material, but is considered from the viewpoint of the production method to achieve high functionality by controlling the shape and structure of the powder. , Local hydrolysis using a water film formed on the surface of particles in a humidified atmosphere, heteroaggregation using the charge sign difference of ζ potential of the electric double layer proposed by Harding (1972) et al., Emulsion method, suspension There are turbid polymerization methods.

  These so-called “liquid phase processes” are methods that are relatively common in the cosmetics and pharmaceutical fields to which powders made from clay minerals, especially plate-like or scale-like powders, are applied (microcapsule production). It is also a typical liquid phase method relating to the control of the shape and structure of the powder. The manufacturing principle uses uniform dispersion of constituent components resulting from the repulsion of the aqueous phase and the oil phase, and composite using a surfactant. It is exemplified as a method having a relatively high controllability of the particle structure, but is not particularly limited, and is classified into a general liquid phase method (for example, wet surface treatment, silane coupling, titanyl sulfate). There is no problem even if it is a hydrolysis method or a sol-gel method).

  Among them, the hetero-aggregation method (for example, Non-Patent Documents 41 to 43) using the charge sign difference of the ζ potential of the electric double layer is a general-purpose manufacturing method proposed by Harding et al. In the 1970s, and is called a target concentrated slurry. Highly reliable under realistic concentration conditions (for example, 40 wt (% by weight) or more) at the actual manufacturing site, electrostatic “repulsive force” is applied to uniform dispersion of the same type of mother and child particles, and electrostatic “attraction” is applied. It is recommended to use it together for uniform adhesion of different types of mother and child particles.

FIG. 10 illustrates the relationship between pH and ζ potential of a suitable substance (material) group. Plate-like or scale-like powders made from clay minerals vary depending on the constituents, but are roughly intermediate between silica (SiO ₂ ) and alumina (typically γAl ₂ O ₃ and αAl ₂ O ₃ ). Indicates the value. On the other hand, the ζ potential of titania suitable as the second component (child particle) nanometer order particle is also relatively close to that of the clay mineral (depending on the material). This is disadvantageous from the viewpoint of using electrostatic "attraction" together.

Therefore, a method of coating the surface of titania particles with alumina (particularly polymorphic alumina such as γAl ₂ O ₃ ) is shown as a preferred example. However, depending on the selection of other material systems, for example, a system having a large charge sign difference between the ζ potential of clay mineral and titania, other than alumina (for example, polymer coating if positive charging is advantageous), etc. are particularly limited. Is not to be done.

  (A) In the heat treatment process of the liquid droplet material, the liquid material droplets in which the raw material is dissolved (or dispersed) are transported to the temperature control field while controlling the droplet diameter, and the dispersion medium in the droplets is dried. As long as it uses the physical phenomenon that occurs from around the droplet, spray drying, spray pyrolysis, mist pyrolysis, supercritical, freeze drying, thermal plasma, gas phase reaction, etc. Although illustrated, it is not particularly limited.

  (C) An example of an apparatus configuration used when the conversion process of liquid substance → particulate substance is embodied. Considering mass productivity and continuous productivity, the gas phase synthesis method (gas phase method) is relatively superior when a production method for controlling the shape and structure of the powder is examined. Above all, the “droplet process” centered on the “spray method” such as spray drying method, spray pyrolysis method, freeze drying method, supercritical method, etc. is a typical example of success in industrializing lactose and inhalation preparations. It is a phase method.

  That is, a mixed material is prepared by dissolving / dispersing the constituent granular materials in an aqueous dispersion medium, and this is liquidized from a low temperature to a heating temperature range in each process of spraying → drying → precipitation → crystallization (solidification). When the droplets are introduced, the solvent and the like evaporate from the droplets, and when the solute deposits from the surroundings in the liquid substance state, the solutes having a low solubility tend to precipitate first (this Other solutes, etc. are still in the liquid state inside the droplets). Furthermore, when the droplets travel through the heating section, and the solvent evaporates and precipitation of solutes progresses, target composite particles are generated.

  The method for transporting the droplets is preferably a method for transporting the droplets with a gas flow of a gaseous substance such as an inert gas. Any method may be used.

  A temperature control field or a device that can be given a temperature control function simultaneously or continuously or intermittently is equipped with reaction tubes and reaction walls made of quartz, alumina, heat-resistant steel, etc. to control the atmosphere and the efficiency of generated heat energy A closed structure that can be used in a general manner is preferable, but a free space may be used if there is no problem in the reaction.

As the reaction driving force, self-excited reaction of the raw material is most desirable from the economical viewpoint, but external heating (CVD) method frequently used for the purpose of promoting the reaction and shortening the reaction time ( Electric furnace heating) method, plasma, arc, flame (“flame” means complete combustion, a phenomenon that is completely decomposed into water vapor (H ₂ O) and carbon dioxide (CO ₂ )), high Partial combustion of the reduction ratio (where “reduction ratio” is the ratio of water vapor + carbon dioxide to hydrogen (H ₂ ) + carbon monoxide (CO)), ice or liquid nitrogen, carbon dioxide in a supercritical state, etc. This does not preclude the use or combination of these.

  As a method of using the produced composite particles or aggregates, and a molded body or sintered body using the composite particles or aggregates, cosmetic materials are preferable, but further, protection and insulation of semiconductor elements, etc. Packaging (sealing) materials, insulating materials, electrodes / conductive materials, electrorheological fluids, chemical mechanical polishing slurries, ceramic molding process raw materials such as injection molding and casting, substrate materials, ceramic electronic materials, ceramics Examples of the material system include structural materials, various filler powders such as fillers and bulking agents, pulmonary drugs for inhalation therapy, and drug powders for tablets.

  The medicinal (makeup) function such as the ultraviolet shielding ability (and visible light transmission ability) is based on the condition that the state used on the human skin as a cosmetic product can be schematically reproduced (simulated). For example, cosmetic raw materials are mixed and kneaded in a solvent such as silicone, which is actually blended as a foundation composition, with pigments and paints such as Hoover Mahler, paint concentration, hue, meatiness, consistency, and color matching tester And the sample film disperse | distributed with the doctor blade etc. between the glass substrates etc. is illustrated. The optical properties are evaluated by spectrophotometer (integrated sphere unit is optional), digital variable glossiness meter (Suga Test Instruments Co., Ltd.) of OPACITY CHARTS (manufactured by LENETA, etc.), black / whiteness (hiding ratio) color difference Any method, such as a total, may be used.

  In general, in the measurement of transmittance of film-like samples such as ultraviolet rays and visible rays, the reflection, refraction, scattering, and shielding effect (ability) under the ultraviolet to visible light to infrared region is specific to the substance (for example, titania or zinc oxide). Depends on the synergistic effect of the light absorption effect based on the band gap and the refraction effect and the scattering (shielding) effect based on the primary particle size and secondary particle size (dispersion size or degree of aggregation) of the cosmetic raw material dispersed in the film. . The evaluation of the medicinal effect (makeup) function such as the ultraviolet shielding ability (and visible light transmission ability) is not limited as long as it satisfies the resolution of these various effects.

  Pigment (makeup) functions such as texture, wrinkle concealment, smoothness, and feeling of use are not raw data obtained by direct measurement of the adhesive force acting on each particle, but an aggregate of individual particles The numerical values obtained from the powder layer were normalized by weight and surface area. That is, a method or device that is a calculated value and not raw data obtained by direct measurement.

  For example, the angle of repose, the angle between the free surface of the deposited powder layer and the horizontal plane, the spatula angle, the difference angle, the shear stress test method using the Jenike cell with ISO planning, the fracture envelope of the Mohr stress circle Calculated based on the internal friction angle, empirical index on fluidity and jetting based on Carr's proposal, solidification / relaxation bulk density on weight or volume basis, compression ratio, ratio of both, tensile fracture test method , Tablet rupture test method, bending test method, and chemical analysis methods such as specific surface area, powder charge amount, particle diameter and aspect ratio (= the ratio of the maximum length and thickness of plate-like particles in the cosmetic industry) , Hydrophilic / hydrophobic balance of powder layer, electron microscope observation, screening and static electricity evaluation, questionnaire survey with multiple monitors (so-called sensory evaluation), artificial skin model (bio skin) used on human skin Reproduction (Simulation) powder was characterization, etc. are exemplified.

  As a preferred example, the method of quantifying pigment functions such as lubricity and feeling of use includes evaluation of the internal friction angle based on the shear stress test method by Jenike cell etc., but the actual production site called the target concentrated slurry Any method may be used as long as it can realize the realistic concentration conditions (for example, 40 wt.% Or more).

The following effects are produced.
(1) Control method of external form and internal structure of one particle and / or particle group (including powder layer, particle packed layer, molded body, green compact, etc.), and its composite particles and aggregates, and control Regarding the equipment, the technical problems of the existing technology from the three viewpoints of 1) extender pigment, 2) pearl pigment, and 3) particle composite method,
1) A configuration in which particle / powder uniform dispersion (Breaking Down) and dense filling / molding (Building Up) are controlled simultaneously is impossible.
2) It is impossible to extract technical items based on the powder dispersion theory in the liquid phase and the nanoparticle packing theory as simultaneous control conditions.
3) Synergy of pigment function (color rendering property, lubricity, etc.) and medicinal function (ultraviolet ray shielding, etc.) essential for functional cosmetics is impossible.
The above three drawbacks can be overcome.
(2) And, further,
1) Subtraction (difference) of the transmittance at an optical wavelength of 800 nm of a composite particle or an aggregate of the above-mentioned aggregates (including a powder layer, a particle packed layer, a molded body, a green compact, etc.) by a transmittance of 400 nm. When each index is defined by subtracting (difference) from the transmittance at 290 nm to the visible light transmittance, the transmittance at the optical wavelength of 400 nm, the ultraviolet light shielding rate, the visible light transmittance is 20% or less, and the ultraviolet shielding rate Is over 40%,
2) The internal friction angle of the lubricity / use feeling index of the composite particle or the aggregate of the aggregate is 15 ° or less,
3) Operation conditions that do not require costly human operation and are economically acceptable (improvement of the process),
4) In particular, hydrated aluminum potassium silicate having a mean particle diameter of 15 μm or less and an aspect ratio (= average particle diameter ÷ average particle thickness) of 100 or less, or lamellar silicate, mica, or plate-like granules made of clay mineral A technical component suitable as an invention suitable for a material raw material and a pre-solidified (crystallized) metal oxide additive having an average particle size of 0.1 μm or less,
The remarkable effect that the four purposes can be achieved is achieved.
(3) As a result, in the composite particles in which the plate-like particles are the mother particles and the nanometer order particles previously solidified (crystallized) are the child particles, the aggregation of the mother particles and the child particles is free, and the child particles are formed on the surface of the mother particles. It is possible to provide a novel shape control method, a composite particle, and a control device, which are impossible at present, that the particles can be finely and uniformly compounded.
(4) Realizing the theoretical particle compounding method of powder engineering as a methodology for real materials, and realistic concentration conditions (for example, 40 wt ( It is useful for expanding the technical field of mica-based particulate materials used as fillers and cosmetics, as well as an ordered mixture (uniform composite + aggregation-free) manufacturing method (by weight)%).

It is a technology positioning map that clearly shows the difference between the present invention / reference invention and the existing technology. It is a patent map which shows each structure, relationship, and difference (difference) between the present invention / reference invention and the prior invention. It is a list of technical outlines of the present invention and reference invention (the difference from the prior invention is clearly shown). It is the list figure which illustrated STF (novelty and control condition) of this invention and reference invention. It is a list figure of all the contents of an example and a reference example. The control mechanism of the first half of the technical features of the present invention / reference invention (surface potential control in the liquid phase) (calculation example of potential curve considering van der Waals attraction and electrostatic repulsion calculated from DLVO theory) (1) 20 nm, (2) 100 nm, (3) 300 nm). This is the control mechanism of the latter half of the technical features of the present invention / reference invention (particle-to-surface distance control of particle filling) (particle average surface distance L _Woodcock theoretical calculation example by Woodcock equation, (1) 20 nm, (2) 100 nm, (3) 300 nm). It is a control mechanism of the technical feature of the present invention / reference invention (fusion of surface potential and inter-surface distance control) ((1) L _{DLVO of} nanometer order particles (two types of surface potentials of 25 and 50 mV)), ( 2) L _{Woodcock of} each hexagonal close packed model of submicron particles / nanoparticles / nanoparticles). This is a case where the technical feature of the present invention / reference invention is “L _DLVO ≧ L _Woodcock ” of 50 nm. Among the technical features of the present invention / reference invention (micro force control), there are two types of electrostatic force control mechanisms (relationship between pH and ζ potential of substances (materials) suitable for the present application, clay, kaolin, (γ alumina, α alumina, silica). It is the first half of the reference example (particle composite of uniform and local control). It is the list figure which illustrated the control mechanism (control of mobility) and STF " _LDLVO > = _LWoodcock " of the first half of the reference example (uniform and local control particle composite). It is the list figure which illustrated the relationship of the control mechanism (control of mobility) of an Example (solid and hollow granulation) and the technical feature " _LDLVO > = _LWoodcock ". It is an improvement result and a list | wrist of the visible light transmittance | permeability and ultraviolet-ray shielding property of an Example and a reference example. The scanning electron micrograph of the reference example 1 is shown. (<1-1> titania 20 wt%, laboratory level preparation of fine particle titanium oxide). The scanning electron micrograph of the reference example 2 is shown. (<1-2> titania 25 wt%, laboratory level preparation of fine particle titanium oxide). The scanning electron micrograph of the reference example 3 is shown. (<1-3> titania 50 wt%, preparation of laboratory level of fine particle titanium oxide). The scanning electron micrograph of the reference example 4 is shown. (<1-4> titania 15 wt%, lab level preparation of fine particle titanium oxide). <1> Lab level preparation of fine particle titanium oxide [Reference Example 1] to [Reference Example 4] are the results of improving the visible light transmittance and the ultraviolet shielding property. The scanning electron micrograph of Reference Example 5 is shown. (<2-1> standing for 1 week (titania 20 wt%) / preparation of production specifications). The scanning electron micrograph of Reference Example 6 is shown. (<2-2> Mass production type (titania 25 wt%) and preparation of production specifications in one week of standing). <2> Production specifications (slurry standing and treatment amount) [Reference Examples 5 to 6] are the results of improving the visible light transmittance and the ultraviolet shielding property. The scanning electron micrograph of Reference Example 7 is shown. (<3-1> Ethanol 10 wt% mixed dispersion medium / dispersion and antibacterial organic solvent combined use). The scanning electron micrograph of Reference Example 8 is shown. (<3-2> Ethanol 10 wt% dielectric constant adjusting additive / dispersion and antibacterial organic solvent combined use). The scanning electron micrograph of Reference Example 9 is shown. (<3-3> 100 wt% ethanol / dispersion and antibacterial organic solvent combined use). <3> It is an improvement result of visible light transmittance and ultraviolet shielding property of the organic solvent ethanol combined use [Reference Examples 7 to 9] for dispersion and bacteria prevention. The scanning electron micrograph of Reference Example 10 is shown. (<4> Strengthening of fine plasma melt bead / medium stirring control) The scanning electron micrograph of Reference Example 11 is shown. (<5-1> There is an edge boundary of the thin film flow, and the spray amount is increased (four-fluid nozzle method)). The scanning electron micrograph of the reference example 12 is shown. (<5-2> No edge boundary in thin film flow, increase in spray amount (4-fluid nozzle method)). The scanning electron micrograph of Reference Example 13 is shown. (<5-3> Preparation of production specifications and increase in spray amount (four-fluid nozzle method)). <5> Increase in spray amount This is a result of improving the visible light transmittance and the ultraviolet shielding property of the four-fluid nozzle method [Reference Examples 11 to 13]. The scanning electron micrograph of Reference Example 14 is shown. (<6-1> Types of fine nanoparticles and fine titanium oxide (particle diameter and external shape)). The scanning electron micrograph of Reference Example 15 is shown. (<6-2> Types of large spherical nanoparticle / fine particle titanium oxide (particle diameter and external shape)). The scanning electron micrograph of Reference Example 16 is shown. (<6-3> Types of spindle-shaped nanoparticles / fine-particle titanium oxide (particle diameter and external shape)). <4> Enhanced Medium Stirring Fine Beads 15 μm [Reference Example 10] <6> Fine Titanium Oxide Type: Particle Size and Shape [Reference Examples 14 to 16] These are the results of improving the visible light transmittance and ultraviolet shielding properties. The scanning electron micrograph of Reference Example 17 is shown. (<7-1> Control of affinity with medium (hydrophobization) / control of surface charge of mother particles). The scanning electron micrograph of Reference Example 18 is shown. (<7-2> Positive charge on both end face and table face, surface charge control of mother particle). <7> Mother particle charge control: results of improvement in visible light transmittance and ultraviolet shielding property of synthetic mica and alumina [Reference Examples 17 to 18]. The scanning electron micrograph of Example 1 is shown. (<8-1> solid granules, 5 micron level). The scanning electron micrograph of Example 2, the transmission image of a polarizing microscope, and the swelling reversible change result in water are shown. (<8-2> hollow granules, 5 micron level). The scanning electron micrograph which controlled the particle size of Example 2 is shown. (<8-2> hollow granules, 5 micron level). The photograph and particle size distribution of Example 3 which controlled the particle size by the disk rotation speed are shown. (<8-3> hollow granules, 50 micron level). The scanning electron micrograph which controlled the particle size of Example 3 is shown. (<8-3> hollow granules, 50 micron level). The scanning electron micrograph of the comparative example 1 is shown. (<9> Mixed powder by general-purpose mechanical compounding method (solid phase method)). The scanning electron micrograph of the comparative example 2 is shown. (<10-1> fine nanoparticle, general-purpose spraying method (two-fluid nozzle method)). The scanning electron micrograph of the comparative example 3 is shown. (<10-2> Hydrophilic and well-dispersible nanoparticles, general-purpose spraying method (two-fluid nozzle method)). <9> Mixed powder by general-purpose / mechanical composite method [Comparative Example 1] <10> Visible light transmittance of mixed powder [Comparative Examples 2-3] of general-purpose spraying method (two-fluid nozzle method) And UV shielding results. The scanning electron micrograph of the comparative example 4 is shown. (<11-1> Raw material without surface charge control. Control of the reference invention is partially returned to the general-purpose method). The scanning electron micrograph of the comparative example 5 is shown. (<11-2> well-dispersed nanoparticles + mica with no charge control-part of the control of the reference invention is returned to the general-purpose method). The scanning electron micrograph of the comparative example 6 is shown. (<11-3> Spindle-shaped titania 20 wt%. The control of the reference invention is partially returned to the general-purpose method). The scanning electron micrograph of the comparative example 7 is shown. (<11-4> Spindle-shaped titania 30 wt%. The control of the reference invention is partially returned to the general-purpose method). <10> The results of the visible light transmittance and the ultraviolet shielding property of the mixed powder [Comparative Examples 2 to 3] of a general spray method (two-fluid nozzle method). The scanning electron micrograph of the comparative example 8 is shown. (<11-5> Hollow granules by homomixer, 5 micron level).

  Next, the present invention and the reference invention will be specifically described by way of examples, reference examples, and comparative examples, but are not limited by the following examples, reference examples, and comparative examples.

  In Examples / Reference Examples / Comparative Examples, as a control factor (special technical feature) of novelty evaluation, fine force governing dispersion and composite, primary characteristics of powder focusing on one particle, mainly agglomerates And secondary powder characteristics (morphological / structure control of composite particles and granules) focusing on the powder layer were selected and arranged as follows (FIGS. 4 to 10).

(1) Top-level concept of control Average surface-to-surface distance L _DLVO and L _{Woodcock of} mother particle and child particle
(2) Preparation factor to be controlled = micro force (repulsive force, cohesive force)
1) van der Waals cohesive force (in the mixed liquid, in the stationary mother particle / child particle)
2) Electrostatic homo repulsive force (in mixed liquid)
3) Liquid cross-linking cohesion (in the droplet, in the droplet formation process, in the stationary mother particle / child particle)
4) Electrostatic hetero-cohesive force (from mixed liquid to inside droplet)

(3) Directly controlled powder primary characteristics 1) Primary particle size and particle size distribution (for parent and child particles)
2) Surface treatment (hydrophilic and hydrophobic, mother and child particles, but primary particles, wet or dry)
3) Surface potential (positive or negative, but the primary particle's edge (positive) and table (negative) respectively)

(4) Secondary characteristics controlled directly 1) Complexity (surface coverage and uniformity of child particles)
2) Secondary particle size, aggregate size, aggregate size distribution (for mother and child particles, especially child particles)
3) Aggregate strength (or dispersion degree of mother particles and child particles, card house structure strength of plate-like particles)
4) Surface treatment (both hydrophilic and hydrophobic, mother and child particles, but secondary particles as a whole, wet or dry)

  In this reference example, electrostatic “repulsive force” is used for uniform dispersion of the same kind of mother and child particles, and electrostatic “attraction” is used in combination for uniform adhesion of different kinds of mother and child particles. Therefore, as one method for controlling such a micro force, fine particle titanium oxide with an alumina surface treatment was used.

  The operating conditions actually adjusted in the reference examples and comparative examples, particularly for micro forces, are the primary characteristics of the mother particles and the child particles, the method of controlling the degree of dispersion, the method of drying the mixed liquid, and the method of forming droplets as follows: (Figs. 4 and 5).

(1) Surface potential of plate-like particles (or dispersion of mother particles, primary characteristics of mother particles)
1) Natural or synthetic mica (end face (positive) and table face (negative)) and plate-like alumina (end face and table face both positive charge) both end face and table face are positive charge-end face positive table face negative-end face negative table face positive ~ Negative charge on both the end face and the table face 2) Flocculants (polyaluminum chloride (PAC), etc.) during the purification of natural mica = cation amount

(2) Agglomerate size and strength of child particles (or degree of dispersion of child particles. Primary characteristics of child particles)
1) Primary particle diameter of child particle 20 or less to 30 to 40 to 50 nm or more 2) Surface treatment of child particle (no treatment, silica, alumina, aluminum hydroxide, alginic acid) positive charge to neutral to negative charge

(3) Dispersion degree control method (that is, mixed liquid dispersion method, medium stirring mill method, filtration, presence of coagulant)
1) Bead diameter (the amount of beads occupied per unit volume of the mixed liquid “bead concentration”)
15 or less to 30 μm to general-purpose ball mill to mill unused 2) Amount of prepared mixed liquid (slurry) Mass production to trial level to lab level to batch processing 3) Allowed standing time (period) of mixed liquid to stand for several days or more ~ Continuous treatment ~ Simultaneous treatment ~ 1 process 4) Solid content concentration of liquid mixture (% by weight of dispersion medium of mother particles + child particles)
Thick slurry (40 wt% or more) to dilute slurry (less than 40 wt%)
5) Dielectric constant of dispersion medium (proportional to electrostatic repulsion, inversely proportional to hetero cohesion)
Addition amount of ethanol to water / ethanol / mixed medium and mixed liquid (0-100%)
6) Drying method of mixed liquid (or solidifying method of particles)
Liquid method, electric furnace method, filtration / drying method

(4) Droplet formation method 1) 3 or 4 fluid nozzle 2) Type of 4 fluid nozzle = Presence / absence of edge of inclined surface through which thin film flow flows (Yes = ○, No = Δ)
3) 2-fluid nozzle (= droplet of several tens of μm)
4) Rotating disk method (= drops of several tens to several hundreds μm)
5) Filtration / drying method (general-purpose method, liquid phase state → so-called droplets of several hundred μm or more)

  In addition, as an evaluation index of the effect (result), the characteristics, visible light transmittance, ultraviolet ray shielding rate, powder layer lubricity, and thermal conductivity of the particle aggregate produced using the above granular material as a raw material were selected. The visible light transmittance and the ultraviolet shielding rate were standardized as follows (FIG. 14).

(1) Normalization / Visible light transmittance Subtracting (difference) from the transmittance at an optical wavelength of 800 nm by the transmittance at 400 nm is regarded as the visible light transmittance, and the visible light transmittance is evaluated to be 20% or less as an effect.

(2) Normalization and UV shielding rate Subtraction (difference) of the transmittance at an optical wavelength of 400 nm by the transmittance at 290 nm is regarded as the UV shielding rate, and the UV shielding rate of 40% or more is evaluated as an effect.

  In the following examples and reference examples, natural and synthetic sericite and plate-like alumina (trade name “Seraph”) are used as mother particles, and titania is used as child particles. , Used each.

Reference example 1

<1> “Lab level preparation of fine particle titanium oxide” (common to [Reference Examples 1 to 4], FIGS. 11 to 19)
<1-1> “Titania weight% (definitions [0094] to [0100]) 20 wt%”
30 g of fine particle titanium oxide (MT-500H manufactured by Teika Co., Ltd., alumina surface-treated product, light diffraction / scattering diameter 30 nm) was added to 350 g of purified water and dispersed with a magnetic stirrer. Using a wet medium mill method (UAM-015 type bead mill manufactured by Kotobuki Kogyo Co., Ltd.), plasma melting beads (diameter 30 μm, made of yttrium (Y) reinforced ZrO ₂ ) were used for 30 minutes to prepare a child particle slurry.

  Add 120 g of sericite (from Shinei, Toei-cho, Kitasakuraku-gun, Aichi Prefecture, flocculant (polyaluminum chloride (PAC)) not used in the purification of natural mica, light diffraction / scattering diameter 7 μm) to the child particle slurry, and further for 30 minutes Distributed.

  The mixed slurry was dried with a spray dryer (MDL-050B type manufactured by Fujisaki Electric Co., Ltd., nozzle PN3005 type, three-fluid nozzle method), and the powder recovered by the cyclone method was used as Reference Example 1 (Composite Powder 1). ).

Here, with respect to the second component (child particles), the above-mentioned means [D] (L _DLVO ≧ L _Woodcock ) was confirmed (see the conversion method of volume% and weight% of the mixed liquid). From the titania true density (assuming monodisperse) 4.26 g / cc, the titania volume V _TiO2 charged into the system is
V _TiO2 = 30 ÷ 4.26 ≒ 7 (cc)
It becomes.

When the amount of water circulating in the bead mill system 200 g = 200 cc is added to the distilled water 350 g = 350 cc, the titania volume (vol) ratio% ^V _{TiO2 charged} into the system is
% ^V _TiO2 = 7 ÷ (7 + 350 + 200) ≈0.013 (1 vol%)
It becomes.

  Therefore, under the common-sense operating conditions of the surface potential shown in FIGS. 8 and 9, among the threshold values allowable for the second component (child particles) in the nanometer order, the stricter number vol% @ Woodcock equation (In the case of the hexagonal close packing model, several tens vol% (˜30 vol%) is allowed in the hexagonal close packing model, and the reference example 1 using the heteroaggregation method still has a margin. Can be said).

  As shown in FIGS. 11 to 15, the composite state and the like of the obtained powder were confirmed with a transmission electron microscope TEM and a scanning electron microscope SEM.

12 and 13 show the results of producing uniform / local non-uniform composite particles and solid / hollow granules using the above description and “L _DLVO ≧ L _Woodcock ” shown in FIGS. 8 and 9.

  As shown in Table 1, the visible light transmittance and the ultraviolet shielding rate were measured by the following methods. A dispersion film in silicone was produced with the composition shown in Table 1 so that the powder was 5 wt%. The obtained film was placed immediately before the light receiving part of an ultraviolet-visible spectrophotometer (Shimadzu Corporation UV-160A type, integrating sphere, unused), and the transmittance (%) of ultraviolet to visible light at 290 to 800 nm was measured. .

  For each powder, the difference in transmittance between 400 nm and 290 nm was normalized as the ultraviolet shielding power, and the difference between 800 nm and 400 nm was normalized as the visible light shielding power. In FIG. 14, the normalized ultraviolet shielding rate, the normalized visible light transmittance, and the transmittance at 290 nm are arranged.

  In addition, the titanium oxide content of the composite powder was quantified by comparing with the peak of silicic anhydride derived from sericite with a fluorescent X-ray analyzer.

Reference example 2

<1-2> “Titania weight% 25 wt%”
Fine particle titanium oxide (MT-500H manufactured by Teika Co., Ltd., alumina surface treatment product, light diffraction / scattering diameter 30 nm) 37.5 g, sericite (from Shincho, Toei-cho, Kitashiraku-gun, Aichi Prefecture) flocculant during purification of natural mica (poly Aluminum chloride (PAC)) (not used) was prepared in the same manner as in Reference Example 1 using 112.5 g. FIG. 16 shows a scanning electron microscope SEM.

Reference example 3

<1-3> “Titania weight% 50 wt%”
Fine particle titanium oxide (MT-500H manufactured by Teika Co., Ltd., alumina surface treatment product, light diffraction / scattering diameter 30 nm), 75 m, sericite (from Shincho, Toei-cho, Kitasaraku-gun, Aichi Prefecture) flocculant during purification of natural mica (polyaluminum chloride) (PAC)) Unused) 75 g was prepared in the same manner as in Reference Example 1. FIG. 17 shows a scanning electron microscope SEM.

Reference example 4

<1-4> “Titania weight% 15 wt%”
Fine particle titanium oxide (MT-500H manufactured by Teika Co., Ltd., alumina surface treatment product, light diffraction / scattering diameter 30 nm) 22.5 g, sericite (produced in Shinei, Toei-cho, Kitashiraku-gun, Aichi Prefecture), flocculant during purification of natural mica (poly Aluminum chloride (PAC)) (not used) was prepared in the same manner as in Reference Example 1 using 127.5 g.

Using “L _DLVO ≧ L _Woodcock ” (shown in FIGS. 8 and 9), uniform and local non-uniform particle complexation was performed. As a result, the mobility of the mother particles and the child particles can be controlled by adjusting the micro force, and any combination can be implemented.

  FIG. 11 shows a cross-sectional TEM photograph, a WDS surface analysis map, a line analysis, and an EDS spectrum of typical sericite-titania composite particles. It can be seen that the Ti—O compound is distributed in the form of an outer shell around the Al—Si—O compound distributed on the central lump, and uniform particle formation is performed.

FIG. 12 shows the result of producing uniform and locally non-uniform composite particles by electrostatic heterocohesion force in the range of L _{DLVO ≈L Woodcock} in FIGS. As can be seen from the theory of the reference invention, the structure controllability is high.

  Further, as shown in FIGS. 12 and 15 to 18, the composite amount on the surface of the mother particle can be arbitrarily controlled by the added amount of the child particles. Further, the control method using the average particle surface distance of the reference invention has high controllability of child particles, and no traces showing poor controllability of composites such as titania particles released on the SEM substrate are confirmed.

  As a result, as shown in FIGS. 14 and 19, the normalized visible light transmittance stably maintains a low value and exhibits high transparency up to a wide range of light wavelengths. Further, the normalized ultraviolet shielding rate shows a high value and represents a high shielding property in the ultraviolet region.

Reference Example 5

<2> “Preparation of production specifications (slurry standing and processing amount)” (common to [Reference Examples 5 to 6], FIGS. 20 to 22)
<2-1> “Standing for 1 week (titania weight% 20 wt%)”
After preparing the mixed slurry of Reference Example 1, the mixture was allowed to stand for 1 week, and then prepared in the same manner as Reference Example 1. FIG. 20 shows a scanning electron microscope SEM.

Reference Example 6

<2-2> “Standing in 1 week for mass production (titania weight% 25 wt%)”
Using fine particle titanium oxide 300g, purified water 4800g, propeller mixer dispersion, wet medium mill method (UAM-1 type bead mill manufactured by Kotobuki Industries Co., Ltd.), sericite (coagulant (polyaluminum chloride (PAC)) unused) 900g, After standing for 1 week, it was prepared in the same manner as in Reference Example 1. FIG. 21 shows a scanning electron microscope SEM.

Reference Example 7

<3> “Combination of Dispersion and Antibacterial Organic Solvent Ethanol” (Common to [Reference Examples 7 to 9], FIGS. 23 to 26)
<3-1> “Ethanol 10 wt% mixed dispersion medium (titania weight% 20 wt%)”
It was prepared in the same manner as in Reference Example 1 using a mixed dispersion medium of 280 g of purified water and about 70 g of ethanol (Wako Pure Chemical Industries, 99%). FIG. 23 shows a scanning electron microscope SEM.
In addition, ethanol weight% was made into the ratio with respect to the total amount of liquid mixture similarly to the above.

Reference Example 8

<3-2> “Ethanol 10 wt% dielectric constant adjusting additive (titania weight% 20 wt%)”
After preparing the mixed slurry of Reference Example 1, about 70 g of ethanol was added as a dielectric constant adjuster and dispersed for 15 minutes, and the mixture was prepared in the same manner as Reference Examples 1 and 7. FIG. 24 shows a scanning electron microscope SEM.

Reference Example 9

<3-3> “Ethanol 100 wt% (titania weight% 20 wt%)”
In place of purified water, about 350 g of ethanol was used, and the inside of the bead mill system was further replaced with ethanol. FIG. 25 shows a scanning electron microscope SEM.

Reference Example 10

<4> “Enhanced medium agitation, fine beads 15 μm” ([Reference Example Reference Example 10] FIGS. 27 and 35)
Y-reinforced ZrO ₂ beads (diameter: 15 μm) were used and prepared in the same manner as in Reference Example 1. FIG. 27 shows a scanning electron microscope SEM.

Reference Example 11

<5> “Increasing spray amount, 4-fluid nozzle method” (common to [Reference Examples 11 to 13], FIGS. 28 to 31)
<5-1> “Lab level preparation of fine particle titanium oxide (with edge boundary of thin film flow)”
After preparing the mixed slurry of Reference Example 1, it was prepared in the same manner as Reference Example 1 with a spray dryer (MDL-050B type manufactured by Fujisaki Electric Co., Ltd., nozzle SE4003 type, four-fluid nozzle method with edge boundary of thin film flow). FIG. 28 shows a scanning electron microscope SEM.

Reference Example 12

<5-2>"Lab level preparation of fine particle titanium oxide (no edge boundary in thin film flow)"
After preparing the mixed slurry of Reference Example 1, it was prepared in the same manner as Reference Example 1 with a spray dryer (NL-5 type manufactured by Okawara Kako Co., Ltd., twin jet nozzle, four-fluid nozzle method without edge boundary of thin film flow). FIG. 29 shows a scanning electron microscope SEM.

Reference Example 13

<5-3> “Preparation of production specifications”
Using fine particle titanium oxide 270 g, purified water 3950 g, propeller mixer dispersion, wet medium mill method (UAM-1 type bead mill manufactured by Kotobuki Industries Co., Ltd.), sericite (coagulant (polyaluminum chloride (PAC)) unused) 1080 g, After standing for 1 week, it was prepared in the same manner as in Reference Example 1 using a spray dryer (MDL-050B type manufactured by Fujisaki Electric Co., Ltd., nozzle SE4003 type, 4-fluid nozzle method). FIG. 30 shows a scanning electron microscope SEM.

Reference Example 14

<6> “Types of fine particle titanium oxide: particle diameter and shape” (common to [Reference Examples 14 to 16], FIGS. 32 to 35)
<6-1> “Fine spherical titania (titania weight% 20 wt%)”
Prepared in the same manner as in Reference Example 1 using fine particle titanium oxide (TTO-51 (A) manufactured by Ishihara Sangyo Co., Ltd., alumina surface-treated product, light diffraction / scattering diameter 20 nm). FIG. 32 shows a scanning electron microscope SEM.

Reference Example 15

<6-2> “Spherical titania with relatively large particle size (titania weight% 20 wt%)”
Prepared in the same manner as in Reference Example 1 using fine particle titanium oxide (TTO-55 (A) manufactured by Ishihara Sangyo Co., Ltd., alumina surface-treated product, light diffraction / scattering diameter 40 nm). FIG. 33 shows a scanning electron microscope SEM.

Reference Example 16

<6-3> “Spindle-like titania + refined plasma fusion beads (diameter 15 μm)”
Fine particle titanium oxide (TTO-S-3, manufactured by Ishihara Sangyo Co., Ltd., alumina surface-treated product, spindle shape (short axis 20 × long axis 80 nm), Y-reinforced ZrO ₂ beads (diameter 15 μm) were used as in Reference Example 1. 34 shows a scanning electron microscope SEM.

Reference Example 17

<7> “Mother Particle Charge Control: Synthetic Mica and Alumina” (common to [Reference Examples 17 to 18], FIGS. 36 to 38)
<7-1> “Synthetic mica (titania weight% 20 wt%)”
As a charge adjustment method using mother particles, a method for controlling (hydrophobizing) affinity with a medium is used, and synthetic mica containing no crystal water (PDM-8W manufactured by Topy Industries, Ltd., light diffraction / scattering diameter 10 μm) is used. And prepared in the same manner as in Reference Example 1. FIG. 36 shows a scanning electron microscope SEM.

Reference Example 18

<7-2> “Surface charge (plate-like alumina) preparation (titania weight% 20 wt%)”
As a method for positively controlling both the end surface and the table surface of the mother particles, plate-like alumina (Seraph YFA05070 manufactured by Kinseimatic Co., Ltd., light diffraction / scattering diameter: 5 μm) was used and prepared in the same manner as in Reference Example 1. FIG. 37 shows a scanning electron microscope SEM.

<8> “Solid / Hollow Granules of Fine Particle Titanium Oxide” (Common to [Examples 1 to 3], FIGS. 39 to 43)
<8-1>"Solid granules, 5 micron level (small droplet diameter, 3 fluid nozzle method)"
To reduce the electrostatic repulsion force by reducing the particle size and neutralizing, increase the degree of aggregation, and suppress the mobility of nanoparticles in the condensation process, fine particle titanium oxide (MT-100HP manufactured by Teika Co., Ltd., hydrous silicic acid) 70 g of surface treatment, light diffraction / scattering diameter 15 nm) was used (in the following examples, plate-like particles are not used).
Then, it prepared by bead mill, spray drying, etc. similarly to the reference example 1. FIG. 39 shows a scanning electron microscope SEM.

<8-2> “Hollow granules, 5 micron level (small droplet diameter, 3 fluid nozzle method)”
In order to increase the electrostatic repulsive force by increasing the particle size and negative polarity, to suppress the degree of aggregation, and to increase the mobility of nanoparticles in the condensation process, fine titanium oxide (Maxlite TS-04 manufactured by Showa Denko KK, anhydrous It was prepared in the same manner as in Reference Example 1 and Example 1 using a silicic acid surface-treated product (surface / negative charge), light diffraction / scattering diameter 40 nm).

  Moreover, in order to control the mobility of the nanoparticles in the condensation process to adjust the granule diameter, the medium stirring condition was selected as a control factor, the bead diameter was adjusted to 15 to 50 μm, and the treatment time was adjusted to 30 minutes to 4 hours. 40 and 41 show a scanning electron micrograph of Example 2, a transmission image of a polarizing microscope, and the result of reversible swelling change in water.

<8-3> “Hollow granules, 50 micron level (large droplet diameter, rotating disk spray method)”
In order to increase the particle size of the granules, 70 g of fine particle titanium oxide (Maxlite TS-04, Showa Denko KK, silica surface treatment product (surface / negative charge), light diffraction / scattering diameter 40 nm) is used and spray dried. It was prepared in the same manner as in Reference Example 1 and Example 1 using a machine (Okawara Kako Mold, rotary disk method). FIG. 43 shows a scanning electron microscope SEM.

For the above example, FIG. 13 is a graph of FIG. 8 where L _DLVO ≒ L _Woodcock range and L _DLVO > L _Woodcock range of FIG. 9 are used to adjust the nanoparticle mobility and to arbitrarily perform surface condensation (condensation) and volume condensation. This is the result of producing solid and hollow granules under control. As can be seen from the theory of the present invention, the structure controllability is high.

As is apparent from FIGS. 39 to 42, solid and hollow granules can be produced arbitrarily.
As is clear from FIG. 40, a reversible swollen powder that can be swollen (expanded) in water and reversibly changed in brine in air can be produced.

As is clear from FIG. 42, the granule diameter of the solid granules can be arbitrarily controlled using the rotational speed of the rotating disk as a control factor.
As is apparent from FIGS. 40 to 43, hollow granules having a reversible swelling function can be produced with an arbitrary granule size.

(Comparative Example 1)
<9> “Mixed powder by general-purpose / mechanical composite method” ([Comparative Example 1] FIGS. 44 and 47)
Fine particle titanium oxide (manufactured by Teika Co., Ltd., MT-500B, no surface treatment, light diffraction / scattering diameter 35 nm), sericite (from Toshincho, Kitasakura-gun, Aichi Prefecture), flocculant during purification of natural mica (polyaluminum chloride ( PAC)) “Usage”, a commercially available product, light diffraction / scattering diameter 7 μm), a Henschel mixer and a hammer mill (Labo Mill LM05 manufactured by Fuji Powder Co., Ltd.) were used in the same manner as Reference Example 1 for the dispersion process. FIG. 44 shows a scanning electron microscope SEM.

(Comparative Example 2)
<10> “Mixed powder of general-purpose spraying method (two-fluid nozzle method)” (common to [Comparative Examples 2-3], FIGS. 45 to 46)
<10-1> “Lab level preparation of fine particle titanium oxide”
Use fine particle titanium oxide (MT-500H manufactured by Teika Co., Ltd., alumina surface-treated product, light diffraction / scattering diameter 30 nm), spray dryer (Palvis Mini Spray GB-22, manufactured by Yamato Scientific, 2 fluid nozzle method) for reference Prepared as in Example 1. FIG. 45 shows a scanning electron microscope SEM.

(Comparative Example 3)
<10-2> “Types of fine particle titanium oxide (hydrophilic and well-dispersed nanoparticles)”
Fine particle titanium oxide (Maxlite TS-04 manufactured by Showa Denko KK, Silicic anhydride surface-treated product (surface / negative charge), light diffraction / scattering diameter 40 nm), spray dryer (Palvis Mini Spray GB-22 manufactured by Yamato Scientific) Using a mold, two-fluid nozzle method). FIG. 46 shows a scanning electron microscope SEM.

(Comparative Example 4)
<11> “Example of partially returning the control of the reference invention to the general-purpose method” (common to [Comparative Examples 4 to 8], FIGS. 47 to 53)
<11-1> “Fine particle titanium oxide and sericite that do not control surface charge”
Fine particle titanium oxide (manufactured by Teica Co., Ltd., MT-500B, no surface treatment, light diffraction / scattering diameter 35 nm), sericite (produced in Shinsakucho, Toei-cho, Kitashiraku-gun, Aichi Prefecture), flocculant (polyaluminum chloride ( PAC)) was used and was prepared in the same manner as in Reference Example 1, using a commercially available product that does not control the surface charge by cation control, light diffraction / scattering diameter 7 μm). FIG. 48 shows a scanning electron microscope SEM.

(Comparative Example 5)
<11-2> “Hydrophilic and well-dispersed nanoparticles and sericite that does not control surface charge”
Fine titanium oxide (MT-100HP manufactured by Teika Co., Ltd., hydrous silicic acid surface treatment, light diffraction / scattering diameter 15 nm), sericite (ordinary commercial product from Tosaka-cho, Tosaka-cho, Aichi Prefecture, light diffraction / scattering diameter 7 μm) And prepared as in Reference Example 1. FIG. 49 shows a scanning electron microscope SEM.

(Comparative Example 6) (← Counter example of [Reference Example 16])
<11-3> “Spindle-like titania, titania weight% 20 wt%”
Using fine particle titanium oxide (TTO-S-3 manufactured by Ishihara Sangyo Co., Ltd., alumina surface treatment product, spindle shape (short axis 20 × long axis 80 nm), it was prepared in the same manner as in Reference Example 1. FIG. A microscope SEM is shown.

(Comparative Example 7) (← Counter example of [Reference Example 16])
<11-4> “Spindle-like titania, titania weight% 30 wt%”
Fine particle titanium oxide (TTO-S-3 manufactured by Ishihara Sangyo Co., Ltd., alumina surface-treated product, 45 g of spindle shape (short axis 20 × long axis 80 nm), sericite (produced in Shinei, Toei-cho, Kitashiraku-gun, Aichi Prefecture, refined natural mica) 10 g of the flocculant (polyaluminum chloride (PAC) unused) was prepared in the same manner as in Reference Example 1. Fig. 51 shows a scanning electron microscope SEM.

(Comparative Example 8)
<11-5> “Hollow granules by homomixer, 5 micron level”
A homomixer (TK homomixer AM-M2.5 manufactured by Tokushu Kika Kogyo Co., Ltd.) was used as a disperser and prepared in the same manner as in Reference Example 1 and Example 1. FIG. 53 shows a scanning electron microscope SEM.

  As apparent from FIGS. 46, 48 to 51, and 53 regarding the above comparative example, when the general-purpose method or the control of the present invention is incompletely performed, the isolated particles remaining due to aggregation of the child particles or incomplete complexation. Problems occur in the structure controllability such as

  As is clear from FIGS. 47 and 52, also in the optical characteristics (inventive step), sufficient visible light transmittance and ultraviolet shielding ratio cannot be obtained, the normalized values and the margin of both are small, and the characteristics are improved. I can't.

  As described above, in the composite particles in which the plate-like particles are the mother particles and the nanometer order particles previously solidified (crystallized) are the child particles, the aggregation of the mother particles / child particles is free and the child particles are formed on the surface of the mother particles. It is possible to provide a new form control method, its particulate material, and a control device, which were impossible at present, that the particles can be finely and uniformly combined. In addition, the material properties of powder products such as cosmetics, foods, pharmaceuticals, industrial fillers, swellable powders, ceramic green compacts, molded bodies and sintered bodies can be significantly improved. The reference invention embodies the theoretical particle compounding method of powder engineering as a methodology for actual materials, and is used as an ordered mixture manufacturing method with thick slurry (for example, 40 wt.% Or more), as a filler or cosmetics. It is useful as an extension of the technical field of mica-based particulate matter.

Claims (10)

In the method for producing a solid or hollow aggregate obtained by agglomerating a metal oxide particulate material having a particle diameter of less than 0.1 μm,
Dispersing the particulate material in a dispersion medium selected from an aqueous solvent, alcohol or ether solvent to produce a mixed liquid containing the particulate material,
The average inter-surface distance of the particulate matter in the mixed liquid determined by the interaction between both micro forces of the van der Waals attractive force acting in the mixed liquid and the electrostatic repulsive force based on the overlap of the interfacial electric double layer ( L _DLVO ) and calculating the average inter-surface distance (L _Woodcock ) of the particulate material in the mixed liquid determined by the solid content concentration and particle size of the particulate material contained in the mixed liquid,
Dispersing the particulate material in the mixed liquid so that the average inter-surface distance of the particulate material in the mixed liquid is “L _DLVO ≧ L _Woodcock ”;
A method for producing an agglomerate, wherein the mixed liquid is made into droplets of less than 100 μm, and the dispersion medium is evaporated from the droplets and dried.   The method for producing an aggregate according to claim 1, wherein the dispersion of the particulate material in the mixed liquid is performed by a bead mill.   The method for producing an agglomerate according to claim 1 or 2, wherein the suitable drying is performed by a spray drying method.   The manufacturing method according to any one of claims 1 to 3, wherein the particulate material is selected from alumina, silica, titania, zirconia, zinc oxide, iron oxide, barium sulfate, boron nitride, and carbon-based organic matter. The manufacturing method of the aggregate characterized by comprising.   5. The production method according to claim 1, wherein the solid aggregate is obtained by using particles having a neutral surface charge as the particulate material. Manufacturing method.   6. The method for producing an aggregate according to claim 5, wherein the particulate material is fine particle titanium oxide surface-treated with hydrous silicic acid.   In the manufacturing method as described in any one of Claims 1-4, the said aggregate with a hollow is obtained by using the particle | grains in which the surface is tinged with the positive charge or the negative charge as the said granular substance. A method for producing an aggregate.   8. The method for producing an aggregate according to claim 7, wherein the particulate material is fine particle titanium oxide surface-treated with silicic anhydride.   The aggregate manufactured by the manufacturing method as described in any one of Claims 1-8.   The aggregate according to claim 9 is used as a raw material powder for any product selected from cosmetics, drugs, industrial fillers, ceramic green compacts, molded bodies, and sintered bodies. Aggregation.