JP2006022176A - Coated microparticle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide coated microparticles improved in at least one property selected from among color, gloss, luminescence (fluorescence or phosphorescence), luminance, light reflection, and ultraviolet shielding. <P>SOLUTION: The coated microparticles are ones prepared by rotating a vacuum container 1 the inside of which is polygonal in a cross section about a rotation axis being the direction substantially perpendicular to the cross section to sputter microparticles 3 under agitation or rotation in the container 3 to thereby surface-coat the microparticles 3 with ultramicroparticles or having a smaller particle diameter than the microparticles or with a thin film thereof, wherein the ultramicroparticles or the thin film comprises one member selected from the group consisting of a metal, an oxide, a nitride, and a carbide or comprises a composite of at least two members selected from the above group and characterized by being capable of being used in cosmetics or coating materials. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to coated fine particles, and more particularly to coated fine particles whose surfaces are coated with ultrafine particles or thin films made of cosmetic materials or paint materials.

  Many inorganic and organic powders (fine particles) are used in cosmetics. Among these, inorganic powders are utilized by taking advantage of the properties of materials such as color, light reflection / scattering rate, color development, and ultraviolet reflection.

  In order to improve the color and color development of the powder (fine particles), it is a very effective means to modify (cover) the ultra fine particles or thin film on the surface of the powder. This is because the optical properties of the material greatly depend on the properties of the powder surface, so that color and color development can be greatly changed by surface modification of the powder. In addition, in the surface modification of the powder, it is possible to impart the characteristics (for example, ultraviolet reflection, fluorescence, etc.) of the material to be modified.

  The conventional powder surface modification method is a method in which a modifying material is made into fine particles, and the modifying material is modified on the surface of fine particles as a base by a weak adsorbing force such as electrostatic force and surface tension of moisture. However, the surface modification method of the powder cannot actually be used unless the modifying material is finely divided to an average particle size of several tens to several hundreds of nanometers. limited. In addition, since the particle diameter and shape of the fine particles vary, it is difficult to uniformly modify the surface of each fine particle. In addition, since the powder can be modified only in the form of fine particles, there is a drawback that a flat surface with high reflectivity cannot be formed.

  As another conventional example, the surface modification of the powder has been performed also by a plating method. However, the preparation process is complicated, contamination of impurities is unavoidable during preparation, oxide materials that are widely used in cosmetics cannot be modified, and plating waste liquid is difficult to process due to environmental problems, etc. For this reason, the surface modification method of the powder by the plating method is not widely used in the cosmetics field.

  On the other hand, as materials used for coating products, many powder coatings and pigments used in coatings are used as powders. Most of these powders use the color and color development of the material itself. However, conventional paint materials alone cannot meet various needs in terms of color and color development. In addition, new needs such as paints having anticorrosion and antibacterial properties have been born, and development of paints that meet these needs is expected.

  As a method for solving the above problem, it is conceivable to modify (cover) a substance on the surface of the powder as in the case of cosmetics. The color and color development of paint greatly depend on the surface of the powder material such as pigment, the light reflectance, the refractive index, etc., so the color and color development can be changed by modifying the powder surface with other substances. it can. At the same time, it is also possible to impart properties (for example, anticorrosive property, antibacterial property, etc.) of the modifying substance.

  By the way, demands for cosmetics in recent years have become stricter, and improvement of coloring, development of high-intensity powder materials, and the like are required. On the other hand, conventional paint materials alone cannot meet various needs in terms of color and color development. In addition, new needs such as paints having anticorrosion and antibacterial properties have been born, and development of paints that meet these needs is expected.

  The present invention has been made in consideration of the above-described circumstances, and its purpose is at least one of color, color development, gloss, phosphorescence / luminescence (fluorescence and phosphorescence), high luminance, light reflection, and UV protection. It is an object of the present invention to provide coated fine particles having improved properties. Another object of the present invention is to provide coated fine particles coated with ultra fine particles or thin films made of a cosmetic material or a paint material functionalized on the surface of the fine particles.

  In order to solve the above problems, attention was paid to a sputtering method which is one of physical vapor deposition methods. This method is also very versatile because it is difficult to uniformly coat the entire powder with fine particles, but the carrier can be selected, metal to inorganic materials can be modified on the powder surface, the environmental impact is small, etc. it is conceivable that. Therefore, we have invented the polygonal barrel sputtering method, which is a new modification method for powder surfaces. This method uses a dry sputtering method, it is possible to substantially uniformly modify the metal, oxide, etc. on the powder surface, the modification process is very short compared to the conventional method, There is almost no contamination of impurities, no need for waste liquid treatment, and various combinations of modified products (ultrafine particles or thin film) and modified products (fine particles) are possible. The material can be modified on the surface of the fine particles, and the form (from thin film to fine particles) of the material modified (coated) on the surface of the fine particles can be controlled to manipulate the light reflectance and refractive index of the powder and freely change the color. There are many advantages such as being able to. The development of this method has made it possible to freely modify the powder surface, which makes it possible to modify oxide materials with various properties (fluorescence properties, etc.) on the powder surface. It became easy to modify the surface in the form of a thin film.

This will be specifically described below.
The coated fine particles according to the present invention are prepared by rotating a vacuum vessel having a polygonal cross-sectional shape about a direction perpendicular to the cross-section as a rotation axis, while stirring or rotating the fine particles in the vacuum vessel. By performing sputtering, the surface of the fine particles is coated with ultrafine particles or thin film having a smaller particle diameter than the fine particles, and is coated fine particles used for cosmetics or paints,
The ultrafine particles or the thin film is characterized by comprising one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group.

The coated fine particles according to the present invention are agitated or rotated with respect to the fine particles in the vacuum vessel by rotating a vacuum vessel having a polygonal cross-sectional shape about a direction perpendicular to the cross-section as a rotation axis. By performing sputtering while applying vibration to the fine particles, the surface of the fine particles is coated with ultrafine particles or thin films having a particle diameter smaller than the fine particles, and are coated fine particles used for cosmetics or paints,
The ultrafine particles or the thin film is characterized by comprising one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group.

The coated fine particles according to the present invention directly or indirectly heat a vacuum vessel having an internal cross-sectional shape of a polygon, and rotate the vacuum vessel with a substantially vertical direction as a rotation axis. Sputtering is performed while stirring or rotating fine particles in the vacuum container so that the surface of the fine particles is coated with ultrafine particles or thin films having a particle diameter smaller than the fine particles, and is used for cosmetics or paints. ,
The ultrafine particles or the thin film is characterized by comprising one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group.

  According to the above coated fine particles according to the present invention, generally used cosmetic fine particles having an average particle diameter of 50 μm or less are coated with thin or ultra fine particles made of a cosmetic material or a paint material almost uniformly. (Modification) becomes possible. However, even when a powder of 50 μm or more is used as a material for cosmetics or paints, the surface modification can be performed. That is, there is almost no restriction on the particle size of the base fine particles. For this reason, at least one of color, color development, gloss, fluorescence and phosphorescence, high luminance, light reflection, and ultraviolet protection can be improved in the coated fine particles coated with the cosmetic material or the paint material.

  The coated fine particles according to the present invention are coated fine particles used in cosmetics or paints, in which the surface of fine particles is coated with ultrafine particles or thin films having a particle diameter smaller than the fine particles, and the ultrafine particles or the thin film is a metal, It is characterized by comprising one selected from the group consisting of oxides, nitrides and carbides, or two or more composites selected from the group.

  As described above, according to the present invention, it is possible to provide a coated fine particle having at least one of color, color development, gloss, light emission (fluorescence and phosphorescence), phosphorescence, high luminance, light reflection, and ultraviolet protection. Can do. According to another aspect of the present invention, coated fine particles can be provided in which the surfaces of the fine particles are coated with ultrafine particles or a thin film made of a cosmetic material or a coating material.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a configuration diagram showing an outline of a polygonal barrel sputtering apparatus used when manufacturing coated fine particles according to an embodiment of the present invention.

  This polygonal barrel sputtering apparatus is an apparatus for coating the surface of fine particles (powder) with ultrafine particles or a thin film having a smaller particle diameter than the fine particles.

  The polygonal barrel sputtering apparatus has a vacuum vessel 1 for coating fine particles 3 with ultrafine particles or a thin film. The vacuum vessel 1 has a cylindrical portion 1a having a diameter of 200 mm and a hexagonal barrel ( Hexagonal barrel) 1b. The cross section shown here is a cross section substantially parallel to the direction of gravity. In the present embodiment, the hexagonal barrel 1b is used. However, the present invention is not limited to this, and a polygonal barrel other than the hexagon (for example, 4 to 12 squares) can be used. .

  The vacuum vessel 1 is provided with a rotating mechanism (not shown). By rotating or reversing the hexagonal barrel 1b as indicated by an arrow or shaking like a pendulum by the rotating mechanism, the hexagonal barrel 1b is provided. The coating process is performed while stirring or rotating the fine particles 3 therein. The rotation axis when the hexagonal barrel is rotated by the rotation mechanism is an axis parallel to the substantially horizontal direction (substantially perpendicular to the direction of gravity).

  Further, in the vacuum container 1, a material made of cosmetics such as a pearl pigment, a high-brightness reflection material, a material having an ultraviolet protection effect, a photochromic material, a fluorescent material, or the like on the central axis of the cylinder, or this substance is reactive A sputtering target 2 made of a material that can be created by sputtering is disposed, and the target 2 is configured so that the angle can be freely changed. Thus, when the coating process is performed while rotating or reversing the hexagonal barrel 1b or shaking like a pendulum, the target 2 can be directed in the direction in which the fine particles 3 are located, thereby increasing the sputtering efficiency. It becomes possible.

The substance that constitutes the target 2 is a cosmetic material that can be used as a cosmetic product, consisting of one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the above group. is there. For example, it is a cosmetic material such as a pearl pigment, a high-brightness reflective material, a material having an ultraviolet protective effect by reflecting ultraviolet light, a photochromic material, or a fluorescent material.
In addition, the material constituting the target 2 is one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the above group, and can be used as a coating material. Material. For example, paint materials such as high-brightness metallic pigments, inorganic fluorescent materials, materials having corrosion resistance, materials having antibacterial properties, and materials having an ultraviolet protection effect.

  Moreover, the target 2 arrange | positioned in the vacuum vessel 1 may be one type, but multiple types may be sufficient as it. For example, as the target 2, a plurality of targets made of a plurality of materials selected from the above-described cosmetic materials or paint materials may be arranged side by side. Moreover, you may arrange | position the target which consists of one material chosen from the above-mentioned cosmetic material or coating material, and the target which consists of an oxide of the material contained in the above-mentioned cosmetic material or coating material side by side.

  The substance covering the fine particles 3 is a substance constituting the target 2. When there are a plurality of types of targets 2, these are mixtures or alloys thereof. Further, when the target 2 is made of one or a plurality of materials selected from the above-mentioned cosmetic materials or paint materials, and reactive sputtering is performed, the substance covering the fine particles 3 constitutes the target 2. It is a substance (for example, oxide) generated from the substance or a mixture of the substance and the substance constituting the target 2.

  One end of a pipe 4 is connected to the vacuum vessel 1, and one side of the first valve 12 is connected to the other end of the pipe 4. One end of the pipe 5 is connected to the other side of the first valve 12, and the other end of the pipe 5 is connected to the intake side of the turbo molecular pump (TMP) 10. The exhaust side of the turbo molecular pump 10 is connected to one end of the pipe 6, and the other end of the pipe 6 is connected to one side of the second valve 13. The other side of the second valve 13 is connected to one end of the pipe 7, and the other end of the pipe 7 is connected to the pump (RP) 11. The pipe 4 is connected to one end of the pipe 8, and the other end of the pipe 8 is connected to one side of the third valve 14. The other side of the third valve 14 is connected to one end of the pipe 9, and the other end of the pipe 9 is connected to the pipe 7.

  This apparatus includes a heater 17a for directly heating the fine particles 3 in the vacuum vessel 1 and a heater 17b for indirectly heating. In addition, this apparatus includes a vibrator 18 for applying vibration to the fine particles 3 in the vacuum vessel 1. The apparatus also includes a pressure gauge 19 that measures the internal pressure of the vacuum vessel 1. In addition, the apparatus includes a nitrogen gas introduction mechanism 15 that introduces nitrogen gas into the vacuum vessel 1 and an argon gas introduction mechanism 16 that introduces argon gas into the vacuum vessel 1. Moreover, the gas introduction mechanism 20 which can introduce | transduce oxygen etc. is also provided so that reactive sputtering can be performed. In addition, this apparatus includes a high frequency application mechanism (not shown) that applies a high frequency between the target 2 and the hexagonal barrel 1b. A direct current can be applied between the target 2 and the hexagonal barrel 1b.

Then, the fine particles 3 by using the polygonal barrel sputtering device will be described polygonal barrel sputtering method for coating ultrafine particles or a thin film made of TiO ₂ which is an example of a cosmetic material.
First, for example, 6 grams of fine particles 3 are introduced into the hexagonal barrel 1b. As the fine particles 3, for example, SiO ₂ or Al ₂ O ₃ powder having a size of about 100 μm is used, but is not limited thereto. The fine particles 3 are not limited in shape, and may have, for example, a flake shape. Moreover, there is no restriction | limiting also about the material of the microparticles | fine-particles 3, For example, it may consist of cosmetic materials.

Next, the turbo molecular pump 10 is used to create a high vacuum state in the hexagonal barrel 1b, and the hexagonal barrel is heated by the heater 17 from room temperature to 400 ° C. according to circumstances, for example, 1 × in the hexagonal barrel. The pressure is reduced to 10 ⁻⁵ Pa. Thereafter, argon and oxygen are introduced into the hexagonal barrel 1b by the argon gas introduction mechanism 16 and the gas introduction mechanism 20. The pressure in the hexagonal barrel at this time is, for example, about 0.1 to 3.5 Pa. Depending on the material of the ultrafine particles or thin film to be coated, a mixed gas of oxygen, nitrogen, methane, and hydrogen may be introduced into the hexagonal barrel 1b, or the material of the target may be changed as appropriate. And the fine particle 3 in the hexagonal barrel 1b is rotated and agitated by rotating the hexagonal barrel 1b at 200W for 60 minutes at 20 rpm by the rotation mechanism. At that time, the target is directed in the direction in which the fine particles 3 are located. Thereafter, a high frequency is applied between the target 2 and the hexagonal barrel 1b by a high frequency application mechanism to coat the surface of the fine particles 3 with a substance made of a cosmetic material. In this way, TiO ₂ can be supported on the surface of the fine particles 3 as ultrafine particles or a thin film. In addition, these conditions are examples and are not limited to this.

  According to the polygonal barrel sputtering apparatus, the powder itself can be rotated and stirred by rotating the hexagonal barrel itself, and the powder can be periodically dropped by gravity by making the barrel hexagonal. . For this reason, the stirring efficiency can be dramatically improved, and aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling the powder, can be prevented. That is, stirring by rotation and pulverization of the agglomerated powder can be performed simultaneously and effectively. Moreover, it becomes difficult for fine particles to adhere to the wall surface of the hexagonal barrel 1b. Accordingly, it is possible to coat ultrafine particles or a thin film, which is made of a cosmetic material or a coating material, and has a smaller particle size than the fine particles having a very small particle size. Specifically, it becomes possible to coat fine particles having a particle diameter of 5 nm or more with ultrafine particles or a thin film made of a cosmetic material or a coating material. Here, the impurities contained in the thin film and the ultrafine particles are very little or not as compared with those prepared by the conventional method. In addition, the ultrafine particles may adhere to the surface of the fine particles continuously, or may adhere to the surface of the fine particles discontinuously as a single body or an aggregate.

Note that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
For example, in the above-described embodiment, vibration is applied to the fine particles 3 in the hexagonal barrel by the vibrator 18, but a state in which a rod-shaped member is accommodated in the hexagonal barrel instead of or in addition to the vibrator 18. It is also possible to apply vibration to the fine particles 3 by rotating the hexagonal barrel. This makes it possible to more effectively prevent agglomeration, which is a problem when handling powder.

  Next, the coated fine particles according to the embodiment of the present invention will be described. The coated fine particles are preferably produced using the polygonal barrel sputtering apparatus shown in FIG. 1, but are not limited to using the polygonal barrel sputtering apparatus.

  The coated fine particles according to the present embodiment are those in which the surface of fine particles (powder) is coated with ultrafine particles or thin films smaller than the fine particles by performing sputtering using the polygonal barrel sputtering apparatus shown in FIG. The ultrafine particles or the thin film is made of a cosmetic material or a paint material. It is also possible to use flake-shaped fine particles 23 as shown in FIG.

Hereinafter, specific examples of the coated fine particles used in cosmetics will be described.
The flake shaped fine particles (powder) 23 shown in FIG. 2 are accommodated in the vacuum container of the polygonal barrel sputtering apparatus shown in FIG. 1, and the fine particles 23 are made of metal, oxide, nitride and carbide by the polygonal barrel sputtering method. A thin film or ultrafine particles composed of one selected from the group or two or more composites selected from the group are coated. Although the flake shaped fine particles 23 are used here, fine particles having other shapes such as a spherical shape may be used. The metal is at least one selected from the group consisting of Pt, Au, Ag, Cu, Al, Si, Ti, Mn, Fe, Co, Ni, Zn, In, Sn, W, Os, and Ir. The oxide is at least one metal oxide selected from the metal group, the nitride is at least one metal nitride selected from the metal group, and the carbide is selected from the metal group. At least one metal carbide.

The cosmetic material is preferably a substance that is safe and highly adaptable to the human body and skin, and further chemically stable to light, heat, moisture, and the like. Specifically, when used as a cosmetic material, the metal is at least one selected from the metal group consisting of Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu and W, The oxide is preferably at least one oxide selected from the group consisting of SiO ₂ , TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Ag ₂ O, and WO ₃ . However, even if a substance that is not harmless to the human body or skin, or a substance that has not been used as a cosmetic product up to now and has not been tested for safety, the coated fine particles are prepared after the coated fine particles are prepared. It can be used if the fine particles are further coated with an inorganic material or polymer suitable for the human body or skin.

In this way, coated fine particles used as a pearl pigment, a high-intensity reflective material, a material having an ultraviolet protection effect by reflecting / scattering ultraviolet rays, and the like can be produced. Accordingly, it is possible to realize a new makeup cosmetic that emits pearly luster. Further, it is possible to realize an ultraviolet protective cosmetic product having an ultraviolet cut rate of almost 100%. The metal suitable for the high brightness reflective material is at least one selected from the metal group consisting of Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu and W, and the oxide is SiO. ₂ , at least one oxide selected from the group consisting of TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Ag ₂ O, and WO ₃ . The metal suitable for the material having an ultraviolet protection effect is at least one selected from the metal group consisting of Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu and W, and the oxide. Is at least one oxide selected from the group consisting of SiO ₂ , TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Ag ₂ O and WO ₃ .

  In addition, coated fine particles used as a fluorescent material or a phosphorescent material can also be produced. In this case, the ultrafine particles or thin film to be coated is at least one selected from the group consisting of rare earth metals containing rare earth ions, rare earth metal oxides, and oxides of metal having photochromic properties (for example, tungsten oxide). It is preferable to use what consists of. The photochromic material is a material whose color changes with light.

  The fine particles to be coated are not particularly limited (for example, metals, oxides, nitrides, carbides, carbon materials, polymers), and those usable as cosmetics may be used.

  Pearl pigments are glossy pigments in which flake-like fine particles such as natural mica are coated with titanium dioxide or iron oxide. Depending on the size of the coated fine particles and the thickness of titanium dioxide, various glossy appearances can be obtained due to interference effects. It is done. Pearl pigments are currently used in many products. In addition to pearl pigments used in cosmetics, pearl pigments include exterior pearl pigments that require weather resistance and general industrial pearl pigments.

  It is no exaggeration to say that the characteristics of powder are determined by its surface condition. New cosmetics can be developed by using the polygonal barrel sputtering method. Moreover, the feeling of use of cosmetics by the surface modification of fine particles can be improved. Further, dispersibility due to a change in specific gravity of the fine particles can be improved. By utilizing these advantages, it can be expected to prepare further novel cosmetics.

In addition, the coated fine particles can be colored (colored) by coating the surface of the fine particles with ultrafine particles or a thin film. As a result, coated fine particles with various color tones can be realized, and for example, a new cosmetic foundation can be produced.
The surface of fine particles (SiO ₂ , polymer beads, mica, etc.) serving as the base of the foundation is modified with an oxide (eg, TiO ₂ ) as a thin film, and the film thickness is controlled. Thus, powders having various colors can be prepared using the interference action. Cosmetic foundations are made by mixing red, yellow, white and black particulates. For example, skin color foundations also produce powders of red, yellow, white, and black colors by mixing them at an appropriate ratio, but there are very few powders with red and yellow colors. In general, Fe ₂ O ₃ is used for red and pigment is used for yellow. However, in order to control various color tones, it is required to produce various red and yellow inorganic fine particles that can be selectively used depending on applications. It is also difficult to control subtle colors. By using the coated fine particles according to the present invention, coated fine particles having various color tones can be realized.

In addition, a UV scattering powder foundation can be prepared by supporting TiO ₂ and ZnO ₂ as ultrafine particles or a thin film on the surface of fine particles (SiO ₂ , polymer beads, mica, etc.) serving as a base of the foundation. Moreover, the light-scattering powder foundation which has the effect | action which hides the color unevenness of skin can be prepared by disperse | distributing other oxides as ultrafine particles uniformly on the surface of the base fine particles.

  In addition, ultrafine particles or thin films made of cosmetic materials are supported on the surface of the fine particles, and further, a pearl pigment using multiple reflections can be prepared by sandwiching a polymer or the like in the middle of a multilayer film or the same material of different substances, High brightness powder (gross) can be realized.

In addition, a photochromic powder having various colors can be prepared by supporting ultrafine particles or a thin film made of a color tone changing material made of, for example, WO ₃ , TiO ₂ , or a composite material thereof on the surface of the fine particles. Also, by modifying the surface of the fine particles with rare earth oxides or ultrafine particles or thin films in which various rare earth ions are added to rare earth oxides, sunlight is absorbed (stored) outdoors and emitted as fluorescence or phosphorescence indoors. A new powder can be prepared.

Hereinafter, specific examples of the coated fine particles used in the paint will be described.
The fine particles to be the base are accommodated in the vacuum container of the polygonal barrel sputtering apparatus shown in FIG. 1, and the fine particles are selected from the group consisting of metal, oxide, nitride and carbide by the polygonal barrel sputtering method, or the above A thin film or ultrafine particle comprising two or more composites selected from the group is coated. The fine particles may be made of a coating material. The metal is made of Pt, Au, Ag, Cu, Al, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, In, W, Os, Ir, or a rare earth metal. At least one selected from the group, the oxide is at least one metal oxide selected from the metal group, and the nitride is at least one metal nitride selected from the metal group. The carbide is at least one metal carbide selected from the metal group. Thereby, it is possible to realize a high-brightness metallic pigment, an inorganic fluorescent / phosphorescent material, a material having corrosion resistance or antibacterial properties, a material having an ultraviolet protection effect by reflecting or absorbing ultraviolet rays, and the like. The metal suitable as a material having corrosion resistance is at least one selected from the metal group consisting of Pt, Au, Si, Ti, Zn, Zr, Nb and W, and the oxide is selected from the metal group. At least one metal oxide selected, wherein the nitride is at least one metal nitride selected from the metal group, and the carbide is at least one metal carbide selected from the metal group.
However, the metal does not include environmentally harmful substances (recently, Sn, Pd, Hg, As, radioactive substances, etc., and further compounds thereof (oxides, etc.)).

The surface of fine particles (SiO ₂ , Al ₂ O ₃ , mica, etc.) that are the base of the powder coating is modified as a thin film with the above metal (eg, Au, Ti) or oxide (eg, TiO ₂ ) By controlling, powders having various colors can be prepared. Although organic pigments can produce various colors, they are inferior in heat resistance, light resistance (ultraviolet light resistance), and durability (oxidation over many years), so it is necessary to prepare inorganic pigments having various colors.

  The substance (particularly metal) is supported as a thin film on the surface of the base fine particles. At present, metallic pigments are required to have a delicate metallic luster, but there are few metallic pigments that match Japanese delicate sensations. Furthermore, a pearl pigment using multiple reflection can be prepared by modifying a multilayer film made of different materials, and a high-intensity reflective powder can be realized.

According to the coated fine particles used in the coating material, it is also possible to produce a coating material imparted with characteristics such as corrosion resistance and antibacterial properties of the coated ultrafine particles or thin film. Also, a high-intensity paint for nighttime can be realized by using a fluorescent material or a high-intensity metallic material. Further, it is possible to realize a coating material having an ultraviolet cut rate of approximately 100%. In addition, it is possible to realize a product such as a highly durable paint used for outdoor building materials having both corrosion resistance and UV protection effect.
In addition, the surface of the fine particles can be colored (colored) by coating the surface of the fine particles with a fine particle or a thin film. As a result, coated fine particles with various color tones can be realized.

In addition, according to the coated fine particles according to the above-described embodiment, it is possible to coat (modify) thin particles or ultrafine particles made of a cosmetic material or a coating material almost uniformly on fine particles having an average particle size of 50 μm or less. However, even when a powder of 50 μm or more is used as a material for cosmetics or paints, it is of course possible to modify the surface. That is, there is almost no restriction on the particle size of the base fine particles. For this reason, at least one of color, coloring, gloss, light emission (fluorescence), phosphorescence, high luminance, light reflection, and ultraviolet protection can be improved in the coated fine particles coated with the cosmetic material. It is also possible to produce a coating material in which the color or color development is changed.
Further, by using a polygonal barrel sputtering apparatus, coated fine particles having almost no impurities can be prepared.

Next, the analysis results of the coated fine particles obtained by coating the fine particles with TiO ₂ on the fine particles using the barrel sputtering method will be described.

TiO ₂ is industrially used as a water photodecomposition reaction utilizing the photocatalytic properties of anatase crystals, decomposition removal of environmental pollutants, and metallic paint pigments and UV scattering absorbers utilizing the photophysical properties of rutile crystals. Has been. However, in the photocatalyst, aiming at further improvement of the catalyst efficiency, a high surface area has been sought, and the development of a low specific gravity photocatalyst capable of photodegrading marine pollutants is also being studied. On the other hand, development of new materials with new functions or high functions is also desired for optical physical materials. Therefore, by modifying TiO ₂ on the surface of an arbitrary fine particle carrier, it was considered to answer such a requirement, and the basic research was conducted.

First, the experimental method will be described. A polygonal barrel sputtering apparatus shown in FIG. 1 was used for the production of the coated fine particles. A Ti target is used as the barrel center target 2, a sample is placed under the Ti target, and the vacuum vessel 1 is evacuated. Then, oxygen was mixed with argon by arbitrary composition ratios, and reactive sputtering was performed. When SiO ₂ glass plate or quartz plate is used for the substrate, the barrel is fixed, and when SiO ₂ glass powder (particle size is 74 to 149 μm) or Al ₂ O ₃ powder (120 mesh) is used, the barrel is rotated. Sputtering was performed. In both cases, the condition was that the RF output was 200 W. The prepared sample is crystal structure and crystallinity with "X-ray diffractometer", surface observation with "scanning electron microscope", element distribution with "energy dispersive spectrometer", color tone with "optical microscope", and "UV-visible spectroscopy" The chemical composition was evaluated with a “photometer”.

(Gas pressure change)
First, a silica glass plate was used as a substrate, and the change in crystal structure due to the difference in total pressure (Ar + O ₂ gas) was examined. The oxygen partial pressure here was 50%. FIG. 3 is a diagram showing an X-ray diffraction (XRD) pattern of a silica glass substrate. In this pattern, other peaks were hardly recognized except for a broad peak around 2θ = 23 °. On the other hand, FIG. 3 also shows a pattern of a sample prepared under conditions of a total pressure of 1 Pa, but the rutile-type crystal (110) peak and (211) peak at 2θ = 27.3 ° and 54.1 °, respectively. Intensities were observed at 208 cps and 43 cps, and anatase type crystal (101) peak was observed at 2θ = 25.3 ° at an intensity of 45 cps. The lower side of FIG. 3 shows high sensitivity measurement in the range of 2θ = 20 to 35 °. Also in this figure, anatase peaks are confirmed. Next, in the sample having a total pressure of 3 Pa, only the rutile crystal (110) peak and the (211) peak were confirmed at intensities of 125 cps and 30 cps. Only the rutile-type peak was confirmed at the lower side of FIG. Therefore, it was found that the crystal form changes depending on the difference in total pressure. The examination by changing the oxygen partial pressure was performed in the same manner, but it was found that the change in the oxygen partial pressure did not affect the crystal type and only the crystallinity changed.

(Correlation diagram)
FIG. 4 is a correlation diagram between the total pressure and the oxygen partial pressure with respect to the crystal form of the modifying substance. From this figure, it is an amorphous region at a total pressure of 0.7 Pa or less, a mixed crystal region of rutile + anatase type crystal at a total pressure of 0.7 to 1.2 Pa, and a rutile at a portion of 1.2 Pa or higher. It was found to be a type crystal region. Here, paying attention to the rutile crystal, the conditions under which the crystallinity was highest were a total pressure of 1.1 Pa and an oxygen partial pressure of 30%. Next, a fine particle surface modification of TiO ₂ was attempted under this gas condition.

(Color tone)
FIG. 5 (A) is a photograph showing a powder sample before modification, and FIG. 5 (B) is a photograph showing a powder sample after modification. FIG. 6A is a photograph of a powder sample before modification taken with an optical microscope, and FIG. 6B is a photograph of a powder sample after modification taken with an optical microscope.

  First, looking at the color of the prepared powder sample, as shown in FIG. 5, the unmodified alumina was white, whereas the modified sample was light yellow. Further, even when one particle was observed with an optical microscope, the sample after modification was similarly light yellow as shown in FIG.

(SEM / EDS)
FIG. 7 is a photograph showing the results of surface analysis of a sample using unmodified alumina and modified alumina using SEM and EDS. The surface of the sample before modification was relatively flat, and no Ti element was observed. On the other hand, no island-like structure was observed in the modified sample, and the surface was flat, but it was confirmed that Ti element was uniformly distributed on the surface. From this result, it was found that the sample surface was coated with a uniform film.

(UV spectrum)
FIG. 8 is a graph showing the results of measuring the ultraviolet / visible absorption spectrum. Reference numeral 31 is based on the sample prepared this time. Reference numeral 32 is measured using a commercially available rutile crystal powder. Reference numeral 33 is an anatase-type spectrum quoted from the literature. From FIG. 8, the spectrum of the prepared sample showed a remarkable rise in absorption from around 380 nm. This is considered to be light absorption corresponding to the photoelectron excitation between the band gaps of the substance, and the coating film is considered to be TiO _{2 when} considered together with the results of the previous optical microscope, SEM, and EDS. However, it can be seen that the obtained spectrum is close to the anatase type even though the rutile crystal was produced under the main conditions. This was considered back to the sample prepared on the plate. FIG. 9A is a diagram showing a result of XRD measurement of a powder sample before annealing, and FIG. 9B is a diagram showing a result of XRD measurement of a powder sample after annealing. Here, a mixed crystal sample was used, but it was found that when this sample was annealed at 600 ° C. for 1 hour under the condition of transition from amorphous to anatase, the peak intensity of anatase increased significantly. This indicates that the prepared film contains amorphous TiO ₂ . In other words, when viewed macroscopically, in addition to the rutile and anatase type crystals recognized by XRD, there are amorphous parts that cannot be observed. Can explain.

It is a block diagram which shows the outline of the polygon barrel sputtering apparatus used when manufacturing the coating fine particle by embodiment of this invention. It is a perspective view which shows the flake-shaped fine particle which is an example of the fine particle used for the coating fine particle by embodiment of this invention. It is a figure which shows the X-ray-diffraction (XRD) pattern of a silica glass substrate. It is a correlation diagram of the total pressure and oxygen partial pressure with respect to the crystal form of a modifier. (A) is a photograph showing a powder sample before modification, and (B) is a photograph showing a powder sample after modification. (A) is a photograph of a powder sample before modification taken with an optical microscope, and (B) is a photograph of a powder sample after modification taken with an optical microscope. It is a photograph which shows the result of having performed the surface analysis of the sample for unmodified alumina and modified alumina using SEM and EDS. It is a graph which shows the result of having measured an ultraviolet and visible absorption spectrum. (A) is a figure which shows the result of having performed the XRD measurement of the powder sample before annealing, (B) is a figure which shows the result of having performed the XRD measurement of the powder sample after annealing.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Vacuum container 1a ... Cylindrical part 1b ... Hexagonal barrel 2 ... Target 3 ... Fine particle (powder sample)
3a ... Thin film 3b ... Ultra fine particle 3c ... Aggregation of ultra fine particle 4-9 ... Piping 10 ... Turbo molecular pump (TMP)
11 ... Pump (RP)
DESCRIPTION OF SYMBOLS 12-14 ... 1st-3rd valve 15 ... Nitrogen gas introduction | transduction mechanism 16 ... Argon gas introduction | transduction mechanism 17a, 17b ... Heater 18 ... Vibrator 19 ... Pressure gauge 20 ... Gas introduction mechanism 23 ... Flakes-shaped fine particles 31 ... Preparation sample 32 ... rutile 33 ... anatase

Claims (14)

By rotating a vacuum vessel having an internal cross-sectional shape of a polygon about a rotation axis in a direction substantially perpendicular to the cross-section, sputtering is performed while stirring or rotating the fine particles in the vacuum vessel. Coated with ultrafine particles or thin film having a particle diameter smaller than that of the fine particles, and used for cosmetics or paints,
The coated fine particles, wherein the ultrafine particles or the thin film comprises one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group. By rotating a vacuum vessel having a polygonal cross-sectional shape about a direction perpendicular to the cross section as a rotation axis, the fine particles in the vacuum vessel are agitated or rotated, and sputtering is performed while vibrating the fine particles. The surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles, and are coated fine particles used for cosmetics or paints,
The coated fine particles, wherein the ultrafine particles or the thin film comprises one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group. While directly or indirectly heating a vacuum vessel having an internal cross-sectional shape of a polygon, the fine particles in the vacuum vessel are agitated by rotating the vacuum vessel about a direction substantially perpendicular to the cross-section. Alternatively, by performing sputtering while rotating, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles, and are coated fine particles used for cosmetics or paints,
The coated fine particles, wherein the ultrafine particles or the thin film comprises one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group. A fine particle or a thin film having a particle diameter smaller than that of the fine particle is coated on the surface of the fine particle, and the fine particle or the thin film is made of a metal, an oxide, a nitride, and a carbide. A coated fine particle comprising one selected from the group consisting of two or more composites selected from the group. The coated fine particles used in the cosmetic or paint according to any one of claims 1 to 4 are pearl pigments, and the metal is Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu. And the oxide is selected from the group consisting of SiO ₂ , TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Ag ₂ O and WO _3. Coated fine particles, which are at least one oxide selected from the group consisting of: The coated fine particles used in the cosmetic according to any one of claims 1 to 4 are high-intensity reflective materials, and the metal is Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu. And the oxide is selected from the group consisting of SiO ₂ , TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe ₂ O ₃ , Ag ₂ O and WO _3. Coated fine particles, which are at least one oxide selected from the group consisting of: The coated fine particles used in the cosmetic according to any one of claims 1 to 4 are materials having an ultraviolet protection effect by scattering or reflecting ultraviolet rays, and the metal includes Pt, Au, Ti, Ni , Si, Al, Fe, Ag, Cu, and W, and the oxide is SiO ₂ , TiO ₂ , NiO, ZnO ₂ , Al ₂ O ₃ , MgO, Fe _2. Coated fine particles, which are at least one oxide selected from the group consisting of O ₃ , Ag ₂ O and WO ₃ . The coated fine particles used in the cosmetic or paint according to any one of claims 1 to 4 are a photochromic material, a fluorescent material, or a phosphorescent material, wherein the ultrafine particles or the thin film contains a rare earth ion. A coated fine particle comprising at least one selected from the group consisting of metal or rare earth metal oxides and metal oxides having photochromic properties. The coated fine particles used in the paint according to any one of claims 1 to 4 are high-brightness metallic pigments, and the metal is Pt, Au, Ag, Cu, Al, Si, Ti, Ni, V , Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, In, W, Os, and Ir, and the oxide is at least selected from the metal group. It is one metal oxide, the nitride is at least one metal nitride selected from the metal group, and the carbide is at least one metal carbide selected from the metal group. Coated fine particles. The coated fine particles used in the paint according to any one of claims 1 to 4 are corrosion-resistant materials, and the metal is made of Pt, Au, Si, Ti, Zn, Zr, Nb, and W. At least one selected from a metal group, the oxide is at least one metal oxide selected from the metal group, and the nitride is at least one metal nitride selected from the metal group. The coated fine particles, wherein the carbide is at least one metal carbide selected from the metal group. The coated fine particles used in the paint according to any one of claims 1 to 4 are materials having antibacterial properties, and the metal includes Pt, Au, Ag, Cu, Al, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, Ag, In, W, Os and at least one selected from the metal group, and the oxide is selected from the metal group At least one metal oxide, wherein the nitride is at least one metal nitride selected from the metal group, and the carbide is at least one metal carbide selected from the metal group. Feature coated fine particles. The coated fine particles used in the paint according to any one of claims 1 to 4 are materials having an ultraviolet protection effect by scattering, reflecting or absorbing ultraviolet rays, and the metal includes Pt, Au, Ag At least one selected from the group consisting of Cu, Al, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, Ag, In, W, Os, and Ir. The oxide is at least one metal oxide selected from the metal group, the nitride is at least one metal nitride selected from the metal group, and the carbide is selected from the metal group. Coated fine particles, wherein the coated fine particles are at least one metal carbide. The fine particles according to any one of claims 1 to 12, wherein the fine particles are selected from the group consisting of metals, oxides, nitrides, carbides, carbon materials, and polymers, or two or more selected from the groups. Coated fine particles comprising a composite of 5. The coated fine particle according to claim 1, wherein the surface of the fine particle is colored by coating with an ultra fine particle or a thin film.

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