WO2006006397A1

WO2006006397A1 - Coated fine particles

Info

Publication number: WO2006006397A1
Application number: PCT/JP2005/011888
Authority: WO
Inventors: Takayuki Abe; Yuuji Honda
Original assignee: Youtec Co., Ltd
Priority date: 2004-07-07
Filing date: 2005-06-22
Publication date: 2006-01-19
Also published as: JP2006022176A

Abstract

Coated fine particles that are improved in at least one of color, color development, gloss, luminescence (fluorescence/phosphorescence), high brightness, light reflection, and protection against ultraviolet light. The coated fine particles are produced by rotating a vacuum vessel (1) having a polygonal internal sectional form in a direction substantially perpendicular to the section as a rotation axis to perform sputtering while agitating or rotating fine particles (3) contained in the vacuum vessel (1) and, thus, to coat ultrafine particles having a smaller particle diameter than the fine particles or a thin film onto the surface of the fine particles (3). The ultrafine particles or the thin film comprise(s) one member selected from the group consisting of metals, oxides, nitrides, and carbides, or a composite of two or more members selected from the above group, and the coated fine particles can be used as cosmetic preparations or coating materials.

Description

Coated fine particles 1. Technical field

The present invention relates to coated fine particles, and more particularly, to coated fine particles having a surface coated with ultrafine particles or a thin film made of a cosmetic material or a coating material.

2. Background Technical Document

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

In order to improve the color and color development of powder (fine particles), modifying (coating) ultra fine particles or thin film on the surface of the powder is a very effective means. 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, the surface modification of the powder can impart the properties of the material to be modified (for example, UV reflection, fluorescence, etc.).

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 the base particles by a weak adsorption force such as electrostatic force and surface tension of moisture. However, if the modifying material is not micronized to an average particle size of several tens to several hundreds of nanometers, the powder surface modification method cannot actually be used. Limited modifier material. In addition, since the particle size and shape of the fine particles vary, it is difficult to uniformly modify the surface of each fine particle. In addition, since it can be modified to powder only in the form of fine particles, there is a disadvantage that a highly reflective flat surface or the like cannot be formed.

As another conventional example, the surface modification of the powder has been performed also by the plating method. However, the preparation process is complicated and it is difficult to avoid contamination during preparation. In the cosmetic field, the surface modification method of the powder by plating is difficult because it is difficult to modify oxide materials that are widely used in cosmetics, and that it is difficult to treat slag waste liquid due to environmental problems. It is not used much. On the other hand, many of the materials used in paint products, such as powder paints and pigments used in paints, are used as powders. Most of these powders use the color and color of the material itself. However, conventional paint materials alone cannot meet diverse needs in terms of color and color development. In addition, new needs such as anti-corrosion and antibacterial paints are emerging, and the development of paints that meet these needs is expected.

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

3. Disclosure of the Invention

By the way, demands for cosmetics in recent years have become stricter, and there is a demand for improvement of coloring and development of high-intensity powder materials. On the other hand, conventional paint materials alone cannot meet diverse needs in terms of color and color development. In addition, new needs such as anti-corrosion and antibacterial paints are emerging, and development of paints that meet these needs is expected.

The present invention has been made in view of the above circumstances, and its purpose is to provide at least one of color, color development, gloss, phosphorescence / luminescence (fluorescence and phosphorescence), high brightness, light reflection and UV protection. The object is to provide coated fine particles which are improved by one. Another object of the present invention is to provide coated fine particles coated with ultrafine particles or a thin film made of a functional cosmetic material or coating material on the surface of the fine particles. In order to solve the above problems, we focused on sputtering, which is one of physical vapor deposition methods. This method also makes it difficult to uniformly coat the entire powder with fine particles, but it is extremely versatile because it does not require a support, can be modified from metal to inorganic on the powder surface, has a low environmental impact, and so on. Is considered high. This time, we invented the polygonal barrel sputtering method, which is a new modification of the powder surface. This method uses a dry sputtering method, and it is possible to modify metals, oxides, etc. almost uniformly on the powder surface, and the modification process is much shorter than conventional methods. Because there is almost no impurities mixed in, there is no need for waste liquid treatment, and various combinations of modified products (ultrafine particles or thin films) and modified products (fine particles) are possible. It is possible to modify the material with the characteristics of fine particles on the surface of the fine particles and to control the form of the material (from thin film to fine particles) to be modified (coated) on the surface of the fine particles. There are many advantages such as being able to change colors. 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 characteristics, etc.) on the powder surface. It was also easy to modify the surface of the film in the form of a thin film.

This will be specifically described below.

The coated fine particles according to the present invention rotate 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. Sputtering is performed so that 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 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 agitate or rotate 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. Along with vibration to the fine particles The surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle size than the fine particles, and the coated fine particles are used for cosmetics or paints.

The coated fine particles according to the present invention directly or indirectly heat a vacuum vessel having a polygonal cross-sectional shape, and rotate the vacuum vessel about a direction perpendicular to the cross-section as a rotation axis. By performing sputtering while stirring or rotating the fine particles in the vacuum vessel, the surface of the fine particles is coated with ultrafine particles or thin films having a particle diameter smaller than the fine particles, and the coated fine particles used in cosmetics or paints There,

According to each of the coated fine particles according to the present invention, a generally used thin film or ultrafine particle made of a cosmetic material or a coating material is substantially added to a base particle of a cosmetic or paint having an average particle diameter of 50 im or less. It becomes possible to coat (modify) uniformly. However, even when powder of 50 m or more is used as a material for cosmetics or paints, it is of course possible to modify the surface. In other words, there are almost no restrictions on the particle size of the base particles. For this reason, at least one of color, coloring, gloss, fluorescence and phosphorescence, high brightness, light reflection, and ultraviolet ray protection can be improved in the coated fine particles coated with cosmetic materials or paint materials.

The coated fine particles according to the present invention are coated fine particles whose surface is coated with ultra fine particles or a thin film having a particle diameter smaller than that of the fine particles, and used for cosmetics or paints, wherein the ultra fine 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 above group. As described above, according to the present invention, the coated fine particles that improve at least one of color, color development, gloss, luminescence (fluorescence phosphorescence), phosphorescence, high brightness, light reflection, and UV protection can be obtained. Can be provided. According to another aspect of the present invention, coated fine particles in which the surface of the fine particles is coated with ultrafine particles or a thin film made of a cosmetic material or a coating material can be provided.

4. Brief description of 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.

FIG. 2 is a perspective view showing flake-shaped fine particles which are an example of fine particles used for the coated fine particles according to the embodiment of the present invention.

FIG. 3 is a diagram showing an X-ray diffraction (XRD) pattern of a silica glass substrate. Figure 4 shows the correlation between the total pressure and oxygen partial pressure for the crystalline form of the modifier. 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. 6 (A) is a photograph of the powder sample before modification taken with an optical microscope, and Fig. 6 (B) is a photograph of the powder sample after modification taken with an optical microscope.

Figure 7 is a photograph showing the results of surface analysis of the sample using unmodified alumina and modified alumina using SEM and EDS.

Fig. 8 is a graph showing the results of measurement of the ultraviolet / visible absorption spectrum. Fig. 9 (A) shows the result of XRD measurement of the powder sample before annealing, and Fig. 9 (B) shows the result of XRD measurement of the powder sample after annealing.

5. BEST MODE FOR CARRYING OUT THE INVENTION

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

This polygonal barrel sputtering device has fine particles (powder) on its surface. It is an apparatus for coating ultrafine particles or thin films having a particle diameter smaller than that of a child.

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

The vacuum vessel 1 is provided with a rotating mechanism (not shown). By this rotating mechanism, the hexagonal barrel 1b is rotated or reversed as indicated by an arrow, or is shaken like a pendulum. The coating process is performed while stirring or rotating the fine particles 3 in the mold barrel 1b. 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 cosmetic material such as a pearl pigment, a high-intensity reflective material, a material having an ultraviolet protection effect, a photochromic material, a fluorescent material, or the like is placed on the central axis of the cylinder. A sputtering target 2 made of a material that can be produced by reactive sputtering is arranged, and this target 2 is configured so that the angle can be freely changed. This allows the target 2 to be directed in the direction in which the microparticles 3 are positioned when the hexagonal barrel 1 b is rotated, inverted, or coated while being shaken like a pendulum, thereby increasing the sputtering efficiency. Can be raised.

The substance constituting the target 2 is composed of one selected from the group consisting of metals, oxides, nitrides and carbides, or a composite of two or more selected from the above group, and can be used as cosmetics. Material. For example, pearl pigments, high-brightness reflective materials, materials that protect against ultraviolet rays by reflecting ultraviolet rays, photochromic materials, or fluorescent materials, and other cosmetic materials. The substance constituting the target 2 is composed of 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 paint. It is a paint material. For example, paint materials such as high-brightness metallic pigments, inorganic fluorescent materials, materials with corrosion resistance, materials with antibacterial properties, and materials with UV protection effects.

In addition, the target 2 arranged in the vacuum vessel 1 may be one type or a plurality of types. For example, as the target 2, a plurality of targets each made of a plurality of materials selected from the above-described cosmetic materials or paint materials may be arranged in parallel. Further, a target made of one material selected from the above-mentioned cosmetic material or paint material and a target made of an oxide of the material contained in the above-mentioned cosmetic material or paint material may be arranged side by side. Good. The substance that coats the fine particles 3 is the substance that constitutes the target 2. If there are multiple types of target 2, they are a mixture or alloy of these. In addition, when target 2 is composed of one or more materials selected from the above-mentioned cosmetic materials or paint materials, and reactive sputtering is performed, the substance covering fine particles 3 is the target. It is a substance (for example, oxide) generated from the substance that constitutes 2 or a mixture of this and the substance that constitutes 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 17 a for directly heating the fine particles 3 in the vacuum vessel 1 and a heater 17 b for heating indirectly. In addition, this apparatus includes a vibrator 18 for applying vibration to the fine particles 3 in the vacuum container 1. The apparatus also includes a pressure gauge 19 that measures the internal pressure of the vacuum vessel 1. The apparatus also includes a nitrogen gas introduction mechanism 15 that introduces nitrogen gas into the vacuum container 1 and an argon gas introduction mechanism 16 that introduces argon gas into the vacuum container 1. A gas introduction mechanism 20 that can introduce oxygen or the like is also provided so that reactive sputtering can be performed. The apparatus also 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, polygonal barrel sputtering method for coating ultrafine particles or a thin film composed of T i 0 ₂ is an example of cosmetic material will be described.

First, for example, 6 grams of fine particles 3 are introduced into the hexagonal barrel 1b. As the fine particles 3, for example, Si 0 ₂ or A 1 ₂ 0 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 a flake shape, for example. The material of the fine particles 3 is not limited, and may be made of, for example, a cosmetic material.

Next, a high vacuum state is created in the hexagonal barrel 1b using the turbo molecular pump 10, and the hexagonal barrel is heated with the heater 17 from room temperature to 400 ° C, for example, depending on the case. The pressure in the barrel is reduced to 1 X 1 0 ^{_ 5} Pa, for example. Thereafter, argon and oxygen are introduced into the hexagonal barrel 1 b 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 target material may be changed as appropriate. And rotate By rotating the hexagonal barrel 1 b at 20 W for 60 minutes at 20 rpm by the mechanism, the fine particles 3 in the hexagonal barrel 1 b are rotated and stirred. At that time, the target is directed in the direction in which the 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, T i 0 ₂ can be supported on the surface of the fine particles 3 as ultrafine particles or a thin film. These conditions are merely examples, and the present invention is not limited to these conditions.

According to the above-mentioned polygonal parel sputtering apparatus, the hexagonal barrel itself can be rotated to rotate and stir the powder itself, and the barrel can be made to be hexagonal so that the powder can be periodically dropped by gravity. Can do. For this reason, the stirring efficiency can be remarkably improved, and agglomeration of the powder due to moisture or electrostatic force, which is often a problem when the powder is formed, can be prevented. In other words, the stirring and the pulverization of the agglomerated powder can be performed simultaneously and effectively by rotation. Also, it is 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 made of a cosmetic material or a coating material and having a particle size much smaller than that of the fine particles having a very small particle size. Specifically, the particle size is

It becomes possible to coat ultrafine particles or thin films made of cosmetic materials or paint materials on fine particles of 5 nm or more. 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. The ultra fine 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.

The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

For example, in the embodiment described above, vibration is applied to the fine particles 3 in the hexagonal barrel by the vibrator 18, but instead of the vibrator 18 or in addition to the vibrator 18, a rod-like shape is formed in the hexagonal barrel. It is also possible to apply vibration to the fine particles 3 by rotating the hexagonal barrel while the member is accommodated. This makes it possible to more effectively prevent agglomeration, which is a problem when handling powder. It becomes.

Next, the coated fine particles according to the embodiment of the present invention will be described. The coated fine particles are preferably manufactured 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 sputtered using the polygonal barrel sprack apparatus shown in FIG. 1, so that the surface of the fine particles (powder) is coated with ultrafine particles or a thin film having a smaller particle size than the fine particles. 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 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 a polygonal barrel sputtering method. A thin film or ultrafine particles composed of one selected from the group consisting of or two or more composites selected from the group described above 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 Pt, Au,

Ag, Cu, Al, Si, Ti, Mn, Fe, Co, Ni, Zn, In, Sn, W, Os, and Ir selected from a metal group consisting of Ir force 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 at least one metal carbide selected from the group of metals. As cosmetic materials, it is desirable to use materials that are safe and highly adaptable to the human body and skin, and that are chemically stable to light, heat, moisture, etc. Specifically, when used as a cosmetic material, the metal is selected from the metal group consisting of Pt, Au, Ti, Ni, Si, Al, Fe, Ag, Cu, and W. at least is one, the oxide S I_〇 _2, T I_〇 _2, N i O, Z N_〇 _{_2,} a 1 ₂ 0 _3,

At least one selected from the group consisting of Mg 0, Fe ₂ 0 ₃ , Ag ₂ 0 and W 0 ₃ One oxide is preferred. However, substances that are not harmless to the human body and skin, or substances that have not been used as cosmetics until now and have not been tested for safety, can be used after the coated fine particles have been 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 that can be used as pearl pigments, high-brightness reflective materials, and materials that have an ultraviolet protection effect by reflecting and scattering ultraviolet rays can be produced. Therefore, it is possible to realize a new makeup cosmetic that emits pearly luster. Moreover, it is possible to realize an ultraviolet ray protection cosmetic product having an ultraviolet ray cut rate of approximately 100%. The metal suitable for the high-intensity reflective material is at least one selected from the metal group consisting of Pt, Au, Ti, Ni, Si, A1, Fe, Ag, Cu, and W. One, and the said oxide is S i 0 _2, T I_〇 _2, N i O, Z N_〇 _{_2,} A 1 ₂ 0 _3, Mg_〇 from _{_{F e 2 0 3, A g}} 2 0 and WO ₃ And at least one oxide selected from the group consisting of In addition, the metal suitable for the material having an ultraviolet protection effect is at least selected from the metal group consisting of Pt, Au, Ti, Ni, Si, A1, Fe, Ag, Cu, and W. is one with, the oxide S I_〇 _2, T I_〇 _2, N i O, Z N_〇 _{_{_{2, a 1 2 0 3,}}} Mg _{_{〇, F e 2 0 3, a}} g 2 0 and WO _And at least one oxide selected from the group consisting of ₃ .

Further, 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 selected from the group consisting of rare earth metals containing rare earth ions, oxides of rare earth metals, and oxides of metals having photochromic properties (for example, tungsten oxide). It is preferable to use one consisting of both. A photochromic material is a material that changes color with light.

Further, 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, the thickness of the titanium dioxide has various glossiness due to interference effects. Appearance is obtained. 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 multi-angle barrel sputtering method. In addition, it is possible to improve the feeling of use of cosmetics by modifying the surface of the fine particles. In addition, dispersibility due to changes in the specific gravity of the fine particles can be improved. By taking advantage of these advantages, it is expected to prepare further new 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. For example, a new cosmetic foundation can be produced.

Fine particles comprising as a base foundation (S I_〇 _2, polymer beads, mica, etc.) a metal (e.g. A u, T i) as described above to the surface of the oxide (e.g., T i 0 ₂₎ was modified as a thin film, its By controlling the film thickness, powders with various colors can be prepared using the interference action. Cosmetic foundations are made by mixing fine particles of red, yellow, white and black. For example, skin color foundations are made by mixing powders with red, yellow, white and black colors at an appropriate ratio to produce skin color, but there are very few powders with red and yellow colors. In general, red F e ₂ 〇 _3, yellow is using a pigment, to control the various color tones and the this make various red and yellow inorganic fine particle to be selectively used depending on the use of other materials is required The 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. Further, T i 0 _2, Z N_〇 ₂ a base foundation particles (S i O _2, polymer beads, mica, etc.) By carrying as ultra-fine particles or thin film on the surface of the UV scattering powder foundation prepared can do. In addition, a light scattering powder foundation capable of hiding skin color unevenness can be prepared by uniformly dispersing other oxides as ultrafine particles 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 fine particles, and pearl pigments using multiple reflections can be prepared by sandwiching multiple layers of different materials or polymers between the same materials. High-intensity powder (Daros) can be realized.

Further, the surface of the microparticle, for example W_〇 _3, T io _2, or ultra-fine particles or bearing a thin film consisting of a composite material or Ranaru color change material, the the Photo chromic powder that have a variety of colors prepared can do. 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 (phosphorescent) outdoors, and as indoors fluorescent or phosphorescent. New powders that emit light can be prepared.

Hereinafter, specific examples of the coated fine particles used in the paint will be described.

The base fine particles are accommodated in a vacuum container of a polygonal barrel sputtering apparatus shown in FIG. 1, and the fine particles are selected from the group consisting of metals, oxides, nitrides and carbides by the polygonal barrel sputtering method, or the above-mentioned A thin film or ultrafine particle composed of two or more composites selected from the group is coated. The fine particles may be made of a coating material. The metals are Pt, Au, Ag, Cu, Al, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, In. , W, Os and Ir, or at least one selected from a metal group consisting of rare earths, and 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, and the carbide is at least one metal carbide selected from the metal group. As a result, high-intensity metallic pigments, inorganic fluorescent and phosphorescent materials Materials with anti-corrosion or antibacterial properties, and materials with ultraviolet protection effects by reflecting or absorbing ultraviolet rays. The metal suitable as a material is at least one selected from the group consisting of Pt, Au, Si, Ti, Zn, Zr, Nb and W. 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 the metal group. Is at least one metal carbide selected from

However, substances that are harmful to the environment (excluding Sn, Pd, Hg, As, radioactive substances, etc., and their compounds (oxides, etc.)) are excluded from the above metals.

Fine particles comprising a mother powder coating (S I_〇 _{_2,} A 1 ₂ 0 _3, mica) above Symbol metal surface (e.g., A u, T i) or oxide (e.g., T I_〇 ₂₎ thin film By controlling the film thickness, powders with various colors can be prepared. Organic pigments can produce a variety of colors, but they are inferior in heat resistance, light resistance (ultraviolet ray resistance), and durability (oxidation over many years), so it is necessary to prepare inorganic pigments with various colors.

The above substance (especially 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 the delicate sensations of Japanese people. Furthermore, pearl pigments using multiple reflections 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. In addition, a high-intensity paint for nighttime can be realized by using a fluorescent material or a high-intensity metallic material. Also, it is possible to realize a coating material having an ultraviolet cut rate of approximately 100%. In addition, it is possible to realize products such as highly durable paints used for outdoor building materials that have both corrosion resistance and UV protection effects.

Also, the surface of the fine particles can be colored by coating them with ultra fine particles or a thin film. (Color development). 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 embodiment, thin films or ultrafine particles made of cosmetic materials or paint materials can be coated (modified) almost uniformly on fine particles having an average particle size of 50 μΠ1 or less. It becomes possible. However, even when powder of 50 Aim or more is used as a cosmetic or paint material, surface modification is possible. In other words, there are almost no restrictions on the particle size of the base fine particles. For this reason, at least one of color, color development, gloss, luminescence (fluorescence), phosphorescence, high brightness, light reflection, and UV protection can be improved in coated fine particles coated with cosmetic materials. It is also possible to produce a coating material in which the color or color development is changed. Also, by using a polygon barrel sputtering apparatus, coated fine particles with almost no impurities can be prepared.

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

T I_〇 _2, anatase photolysis reaction of water utilizing the photocatalytic decomposition removal of environmental pollutants, also methallyl click paint pigments and UV scattering agents which make use of photophysical qualities of rutile crystals As industrially used. However, with regard to photocatalysts, efforts have been made to increase the surface area with the aim of further improving the catalyst efficiency, and development of low specific gravity photocatalysts 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 materials. Therefore any particulate support surface, by modifying T i 〇 _2, believed to answer such a request, made the basic research. First, the experimental method will be explained. The polygonal barrel sputtering device shown in Fig. 1 was used for the production of coated fine particles. Use a Ti target for the barrel center target 2, place a sample under this Ti target, and evacuate the vacuum vessel 1. Thereafter, oxygen was mixed with argon at an arbitrary composition ratio, and reactive sputtering was performed. When using S i 0 ₂ glass plate or quartz plate for the substrate, fix the barrel, and also use S i 0 ₂ glass powder (particle size 7 4 to 14 9 im) or A 1 ₂ 0 ₃ powder. When using the powder (1 2 0mesh), sputtering was performed by rotating the barrel. In both cases, the condition was that the RF output was 200 W. Samples were prepared using an X-ray diffractometer with a crystal structure, crystallinity, surface observation with a scanning electron microscope, element distribution with an energy dispersive spectrometer, color tone with an optical microscope, and UV-visible. The chemical composition was evaluated with a spectrophotometer.

(Gas pressure change)

First, a silica glass plate was used as the substrate, and changes in the crystal structure due to differences in total pressure (A r +0 ₂ gas) were 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, there were almost no other peaks except for a broad peak around 20 ° = 23 °. On the other hand, Fig. 3 shows the force S, 2 0 = 27.3 °, 54.1 ° indicating the pattern of the sample prepared under the condition of 1 Pa of total pressure. ) And (2 1 1) peaks were observed at intensities of 20 8 cps and 4 3 cps, respectively, and anatase crystal (1 0 1) peaks were observed at 2 0 = 2 5.3 cps at an intensity of 45 cps. It was. The lower side of Fig. 3 shows high-sensitivity measurements in the range of 20 = 20 to 35 °. Also in this figure, anatase peaks are confirmed. Next, in the sample with a total pressure of 3 Pa, only the rutile crystal (1 1 0) peak and (2 1 1) peak were confirmed at intensities of 1 2 5 cps and 30 cps. Only the rutile peak was observed at the bottom of Fig. 3. Thus, it was found that the crystal form changes due to the difference in total pressure. The examination by changing the oxygen partial pressure was carried out in the same way, but it was found that the change in the oxygen partial pressure did not affect the crystal form and only the crystallinity changed.

(Correlation diagram)

Figure 4 shows the correlation between the total pressure and oxygen partial pressure for the crystalline form of the modifier. From this figure, it is an amorphous region under the condition of a total pressure of 0.7 Pa or less, and a portion of the total pressure of 0.7 to 1.2 Pa is a mixed crystal region of rutile + anatase type crystal.

It was found that the portion above 2 Pa was a rutile crystal region. Here, focusing on the rutile crystals, the conditions under which the crystallinity was highest were the total pressure 1. l Pa and the oxygen partial pressure 30%. Then, the fine particle surface modification of T I_〇 ₂ in the gas condition Tried.

(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. 6 (A) is a photograph of the powder sample before modification taken with an optical microscope, and Fig. 6 (B) is a photograph of the 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, while the modified sample was light yellow. In addition, even when one particle was observed with an optical microscope, the modified sample showed a light yellow color as shown in FIG.

(S EM-ED S)

Figure 7 is a photograph showing the results of a surface analysis of the 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 the Ti element was uniformly distributed on the surface. From this result, it was found that the sample surface was covered with a uniform film.

(UV spectrum)

Fig. 8 is a graph showing the results of measurement of 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 significant rise in absorption from around 380 nm. This is considered to be light absorption corresponding to photoelectron excitation between the bandgap of the material, and the coating film is considered to be T i 0 ₂ in combination 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 type crystal was produced under the main conditions. This was considered by going back to the sample prepared on the plate. Fig. 9 (A) shows XRD measurement of powder sample before annealing. FIG. 9 (B) is a diagram showing the result of XRD measurement of the powder sample after annealing. Here, a mixed crystal sample was used, but it was found that if the sample was annealed at 60 ° C for 1 hour under the conditions for transferring from amorphous to anatase, the peak intensity of the anacousse increased significantly. This indicates that it contains T i 0 ₂ of amorphous preparation membrane. In other words, when the cover film is viewed macroscopically, in addition to the rutile and anatase type crystals observed in XRD, there are amorphous parts that cannot be observed. I can explain.

Claims

The scope of the claims

1. By rotating a vacuum vessel having an internal cross-sectional shape of a polygon with a substantially perpendicular direction to the cross-section as a rotation axis, sputtering is performed while stirring or rotating fine particles in the vacuum vessel. A fine particle having a particle diameter smaller than that of the fine particle or a thin film is coated on the surface of the fine particle, and the fine particle is used for cosmetics or paint,

The ultrafine particles or the thin film is composed of one selected from the group consisting of metals, oxides, nitrides and carbides, or two or more composites selected from the group. .

2. 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, the fine particles in the vacuum vessel are agitated or rotated and the fine particles are vibrated. Sputtering while adding, the surface of the fine particles are coated with ultrafine particles or thin film having a smaller particle diameter than the fine particles, and are coated fine particles used in cosmetics or paints,

3. Directly or indirectly heating a vacuum vessel having an internal cross-sectional shape of a polygon, and rotating the vacuum vessel about a direction substantially perpendicular to the cross-section as a rotation axis, By performing sputtering while stirring or rotating the fine particles, ultrafine particles or thin films having a smaller particle diameter than the fine particles are coated on the surface of the fine particles, and the coated fine particles are used for cosmetics or paints.

4. Ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles are coated on the surface of the fine particles, and the coated fine particles are used for cosmetics or paints. The coated fine particles, wherein the film is made of one selected from the group consisting of metal, oxide, nitride, and carbide, or two or more composites selected from the group.

5. The covered 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, A l, F e, Ag, is one least selected from a metal group consisting of C u and W, said oxide S I_〇 _2, T I_〇 _{2, N i O, Z n0} 2, a 1 _{_{2 0 3, Mg 0, F}} e 2 0 3, a g 2 〇 and coated fine particles, characterized in that W_〇 be at least one oxide selected from the group consisting of _3.

6. 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,

At least one selected from the group consisting of A1, Fe, Ag, Cu, and W, and the oxide is S i 0 ₂ , T i 0 ₂ , N i 0, Z n 0 ₂ , A 1 ₂ 0 _3, M G_〇, F e ₂ 〇 _3, a g ₂ 0 and coated fine particles, characterized in that at least one oxide selected from the group consisting of WO _3.

7. The coated fine particles used in the cosmetic product 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, T i, N i, S i , a l, F e, Ag, a least one ^^ less selected from the metal group consisting of C u and W, said oxide S i O 2, T I_〇 ₂ , N i O, characterized by a _{_{Z n0 2, a 1 2 0}} 3, Mg O, F e 2 〇 _3, Ag ₂ 〇及beauty W_〇 ₃ oxide single at least selected from the group consisting of Coated fine particles.

8. The covered 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, and

'The ultrafine particles or the thin film is composed of at least one selected from the group consisting of rare earth metals containing rare earth ions, oxides of rare earth metals, and oxides of metals having photochromic properties. Coated fine particles.

9. The coated fine particles used in the paint according to any one of claims 1 to 4 are high-intensity metallic pigments, and the metal is Pt, Au, Ag, Cu, A Selected from the metal group consisting of I, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, In, W, Os and Ir And 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.

1 0. The coated fine particles used in the paint according to any one of claims 1 to 4 are materials having corrosion resistance, and the metal includes Pt, Au, Si, Ti, Zn, At least one selected from a metal group consisting of Zr, Nb, and W, the oxide is at least one metal oxide selected from the metal group, and the nitride is from the metal group. The coated fine particles, wherein the coated fine particles are at least one metal nitride selected, and the carbide is at least one metal carbide selected from the metal group.

I I. The coated fine particles used in the paint according to any one of claims 1 to 4 are antibacterial materials, and the metal is Pt, Au, Ag, Cu, Al,

S i, T i, N i, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, Ag, In, W, 0s and Ir are selected from the metal group At least one, 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.

1 2. 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 is P t , Au, Ag, Cu, Al, Si, Ti, Ni, V, Mn, Fe, Co, Zn, Zr, Nb, Mo, Ru, Ag, In, W,

At least one selected from the metal group consisting of Os and Ir, the oxide is at least one metal oxide selected from the metal group, and the nitride is selected from the metal group. At least one metal nitride, the carbonized The object is at least one metal carbide selected from the metal group.

1 3. The method according to claim 1, wherein the fine particles are selected from the group consisting of metals, oxides, nitrides, carbides, carbon materials, and polymers, or from the group. A coated fine particle comprising two or more selected composites.

14. The coated fine particles according to any one of claims 1 to 4, wherein the fine particles are colored by coating ultrafine particles or thin films on the surfaces thereof.