JP2008050242A - Light multiply-scattering titanium oxide and composite body of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide titanium oxide ultrafine particles which can shield ultraviolet rays in the whole ultraviolet region, has various cosmetic characteristics, for example, glossiness caused by light scattering is generated by multiply scattering of light by particles or by interference, phase shift, or the like of reflected light, and which can prevent total reflection (whitening) of the skin of a photographic subject and make hair roots or wrinkles to be hardly seen by Mie scattering under photographing conditions of photograph, VTR, high vision or the like. <P>SOLUTION: The light scattering titanium oxide is spherical or automorphic titanium oxide, obtained by adsorbing an iron-metal organic compound onto titanium oxide particles, degreasing the resulting particles, and fixing Fe atom on the titanium oxide crystal surface by completely decomposing organic functional groups by atmospheric pressure plasma, intermediate pressure plasma, low pressure plasma, vacuum ultraviolet rays, heating or the like. Alternatively, the light scattering titanium oxide is a powder mainly comprising light scattering titanium oxide particles, obtained by completely covering the surface of each particle of the titanium oxide with a silicon oxide film having a thickness of 1-10 nm. The light scattering titanium oxide has primary particle diameters of 10-1,000 nm and forms no secondary particle. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a light multiple scattering nanospace ion-manipulated titanium oxide and a composite thereof, and relates to basic cosmetics, makeup cosmetics, powdered white powder, hair styling, containers, glass products, plastic moldings, pigment dispersion inks, inkjet inks, paints Applies to composites selected from the group of flat panel displays, FED dispersions, fibers, fabrics, paper, electronic devices, filters.

  Conventionally, the pearl light emitting material is typically composed of inorganic fine particles such as titanium oxide film formed on mica, or birefringent particles formed with alumina, silica, carbonate, protein, or the like. These are characterized by forming a low-refractive index layer on high-refractive-index particles and multiply-scattering light to produce a light-scattering gloss by utilizing phase shifts due to light refraction and light interference. Many of them have a flat structure except for some pearls. Naturally, there are sericite and mica exhibiting light-scattering luster.

  On the other hand, the inventors have confirmed that spherical titanium oxide infused with iron or aluminum has a light scattering gloss by a high temperature thermal plasma method, and has already been used for cosmetics such as foundations.

Among inorganic light-scattering glossy materials, the most prominent titanium mica has a titanium oxide content of 15-25% by weight coated on the particle surface, but it is not perfect as an ultraviolet shielding material itself. . In particular, titanium oxide only blocks ultraviolet rays of 320 nm or less. Further, it has been proved that ultraviolet shielding cannot be expected if the core is particulate pigment grade titanium oxide (particle diameter 0.1 to 0.4 μm). Pure titanium oxide (hereinafter “titanium oxide, TiO ₂ ”) has the disadvantage of not having absorption in the UV-A region.

  Spherical titanium oxide infused with iron or aluminum obtained by the high-temperature thermal plasma method requires a highly skilled manufacturing method, cannot be operated continuously, has a low manufacturing capacity, and is difficult to control the reaction in the plasma. Because it is difficult to adjust the coloring and it is expensive, it is a material that is only suitable for small-scale production in the cosmetics field.

  In this way, all ultraviolet rays can be shielded, and when used alone as a point makeup or top coat of cosmetics, it can cleanly cover the ugly parts of the skin such as good spread, smoothness, safety for eyes, pores, In addition, a fine particle powder that exhibits a light multiple scattering property that selectively and strongly adsorbs sebum that is resistant to sweat and at the same time does not produce active oxygen is not provided by the sol-gel method.

  The present invention has been made in view of such circumstances, and after dissolving a metal organic compound in an organic solvent, adsorbing the spherical titanium oxide particles that have not been surface-treated, degreasing, and atmospheric pressure, Titanium oxide mother crystal surface by a method in which only the metal or metal-oxygen skeleton is injected into the titanium oxide crystal surface by breaking and decomposing organic functional groups by collision of ions and electrons such as medium / low pressure, low pressure plasma, and vacuum ultraviolet rays. Introduce new metal optical band gaps to shield the entire ultraviolet region, and the resulting particles are subject to multiple scattering and reflected light interference and phase shift due to light absorption inside the particles. Gives the skin and objects light multiple scattering similar to that of pearl and opal due to the physical phenomena of the particles, and the smoothness of the particles, the ease of spreading, and the adsorption of sebum by plasma treatment Prevents total reflection (whitening) of the subject's skin and makes it difficult to see hair roots and wrinkles due to Mie scattering under shooting conditions such as particle drop-off resistance to water and sweat, dispersibility to various skins, photography, VTR, hivation, etc. An object is to provide ultrafine titanium oxide particles.

Further, the present invention is not construed as being limited to the description of provision of these cosmetics. That is, a so-called nanoparticle having a particle size of 10 to 100 nm can impart transparency to various substances and objects, and is a composite that shields visible and ultraviolet rays after forming a complete dispersion, that is, for automobiles. Glass, pharmaceutical container, insect filter, contact lens, macular lens, cataract lens,
Water-based paints, film coatings for flat panel displays, large glass for construction, various printing inks, textiles, parasols, UV shielding prevention, solar cells, light protection agents for spacecraft, PET bottles, food packaging materials, cosmetic containers, and more It is an object of the present invention to provide a composite provided with the light shielding effect of the present invention and a very homogeneous dispersed thin film in an application field.

  The ultraviolet shielding powder according to claim 1 is a titanium oxide which is not subjected to any surface treatment mainly composed of anatase type single crystal particles, rutile type single crystal particles, brookite type single crystal particles, or mixed particles thereof. The particles are metal-implanted titanium oxide particles in which metal ions such as aluminum, iron, zirconium, silicon, etc. are implanted in an amount of 0.05 to 2.5% by weight with respect to titanium oxide, and the primary particle size is 10 It is characterized by the fact that it does not form secondary particles at 1000 nm, and it is an ultraviolet full-wavelength shielding powder that gives light-scattering luster to the skin by itself. It is spherical, strong against sweat, and prevents makeup collapse. It is characterized by concealing the texture that makes skin tissue stand out and providing a very delicate skin surface in photography, video photography, and high-definition photography.

    In order to adsorb the metal organic compound on the surface of the titanium oxide crystal or in the vicinity thereof, even if it is not under reduced pressure, it is possible if the concentration is low, but the substance cannot be freely moved to the deep part. The inventors tried to decompose simply after adsorbing the organometallic compound using plasma or ultraviolet rays, but the odor and undecomposed matter of the organic matter were dissolved and deposited, which became a big problem in terms of safety and quality. Therefore, for the purpose of blending in cosmetics, thorough removal of impurities becomes the biggest problem, so after injecting a metal organic compound to a relatively deep portion of the titanium oxide particles, and fixing the metal or metal ion to the crystal surface, The present invention provides a strict manufacturing method that does not leave residual odors and allergens, and provides extremely safe light multiple scattering titanium oxide.

  In the conventional technology developed by the inventors, titanium oxide itself also performs plasma synthesis at the same time, so that the production amount is limited to the capability of the plasma apparatus. In thermal plasma, the rubber O-ring vaporizes and re-adsorbs on the surface of the produced particles, and the odor can be easily identified. To remove the functional group of the rubber, it is washed with organic matter. Sometimes you have to. Since these organic functional groups are radicals and have a strong possibility of adversely affecting the skin and DNA, they offer the development of a system for injecting metal at a lower temperature and can be highly dispersed without any surfactant in both the aqueous phase and the oil phase. An object of the present invention is to provide a cosmetic material having a transparent state with a high light scattering property in which the surface state and the particles are dispersed.

  That is, the light-multi-scattering titanium oxide powder capable of shielding ultraviolet rays according to claims 1 to 4 has oxygen absorptivity by metal ions such as iron or aluminum trapped in the crystal lattice, and further has an ultraviolet wavelength range. In (1) 280 to 310 nm, (2) 320 to 350 nm, and (3) 360 to 390 nm, a titanium oxide ultrafine particle having a high background maximum absorption and further having a high absorption ability in the visible light region. A powder mainly composed of ultrafine particles that can be highly dispersed in many media that do not form secondary particles.

  In the light-scattering titanium oxide powder according to claims 1 to 4, the iron or aluminum ion is preferably in an unsaturated state and in a low-order oxidation number state. In the powder, at least one selected from the group of divalent or trivalent metal ions in which the titanium oxide particles according to claim 1 and claim 4 are low-order oxidized and captured in a crystal lattice is in an unsaturated state. It is a powder mainly composed of ultrafine titanium oxide particles which are low-order oxidized at a low level, are given a wider optical wide band gap, and can simultaneously block light of 200 to 600 nm.

  In the powder, it is desirable that the metal organic compound of iron is completely dissolved in a polar solvent such as ethanol and has a stable structure that is not subject to hydrolysis. Furthermore, when creating precursors such as plasma, ultraviolet rays, electron beams, etc., in order to prevent the powder from causing secondary agglomeration under these processing conditions, the particles are put into an ultrasonic horn or a high-speed rotating device in the reaction chamber. For example, it is decomposed into single particles by a Henschel mixer.

  The present invention will be described in detail below with reference to embodiments and examples, but the present invention should not be construed as being limited to these descriptions.

  The light-scattering titanium oxide according to the present invention is a titanium oxide powder mainly composed of titanium oxide single crystal particles, and the particles emit ions such as iron or aluminum to 0.05 to 2.5 with respect to titanium oxide. Metal ion-implanted titanium oxide particles implanted by weight%, and the primary particle diameter is 10 to 1000 nm, and secondary particles are not formed (hereinafter referred to as ion implantation type). Here, the titanium oxide single crystal particles are anatase type single crystal particles, rutile type single crystal particles, brookite type single crystal particles, or a mixed particle thereof. The ion-implanted titanium oxide mother crystal is titanium oxide that is not subjected to any surface treatment and is obtained from sol-gel method titanium oxide, oxidation combustion type titanium oxide, plasma synthesized titanium oxide, titanium hydroxide or the like. The sol-gel titanium oxide particles are composed of particles obtained by hydrolyzing metal alkoxytitanate.

  The light multiple scattering titanium oxide according to the present invention is a titanium oxide powder mainly composed of titanium oxide single crystal particles, and the particles are thin film-forming particles already filed by the inventors of the present invention. An ion-implanted titanium oxide particle in which a silicon oxide film is coated on the particle surface to a thickness of 1 to 10 nm and metal ions are implanted in an amount of 0.05 to 2.5% by weight with respect to titanium oxide. The secondary particles may not be formed at 000 nm.

  Here, the ion-implanted titanium oxide particles exhibit a photocatalytic effect, and the ion-implanted and rutile-type titanium oxide particles have a weak negative repulsion effect based on the zeta potential and form aggregates with water. Therefore, it is necessary to cover the particle surface with a silicon oxide film in order to suppress the photocatalytic effect, and the silicon oxide film having a negative repulsion effect based on the zeta potential prevents the formation of aggregates. Furthermore, since the particles are coated with iron or aluminum ion implantation or a silicon oxide film, the particles themselves can be widely applied including titanium oxide produced by a sol-gel method.

  The reason why the titanium oxide single crystal particles are used is to make the particle shape of the primary particles uniform and to approximate a spherical shape. By controlling the primary particle diameter to 10 to 1000 nm, the self-crystal growth of the single crystal particles can be appropriately suppressed to be close to a sphere, and the particle aspect ratio can be reduced. When the primary particle size is less than 10 nm, handling of the powder becomes difficult, and the volume ratio of titanium oxide / silicon oxide in the particles becomes small, so that it does not necessarily lead to the original characteristics of titanium oxide. In addition, particles having a size of 10 nm or less are not outside the scope of the present invention, but are defined by the particle size of titanium oxide that is generally sold. On the other hand, when the primary particle diameter exceeds 300 nm, the ultraviolet shielding effect is reduced, but the special properties of scattering and reflection of visible light and some infrared rays are dramatically improved.

  In the present invention, it is preferable to have a normal distribution in a particle size range exceeding 20 to 50 nm, 100 to 300 nm, and 300 nm after controlling the primary particle diameter to 10 to 1000 nm. The reason for having such a particle size distribution is that Rayleigh scattering is performed in the minimum particle size range, and visible light is scattered from ultraviolet rays in the range beyond that.

  In the present invention, titanium oxide particles obtained by hydrolyzing isopropyl titanate as a starting material of titanium oxide using a sol-gel method are ion-implanted using a compound such as acetylacetonate of iron or aluminum in the crystal lattice of titanium oxide. In doing so, the simple adsorption means or forced adsorption means are usually employed, whereas the solubility of metal ions in the medium is increased from about 4% by weight to 15% by weight or more as a metal, and generally 1.1 to 1. A predetermined amount of metal ions is implanted by a treatment such as replasma that requires the organic functional groups to be divided into molecular sizes that can be implanted into a titanium oxide crystal lattice of about 5 angstrom square. As a result, a large impurity level is generated in the crystal lattice, an optical band gap and an electron gap are developed, and three places in the entire ultraviolet region, particularly (1) 280 to 310 nm, (2) 320 to 350 nm and (3) 360 to It has a maximum absorption in each region of 390 nm, and the metal ions implanted at the same time cause light scattering, resulting in light interference and manifesting a clear light scattering gloss that can be identified with the naked eye. In particular, the maximum absorption in each region of (2) 340 to 350 nm and (3) 360 to 380 nm is not possessed by pigment grade titanium oxide.

  Moreover, the expansion of the shielding area can be adjusted by injecting 0.05 to 2.5% by weight of iron ions with respect to titanium oxide. The iron ions are implanted in the form of a solid solution in the crystal lattice of titanium oxide. When the injection amount is less than 0.05% by weight, the expansion width of the shielding region is small, and when it exceeds 5.5% by weight, the solid solution region may be exceeded. In the case of aluminum ions, a larger amount is implanted into the crystal lattice.

  The iron ions injected into the titanium oxide particles are preferably in a low-order oxidation number state. This is because by setting the low-order oxidation number state, absorption of 400 nm or more is increased, and the shielding area can be expanded.

  In the present invention, the surface of the particle is manipulated by the above band gap, and the equipotential point of the particle or the zeta potential in the vicinity of neutrality is greatly shifted to the negative side, so that the dispersibility with respect to the solvent is improved at once. is there. In the present invention, a silicon oxide film having a light refractive index lower than that of titanium oxide is further formed on the surface of the metal ion-implanted titanium oxide so as to have a thickness of 1 to 10 nm. A group is bonded to individual particles and all particles are negatively charged to separate the particles. Here, the silicon oxide film is an amorphous silica film.

  Further, this silicon oxide film is a plasma silicon oxide film that does not have residual functional groups such as OH groups and alkyl groups remaining when it is formed by the sol-gel method, or intentionally leaves organic functional groups. A silicon oxide film having no residual functional group can make the surface potential uniform over the entire particle surface, achieve a good aqueous dispersion state, and stabilize the dispersion state. The silicon oxide film in which the residual functional group remains can realize a good dispersion state with respect to the hydrocarbon-based organic material and can stabilize the dispersion state. Therefore, it is preferable that this silicon oxide film completely covers the surface of the ion-implanted iron oxide particles. The reason for applying a silicon oxide film is not only to suppress photocatalysis and to make the zeta potential negative, but also because silicon oxide has a lower refractive index than titanium oxide, so that the silicon oxide film scatters and reflects light no matter how thin it is. This is because the light reflection efficiency can be improved and the light scattering gloss can be clearly produced compared with the titanium oxide particles alone.

  The reason why the silicon oxide film has a thickness of 1 to 10 nm is as follows. This is because if it exceeds 10 nm, the volume ratio of the titanium oxide particles in the particles must be reduced, and the characteristics inherent to titanium oxide cannot be exhibited. On the other hand, the lower limit of the thickness of the silicon oxide film is 0.3 nm, which is the thickness when a tetrahedral 1-unit layer of silicon oxide is formed. However, in order to completely coat the entire surface of the titanium oxide particles with silicon oxide, coating with a 0.3 nm silicon oxide film may cause defective coating, and it is difficult to establish a film thickness analysis method. Therefore, it is preferable to set the film thickness to 1 nm or more from the viewpoint of suppressing the occurrence of defective coating and analysis means.

The invention's effect

  Since the present invention is configured as described above, the following effects can be obtained. By implanting ions having a relatively high impurity level, such as iron, into the spherical ultrafine particle titanium oxide crystal lattice, the maximum ultraviolet absorption that has conventionally been only one at 280 nm to 320 nm is (1) 280 nm to 310 nm, (2) ▼ 320 nm to 350 nm, and ③ 360 nm to 390 nm, respectively, so that a wide range of light shielding and light multiple scattering characteristics such as optical band gap, electron gap, etc. that could not have the original pure mineral crystals can be exhibited. did. At the same time, when the skin surface is coated with a thin film, the light scattering gloss is strongly expressed. The amount used at this time is approximately several tens of mg, and a face protective film can be formed. In addition, the touch is smooth, sweat-resistant, and it is difficult to cause makeup collapse even in midsummer. Therefore, the light-scattering titanium oxide coated with silica is extremely high in functionality and has good dispersibility in both aqueous and solvent systems, and various applications are possible. In addition, since sebum is not oxidized, it is possible to prevent squalene, which is the main component of sebum, from changing to a steroid structure, which is excellent in safety and hygiene.

  At the same time, since light scattering is increased and Rayleigh scattering that occurs in spherical ultrafine particles of several tens of nanometers and Mie scattering that occurs in a wider particle range can be obtained, it is possible to suppress active oxygen in which radical reaction is considered dangerous. Moreover, even if active oxygen is generated by the activated force of the implanted ions, it can be immediately adsorbed and fixed, so that radicals can enter the container and prevent the contents from being altered.

  In addition to the function of the light-scattering titanium oxide itself, mixing with a foundation or base cream further increases the degree of adhesion to the skin and can provide smooth skin and transparency. In addition, although a single color can be used, the color development and durability of the makeup can be remarkably enhanced by applying it before the color makeup. In addition, the light scattering effect makes the skin texture beautiful and eliminates skin problems peculiar to women such as fine lines and pores.

  The light-scattering titanium oxide of the present invention can be used not only for the face but also for the whole body such as hands, arms, decollete, and neck and legs, and suppresses total reflection of the light source and prevents whitening even in professional shooting such as models and actresses It can provide beautiful and elegant skin, and can provide breakthrough characteristics compared to conventional light scattering diffused titanium mica with coarse particles of micron size or larger.

  Since the light-scattering titanium oxide of the present invention can be easily dispersed in a medium due to its high dispersion characteristics in fields other than cosmetics, a non-polar solvent can be obtained by adjusting pure water, polar solvent, oil agent and surface functional groups. It is possible to disperse without forming an agglomerate without a surfactant in a part of the surface, and it is possible to compound an excellent light shielding substance in the region from the ultraviolet to the ultraviolet side of the visible part while being transparent. Moreover, not only a coating agent as a composite material but also a functional composite material which is formed by forming a thin film of the coating agent and does not cause photodegradation can be provided.

  In the present invention, ion doping, which has been required only by the conventional thermal plasma method, is performed by injecting an organometallic compound into a titanium oxide crystal lattice represented by the following examples and decomposing and removing unnecessary molecular chains by plasma. However, the present invention should not be construed as being limited to the modes of the invention described below.

(Example 1)
In Example 1, titanium oxide fine particles having an average particle diameter of 200 nm obtained by a sol-gel method were used as the starting titanium oxide. This titanium oxide has a maximum absorption at 305 to 310 nm and does not absorb at a wavelength longer than 320 nm. Also, when it is rubbed against the skin, there is some shine, but when it is actually used on the skin, whitening occurs. Naturally, active oxygen is generated. The fluidity is poor, and furthermore, the dispersion in water once disperses even when ultrasonic waves are used, but the sedimentation rate is fast. If these titanium oxide particles are simply dropped into pure water, they immediately settle rapidly. To this particle, a reagent-grade trivalent iron acetylacetonate (manufactured by Dojin Chemical Laboratory Co., Ltd.) was dissolved in ethanol and then adsorbed onto titanium oxide particles so that the Fe content was 1 to 3% by weight. . Then, after degreasing and drying the solvent, the particles are introduced into an atmospheric pressure plasma apparatus that can be rotated with a carrier gas He, and plasma is generated using a He—O ₂ mixed gas for 1 to 10 minutes. went. As a result, when the injection ratio of iron was 1% by weight, titanium oxide changed to a yellowish color. At 3% by weight, a deep beige color was obtained. The tactile sensation was smooth, and it was in a state where it could be sufficiently extended with a finger after makeup without treatment of the oil or fat on the surface. The average weight used at one time was 50 mg, and point makeup was almost complete, and the face showed a very beautiful pearl luster. In addition, sebum adsorption was good, and even during daytime use, makeup did not run off with sweat. Moreover, in the UV-VIS measurement result by the KBr method, the maximum absorption in the ultraviolet region was recognized at three locations of 305, 345, and 378 nm, and the visible region could be shielded to approximately 450 nm.

  The particle size distribution of the light-scattering titanium oxide spherical ultrafine particles obtained in Example 1 has a population distribution maximum peak at 200 nm and a weight distribution maximum peak at 100 to 300 nm. In the dispersion test, it was observed that when it was put into pure water, it settled while being gently dispersed. When ultrasonic waves were used, they were completely dispersed, the light scattering function (Rayleigh scattering and Mie scattering) was remarkably enhanced, and the transparency was high.

  The light-scattering titanium oxide spherical ultrafine particles obtained in Example 1 may have strong residual functional groups of acetylacetonate (hereinafter “AA”) or may cause skin irritation in the above production method. In general, the existence of irritating iron organic compounds is also known, and since it is desired for cosmetics to leave almost no AA residue, an elution test with ethanol was performed. As a result, AA sometimes reached 20-10 ppm depending on the plasma irradiation conditions. This is caused by insufficient decomposition of AA in the plasma and re-adsorption of the decomposition functional group on the titanium oxide particles on the downstream side of the plasma. Therefore, ethanol washing was performed until the AA residual component became 1 ppm. As a result, AA was reduced to 0.1 ppm or less as measured by a specific red absorption part. However, the obtained titanium oxide was poor in fluidity and slightly reduced in reflectance.

(Example 2)
In Example 2, titanium oxide fine particles having an average particle diameter of 200 nm obtained by the sol-gel method of the same product as Example 1 were used as the starting titanium oxide. The amount of ethanol becomes very large in the adsorption step unless 15% or more of reagent-grade trivalent iron acetylacetonate (manufactured by Dojin Chemical Laboratory Co., Ltd.) is dissolved in these particles. Therefore, firstly, the iron AA is mixed in a ratio of 15 parts of iron (as Fe) to 100 parts of ethanol so as to make a 15% solid content ignoring the solubility of iron AA, and carbon dioxide gas while stirring and dissolving. In the balance, it was melted by irradiation with vacuum ultraviolet rays 184 to 163 nm for 3 hours. As a result, the solid content that could not be dissolved was separated and weighed, resulting in an iron content of 10.7% by weight. This was 2.7 times the normal solubility. While taking 23.4 g of this solution and impregnating with 97.5 g of titanium oxide, the solution was kept in a vacuum chamber for 1 hour to completely adsorb the ions to the particles.
Furthermore, in order to remove the solid content that could not be adsorbed by ions, it was filtered several times using a Millipore filter, solid-liquid separated, and the iron content in the liquid was measured. As a result, the amount of iron that could be injected into the titanium oxide crystal was 2.20% by weight. Further, the ion-implanted titanium oxide was dried at 65 ° C. for 2 hours, and then washed with ethanol using ultrasonic waves. As a result, the final Fe content was 2.0% by weight. In the conventional method of Example 1, iron was 0.6% by weight as a result. This precursor ion-implanted titanium oxide was blown into the downstream side of the microwave plasma using argon / oxygen as the source gas and was strongly oxidized. As a result of repeating this operation several times, almost no odor was felt and the reaction was stopped. The obtained titanium oxide was light brown, but showed a reflected light resembling a clear pearl color when applied to the skin. The fluidity is very good. Even if you don't mix any oils and fats, you can get on the skin smoothly, coat the skin thinly, play tennis for 3 hours, and test the removal of the particles from the skin with a total of 20 expert samples. Carried out.
As a result, it was confirmed that the particles of the invention did not fall off due to sweat that could be discharged from the skin, and that strong adsorption characteristics and sun protection by ultraviolet rays were proved. In addition, as a result of a long-term use test, when the particles were used directly on the skin, dullness and pigmentation due to sunburn decreased significantly after one year.

(Example 3)
In Example 3, spherical titanium oxide fine particles having an average particle size of 200 nm manufactured by Toho Titanium Manufacturing Co., Ltd. were used as the starting titanium oxide. This titanium oxide has a maximum absorption at 305 to 310 nm and does not absorb at a wavelength longer than 320 nm. In addition, when it is rubbed against the skin, it has a white glow, but when it is actually used on the skin, whitening occurs and it is rough. Naturally, active oxygen is generated. The fluidity is poor, and furthermore, the dispersion in water once disperses even when ultrasonic waves are used, but the sedimentation rate is fast. If these titanium oxide particles are simply dropped into pure water, they immediately settle rapidly. In order to dissolve a reagent-grade Al acetylacetonate (hereinafter referred to as ALAA) (manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 15% by weight or more in these particles, firstly, the solubility of ALAA is ignored and the solid content is 20% The ALAA was mixed at a ratio of 20 parts (as Al) to 100 parts of ethanol, and dissolved by stirring and dissolving under vacuum carbon dioxide balance at 184 to 163 nm for 3 hours. As a result, the solid content that could not be dissolved was separated and weighed, resulting in an iron content of 14.2% by weight. This was three times the normal solubility. 21.2 g of this solution was taken and impregnated with 97.0 g of titanium oxide, and held in a vacuum chamber for 1 hour to completely adsorb the ions to the particles.
Furthermore, in order to remove the solid content that could not be adsorbed by ions, it was filtered several times using a Millipore filter, solid-liquid separated, and the iron content in the liquid was measured. As a result, the amount of Al that could be injected into the titanium oxide crystal was 2.5% by weight. Further, the ion-implanted titanium oxide was dried at 65 ° C. for 2 hours, and then washed with ethanol using ultrasonic waves. As a result, the final Al content was 2.4% by weight. This precursor ion-implanted titanium oxide was blown into the downstream side of the microwave plasma using argon / oxygen as the source gas and was strongly oxidized. Further, the obtained titanium oxide was irradiated for 3 hours while flowing under reduced pressure by a vacuum ultraviolet lamp composed of a Sprazil quartz tube from which 163 to 254 nm was emitted, and further residual functional groups were removed in the vacuum chamber for 1 hour. Aluminum ion-implanted titanium oxide was obtained.
As a result, almost no odor was felt in the titanium oxide. The obtained titanium oxide was white, but when applied to the skin, it showed reflected light resembling a clear pearl color. The fluidity is very good. Even if you don't mix any oils and fats, you can get on the skin smoothly, cover the bare skin thinly, and then play golf for 6 hours at 34-36 ° C and 75% humidity. A drop test of the particles was performed on a total of 6 expert samples.
As a result, it was confirmed that the particles of the invention did not fall off due to sweat that could be discharged from the skin, and that strong adsorption characteristics and sun protection by ultraviolet rays were proved.

Example 4
In the method of Example 3, the same treatment was performed using triethylaluminate instead of aluminum ethylacetonate, and 3.0 wt% aluminum oxide-implanted titanium oxide as aluminum was again used in ethanol using ultrasonic waves. As a result of dissolution and confirmation of the presence of residual organic molecules by HPLC high-performance chromatography, no organic molecules were confirmed. Therefore, it adjusted so that the said titanium oxide might be mix | blended in 3 weight part skin care cream. As a first step, 10 parts of the titanium oxide and 90 parts of ultrapure water were mixed and dispersed for 2 minutes by a Ginsen ultrasonic dispersion apparatus to obtain a complete dispersion. Next, after the oil phase mixture was dissolved at 80 ° C. as a second step, the dispersion heated to 50 ° C. was mixed and emulsified by low-speed rotation. After that, it was naturally cooled to form a cream. As a result, a foundation cream with a smooth and smooth skin was obtained. This was used as an announcer in a broadcasting station as a test for high-definition photography, and it was found that the light scattering effect on the high-hidge camera was extremely high. Normal dolan was applied to half of the face and the cream of the present invention was used on one side. The cream of the present invention did not show wrinkles and dullness compared to dolan, and it appeared to be natural skin quality and was observed younger than 10 years. Furthermore, when using the iron ion-implanted titanium oxide powder obtained in Example 2 from this surface, the whitening and total reflection peculiar to strong lighting in the studio do not occur, the stain is difficult to see, and at the same time, natural and bright gloss It became skin quality. At this time, the time required for the makeup was within 5 minutes, which was 5 to 10 times shorter than usual.
As a result, an actual high-definition photography test was conducted by female performers of regular programs in foreign language courses. When observed on the monitor, the white foreign performer is fair-skinned, but the cosmetic complex of the present invention is extremely bright and natural and has a facial expression, while the cosmetics are very thick and dull and unnatural. It was rich.

(Example 5)
A silica thin film was formed on the surface of the light-scattering titanium oxide fine particles obtained in Example 1. Dilute tetraethoxysilane (TEOS) in semiconductor grade ultrapure water (30% semiconductor grade ultrapure water) to coat a single nanoparticle of silicon oxide film (amorphous silica thin film) with a thickness of several nanometers. And uniformly adsorbed onto the target powder. This is reacted in a sealed container at 40 ° C. for 24 hours, TEOSs begin to have a counter potential (counter charge), and gradually, individual particles are surrounded by a strong negative potential charge and are dissolved (monodisperse). Next, it is dried at 60 ° C. As a result, the TEOS film is completely attached to the single particle. Next, plasma was generated in helium and oxygen at 0.01 to 0.1 atm. At this time, the ethyl group of TEOS is cut and a silicon oxide skeleton is formed in an amorphous state. Thereafter, particles having a primary particle diameter of 100 to 500 nm were taken out by classification. The light-scattering properties of the plasma-treated silica-coated ultrafine particles increased. The surface properties changed from + (plus) to-(minus). Thus, when dispersed in a solvent, it does not aggregate and does not form secondary particles. Since this method is non-catalytic, it does not aggregate. As a result of actually measuring the film thickness of the coated silicon oxide with a transmission electron microscope (TEM), the surface of fine particles having a particle diameter of 100 to 300 nm was completely covered, and the film thickness was an average of 2 nm. The light scattering gloss was quite good. Since AA residual fragments adhere to the surface of the silica film, it is considered that these were completely removed by the decomposition / vacuum system by the plasma treatment. In this case, ultraviolet irradiation may be performed in a vacuum ultraviolet chamber.

  The particle size distribution of the titanium oxide spherical ultrafine particles obtained in Example 2 of the present invention has a maximum population distribution peak at 120 nm and a maximum weight distribution peak at 100 to 300 nm. However, unlike normal titanium oxide, the equipotential point exists in the vicinity of pH≈4, and the zeta potential in pure water (pH≈6) is extremely large as -30 mV to -80 mV. As a result, the light scattering function (Rayleigh scattering and Mie scattering) was remarkably increased, and when the coarse particles were removed after dispersion, the transparency became higher.

(Example 6)
In the multi-scattered titanium oxide obtained in Example 1, after classifying titanium oxide fine particles having an average particle diameter of 50 nm, 5% by weight is blended in an acrylic emulsion having a solid content of 35%. The mixture was dispersed for 3 minutes using an ultrasonic dispersion apparatus having a longitudinal amplitude of 50 microns. The composite obtained as a result of stirring and mixing 9.2 parts of the obtained dispersion and 100 parts of an acrylic emulsion is extremely transparent and does not easily solid-separate, and the thin film is 4 microns thick on a glass substrate. When the film was formed, the film thickness after drying was 1.5 microns. Its optical characteristics were widely shielded from ultraviolet to visible light, and had maximum absorption at 305 nm, 345 nm, and 383 nm.

  The multi-scattered titanium oxide of the present invention has many aesthetic disadvantages when all of the skin is photographed, compared to a resolution that can reach four times the number of scanning lines in the next-generation terrestrial digital high-definition broadcasting. And can reduce secondary damage caused by dangerous whitening and supplements, so it can solve not only future TV shooting but also problems with home-use high-definition imagers. Sun rays can be blocked without generation of active oxygen. Moreover, it is possible to protect the skin safely without producing lipid peroxide. At the same time, because of its excellent adsorption performance for fats and oils, it does not collapse. In these applications, the potential demand for luxury cosmetics in Japan and overseas reaches several hundred billion yen. In addition, the need as an effect to stop itching is regarded as 30 billion yen in the medical field. Furthermore, it is considered that the possibility of use as a revolutionary substrate material and technology will be widespread in a very wide range of fields such as packaging containers, solar cell deterioration prevention protective films, various printing systems, electronic / medical devices, plastics and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a drawing (FIG. A) showing a unit (white octahedron) and crystal space (gap) of a titanium oxide anatase basic crystal model TiO ₆ of light-scattering titanium oxide spherical ultrafine particles according to the present invention. In FIG. B, the crystal lattice in the (112) direction of the anatase crystal is three-dimensionally represented, which means that the basic unit of SiO ₁ can completely pass through the gap. That is, the metal ions of the organometallic compound cut by plasma can be easily implanted into the titanium oxide crystal lattice. The change of the skin texture when 20 mg of light-scattering titanium oxide ultrafine particles according to the present invention are applied to one hand with a brush is shown. It is a drawing showing that the right hand spot of the expert sample is difficult to see. In the plasma apparatus of light scattering titanium oxide ultrafine particles according to the present invention, the attached functional groups are removed by plasma oxidation. The ion-implanted titanium oxide is introduced from the powder supply unit to the downstream side of the microwave plasma (argon / oxygen) in an argon stream, indicating that the functional group is removed by instantaneous reaction. When ion-implanted titanium oxide is dissolved in ethanol after plasma treatment after a general surface treatment, several tens of ppm of acetylacetonate is washed, and in the case of iron, as in the upper part of the liquid level in the right container. Gives a noticeable color. However, when the iron acetylacetonate molecular chain was cleaved before adsorption and adsorbed on titanium oxide and plasma treated, residual functional groups were not detected as in the left container even after washing in ethanol. ing.

Claims (5)

  Particles whose starting matrix is titanium oxide particles whose surface is not covered with foreign matter at all, and 0.05 to 5.5% by weight of metal atoms and / or metal ions are injected into the titanium oxide particles. 300 nm ± 10 nm, 330-350 nm, 360-390 nm while giving a multiple scattering gloss to the skin alone without forming an aggregate of 1000 nm or more with a primary particle diameter of 10 to 1000 nm. Having a maximum absorption at the same time and capable of shielding the entire wavelength region of ultraviolet rays, and simultaneously shielding the visible light region of 400 to 600 nm, wherein the zeta potential in pure water in the neutral region around pH = 6 is at least −. Ultra-dispersed crystal particles of 20 mV to -100 mV, and has amphoteric affinity for instantaneously adsorbing sebum. Skin break-up due to falling off the surface does not occur until the face is washed, and the skin tissue such as hair roots and wrinkles can be directly and evenly covered, and the stain pigments appear unclear and are extremely delicate in photography, video photography, and digital high-definition photography. Light-scattering titanium oxide characterized by providing a beautiful and beautiful skin surface.   The metal ion is a compound containing a metal selected from metal acetylacetonate, metal carbonyl, metal alkoxide, metal acetate, metal alcoholate, ionic metal aqueous solution, etc., and after dissolving it in a medium, the metal ion 2. The light multiple scattering property according to claim 1, wherein the bond between the central portion and the organic functional group is a metal ion formed by cutting and downsizing by colliding with an ion or electron of at least 3 electron volts (eV) or more. Titanium oxide.   The metal ions are forcibly injected into the titanium oxide crystal space by vacuum or long-term aging after forming a small metal molecule that is forcibly divided by plasma, ultraviolet rays, electron beams, and light rays. 3. The light multiple scattering titanium oxide according to claim 1, wherein the metal molecular body is moved and adsorbed in a three-dimensional space of sub-nano units formed by a mother crystal to form a nanostructure ion implantation precursor.   The nanostructure ion implantation precursor according to claim 3, wherein a trace amount of the organic functional group or / and the cleaved organic fragment existing on the surface of the precursor or the crystal matrix are completely removed under atmospheric pressure or reduced pressure. 4. The light multiple scattering titanium oxide according to claim 1, wherein the light multiple scattering titanium oxide is odorless and contains no more than 1 ppm of allergen.   The light multiple scattering titanium oxide according to any one of claims 1 to 4 is a basic cosmetic, makeup cosmetic, powder white powder, hair dressing, container, glass product, plastic molded article, pigment dispersion ink, inkjet ink, paint, flat panel display , FED dispersion, fiber, fabric, paper, electronic device, light multiple scattering oxidation characterized by being uniformly dispersed and integrated transparently or opaquely on the surface or inside of a composite selected from the group of Titanium composite.