TW434027B - Ultraviolet shielding composite fine particles, method for producing the same, and cosmetics - Google Patents

Abstract

The ultraviolet shielding composite fine particles having transparency in a visible light region include (a) matrix particles comprising an aggregate of primary particles having an average particle diameter of from 0.001 to 0.3 mu m, the aggregate being formed while the primary particles retain their shapes; and (b) daughter particles having an average particle diameter of from 0.001 to 0.1 mu m, the daughter particles being dispersed in and supported by the matrix particles. In the composite fine particles, the daughter particles have a smaller band gap energy than the particles constituting the matrix particles and are capable of absorbing ultraviolet light, and the resulting ultraviolet shielding composite fine particles have substantially no catalytic activities.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 434027 · _ ^ V. Description of the Invention (1) Technical Field The present invention relates to ultraviolet shielding composite microparticles, which are not substantially catalytically active and have light transmission in the visible light region. And has a high shielding ability in the ultraviolet region. The present invention also relates to a method for preparing composite fine particles, and granules containing the composite fine particles. BACKGROUND ART The sunlight reaching the earth includes infrared light, visible light, and ultraviolet light, 5 to 6% of which are ultraviolet light. Ultraviolet light has a short wavelength and is therefore a high-energy electromagnetic wave. Therefore, ultraviolet light is known to decompose many substances and cause considerable harm to the human body. Therefore, use UV shielding agents to protect your skin from inflammation or skin cancer when the skin is exposed to harmful UV light. For this purpose, an ultraviolet shielding agent is added to the cosmetic. It can also be used to prevent discoloration of pigments due to the decomposition of ultraviolet light. For this purpose, a UV shielding agent is mixed in the paint. In these cases, it is possible to prevent unnatural skin whitening and color change of the paint by adding the light transmittance of these granulated pellets or paint in the visible light region. Therefore, it is preferable that the ultraviolet light is blocked to maintain the transparency in the visible light region. An ultraviolet shielding agent containing an organic compound as an effective ingredient can suppress the transmission of ultraviolet light because these compounds absorb ultraviolet light. For example, a UV-absorbing composition containing substituted N, N and di-arylformamidine is known (Japanese Patent Examined Publication No. 61-09993). However, organic ultraviolet shielding agents have the following problems, that is, although they can absorb ultraviolet light, they may be decomposed by ultraviolet light at the same time. As a result, their shielding ability is invented over time (please read the precautions on the back first) Save and fill in this book f)-V—i 4 ------ Order ------ 1 ---- ml 1 m »Printed by the Central Standard of the Ministry of Economic Affairs 扃 贝 工 consuming cooperatives ^ 4 34027-5 A7. _B7_ V. Description of the invention (2) Reduction of defects. In addition, in its application to cosmetics, the types and amounts of ultraviolet shielding agents are limited due to their effects on the human body, making it difficult to achieve good shielding performance within the control range. On the other hand, an ultraviolet shielding agent containing an inorganic compound contains inorganic fine particles and suppresses ultraviolet light transmission through the absorption ability and scattering ability of the composition. The inorganic ultraviolet shielding agent is superior to the organic ultraviolet shielding agent because the composition containing the inorganic ultraviolet shielding agent is not decomposed by ultraviolet light over time and has little effect on the human body. However, since the inorganic ultraviolet shielding agent exists in the form of particles, it is more difficult to use the inorganic ultraviolet shielding agent than to use the organic ultraviolet shielding agent to block ultraviolet light while maintaining high light transmittance in the visible light region. In order to have effective light shielding ability in the ultraviolet region while maintaining high light transmission in the visible region (400 to 800 nanometer (nm) light wavelength), the composition must be micronized to obtain a highly dispersed ultra-fine Micro-particles to increase UV-scattering ability. However, in the case of using ultrafine particles, dispersion stability problems may occur due to the aggregation of the ultrafine particles and the catalytic ability of the ultrafine particles. In order to improve the dispersibility, the surface of the ultrafine particles may be coated with other substances. For example, dermal granules of edible oil-based cosmetic base material and hydrophobic titanium oxide powder are known (Θ has been examined and published No. 59 · 15885). However, an appropriate solvent must be selected depending on the nature of the substance coated on the surface. In addition, since the particles are still ultrafine, even if surface treatment is performed, the aggregation of the ultrafine particles can only be reduced to a limited extent. In the publications other than the above, it is known to contain a mixture of silicate hydrate and aluminum hydrate in a special amount __ 丄 5- This paper size is applicable to China National Standards (CNS) Standard 8 (210X297 mm ) ----------- / Table ------ Order (please read the notes on the back before filling out this page); 4 340272 at Β7 V. Description of the invention (3) Hydrate Cosmetic powder coated with titanium oxide. The titanium oxide is almost spherical or irregularly shaped and has an average particle diameter of 30 to 70 nanometers. The surface of the oxidized drink coated with hydrate may be more concentrated as required. Dream Oxygen Oil Coating (Japanese Patent Publication No. 2-247109). However, in this bulletin, the above powder is obtained by drying and pulverizing the product after coating with a mixed hydrate containing crushed salt hydrate and Ming hydrate, or coating the powder with polyoxygen oil. It is obtained after drying and pulverizing the surface. Because the titanium oxide ultrafine particles will aggregate and show a large particle size, it is extremely difficult to powder the oxidized ultrafine particles to the size of the original particles, so that the light transmittance of the powder obtained above And UV shielding ability are reduced. In addition, since the uncoated surfaces are exposed after the pulverization process is performed, the water or oil repellency of these surfaces is unfavorably reduced. This technical problem occurs in maintaining the dispersion of ultrafine particles stable. Therefore, it is important to find a way to achieve high dispersion of super-coated particles and keep them at this level. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

In 1 — —r ^ i In addition, for a cosmetic material containing ultrafine particles, the ultrafine particles can be dispersed easily and uniformly, and the problem of difficult to handle the ultrafine powder has been eliminated. The starting material contains metal oxide ultrafine particles having a particle size of not less than 0.1 micron, a dispersion medium, and a dispersant, wherein the content of the ultrafine particles is not less than 10% by weight. /. (Japanese Patent Publication No. 6-239728). However, although there are known problems regarding the aggregation of ultrafine particles and the deterioration of dispersants, dispersion media, and cosmetic base materials caused by the catalytic activity of metal halide ultrafine particles, they have not been mentioned in this disclosure. And, let ’s say there is a solution. Furthermore, the starting material of the granulated material — ^ _ · 〇-The paper money is applicable to the Chinese National Standard (CNS) Eighty-fourth Secret (21GX297 mm) w 4 341) 2 7 Central Ministry of Economic Affairs A7 B7 printed by the Employees ’Cooperative Cooperative in V. Bureau 5. Description of the invention (4) The content of ultrafine particles of metal oxides in the substance is limited in this publication from the viewpoint of controlling its amount in the overall cosmetic. Less than 10% by weight. However, as long as the metal oxide ultrafine particles are uniformly and stably dispersed, for any kind of chemical material, the metal oxide ultrafine particles have a high function, and the metal oxide ultrafine particles are used in cosmetics. The content in the starting material need not be limited to a minimum amount of 10% by weight. Therefore, in order not to reduce the ultraviolet scattering ability by the aggregation of inorganic ultrafine particles, inorganic ultrafine particle composites are often formed with other relatively large carrier particles. For example, a sheet-like material in which ultrafine particles of a metal compound are dispersed is known (Japanese Patent Laid-Open No. 63-126818). However, this publication does not disclose the special structure of the microparticles used to simultaneously improve the shielding ability in the ultraviolet region and the transparency in the visible region. In addition, it has also been proposed that ultrafine particles are dispersed in a solid substance and supported by it. Composition of composite particles. Conventional ultraviolet shielding composite particles include, for example, a composite powder in which a fine particle powder such as T i 0 2 is uniformly dispersed in plate-shaped metal oxide particles such as Si02 (Japanese Patent Laid-Open No. 1-143821); And composite granules, in which the surface of the matrix particles containing materials such as nylon resin, polysiloxane resin, and silicon oxide is loaded with oxide powder or alumina powder, and titanium oxide powder or oxide is dispersed inside the matrix particles. Zinc powder (Japanese Patent Publication No. 2-49717). However, in order to use the composite particles as an ultraviolet shielding agent, it is generally necessary to disperse the composite particles in a medium in an actual environment. In this example, since the metal oxides contained in the composite particles, such as oxidation, are catalytically active, media deterioration may occur. In addition, when the composite particles and -7- this paper size are applicable to China National Standard (CNS) 8 4 specifications (2 丨 〇X297 公 嫠) (Please read the note ^ K on the back before filling out this page} • In nn I nnn IM ^ III n 1 ^ 1 III-n ^ ^ n 1 i J \ JJ tj ---- ^ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 34 0 2 7 'ί A7 —---- B7 5 2. Description of the invention (5> When the difference between the refractive indices of the two media is large, light scattering occurs on the interface between the composite particles and the media, thereby making the light transmittance in the visible light region and the ultraviolet The shielding ability in the light area is both poor. Although these problems need to be solved, they are not considered in the above disclosure. In order to suppress the catalytic activity of ultrafine particles, various materials have been used to coat the surface of ultrafine particles. For example, Japanese Patent Laid-Open No. 5_yog31 discloses the preparation of a cosmetic material containing fine particles, in which at least one basic compound is added to the production of titanium hydroxide obtainable by alkoxylation and hydrolysis. Hydrocarbon compounds with a boiling point of 100 to 200 ° C and It has a special molecular structure. However, in order to obtain titanium hydroxide fine particles, the process must include procedures such as drying and pulverization, which results in the obtained titanium hydroxide fine particles having a large particle size. In this way, it is difficult for the particles to be made by hand. Highly efficiently scatters ultraviolet light B (light wavelengths from 280 to 320 nm) while maintaining high light transmittance in the visible light region. In addition, the above publication neither considers nor reveals the production of titanium hydroxide ultrafine particles Any method or method of dispersing titanium hydroxide ultrafine particles in a cosmetic material to satisfy both the high light transmittance in the visible region and the high shielding ability to ultraviolet light. Furthermore, the ultraviolet light disclosed in this publication Among the shielding materials, titanium hydroxide or titanium oxide may absorb ultraviolet light B (light wavelengths of 280 to 320 nm). The ultraviolet light b only penetrates the relatively higher layers of the epidermis and the epidermis, causing tanning or skin cancer. However, titanium hydroxide or titanium oxide does not absorb light with a wavelength of 350 to 400 nm, that is, visible light having a wavelength closer to ultraviolet light a (those having a wavelength of 320 to 400 nm). Ultraviolet light a will reachThe skin layer under the skin produces a brownish-yellow or fibrous modification of the skin. _ _ 8 _ This paper size applies to China National Standard (CNS) A4 (210X297). {Please read the note on the back first (Fill in this page) Order 4340 2 7 ^ at B7 Printed by the Men ’s Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) In other words, the UV absorbers disclosed in this publication mainly exhibit titanium hydroxide or titanium oxide The absorption of ultraviolet light B, but its ultraviolet absorption effect is limited to a light wavelength of up to about 300 nm for detitanium-type titanium oxide and a light wavelength of up to about 320 nm for rutile-type titanium oxide. Of the ultraviolet light reaching the earth, the energy ratio of ultraviolet light A is about 15 times the energy of ultraviolet light B. Therefore, from the above-mentioned energy ratio of the ultraviolet light a and B, it is important to shield the ultraviolet light A and the ultraviolet light B at the same time, and it is not enough to shield only the ultraviolet light B. Furthermore, it has become increasingly important to shield both ultraviolet light b and ultraviolet light a while maintaining high light transmittance in the visible light region. In particular, in a case where the ultraviolet light A is shielded, it is important to shield a light wavelength of 350 to 400 nm, which is closer to the wavelength of visible light. As mentioned above, in order to achieve effective shielding in the ultraviolet region while maintaining high transmittance in the visible region, the ultraviolet shielding material must be made ultrafine so that it exists in a highly dispersed state. To improve the transmittance in the visible light region, it is important to keep the refractive index difference between the ultraviolet shielding substance and the surrounding medium to a small extent. Since the refractive index of titanium oxide-containing composite powders disclosed in Japanese Patent Laid-Open Nos. 1-143 821 and 6-116119 is limited to a certain range determined by the composition ratio of each component, the refractive index corresponds to the refractive index of the composite powder. The number of classes of properly dispersed media is also inevitably limited. Therefore, a large problem is encountered in controlling the refractive index of the composite to match the refractive index of the dispersion medium used. Therefore, there is a great need for effective means to solve these problems. In addition, Japanese Patent Laid-Open No. 4-653 No. 12 relates to pore-type silica beads containing metal compounds, a method for producing the same, and a powder deodorant produced therefrom. 9- (Please read the note ^^ on the back before filling this page >

5 / '5 V -T- rr I Printed by I Industrial Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ^ 434027 -ί at _: __Β7_ V. Description of the invention (7) In this disclosure,' This should have a primary particle size 0.00 丨 to The content of 0.3 micron metal compound fine particles in the pore-type silica beads is 0 to 30% by weight, and the pore-type silica beads do not substantially contain voids of not less than 0.3 micrometers. In this case, when the metal compound fine particles contained therein are appropriately selected so that their refractive index is close to the refractive index of silicon oxide (with a refractive index in the range of 1.4 to 2.0), a further improvement can be obtained. Light transmission of silicon oxide particles. However, this publication only discloses the refractive index of the metal compound fine particles contained inside the composite particles, but does not mention the total refractive index of the composite particles. As explained above, in order to solve the problem of ultraviolet shielding agent containing ultraviolet rays, there have been several attempts to use a composite material mainly containing a metal oxide. However, many of the compounds 'such as Ti02 and ZnO exhibiting good UV absorption properties have relatively high refractive indices, so that the composite microparticles doped with these ultrafine particles have a significantly higher ratio than aqueous solutions and traditional organic solvents' polymers High refractive index. When the above-mentioned composite fine particles were dispersed in a medium, the inventors found that the scattering phenomenon in the visible light region occurred at the interface between the composite fine particles and the medium, and the light transmittance of the medium was dramatically reduced. However, a method for controlling the refractive index of the ultraviolet shielding particles contained in the composite fine particles has not been proposed so far. In the field of resin fillers, fluorine-based inorganic compounds, such as MgF2 * CaF2 'or fluorine-based organic polymers, such as polytetrafluoroethylene, are known as low-refractive index materials with high light transmittance and can be used to add powder Etc. as the starting material to reduce its refractive index. For example, Japanese Patent Laid-Open No. 4_85346 discloses a glass powder used as ------------. 10- This paper is applicable (please read the precautions on the back before filling this page) rn ^ 1 -n —Ί —Ίν / 1 Uhl—- · 4 ------ if ------ 43402 7 ~ A7 B7 Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (8) Light-transmitting inorganic powder resin filler v contains a metal oxide, such as

Si02 'A1203' B203, BaO 'SrO, ZnO, and Mg0; and metal fluoride' The glass powder has a refractive index (nD) adjusted within a range of 1.44 to 1.70. The publication reveals that since the glass frit has high light transmittance and does not show strong alkalinity, the resin does not undergo any substantial modification, and is significantly stabilized in the hardening of the street fat. However, this publication only discloses highly translucent inorganic powders that can be used as resin fillers by changing the composition ratio of the materials, and the above-mentioned metal oxides and the like are manufactured because of high-temperature melting, and are not present in the final product in the form of particles. In addition, the publication does not mention ultraviolet shielding ability. In addition, the publication does not disclose that the composite fine particles have aggregates composed of two or more kinds of fine particles as in the present invention, or that the composite fine particles have a composition correlation with respect to the average refractive index of the composite fine particles. DISCLOSURE OF THE INVENTION An object of the present invention is to propose ultraviolet shielding composite fine particles, which have substantially no catalytic activity, are uniformly and stably dispersed in a medium (such as cosmetics and lacquer), and have high light transmission in the visible light region. It has high shielding ability in the ultraviolet region and can be easily processed. Another object of the present invention is to propose a method for producing the ultraviolet shielding and shielding composite fine particles. It is still another object of the present invention to provide pellets containing the ultraviolet shielding composite microparticles. These goals have been achieved by finding the high performance of inorganic UV shielding agents in composite microparticles, which contain good UV shielding energy. 11-Private Paper Standards China National Standard (CNS) A4 Specification (210X297 mm) (Please read the note on the back before filling in this page) Order the stamp of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 4 34 0 2 7-a7 _B7_ V. Description of the invention (9) Force ) Sub-particles and matrix particles having the sub-particles dispersed therein and supporting the sub-particles, the matrix particles have a high degree of sub-particle dispersibility. In addition, the inventors also found that the advantageous effect of the ultrafine particles can be optimally achieved by appropriately combining the matrix particles and the daughter particles according to the difference in energy of the band gap energy. In addition, the inventors of the present invention have found that the refraction of composite fine particles can be controlled by controlling the refraction ratio of composite fine particles that can be achieved by a suitable combination of matrix particles containing a metal oxide and a low-refractive index fluorine compound and the daughter particles. When the rate is substantially equal to the refractive index of the medium, the light scattering between the composite fine particles and the medium is rather limited. In this case, regardless of the shape of the composite fine particles being spherical, flake-shaped, or needle-shaped, and regardless of the surface roughness of the composite fine particles, light can be transmitted well into the composite fine particles 妁. In this way, the ultra-fine particles dispersed inside the composite fine particles can achieve a significant improvement in the transmittance in the visible light region, and can achieve a high shielding ability in ultraviolet light. In addition, the inventors have found that When the microparticles having a refractive index and a particle diameter of not more than 0.3 micrometers, the total refractive index of the composite microparticles can be reduced without causing visible light scattering even if the inside of the composite microparticles forms below the microparticle size region. In addition, the inventors have found that the catalytic activity of the ultraviolet shielding composite fine particles can be substantially reduced by coating the surface of the composite fine particles with an inorganic substance having substantially no catalytic activity. Furthermore, the inventor of the present case found that the composite fine particle powder can be obtained by applying a water-repellent treatment to the surface of the composite fine particles coated with a substantially non-catalytically active inorganic substance and pulverizing the managed composite fine particles. _____- 12 -____ This paper size is applicable to China National Standard (CNS) A4 (210X297 cm) (Please read the precautions on the back before filling this page) -1—, II J7 nn \, wr tMf I n In n I. Printed by Shellfish Consumer Cooperative Bureau of Central Bureau of Standards, Ministry of Economic Affairs: 434027 "A7 ______B7 __ V. Description of the invention (10) Water-repellent treatment is applied to the surface of microparticles, and the composite microparticles as processed here are dispersed in oil In the agent, an ultraviolet shielding composite fine particle having easy handling properties can be obtained. In summary, the gist of the present invention is as follows: (1) Ultraviolet-shielding composite microparticles having translucency in the visible light region, which include: (a) matrix particles containing a primary particle having an average particle diameter of 0.001 to 0.3 microns; Aggregates of particles formed by the original particles maintaining their shape; and (b) daughter particles having an average particle size of 0,001 to 0.1 micron, the daughter particles being dispersed among the matrix particles And is a supporter thereof, wherein the particles have a smaller band gap energy than particles constituting the matrix particles and can absorb ultraviolet light, and wherein the ultraviolet shielding composite particles are substantially non-catalytic; (2) above (1) The ultraviolet shielding composite fine particles described in the item (1), wherein the surface of the ultraviolet shielding composite fine particles is coated with an inorganic substance having substantially no catalytic activity; (3) (1) or (2) above The ultraviolet shielding composite fine particles described in above, wherein the particles constituting the matrix particle have an interband energy of 3 to 9 ev * ⑷ The ultraviolet shielding composite fine particles described in any one of the items (3) to (3) above Particles, in which the difference between the band gap energy of the sub-particles and the particles constituting the matrix particles is not less than 0.2 eV; the ultraviolet shielding composite micro-elements described in any one of the above items ⑴ to ⑷ (please first Read the notes on the back and then fill out this page) — ^ ϋ ih, clothing ------ order * nnn Hi In —I- -13-

Printed by the Central Standards Bureau of the Ministry of Economy—Industrial and Consumer Cooperatives, 4 34027 ^ A7 _____B7 V. Description of the invention (11) Particles, in which the amount of the sub-particles dispersed in the matrix particles and supported by it is 0.1 to 85% by volume; (6) the ultraviolet shielding composite fine particles described in any one of the items (1) to (5) above, wherein the average particle diameter of the ultraviolet shielding composite fine particles is not more than 0.5 micrometers; (7) the above ( 1) The ultraviolet shielding composite fine particles according to any one of (6), wherein the ultraviolet shielding composite fine particles have an average refractive index of 13 to 2.5; (8) any of the above (1) to (7) The ultraviolet shielding composite microparticles according to one item, wherein the particles constituting the base particle are selected from the group consisting of metal oxides, fluorine compounds, and mixtures thereof; (9) Ultraviolet-shielding composite fine particles, wherein the metal oxide is selected from the group consisting of SiO2, ai2o3, and mixtures thereof; (1 0) the ultraviolet-shielding property as described in any one of (1) to (9) above. Composite fine particles, wherein the sub-particle system is selected from Ti02, ZnO , Ce02, SiC, Sn02, W03, BaTi03, CaTi03, SrTi03, and mixtures thereof; (1 1) The ultraviolet shielding composite fine particles described in any one of the items (2) to (10) above Wherein the inorganic substance is a metal oxide; (12) the ultraviolet shielding composite fine particles described in the item (1 1) above, wherein the metal oxide used in the inorganic substance is selected from the group consisting of Si02, Al2O3, and a mixture thereof; (1 3) The ultraviolet shielding composite microparticles according to any one of (1) to (12) above, wherein the surface of the composite microparticles has been treated with a water-repellent agent;. _ -14- The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) N--; —ί -------- Order ---- -4 34 0 2 7 ,, at ____; __B7_ V. Description of the invention (12) (1 4) The ultraviolet shielding composite microparticles according to any one of (1) to (1 3) above, wherein the ultraviolet rays The shielding composite fine particles have a light transmittance of not less than 80% at a wavelength of 800 nanometers and a light transmittance of not less than 20% at a wavelength of 400 nanometers. And has a light transmittance of not higher than 5% at at least one wavelength in the range of 380 nanometers to 300 nanometers. The transmittance is measured by suspending the composite fine particles with a refractive index substantially the same as that of the composite fine particles In a horizontal medium, measure with an ultraviolet-visible light spectrophotometer using an analysis box with a light path length of 1 mm; (15) The ultraviolet shielding compound according to any one of (1) to (14) above Microparticles can be obtained by the following steps: (a) preparing a liquid mixture containing: (i) a starting material of matrix particles, which is one or more forms selected from the group consisting of: A sol of particles and a matrix particle powder, the matrix particles having primary particles having an average particle diameter of 0-001 to 0.33 micrometers; and (11) a starting material of daughter particles, which is one or more selected from the following combinations: Medium form: sol containing sub-particles and sub-particle powder, the sub-particles have primary particles with an average particle size of 0.001 to 0.1 microns, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Fill out this page again) and The liquid mixture is placed in a pulverizer and / or a high-pressure dispersing device for processing, thereby preparing composite fine particles, wherein the sub-particles and the matrix particles are aggregated together; (b) a coating step with an inorganic substance (a ); (C) Apply water-repellent treatment to the composite fine particles coated with inorganic substances obtained in step (b); and ~ 15-This paper size applies Chinese National Standard (CNS) A4 ^ (210X297 ^ 7 Ordered by the Ministry of Economic Affairs of the Central Bureau of Quasi-Bureau Shellfish Consumer Cooperative 16- 4 34027 ^ A7 _ B7 V. Description of the invention (13) (d) Drying and / or powdering the water-repellent composite fine particles obtained in step (0) (1 6) A dispersing oil agent for ultraviolet shielding composite fine particles as defined in any one of the items (1) to (1 4) above, which can be obtained by the following steps: (a) preparing a liquid mixture containing; (i) The starting material of the matrix particles, which is in the form of one or more selected from the group consisting of a sol containing the particles constituting the matrix particles and a matrix particle powder, the matrix particles having an average particle size of 0.001 to 0.3 micron primary particles; and (ii) A particle starting material in the form of one or more combinations selected from the group consisting of a sol containing sub-particles and a sub-particle powder, the sub-particles having primary particles having an average particle diameter of 0,001 to 0.1 micrometers, and The liquid mixture is processed in a pulverizer and / or a high-pressure dispersing device to prepare composite fine particles, wherein the sub-particles and the matrix particles are aggregated together; (b) coating step (a) with an inorganic substance The composite fine particles obtained in the step (a) apply water-repellent treatment to the composite fine particles coated with an inorganic substance obtained in step (b); and (d ·) disperse the water-repellent-treated composite fine particles obtained in step (c) In an oil agent; (1 7) — A method for manufacturing an ultraviolet shielding composite fine particle, the ultraviolet shielding composite fine particle containing sub particles dispersed in and supported by the matrix particles, and having substantially no catalytic activity but The visible light area is transparent, and it can be prepared by the following steps: This paper size is applicable to China National Standard (CNS) A4 size 7 ^ 10X297 / entry sign — f Please read the notes on the back before filling This ear) I-II 1--ί-. 丨 ... 1 J tin I < 1 (^ ----:-I unnn 1 ^ 1 --- I. 4 34 0 2 7-1 A7 B7 Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (14) (a) Preparation of a liquid mixture containing: (丨) a matrix particle starting material, which is one or more selected from the following combinations: In the form of: a sol containing particles constituting matrix particles and matrix particle powder, the matrix particles having primary particles having an average particle diameter of 0.001 to 0.3 micrometers; and (ii) the starting material of the daughter particles, which is one or A plurality of forms selected from the following combinations: a sol containing sub-particles and a sub-particle powder, the sub-particles having a primary particle having an average particle size of 0.001 to 0.1 micron, and the liquid mixture is subjected to pulverization And / or high-pressure dispersing equipment to process composite fine particles, wherein the sub-particles and the matrix particles are aggregated together; and (b) coating the composite fine particles obtained in the coating step with an inorganic substance; (18) The method described in item (17) above, further comprising: after step (b) above: (c) step by step (B) The composite fine particles coated with an inorganic substance obtained in (b) are subjected to water-repellent treatment; (19) The method described in (18) above, further comprising, after step (c) above: (d) step ( c) drying and / or pulverizing the composite fine particles obtained in the water-repellent treatment; (20) a method for preparing an ultraviolet shielding composite fine particle dispersing oil agent, the ultraviolet shielding composite fine particles containing dispersed particles in a matrix And for the daughter particles supported by it, which is not substantially catalytically active but has translucency in the visible light region, it can be prepared by the following steps: (a) preparing a liquid mixture containing: the starting material of the rhenium matrix particles , Which is-or a variety of forms selected from the following combinations: containing basic paper New Zealand standards applicable to Chinese families ((Please read the precautions on the back before filling out this page) -------- ----- ^ — 4-, --- 1 · I --- -m If— 434027 'A7 B7 Yin Peng Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, Yin Li 5. Description of the invention (15) Sol and matrix particle powder, the matrix particle having an average particle diameter of 0.001 to 0.3 micron And (ii) a starting material for daughter particles, which is one or more forms selected from the group consisting of a sol containing daughter particles and a daughter particle powder, the daughter particles having an average particle diameter of 0. 001 to 0.1 micron primary particles, and the liquid mixture is processed in a pulverizer and / or high-integration dispersing equipment to prepare composite fine particles, wherein the sub-particles and the matrix particle system are aggregated together (B) coating the composite fine particles obtained in step (a) with an inorganic substance p; (c) subjecting the composite fine particles coated with an inorganic substance obtained in step (b) _ to a water-repellent treatment; and (d ') subjecting the step ( c) the water-repellent composite fine particles obtained in c) are dispersed in an oil; (21) a cosmetic containing the ultraviolet-shielding composite fine particles as defined in any one of (1) to (15) above; (22) ) Granulated material containing the ultraviolet shielding composite fine particle dispersing oil agent as defined in the item (16) above; (23) The cosmetic material according to any one of the items (18) to (21) above, wherein the ultraviolet rays The amount of the shielding composite fine particles is 0.1 to 50% by weight; (24) (21) The cosmetic according to any one of items (23), which further contains an ultraviolet protective agent; (25) The pelletized material according to any one of (2 1) to (24) above, wherein The SPF 値 measured by using an analyzer "SPF-290" made by The Optometries Group is not lower than 8, and wherein ΔE'b before and after skin application is not higher than 3 as defined in JIS Z 8729-1980 ; And -18- This paper size is applicable to China National Standards (CNS) A4 specification (210X297 mm) Μ ----- 1, private ------ order-(Please read the note on the back before (Fill in this page) X m _ · Α 1 ^ 1 * Printed by the Ministry of Economic Affairs of the Bureau of Quasi Bureau Shellfisher Consumer Cooperative * 434027 ', A7 __________B7_ V. Description of the invention (16) (26) Above (1) to (15) Use of the ultraviolet shielding composite fine particles as defined in any one of the above items as granulated materials. Brief description of the drawing The present invention can be more fully understood from the detailed description given below and the accompanying drawings for the purpose of clarification and not to limit the present invention, in which: Figure 1 shows the ultraviolet shielding composite fine particles obtained in Example 1 of the present invention, A graph showing the relationship between the light wavelength and the light transmittance measured by an ultraviolet-visible light spectrophotometer; FIG. 2 shows the ultraviolet shielding composite particles obtained in Example 2 of the present invention. The graph of the relationship between the measured light wavelength and light transmittance; Figure 3 shows the light wavelength and light transmittance measured by the ultraviolet-visible light spectrophotometer obtained from the ultraviolet shielding composite microparticles obtained in Example 3 of the present invention Fig. 4 is a graph showing the relationship between the light wavelength and the transmittance of the ultraviolet shielding composite fine particles obtained in Example 4 of the present invention, as measured by an ultraviolet-visible light spectrophotometer; 5 shows the light-shielding composite fine particles obtained in Example 5 of the present invention, and the light wavelength and transmission measured by a UV-visible light spectrophotometer Fig. 6 is a graph showing the relationship between the light wavelength and the transmittance of the ultraviolet shielding composite microparticles obtained in Example 6 of the present invention, measured by an ultraviolet-visible light spectrophotometer; 7 shows the ultraviolet shielding composite particles obtained in Example 7 of the present invention _ _-19-_ __ This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back first (Fill in this page again) I J --- Γ J111 ^ Clothes -------- Order 11 ---- ^ ---- '.------ Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 4 340271 A7 ___B7 V. Description of the invention (17) The shape of the relationship between the light wavelength and the transmittance measured by an ultraviolet-visible light spectrophotometer; Figure 8 shows the ultraviolet rays obtained in Example 8 of the present invention Masking composite fine particles, the shape of the relationship between the light wavelength and the light transmittance measured by an ultraviolet-visible light spectrophotometer; FIG. 9 shows the ultraviolet shielding composite fine particles obtained in Example 9 of the present invention. Light wavelength and light transmittance measured by light-visible light spectrophotometer Fig. 10 is a graph showing the relationship between the light wavelength and the transmittance of the ultraviolet shielding composite microparticles obtained in Example 10 of the present invention, measured by an ultraviolet-visible light spectrophotometer; FIG. 11 is a graph showing the relationship between the light wavelength and the transmittance of the ultraviolet shielding composite fine particles obtained in Example 11 of the present invention measured by an ultraviolet-visible light spectrophotometer; FIG. 12 is a view showing the present invention A graph showing the relationship between the light wavelength and the transmittance measured by the ultraviolet-visible light spectrophotometer obtained in the ultraviolet shielding composite fine particles obtained in Example 12; FIG. 13 shows the ultraviolet shielding composite obtained in Example 13 of the present invention Microparticles, the shape of the relationship between the light wavelength and the transmittance measured by an ultraviolet-visible light spectrophotometer; FIG. 14 shows the ultraviolet shielding composite microparticles obtained in Example 14 of the present invention through 'UV-visible A graph of the relationship between the light wavelength and the light transmittance measured by a light spectrum photometer; and FIG. 15 is a view showing the ultraviolet shielding composite obtained in Example 15 of the present invention Micro ______-_ _- 20 -_ This paper size applies to China National Standard (CNS) A4 (210X297 mm) '-(Please read the precautions on the back before filling this page)

、 1T Κ MK Central Bureau of Economic Affairs Ministry of Economic Affairs printed i434〇27ti λ7 — --_____ B7 V. Description of the invention (18) Particles, light wavelength and light transmittance measured by ultraviolet and visible light spectrophotometer The relationship between the graphics. Best Mode for Carrying Out Particles having a relatively small particle size and a high ability to block ultraviolet light are liable to form aggregates, which makes it impossible to perform a good masking function when dispersed in a medium. Therefore, by forming a composite material in which microparticles are given to relatively large particles, that is, by supporting microparticles as sub-particles in matrix particles used as a carrier, the microparticles are maintained in a good dispersion state, thereby maintaining their High shielding ability against UV light. In addition, by coating the surface of the composite fine particles with a substantially non-catalytically active inorganic substance, the catalytic activity of the composite fine particles can be substantially suppressed. Therefore, by coating the surface of the composite fine particles with an inorganic substance having substantially no catalytic activity, even if the composite fine particles are subjected to a surface modification treatment, the modifier used is not deteriorated by the catalytic activity or photocatalytic activity of the composite fine particles. Furthermore, the ultraviolet-shielding composite microparticles having easy disposability can be obtained through steps such as subjecting the surface of the composite microparticles coated with an inorganic substance to permanent treatment, and then pulverizing the composite microparticles obtained after the water-repellent treatment into a powder. * In addition, after applying water-repellent treatment to the surface of the composite fine particles, the composite fine particles are dispersed in an oil or the like to obtain ultraviolet shielding composite fine particles. In this specification, the matrix particles of the composite fine particles refer to a matrix capable of containing and supporting the sub-particles dispersed therein. The base plasmids are aggregates formed while retaining the shape of the particles (i.e., the 'primitive particles') constituting the matrix particles. The daughter particles refer to particles having a UV shielding ability other than the matrix particles. _-21 -____ This paper size is in accordance with China National Standards (CNS > A4 size (210X297mm) ~ (Please read the precautions on the back before filling this page) " T Water — II-. ^ Order- ------ II --- Printed by the Consumers ’Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, 1 4 34 η 2 7, " Α7 ___ Β7 V. Description of the Invention (19) 1. The preferred embodiment of the present invention will be The following is a detailed description with reference to the properties of the following composite particles: (1) the band gap energy of the particles, (2) the refractive index of the composite particles, (3) the particle interface of the particles, and (4) the inorganic substances in the composite The coating formed on the surface of the microparticles. (1) The band gap energy of the particles is used in the composite microparticles of the present invention. The microparticles used as the subparticles must have good shielding ability against ultraviolet light. The ultraviolet shielding ability can be divided into two categories: ultraviolet Light absorption and ultraviolet light scattering. Ultraviolet light absorption of inorganic compounds is considered to be exciton absorption of semiconductor compounds, and compounds with band gap energy of 3.0 to 4.0 eV effectively show this property. UV Strong light scattering Appears as Mie scatlering. In the case of high refractive index materials such as Ti0 2 'When the particle diameter of the material is about half of the wavelength of ultraviolet light, that is, no more than 0.2 micron, the scattering can be clearly observed Phenomenon & Since neither valence electron band nor conduction band is continuous in ceramics, ceramics are light that is known to absorb energy whose wavelength corresponds to no less than the energy of the band gap. Band gap energy refers to valence The difference between the energy bands of the electronic and conduction bands. For example, Z η Ο has a band gap energy of 3 · 2 eV, which can absorb light with a wavelength of not more than 3 90 nm. Inorganic ultraviolet shielding agents due to their The interband energy corresponds to the wavelength of ultraviolet light and is capable of absorbing ultraviolet light. Therefore, in the composite fine particles of the present invention, in order for the particles to exhibit effective ultraviolet light scattering ability and absorption ability, the particles constituting the matrix particles must have greater than the sub-particles. The band gap energy of the holder. For example, when using aggregates of Ti〇2 particles (rutile type) as matrix particles, and having less than _____ 22-_ This paper XJL is suitable for China National Standards (CNS) A4 Secret (210X297mm) '(Please read the notes on the back before filling out this page) -—— Ί—t ™ ~ U-^ ----, SH-1--^ IH--n U ·, 1 H-printed by M3402h A7 _______ B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2)

In the case of ZnO microparticles with band gap energy possessed by Ti〇2 as sub-particles, ultraviolet light having a wavelength of not more than 320 nm is corresponding to the particles constituting the matrix particle, that is, Ti〇2. Excitons with gap energy are absorbed. In addition, ultraviolet light with a wavelength of about 350 nanometers can be penetrated by the matrix particles and not absorbed, while being multi-scattered by the seed particles, it is absorbed by the exciton absorption corresponding to the band gap energy of the seed particles. As a result, the ZnO / Ti02 (sub / matrix) composite fine particles have a shielding ability against ultraviolet light having a wavelength of not more than 350 nm. Conversely, when Ti02 is used as the particles constituting the matrix particles and Sn02 particles with a band gap energy greater than Ti02 are used as the sub-particles, ultraviolet light having a wavelength of not more than 320 nm will be corresponding to the band of the Ti02 particles. Gap energy is absorbed by exciton absorption. However, ultraviolet light with a wavelength around 350 nm will penetrate the matrix particles without being absorbed, and will not be absorbed by the exciton absorption corresponding to the gap energy of the Sn02 band. As a result, the S η Ο 2 / T i 0 2 (sub / matrix) composite microparticles cannot provide sufficient shielding for ultraviolet light having a wavelength of around 350 nm for the purpose of use. Based on the above reasons, in the composite microparticles of the present invention, the particles constituting the base plasmid have a band gap energy a of preferably 3 to 9 eV, and more preferably 5 to 9 eV. In order to more stably bring ultraviolet light to the daughter particles, The difference between the lowest band gap energy of the daughter particles and the band gap energy of the particles constituting the matrix particles is preferably not less than 0_2 eV, and has ultraviolet light of a wavelength that can be absorbed and scattered by the daughter particles. (2) The refractive index of the composite fine particles. When the ultraviolet-shielding composite fine particles are actually used, it needs to be within the range of -23-This paper is only applicable to China National Standards (CNS) M regulations ^ (210X297 mm) " (Please Please read the note on the back before filling in this page) Order printed by the Central Government Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives It exhibits high light transmittance while maintaining high shielding ability in the ultraviolet region. At this time, '(1) In order to maintain high shielding ability, the difference between the refractive index of the matrix particles and the sub-particles must be kept as large as possible, because when the difference between the refractive indexes is maintained at a large value, The ultraviolet shielding ability is significantly improved. In the present invention, the difference between the refractive indexes is preferably not less than 0.1. For this reason, in the present invention, a metal oxide and a fluorine compound, both of which have a relatively low refractive index, are used as a substance constituting the matrix particles to mix the daughter particles having a relatively high refractive index. In addition, (ii) In order to exhibit high light transmittance, the difference between the refractive index of the composite fine particles and the surrounding matter (medium) must be kept as small as possible. Thus, the refractive index of the composite fine particles must be controlled so that the difference becomes small. The present invention is characterized in that the refractive index of the composite fine particles is adjusted by controlling the volume ratio between the matrix particles and the daughter particles, and further using a fluorine compound. In composite fine particle suspensions, such as those used in cosmetics, when the refractive index of the composite fine particles is significantly different from the refractive index of the medium, it may be lost due to the visible light being diffracted or reflected at the interface between the composite fine particles and the medium. Transmittance. Here, the refractive index is measured by the commonly known dipping method (see Toshiharu Takou, et al., Optical Measurement Handbook, p. 475, 1981, published by Asakura Publishers in this method. The refractive index of the sample is the Refractive index, its highest transmittance is obtained at a wavelength of 589.3 nm. However, the immersion method is complicated and time-consuming. For convenience, the refractive index can be refracted by the original particles contained in the sub-particles and matrix particles. Ratio and the volume ratio between them are calculated by theory. Since the theoretically calculated refractive index depends on the composite particles, it is very similar to the data obtained by the impregnation method. • 24- This paper size applies the Chinese National Standard (CNS) A4 specification. (210X297 mm) J --- rj-^ ^ ------ Order-- (Please read the precautions on the back before filling out this page) ___Hi -It * Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Μ34 02 7 ^ a? ----_ B7 V. Description of the invention (22) Therefore, the refractive index of the composite fine particles can also be obtained by the above simple calculation method. The refractive index nD2 of common media is 1.3 to 1.8. Another In terms of Many kinds of metal oxides with high ultraviolet shielding ability, such as Ti〇2 and ZnO 'have a refractive index nD20 of not less than 2,0, so when using these metal oxides as the sub-particles, the refractive index of the composite fine particles must pass through A low refractive index substance is used as the sub-particles to approximate the refractive index of the medium. Specifically, the average refractive index of the composite fine particles is 1.3 to 2.5, preferably 1.3 to 2_0, and more preferably 1.3 to 1.8, Particularly preferred is 1.3 to 1.7, and the most preferred is 1.4 to 1.5. In addition, the refractive index difference 的 between the matrix particles and the sub-particles in the composite fine particles of the present invention is preferably not less than 0. By maintaining the refractive index The difference between them can improve the UV light scattering ability. (3) The particle interface of the particles becomes smaller as the particle size of the original particles contained in the matrix particles, that is, the particle interface in the matrix particles becomes smaller. Visible light cannot detect the existence of the particle interface, so that the matrix particles are transparent regardless of whether the original particles of the matrix particles are crystallized. Since the sub-particles also contain ultrafine particles, so It also has good light transmittance. Therefore, the composite fine particles have good light transmittance as a whole. (4) The coating layer formed on the surface of the composite fine particles by the inorganic substance is coated with the composite fine particles by the inorganic substance having substantially no catalytic activity. In the case where the surface of the microparticles suppresses the catalytic activity of the ultrafine particles, the coating formed may be a thin layer or a thin particle layer. If the active sites on the surface of the composite microparticles are substantially coated, the surface activity will be prevented from affecting the composite microparticles. Zhouyuan-25- This paper uses the Chinese National Standard (CNS) A4 size (210 parent 297 race) —in ^^ 1 (Please read the precautions on the back before filling this page) Γ, —I Order —II——μ. ——- V— —1. The staff of the Central Standards Bureau of the Ministry of Economic Affairs printed 434027 ^ * 'A7 _________B7_ V. Description of the invention (23) The thickness of the coating can be regarded as Is enough. In other words, by physically suppressing the surface activity of the composite fine particles, the deterioration of the medium on the surface of the composite fine particles and the medium in contact with the surface can be prevented, and the medium is, for example, the base material of the granules, lacquer, and the like. In addition, since the dispersant is not deteriorated, the dispersibility of the composite fine particles can be stably maintained for a long period of time. Although the foregoing is a problem that cannot be avoided in the case where an inorganic ultraviolet shielding agent is conventionally dispersed in various media, the present invention proposes a means for solving such conventional problems. 2. Next, the method for producing the ultraviolet shielding composite fine particles of the present invention will be explained according to the following steps. The composite microparticle water-repellent treatment referred to in the following steps is optionally used in the present invention. However, in the case where the obtained composite fine particles are to be incorporated into a cosmetic, it is preferable to include the water-repellent treatment step. A manufacturing method including the water-repellent treatment step is listed below as a preferred embodiment of the present invention. There are two specific embodiments: (1) one embodiment includes drying and pulverizing the composite fine particles into a powder form; and (2) another embodiment includes dispersing the composite fine particles in an oil agent. Examples (1) and (2) each include the following steps. (1) Example of turning composite fine particles into powder by drying and pulverizing. In this example, the method of 'preparing composite fine particles includes the following steps: (a) preparing a liquid mixture containing: a starting material of matrix particles, which In the form of one or more selected from the group consisting of a sol containing particles constituting matrix particles and matrix particle powder, the matrix particles having primary particles having an average particle diameter of 0.001 to 0.3 micrometers; and (π) daughter particles The starting material is in the form of one or more selected from the following combinations: containing seed particles-26- This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 OX: 297 public director) (please first Read the note f on the back and fill in this page) Γ 11 I Order I --- I -1. ________ B7 V. Description of the invention (24) A sol and a particle powder of the particle, the particle has primary particles with an average particle diameter of 0.001 to 0.1 micron, and the liquid mixture is placed in a pulverizer and / or a high-pressure dispersing device Processing to produce composite particles Wherein the daughter particles and the matrix particles together by lines; and (b) are coated with an inorganic material in step (a) the resulting composite fine particles. In this embodiment, the following additional steps can be performed. (c) subjecting the composite fine particles coated with an inorganic substance obtained in step (b) to water-repellent treatment; and (d) drying and / or pulverizing the composite fine particles obtained after water-repellent treatment in step (c). (2) An example in which composite fine particles are dispersed in an oil agent. In this embodiment, the method for preparing composite microparticles includes the following steps: (a) preparing a liquid mixture containing: (丨) a matrix particle starting material, which is one or more selected from the following combinations: Form: sol containing particles constituting matrix particles and matrix particle powder, the matrix particles having primary particles having an average particle diameter of 0.001 to 0.3 micrometers; and (丨 丨) starting materials of daughter particles, which are one or more selected from In the form of the following combination: a sol containing sub-particles and a sub-particle powder 'the sub-particles have primary particles having an average particle size of 0.001 to 0.1 micron, and the liquid mixture is placed in a pulverizer and ^ / Or processing in a high-pressure dispersing device, thereby preparing composite fine particles, wherein the sub-particles and the matrix particles are aggregated together; (b) coating the composite fine particles obtained in step (a) with an inorganic substance; (c) the The composite fine particles coated with the inorganic substance obtained in step (b) are subjected to water-repellent treatment; and i -J-^ in -------- order-- (Please read the precautions on the back before filling in this page)

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Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4340274 A7 _ B7 V. Description of the invention (25) (d ') Disperse the water-repellent composite fine particles obtained in step (c) in the oil. In the preparation of the liquid mixture in step (a) above, the sub-particle powder containing ultrafine particles having an average particle diameter of 0.001 to 0.1 micron is appropriately disintegrated and / or pulverized in a pulverizer or a high-pressure dispersing device. Maintain the dispersed state of the sub-particles in the liquid mixture. Examples of mills include bead mills, sand mills, and ball mills. Examples of high-pressure dispersers include microfluidizers and nanometers. (Nanomizers). In the present invention, in the case where the liquid mixture containing the sub-particles of the ultrafine particles and having a large proportion and a high concentration of the sub-particles is subjected to a grinding treatment and / or a high-pressure dispersion treatment, the grinding treatment and / or the high-pressure dispersion Before the treatment, it is preferable to perform pretreatment with a dispersing device capable of dissolving the ultrafine particle powder. The dispersing device includes homomixers and homogenizers. The reason for performing this pretreatment is as follows. By dissolving the ultrafine particle powder in the aggregated state at a high concentration, the treatment subsequent to the pretreatment step, that is, the milling treatment step and / or the high-pressure dispersion treatment step, the required dissolution and / Or the load of pulverization is significantly reduced, so that the disintegration and / or pulverization can be effectively performed, thereby resulting in good dispersion of the ultrafine particles. In the coating step using an inorganic substance in the step (b), the coating method is not particularly limited, and any coating method used in the sol-gel reaction method and the precipitation reaction method can be adopted. The inorganic substance used for coating is also not particularly limited as long as it is an inorganic substance which is substantially non-catalytically active. Among them, the preferred one is metal oxide, the particularly preferred one is Si02, Al203, -28- This paper size is based on the standard of Chinese gardener (CD51) A4 (210X297 mm) (Please read the back page first) (Note $ items, then fill out this page)

.X Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperation Du 34 4 0 2 7 ^ .1 A7 _ B7 _ 1 — —___ V. Description of the Invention (26) and its mixture "Inorganic substances used in the coating step The starting material is not particularly limited, and any metal salt such as a metal alkoxide, a metal nitrate, and a metal sulfate can be used. Specific examples of the metal salt include tetraethoxysilane, alumina isopropoxide, tri-second alumina, sodium silicate, and aluminum sulfate. The inorganic particles can be coated on the surface of the composite fine particles by using a precipitation reaction and a sol-gel reaction according to the properties of the above-mentioned starting materials of the inorganic materials used. Incidentally, after the coating step, a neutralization reaction step may be added as needed before or after the water-bearing treatment step. In this specification, "the sol-gel reaction method" refers to a method including growing colloidal particles contained in a sol by agglomeration or aggregation, thereby inventing gelation of the obtained colloidal particles. Using the above-mentioned sol _In the case where the surface of the composite fine particles is coated by the gel reaction method, the above gelation can be performed on the surface of the composite fine particles. In addition, "precipitation reaction method" refers to adding a precipitant to a solution containing metal A method for generating precipitated particles. In this method, the concentration, p HS, and temperature must be appropriately controlled so that the precipitated particles adhere to the surface of the composite microparticles. Examples of the reaction method include co-precipitation method, precipitation method from homogeneous solution , And the compound precipitation method, etc. Although the mass of the inorganic substance applied in the form of a coating is not particularly limited, an excessively large amount of coating may contribute to the large diameter of the composite fine particles, which dramatically damages the optical properties of the composite fine particles. On the contrary, Too little coating will result in poor catalytic activity of the composite particles. Therefore, the mass of inorganic substances applied in the form of a coating must be Adjust it appropriately so as not to cause their adverse effects. In order to use the water-repellent agent for water-repellent treatment in the water-repellent treatment according to step (c) above -29 · This paper uses the Chinese national standard (CNS> Α4 specification (210X297) (Public Note) (Please read the notes on the back before filling in this page)-Order printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, V. Invention Description (27) and methods are not particularly limited, and any kind of water repellent treatment method is Can be used, including the use of poly dream oxygen compounds, such as methyl hydrogen polysiloxane, high viscosity polysiloxane oil 'Zatulin modified polysiloxane, amino modified polysiloxane, and polysiloxane resin, etc. Treatment; treatment with surfactants, including anionic surfactants, such as stearic and oleic acids, and cationic surfactants; treatment with macromolecular compounds, such as nylon, polymethyl methacrylate, polyethylene, Tefl. nT M, and polyamino acid treatment; treatment with perfluorinated compounds, lecithin, collagen, metal-coated 'affinity' polyacryl alcohol part, and polyacryl alcohol full ester, etc. ; And the use of salt compounds, such as Alkyl tribasic acid salt and dialkyl phosphoric acid ester salt treatment, however, it is not intended to limit the treatment method to those listed above. In principle, the electrostatic force between the surface of the composite particles and the water-repellent agent can be used. In addition, in In the water-repellent treatment method, it is possible to use seed aggregation of a water-repellent agent containing composite fine particles as a seed. In addition, a neutralization reaction step may be added before or after the water-repellent treatment step snails. Although the steps in Example 1 (C) is the selection procedure. However, from the viewpoint of suppressing surface activity and dispersing the composite fine particles, it is preferable to perform the coating step. Second, the step of drying and pulverizing the composite fine particles that have been subjected to water-repellent treatment (d ), The drying method and the pulverization method are not particularly limited. For example, 'the drying method and s' can use hot air drying and direct processing methods', and for the pulverization method, such as sand grinding and impeller type grinding can be used Machine and other tools. The composite fine particles obtained after the pulverizing step can be classified to a given size by classification. In order to measure the particle size and shape of the obtained composite fine particles, or the particle sizes of the daughter particles and the base particles, an electron microscope can be used. In step (d ·) where the composite fine particles are dispersed in the oil, the composite fine particles -30 (please read the note on the back ^^^ before filling this page) Order KS____ -4 34 0 2 7 ^ 1 Α7 _ Β7 V. Description of the invention (28) Printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives (please read the precautions on the back before filling this page) The method of dispersing the particles in oil is not particularly limited. For example, after mixing an oil agent with a liquid mixture dispersion liquid containing composite microparticles subjected to water-repellent treatment, when the solvent of the liquid mixture dispersion liquid is a volatile agent, such as ethanol, etc. . In addition, after the above-mentioned mixing step, in the case where the solvent is non-volatile, a conventional solvent replacement method may be performed. Incidentally, examples of the oil agent include various hydrocarbons, higher carbon number lipoic acid 'fat and oil' esters, higher alcohols, and waxes such as squalane, paraffin, 'liquid paraffin', VaselineTM 'microcrystalline wax Floor wax, pure floor wax 'myristic acid, palmitic acid' stearic acid, oleic acid, isostearic acid, cetyl alcohol, cetyl alcohol, oleyl alcohol, cetyl 2-ethylhexanoate, brown 2-ethylhexyl gallate, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate Sg, glyceryl di-2-ethylhexanoate oleate 2- Octyl twelve tiger vinegar, isopropyl myristate, tri-isostearate, triglyceride fatty acid esters, olive oil, avocado oil, camellia oil, simon oil, beeswax, whale Wax, palm tincture, myristyl myristate, mink oil, and lanolin; silicone oils, such as volatile silicone oils and non-volatile silicone oils. In addition, in the case where the composite fine particles surface-treated with the volatile substance are dispersed in the oil agent, it is preferable to remove the water of the composite fine particles and the liquid mixture dispersion to prevent the formation of a water / oil emulsion. Suitable dehydration methods are refluxing and straight distillation using solvents such as hexane and cyclohexane. The concentration of the composite fine particles in the oil agent is not particularly limited, and the concentration of the composite fine particles dispersible in the oil agent is highly related to the particle diameter of the composite fine particles and the type of the water-repellent agent and the oil agent. When the concentration of the composite fine particles is too high, the composite fine particles may aggregate in the oil agent, thereby significantly damaging the composite fines .....-31 ~ This paper is applicable to China National Standards (CNS) ) A4 specification (2 丨 ο X 297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 43702713 A7 B7 V. Description of the invention (29) Dispersion and optical properties of the particles, which in turn impair the properties of the oil agent. Therefore, the concentration of the composite fine particles in the oil must be appropriately adjusted so as not to cause adverse effects. 3. The various starting materials used in the manufacturing method of the present invention will be explained in detail in the following. 6 (1) The sub-particles constituting the composite fine particles of the present invention maintain good light transmittance in the visible light region and have good light transmittance in the ultraviolet light region. Shielding ability. Therefore, the sub-particles must not absorb light in the visible light region and have a particle size small enough to not scatter visible light. In order to meet the requirements of not absorbing visible light but absorbing ultraviolet light, it is preferred that the material constituting the particles should have an inter-band Chen energy exciton absorption wavelength corresponding to the wavelength in the ultraviolet region. In particular, semiconductor compounds having a band gap energy of 3.0 to 40 eV are preferred, including, for example, Ti〇2, Zn〇, Ce02 'SiC, Sn02, W03, SrTi〇3, BaTi〇3 ,with

CaTi03 'exhibits the above-mentioned properties characteristically. Among them, Ti〇2, Z η Ο ′ and Ce 0 are conventionally used as ultraviolet shielding agents, and these compounds are particularly preferable examples, and can be used alone or in combination. In particular, ZnO and CeO 2 can be effectively used in order to shield ultraviolet light in the ultraviolet light region A (320 to 400 nm). In addition, in order to shield the ultraviolet light in the ultraviolet light region B (280 to 320 nm), Ti02 can be effectively used. Incidentally, in order to shield the ultraviolet light in the ultraviolet region B and the ultraviolet region A at the same time, it is preferable to use a combination containing Ti02 and one or more compounds selected from ZnO, Ce02, BaTi03, CaTi03, SrTi03, and SiC. use. In addition, in the case of using Ti〇2, you can add impurities as impurities by adding -32- This paper is used in accordance with Chinese National Standard (CNS) A4 specifications (210 parent 297) (Please read the back Please fill in this page again for the item)-Order • JI. Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 1340272 A7 B7 V. Description of the invention (30) The supplement form has elements with a price of 5 or higher, such as W , P, Ta, Nb, Sb, or Mo, or an element having a valence of 3 or lower, such as Zn, Al, Mg, and Ca, so that the shielding region is extended to the ultraviolet region a. The shape of the daughter particles is not particularly limited, and may be spherical, plate-like, or needle-like. The particle diameter of the daughter particles is preferably substantially the same as the particle diameter of the original particles of the matrix particles from the viewpoint of providing good dispersion of the particles in the matrix particles. Furthermore, the light scattering ability in the ultraviolet region is strongly exhibited by Mie scattering, and the scattering can be clearly observed when the particle diameter is about half of the wavelength of the ultraviolet light, that is, not more than 0.2 micrometers. phenomenon. Therefore, in order to satisfy both the good light transmittance in the visible light region and the good shielding ability in the ultraviolet light region, the sub-particles must have a size of not more than 0.2 μm, and a size of not more than 0.1 μm, especially An average particle size of 0.001 to 0.1 micrometers, and more particularly no greater than 0.05 micrometers. In the present invention, the term "sub-particles" refers to primary particles and / or aggregates of primary particles which are individually dispersed in the matrix particles and supported by them. Therefore, the average particle diameter of the sub-particles can also mean the average particle diameter of the aggregate. In the present invention, a particle starting material is prepared using a particle-containing sol and a particle powder. Since the sub-particles are preferably present in the interior of the composite fine particles in a dispersed state, the sub-particles need higher dispersibility and stability in the sol. In order to achieve the state of the sub-particles in the sol, the surface of the sub-particles may be coated with other substances, or the sub-particles may be mixed with a sol stabilizer. For example, in the case where T i 02 ultrafine particles are used as the sub-particles, a compound such as SiO2 and Ai203 may be coated on the surface of the ultrafine particles to improve the dispersibility. In addition, ultrafine particles and alkaline stabilizers such as Ν η 3 can be blended to secure _____ -33- (Please read the precautions on the back of Jing before filling this page)

434027α Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (31) '' ~~ 'The state of the fixed Ti〇2 sol. Further, in the case where the fine particle powder is surface-treated to achieve good dispersion, the treated fine particle may be used as a starting material of the fine particles. The sol used in the present invention refers to a fluid containing particles that are generally not observed by ordinary electron microscope but have a particle size larger than that of an atom or a low molecular compound (see Iwanami Dictionary of Physics and Chemistry, Third Edition, published by Iwanami Publishers). Examples of the sol include a silica hydrosol and a Ti02 ultrafine particle pre-suspension. (2) Matrix particles The matrix particles constituting the composite fine particles must have good light transmittance in the visible light region as the child particles, so that the composite fine particle suspension has good light transmittance. In particular, the matrix particles are suitably composed of a substance that does not absorb visible light, and it is preferable that the original particles of the matrix particles do not have a particle size exceeding 0.3 m. For example, an ultrafine particle aggregate is preferable, and each ultrafine particle has an average particle diameter of 0 01 as meters. As for the substance constituting the matrix particles, a substance having a high light transmittance, for example, a metal oxide, a fluorine compound, and a mixture thereof can be used. For example, metal oxides, fluorine compounds, and mixtures thereof can be used. Since the person constituting the matrix particles is usually an aggregate of sub-particles, the microparticles (ie, the original particles) constituting the aggregate must have an average particle size of not more than 0.3 micrometers, in particular, not more than 0_001 to 0.3 micrometers in order to satisfy the above The requirement β for the matrix particles is preferably particles having an average particle size of not more than 0.15 micrometers, more preferably not more than 0, 1 micrometer, and particularly preferably not more than 0.05 micrometers. The sol containing the particles constituting the matrix particles and the powder of the matrix particles are the starting materials for the matrix particles. Based on the same reason for the above-mentioned pair particles, the particles constituting the matrix particles can be used. -34- The size of this paper applies to China National Standards (CNS) A4 specification (210X297 mm) (Please read the note on the back before filling in this page)

434027 ^ A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -35- V. Description of the Invention (32 Surfaces are coated with other substances, or fine particles are mixed with sol stabilizers. Here, the coating substances used Or stabilizers can be similar to those used for daughter particles. Many metal oxides can be obtained in the form of chemically stable solids, so that the metal oxide can be suitably used as a substance constituting the base particle. The metal oxide contained in the matrix particles is oxidized. Examples of the substance include Ti02, CuO,

ZnO, MgO, Ce02, Sn02, Si02, Fe203, Al203,

Ni02 'and Mn02. Preferred are Si02 and Al203 'because they have a suitable refractive index and good light transmittance as explained above. In addition, from the viewpoint of using a large band gap energy, preferred are Sn02, In203, SiO2, ZnO, and A1203 fine particles. Many fluorine compounds are chemically stable and have a low refractive index, making these compounds highly useful for controlling the refractive index of the resulting composite fine particles. Fluorine compounds include all that are solid or liquid at room temperature. Examples of such solid inorganic fluorine compounds include MgF2, CaF2, A1F], LiF, NiFz, and BaF2. Examples of the solid organic fluorine compound include a fluororesin, such as polytetrafluoroethylene (hereinafter abbreviated as " PTFE "), a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-ethene copolymer, a polyfluorinated vinylidene , And polyvinyl fluoride. Among them, 'MgF2, polytetrafluoroacetamidine, and mixtures thereof allow the obtained composite particles to have an appropriate refractive index and good light transmittance and are suitable for use as a fluorine compound. 0 The average particle diameter of a fluorine compound that is solid at room temperature It is preferably not more than 0.3 μm, and more preferably not more than 0.2 μm. The reason is that when the average particle diameter exceeds 0.3 microns, the aggregation force between the particles will be weakened, so that the recombination _ scale is applicable to China {Please read the precautions on the back before filling this page} Order. ^ 4 34027 ^ A7 A7 _____B7 V. Description of the invention (33) The intensity of micro particles. Examples of fluorine compounds which are liquid at room temperature include perfluoropolyethers (hereinafter referred to as " PFPE "). An example of PFPE is perfluoropolymethyl isopropyl ether (e.g. " FOMBLIN HC " made by Nikko Chemicals K.K.). PFPE can be used not only to reduce the refractive index of composite olive particles, but also to provide moisture that promotes smooth skin texture, making PFPE highly suitable for use as a microparticle in cosmetics. When a liquid fluorine compound is used, the solvent used may be appropriately selected so as not to cause phase separation of the daughter particle starter and the matrix particle starter in the solvent. However, when the solvent is water, it is preferable to use an emulsion emulsified with various surfactants to contain a liquid fluorine compound at room temperature. For example, a perfluoropolyether emulsion (oil-in-water type) can be used. The diameter of the emulsion preferably has a size not exceeding 0.1 times the droplet size. When the diameter of the emulsion exceeds the diameter of the droplet by approximately 0.1 times, the emulsion becomes larger than the produced particles, thereby making the production of the particles difficult. In the present invention, the liquid fluorine compound may also be used as a substance having a low refractive index based on the above explanation. In this case, the liquid fluorine compound may be used together with a metal oxide and / or a solid fluorine compound to increase the refractive index. Degrees of freedom in control. Printed by the Central Bureau of Standards, Ministry of Economic Affairs and Consumer Cooperatives (please read the note f on the back before filling out this page) About the proper combination of the daughter particles and matrix particles of the present invention from the viewpoint of providing the stability and stability of the obtained ultraviolet shielding agent In view of this, the following combinations are preferred: the daughter particle system is selected from τ i 〇2, Z ηΟ, and mixtures thereof; the matrix particle system is selected from SiO2, Al203, and mixtures thereof, and the combination of SiO2 and perfluoropolyether Mixtures; coatings of inorganic substances are selected from Si Ο 2, A12 Ο 3, and mixtures thereof; and water-repellent agents are one or more compounds selected from: methyl hydrogen _____ ___- 36 -_____ This paper size applies China National Standard (CNS) A4 Specification (210X297 mm) " Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 434027;. A? B7 'Sa ------ -------- 5 Explanation of the invention (34) Polysiloxane, oxazoline-modified polysiloxane, amine-modified polysiloxane, stearic acid, monoalkyl phosphate, and dialkyl phosphate. In the present invention, substances other than the above-mentioned metal oxides and fluorine compounds may be added to the pre-particles and the matrix particles. For example, when the composite fine particles are made of a starting material sol stabilizer or a sol particle coating agent, they can be added to the matrix particles as long as the optical properties of the composite fine particles are not impaired. 4. The following is a more detailed explanation of the preparation of the starting material liquid mixture by using the above-mentioned starting material and the method for preparing composite microparticles. When preparing the liquid mixture of the starting material, it is important that the starting material and the matrix containing the daughter particles are The liquid mixture of the granulated starting material is uniformly dispersed and blended 'so that the daughter particles are easily dispersed within the matrix particles. By fully blending the starting material of the daughter particles and the starting material of the matrix particles to achieve a high degree of dispersion of the daughter particles in the matrix, the seeds can be present on the surface and / or inside the matrix particles. . At this time, the microparticles containing the particle particle starting material and the matrix particle starting material can be concentrated together by the electrostatic force to generate aggregated composite particles. For example, 'Ti02 ultrafine particle powder is used as the seed particle starting material and SiO2 sol (hydrosol, "ST_C", manufactured by Nissan Chemical Industries, Ltd .; pH 8.5 to 9.0) is divided into matrix particle starting materials In the case where the above starting materials are processed in a mill or a high-pressure dispersing device under appropriate conditions and the pH of the resulting liquid mixture is adjusted to 7, the pH having an isoelectric point of about 5 to 7 is 1 ^ 02 is a negatively charged person according to its isoelectric point, and Si0 2 forms a positively charged electric double layer on the surface, so that under the electrostatic force generated between the Ti02 seeds and the Si0 2 matrix particles, the daughter particles and the matrix The particles aggregate to form a complex --------__ _ —, —— This paper uses the Zhongguanjia Standard (CNS) (21GX297 mm) {Please read the precautions on the back before filling this page) II- * I-" 1 ^ 1 ^^ 1 f, ----------,-ιτ--i t---V 11 -1-J— -1'mij— ^ 4 34 0 2 7 '? A7 B7 V. Description of the invention (35) Please read the note ^^ on the back before filling out this page} Composite particles. In addition, ZnO ultrafine particle powder was used as the seed particle starting material and SiO 2 sol (hydrosol; "ST-C", Nissan Chemical Industries, Ltd .; pH 8.5 to 9.0) was used as the matrix particle starting material, and In the other case where the starting material is placed in a mill or a high-pressure dispersion device under appropriate conditions and the pH of the resulting liquid mixture is 値, ZnO having an isoelectric point of about pH 9.3 is charged according to its isoelectric point. Electricity, and Si02 forms a positively charged electric double layer on its surface. Observation with a transmission electron microscope led to the discovery of composite microparticles formed by the aggregation of ZnO sub-particles and Si02 matrix particles. Incidentally, when the composite fine particles are formed, a slippable layer in the SiO2 electric double layer may be cracked to thereby charge the surface negatively, and the negatively charged surface contacts the ZnO sub-particles. The SiO2 sol used in the above embodiments has the following functions: (1) It is used as a medium to effectively disperse the sub-particles that usually exist in an aggregated state to a size approximately equal to the particle size of the original particles and / or as a medium to powder the sub-particles Reduced to a size not greater than the particle size of the original particles; (2) they form a basic structure in which, while disintegrating and / or pulverizing, the sub-particles are adhered to the matrix particles; and the employees of the Central Standards Bureau of the Ministry of Economic Affairs consume Printed by the cooperative (3) It acts as a dispersant to inhibit the aggregation of the composite fine particles through the electrostatic repulsion of SiO 2 on the surface of the composite fine particles after the formation of the composite fine particles. The particle size of the S i 0 2 sol can be appropriately selected according to the functions (丨) to (3). For example, in a case where the function (3) is considered to be very important, the particle size of the si 2 sol is preferably about the same as or, and the particle size of the daughter particles. In particular, the particle size of the SiO2 sol is suitably not larger than 0 m, more preferably not larger than 0.05 m, and more preferably not larger than 0.02 m. Incidentally, Si02 is soluble -38-

ι 434 02 7 A7 ____ B7 V. Description of the invention (36) The solvents used in the gum include hydrosol (water) and organosol, which can be appropriately selected in consideration of the type of the sub-particles and the stability of the dispersion. According to the above method, a composite fine particle containing sub-particles and matrix particle aggregates is formed, and in order to stably maintain the aggregated state of the composite micro-particles and substantially not contain the catalytic activity caused by the sub-particles, an inorganic substance having substantially no catalytic activity is used. The surface of the composite fine particles is coated. As explained above, the coating layer may be a thin layer or a thin particulate layer. Regarding the thickness of the coating layer, if the active parts on the surface of the composite fine particles are substantially coated so that the surface effect does not affect the surrounding medium of the composite fine particles, then the thickness is sufficient. The appropriate solvent for the starting material of the seed particles and the starting material of the matrix particles mentioned above is any aqueous or organic solvent, which will not inhibit the production of composite particles of the sub-particles / matrix particles in the starting liquid mixture. can. Examples of the organic solvent include alcohols such as methanol and ethanol, and polar solvents such as N, N-dimethylformamide, dimethylmethylene, hexamethylphosphonium, and ethyl acetate. As long as the formation of the ultraviolet shielding composite fine particles is not adversely affected, the solvent of the metal oxide sol solution mentioned above or a different one can be used. The concentration of the matrix particle starter in the starter liquid mixture containing the daughter particle starter and the matrix particle starter is preferably 10-5 to 10 moles / liter, and more preferably 10- Within the range of 4 to 1 mole / liter. In particular, the concentration of the starting material of the matrix particles is preferably not less than 10-5 mol / liter from the viewpoint of maintaining good dispersion of the daughter particles in the composite fine particles, and from the viewpoint of maintaining the From the viewpoint of good dispersion of the starting material liquid mixture __- 39- A4 size (2 丨 〇χ 297 mm) This paper size is applicable to the Chinese National Standard (CNS) Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs f 4340 27 A7 —____________ B7 V. Explanation of the invention (37 ^-Come 'the concentration is preferably not more than 10 moles / liter. When using a fluorine compound as the starting material of the matrix particles, the fluorine compound starts with the daughter particles. The concentration of the starting material liquid mixture of the starting material and the matrix particle starting material is preferably in the range of 10-5 to 10 mol / liter, and more preferably 10-4 to 1 mol / liter. In particular, from the viewpoint of generating an effective amount of fine particles of the fluorine compound, the concentration of the fluorine compound is preferably not less than 10_5 mol / liter, and from the viewpoint of the solubility of the fluorine compound, the concentration is preferably not higher than 10 Moore / liter β The concentration of the starting material liquid mixture of the daughter starter and the matrix particle starter is preferably in the range of 10-5 to 10 mol / liter, and more preferably in the range of 10-4 to 1 mol / liter. In other words, from the viewpoint of providing the minimum amount required for achieving the optical properties of the composite particles in the composite particles, the concentration of the daughter particles is preferably not less than 10_5 mol / liter, and from the point that the daughter particle starting material is sufficient From the viewpoint of dispersedly dispersing in a liquid mixture to produce composite fine particles having a uniform composition, the concentration is preferably not higher than 10 mol / l. The content of the sub-particles dispersed in and supported by the matrix particles is not particularly limited. As long as the sub-particles can be well dispersed in the matrix particles without causing the sub-particles to aggregate excessively in the matrix particles. The amount of the sub-particles contained in the matrix particles is usually from 0.1 to 85% by volume, preferably 0.1 to 50% by volume, more preferably 0.1 to 30% by volume, particularly preferably 0.5 to 20% by volume. In the case where the composite fine particles are coated with an inorganic substance, the amount of the sub-particles should be reduced when calculating Remove the coating amount of inorganic substances. In the case of metal oxides and fluorine compounds, the minimum content of fluorine compounds is not less than the compound __- 40 -___ This paper size applies to Chinese national standards (CMS > A4 specifications (210X297 mm) (please first (Read the back note and fill out this page)

; 434027

V. Description of the Invention (Qiu) The consumption cooperation of staff of the Central Standards Bureau of the Ministry of Economic Affairs Du Yinpu 1% by weight based on micro particles. The amount of daughter particles is calculated from the density (in the case of particles, the particle density) of the substance constituting the composite microparticles and the composition ratio of the starting liquid-liquid mixture. The concentration of the inorganic substance starting material in the starting material liquid mixture containing the composite fine particles containing the sub-particles and the matrix particles is preferably 10.5 to 1 when the composite fine particle concentration is 10.5 moles / liter. Moores / liter, more preferably within the range of 104 to 1 mole / liter. In particular, from the viewpoint of coating the surface of the composite fine particles to a degree sufficient to provide a good coating effect, the concentration of the inorganic substance is preferably not less than 10-5 mol / liter. From the viewpoint of the solubility of the starting material of the inorganic substance, it is preferable that the concentration is not higher than 10 mol / liter, which is a composite fine particle coated with the inorganic substance and containing the sub-particles and matrix particles dispersed in the liquid mixture. The average particle size is preferably from 0.02 to 0.05 micron, the specific one is not larger than 0.4 micron, especially not larger than 0.3 micron, and not larger than 0.2 micron, and the particle size distribution must be kept as high as possible. Possibly narrow. When the average particle diameter exceeds 0.5 micrometers, visible light may be scattered due to a large particle diameter, which may reduce transmittance and ultraviolet shielding ability. Conversely, when the average particle diameter is not greater than 0-5 micrometers, even if the difference between the refractive index of the composite fine particles and the refractive index of the dispersion medium is large, the light transmittance of the composite fine particles can be maintained at a high level and Does not scatter visible light. The average particle size mentioned herein is obtained by dispersing the cake containing the coated composite particles in water and using a particle size analyzer (such as a laser doppler-type particle size analyzer manufactured by OTSUKA ELECTRONICS CO., LTD.). "DLS-700 ") obtained by measuring its particle size. -41 Private paper size applies Chinese national standard (CNS > A4 size (210x297 mm), s >-1. y clothes I __Order ---- --1--IT ----------- (Please read the notes on the back before filling out this page] ^ 434027 ^ A7 B7 V. Description of the invention (39) — ^ 'UV shielding property of the present invention The composite fine particles can be produced by the manufacturing method explained above, and the structure of the ultraviolet shielding composite fine particles is such that the matrix particles contain aggregates of primary particles, which are formed while the original particles maintain their shape. Each primary particle All of the sub-particles are dispersed on the surface and inside of the matrix particles, and the composite particles containing the pre-particles and the matrix particles are preferably coated with an inorganic substance having substantially no catalytic activity. When daughter particles are not well dispersed, Shows good optical properties "When the daughter particles are present on the surface of the matrix particles, the ultraviolet light colliding with the daughter particles will be partially absorbed and the remaining ultraviolet light will be scattered by the composite particles. Ultraviolet light that the sub-particles collide with and continues to enter the matrix particles is absorbed and scattered by the sub-particles contained inside the matrix particles, so that the ultraviolet light is effectively shielded. In addition, since the coating contains inorganic substances, the sub-particles and matrix particles have The catalytic activity is substantially suppressed, so that the composite fine particles can stably exist in the medium without causing deterioration of the medium. The shape and size of the final product of the composite fine particles of the present invention obtained after the above-mentioned drying and pulverizing step (d) are not particular Restrictions, and various shapes and sizes can be used according to different situations. For example, when used as granulated powder, it is best to use a sphere with a particle size of submicron to several micrometers from the viewpoint of good touch and easy handling. Particle powder, while providing strong adhesion to the skin, excellent spreadability on the skin, and easy handling From the viewpoints of properties, it is best to use plate-like particle powders having the above-mentioned particle size. 5. Optical properties of composite fine particles The optical properties of the ultraviolet shielding composite fine particles of the present invention can be applied by using this paper standard. China National Standard (CNS) A4 specification (210X297 mm) {Please read the precautions on the back before filling this page} -------------- yiyi ------- order --- --- ζ ----- Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs Printed by the Consumer Procurement Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs 4 34 027 J at B7 V. Description of the invention (40) UV-Visible The spectrophotometer measures its light transmittance for quantitative evaluation. The ultraviolet shielding ability of the ultraviolet shielding composite fine particles of the present invention is preferably at a wavelength of 800 nm, j, at 80 ° /. The light transmittance is determined by a light transmittance of not less than 20% at a wavelength of 400 nm and a light transmittance of not more than 5% at at least one wavelength in the range of 380 to 300 nm. The measurement of the light transmittance is obtained by suspending the composite fine particles in a medium having substantially the same refractive index level as the composite fine particles, and measuring it with an ultraviolet-visible light spectrophotometer using a spectrometer with an optical path length of 1 mm. . With the above-mentioned optical properties, it is possible to satisfactorily achieve a high light transmittance in the visible light region and a high shielding ability in the ultraviolet light region. Here, "the light transmittance is not greater than 5% at at least one wavelength within the range of 380 nanometers to 300 nanometers, and the term means at least one wavelength in the range of 380 nanometers to 300 nanometers, Its light transmittance is not more than 5%, including the case where the light transmittance exceeds 5% in a certain other range in the wavelength of 380 nm to 300 nm. In addition, "it has substantially the same refractive index as the composite fine particles The term "horizontal medium" means that the refractive index difference between the composite fine particle sample and the medium is within ± 0.1, and preferably within ± 0.05. In this case, the concentration of the composite fine particles dispersed in the medium is, for example, not less than 0.1% by weight. The above-mentioned ultraviolet shielding ability can be evaluated using ultraviolet-visible light spectroscopy described below. The composite fine particles of the present invention are suspended in a medium having substantially the same refractive index level as the composite fine particles to prepare a composite fine particle suspension having a given concentration. In order to prepare a uniform suspension, for example, an ultrasonic disperser or the like can be used to stir and sufficiently disperse the composite fine particles. Fill with the above suspension _ -43- (Please read the note on the back before filling this page)

D- *-i A7 B7 434027 V. Description of the invention (41 light analysis box with 1 mm optical path length. The light analysis box used in the present invention does not absorb light nor cause light scattering in the ultraviolet and visible light regions. This may be used. For example, a silicon oxide light box. The light transmission through the light box is measured with a UV-visible light spectrophotometer. In this method, another medium filled with a suspension containing no composite particles is used. An analysis box is used as a control to remove the background. In addition, the composite microparticles of the present invention are substantially not catalytically active, and this can be confirmed by the following method. Specifically, the composite microparticles are dispersed in white petrolatum in an amount of 1 weight. / 〇, and an ultraviolet light source (" ENB-260C / J ", manufactured by SPECTRONICS CORPORATION) was subjected to a 60-minute irradiation treatment with ultraviolet light having a center wavelength of 3 12 nm to measure the Whether white petrolatum will be discolored by the above-mentioned irradiation treatment. In the case that white petrolatum is affected by the catalytic activity, a white to brown color change occurs, so it is easy to use the above method In summary, "in the present invention," composite fine particles having substantially no catalytic activity "refers to composite fine particles whose catalytic activity is suppressed to show practically no catalytic activity for practical purposes For example, when the above method was used to test the catalytic activity, no color change of vaseline was found. 6. Cosmetics The cosmetic of the present invention can be used in addition to the above-mentioned ultraviolet-shielding composite microparticles, and various adjuvants commonly used as adjuvants and as The medium is prepared by dispersing an oil-dispersing agent for dispersing ultraviolet-shielding composite fine particles. Examples of cosmetic adjuvants are listed below. (1) Inorganic powders such as talc, kaolin, sericite, muscovite, phlogopite 44-wood paper Standards apply Chinese National Standard (CMS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) Printed by the Central Bureau of Standardization of the Ministry of Industry and Commerce—Printed by Industrial and Consumer Cooperatives 434027 A7 B7 Central Printing by Standard Bureau Shellfish Consumer Cooperatives V. Description of the invention (42) Mica, scale mica, biotite, synthetic phlogopite, warp stone, carbonic acid Calcium carbonate, diatomite, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silicon oxide, hydroxyapatite, zeolite, boron nitride And ceramic powder. (2) Organic powder, for example, nylon powder, polyethylene powder, polystyrene powder, benzoguanamine resin powder, polytetrafluoroethylene powder, stilbene benzene polymer powder, epoxy resin powder. , Acrylic resin powder, and microcrystalline cellulose. (3) Inorganic white pigments, such as titanium oxide and zinc oxide; inorganic red pigments, such as iron oxide (red oxide) and iron titanate; inorganic brown pigments, such as r- Iron oxides; inorganic yellow pigments such as yellow iron oxide and yellow vermiculite; inorganic melanins such as black iron oxide and black-breaking; inorganic purple pigments such as face purple and amethyst; inorganic green pigments such as chromium oxide, chromium hydroxide, and titanium Cobalt acid; inorganic blue pigments, such as ultramarine and Prussian blue, pearly pigments, such as titanium oxide-coated mica ', titanium oxide-coated bismuth, oxygen bismuth, talc coated with titanium oxide, fish scales, colored Titanium oxide coated mica; and metal powder Pigments such as aluminum powder and copper powder. (4) Organic pigments, including Pigment Red 57-1, Pigment Red 57, Pigment Red 53 (Ba), Pigment Red 49 (Na), Pigment Red 63 (Ca), Violet Red 1, Pigment Red 4, Pigment Red 48 , Pigment orange 5, pigment orange 13, pigment yellow 12, pigment yellow 1, and pigment blue 15; organic pigments include the following zirconium lakes, barium lakes, and aluminum lakes; acid red 5 1, acid red 9 2, Acid Red 5 2, Acid Red 33, Acid Red 87, Acid Violet 9, Solvent Orange 7, Acid Orange 7, Acid Yellow 23, Acid Yellow 5, Acid Yellow 7 3, Acid Yellow 3, Food Green 3, and Food Blue 1 -45- This paper size is applicable to China National Standard (CNS) A4 (210X297mm) ttft ttaf it— (Please read the precautions on the back before filling this page) Order by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperatives Packing " 4 34 0 2 7 " ^ Α7 ------------ B7 V. Description of the invention (43) (5) Natural pigments, such as chlorophyll and 々 · carotene. (6) A variety of hydrocarbons, high-carbon fatty acids, fats and oils, esters, high-grade alcohols, and waxes, such as squalane, paraffin, liquid paraffin, petroleum jelly 71 ^, microcrystalline wax, ceresin, pure ceresin, nutmeg Acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, cetyl alcohol, oleyl alcohol, 2-ethylhexanoic acid cetyl alcohol, 2-ethylhexanoic acid palmitic acid, Myristic acid 2-octyldodecane ester, neopentyl glycol di · 2 · ethylhexanoic acid vinegar 'glycerol tri-2. Ethylhexanoate, oleic acid 2_octyldodecane riding' beans Isopropyl acetate, triglyceride, triglyceride, triglyceride, coconut oil, olive oil, argan oil, camellia oil, simond oil, beeswax, cetyl 'palm wax, nutmeg Myristyl acid, mink oil, and lanolin; silicone oils such as volatile silicone oil and non-volatile silicone oil. (7) UV protective agents such as UV absorbers can be added if necessary. Examples of ultraviolet light absorbers include the following: (1) Benzoic acid derivatives: p-aminobenzoic acid (PABA), glycerol-p-aminobenzoate, p-N, N · dipropoxy Ethyl aminobenzoate, p-ν, ν-diethoxyaminobenzoic acid ethyl ester, p-N, N-diamidinoethyl benzoate, p-N, N-dimethylaminobenzoic acid Butyl ester, p-N, N-dimethylaminobenzoic acid amyl ester, and p-N, N-dimethylaminobenzoic acid octyl ester. (2) O-amino-Ethanoic acid derivative: N-ethylamido-o-amino anthracenecarboxylic acid isocaprate. (3) Salicylic acid derivatives: amyl salicylate, caprylate salicylate, homococoyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropylamylphenyl salicate. -46- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page) ——Order ----- A ------

Jt I 1 »Imprint of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs? 4 3 4 Ο 2 7Α7 _Β7_ V. Description of the invention (44) (4) Cinnamic acid derivatives: Octyl cinnamate, ethyl 4-isopropylcinnamate Esters, methyl 2,5-diisopropylcinnamate, ethyl 2,4 · diisopropylcinnamate, methyl 2,4 · diisopropylcinnamate, propyl p-methoxycinnamate , Isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), p-methyl 2-ethoxyethyl oxycinnamate, cyclohexyl p-methoxycinnamate, ethyl α-cyano-lu-phenylcinnamate, cyano-/?-Phenylcinnamate 2-ethyl Hexyl ester, and glycerol mono-2-ethylhexyl-di-p-methoxycinnamate. (5) Benzophenone derivatives: 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4, Dimethoxybenzophenone, 2,2 ', 4,4 * -tetrahydroxymonobenzophenone' 2-transyl-4-methoxydibenzamine, 2-transyl-4-methoxy -4'-Methyldibenzylmethylammonium, 2 · Hydroxy-4-methoxybenzophenone · 5 · Acid salt, 4-Phenylbenzophenone, 4 * -Phenylbenzophenone Ketone-2 · carboxylic acid-2-ethylhexyl ester, 2-hydroxy · 4 · n-octyloxybenzophenone, and 4-hydroxy-3 · carboxybenzophenone. (6) Other UV absorbers: 3- (4, methylmethylene) d, l-camphor, 3-methylene d, l-camphor, uric acid, ethyl urate, 2 · phenyl 5 -Fluorenylbenzimidazole, 2,2, -hydroxy 5-methylphenylbenzotriazole, 2- (2, -hydroxy-5'-third octylbenzyl) benzotriol'diphenyl Dibenzarsine, dicumin, methylbenzene, 4 -methoxy 4 '· third butyl dibenzylidenemethane' 5- (3,3, -dimethyl-2-n-n-pentyl) .3-Pentanone, and 1- (3,4-dimethoxyphenyl) -4,4, -dimethyl --47- This paper-size standard car (CNS) from Waki (21 () > < 297 mm) (Please read the note on the back ^! ^ before filling this page)

1. Printed by the Shelley Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs, 1T. A7 _B7_ V. Description of the invention (45) -1,3-pentanedione. (8) In addition, a surfactant may be used as appropriate. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, alkyl polyoxyethylene hardened castor oil sulfate , Alkyl polyoxyethylene sulfate, alkyl phosphate, alkyl polyoxyethylene phosphate, alkali metal fatty acid salts, sorbitan fatty acid esters, glycerin fatty acid esters, and polysiloxane surfactants , Such as poly bond modification poly Zhen oxygen. (9) Furthermore, a water-soluble polyhydric alcohol may be used as appropriate. Examples of water-soluble polyhydric alcohols are water-soluble polyhydric alcohols having two or more hydroxyl groups in one portion, including diethanol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Monoglycerol 'glycerol, polyglycerols such as diglycerol, triglycerol, and tetraglycerol, glucose, maltose, maltitol, sucrose, fructose, xylitol' sorbitol, maltotriose, threitol, red Mositol, and sugar alcohols derived from degraded starch. (10) In addition, other cosmetic adjuvants may be added as necessary, including amino acids such as lysine and spermine; organic acids such as lactic acid, citric acid, succinic acid, and glycolic acid and organic salts thereof. Resins such as alkyd resins and urea resins; plasticizers such as camphor and tributyl citrate; antioxidants such as alpha-tocopherol; preservatives such as butyl para-hydroxybenzoate and para-hydroxybenzoic acid Flat esters; plant extracts such as cornflower, Shucai, and Xiaoliansu (Hypericuor; biologically active substances such as retinol and allantoin; binders such as xanthan gum and carrageenan; and spices, etc. Touch and enjoy the continuity of the UV shielding effect, can be standard in the country of this paper. Α4 size (210 × 297 mm) '(Please read the note on the back before filling this page)

'• IT 4 3 4 0 2 " 7 A7 B7 V. Description of the invention (milk) i Invented one or more polysiloxane oil and ether modified polysiloxane in cosmetic materials. Juzhen oxygen is not limited as long as it is usually incorporated in cosmetics. Examples include octamethylpolysiloxane, tetramethylmethylpolyoxane, methylpolyoxane, polymer methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane Oxyalkane, decamethylcyclopentasiloxane, trimethylsilicyloxysilicic acid, and organic-based polyoxygenated fired units having repeating units represented by the following general formula (1) or general formula (_2): R 1 ~ (Si—0) e — R2 R9-(S i (1) (2) (Please read the notes on the back before filling out this page) Order-Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Wherein R1 and R2 may be the same or different, and respectively represent alkyl groups having 1 to 4 carbon atoms; R3 represents linear, branched or cyclic alkyl groups, linear, branched or cyclic alkenyl groups each having 1 to 40 carbon atoms. , Or linear, branched or cyclic fluoroalkyl; " e " represents a number not less than 2, and "f" represents a number less than 3, where the sum of "e " and" f " is 5 to 6,000 The content of the aforementioned polysiloxane oil is 2 to 80% by weight of the cosmetic composition, preferably 5 to 50% by weight, and more preferably 8 to 40% by weight 0/0. Ether-modified polysiloxane It is not particularly limited as long as it is among them. At least a part of the siloxane compound may be substituted by one or more groups having an ether bond. Examples are listed below, which can be used alone or in a combination of two or more -_ _ -49 -… This paper size applies to Chinese National Standard (CNS) A4 specification (210X297mm) Yin Ju, Staff Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs-4 34 0 27- A7 --- 'B7 V. Description of Invention (47); --- Combined use. The special particles of ether-modified polysiloxane include the following compounds [^ to ^]: [1] Ether-modified polysiloxane with the following general formula (3): strict ch3 CHs RM- ( S i -〇) m (si -〇〇n-si-R '* • iH3 ^ iH / (3)', where at least one of R11, R12, and R13 has the formula R14 (OC3H6) b (〇C2H4 ) a〇 (CH2) p-, in which r14 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; ', a »and " & " " a " and " b "are average 値; and p is a number from Tables 1 to 5; and R11, Rl2, and r13 represent methyl groups except those defined above; " m " Tables 1 to 200 "'&';" Tables 0 to 50, "m " and " n, is the average 値.-Among the ether-modified polysiloxanes defined in Π] above, the molecular weight is preferably 2,000 to 50,000, and the amount of the substituents R11 to R13 is 5 to 40%. . By. In addition, in the general formula (3), the "ether modified polysiloxane" as defined in "preferred [1]" is "m " is 5 to 80 ', and" η "is 0 to, 2' is 9 to 10, "b" is equal to 0 ', "p" is equal to 3, and R14 represents a hydrogen atom, or "m " in the ether modified polysiloxane as defined in the above [/] is 90 to 110, " n, Is 0, " a " is 1 i to 13, "b" is equal to 0, " p "is equal to 3, and R14 represents a hydrogen atom. The ether modified polysiloxane having the general formula (3) shown above Specific examples include commercially available products " S Η-3 775 series "'Made by Toray-Dow Corning Corporation -50- This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) (Please read the back first Please note this page before filling in this page) Form ------- Order-_r I n 11 ^ k II I— ^^ 1 11—--If υ \ .ί III— 1 I 1 ^ 1 ^ 434027 ^ A7 B7. 5. Description of the invention (48). [2] Polyether-alkyl-modified polysiloxane having the following formula (4):

R 0 3 i 3 H i H o-slrc o 3 1 o H .1 H c-sIc

o 3-- THX 2 tha i 2c-sIR c1sIQ—

3 H o- 3 | ^ Hjn c—s——c

Printed by the Central Laboratories of the Ministry of Economic Affairs, Consumer Cooperatives, where R21 has a hydrocarbon group of 1 to 5 carbon atoms, R22 has a hydrocarbon group of 6 to 16 carbon atoms, Q represents' secondary alkyl groups, and R23 has general formula -(〇C2H4) q- (0 <: 31 {6) "01124, where 24 feet in the table represents a hydrogen atom or a lower alkyl group, " fen " or "]: " each table satisfies £ 1 Order the number of relations, where-(〇 (: 2114) (1- (OC3H6) r-partial molecular weight is 600 to 3,500; z the numbers of Tables 1 to 3; each table of X and y satisfies x < 3y and x + y + z = 3 0 to 400, but the limitation is-(OC2H4) q- (OC3H6) r- the weight of the partial body does not exceed the total of polyether-methyl-modified polysiloxane One third by weight. The hydrocarbon group having 1 to 5 carbon atoms represented by R21 in the general formula (4) includes an alkyl group having 1 to 5 carbon atoms and an alkenyl group. Examples thereof include methyl, ethyl, Propyl'isopropyl'butyl'pentyl 'or vinyl, of which methyl is preferred. In addition, examples of the hydrocarbon group having 6 to 16 carbon atoms represented by R22 include linear alkyl groups such as hexyl, heptyl Octyl, nonyl, decyl, undecyl, dodecyl Tetradecyl'hexadecyl; branched alkyls, such as isooctyl, second octyl, and 2-ethylhexyl, the preferred of which is dodecyl. Incidentally, 'y is greater than 1 In the case of r22, it can be the same for each repeat unit ___- 51-This paper is from China National Standards (CNS) A4 specification (21〇x297). (Please read the precautions on the back before filling this page ) 'Yi ------ order-η ___ ίV t. 4340 2 A7 B7 V. Description of the invention (49) t • 1 or different.. Examples of the alkylene group represented by Q in the general formula (4) include Methyl, butylene, trimethylene, trimethylene, and tetramethylene, the most preferred of which are butylene and trimethylene. In the general formula (4), it is included in the base of R23. The R24 group represents a hydrogen atom or a low-carbon group, such as methyl, ethyl, propyl ', isopropyl, or butyl, and the preferred one is a hydrogen atom. In addition, the preferred " q "値 and & quot r " 値 is q = 15 and r = 0; or q = r = 25; or q = 29 and r = 7. The polyether-alkyl · modified polysilicone of (4) is special Examples include " DC Q by Toray Dow Corning Corporation 2-2500 " (laurylmethycone copolyol: (laurylmethycone copolyol), wherein R2l represents methyl in formula (4), R22 represents dodecyl, and χ ^ κ). [3] An alkyl glyceryl ether modified polysiloxane having the following general formula (5):

R R32 R33

Si —〇— ($ i _〇) s_ —〇) t. R31 R pj 33 (5) R3i R31 (S i a 0) u—S i —R3 R34 R3 '(Please read the precautions on the back before reading (Fill in this page) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, where at least one of R31, r32, R33, and r34 has a base of the general formula (6) -A-OCH2CH (OR41) CH2OR42, where Table A A divalent hydrocarbon group having 3 to 20 carbon atoms; and R41 and R42 each represent a nitrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, but the restriction is that at least one of R4 1 and R4 2 is a hydrogen atom; except R31, R3 2, -52 other than those defined above, this paper uses Chinese National Standard (CNS) A4 specifications (210X297 public shame) .............. I-- -1- -I HI «1— HI 1 ^ 1 i 11 ^^ 1 In ^^^ 1 Printed by Beige Consumers Cooperative of Central Provincial Bureau of Ministry of Economic Affairs ^ 434027; A7 ---- B7 V. Description of the invention (50) R33, and R3 4 each represent a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a group having the general formula -BR4 3, wherein b represents a divalent having an ether bond and / or an ester bond. Hydrocarbyl; R43 represents a linear, branched or cyclic hydrocarbon having 1 to 30 carbon atoms ; &Quot; s ", "t " 'and ,, u ,, each of the numbers from 0 to 200, and when s + t + u = 0, one or more R31 base tables have the general formula shown above (6), but excluding at least one r31 group having the general formula (6) such that a represents a trimethylene group, and R41 and R42 each represent a hydrogen atom; and the remaining R31, R32, and R33 other than those defined above , And the substituents each represent a methyl group. Examples of the divalent hydrocarbon group having 3 to 20 carbon atoms represented by A in the above general formula (5) include linear alkylene groups such as trimethylene, tetramethylene, and pentaethylene Methyl 'hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, unmethylene, dodecyl methylene, tetradecamethylene, hexamethylene And octadecylene; and branched alkylenes, for example, propylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, and 3 · Examples of pentamethylene, R41 and R42 hydrocarbon groups having 1 to 5 carbon atoms include linear, branched, or cyclic alkyl groups, for example, methyl, ethyl, propyl, 'isopropyl, butyl Pentyl , Tertiary butyl, neopentyl, and cyclofluorenyl. In addition, examples of the divalent hydrocarbon group having an ether bond and / or an ester bond represented by B include the following compounds (0C3H6) j-0- '-(CH2 ) h-0-C0-, and-(CH2) h-COO-, where "h" is an integer from 3 to 20, and " i " and " j "are numbers from 0 to 50, respectively. In addition, examples of linear, branched or cyclic nicotyl groups having 1 to 30 carbon atoms represented by R43 include linear groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Base, nonyl, decyl, ^-alkyl, ten ____-53-This paper size applies to Chinese national standards (CNS > Α4 size (210 × 297 mm) ') (Please read the precautions on the back before filling in this P) Γ f, n ml ^ I nn 1 ^ .------- --I--i I-Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperation, Du K 4 3 4 Ο 2 7 'a? Β7 V. Description of the invention (51) Ergonomics, 14-bases, 16-bases '18 -bases' bases, 2 bases, 4 bases > bases, 6 bases Octyl 'and tridecyl; branched oxanyl, for example, isopropyl, second butyl' third butyl, neopentyl, 1 · ethylpropyl, and 1-heptyldecyl; and Cyclic alkyl groups such as cyclopentyl, cyclohexyl, rosinyl, and cholesterol groups etc. The alkyl glyceryl ether modified polysiloxane represented by the general formula (5) can be disclosed in Japanese Patent Laid-Open No. 4-108795 Method for making. The amount of oxygen is preferably from 0.05 to 20% by weight, and particularly from 1 to 10% by weight in the pellet composition. Although the amount of the ultraviolet shielding composite fine particles of the present invention in the cosmetic is determined by the preparation The type of cosmetic, however, the amount is preferably 0.01 to 50% by weight, more preferably 0.05 to 40% by weight, and particularly 0.1 to 30% by weight. When the ultraviolet shielding composite fine particles are lower than 0 · When the weight is 01 weight, the sufficient shielding effect against ultraviolet light cannot be achieved, and when the amount exceeds 50% by weight, when used as a cosmetic, the pleasing touch will be lost. When the dispersing oil composition is used in chemical granules, the amount of ultraviolet shielding composite fine particles must be determined so as to satisfy the amount stated in the cosmetic contained in the dispersing oil, and the cosmetic contains the aforementioned ultraviolet shielding Sexual composite particles 化妆 The cosmetic of the present invention can be formulated into various forms traditionally made. Although the form is not particularly limited, the cosmetic can be formulated into various cosmetic products, including lotions, emulsions, creams, ointments , Gas soluble Cosmetics, foundation, eye shadow, cream, cream, lipstick, hair preparation, and skin cleanser, etc. ___- 54- This paper is suitable for financial matters_ (〔叫 八 4 胁 (21 (^ 297 mm) ^ (Please read the notes on the back before filling this page) h, --11 丨: J m-—i--........ I-I i.tt ^^ 1 Economy Ministry of Standards and Standards Bureau Industrial and Consumer Cooperatives M 3 4 〇 2 7, Α7 ___ Β7 V. Description of the Invention (52) In addition, the cosmetic of the present invention preferably has an SPF of not less than 8 and before and after the application of the skin-wide 'The color change measured by the color-and-color difference meter is not more than 3. From the standpoint of fully exhibiting the ultraviolet shielding effect, the SPF is preferably not less than 8, more preferably not less than 10, and especially not less than 13. From the standpoint of maintaining good appearance after skin application, AE * ab is preferably not more than 3, more preferably not more than 2, especially not more than 1. In the present invention, the SPF uses an analyzer

" SPF-290 " (manufactured by The Optometries Group) and 値 defined in JIS Z8729-1 980. The present invention will be explained in more detail by the following examples, but they are not intended to limit the scope of the present invention. Example 1 366_5 grams of silica sol (" ST-C ", manufactured by Nissan Chemical Industries, Ltd .; SiO2 concentration: 20.5 weight./〇) and 20.0 grams of oxidized ultrafine particles (" TTO-51 ( A) ", Ishihara Sangyo Kaisha,

Ltd .; Rutile type) mixed. Water was added to the mixture to make up to a volume of one liter to obtain a starting liquid mixture. In particular, the concentration of SiO2 * TiC ^ in the starting material liquid mixture was i.25 moles / liter and 0.25 moles / liter, respectively, and the daughter particles / matrix particles in the starting material liquid mixture The amount of the mixture was about 10% by weight. Next, glass beads (average particle diameter: 0.1 mm) were added to the above-mentioned starting material liquid mixture to obtain a weight ratio of the starting material liquid mixture to the glass beads of 175: 325. The obtained mixture was dispersedly processed with a grain mill (" TSG-6H ", a product of Igarashi Kikai) at a moving speed of 2000 rpm ·. (210X297mm > ~~~~ '* --- (Please read the note on the back before filling this page)

434 02 7 ^ 1 Shellfish Consumption Cooperation of the Central Bureau of Standards, Ministry of Economic Affairs, Du Yin7 Α7 Β7 V. Invention Description (53) — 6 hours. After the dispersion treatment is terminated, the glass beads are removed to obtain a liquid dispersion containing Ti0 2 / Si0 2 composite fine particles (the expression form shown here means daughter particles / matrix particles, which is the same in other examples below) . 84-6 g of the above liquid dispersion, 500 g of ethanol, and 26 g of tetraethoxysilane were mixed, and the contents were heated to 500 c in a water bath. After the temperature of the obtained mixture reached 50X :, 3.9 ml of a 1 N hydrochloric acid / 300 g ethanol mixed solution was added dropwise to the liquid dispersion. After the dropwise addition was completed, the contents were reacted with each other at 50 ° C for 2 hours and 30 minutes to thereby use

SiO 2 is coated on the surface of the composite fine particles. After the coating treatment was completed, 0.98 ml of a 4N sodium hydroxide aqueous solution and 50 g of a ethanol-containing solution were added to the obtained mixture to neutralize hydrochloric acid. All the above steps are performed under stirring. After the coating treatment, the liquid Zhao dispersion is subjected to solid-liquid separation with a centrifuge to obtain an ethanol-containing cake. The procedure of adding ethanol to the obtained cake to disperse the cake in ethanol, and then performing a solid-liquid separation of the obtained dispersion with an ion machine was repeated five times to obtain a solid content concentration of about 40 weight 0 / 〇. Ethanol complex fine particle cake. After that, 12.5 g of the ethanol-containing cake obtained above was mixed with 500 g of propane, and the resulting mixture was subjected to ultrasonic dispersion treatment. After the cake was completely dispersed in acetone, 2.0 g of fluorenyl hydropolysiloxane (" KF99P ", manufactured by Shin-Etsu Silicone Corporation) was added to the liquid dispersion obtained above for water repellent treatment. . Thereafter, the obtained liquid mash dispersion was dried under 80 ° C, and then the resulting mixture was left to stand! 3 (). 〇Bake for 2 hours to dry the composite particles. Β-Mill the obtained powder with a pulverizer_ -56- This paper size is generally Chinese National Standard (CNS) Α4 size (210 × 297 mm) (Please read the precautions on the back first (Fill in this page again)

M340 2 7 A7 A7 __B7_ printed by Shellfish Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (54) (" AlO ", made by IKA-Labourtechnik) was repeatedly pulverized ten times to obtain composite microparticles. The particle size of the composite fine particles before the water repellent treatment is obtained by dispersing the composite fine particle cake containing ethanol in water and using a laser-dubler type particle size analyzer (" DLS-700 ", OTSUKA ELECTRONICS CO., LTD. (Made) to measure its particle size. The average particle size was measured to be about 0.08 microns by volume. After the water repellent treatment, the composite fine particles were white. The particles were observed with a scanning electron microscope (JSM-T100, manufactured by JEOL Ltd.). As a result, the particles were found to have an average particle diameter of about 1 m. In addition, the transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) was also used to observe the cross section of the particles by the ultra-thin section method. As a result, it was found that Ti02 ultrafine particles (average particle diameter: about 0.01 μm) were dispersed in and supported by the SiO2 ultrafine particles (average particle diameter: about 0.01 micron). In other words, the composite fine particles are Ti02 / Si02 composite fine particles; the matrix particles are Si02 particle aggregates, which have an interband energy of about 6.2 eV and a refractive index of about ι · 46; and the daughter particles are Ti〇2 particles, It has a band gap energy of about 3.3 eV and a refractive index (rutile type) of about 2.71. The content of the daughter particles in the composite fine particles is about 8.5% by volume, which is calculated based on the composition ratio of each particle in the starting liquid mixture and the coating amount of SiO2, where the particle density of SiO2 * Ti02 is respectively It is 2_27 grams / cubic centimeter and 3,84 grams / cubic centimeter. The refractive index of the composite fine particles was about 1.57, and the refractive index was calculated from the amount of the fine particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in the matrix particle aggregates and supporting it 'without including the SiO 2 coating portion is about 136% by volume. -------------- Of-This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

434 0 2 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (55) Disperse the composite fine particles before and after the water-repellent treatment in white petrolatum (made by Wako Pure Chemical Industries, Ltd.) to The concentration of the daughter particles in the mixture containing white petrolatum and the composite fine particles was set to 1 weight. / 〇. The resulting mixture was irradiated with ultraviolet light (" ENB-260 C / J ", manufactured by SPECTRONICS CORPORATION) with ultraviolet light having a center wavelength of 3 12 nm for 60 minutes. As a result, before and after water repellent treatment No change in the color of white petrolatum was observed in the two liquid dispersions containing composite microparticles. It can be confirmed from the above that the catalytic activity in the obtained composite fine particles has been substantially suppressed. After the water repellent treatment, when the composite fine particles are mixed with water, they exhibit strong water repellent properties. When the composite fine particles are mixed with polysiloxane (" KF96A ", manufactured by Shin-Etsu Silicone Corporation; refractive index: 1,40), the composite fine particles can be quickly dispersed in the polysiloxane. 8 4 mg of the composite fine particles having the above-mentioned refractive index were dispersed in 2 g of the polyoxymethylene oil. The light transmittance of the obtained liquid dispersion was evaluated with an ultraviolet-visible light spectrophotometer (" UV-160A ", manufactured by Shimadzu Corporation). The transmittance is measured in a silicon light box with a light path length of ^ ml at a wavelength of 200 to 8 nm. The results are shown in Figure 1. In the figure, the composite particles are in the ultraviolet region. The light transmittance in the wavelength range B and ultraviolet c is not longer than 300 nm. On the contrary, the composite microparticles show a clear 咼 light transmittance in the entire visible light region with a wavelength of 400 to 800 nm.値 'Its light transmittance is 52% at 400 nm and 81% at 800 nm. Therefore, the composite particles thus prepared have high light transmittance in the visible light region and ultraviolet light High shielding ability in the area. _ -58- This paper ruler is suitable for China梂 Jun (CNS) A4 specification (2 丨 0X297 mm) (Please read the notes on the back before filling out this page) · · ττ Printed by the Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs ^ 434 02 7-at _____B7 V. Description of the invention (56) Example 2 366.5 grams of oxidized crushed knee (" ST-C ", " made by Nissan Chemical Industries, Ltd .; SiO2 concentration: 20'5 wt%) and 20.3 grams of oxidation Zinc ultrafine particles (" FINEX 75 ", manufactured by Sakai Chemical Irnlumy Co., Ltd '). Water was added to the mixture to make up to a volume of one liter to obtain a starting liquid mixture. Specifically, the concentrations of SiO2 and ZnO in the starting material liquid rhenium mixture were 1.25 mol / liter and 0.25 mol / liter, respectively, and the amount of the sub-particle / matrix particle mixture in the starting material liquid mixture was Approximately 10 weight. /. . Thereafter, the procedure of dispersing the thus-obtained starting material liquid mixture using a high-pressure dispersing device (" LA-3 1 ", manufactured by Nanomizer INC.) Under a teaching force of 1000 kg / cm2 was repeated ten times. Through the above dispersion treatment, a liquid dispersion containing ZnO / SiO2 composite fine particles was obtained. 1500 g of ethanol, 16.26 g of tetraethoxysilane, and 3.9 ml of 1N hydrochloric acid were mixed, and the contents were heated to 50 aC in a water bath. After the temperature of the resulting mixture reached 50 ° C, the reaction mixture was aged for 2 hours and 30 minutes. After the maturation was completed, a mixed solution of 0.98 ml of a 4N aqueous solution of sodium argon and 50 g of ethanol was added to the reaction mixture to neutralize hydrochloric acid. Thereafter, a mixed solution of 84.6 g of the above-mentioned liquid dispersion and 300 g of ethanol was added dropwise to the neutralized solution. After the dropwise addition is completed, the contents are placed at 5 ° C to react with each other to thereby coat the composite fine particles on the surface of SiO2. All the above steps are performed with stirring. After the coating treatment, follow the example 1 The liquid dispersion was subjected to solid-liquid separation in the same manner as in the above to obtain a solid content concentration of about 40% by weight containing ___- 59 -____________. This paper uses the Chinese national standard (CNS > A4 size (210X297 mm) ) (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 4 34 02 7 'A7 B7 Five' Invention Note (57) Ethanol compound particle cake. After that, 12.5 g of the ethanol-containing cake obtained above was mixed with 500 g of acetone, and the resulting mixture was subjected to ultrasonic dispersion treatment. After the cake was completely dispersed in acetone, 0.5 g of methylhydrogen polysiloxane (" KF99P ", manufactured by Shin-Etsu Silicone Corporation) was added to the liquid dispersion obtained above for water repellent treatment. "After that, the resulting liquid dispersion was dried at 80 eC, and then the resulting mixture was further placed at 130. (: Baking for 2 hours to dry the composite fine particles. The obtained powder was repeatedly pulverized ten times with a pulverizer (" A10 ", manufactured by IKA-Labourtechnik) to obtain composite fine particles. Compound before water-repellent treatment The particle size of the microparticles is obtained by dispersing a cake of composite fine particles containing ethanol in water and measuring the particle size in the same manner as in Example 1. The average particle size by volume was measured to be about 0.07. Micron. After the water repellent treatment, the composite fine particles were white. The particles were observed with a scanning electron microscope (JS M · T 100, manufactured by JEOL Ltd.). As a result, the particles were found to have an average particle diameter of about 1 micron. The cross section of the particles was also observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) using the ultra-thin section method. As a result, it was found that ZnO ultrafine particles (average particle size: about 0.01 micron) were dispersed in Si02 ultrafine particles (average particle size: about 0.01 micron) are aggregated and supported by it. In other words, the composite fine particles are Zn0 / Si02 composite fine particles; the matrix particles are Si02 particle aggregates, which have about 6.2 eV Band Interstitial energy and a refractive index of about 1.46; and its daughter particles are ZnO particles, having a band gap energy of about 3.2 eV and a refractive index of about 1.99. The content of the daughter particles in the composite microparticles is about 5.9% by volume. -60- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling this page) Order the central standard of the Ministry of Economic Affairs 扃 贝 工 consuming cooperatives' seal 褽 434027 Λ Α7 ~~ — Β7 V. Description of the invention (58) Calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, where the particle density of SiO2 and ZnO is 2.27 g / cm3, respectively. And 5.78 grams per cubic centimeter. The refractive index of the composite microparticles is about 1.49, and the refractive index is calculated from the amount of the subparticles in the composite microparticles. Incidentally, it is dispersed in and supported by the matrix particle aggregate, and The amount of daughter particles excluding the SiG2 coating portion was about 9.6% by volume. The composite fine particles before and after the water repellent treatment were dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that The concentration of the particles in the mixture containing white petrolatum and the composite fine particles was 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The results showed that no color change occurred in the white petrolatum and the catalysis in the obtained composite fine particles The activity has been substantially suppressed. After the water repellent treatment, when the composite fine particles are mixed with water, they show strong water repellent properties. When the composite fine particles are mixed with silicone oil (" KF96A ", Shin-Etsu Silicone Corporation (Made; refractive index: 1.40) When mixed, the composite fine particles can be quickly dispersed in the silicone oil. 28 mg of the composite fine particles having the above-mentioned refractive index were dispersed in 2 g of the silicone oil. The light transmittance of the obtained liquid dispersion was evaluated in the same manner as in Example 1. The results are shown in Fig. 2. In the figure, the transmittance of the composite microparticles in the ultraviolet region A, ultraviolet region B, and ultraviolet region C of wavelengths not longer than 350 nm is substantially equal to 0%. In contrast, the composite particles exhibited a significantly high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm, with a light transmittance of 30% at 400 nm and 8 at 800 nm. 4%. For this reason, -61-This paper size is applicable to China National Standards (CNS) Α4ΐ1 grid (210X297 mm) — J — —11 κ ·-^ 11 f Please read the note ^ Fill out this page}.

-K Printed by the Central Laboratories of the Ministry of Economic Affairs, Consumer Cooperatives ^ 4 34 0 2 7 '-A7 __B7_ V. Description of the Invention (59) Composite microparticles have high transmittance in the visible light region and high in the ultraviolet light region Shielding ability. Example 3 The formation of Ti02 / Si02 composite particles was performed in the same manner as in Example 1. The surface of Si02 was coated and separated from solid-liquid to obtain a composite particle cake containing ethanol with a solid content concentration of about 40% by weight. Piece. Thereafter, 12.5 g of the ethanol-containing cake obtained above was mixed with 500 g of ethyl acetate, and the resulting mixture was subjected to ultrasonic dispersion treatment. After the cake was completely dispersed in ethyl acetate, 2.5 g of amine-modified polysiloxane (" X-2 2-926 Γ, manufactured by Shin-Etsu Silicone Corporation) was added to the liquid dispersion obtained above. ; Molecular weight: 30,000; amine equivalent: 4980) for water repellent treatment 'and the resulting mixture was subjected to ultrasonic treatment at 50X for 3 hours. 42.5 g of a silicone oil (" KF96A " made by Shin-Etsu Silicone Corporation; refractive index: 1.40) was added to the liquid partition, followed by stirring and mixing. Thereafter, the resulting mixture was subjected to straight distillation at 80 ° C using a rotary evaporator to remove ethyl acetate so that the composite fine particles were phase-transmitted and dispersed in a silicone oil to obtain a composite fine particle concentration of 10 wt. 0 / 〇 composite fine particle silicone fluid dispersion. The particle size of the composite fine particles before the water-repellent treatment was obtained by dispersing the cake of composite fine particles containing ethanol in water and measuring the particle size in the same manner as in Example 1. It was found that the average particle size by volume was about 0.08 microns. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin section method. It was found that __ -62- This paper size is in accordance with the Chinese National Standard (CNS) specification (21〇 × 297 mm) (Please read the note on the back before filling this page)

--------------- ut fI order

h --- _-_ = * ·---- -I * HI «Τ---IJ—. 4 340271 Α7 Β7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (60) Ti02 ultrafine particles (average particle size: about 0.01 microns) are dispersed in and supported by 8102 ultrafine particles (average particle size: about 0.01 microns). In other words, the composite microparticles are Ti02 / Si02 composite particles; the matrix particles are Si02 particle aggregates, which have an inter-band aging energy of about 6.2 eV and a refractive index of about 1.46; and the daughter particles are Ti02 particles, which have about 3.3 The band gap energy of eV and the refractive index (rutile type) of about 2.71. The content of the sub-particles in the above-mentioned composite micro-particles is about 8.5 cross-sectional area, which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, among which the particle density of Si02 * Ti02 They are 2.27 grams per cubic centimeter and 3.84 grams per cubic centimeter. The refractive index of the composite fine particles was about 1.57, and the refractive index was calculated from the amount of the fine particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in and supported by the matrix particle aggregate without including the SiO 2 coating portion was about 13,6 vol./0. The thus-obtained composite fine particle silicone oil dispersion was dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of Ti02 particles in a mixture containing white petrolatum and composite fine particles was ^ wt%. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above results show that no color change occurs in white vaseline and the catalytic activity in the obtained composite fine particles is substantially suppressed. After diluting 0.1 g of the composite microparticle polysecond oxygen oil dispersion thus obtained with 4.9 g of polysiloxane oil ("KK96A" used above), the permeability of the obtained liquid dispersion was estimated in the same manner as in Example 1. Photometric. The results are shown in Figure 3. In this figure, the wavelength of the composite fine particles in the ultraviolet region B and the ultraviolet region C is -63. This paper scale is applicable to the Chinese national standard (CNS > Α4 size (210 × 297 mm)) ; (Please read the note on the back before filling in this page) r 'r · -—HIJi ulu. ^ 1 1-IT—-I, --I n —1 n It Order -i ^ i ^^ 1 1 ^ 1 Iff * 4 34 0 2 7 '; A7 B7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (61 The light transmittance among those who are not longer than 300 nm is substantially equal to 0%. On the contrary Ground, the composite fine particles show extremely high light transmittance in the entire visible light region of the wavelength of 400 to 800 nm, the light transmittance is 800% at 400 nm, and 97% at 800 nm Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 4 366.5 g of an oxide dream sol (" ST-C ", Manufactured by Nissan Chemical Industries, Ltd .; Si02 concentration: 20.5 wt./%), 10.0 g of ytterbium oxide ultrafine particles (" TTO-5 1 (A) " 'Ishihara Sangyo (Made by Kasisha, Ltd .; rutile type), and 40.7 g of zinc oxide ultrafine particles (" FINEX 75 ", made by Sakai Chemical Industry Co., Ltd.). Water was added to this mixture to make up to one liter The volume of the starting material liquid mixture was obtained. In particular, the concentrations of SiO2, TiO2, and ZnO in the starting material liquid mixture were 1.25 moles / liter, 0.125 moles / liter, and 0.5 moles, respectively. And the amount of the child particles / matrix particle mixture in the above-mentioned starting material liquid mixture was about 12% by weight. The obtained starting material liquid was subjected to dispersion treatment in the same manner as in Example 1 to obtain Ti02 + Liquid dispersion of Zn0 / Si02 composite fine particles. After that, the obtained liquid dispersion was surface-coated and treated in the same manner as in Example 2. After the coating treatment, the liquid dispersion was heated to 70 ° C, and 0.74 was added. Gram amine modified polysiloxane (,, XF-42-B0819 ,, manufactured by Toshsba Silicone Corporation; molecular weight: 10,000; amine equivalent: 1600) in the liquid dispersion obtained above, and the resulting mixture was at 70 ° c under Ti02 + Zn0 / Si02 The composite microparticles are subjected to further ultrasonic waves. The degree of 64-sheet paper conforms to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the precautions on the back before filling this page.) Clothing A7 B7 434027 5. Description of the invention ( 62) Treatment 0 After the water-repellent treatment, the liquid mixture was subjected to a rotary evaporator at 75 ° C. 〇 After the ethanol treatment and the removal of ethanol and water to produce a liquid dispersion β that is three times thicker than the liquid dispersion before the straight distillation treatment, 900 g of n-hexane was added, and the resulting mixture was subjected to reflux at 70 ° C and Dehydration treatment. After the reflux and dehydration treatments, 132 8 g of a polysiloxane (" KF96A ", manufactured by Shin-Etsu Silicone Corporation; refractive index: 1.40) was added to the above liquid dispersion, followed by stirring and mixing. Then, the obtained mixture was subjected to straight distillation treatment at 80 * C using a rotary evaporator to remove ethanol and water, so that the composite fine particles were phase-transferred and dispersed in silicone oil to obtain composite fine particles having a concentration of 10% by weight of the composite fine particles. Silicone oil dispersion. After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain a composite fine particle cake containing 6 alcohols. After that, the particle size of the composite fine particles before the water repellent treatment was dispersed in water by dispersing the composite fine particle cake containing ethanol in water, and a laser Doppler type particle size analyzer (" DLS-700 ", OTSUKA ELECTRONICS CO · , LTD.) Measured its particle size. The average particle size was measured to be about 0.09 micrometers by volume. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin section method. As a result, it was found that 1 ^ 02 ultrafine particles (average particle diameter: about 0.01 micron) and ZnO ultrafine particles (average particle diameter: about 0.01 micrometer) were dispersed in the aggregate of Si02 ultrafine particles (average particle diameter: about 0.01 micrometer). And supported by it. In other words, the composite microparticles are Ti02 + ZnO / Si〇2 composite microparticles; the matrix particles are Si02 particle aggregates, which have a band gap energy of about 6.2 eV and about -65- This paper size is applicable to the Chinese national standard (CNS M4 Specifications (210X297 mm) 11 «---;-i-! J-Nong (Please read the precautions on the back before filling out this page) Order the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Consumer Cooperatives, and print the Central Standards Bureau of the Ministry of Economic Affairs Printed by Shelley Consumer Cooperative, 4 34 0 2 7, A7 _____B7_ V. Description of the invention (63) 1.46 refractive index; and its daughter particles are Ti02 particles, with a band gap energy of about 3.3 eV and a refractive index of about 2.71 And ZnO particles, which have a band gap energy of about 3.2 eV and a refractive index of about 1,99. The content of the sub-particles in the composite microparticles is about 14.1 vol%, which is determined by the particles in the starting material liquid mixture. The composition ratio and si 〇2 coating amount were calculated, in which the particle densities of Si02, Ti02 and ZnO were 2.27 g / cm3, 3,84 g / cm3 and 5.78 g / cm3, respectively. The refractive index is about 1.556. The ratio is calculated using the amount of daughter particles in the composite microparticles. Incidentally, the amount of daughter particles dispersed in and supported by the matrix particle aggregates without including the SiO 2 coating portion is about 22.6% by volume. The composite fine particles before the water-repellent treatment were dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the degree of 1 ^ 2 particles in a mixture containing white petrolatum and composite fine particles was 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above results showed that no color change occurred in white vaseline and the catalytic activity in the obtained composite fine particles was substantially suppressed. 0.1 g of the composite fine particles thus obtained The polysiloxane dispersion was diluted with 49 grams of polysiloxane (" KP96A ", used above), and the transmittance of the obtained liquid dispersion was measured in the same manner as in Example 1. The results are shown in FIG. 4 In the figure, the transmittance of the composite particles in the ultraviolet region A, ultraviolet region B, and ultraviolet region C with a wavelength not longer than 3 50 nm is substantially equal to 0%. On the contrary Ground, the composite microparticles are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) over the entire I paper 4 scales at a wavelength of 400 to 800 nm. --- (Please read the note on the back before filling this page)

.C,? Τ k 4 4 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (· 4 34027 _______B7 V. Description of the invention (correction) Extremely high light transmittance is displayed in the visible light area, which is 400 nm The light transmittance is 40%, and it is 94% at 800 nm. Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 5 The preparation and dispersion treatment of the starting material liquid mixture was performed in the same manner as in Example 1 to obtain a liquid dispersion containing Ti02 / Si02 composite particles. 84.6 g of the above-mentioned liquid dispersion, 1500 g of ethanol, It was mixed with 26 g of tetraethoxy silicon blocks, and the contents were heated in a water bath to 50 ° C. After the temperature of the resulting mixture reached 50. <: After that, 3.9 was added dropwise to the liquid dispersion. 1 ml of a mixed solution of 1N hydrochloric acid / 300 g of ethanol. After the dropwise addition was completed, 'the contents were allowed to react with each other at 50 ° C for 2 hours and 30 minutes, thereby coating the surface of the composite fine particles with Si02. § 丨〇 After the surface coating is formed, the obtained 199.1 g of an isopropanol solution containing 0.04% by weight of isopropoxide was added dropwise to the mixture, and the mixture was allowed to react with each other at 75 ° C for 5 hours to thereby form an 8203 surface coating. After the coating treatment is completed, 0.98 ml of a 4N sodium hydroxide aqueous solution and 50 g of ethanol mixed solution are added to the resulting mixture to neutralize hydrochloric acid. All the above steps are performed with stirring. After the coating treatment, the liquid 6.6 g of oleic acid was added to the dispersion, and the resulting mixture was stirred. Thereafter, the resulting mixture was subjected to ultrasonic treatment at 50 * c for 3 hours to perform water-repellent treatment of Ti〇2 / Si02 composite fine particles. Then, use a rotary evaporator at 75 ° C to straighten the liquid dispersion. -67- This paper size is applicable to China National Standard (CNS) A4 (210X297) (please read the precautions on the back first and fill in this note) ) II ^-----1—--II n If In nn-n If I _-Printed by the Ministry of Economic Affairs, Bureau of Standards and Loss of Consumer Goods Cooperatives 4 340271 A7 __ B7 V. Description of Invention (65) Full treatment In order to remove ethanol 'isopropanol and water, thereby generating more than straight The previous liquid dispersion was three times thicker than the liquid mash dispersion. Thereafter, 900 g of n-hexane was added, and the resulting mixture was subjected to reflux and dehydration treatment at 70 ° C. After the reflux and dehydration treatment, the above liquid was dispersed To this was added U1.7 g of polysecond oxygen oil (" KF96A " made by Shin-Etsu Silicone Corporation; refractive index: 1.40), followed by stirring and mixing. Thereafter, the obtained mixture was subjected to a straight distillation treatment at 80 ° C to remove ethanol, isopropanol 'and water, so that the composite fine particles were phase-transferred and dispersed in a silicone oil to obtain a compound having a weight of 10% by weight. Micro-particle concentration polysiloxane dispersion. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JE0L Ltd.) by the ultra-thin section method. As a result, it was found that Ti02 ultrafine particles (average particle size: about 0.01 micron) were dispersed in and supported by the ^ 02 ultrafine particles (average particle size: about 0.01 micron) aggregate. In other words, the composite microparticles are Ti02 / Si02 composite microparticles; the matrix particles are Si02 particle aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1'46; and their daughter particles are 1 '丨 〇2 particles It has a band gap energy of about 3,3 eV and a refractive index (rutile type) of 2.71. The content of the daughter particles in the composite fine particles is about 8.5% by volume, which is calculated based on the composition ratio of each particle in the starting liquid mixture and the coating amount of S i 〇 2, among which the particle densities of Si02 and Ti02 They are 2.27 grams per cubic centimeter and 3.84 grams per cubic centimeter. The refractive index of the composite fine particles was about 1.57, and the refractive index was calculated from the amount of the daughter particles in the composite fine particles. Incidentally, it is dispersed in the matrix particle aggregates and is suitable for it -68- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm > (Please read the precautions on the back before filling this page)

Central Standards Bureau, Ministry of Economic Affairs-Industrial-Consumer Cooperation Du Yinzhong 4340271 A7 ______B7_ V. Description of the invention (66) Supported, the amount of sub-particles excluding the coating of Si0 2 is about 13.6% by volume. 0 Before water-repellent treatment And the subsequent composite fine particles were dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of the daughter particles in the mixture containing white petrolatum and the composite fine particles was 1% by weight. After that, the color change measurement was performed in the same manner as in Example 1. The above shows that no color change occurs in the white vaseline, and the catalytic activity in the obtained composite fine particles has been substantially suppressed. After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain a composite fine particle cake containing ethanol. Thereafter, the particle size of the composite fine particles before the water repellent treatment was dispersed in water by dispersing the composite fine particle cake containing ethanol in water, and a laser-Doppler type particle size analyzer (" DLS-700 ", OTSUKA ELECTRONICS CO "Manufactured by LTD.), Its particle diameter was measured. The average particle diameter was measured to be about 0.09 micrometers by volume. A polysiloxane dispersion of 0.15 g thus obtained was used with 4,85 g After the silicone oil ("KP96A" used above) was diluted, the transmittance of the obtained liquid dispersion was measured in the same manner as in Example 1. The results are shown in FIG. 5. In the ultraviolet region B and the ultraviolet region C, the light transmittance among those having a wavelength not longer than 300 nm is substantially equal to 0%. On the contrary, the composite fine particles show in the entire visible light region with a wavelength of 400 to 800 nm Extremely high light transmittance 値, which has a light transmittance of 5 9% at 400 nm and 8 7% at 800 nm. Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region And has a high shielding ability in the ultraviolet region. &Quot; 69 ~ This paper is in use National Standard (CNS) A4 Specification (210X297 mm) (Please read the precautions on the back before filling in this card) 'Cloth-Order Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Printed by the Bayer Consumer Cooperative 134071 A7 _ B7 V. Description of the Invention (67) Example 6 The liquid dispersion of the starting material liquid mixture was prepared and dispersed in the same manner as in Example 4 to obtain a liquid dispersion containing Ti02 + Zn0 / Si02 composite fine particles. 1500 g of ethanol, 16,26 g of four Ethoxylan silane was mixed with 3.9 ml of 1N hydrochloric acid, and the contents were heated in a water bath to 50 ° C. After the temperature of the resulting mixture reached 50 ° C, the reaction mixture was aged for 2 hours and 30 minutes. To the reaction mixture was added 0,98 ml of a 4N sodium hydroxide aqueous solution and 50 g of a ethanol mixed solution to neutralize hydrochloric acid. Then, 84.6 g of the above-mentioned liquid dispersion containing the composite particles of Ti02 + Zn0 / Si02 was mixed with 300 g of ethanol. The solution was added dropwise to the neutralization solution. After the dropwise addition was completed, the contents were placed at 50eC and allowed to react with each other for 2 hours and 30 minutes, whereby the Ti02 + Zn〇 / Si02 composite fine particles were coated on the surface of 5 丨 02. Be After the formation of the Si02 surface coating layer, 199.1 g of an isopropanol solution containing 0.04% by weight isopropyl aluminum oxide was added dropwise to the resulting mixture, and the resulting mixture was allowed to react with each other at 75 ° C for 5 hours, thereby further A1203 surface coating was formed. All the above steps were performed with stirring. After the coating was treated, 1.5 g of stearic acid was added to the liquid dispersion, and the resulting mixture was stirred. Thereafter, the obtained liquid mixture was subjected to ultrasonic treatment at 7 ° C. for 2 hours to perform water repellent treatment of Ti02 + Zn0 / Si02 composite fine particles. The liquid dispersion obtained by the water repellent treatment was refluxed in the same manner as in Example 5. And dehydration treatment. After the reflux and dehydration treatments, 132.0 g of polysiloxane oil (" KF96A ", Shin-Etsu -70-, X-degree of this paper is applicable to the Chinese Standard for Householder (CNS)). A4 specification (210X297 mm) τι I .....; 4 I -ifc fn I (Please read the notes on the back before filling in this page) Order h Printed by the Central Bureau of Prospecting and Testing, Cooperate of the Ministry of Economic Affairs 4 3 4 Ο 2 713 Α7 _____ Β7_ V. Description of the invention (68)

Manufactured by Silicone Corporation; refractive index: 1.40), followed by stirring and mixing. Thereafter, the obtained mixture was subjected to a straight distillation treatment at 80 ° C with a rotary evaporator to remove ethanol, isopropanol, and water, so that the composite fine particles were phase-transferred and dispersed in a silicone oil to obtain 10% by weight. Composite fine particle polysiloxane dispersion. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin section method. As a result, it was found that ZnO ultrafine particles (average particle diameter: about 0.01 micrometers) and Ti02 ultrafine particles (average particle diameter: about 0.01 micrometers) were dispersed in the aggregates of the SiO2 ultrafine particles (average particle diameter: about 0.01 micrometers) and were used as their targets. stand by. In other words, the composite particles are Ti02 + Zn0 / Si02 composite particles; the matrix particles are SiOji daughter aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1.46; and their daughter particles are ZnO particles, which have The band gap energy of about 3.2 eV and the refractive index of about 1.99 and the Ti02 particles have a band gap energy of about 3.3 eV and a refractive index of about 2.71. The content of the daughter particles in the composite fine particles was about 14.1 volumes. /. , Which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, where the particle density of SiO2, Ti02, and ZnO are 2.27 g / cm3 and 3.84 g / cm3, respectively. Cubic centimeters and 5.78 grams per cubic centimeter. The refractive index of the composite fine particles was about 1.56, and the refractive index was calculated from the amount of the particles in the composite fine particles. Incidentally, the amount of daughter particles dispersed in and supported by the base particle aggregates without including the SiO 2 coating portion was about 22.6 volumes. / 〇. After the coating is treated, the liquid dispersion is fed in the same manner as in Example 1. 71 -_ This paper XA applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm)--HI I * -1- ---- 广-(Please read the notes on the back before filling this page) I — I order _____- C________________ A7 4340271 ___B7 V. Description of the invention (69) Solid-liquid separation to obtain ethanol-containing composite particles After the "cake", the particle size of the composite microparticles before the water repellent treatment was dispersed by dispersing the ethanol-containing composite fine particle cake in water and using a laser-Doppler particle size analyzer (" DLS · 700 ", OTSUKA ELECTRONICS (Manufactured by CO., LTD.), Its particle size was measured. The average particle size was measured to be about 0, 10 microns by volume. The composite fine particles before water repellent treatment were dispersed in white petrolatum (Wako

Pure Chemical Industries, Ltd.) so that the concentration of 1 ^ 02 particles in a mixture containing white petrolatum and composite fine particles is 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above results show that no color change occurs in white vaseline, and the catalytic activity in the obtained composite fine particles is substantially suppressed. After diluting 0 to 1 g of the thus-obtained composite fine-particle polysiloxane dispersion with 4 · 9 g of polysiloxane (" K96A ", used above), the obtained liquid was measured in the same manner as in Example i. The transmittance of the dispersion. The results are shown in Figure 6. In this figure, the transmission of the composite particles in the ultraviolet region A, ultraviolet region B, and ultraviolet region C is not longer than 350 nm. The transmittance is substantially equal to the opposite. The composite fine particles exhibit high transmittance 値 in the entire visible light region with a wavelength of 400 to 800 nm. The transmittance at 400 nm is 3 3 ° / 〇, and at 800 Nanometer is 93%. Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 7 T was performed in the same manner as in Example 1. i Ο 2 / si Ο 2 composite microparticles ___-72-This paper size is applicable to the Chinese national standard (CNS > A4 size (210X297 mm) ~ ---------- (Please read the back first Please fill in this page for the note items} — Γ printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and Consumer Cooperatives £ 7 ______ £ 7 ______ A 7 Consumption cooperation by employees of the Central Bureau of Economic Affairs, Ministry of Economic Affairs, Du Tian 34027Ί 5. The invention description (70) was formed. After that, the S102 surface coating and Al203 surface coating were performed in the same manner as in Example 5. Be processed.

After the surface coating was treated, 0.66 g of a dithiocarbamate (" DAP60H ", manufactured by Kao Corporation) was added to the liquid dispersion for water-repellent treatment, and the resulting mixture containing Ti02 / Si02 composite fine particles was placed in 75 ° C ultrasonic treatment for 1 hour. After the water repellent treatment, the liquid dispersion was subjected to a straight distillation using a rotary evaporator at 75 to remove ethanol, isopropanol and water, thereby producing a liquid dispersion three times thicker than the liquid dispersion before the straight distillation treatment. Thereafter, 900 g of cyclohexane was added, and the resulting mixture was refluxed and dehydrated under 70 Torr. After the reflux and dehydration treatments, 117.7 g of polyammonium oil (" KF96A ", manufactured by Shin-Etsu Silicone Corporation; refractive index: 1.40) were added to the above liquid dispersion, followed by stirring and mixing. Thereafter, the obtained mixture was subjected to a straight distillation treatment at 80 ° C using a rotary evaporator to remove ethanol, isopropanol, and water, so that the composite fine particles were phase-transferred and dispersed in silicone oil to have a weight of 10. /. The concentration of composite microparticles is a composite microparticle polyoxygen oil dispersion. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by an ultra-thin cross-section method. As a result, Ti02 ultrafine particles (average particle size: about 001 μm) The system is dispersed in and supported by aggregates of 8 〇 2 ultrafine particles (average particle size: about 0.01 micron). In other words, the composite particle is a Ti〇2 / Si〇2 composite particle; the matrix particle is a Si02 particle aggregate, which has a band gap energy of about 6.2 eV and a refractive index of about 1.46; and its daughter particle is Ti 〇2 particles, with about 3 3 pieces of paper freely used by China Post (CNS > M size (21Gx) 97), (please read the notes on the back before filling in this card)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 434027ts A7 _______B7 __ V. Description of the invention (71) The band gap energy of eV and the refractive index of 2.71. The content of the daughter particles in the composite fine particles was about 8.5 volumes. / 〇, which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, where the particle density of SiO2 * Ti02 is 2.27 g / cm3 and 3.84 g / cm3, respectively. The refractive index of the composite fine particles was about 1.57, and the refractive index was calculated from the amount of the daughter particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in and supported by the matrix particle aggregates without including the Si02 coating portion is about 13.6% by volume. After the coating is treated, 'in the same manner as in Example 1 The liquid dispersion was subjected to solid-liquid separation to obtain a composite fine particle cake containing ethanol. Thereafter, the particle size of the composite fine particles before the water-repellent treatment was dispersed in water by dispersing the composite fine particle cake containing ethanol in water, and a laser-Doppler type particle size analyzer (" DLS.700 "'OTSUKA ELECTRONICS CO. (Made by LTD.)) Its particle diameter was measured \ The average particle diameter was measured to be about 009 micrometers by volume. The composite fine particles obtained from the composite fine particle cake containing ethanol before water-repellent treatment were diluted in white Among petroleum jelly (manufactured by Wako Pure Chemical Industries, Ltd), the concentration of Ti02 particles in a mixture containing white petrolatum and composite fine particles was 1% by weight. Thereafter, the color was changed in the same manner as in Example i. The results showed that the color change did not occur in the white petrolatum, and the catalytic activity in the obtained composite fine particles was substantially suppressed. 0. 9 g of polysiloxane was used to disperse 0.1 g of the silicone oil dispersion of the composite fine particles thus obtained. Oil (" KP96A ", used above) is diluted according to Example 1 _ 7 4-This paper size applies the Chinese National Standard (CNS) A4 Regulation (ϋχϋmm) ----- (Please read the back first Note to fill out this page)

—C year 4 34 0 2 7 ^ .1 Α7 __ B7 V. Measure the light incidence rate of the obtained liquid dispersion in the same way as in the description of the invention (72). The results are shown in FIG. 7. In this figure, the transmittance of the composite fine particles in the ultraviolet region B and the ultraviolet region C having a wavelength not longer than 300 nm is substantially equal to 0%. In contrast, the composite fine particles exhibit extremely high light transmittance in the entire visible light region of a wavelength of 400 to 800 nm. Its transmittance is 74% at 400 nm and 96% at 800 nm. For this reason, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 8 Ti0 2 + ZnO / Si02 was performed in the same manner as in Example 6. Formation of composite particles, SiO2 surface coating treatment, and A1203 surface coating treatment. After the surface coating treatment, 0.74 g of a dialkyl carboxylate (" DAP60H ", manufactured by Kao Corporation was added to the liquid dispersion. (Manufactured) is subjected to a water repellent treatment, and the resulting mixture containing the Ti02 + ZnO / Si0 2 composite fine particles is subjected to ultrasonic treatment at 75 ° C. for 1 hour. After the water repellent treatment, the same method as in Example 5 was used. The liquid dispersion was subjected to reflux and dehydration treatment. After the reflux and dehydration treatment, 132,8 g of polysiloxane oil ("KF96A ", manufactured by Shin-Etsu Silicone Corporation) was added to the above liquid dispersion; refractive index: 1.40), followed by stirring and mixing. After that, the obtained mixture was subjected to straight distillation treatment at 80 eC to remove ethanol, isopropanol, and water, so that the composite fine particles were phase-transferred and dispersed in the silicone oil to obtain a composite fine particles having a concentration of 10% by weight. Composite fine particle silicone fluid dispersion. -75- This paper is printed with the National Standard of China (CNS > A4 size (210X297 mm) (Please read the precautions on the back before filling out this page), and printed by the Offshore Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Production A7 B7 4340271 V. Description of the invention (73) After the water repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) with an ultra-thin section method. As a result, ZnO ultrafine particles were found. (Average particle size: about 0.01 micron) and Ti02 ultrafine particles (average particle size: about 0.01 microns) are dispersed in and supported by the aggregates of SiO2 ultrafine particles (average particle size: about 0.01 microns). In other words, The composite fine particles are Ti02 + Zn0 / Si02 composite fine particles: the matrix particles are SiOJi daughter aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1.46; and the daughter particles are ZnO particles, which have about 3.2 eV The band gap energy and the refractive index of 1.99 and the TiO 2 particles have a band gap energy of about 3.3 eV and a refractive index of about 2.71. The content of the daughter particles in the above-mentioned composite fine particles is about 14.1 vol. Based on The composition ratio of each particle in the starting material liquid mixture and the coating amount of S i02 were calculated. The particle densities of Si02, Ti02 and ZnO were 2.27 g / cm3, 3.84 g / cm3, and 5,78 g / cm. "The cubic refractive index" of the composite microparticles is about 1.56, and the refractive index is calculated from the amount of the sub-particles in the composite microparticles. Incidentally, it is dispersed in and supported by the matrix particle aggregate, excluding Si02 The amount of sub-particles in the coating portion was about 22.6% of the cross-section. After the coating was treated, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain an ethanol-containing composite fine particle cake. The particle size of the composite fine particles before the water-repellent treatment is dispersed by dispersing the composite fine particle cake containing ethanol in water and using a laser-Doppler type particle size analyzer (" DLS-700 ", OTSUKA ELECTRONICS CO., LTD (Manufactured) Its particle size was measured. Its average particle size was measured to be about 0.10 micrometers in volume. Private paper from the applicable countries and countries (CNS) Cong Mi (21Gx297 public magic · J. H ΙΠ _ n 0 4 ^ 1-I (Please read the back first (Please fill out this page again)

• 1T Printed by the Central Government Bureau of Standards, Ministry of Economic Affairs, Machining and Consumer Cooperatives-76- A7 B7 434027] V. Description of the Invention (74) Composite microparticles will be obtained from composite microparticles containing ethanol before water-repellent treatment (please read the back first) Note: Please fill in this page again) The particles are dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of Ti02 particles in the mixture containing white petrolatum and composite fine particles is 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above shows that no color change occurs in white vaseline and the catalytic activity in the obtained composite fine particles is substantially suppressed. After diluting 0.1 g of the thus-obtained composite fine-particle polysiloxane dispersion with 49 g of polysiloxane (" KP96A ", used above), the obtained liquid cross-body dispersion was measured in the same manner as in Example 1. Light transmittance. The results are shown in Fig. 8. In this figure, the transmittance of the post-combined particles in the ultraviolet region A, ultraviolet region b, and ultraviolet region C with a wavelength not longer than 350 nm is substantially equal to 0%. In contrast, 'the composite fine particles exhibit extremely high light transmittance in the entire visible light region of the wavelength of 400 to 800 nanometers, and their transmittance is 36% at 400 nanometers' and 93 at 800 nanometers % ^ Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 9 Printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The preparation and dispersion treatment of the starting material liquid mixture were performed in the same manner as in Example 2 to obtain a liquid dispersion containing Zn0 / Si02 composite fine particles. 1500 g of ethanol, 16.26 g of tetraethoxy, and 3.9 ml of 1N hydrochloric acid were mixed, and the contents were heated in a water bath to 50 ° C. After the temperature of the resulting mixture reached 50 ° C, the reaction mixture was aged for 2 hours and 30 minutes. After the maturation is complete, add 0.98 ml of 4N hydrogen to the reaction mixture. -77-private paper size. Use China National Standard (CNS) 8 4 size (210X297 mm) 4 34 0 2 7: 3 A7 B7 5 2. Description of the invention (75) A mixed solution of an aqueous sodium sulfide solution and 50 g of ethanol to neutralize hydrochloric acid. Thereafter, to the neutralized solution, a mixed solution of 84.6 g of the above-mentioned liquid dispersion containing the ZnO / SiO 2 composite microparticles and 300 g of ethanol was added dropwise. After the dropwise addition was completed, the contents were reacted with each other at 50 ° C to coat the ZnO / Si02 composite particles with the surface of Si02. After the formation of the SiO2 surface coating layer is completed, '9.6 g of a mixed solution of tri-second alumina, isopropanol and ethanol (weight ratio: 1: 9: 90 (% by weight)) is added dropwise to the resulting mixture, and The mixture was allowed to react with each other at 75 ° C for 5 hours, thereby further forming an ai2o3 surface coating. All the above steps are carried out with stirring. After the surface coating treatment, 0.66 g of dialkyl phthalate (manufactured by 11DAP60H " Kao Corporation) is added to the liquid cross dispersion to perform water repellent treatment. The mixture containing ZnO / SiO2 composite fine particles was subjected to ultrasonic treatment at 75eC for 1 hour. Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Consumer Cooperatives (please read the precautions on the back before filling this page). After the water repellent treatment, the liquid dispersion is refluxed and dehydrated in the same manner as in Example 5. After the reflux and dehydration treatments, 117.7 g of a silicone oil (" KF96A ", manufactured by Shin-Etsu Silicone Corporation; refractive index: 1.40) was added to the above liquid dispersion, followed by stirring and mixing. Thereafter, the resulting mixture was subjected to a straight-line distillation at 80 ° C to remove ethanol, isopropanol, and water, so that the composite fine particles were phase-transferred and dispersed in a silicone oil to obtain 10% by weight of Compound microparticles with a pre-concentration of polysiloxane dispersion. After water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) using the ultra-thin section method. As a result, it was found that 211〇-78- This paper size applies Chinese National Standard (CNS) A4 ^ (210X297 mm) Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ^ 434 0 2 7 A7-^ _ __B7__ 5. Description of the invention ( 76) Ultrafine particles (average particle size: about 0.01 micron) are dispersed in and supported by aggregates of Si02 ultrafine particles (average particle size: about 0.01 micron). In other words, the composite microparticles are Zn0 / Si02 composite microparticles; matrix particles are Si02 particle aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1_46; and their daughter particles are ZnO particles, which have a band gap energy of about 3.2 eV and about 1.99 Index of refraction The content of the composite fine particles is about 5.9% by volume, which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, wherein the particle density of SiO2 and ZnO is 2.27 g / cubic, respectively. Cm and 5.78 g / cm3. The refractive index of the composite microparticles is about 1.49, which is calculated from the amount of daughter particles in the composite microparticles. Incidentally, it is dispersed in and supported by the matrix particle aggregates. 'The amount of daughter particles excluding the SiO 2 coating portion was about 9.6% by volume. After the coating was treated, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain an ethanol-containing composite fine particle cake. After that, the particle size of the composite fine particles before the water-repellent treatment was dispersed in water and the laser-Doppler type particle size analyzer (" DLS_700 " 'OTSUKA ELECTRONICS CO ., LTD.) Its particle size was measured. The average particle size was measured to be about 0,08 microns in volume. The compound obtained from the composite fine particle cake containing ethanol before water repellent treatment was obtained. The fine particles are diluted in white petrolatum and the composite fine particles before and after the water treatment are dispersed in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of the pre-particles in the mixture containing the white petrolatum and the composite fine particles is 1 % By weight. After that, proceed in the same way as in Example 1 _____- 79 -___ This paper size is applicable to China National Standards of Standards (CNS) Μ Appearance (210X297);

Id --- 5 ------------— / 求-(Please read the notes on the back before filling in this page) Order 434027 at Β7 Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (77) Determination of color change. The above shows that no color change occurs in white vaseline, and the catalytic activity in the obtained composite fine particles has been substantially suppressed. After diluting 0.4 g of the polysilicone oil dispersion liquid thus obtained with 46 g of polyarsenic oil ("KP96A" used above), the light transmittance of the obtained liquid dispersion was measured in the same manner as in Example i. The results are shown in Fig. 9. In this sample, the transmittance of the 'composite microparticles' in the ultraviolet region A, ultraviolet region B, and ultraviolet region C of wavelengths not longer than 350 nm is substantially equal to. %. Conversely, 'the composite microparticles exhibited high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm, and the light transmittance was 30% at 400 nm' and at 800 nm The meter is 93%. Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 10 0 366.5 g of silica sol (" ST-C ", made by Nissan Chemical 111 <! 1 ^ | 4«, 1 ^ < 1 .; 5 2 concentration: 20.5% by weight) and 39.9 grams of oxidized "ultrafine particles (" IT-S, ' , Manufactured by Idemitsu Kosan Co., Ltd .; amorphous-type) mixed. Water was added to this mixture to make up to a volume of one liter ' To the starter liquid mixture. In particular, the concentrations of SiO2 and Ti〇2 in the starter liquid mixture were 1.25 mol / L and 0.5 mol / L, respectively, and the above-mentioned starter liquid The amount of the daughter particle / matrix particle mixture in the mixture was about 11% by weight. The above-mentioned starting material solution was prepared using a disperser (" BIOMIXER "'made by Nippon Seiki Co., Ltd.) at 15,000. r, pm _ -80- This paper is a standard of China National Standard (CNS) A4 (21 OX 297 mm) (Please read the precautions on the back before filling this page)

h ^ —ΛΊ J— —1 u ♦ V mining-, 1T ^. _ n —-.....--—- fen 4 34 02 7 Α7 ____ Β7 Printed by the Employees' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs Preparation 5. Description of the invention (78) The dispersion rate is obtained by applying a dispersion treatment to the agitation rate to obtain a liquid dispersion containing Ti02 / Si02 composite fine particles. After the surface coating was treated, 0.70 g of diquinoline phosphonate (" DAP60H ", manufactured by Kao Corporation) was added to the liquid dispersion to perform water-repellent treatment, and the resulting solution contained Ti〇2 / Si. 2 The mixture of composite microparticles was ultrasonically treated at 75 ° C! For hours. After the water repellent treatment, the liquid dispersion was subjected to reflux and dehydration treatment in the same manner as in Example 5. After the reflux and dehydration treatment, the above liquid To the dispersion was added 125.6 g of polysiloxane (" KF96A ", manufactured by Shin-Etsu Silicone Corporation; refractive index: 1.40), followed by stirring and mixing. Thereafter, the resulting mixture was subjected to a rotary evaporator at 80 * C straight-run treatment removes ethanol, isopropanol, and water, so that the composite microparticles undergo phase transfer and are dispersed in the silicone oil to obtain a composite microparticles polycrystalline oil dispersion having a composite particle concentration of i 0% by weight. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin section method. As a result, Ti02 ultrafine particles (average particle size: about 0.0%) were found. 1 M) is dispersed in and supported by the SiO2 ultrafine particles (average particle size: about 0.01 micron). In other words, the composite fine particles are Ti02 / Si02 composite fine particles; the matrix particles are Si02 particle aggregates. , Which has a band gap energy of about 6.2 eV and a refractive index of about 1.46; and its daughter particles are Ti02 particles, which have a band gap energy of about 3.4 eV and a refractive index of about 2.52. The daughter particles are in the above composite particles. The content is about 15.1% by volume, which is based on the composition ratio of each particle in the starting material liquid mixture and S i 〇 2 -81-This paper size applies the Chinese Standards (CNS) 2 丨 0X297 mm) ( Please read the notes on the back before filling out this page) 4 Orders (-h LT · Seal of the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, Seal 434027 ^ A7 ________ B7 V. Description of the invention (79) Calculated by coating amount, The particle density of 8 丨 〇2 and Ti02 is 2.27 g / cm3 and 3.84 g / cm3, respectively. The refractive index of the composite fine particles is about 1,62.量 算。 Incidentally The amount of particles in the matrix particles are dispersed in the aggregate and for its support 'S i 02 does not include the part of the coating of about 23.9% by volume

C After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain a composite fine particle cake strain containing ethanol. Thereafter, the particle size of the composite fine particles before the water-repellent treatment was disperse the composite fine particle cake containing ethanol in water and use a laser-Doppler type particle size analyzer (" 〇1 ^ · 700, ·, Manufactured by LTD.) Its particle diameter was measured. The average particle diameter was measured to be about 010 micrometers by volume. The composite fine particles before and after the water repellent treatment were dispersed in white petrolatum (Wako Pure Chemical Industries, Ltd. (Manufactured) so that the concentration of Ti02 particles in the mixture containing white petrolatum and composite fine particles is 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above shows that no white petrolatum occurs The color changes, and the catalytic activity of the obtained composite fine particles has been substantially suppressed. 0.1 g of the composite fine particle polysiloxane fluid thus obtained is diluted with 49 g of silicone oil ("KP96A " used above"). Then, the transmittance of the obtained liquid dispersion was measured in the same manner as in Example i. The results are shown in 囷 10. In the figure, the transmittance of the composite microparticles in the ultraviolet region B and the ultraviolet region C not longer than 300 nanometers is substantially equal to 0. On the contrary, the composite microparticles have a total wavelength of 400 to 800 nanometers. Display in visible light area ___-82-Zhang scale is applicable to Zhongguanjia Standard (CNS) A technique ^ (21GX297 mm) ---- ---------- \ " ---- ( Please read the notes on the back before filling out this page.) Order-Printed by the Consumers' Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs ^ 434 0 2 7- A7 ___ B7 V. Description of the invention (8〇) Extremely high light transmittance値 'has a transmittance of 43% at 400 nm and 83% at 800 nm. For this reason, the composite fine particles thus obtained have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 11 1 268.3 g of a silica sol (" ST-C ", Nissan Chemical

Manufactured by Industries, Ltd .; Si02 concentration: 20.5% by weight) and 50 · 0 g of oxidized ultrafine particles (" TTO_51 (A) ", manufactured by Ishihara Sangyo Kaisha, Ltd .; rutile type) are mixed here" Water was added to the mixture to make up to a volume of one liter to obtain a starting liquid mixture. In particular, the concentrations of § 〖02 and Ti02 in the starting liquid mixture were 0 92 mol / L and 0'63, respectively. Moore / liter, and the amount of the daughter particle / matrix particle mixture in the above-mentioned starter liquid mixture is about 11% by weight. The above-mentioned starter liquid mixture thus prepared was subjected to a dynomill (" KDL-PILOT, manufactured by Willy A. Bachofen AG) under the conditions of agitation rate of 3600 rpm and a solution / media ratio of 600 cm ^ / 1200 cm ^ for 30 minutes, repeat this process step 2 more times and A liquid dispersion containing Ti02 / Si02 ultrafine aggregates with Ti02 as daughter particles and Si02 as matrix particles was obtained. 188 g of the above liquid dispersion, 1400 g of ethanol, and 32.6 g of tetraethoxysilicon Mix and place the contents in a water bath. To 50 ° C. After the temperature of the resulting mixture reached 50 ° C, 1.56 ml of a 1N lactic acid / 600 g ethanol mixed solution was added dropwise to the liquid dispersion. After the dropwise addition was completed, the content The objects were allowed to react with each other at 50 ° C for 2 hours and 30 minutes, thereby coating the surface of the composite fine particles with SiO2. All the above steps were performed at -83- This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 〇 X 297 mm) ^^ 1- ^ Ί · II j j 1-- · t ^ —ί .1 ^ (Please read the notes on the back before filling this page)

* 1T Printed by the Consumers 'Cooperative of the Central Government Bureau of the Ministry of Economic Affairs ^ 4 34 02 7 -ί Α7 _______ Β7 V. Description of the Invention (81) "' Agitated. After the straight distillation treatment, the liquid dispersion was placed on a rotary evaporator at 75 ° C. 〇The straight-run treatment removes ethanol and water, thereby producing a liquid dispersion ten times thicker than the liquid dispersion before the straight-run treatment. Thereafter, 2782 g of isopropyl alcohol was added dropwise to the concentrated liquid dispersion with stirring. In. After the above-mentioned straight distillation treatment, the liquid dispersion was subjected to another straight distillation treatment at 75 C using a rotary evaporator to remove ethanol, isopropanol, and water, thereby producing five times as much concentration as the liquid dispersion before the straight hall treatment. Liquid dispersion. After the concentration of the liquid dispersion was completed, 0.39 ml of a mixed solution of a 4N sodium hydroxide aqueous solution and 20 g of ethanol was added to the liquid dispersion to neutralize hydrochloric acid. All the above steps were performed with stirring. While stirring the liquid dispersion obtained above, 600 g of silicone oil (WSH244 " manufactured by Toray-Dow Corning Corporation; refractive index: 1.39) was added dropwise, and mixed with the liquid dispersion. Thereafter, 0.6 g of amine-modified polysiloxane (" XF42_B〇819 ", manufactured by Toshiba smcone Corporation; molecular weight: ι〇〇〇; amine equivalent: ι 600) was added dropwise and 240 g of a mixed solution of polysiloxane (" SH244 ", used above) and mixed the mixed solution with the obtained liquid dispersion; and then the obtained liquid dispersion was subjected to a straight distillation treatment at 80 ° C using a rotary evaporator. Remove ethanol, isopropanol, and water; then, after the straight run, 24 grams of amino modified polysiloxane (" XF42-B0819 ", used above) and 36 grams of polysiloxane are added dropwise. (&Quot; SH244 ", used above) and mix the mixed solution with the liquid dispersion. The obtained liquid dispersion is subjected to a dispersion treatment with an ultrasonic disperser for one hour mi J! —It (^ n HI tn I n τ ϋ ___ (Please read the notes on the back before filling out this page) -84-This paper is A-degree compatible with the Chinese National Standard (CNS) A4 specification (210X297 male II) Printed by the Employees' Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs ^ 4 340 27 ： A7 ____B7 V. Description of the invention (82) After β The obtained mixture was subjected to straight distillation at 80 ° C to remove ethanol, isopropanol, water, and silicone oil, so that the composite fine particles were phase-transferred and dispersed in the silicone oil to obtain 35% by weight. After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain a composite fine particle cake containing ethanol. Thereafter, The particle size of the composite fine particles before the water-repellent treatment is obtained by dispersing the composite fine particle cake containing ethanol in water and using a laser-Doppler type particle size analyzer ("〇1 ^ -700 ", OTSUKA ELECTRONICS CO., LTD. (Manufactured) The particle size was measured. The average particle size was measured to be about 0.08 micrometers by volume. After water repellent treatment, a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) was used for ultra-thin breaking. The cross section of the particles was observed by surface method. As a result, it was found that Ti02 ultrafine particles (average particle size: about 0.01 micron) were dispersed in the SiO2 ultrafine particles (average particle size: about 0.01 micron) aggregate. And support it. The composite fine particles are Ti02 / Si〇2 composite fine particles; the matrix particles are S i 〇2 particle aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1.46; and their daughter particles are Ti02 particles, having about The band gap energy of 3.3 eV and the refractive index of 2.71. The content of daughter particles in the above-mentioned composite fine particles is about 22.3% by volume, which is coated according to the composition ratio of each particle in the starting liquid mixture and SiO 2 coating. The particle density of Si02 * Ti02 was 2.27 g / cm3 and 3.84 g / cm3, respectively. The refractive index of the composite fine particles was about 1.74, and the refractive index was calculated from the amount of the daughter particles in the composite fine particles. Incidentally, it is dispersed in the matrix particle aggregate and it is ________-85-This paper XJUt Caishenzhuan (CNS) A4 specification (210X297 mm) '(Please read the precautions on the back before filling this page) Packing-, 11 Λ 4340 27 ^ V. Description of the invention (83) A7 B7 Printing support from the Central Consumers' Association of the Ministry of Economic Affairs, Consumer Cooperatives, and the amount of daughter particles excluding the coating of Si02 is about 35.0% by volume. The composite fine particles before the water-repellent treatment were diluted in white petrolatum (manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of the particles of tincture in the mixture containing white petrolatum and the composite fine particles was 1 weight. After / j ^, the color change measurement was performed in the same manner as in Example 1. The above shows that no color change has occurred in white vaseline, and the catalytic activity in the obtained composite fine particles has been substantially suppressed. After diluting 0.057 g of the composite fine particle poly dream oil dispersion obtained above with 9-943 g of polysiloxane oil ("KP96A" used above), the light transmittance of the obtained liquid dispersion was estimated in the same manner as in Example 1. rate. The results are shown in Fig. 11. In the figure, the transmittance of the composite fine particles in the ultraviolet region B and the ultraviolet region C having a wavelength not longer than 300 nm is substantially equal to zero. / (^ In contrast, the composite microparticles exhibit extremely high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm. The light transmittance at 400 nm is 57%, and at 800 nm is 95%. Therefore, the composite fine particles thus obtained have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 1 2 τ i was performed in the same manner as in Example 11 〇 2 / si 〇 2 the formation of composite particles and SiO 2 surface coating treatment. After the coating step is completed, to the reaction mixture is added 039 ml of a mixed solution of 4N sodium hydroxide aqueous solution and 20 g of ethanol to neutralize hydrochloric acid. All The above steps are all carried out with stirring. 86- This paper closes the family t (CNS) A4 size from the towel (21〇x ^^ f (Please read the precautions on the back before filling this page) '' J— II Ji Order Printed by the Central Bureau of Quasi-Ministry of Economic Affairs, Shellfish Consumer Cooperatives 4 34027 < A7 _______B7 V. Description of the Invention (84) While stirring the liquid dispersion obtained above, it is added dropwise with 30 grams ** and so on. -Modified poly dream oxygen (" OS96-20 ", Kao Corporatio (made by n) / 860 g of ethanol solution and mixing the mixed solution with the liquid dispersion to perform a water repellent treatment of the Ti02 / Si02 composite particles. After the water repellent treatment, the liquid dispersion was subjected to a rotary evaporator at 75 ° C. The lower straight distillation process removes ethanol and water, thereby producing a liquid dispersion five times thicker than the liquid dispersion before the straight distillation process. While stirring the liquid dispersion obtained above, 575 grams of silicone oil is added dropwise. (SH244 " made by Toray-Dow Coming Corporation; refractive index: 1.39) and mixed with the liquid dispersion. After that, the obtained liquid dispersion was subjected to straight distillation at 80 ° C using a rotary evaporator to remove ethanol and water. The obtained liquid dispersion was dispersed and treated with a homogenizer for one hour. Thereafter, the obtained mixture was subjected to a rotary evaporator at 80 ° C: straight distillation to remove ethanol, water, and polysilicon oil, so that the composite fine particles were phase-transferred and The composite fine particle polysiloxane oil dispersion liquid having a composite fine particle concentration of 15% by weight was dispersed in polysiloxane oil. After the coating treatment, the liquid dispersion was charged in the same manner as in Example 1. The solid-liquid separation was carried out to obtain a composite fine particle cake containing ethanol. After that, the particle size of the composite fine particles before the water-repellent treatment was dispersed in water by using the laser-dubler type particle size The particle size was measured by an analyzer (" DLS-700 ", manufactured by OTSUKA ELECTRONICS CO., LTD.). The average particle size was measured to be about 0.08 micrometers by volume. After the water-repellent treatment, the cross section of the particles was observed by a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin section method. It was found that -B7 ~ _______ This paper size is in accordance with the Chinese standard for household furniture (CNS) 8 4 size (21〇 X 297 mm) (please read the precautions on the back before filling this page)

Printed by the Central Laboratories of the Ministry of Economic Affairs and Consumer Cooperatives 4340273 A7 _____B7_ 5. Description of the Invention (85) Ding 102 ultrafine particles (average particle size: about 0.01 micron) are dispersed in Si02 ultrafine particles (average particle Diameter: about 0.01 microns) and supported by the aggregates. In other words, the composite microparticles are Ti02 / Si02 composite microparticles; the matrix particles are Si02 particle aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1.46; and their pre-particles are Ti02 particles, with about 3.3 eV. Band gap energy and refractive index of about 2.71. The content of the daughter particles in the above-mentioned composite fine particles is about 22.3% by volume, which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO2, where the particle density of SiO2 * Ti02 is 2.27 respectively G / cm3 and 3.84 g / cm3. The refractive index of the composite fine particles was about 1.74, and the refractive index was calculated from the amount of the daughter particles in the composite fine particles. Incidentally, the amount of daughter particles dispersed in and supported by the matrix particle aggregates excluding the SiO 2 coating portion is about 35.0% by volume. 〇The composite fine particles before water repellent treatment are diluted in white petroleum jelly (Wako Pure (Manufactured by Chemical Industries, Ltd.) so that the concentration of Ti02 particles in a mixture containing white petrolatum and composite fine particles is 1% by weight. Thereafter, the color change measurement was performed in the same manner as in Example 1. The above results show that no color change occurs in the white petrolatum, and the catalytic activity in the obtained composite fine particles is substantially suppressed. After diluting 0.13 g of the obtained composite fine particle polysiloxane dispersion with 9,87 g of polysiloxane oil ("KP96A" used above), the liquid dispersion of the obtained liquid dispersion was estimated in the same manner as in Example 1. Light transmittance. The results are shown in Figure 12. -88-A4 size (210 X297 mm) (Please read the precautions on the back before filling in this page) -------- J —_--- ------- ^ ^ ------, 玎 -------- ^ 1 ----------------- A7 ^ 434 0 2 7 __________B7 V. Description of the invention (86) In this invention, the transmittance of the composite particles in the ultraviolet light region B and the ultraviolet light region C with a wavelength not longer than 300 nm is substantially equal to 0. On the contrary, the composite particles are in The entire visible light region with a wavelength of 400 to 800 nm shows extremely high light transmittance 値, which has a transmittance of 65% at 400 nm and 95% at 800 nm. Therefore, this system The obtained composite fine particles have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 1 3 In the same manner as in Example 11, the formation of the Ti02 / SiO2 composite particles and the surface of SiO2 were performed. To be coated After the completion of this step, a mixed solution of 0.39 ml of a 4N sodium hydroxide aqueous solution and 20 g of ethanol was added to the reaction mixture to neutralize hydrochloric acid. All the above steps were performed under agitation. While stirring the liquid dispersion obtained above, A mixed solution containing 0.6 g of polyvinylpyrrolidone (" K-30 " for pellets, manufactured by Woko Pure Chemical Industries, Ltd.) / 30 g of ethanol was added dropwise, and the mixed solution was dispersed with a liquid After the compound was blended, 3.0 g of oxazoline-modified polysiloxane (" OS96-20 ", manufactured by Kao Corporation) / 860 g of ethanol solution was added dropwise and the mixed solution was mixed with the liquid cross dispersion The water-repellent treatment of the Ti02 / Si02 composite fine particles was carried out in the other steps. The liquid rhenium dispersion thus obtained was subjected to a straight distillation treatment at 75 ° C using a rotary evaporator to remove ethanol and water, thereby generating a liquid dispersion which was lower than that before the straight distillation treatment. Five times thicker liquid dispersion. While stirring the liquid dispersion obtained above, add 575 grams of polyoxygenated oil (" SH244 ", manufactured by Toray-Dow Corning Corporation; fold -------- ----------- ---------------------------- 89 · _______-- This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) } (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs * m ^^ 1 m tn ^ n · 4 印 Printed by the Shellfish Consumer Cooperative of the Central Government Standards Bureau of the Ministry of Economy «4 34 0 2 7 'a? _____B7 V. Description of the invention (87) Emissivity: 1.39) and mixed with the liquid dispersion. Thereafter, the resulting liquid dispersion was subjected to a straight distillation treatment at 80 ° C using a rotary evaporator to remove ethanol and water. The obtained liquid mash dispersion was subjected to dispersion treatment for one hour with a homogenizer. Thereafter, the resulting mixture was subjected to straight distillation at 80 eC to remove ethanol, water, and silicone oil, so that the composite fine particles were phase-transferred and dispersed in the silicone oil to obtain 25% by weight composite fine particles. Concentration of compound fine particles silicone fluid dispersion. After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain an ethanol-containing composite fine particle cake. Thereafter, the particle size of the composite fine particles before the water-repellent treatment was disperse the composite fine particle cake containing ethanol in water and use a laser-Doppler particle size analyzer ("〇1 ^ -700", OTSUKA ELECTRONICS CO. , LTD.) Measured its particle size. The average particle size was measured to be about 0.08 microns by volume. After the water-repellent treatment, the cross section β of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by the ultra-thin surface method. As a result, T102 ultrafine particles were found (average particle diameter: about 0.01 μm). It is dispersed in and supported by the aggregates of § 102 ultrafine particles (average particle size: about 0.01 microns). In other words, 'the composite fine particles are Ti02 / Si02 composite fine particles; the matrix particles are SiO2 particle aggregates', which has a band gap energy of about 6,2 eV and a refractive index of about 1.46; and its daughter particles are Ti 〇2 particles, having a band gap energy of about 3 3 eV and a refractive index of about 2.71. The content of the daughter particles in the above-mentioned composite fine particles is about 223% by volume, which is calculated based on the composition ratio of each particle in the starting material liquid mixture and the coating amount of SiO 2, among which Si 2 * Ti. The particle densities of 2 are _ 90-) A4 size (210X297 mm) IY—I-; --Ί HI—Ί ^ · Wave | (Please read the precautions on the back before filling this page) Order h 43402 Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (88)'-2.27 g / cm3 and 3.84 g / cm3. The refractive index of the composite fine particles was about 1.74, and the refractive index was calculated using the amount of pre-particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in and supported by the matrix particle aggregates excluding the SiO 2 coating portion is about 35.0% by volume. 0 The composite fine particles before the water-repellent treatment are dispersed in white Vaseline (Wak0

Pure Chemical Industries, Ltd.) performed a color change measurement in the same manner as in Example 1 so that the concentration of Ti02 particles in a mixture containing white petrolatum and composite fine particles was 1% by weight β. The above results show that no color change occurs in white vaseline, and the catalytic activity in the obtained composite fine particles is substantially suppressed. After diluting 0.08 g of the above-obtained composite fine particle polysiloxane oil dispersion with 9 92 g of polysiloxane oil (" KP96A " used above), the resulting liquid dispersion was estimated in the same manner as in Example 1. Liquid transmittance. The results are shown in 囷 13. In this case, the transmittance of the composite fine particles in the ultraviolet region B and the ultraviolet region c with a wavelength not longer than 300 nm is substantially equal to 0%. In contrast, the composite microparticles exhibit extremely high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm. The light transmittance is 39% at 40 nm and 8 7 at 800 nm. %. For this reason, the composite fine particles thus obtained have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 14 In the same manner as in Example 11, the formation of Ti02 / Si02 composite fine particles and the surface coating of Si02 were performed. -91-Universal Paper Standards China National Standards (CNS> (210X297 mm) (Please read the notes on the back before filling out this page)-Order Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy -434 0 2 A7 B7 V. Description of the invention (89) After the coating step is completed, 0.39 ml of a mixed solution of a 4N sodium hydroxide aqueous solution and 20 g of ethanol is added to the reaction mixture to neutralize hydrochloric acid. All the steps of simmering are performed under stirring. While stirring the liquid dispersion obtained above, 0.6 g of polyethylpyrrolidone (" K-3 0 ", for cosmetics, made by Woko Pure Chemical Industries, Ltd.) was added dropwise via 3/3 A mixed solution of 0 g of ethanol, and the mixed solution was blended with the liquid dispersion. Then, 3.0 g of oxazoline-modified polysiloxane (" OS96-20 ", manufactured by Kao Corporation) was added dropwise via / 860 g of a solution of ethanol and mixing the mixed solution with the liquid dispersion were subjected to water-repellent treatment of the Ti02 / Si02 composite fine particles. The liquid dispersion obtained above was dried at 80 ° C, thereby drying the composite fine particles The obtained powder was pulverized twice with a pulverizer (" A 1 0 ", manufactured by IKA-Labourtechnik) to obtain composite fine particles. After the coating treatment, the liquid hip dispersion was solidified in the same manner as in Example 1. Ethanol-liquid separation to obtain ethanol-containing composite fine particle cakes. Thereafter, the particle size of the composite fine particles before water repellent treatment was obtained by dispersing the ethanol-containing composite fine particle cakes in water and analyzing them by laser-Doppler type particle size analysis. (&Quot; 〇1 ^ -700 ", manufactured by OTSUKA ELECTRONICS CO., LTD.) To measure its particle size. The average particle size was measured to be about 0.08 micrometers by volume. After water repellent treatment, The transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) was used to observe the cross section of the particles by the ultra-thin section method. As a result, it was found that Ti〇2 ultrafine particles (average particle size: about 0.01 micron) were dispersed in si〇2 ultrafine particles (average particle size: about 0.01 microns) in the aggregate and supported by it. In other words, the composite fine particles are Ti〇2 / Si02 composite fine particles ·, matrix ___ 92, this paper size applies to the country of China Standard (CNS) A4 size (210X297 mm) (Please After reading the note on the back of the article, please fill in this page.) Ordered by the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative, 434027, A7 ____B7 V. Description of the invention (9 °) The particles are Si02 particle aggregates, which have about 6.2eV The chirp energy between the bands and the refractive index of about 1.46; and its daughter particles are Ti02 particles, which have a band gap energy of about 3.3 eV and a refractive index of about 2.71. The content of the daughter particles in the above-mentioned composite fine particles is about 22.3% by volume, which is calculated based on the composition ratio of each particle in the starting liquid mixture and the coating amount of S i Ο 2, among which the particle density of Si02 * Ti02 They are 2.27 grams per cubic centimeter and 3.84 grams per cubic centimeter. The refractive index of the composite fine particles was about 1.74, and the refractive index was calculated from the amount of the daughter particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in and supported by the matrix particle aggregates without including the SiO 2 coating portion is about 35.0% by volume. 〇The composite microparticles before and after the water-repellent treatment are diluted in white petrolatum ( (Made by Wako Pure Chemical Industries, Ltd.) so that the concentration of 1 ^ 02 particles in a mixture containing white petrolatum and composite fine particles is 1% by weight. Thereafter, the result of the color change measurement β in the same manner as in Example 1 showed that no color change occurred in the white petrolatum, and the catalytic activity in the obtained composite fine particles was substantially suppressed. After the water repellent treatment, when the composite fine particles are mixed with water, they exhibit strong water repellent properties. When the composite particles are combined with polysiloxane (" SH244 ",

Toray-Dow Corning Corporation; refractive index: 1.39) When mixed, the composite fine particles can be quickly dispersed in the silicone oil. 10 mg of the composite particles having the above-mentioned refractive index were pre-dispersed in 10 g of the above-mentioned polyoxygenated oil. The transmittance of the obtained liquid dispersion was examined in the same manner as in Example 丨. The results are shown in FIG. 14. • 93- This paper is applicable to the National Building Standard (CNS) and M inspection of the country (plus 7 public envy) (Please read the precautions on the back before filling this page)

4 3 4 0 2 7 Printed on A7 B7 by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (91) In the figure, the transmittance of the composite microparticles is in the ultraviolet region B with a wavelength not longer than 300 nm Is not more than 3%, and it is substantially equal to 0% in the ultraviolet region C with a wavelength not longer than 26 nm. In contrast, the composite microparticles exhibit extremely high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm, with a transmittance of 48% at 400 nm and 82 at 800 nm. %. For this reason, the composite fine particles thus obtained have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 1 5 61.0 g of silica sol (" ST-C ", manufactured by Nissan Chemical Industries, Ltd .; SiO2 concentration: 20.5 wt%) and 87.5 g of titanium oxide ultrafine particles (" MT-600B ";, Manufactured by TAYCA CORPORATION; rutile type) mixed. Water was added to this mixture to make up to a volume of one liter to obtain a starting liquid mixture. Specifically, the concentrations of Si02 * Ti02 in the starting material liquid mixture were 0.21 mol / liter and 1.10 mol / liter, respectively, and the amount of the daughter particles / matrix particle mixture in the above-mentioned starting material liquid mixture was about 10% by weight. The thus-obtained starting material liquid mixture was pretreated with a homogenizer (" T.K.-ROBOMICS ", manufactured by Tokushu Kika Kogyo Co., Ltd.) at 12000 r.p.m. for 90 minutes. After that, the agitated liquid mixture of the pretreated starting material was again stirred at 7000 rpm using a Deno Mill (" KDL-PILOT ", manufactured by Willy A. Bachofen AG) at an agitation rate of 3600 rpm, and 600 cubic meters. The solution / medium ratio, such as cm / 1200 cm, was dispersed for 8 minutes, and the process was repeated two more times to obtain Ti〇2 / Si02 -94- Paper size applies to Chinese national standard (CMS > A4 size (210X297mm) {Please read the notes on the back before filling this page) r • nf nfll · r ------ Order --- 434027 ^ A7 B7 V. Description of the invention (92) The liquid dispersion of ultrafine particle aggregates printed by Zhengong Consumer Cooperative of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs. 188 grams of the above liquid dispersion was subjected to straight distillation with a rotary evaporator to remove water, thereby The liquid dispersion was about three times thicker than the liquid dispersion before the straight distillation treatment. After that, the liquid dispersion was stirred while using a homogenizer ("T'K.-ROBOMICS", used above). Add dropwise to 1300 grams of ethanol and divide Next, the obtained liquid mash dispersion was subjected to a dispersion treatment with an ultrasonic disperser for 30 minutes. Subsequently, a mixture containing 32 6 g of tetraethoxysilane / 100 g of ethanol was added to and mixed with the above liquid dispersion, and the contents were left to stand. Heat to 50 eC in a water bath. After the temperature of the resulting mixture reaches 50, 1.56 ml of a 1N hydrochloric acid / 600 g ethanol mixed solution is added dropwise to the liquid dispersion. After the dropwise addition is completed, the mixture is placed in They were allowed to react with each other at 50 ° C for 2 hours and 30 minutes, whereby the composite fine particles were surface-coated with 802. All the above steps were performed with stirring. After the coating treatment was completed, in the reaction mixture 0.39 ml of a mixed solution of 4N sodium hydroxide aqueous solution and 20 g of ethanol was added to neutralize hydrochloric acid. All the above steps were performed with stirring. While stirring the liquid dispersion obtained above, the solution containing Ti02 / Si: 2 9 g w showerhead and modified polyoxygen (" OS96-20 ", manufactured by Kao Corporation) / 842 g of ethanol solution and mixing the mixed solution with the liquid dispersion 2 The composite fine particles were subjected to water-repellent treatment. The liquid dispersion thus obtained was subjected to a straight distillation treatment at 75 ° C using a rotary evaporator to remove ethanol and water, thereby producing about five times thicker than the liquid dispersion before the straight distillation treatment. Dispersion of liquid skull. While stirring the liquid dispersion obtained above, add 582.8 grams of poly-95 ΜΛ drops dropwise from the applicable Zhongguanjia Standard (CNS) A4 specification (2lGx297 public director (please read the note on the back first) Please fill in this page again) Clothes · Order 4 340271 A7 ___ B7 V. Description of the invention (93) Silicone oil (" SH244 ", manufactured by Toray-Dow Corning Corporation .; refractive index: 1.39), and dispersed with the liquid物 组合。 Mixing. Thereafter, the resulting liquid dispersion was subjected to a straight distillation treatment at 80 ° C using a rotary evaporator to remove ethanol and water. The obtained liquid dispersion was subjected to a dispersing treatment with a sentencer for one hour. After that, the obtained mixture was subjected to a straight distillation treatment at 80 ° C. to remove ethanol, water and silicone oil, so that the composite fine particles were phase-transferred and dispersed in the silicone oil to obtain a compound having a weight of 25% by weight. Micro particle concentration polyoxygenated oil dispersion. After the coating treatment, the liquid dispersion was subjected to solid-liquid separation in the same manner as in Example 1 to obtain a composite fine particle cake containing ethanol. Thereafter, the particle size of the composite fine particles before the water-repellent treatment was disperse the composite fine particle cake containing ethanol in water and use a laser-Doppler particle size analyzer ("〇1 ^ -700", OTSUKA ELECTRONICS CO_, LTD.) Measured its particle size. The average particle diameter was measured to be about 0.10 microns by volume. After the water-repellent treatment, the cross section of the particles was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) by an ultra-thin section method. As a result, Ti02 ultrafine particles (average particle size: about 0.01 micron) were found. ) Is dispersed in and supported by the Si02 ultrafine particles (average particle size: about 0.01 microns). In other words, the composite microparticles are Ti02 / Si02 composite microparticles; the matrix particles are Si02 particle aggregates, which have a band gap energy of about 6.2 eV and a refractive index of about 1,46; and the sub-particles are T i 0 2 particles, It has a band gap energy of about 3.3 eV and a refractive index of about 2.71. The content of the daughter particles in the above-mentioned composite fine particles is about 45.3% by volume, which is based on the composition ratio of each particle in the starting material liquid mixture and Si02 -96- This paper size applies the Chinese National Standard (CNS) A4 specification (210 × : 297 mm) • nn ϋϋ am m > —γ, 1 — I il ·, /-^ --- (Please read the note on the back before filling out this page) Installed by the Central Ministry of Economics and the Ministry of Economics and Industry, and printed by the consumer cooperation Du Qing 4340 2 7 ί Α7 __Β7 V. Description of the invention (94) Calculated by coating amount, among which the particle density of Si02 * Ti02 is 2.27 g / cm3 and 3.84, respectively G / cm3. The refractive index of the composite fine particles was about 2.03, and the refractive index was calculated from the amount of the sub-particles in the composite fine particles. Incidentally, the amount of the sub-particles dispersed in and supported by the matrix particle aggregates, excluding the Si 0 2 coating portion, was about 80.5% by volume. 〇The composite fine particles before the water-repellent treatment were diluted in white vaseline (Manufactured by Wako Pure Chemical Industries, Ltd.) so that the concentration of Ti02 particles in the mixture containing white petrolatum and composite microparticles is 1% by weight »Thereafter, the color change measurement was performed in the same manner as in Example 1. The results showed that no color change occurred in the white vaseline, and the catalytic activity in the obtained composite fine particles was substantially suppressed. After 0.046 g of the composite fine particle silicone fluid obtained above was diluted with 9.954 g of silicone oil (" KP 9 6 A ", used above), the dispersion of the obtained liquid was measured in the same manner as in Example 1. The transmittance of the object. The results are shown in Fig. 15. In the figure, the transmittance of the composite fine particles in the ultraviolet region B and the ultraviolet region C having a wavelength not longer than 300 nm is substantially equal to 0%. In contrast, the composite microparticles exhibit extremely high light transmittance in the entire visible light region at a wavelength of 400 to 800 nm, with a light transmittance of 30% at 400 nm and 81% at 800 nm. Therefore, the composite fine particles thus prepared have high light transmittance in the visible light region and high shielding ability in the ultraviolet light region. Example 16 (lotion, ___- 97- this paper XJtii towel gg home left t (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling this page)

、 1T 4340273 A7 B7 V. Description of the invention (95) Ingredients (Heavy chapter ethanol 30.0 Glycerin 5.0 · Polyethylene glycol 1500 4.0 Polyoxyethylene (20) Oil-based ether 1.0 Polyoxyethylene (30) hydrogenated castor Sesame oil 0.5 composite fine particles (manufactured in Example 2) 10.0 Uric acid 2.0 Fragrance 0.2 Balance of distilled water The SPF of the lotion having the composition shown above was measured with an SPF analyzer. As a result, its SPF was 3.0 and its PFA is 1.5. According to the discoverer, the skin did not unnaturally whiten after application of the lotion, showing that the granulated material has excellent ultraviolet shielding effect. Example 17 (Emulsion) (Please read the precautions on the back before filling in this (Page) r Jvn IF ^^^ 1 I ----- 'Yi.

、 1T i The amount of printed ingredients (% by weight) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Ester 1.0 __- 98- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) ^ 4 34 0 2 7 '* A7 B7 V. Description of invention (96) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Disperse oil containing composite fine particles (made in Example 3) 25.0 Butyl p-hydroxybenzoate 0.1 Methyl p-hydroxybenzoate 0.1 Ethanol 3.0 Glycerin 2.0 1,3-Butanediol 2.0 Perfume 0.1 The remaining amount of distilled water will have The emulsion of the composition shown above was measured for SPF 値 with an SPF analyzer. As a result, its SPF was 15.9 and its PFA was 5.0. The discoverer did not unnaturally whiten the skin after applying the lotion, showing that the cosmetic has an excellent ultraviolet shielding effect. Example 18 (emulsion) Component amount (% by weight) Dispersion oil containing composite fine particles (manufactured in Example 3) 30.0 Dimethyl oxycarbon-methyl (polyoxyethylene) oxyalkylene copolymer 3.5 Tetracyclosiloxane 20.0 Organopolysiloxane B 1,0 Squalane 2.0 Octyl dodecyl myristate 1.0 Butyl p-hydroxybenzoate 0.1 Methyl p-hydroxybenzoate 0.1 -99- ( (Please read the notes on the back before filling out this page)

This paper size is applicable to China National Standards (CNS) A4 (2I0X297mm) A7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives 4 340 27 i __B7 V. Description of the invention (97) Glycerin 5.0 Fragrance 0.1 Distilled water balance The SPF analyzer was used to measure the SPF of the emulsion having the composition shown above. As a result, the SPF was 2.5 and the PFA was 1.2. According to the discoverer, no unnatural whitening of the skin after application of this lotion 'shows that the cosmetic material has an excellent ultraviolet shielding effect. Example 19 (cream) Ingredient amount (weight stearic acid 2.0 cetyl alcohol 1.0 cholesterol 1.0 squalane 5.0 olive oil 5.0 octyl methoxycinnamate 4.0 cetyl phosphate 0.5 sorbitan-stearate 2.0 polyethylene oxide (40) Hydrogenated castor oil 0.5 composite fine particles (manufactured in Example 4) 15.0 Titanium oxide fine particles 2.0 Butyl p-hydroxybenzoate 0.1 Methyl p-hydroxybenzoate 0.1 -100- This paper size applies to Chinese national standards ( CNS) A4 specification (210X297mm) {Please read the notes on the back before filling in this page)

^ 4 34027 ^ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (98) Glycerin 10.0 L-Arginine 0.3 Fragrance 0.1 Distilled water The cream with the composition shown above was measured with an SPF analyzer Its SPF 値. As a result, its SPF was 18.5 and its PFA was 7.2. It was found that there was no unnatural whitening of the skin after applying the milky green, showing that the pellets had an excellent ultraviolet shielding effect. Example 20 (Milk sound) Composition (weight of dispersion oil containing composite fine particles (manufactured in Example 4) 20.0 Dimethyloctane-methyl (polyoxyethylene) -menoxane copolymer 4.0 Methyl poly Siloxane (6 cSt) 5.0 p-methoxymyristate 2-ethylhexyl ester 3.0 4-methoxy-4'-tert-butylbenzylmethane 2.0 octamethyltetracyclosiloxane 10.0 Squalane 2.0 Octyldodecyl myristate 1.0 Magnesium sulfate 0.5 Butyl p-hydroxybenzoate 0.1 Methyl p-hydroxybenzoate 0.1 Glycerin 6.0 -101-This paper size applies to China National Standard (CNS) A4 (210X297mm) (Please read the notes on the back first and fill in this page)

M34 0 2 7 f A7 _____B7 V. Description of the invention (diglycerol 2.0 polymethylsilsesquioxane powder 4.0 fragrance 0.1 remaining amount of distilled water The SPF analyzer with the composition shown above is used to measure its SPF 値. As a result, its SPF was 23.0 and its PFA was 12.2. According to the discoverer, there was no unnatural whitening of the skin after application of the cream, showing that the cosmetic material has an excellent ultraviolet shielding effect. Example 2 1 (Aerosol cosmetic) Ingredients Triclosan Hydroxylated aluminized talc composite particles (manufactured in Example 2) Propellant dose of isopropyl myristate (wt%) 0.01 1.5 1.0 5.0 2.0 0.2 Balance (please (Please read the notes on the back before filling this page) -1 n SI · Order Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, will print the SPF of an aerosol cosmetic with the above composition using an SPF analyzer. As a result, its SPF was 1.4 and its PFA was 1.2. In addition, it has been found to have excellent UV shielding effects. Example 22 (Foundation, -102- This paper is used for Chinese paper kneading (CNS), Yasaki (210X297 mm) 434027 * A7 __B7 V. Description of the invention (100) Composition amount (% by weight)) ⑴ Composite fine particles (implementation (Made in Example 3) 10.0 ⑵ Mica balance treated with fluorine compound (* 1) (3) Talc 20.0 treated with fluorine compound (* 1), ⑷ Oxidation treated with fluorine compound (* 1) — 8.0 (5) Iron oxide (red, yellow, black) treated with a fluorine compound (* 1) 3.0 ⑹ 锌 Fine zinc oxide particles treated with a fluorine compound (* 1) titanium oxide particles treated with a fluorine compound (* 1) (average particle size: 35 nm) 2.0 1.0 氟 Fluoride treated (* 1) nylon powder 10.0 (9) fluorinated polysiloxane (10cSt) 4.0 (10) perfluoropolyether (`` FOMBLINHC-04 ", AUSIMONTCO. (Manufactured) 8.0 (11) hydrogenated oil (Synchrowax) 1.0 (12) octyl methoxycinnamate 1.0 (13) preservatives, fragrances. 1.0 Mu Um Fung 9) {本 幸 幸 氺 (Please read the precautions on the back first (Fill in this page again.) Printed by the Consumer Consumption Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (* 1): This treatment uses 2% by weight of perfluoroalkylethyl Phosphate phosphate coating. Ingredients (1) to (8) are blended in a Henschel mixer. Ingredients (9) to (13) are blended and heated at 80 ° C beforehand, It is added to the mixture of ingredients (1) to (8). The obtained mixture is pulverized with a pulverizer. A certain amount of pulverized product is placed on a metal plate and pressed with a press to obtain a foundation. The obtained foundation has a significant advantage Ultraviolet shielding effect and good -103- This paper size is applicable to Chinese National Standard (CNS) A4 (2IO × 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 434 0 2 7 j A7 B7 V. Description of the invention (101 ) Spreadability, natural feeling after application. Example 2 3 (Dual-use foundation) Ingredient amount (% by weight) Note (* 2): This treatment is coated with 2% by weight of methyl polysiloxane The ingredients (1) to (6) are blended in a Henschel mixer. The ingredients (7) to (11) are blended and heated at 80 eC in advance, and then added to the ingredients (1) to ( 6) in the mixture. Use a pulverizer to pulverize the obtained mixture. Take a certain amount of powdered product and place it in gold. Pressed on a plate and pressed with a press to obtain a pressed powder. The obtained pressed powder has a significant favorable UV shielding effect and has a good _- 104-_ This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read first (Notes on the back then fill out this page)

⑴ Composite fine particles (manufactured in Example 2) 20.0 (2) Mica balance treated with polysiloxane (* 2) ⑶ Talc treated with polysiloxane (* 2) 20.0 聚 Treated with polysiloxane (* 2) Titanium oxide 9.0 (5) Polysiloxane (* 2) iron oxide (red, yellow, black) Polysiloxane (* 2) zinc oxide particles, 4.0 ⑹ coated 30% by weight of nylon powder 8.0 甲基 methyl polysiloxane (10, 000 cSt) 0.2 ⑻ methyl polysiloxane (6 cSt) 8.0 Sync hydrogenated oil (Synchrowax) 1.0 (10) oxycinnamon Octyl Ester 2.0 (11) Preservative, fragrance 1.0 * if: φ φ φ 4 34 0 2 7 i A7 _B7 V. Description of the invention (102) Spreadability and natural feeling after application. Cream Example 24 (Powder Eyeshadow) Ingredients (% by weight) (1) Dispersion oil containing composite fine particles (manufactured in Example 5) 11.0 (2) Remainder of mica treated with phospholipid (* 3) ⑶ eggs Phospholipid-treated (* 3) titanated mica 6.0 (4) Polysilicone-treated (* 4) Pyrene 8.0 (5) Polysilicone-treated (* 4) Prussian Blue 10.0 (6) Poly Silica-treated (* 4) iron oxide (red, yellow 'black) 2,0 ⑺Spherical polysilicone resin powder (" TOSPEARL 145 ", manufactured by Toshiba J〇 Silicone Corporation) (8) Malic acid Diisostearyl ester 3,0 (9) Hydrogenated oil (Synchrowax) 0.5 (10) Vaseline 1.0 (11) Preservatives, fragrance 1.0 Umbrella 氺 φApplication 本 (Please read the precautions on the back before filling in this Page) Printed by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (* 3): This treatment is performed by coating with 5% by weight of soybean lecithin. (* 4) This treatment is performed by coating with 2% by weight of methyl hydrogen polysiloxane. Ingredients (1) to (7) were blended in a Henschel mixer. Ingredients (8) to (1 1), which were previously blended and heated at 80X, were added to the ingredients (1) to (7); The obtained mixture was pulverized with a pulverizer. Take a certain amount of pulverized product -105- This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 434027 ί Α7 Β7 Five inventions description (103) is placed on a metal plate and pressed with a press Gets powdery eyeshadow. The obtained powdery eyeshadow has a significantly advantageous ultraviolet light shielding effect, has good spreadability, and gives a good color to the skin. Example 25 (emulsion 剞 skin γ component amount (% by weight)) 复合 dispersion oil containing composite fine particles (manufactured in Example 7) 25.0 (2) polysiloxane treated (* 5) titanium oxide 3.0 (3) polymer Silica-treated (* 5) iron oxide (red, yellow, black) 1.5 (4) Polysilica-treated (* 5) zinc oxide fine particles 3.0 (5) Dimethylcyclopolysiloxane 10.0 ⑹ A Octyl oxycinnamate 2.0 ⑺ Dimethyl oxalate · methyl polyoxyethylammonium-menoxane copolymer 1.0 ⑻ Glycerin 2.0 ⑼ Ethanol 10.0 (10) Distilled water * * * * * Balance (please read the first Please fill in this page again.) Printed by the Behr Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (* 5): This treatment is carried out by coating with 2% by weight of methyl argon polysiloxane. Ingredients (1) To (4) and blend in a Henschel mixer. Blend ingredients (5) to (7) separately, and add the mixture containing ingredients (1) to (4) first to ingredient (5) Into the mixture of (7) and disperse the obtained mixture with a stirrer. The mixture containing ingredients (8) to (10) is stirred for 30 minutes period -106 This paper size applies the Chinese standard ( CNS) M specification (2 〖〇χ297mm） ^ ------- ir ------ ^ --------- 4 34 0 2 7-! A7 B7 V. Description of the invention (104) was gradually added to the above dispersion mixture. Then, the obtained mixture containing all the ingredients listed above was stirred with a homomixer for 10 minutes to emulsify. After defoaming the obtained emulsion, it was filled into a bottle to obtain an emulsion-type bottom. The obtained emulsion base has a significant favorable UV shielding effect and has good spreadability and natural feeling after application. Example 26 (Lipstick) Ingredient content (% by weight) ⑴ Dispersion oil containing composite fine particles (Example 8 Produced) 11.0 (2) Silicone-treated (* 6) Pigment Red 57-1 1.0 (3) Silicone-treated (* 6) Pigment Red 57 2.0 ⑷ Silicone-treated (* 6) ) Acid Yellow 23 Aluminum Lake 1.0 (5) Silicone treated (* 6) Titanium oxide 1.0 蜡 Paraffin wax 5.0 (7) Candela wax 10.0 (8) Palm wax 9.0 (9) Isopalmitate Propyl ester 20.0 (10) Isonononyl isononanoate 15.0 (11) Isostearyl malonate 20.0 (12) Methyl polysiloxane (1000 cSt) 5.0 Fung + Fortunately fortunate Shen Fengxing Note (* 6): This treatment is performed by using 2% by weight of Methyl hydrogen polysiloxane coating. -107- This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) (Please read the precautions on the back before filling this page). Order Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards

43402TU A7 Printed by the Central Bureau of Standards of the Ministry of Economy—Industrial and Consumer Cooperatives ____B7_ V. Description of the invention (1G5) The ingredients (1) to (12) are heated to 80 Ό and blended to obtain a homogeneous mixture. 30 ° C temperature. After the cooling mixture is fully blended with a three-roller, it is heated to 80 ° C. The resulting mixture was washed into a mold, and then cooled and solidified to obtain a lipstick. The resulting lipstick has a significantly advantageous UV-shielding effect and has good spreadability ' thus providing good coloration to the lips. Incidentally, the oil used in the composite fine particle-containing dispersion oil prepared in Example 8 was changed from a silicone oil to an ester oil (diisostearyl malate: " COSMOL 222 ", The Nisshin Oil Mills, Ltd.), the same level of UV shielding effect can be obtained. In the following examples and comparative examples, the following five ether-modified polysiloxanes are used, but the ether-modified polysiloxanes of the present invention are not limited to their β (i) ether-modified polysiloxanes: General formula (3) The dimethylsiloxanes-methyl (polyoxyethylene) silane copolymers shown in the table, but the limitation is that both Rii and RH are methyl; Rl3 is H (0C3H6) b (0C2H4) a0 (CH2 ) p-, where " a " is a number from 7 to 15 '" b " is equal to 0, and "p" is equal to 3; " m, is a number from 50 to 100; and "η" is 1 Numbers up to 5. (ii) Ether modified polysiloxane B: Dimethylsilane-fluorenyl (polyoxyethylene) silicone copolymer shown in the general formula (3), but the limitation is that both Rli and Rl2 are shown Methyl; Ri3 means H (〇C3H6) b (〇C2H4) aO (CH2) p-, where " a " is a number from 2 to 5 '" b " equals 0' and "p" equals 3; & quot m ”is a number from 20 to 30; and " η " is a number from 2 to 5. (Please read the notes on the back before filling this page)-^ ϋ— SI I -I— ^^ ^ 1 n ^ l n < nn ^ —. Order

K -108- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (2I × 297mm) 434027 ', Central Polytechnical Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Printed Poly A7 B7 V. Description of the invention (106) ~ s -(iii) Ether-modified polysiloxane C: dimethylsilane-methyl (polyoxyethylfluorene) siloxane copolymer represented by the general formula (3), but the restrictions are 11 and 12 Both represent methyl; R! 3 shows H (OC3H6) b (〇c2H4) a〇 (CH2) p- 'where "a" is equal to 0' " b " is a number from 7 to 13 'and, p ”Is equal to 3 ;, m” is a number from 4 to 10; and “n” is a number from 1 to 6. (iv) Ether-modified polysiloxane D:

The lauryl methyl polysiloxane copolyol represented by the general formula (4), wherein the methyl group is represented; R22 is dodecyl; Rn is represented by (OC2H4) q (〇C3H6V〇H, where "q " is 10 to 30 "Quote" is a number from 10 to 30, Q represents trimethylene; ttx "is equal to" y ", a number from 30 to 70; and" Z "is a number from 1 to 6 (v ) Ether modified polysiloxane E: Polyglyceryl ether-modified polysiloxane, which is represented by the general formula (5), but the limitation is that at least one of R34 has -A-〇CH2CH (OR41) CH2 〇 R42 'where A' represents ciih23; and R41 and R42 both represent hydrogen atoms, " s " and " t " are numbers whose sum is equal to 60; "u" is equal to 40. -109- 本Paper size is applicable to China National Standard (CNS) A4 (210 > < 297 public shame) (Please read the precautions on the back before filling in this page}

-434 0 2 7-A7 B7 V. Description of the invention (107) Example 27 (emulsion) Ingredient amount (% by weight) ⑴ Cetyl alcohol 1.0 (2) Squalane 2.0 (3) Schmond wood oil 4.0 (4 ) Octyl cinnamate 4.0 (5) Polyoxyethylene (10) hydrogenated castor oil 1.0 ⑹ Sorbitan-stearate 1.0 ⑺ Dispersion oil containing composite microparticles (made in Example 12) 25.0 ⑻- Butyl hydroxybenzoate 0.1 (9) Methyl para-hydroxybenzoate 0.1 (10) Ethanol 3.0 (11) Glycerol 4.0 (12) Flavor 0.05 (13) Remaining distilled water (Please read the precautions on the back before filling this page ) Printed by the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China—Industrial and Consumer Cooperatives. Measure the SPF 値 of the emulsion with the composition shown above with an SPF analyzer. As a result, its SPF was 15.9 and its PFA was 6.2. It was found that after applying the lotion, the pimples did not unnaturally whiten, showing that the cosmetic material had an excellent ultraviolet shielding effect. -110- This paper size applies to national standards (CNS > A4 size (210X297 mm) 4 34027 ^ A7 _ B7 V. Description of the invention (1Q8) Example 28 (cream) Ingredient amount (weight (1) whale Alcohol 1.0 (2) Stearic acid 2.0 (3) Cholesterol 1.0 (4) Squalane 5.0 (5) Shimond oil 4.0 (6) Octyl methoxycinnamate 4.0 (7) Polyoxyethylammonium (40) Hydrogenated Castor oil 1.0 ⑻ Sorbitan-stearate 2.0 (9) Disperse oil containing composite particles (manufactured in Example 13) 15.0 (10) Butyl p-hydroxybenzoate 0.1 (11) P-acrylic acid Methyl formate 0.1 (12) Ethanol 3.0 (13) Glycerin 10.0 (14) Fragrance 0.05 (15) Distilled water balance Central Laboratories Bureau of the Ministry of Economic Affairs Employee Consumption Cooperative Print The cream with the composition shown above was measured with an SPF analyzer Its SPF 値. As a result, its SPF was I5.7 and its PFA was 6.3. According to the discoverer, the skin did not have unnatural whitening after the cream was applied, showing that the pellets had an excellent ultraviolet shielding effect. -111-本Paper size applies Chinese National Standard (CNS) A4 specification (210X 297 males) (Please read the precautions on the back before filling this page)

434 0 2 7 i A7 B7 V. Description of the invention (1Q9) Example 2 9 (emulsion type bottom) Composition amount (% by weight) ⑴ Dispersion oil containing composite fine particles (made in Example 13) 25.0 聚 Polysiloxane treatment (* 7) titanium oxide 3.0 (3) polysiloxane (* 7) iron oxide (red, yellow, black) 1.5 ⑷ polysiloxane (* 7) zinc oxide microparticles 3.0 (5) Dimethyl cyclopolysiloxane 10.0 辛 Octyl methoxycinnamate 2.0 ⑺ Dimethyl oxyoxane-methyl polyoxyethylene-second oxane copolymer 1.0 Glycerin 2.0 (9) Ethanol 10.0 (10) Distilled water balance Feng * ben (Please read the notes on the back before filling this page) Note (* 7): This treatment is performed by coating with 2% by weight of methyl polysiloxane. The emulsion base was evaluated for SPF and PFA in the same manner as in Example 1. As a result, when Example 1 was compared, it was possible to achieve substantially the same or higher level of ultraviolet shielding ability. Printed by the Bureau of Specimen Cooperative Consumption, Du-printing -112 This paper size is free to use Chinese National Standards (CNS) M specifications (210X297 mm) ^ 434027 ^ A7 __B7 V. Description of the invention (11Q) Example 30 (lip Fen) Ingredients (% by weight) (1) Dispersing oil containing composite particles (manufactured in Example 13) 11.0 (2) Silicone treated (* 8) pigment red 57-1 1.0 (3) Silicone-treated (* 8) pigment red 57 2.0 ⑷ Silicone-treated (* 8) acid yellow 23 aluminum lake 1.0 (5) Silicone-treated (* 8) titanium oxide 1.0 vermiculite蠘 5.0 ⑺ Candira 蠛 10.0 ⑻ Cotton Creep 9.0 (9) Isopropyl Isopalmitate ~ 20.0 (10) Isononyl Isononanoate 15.0 (11) Isostearyl Malate 20.0 (12) A Polysiloxane (iOOOcSt) 5.0 {Please read the notes on the back before filling this page} Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (* 8): This treatment uses 2% by weight of methyl hydrogen polymer. Silane coating was performed. The upper lipstick was evaluated for SPF and PFA in the same manner as in Example 1. As a result, when Example 1 was compared, it was possible to achieve substantially the same or a higher level of ultraviolet shielding ability. -113- This paper size is applicable to Chinese national sample rate (CNS > A4 size (210X297mm) 4340 2 7 i A7 B7 V. Description of the invention (111) Example 31 1 (water-in-oil cream) % By weight) 的 dispersing oil containing composite particles (made in Example 13) 25.0 醚 ether modified polysiloxane A ("SH-3775C", manufactured by Toray-Dow Coming) 2.0 ⑶ β-methyl-branched Isostearyl Glycerol 2.0 ⑷ Methyl Polysiloxane (6cSt) 5.0 (5) p-methoxycinnamic acid 2-ethylhexyl 3.0 镁 Magnesium sulfate 0.5 ⑺ Glycerin 5.0 丁 p-Hydroxybenzoate Ester 0.1 (9) Methyl p-hydroxybenzoate 0.1 (10) Fragrance 0.05 (11) Residual amount of distilled water The SPF analyzer of the cream having the composition shown above was measured for its SPF. "Result, its SPF is 19.6 and its PF A is 9.2. According to the discoverer, there is no unnatural whitening of the skin after the cream is applied, showing that the cosmetic has excellent UV shielding effect. {Please read the precautions on the back before filling in this 1) Set the central standard of the Ministry of Economy Bureau Consumer Consumption Cooperatives Printed. ΛΛά. This paper size applies to Chinese national standards (CNS > A4 specification (210 × 297 gigabytes) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 43402 7 A7 __B7 V. Description of the invention (112) Example 3 2 (Water-in-oil emulsion) Ingredient content (% by weight) ⑴ Compound Microparticle dispersion oil (manufactured in Example 13) 25.0 (2) Ether modified polyphenylene oxide C (" FZ-2110C ", manufactured by Nippon Unicar) 1.5 (3) Ether modified polysiloxane B (" KF -6015 ", manufactured by Shin-Etsu Silicone) 1.5 (4) ether modified polysiloxane (" DCQ2-2500 ", manufactured by Toray-Dow Coming) 1.0 (5) fluorenyl polysiloxane (6cSt) 5.0 ⑹ Decamethylcyclopentasiloxane 5.0 p-methoxycinnamate 2-ethylhexyl 3.0 酯 Squalane 2.0 (9) Glycerin 3.0 (10) Butyl p-hydroxybenzoate 0.1 (11) p- Methyl phenyl benzoate 0.1 (12) Fragrance 0.05 (13) The remaining amount of distilled water The S PF 组成 of the emulsion having the composition shown above was measured with an S PF analyzer. As a result, its SPF was 19.2 and its PFA It was 8.7. It was found that after applying the lotion, the skin was not unnaturally whitened, showing that the cosmetic had an excellent ultraviolet shielding effect. (谙 Please read the precautions on the back before filling this page) -115- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy -434027 · A7 ____B7 5 Explanation of the invention (113) Example 33 3 (water-in-oil cream) Ingredient content (% by weight) 复合 Dispersion oil containing composite fine particles (manufactured in Example 12) 20.0 (2) Ether-modified polysiloxane E 1.5 (3) ether modified polysiloxane B ("KF-6015ft, manufactured by Shin-Etsu Silicone) 0.5 (4) methyl polysiloxane (6cSt) 5.0 (5) decadecyl cyclopentasiloxane 5.0 ⑹ 2-Ethylhexyl p-methoxycinnamate 3.0 (7) 4-methoxytributylbenzoylmethane 2.0 ⑻ Squalane 2.0 (9) Magnesium sulfate 0.5 (10) Glycerin 5.0 (11 ) Butyl p-hydroxybenzoate 0.1 (12) Methyl p-hydroxybenzoate 0.1 (13) Perfume 0.05 (14) Balance of distilled water The SPF 値 of the cream with the composition shown above was measured with an SPF analyzer. Results , Its SPF is 15.8 and its PFA is 10.2. After applying the cream, it was found that the skin was not unnaturally whitened, showing that the cosmetic had excellent UV Shading effect (Please read the precautions on the back before filling this page) -116- This paper is fully compliant with China National Standard (CNS) A4 (210X297 mm) 4 34 0 2 7 A7 B7 V. Description of the invention (114 ) Example 34 4 (water-in-oil emulsion) Ingredient content (% by weight) 分散 Dispersion oil containing composite fine particles (made in Example 12) 5.0 (2) Ether modified polysiloxane B (" KF-6015 ", Manufactured by Shin-Etsu Silicone) 0.5 (3) ether modified polysiloxane (" SH-3775C ", manufactured by Toray-Dow Coming) 1.0 ⑷ methyl polysiloxane (6cSt) 5.0 (5) Decamethylcyclopentasiloxane 5.0 ⑹ 4-methoxy-1-tert-butylbenzylidenemethane 2.0 (7) p-methoxycinnamic acid 2-ethylhexyl 3.0 ⑻ squalane 2.0 ( 9) Glycerin 3.0 (10) Butyl p-hydroxybenzoate 0.1 (11) Phenyl p-hydroxybenzoate 0.1 (12) Flavor 0.05 (13) Remaining distilled water (Please read the precautions on the back before filling this page ) Order

K Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The SPF analyzer of the emulsion with the composition shown above was measured with an SPF analyzer. As a result, its SPF was 14.9 and its PFA was 10.8. According to the discoverer, the skin was not unnaturally whitened after the application of the emulsion, showing that the pellets had an excellent ultraviolet shielding effect. 117- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 4 340 2 7 i A7 B7 V. Description of the invention (115) Example 35 (water-in-oil cream) Ingredient content (% by weight) (1) Composite fine particles (manufactured in Example 12) 5.0 (2) Ether modified polysiloxane A (" SH-3775C ", manufactured by Toray-Dow Corning) 2.0 (3) α-methyl-branched isomeric Stearyl glyceryl ether 2.0 ⑷ methyl polysiloxane (6cSt) 5.0 (5) p-methoxycinnamate 2-ethylhexyl 3.0 (6) magnesium sulfate 0.5 (7) glycerol 5.0 ⑻ p-hydroxyl Butyl benzoate 0.1 (9) Methyl p-hydroxybenzoate 0.1 (10) Perfume 0.05 (11) Balance of steaming water The SPF 値 of the cream having the composition shown above was measured with an SPF analyzer. As a result, the The SPF is 17.5 and its PFA is 6.9. After applying the cream, the skin was not unnaturally whitened, showing that the cosmetic has excellent UV shielding effect. (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Central Standards Bureau's Consumer Cooperatives -118- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 34 0 2 7. A7 __B7 V. Description of the invention (116) Example 36 (water-in-oil emulsion) Composition amount (% by weight) (1) Composite fine particles Produced by 12) 5.0 (2) Brewing modified polyzhen oxygen C (" FZ-2110C ", manufactured by Nippon Unicar) Ether modified polysiloxane B (" KF ~ 6015 ", manufactured by Shin-Etsu Silicone) 1.5 (3) 1.5 (4) Ether Modified Polysiloxane (" DCQ2-2500 ", manufactured by Toray-Dow Corning) 1.0 (5) Methylpolysiloxane (6cSt) 5.0 ⑹ Decamethylcyclopenta Siloxane 5.0 (7) 2-ethylhexyl p-methoxycinnamate 3.0 Squalane 2.0 (9) Glycerol 3.0 (10) Butyl p-hydroxybenzoate 0.1 (Π) Methyl p-hydroxybenzoate 0.1 (12) Flavor 0.05 (13) Balance of distilled water The SPF 蒸馏 of the emulsion having the composition shown above was measured with an SPF analyzer. As a result, its SPF was 16.8 and its PFA was 6.8. According to the discoverer, there was no unnatural whitening of the skin after application of the lotion, showing that the cosmetic material has an excellent ultraviolet shielding effect. -119- (Please read the notes on the back before filling this page)

K • rl. This paper size is in accordance with Chinese National Standard (CNS) A4 (2 丨 0X297) 漦 434027 A7 B7 V. Description of the invention (117) Example 37 (water-in-oil cream) Ingredient content (% by weight)复合 Dispersing oil containing composite fine particles (made in Example 3) 5.0 (2) Ether-modified polysiloxane E 1.5 (3) Acid-modified polyoxysilane B ("KP-6015", manufactured by Shin-Etsu Silicone ) 0.5 ⑷ methyl polysiloxane (6cSt) 5.0 (5) decamethylcyclopentasiloxane 5.0 ⑹ p-methoxycinnamic acid 2-ethylhexyl 3.0 ⑺ 4 · methoxy-4'- Tertiary butylbenzyl fluorenoxane 2.0 (8) Squalane 2.0 镁 Magnesium sulfate 0.5 (1〇) Glycerin 5.0 (11) Butyl p-hydroxybenzoate 0.1 (12) Methyl p-hydroxybenzoate 0.1 ( 13) Spices 0.05 (14) Remaining amount of distilled water (please read the precautions on the back before filling this page) Order

Printed by the K-Economy Central Standards Bureau Staff Consumer Cooperative. The cream with the composition shown above is measured for SPFF with an SPF analyzer. As a result, its 5 ?? is 18.5 and its? ? It is 9.6. According to the discoverer, there was no unnatural whitening of the skin after application of the cream, showing that the pellets had an excellent ultraviolet shielding effect. -120- This paper size is applicable to China National Standards (CNS > A4 size (210X 297mm), printed by employee consumption cooperation of the Central Standards Bureau of the Ministry of Economic Affairs, Du printed 4 34 0 2 7t: a? ____B7 V. Description of the invention (118 ) Example 3 8 (water-in-oil emulsion) Ingredient content (% by weight) 的 Dispersion oil containing composite particles (manufactured in Example 4) 5.0 (2) Ether modified polysiloxane B (" KF- 6015 ", manufactured by Shin-Etsu Silicone) 0.5 (3) Ether modified polysiloxane A ("SH-3775C ", manufactured by Toray-Dow Coming) 1.0 ⑷ Methylpolysiloxane (6eSt) 5.0 (5 ) Decamethylcyclopentasiloxane 5.0 ⑹ 4-methoxy-4'-tert-butylbenzoylmethane 2.0 ⑺ p-methoxyoxycinnamic acid 2-ethylhexyl 3.0 ⑻ squalane 2.0 ⑼ Glycerin 3.0 (10) Butyl p-hydroxybenzoate 0.1 (11) Methyl p-hydroxybenzoate 0.1 (12) Perfume 0.05 (13) Balance of distilled water The emulsion with the composition shown above was measured with an SPF analyzer SPF 値. As a result, its SPF was 18.7 and its PFA was 9.7. After applying the lotion, it was found that the skin was not unnaturally whitened, showing that the cosmetic has excellent UV shielding -121-This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 434027 A7 _B7 119 V. Description of the invention () Comparative Example 1 (Water-in-oil Cream) Ingredients (% by weight) ) ", manufactured by Ishihara Sangyo Kaisha, Ltd .; average particle size: 30 to 50 microns) 5.0 (2) acid-modified polyphenylene oxide A (" SH_3775C ", manufactured by Toray-Dow Coming) 2.0 ⑶ π-form -Branched isostearyl glyceryl ether 2.0 甲基 methyl polysiloxane (6cSt) 5.0 (5) decamethylcyclopentasiloxane 20.0 ⑹ p-methoxycinnamic acid 2-hexylhexyl 3.0 ⑺ sulfuric acid Magnesium. 0.5 ⑻ Glycerin 5.0 丁 Butyl p-hydroxybenzoate 0.1 (10) Methyl p-hydroxybenzoate 0.1 (Π) Fragrance 0.05 (12) Comparative example of distilled water balance 2 (water-in-oil cream) Ingredients (Wt%) 氧化 oxidized drinking microparticles (" TTO-51 (C) ", manufactured by Ishihara Sangyo Kaisha, Ltd .; average particle size: 10 to 30 microns) 5.0 (2) ether modified polysiloxane A (" SH-3775C ", manufactured by Tomy-Dow Coming) 2.0 ⑶ π-methyl-branched isostearyl glyceryl ether 2.0 (4) methyl polysiloxane (6cSt) 5.0 (5) Decamethylcyclopentasiloxane 20.0 -122- This paper size is applicable to China National Standard (CMS) A4 (210X297 cm) (Please read the precautions on the back before filling this page)

434 0 2 A7 B7 V. Description of the invention (120) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ⑹ p-methoxycinnamate 2-ethylhexyl 3.0 镁 magnesium sulfate 0.5 ⑻ glycerol 5.0 (9) p-hydroxyl Butyl benzoate 0.1 (10) Methyl p-hydroxybenzoate 0.1 (11) Perfume 0.05 (12) Balance of distilled water Comparative Example 3 (water-in-oil emulsion) Ingredient content (% by weight) ⑴ Titanium oxide fine particles ("TTO -55 (C) ", manufactured by Ishihara Sangyo Kaishi Ltd .; average particle size: 30 to 50 microns) 5.0 (2) ether modified polysilicone B (" KF-6015", manufactured by Shin-Etsu Silicone) 0.5 ( 3) Ether Modified Polysiloxane (" SH-3775C ", manufactured by Toray-Dow Corning) 1.0 (4) Methylpolysiloxane (6cSt) 5.0 (5) Decamethylcyclopentasiloxane 5.0 ⑹ 4-methoxy-4'-tert-butylbenzylidene methane 2.0 ⑺ p-methoxycinnamic acid 2-ethylhexyl 3.0 (8) squalane 2.0 (9) glycerol 3.0 (10) pair -Butyl hydroxybenzoate 0.1 (11) Methyl p-hydroxybenzoate 0.1 (12) Flavor 0.05 (13) Remaining amount of distilled water (Please read the precautions on the back before filling this page) Order k! 123 · This paper Standards apply to China National Standards (CNS) A4 ^ grid (2 〖0X29? Mm） \ 34027 * __B7 121 V. Description of the invention () Comparative example 4 (water-in-oil emulsion) A7 composition amount (% by weight) 氧化 oxidation Titanium microparticles (" TTO-51 (C) ", manufactured by Ishihara Sangyo Kaisha ^ Ltd; average particle size: 10 to 30 microns) 5.0 (2) Ether-modified polysiloxane B (" KF-6015 ", Shin- (Made by Etsu Silicone) 0.5 (3) ether modified polysiloxane (" SH-3775C ", manufactured by Toray-Dow Coming) 1.0 (4) fluorenyl polysiloxane (6cSt) 5.0 (5) ten Cyclopentasiloxane 5.0 ⑹ 4-methoxy-4'-tert-butylbenzylidene methane 2.0 (7) p-methoxycinnamic acid 2-ethylhexyl 3.0 鲨 squalane 2.0 ⑼ glycerol 3.0 (1〇) Butyl p-hydroxybenzoate 0.1 (11) Methyl p-hydroxybenzoate 0.1 (12) Spices 0.05 (13) The remaining amount of steaming water (please read the precautions on the back before filling this page) The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed Example 31, Comparative Example 1 and Comparative Example 2 to evaluate the ultraviolet shielding effect and apparent change before and after skin application. The results are shown in Table 1. In addition, Example 34, Comparative Example 3, and Comparative Example 4 were also evaluated for ultraviolet shielding effect and apparent change (light transmittance) before and after skin application. The results are shown in Table 2. The UV shielding effect is evaluated based on the UV shielding index and PCB 値 -124- This paper size is applicable to the Chinese National Standard (CNS) A4g (210X297 mm) 4 340271 A7 A7 * B7 Central Standard of the Ministry of Economic Affairs V. Explanation of the invention (122) r. Here, the UV shading index is calculated using a Hartley day guinea pig using the following equation. The minimum amount of UV light required to tan the cosmetic-applied skin. Ultraviolet occlusion index --------- The minimum amount of external light required to tan the un-applied skin j " In addition, use J. Soc Cosmet. Chem, Jpn. 28 (3.), Ρρ · 254-261 (1994) discloses PFB 値 by UVB method. The apparent change before and after skin application is white calibrated using a color-and-color difference meter (color-and-color difference meter " CR-310 ", manufactured by Minolta Camera Co., Ltd.), And calculate the change of color-and-color difference 値 (I / 0, a * 0, b * 0) before painting and color-and-color difference 値 (L * 1, a * 1, b * 1) after painting ( △ £ * 〇). Here, Z ^ E ^ b is a root defined according to JIS Z 8729-1980, which is calculated using the following equation:, Al * = (L * aL * 0) Δί? + = (Jb + ^-jb * 0) 125- This paper size is in accordance with Chinese solid standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling out this page) 4340271 Printed by Aberdeen Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs A7 B7____- --- ^ _ V. Description of the invention (123) Here, 1/01 * 0, 1) * 0'1 / 1, / 1, and 1) 1 are defined as follows: L · * 0: L before skin application * 値 (psychometric measurement brightness); a * 0: a * 値 before the application of the skin (the psychometric color coordinates are exhausted); b * 0: b * 値 before the application of the skin (the psychometric color coordinates 値); L · 1: L * 値 after Pi Guang application; a + 1: a * 値 after skin application; b # 1: b * 値 after skin application; In addition, the analyzer " SPF-290 " (by The Optomertics Groups) System) and measured SPF and PFA 値 according to the basic measurement techniques described in the instructions given in the attached manual. Incidentally, PFA is listed in the attached manual as "average UVA protection factor". Table 1 _ Example 31 Comparative Example 1 Comparative Example 2 SPF 19.6 19.2 7.5 PFA 9.2 8.9 3.2 Ultraviolet shielding factor 7.5 6.5 3.0 Apparent change (ΛΕΌ 0.9 7.8 2.2 Table 2 Example 34 Comparative Example 3 Comparative Example 4 SPF 14.9 15.7 7.3 PFA 10.8 11.0 4.0 UV shielding factor 6.5 6.7 2.8 Apparent change (△ £,) 0.6 7.4 1.9 _-1? R Applicable to Chinese National Standard (CNS) M specifications (210X297 mm) (Please read the note on the back before filling this page)

A7 B7 434 0 2 7u 5. Description of the invention (124) It is clear from the above results that the products obtained in the examples of the present invention have a significant high ultraviolet shielding effect and high light transmittance. Industrial applicability When dispersed in a liquid skeleton or solid medium, the composite fine particles of the present invention can show high light transmittance in the visible light region and high shielding ability in the ultraviolet light region through the scattering and absorption capabilities of the sub-particles. . In addition, although there are sub-particles with high catalytic activity inside or on the surface of the matrix particles, the surface of the composite microparticles containing sub-particles and matrix particles can be coated with inorganic particles having substantially no catalytic activity to make the sub-particles possess The catalytic activity does not cause deterioration of the dispersant or medium around the composite fine particles. In other words, the composite fine particles of the present invention are ultrafine particle composites with ultraviolet shielding ability, and the surface of the composite fine particles is coated with an inorganic substance having substantially no catalytic activity, so that the obtained composite fine particles have substantially no catalytic activity, while still retaining The inherent optical properties of the ultrafine particles, such as high light transmittance in the visible light region and high shielding ability in the ultraviolet light region, the above-mentioned properties are stably exhibited in the fineness of particles that are easy to handle. In addition, in the case where the composite fine particles of the present invention are subjected to water-repellent treatment, when they are incorporated into a water-in-oil cosmetic or an oil-in-water cosmetic, they can be stably and uniformly dispersed, making it impossible to cause granulation. Material base material deterioration. When the composite fine particles of the present invention are incorporated into a cosmetic, the obtained granules have good smoothness on the skin, excellent spreading on the skin without unevenness, and excellent light transmittance. It has no unnatural whitening, thereby having excellent ultraviolet shielding ability, and having excellent safety and stability. In addition, because the composite fine particles of the present invention have excellent light transmittance, the actual particle size does not occur. -127- This paper size is applicable to China's national kneading rate (CNS > A4 size (210X297 mm) (Please read the back Please note this page, please fill in this page) Order _ Printed by the Consumer Affairs Department of the Central Bureau of the Ministry of Economic Affairs of the People's Republic of China 4 340 2 7 ： A? __B7 _ V. Description of the invention (125) No coloration, and the composite microparticles can be formulated into cosmetic materials The degree of elasticity in medium is also high. The present invention has been described so far, however, it is obvious that it can be modified in many ways. Such changes cannot be regarded as deviating from the spirit and scope of the present invention, and all of them belong to this technology. Obviously, the modification is intended to be included in the scope of patent application later. (Please read the notes on the back before filling in this 1) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics -128- This paper size applies to Chinese national standards ( CNS) A4 size (210X297 mm)

Claims (1)

Printed by the Employees' Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs A8 B8 6. Patent Application Fanyuan 434 0 2? 85102777 Patent Application _ Chinese Patent Application Scope Amendment (Y Li I February) 戠, a kind of ultraviolet shielding composite microparticles with translucency in the visible light region, which contains: (a) Matrix particles containing aggregates composed of proto-particles having an average particle size of OO 丨 to Q 3 microns, which are formed while the protoparticles maintain their shape, and constitute a particle system of the matrix particles Selected from the group consisting of metal oxides, fluorine compounds', and mixtures thereof; and (b) daughter particles having an average particle size of 0.001 to 0 "micrometers, which are dispersed in the matrix particles and are Supporters, wherein the sub-particles have a smaller band gap energy and can absorb ultraviolet light than the particles constituting the matrix particles, and the sub-particles are selected from Ti〇2, ZnO, Ce02, SiC * Sn02, W03, BaTi03 , CaTi03, SrTi03, and their mixtures; and wherein the surface of the ultraviolet shielding composite fine particles is substantially coated with an inorganic substance selected from the group consisting of Si02, A1203 ′ and a metal oxide thereof With catalytic activity. 2- The ultraviolet shielding composite fine particles according to item 1 of the scope of the patent application, wherein the particles constituting the matrix particles have a band gap energy of 3 to 9 eV. 3. The ultraviolet shielding composite fine particles according to item 1 of the scope of the patent application, wherein the difference between the band gap energy of the particles constituting the matrix particles is not less than 0.2 eV = 4. According to the first scope of the patent application The ultraviolet shielding composite fine particles according to the item, wherein the amount of the sub particles dispersed in the matrix particles and supported by the matrix particles is 0.1 to 85% by volume. The dimensions of this paper are applicable to Chinese national standards (CNS > A4 Washing (2 丨 0X297mm) (Please read the notes on the back before filling in this page) "i: Order S 8 8 $ ABCD 434027 ^ points, application Patent Scope 5. The ultraviolet shielding composite fine particles according to item 1 of the patent application scope, wherein the average particle size of the ultraviolet shielding composite fine particles is not more than 0.5 micron. 6.-Ultraviolet shielding composite particles according to the first scope of the patent application The average refractive index of the ultraviolet shielding composite microparticles is 1.3 to 2.5. 7. The ultraviolet shielding composite microparticles according to item 1 of the patent application scope, wherein the metal oxide constituting the matrix particles is selected from the group consisting of Si02, A1203, and Among the mixtures. 8. The ultraviolet shielding composite fine particles according to item 1 of the scope of the patent application, wherein the surface of the composite fine particles has been treated with a water-repellent agent. 9. The ultraviolet shielding composite according to the scope of the application patent No. 1 Microparticles, wherein the ultraviolet shielding composite microparticles have a light transmittance of not less than 80% at a wavelength of 800 nanometers and a wavelength of 400 nanometers It has a light transmittance of not less than 20% 'and has a light transmittance of not more than 5% at at least one wavelength in the range of 3 80 nm to 300 nm. The composite microparticles are suspended in a medium having a refractive index level substantially the same as that of the composite microparticles, and measured by an ultraviolet light-visible light spectrophotometer using a spectrometer with an optical path length of 丨 millimeters. The ultraviolet shielding composite fine particles of the range i can be obtained through the following steps: (a) preparing a liquid chain mixture containing: (1) a starting material of a matrix particle, which is one or more selected from the following Forms in combination: sols and bases containing particles constituting matrix particles »2 * This paper size applies to China National Standard (CNS) A4 specification (2ΐ0χ2974 ^ ΐ-- 一 —: ---;-,- Table — < Please read the notes on the back before filling this page) * 5 * Printed by the Ministry of Economic Affairs-Β-Central Bureau of Quasi-Bureau Shellfish Consumer Cooperative 43402 7 A8 B8 C8 D8 Industrial and consumer cooperatives 'intent, patent application scope plasmid particles' The matrix particles have primary particles having an average particle size of 0.001 to 0.3 micron; and (11) a starting material of the daughter particles, which is-or a plurality of forms selected from the group consisting of: A sol and a sub-particle powder containing sub-particles, the sub-particles having primary particles having an average particle diameter of from 0.001 to 〇 丨 micron, and the liquid mixture is placed in a pulverizer and / or a high-pressure dispersion device for processing In this way, composite fine particles are prepared, in which the sub-particles and the matrix particles are aggregated together; (b) the composite fine particles obtained in step (a) are coated with an inorganic substance; (0) the inorganic substances obtained in step (b) are coated The coated composite fine particles are subjected to water-repellent treatment; and (d) the water-repellent-treated composite fine particles obtained in step (c) are dried and / or powdered. A dispersing oil agent for ultraviolet shielding composite fine particles as defined in any one of the items, which can be obtained by the following steps: (a) preparing a liquid mixture containing: (i) a starting material of a matrix particle, which is one or Many selected from the following combinations Form: a sol containing particles constituting matrix particles and a matrix particle powder 'the matrix particles have primary particles having an average particle diameter of 001 to 0.33 micrometers; and (ii) a starting material of daughter particles' which is one or more selected From the combination of the following: a sol containing sub-particles and a powder of sub-particles, the sub-particles having primary particles with an average particle size of 0.001 to 0.1 microns, -3- This paper is in accordance with China National Standards (CNS) ) Α4 wash grid (210 × 297 mm) Z;-,-7- ", exhibition-(please read the notes on the back before filling out this page),? Τ 434 0 A8 B8 C8 D8 VI. Patent Application Range and place the liquid mixture in a pulverizer and / or a high-pressure dispersing device for processing, thereby preparing composite fine particles, wherein the sub-particles and the matrix particles are aggregated together;-(b) coating with an inorganic substance The composite fine particles obtained in step (a); (c) subjecting the composite fine particles coated with an inorganic substance obtained in step (b) to water-repellent treatment; and (d ') water-repellent obtained in step (c). The treated composite fine particles are dispersed in an oil. 12. · A method for manufacturing an ultraviolet shielding composite fine particle, the ultraviolet shielding composite fine particle containing the sub particles dispersed in the matrix particles and supported by the substrate particles, and having substantially no catalytic activity but having light transmission in the visible light region It can be prepared by the following steps: Printed by the Central Standards Bureau of the Ministry of Economic Affairs and printed by another consumer cooperative-^ --- j--4-- 「「 、 东-(Please read the note on the back " item before (Fill in this page) (a) Prepare a liquid mixture containing: (丨) the starting material of the matrix particles' which is in the form of one or more selected from the group consisting of a sol and a matrix containing particles constituting the matrix particles Granular powder, the matrix particles having primary particles having an average particle diameter of 0.001 to 0.3 micrometers; and (ii) a starting material of daughter particles, which is one or more forms selected from the following combinations. Daughter particles are contained Sol and sub-particle powder, the sub-particles have primary particles with an average particle diameter of 0.001 to 0.1 micron, and the liquid mixture is processed in a pulverizer and / or a high-pressure dispersing device to prepare composite fine particles, wherein The sub-particles and the matrix particles are aggregated together; and (b) the composite fine particles obtained in step (a) are coated with an inorganic substance. 13. The method according to item 12 of the scope of patent application, which further includes, in the Steps This paper size is applicable to the Chinese National Standard (CNS) A4 standard (training X297 mm) ABCD 434027 6. After applying for the scope of patent (b): (c) Apply the inorganic substance obtained in step (b) Water-repellent treatment of the composite microparticles = 14. The method according to item 13 of the scope of patent application, which further includes, after step (c): (d) water-repellent treatment obtained in step (c) Composite fine particles drying and / or pulverizing β 15 · —A method for preparing an ultraviolet shielding composite fine particle dispersing oil agent, the ultraviolet shielding composite fine particles containing sub particles dispersed in and supported by the matrix particles, which are substantially free of Catalytically active but translucent in the visible light region, it can be prepared by the following steps: (a) Preparation of a liquid mixture 'which contains: (i) a starting material for the matrix particles, which is one or more selected from the following: Into groups Among the forms: a sol containing particles constituting a matrix particle and a matrix particle powder, the matrix particle having primary particles having an average particle diameter of 0.001 to 0.3 micron; and (ii) a starting material of the daughter particles, which is a Or multiple forms selected from the group consisting of a sol containing sub-particles and a sub-particle powder, the sub-particles having primary particles having an average particle control of 0.001 to 0.1 micron 'and placing the liquid mixture in a pulverizer And / or processing in a high-pressure dispersing device, thereby preparing composite fine particles, wherein the sub-particles and the matrix particles are aggregated together; (b) coating the composite fine particles obtained in the step with an inorganic substance; (c) pair The composite fine particles coated with the inorganic substance obtained in step (b) are subjected to water-repellent treatment; and -5-this paper size is in accordance with the Chinese National Standard (CNS) A4 (2 丨 0X297 mm), * ϊ »stupid — (Jing first read the note on the back ^, Xiang Zailou wrote this page) Order printed by the Ministry of Economic Affairs, Central Bureau of Standards, Consumer Cooperatives, printed by the Ministry of Economic Affairs, Central Samples Bureau, Consumer Cooperatives, printed 434 027 «? El C8- ----- ^ _ VI. Fan Park (d ') of step (c) is obtained by the water repellent treated composite microspheres in an oil agent. 16. A cosmetic material containing ultraviolet shielding composite fine particles as defined in any one of the claims 1 to 1 of the scope of the patent. Π.—A cosmetic containing an ultraviolet shielding composite fine particle dispersing oil agent as defined in item i 丨 of the scope of patent application. 18. The cosmetic according to item 16 of the application, wherein the amount of the ultraviolet shielding composite fine particles is 0.1 to 50% by weight. 19. The granulated material according to item 16 of the scope of patent application, which further contains an ultraviolet protection agent. 20'Cosmetics according to item 6 of the patent application park, in which the spf value measured by using the analyzer "SPF-290 " made by Optometries Group" is not less than 8, and according to JIS Z 8729-1980 ΔΕ * before and after skin application. Not higher than 3 ^ 21. Cosmetics according to item 17 of the scope of patent application, which further contain UV protection agents " Cosmetics, in which the s PF value measured by using the analyzer "SPF-290" made by The Optometries Group is not lower than 8, and the skin is not high before and after skin application according to JIS Z 8729-1980 On 3 »-6- This paper size is free to use Chinese National Standard (CNS) A4 size (210X297 mm)«. Γ ^ T--K--outfit -------- order ------ --- ^-4--V— > —V (Please read the note on the back before filling in this page)