TWI310397B - - Google Patents

Description

1310397 (1) Field of the Invention [Technical Field] The present invention relates to zinc oxide used in organic polymer compositions, plastic products, paper, cosmetics, paints, printing inks, etc., particularly containing coated ruthenium dioxide A powder having a small amount of coarse particles of zinc oxide fine particles, an organic polymer composition containing the powder, and a molded article thereof. [Prior Art] Zinc oxide, also known as zinc white, is known to be used as a white pigment since ancient times. When the particle size of such zinc oxide is refined to about 1 / 2 of the visible wavelength, the scattering effect of the zinc oxide particles is extremely small, and since zinc oxide has the effect of transmitting visible light but excellent ultraviolet absorption, it is optional. Optically absorbs the optical properties of ultraviolet light. Patent Document 1 discloses a resin molded body in which a zinc oxide fine powder of 0.1 # m or less is added to a transparent resin as such an ultraviolet absorber using zinc oxide particles. Further, in Patent Document 2 or Patent Document 3, in order to improve the weather resistance of the zinc oxide fine powder by photocatalytic action and the dispersibility in the resin, zinc oxide fine particles coated with the ruthenium compound are also disclosed. Further, Patent Document 4 discloses that a water-soluble alkali metal salt of a saturated or unsaturated monocarboxylic acid having 7 to 22 carbon atoms is added to a slurry containing a zinc oxide composition for a pigment, and is selected from the periodic table of the elements. a metal cation of Groups IB, II, III, IV, V, VIB, VIIB and VIII, and a water-soluble solution of inorganic anion-5-(2) 1310397 selected from the group consisting of nitrate ions, sulfate ions and halide ions The metal salt, the water-insoluble metal soap of the saturated or unsaturated monocarboxylic acid is formed and precipitated at the site, and the pigment is coated with the zinc oxide composition by the water-insoluble metal soap to be encapsulated and encapsulated. Further, a method of using a solvent (e.g., water, an organic solvent, etc.) in the surface treatment, a step of filtering and drying the solvent, and the like, and a surface treatment agent which is deposited during drying tends to cause unevenness or agglomeration of the powder. Therefore, this method has a drawback that it is difficult to obtain good dispersibility of the coated zinc oxide particles. On the other hand, in the use of clothing-related applications or packaging materials, applications such as transparency, weather resistance, and flexibility are required to increase, and in this case, a film or fine fiber having sufficient ultraviolet shielding energy is desired. However, the conventional zinc oxide particles are insufficiently sufficient even if the surface treatment is applied, and the effect of suppressing the photocatalytic activity or the zinc ion elution property is insufficient, and the deterioration of the organic material cannot be avoided, and the durability in actual use is insufficient. For example, polyester, polyamide or the like has a high molding temperature, and it is difficult to use an organic ultraviolet absorber. Therefore, when the zinc oxide particles of the inorganic ultraviolet absorber are blended in the composition, the resins are easily decomposed and have a property of being easily degraded by reaction with zinc ions, and a composition having practical durability cannot be obtained. . Further, in order to dye a fiber obtained by spinning a composition of a conventional zinc oxide particle, there is a problem that lead ions are insoluble in the dyeing liquid. Further, since the conventional coated zinc oxide particles are mixed with coarse particles, when the resin composition containing the same is formed, the multifilament-based fine fibers are often broken during the formation of the filaments, and perforations are formed when the extremely thin blown film is formed. The band-shaped -6-(3) 1310397 shape extension ratio cannot be improved. [Patent Document 1] Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. 5 -1. [Problem to be Solved by the Invention] The present invention provides a specific coating which is easily formed into a film or a fine fiber or the like. a powder of zinc oxide fine particles having a small amount of coarse particles, an organic polymer composition containing the powder, and a molded article thereof, and the weather resistance of the film or fine fiber is not deteriorated by photocatalytic action, and organic ultraviolet rays do not occur. The absorbent is exuded, and is excellent in durability such as washing, and has sufficient ultraviolet shielding ability. In order to achieve the above-mentioned object, the inventors of the present invention have found that the coarse particles having a particle size of 5 // m or more are contained in the above-mentioned cerium oxide-containing zinc oxide fine particles and the coarse particles are less coated. The zinc oxide powder of cerium oxide and the combination of a thermoplastic resin can be easily formed into a film which is not deteriorated by the photocatalytic action of (4) 1310397, and does not cause bleed out of the organic ultraviolet absorbing agent, and is excellent in durability such as washing. The present invention has been completed by a film or fine fiber having sufficient ultraviolet shielding energy. That is, the present invention consists of the following inventions. (1)质量质量以下。 The sulphide sulphide sulphide sulphide sulphide sulphide sulphide sulphide sulphide sulphide . (2) A zinc oxide powder containing coated cerium oxide, which is coated with cerium oxide which is coated with cerium oxide coated with cerium oxide on the surface and surface-treated with a hydrophobicity-imparting agent. A powder of zinc oxide fine particles having a coarse particle of 5 m or more is 0.1% by mass or less. (3) The zinc oxide powder containing the coated cerium oxide according to the above two items, wherein the hydrophobicity-imparting agent is one or more selected from the group consisting of anthrone oils, alkoxystanes, decane coupling agents, and higher fatty acids. The hydrophobicity imparting agent of the group of salts. (4) The zinc oxide powder containing the cerium oxide coated according to any one of the above items (3) to (3), wherein the cerium oxide film of the cerium oxide-coated zinc oxide fine particles has a thickness of 0.5 to 100 nm. (5) The zinc oxide powder containing the cerium oxide coated according to any one of the above items (1) to (4), wherein the primary particle diameter of the zinc oxide fine particles coated with cerium oxide is from 1 to 200 nm. (6) The zinc oxide powder containing the cerium oxide according to the above item (2) or (3), wherein the surface-hydrophobized coated metal oxide fine particles 1 (5) 1310397

The secondary particle diameter is 5 to 120 nm, and the ceria film thickness is C. (7) The cerium-containing zinc oxide powder according to any one of the above items (1) to (6), wherein the cerium oxide-coated cerium oxide film is adsorbed at 1150 to 1250 cm·1 and 1000 to 11 The ratio of the absorption peak intensity I (I = 11 / 12 to 1250 CHT1 absorption peak intensity, 12 is 1000 to the absorption peak intensity) is 〇 · 2 or more, and the ruthenium dioxide film is 1 · 4 3 5 or more. (8) The cerium-containing zinc oxide powder according to any one of the above items (1) to (7), wherein the photocatalytic activity measured by the oxidized tetrahydronaphthalene auto-oxidation method containing the cerium oxide is as follows. (9) The cerium-containing zinc oxide powder according to any one of the above items (1) to (8), wherein the dye-removed ABS is measured by the method of coating a cerium oxide-containing sulphide yellow (Sundetye 11 〇w) method 4 9 ο / hour) is 〇. 1 or less. (10) The cerium-containing zinc oxide powder according to any one of the above items (1) to (9), wherein the organic ultraviolet ray absorption (Δ ABS34Q) is measured by the oxidized cerium oxide-based Plasol method. /hour) is less than 0.01. (1) The zinc oxide powder of cerium oxide according to any one of the above items (1) to (10), which comprises coated cerium oxide and is measured by a p-methoxycinnamate ethylhexyl ester method. .5 to 2 5 nm with red oxide of 0 0 c ηΓ 1 coated with zinc dioxide particles; II with refractive index of 1150 1 1 00 cm·1 for coated zinc dioxide powder, coated with zinc dioxide at 60 Pa/min Powder color speed (△ coated zinc dioxide powder at a rate of decomposition rate of the coating of zinc oxide powder organic ultraviolet-9- (6) 1310397 absorbent decomposition rate of 5% or less. (12) above (1) to The zinc oxide powder coated with cerium oxide according to any one of (11), wherein the zinc oxide powder containing the cerium oxide coating contains titanium dioxide. (1 3) The coated cerium oxide according to the above (1 2) The zinc oxide powder containing 2 parts by mass to 5 parts by mass of the oxidized zinc oxide powder in 10 parts by mass of the zinc oxide. (14) The zinc oxide powder containing the coated cerium oxide according to the above item (12) or (13), Wherein at least part of the titanium dioxide is coated with cerium oxide. (15) Above (12) to The zinc oxide powder coated with cerium oxide according to any one of the above items, wherein the titanium dioxide-based one contains a crystal of a titanium-oxygen-hydrazine bond in a primary particle diameter. (16) The content of the above item (15) A zinc oxide powder coated with cerium oxide, wherein the titanium dioxide has a BET specific surface area of Am2/g, and when the SiO2 content is 6% by mass, B/A = 0.02 to 0.5. (17) The above item (15) or (16) The zinc oxide-coated zinc oxide powder having a BET specific surface area of 10 to 200 m 2 /g. (18) The oxidation of the coated cerium oxide according to any one of the above items (15) to (17) The zinc powder, wherein the primary particle diameter of the titanium dioxide is from 0.008 to 5% to 0.15 " m. (19) The cerium oxide powder coated with cerium oxide according to any one of the above items (15) to (18) Among them, 'titanium dioxide has a core -10- (7) 1310397 / shell structure' and is a structure rich in Ti〇2 phase in the core and rich in SiO2 phase in the shell. (20) Contains the above ( 1) to (19), the organic polymer group containing the cerium oxide powder coated with cerium oxide and the thermoplastic resin (21) An organic polymer composition comprising the coated cerium oxide-containing zinc oxide powder according to any one of the above items (1) to (19) and a thermoplastic resin. (22) The above (20) or The organic polymer composition of (21), wherein the thermoplastic resin is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyamine, polyester, and polycarbonate. (23) A molded article obtained by molding the organic polymer composition according to any one of the above items (20) to (22). (24) The molded article according to the above item (23), wherein the molded article is selected from the group consisting of fibers, filaments, films, ribbons, sheets, hollow bodies, and multilayer structures. (25) An article having the molded article of the above (23) or (24), which is selected from the group consisting of interior and exterior building materials, machinery, vehicle interior and exterior materials, glass products, home electric appliances, agricultural materials, electronic equipment, tools, food containers, Bathroom supplies, toilet products, furniture, clothing, weaving, non-woven fabrics, cloth products, leather products, paper products, sporting goods, bedding, containers, glasses, advertising boards, piping, wiring, metal parts, sanitary materials, automotive supplies, tents At least one of the groups of outdoor products, stockings, socks, gloves, masks and undershirts. -11 - (8) 1310397 (26) A cosmetic containing the cerium oxide powder coated with cerium oxide according to any one of the above items (1) to (19). 1质量%以下的含含。 Containing zinc oxide powder coated with cerium oxide coated with cerium oxide particles of the surface of the present invention, containing 5 /2 m or more coarse particles of 0.1% by mass or less The zinc oxide powder coated with cerium oxide is preferred. Further, the powder containing coated cerium oxide-containing zinc oxide fine particles in which the surface of the coated cerium oxide-coated zinc oxide fine particles coated with cerium oxide is further hydrophobized with a hydrophobicity-imparting agent is 5 μm or more. The cerium oxide powder containing the coated cerium oxide is preferably 5% by mass or less. The manufacturing method will be specifically described below. The cerium oxide-coated zinc oxide fine particles coated with cerium oxide on the surface of the raw material of the coated cerium oxide-containing zinc oxide powder of the present invention are not particularly limited, and can be, for example, according to International Publication No. WO098/47476. The method (hereinafter referred to as "this method") is produced. The coated cerium oxide-containing zinc oxide fine particles of the present invention contain a composition for forming a film of at least the following components: lanthanum which does not contain an organic group and a halogen, or which can produce the aforementioned precursor of citric acid, 2) water, 3) 4) organic solvent; -12- (9) 1310397 where the 'water/organic solvent ratio is the volume ratio 〇. 1 to 1 〇 range, and the cerium concentration is 0.000 1 to 5 m / liter range of cerium oxide film Preferably, the composition for formation is a coated dioxide obtained by selectively contacting the surface of the zinc oxide particles with a dense cerium oxide by contacting the raw material zinc oxide particles having a primary particle diameter of 5 to 200 nm. Zinc oxide. The cerium oxide film thus formed can be coated even if the shape of the zinc oxide particles of the substrate is complicated. Even a thin film of about 5 nm has a good coating property and a high ability to shield the photocatalytic activity. Further, since the cerium oxide film having a very small alkali metal content can be formed, the cerium oxide film does not dissolve even in a high-temperature and high-humidity environment, and the physical properties of the zinc oxide coated with cerium oxide do not change. The tannic acid used in the composition for forming a cerium oxide film of the present invention is, for example, the "tannic acid" item of the "Chemical Dictionary (Japan Kyoritsu Publishing Co., Ltd., issued on March 15, 44, 7th edition). The protoporic acid and its polymer shown below, that is, citric acid, citric acid's triterpenic acid, mesotetradecanoic acid, and the like. Tannic acid is an organic group and a halogen. To obtain the acid of the present method, for example, in a tetraalkoxy decane (S i ( 0 R ) 4 ' wherein R is a hydrocarbon group, especially an aliphatic group of C 2 ), specifically, tetramethoxy Base decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, etc. can be added to the precursor of citric acid by adding water, a base and an organic solvent, and stirring to add water. The decomposition reaction can be obtained. This method is excellent for handling and handling of easy and practical methods. Among them, tetraethoxydecane is preferred. Also, the following formula -13- (10) 1310397

XnSi(OH)4-n (wherein X is a hydrocarbon group, a halogen, hydrogen, and n is an integer of 1, 2 or 3) a compound having a hydrophobic group such as a hydrocarbon group, a halogen or hydrogen, which is produced by the present invention Before the tannic acid, the body is different. Therefore, a trialkoxyalkylnonane, a dialkoxyalkyldialkylnonane, a trialkoxyalkylnonane, a dimethoxyoxydecane or the like is not suitable as a precursor. Further, a method of adding water, a base and an organic solvent to the tetrahalogenated decane to form a water, a method of adding a base and an organic solvent to the water glass, or treating the water glass with a cation exchange resin, and adding water, a base, and an organic solvent are used. The method of obtaining a tannic acid-containing composition can be obtained. The oxydecane, the tetrahalogenated decane, and the water glass used as the raw materials are not particularly limited, and may be industrially used or generally used for the test, but those having a higher purity are suitable. In the method, the composition for forming a cerium oxide film may contain an unreacted product of the above-mentioned citric acid raw material. The amount of citric acid contained in the composition for forming a cerium oxide film is not particularly limited, and the cerium concentration is 0. 000 1 - 5 m / liter is better, 0. 001-5 Moll/L range is better. If the concentration is less than 0. 0 00 1 m / liter, the formation of cerium oxide film is extremely slow and not practical. If the concentration of cerium exceeds 5 m/d, it is not preferable to form cerium oxide particles in the composition without forming a film. The cerium concentration can be determined by the addition amount of a citric acid raw material such as tetraethoxy decane, or can be determined by analyzing the atomic absorption of the cerium oxide film forming composition by -14 - (11) 1310397. The spectrum of the measurement is 25 1 _6 nm, and the flame can be acetylene/nitrogen oxide. The water used in the composition for forming a cerium oxide film is not particularly limited. However, since water may contain foreign matter particles and impurities are mixed in the product, it is preferred to use water which removes particles by filtration or the like. The water system used in the composition for forming a cerium oxide film is preferably in a range of a water/organic solvent ratio of from 0 to 1 to 10%. If the water/organic solvent ratio is outside the above range, the film formation rate or the film formation rate may be extremely lowered. More preferably, the volume ratio of water to organic solvent is 〇.  ;! to 0. The scope of 5. If the water/organic solvent ratio is greater than the volume ratio. 1 to 〇. In the range of 5, the type of the base to be used is not particularly limited, but the water/organic solvent ratio is 0. When it is 5 or more, it is preferred to form a film using an alkali metal-free base such as ammonia, ammonium hydrogencarbonate or ammonium carbonate. In the method, the base used in the composition for forming a cerium oxide film may, for example, be an inorganic base such as ammonia, sodium hydroxide or potassium hydroxide; ammonium carbonate, ammonium hydrogencarbonate, sodium carbonate or sodium hydrogencarbonate. Inorganic alkali salts; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, pyridine, aniline, choline, tetramethylammonium hydroxide, hydrazine and other organic bases; ammonium formate, The alkali salt of an organic acid such as ammonium acetate, monomethylamine formate, dimethylamine acetate, pyridine lactate, indole acetic acid or aniline acetate is not limited thereto. Among the above, from the viewpoint of controlling the reaction rate, ammonia, ammonium hydrogencarbonate, ammonium formate, ammonium acetate, sodium carbonate, sodium hydrogencarbonate or the like is particularly preferable. In the composition for forming a cerium oxide film, one or two or more kinds of bases selected from the above group can be used in combination. -15- (12) 1310397 The purity of the base of the method is not particularly limited. Work _ can be used for the test, but it is suitable for those with higher purity. In order to increase the film formation rate of cerium oxide, it is effective to form a film. In this case, it is preferred to use a base or an organic solvent which is selected to form a temperature or a decomposition in the film. In the method, the amount of the base for forming a film is, in some cases, a small amount of about 1 m 2 / liter is added, and a large amount of about 1 mol/liter is added. However, if the amount of alkali exceeds its solubility, it is not suitable for metal oxide powder. Further, by using a metal oxide which does not contain an alkali metal as a main component and has a small alkali metal content, the ammonium oxide or ammonium hydrogencarbonate is preferred in terms of film formation rate and ease of residue removal. In the method, it is preferred that the cerium oxide film forming composition machine solvent forms a homogeneous solution with the composition, alcohols such as alcohol, propanol and pentanol; tetrahydrofuran, 1,4-acetal, acetaldehyde, etc. Aldehydes; acetone, diacetone alcohol, and methyl alcohol; and polyols such as ethylene glycol, propylene glycol, and diethylene glycol are preferably used in the viewpoint of controlling the reaction rate. One or two or more kinds of solvents selected from the above group of solvents can be used. The purity used in the composition for forming a cerium oxide film is not particularly limited. It is widely used in industrial applications or in general. [Use or general: temperature increase: it is not volatile at all.] If it is about liters of sodium carbonate, it can be made. If there is an alkali mixed with impurities in the added solid, particles can be produced. Among them, a ketone derivative such as an ether or ethyl ketone such as methanol or ethylene dioxane may be used in the case of ammonia or carbonic acid. It is preferred, especially if it is mixed with organic solvents, and the tester can be -16-(13) 1310397, but it is suitable for higher purity. For the preparation of the composition for forming a cerium oxide film, a general solution preparation method can be used. For example, a predetermined amount of a base and water are added to an organic solvent, and after stirring, tetraethoxy decane is further added and stirred, and the like, or a mixed order thereof, can form a film. From the viewpoint of controlling the reaction rate, when water is mixed with tetraethoxysilane, both of them are preferably diluted with an organic solvent. The composition for forming a cerium oxide film thus prepared is a stable composition, and does not substantially coat or precipitate before being contacted with the zinc oxide-based metal oxide particles. The cerium oxide film is selectively formed on the surface of the metal oxide particles by the contact of the composition with the metal oxide particles. Here, "selective" means that a film is formed only on the surface of a metal oxide accompanied by precipitation of cerium oxide, and since a solution does not generate a cerium oxide particle due to formation of a uniform nucleus, that is, a chemical theory The amount of cerium oxide coated metal oxide oxide film thickness and cerium oxide content is controlled. The raw material zinc oxide which is coated with the zinc oxide fine particles of ceria is not particularly limited, and may be any method. a product obtained by evaporating and oxidizing an electrogalvanized raw material metal, neutralizing an aqueous solution of zinc sulfate, zinc chloride or the like to obtain zinc hydroxide, calcining zinc carbonate, zinc sulfide, zinc oxalate or the like, or the like, or the like Mixtures are also available. Further, zinc oxide doped with a hetero atom such as Fe, Co, Al, Sn, or Sb, and a crystal containing zinc oxide as a main component and containing an element selected from the group consisting of Si, Al, Fe, Co, Zr, Ce, Sn, and Sb A mixed crystal oxide or a composite oxide of a crystalline or amorphous oxide may be used. However, in terms of controlling the secondary particle diameter, it is preferred that the aggregation is less. The primary particle diameter of the raw material zinc oxide particles used in the method is preferably -17-(14) 1310397 lnm-200 nm or more preferably 5 nm-120 nm. The secondary particle size is 〇. 5#m The following is better. In the method, the raw material zinc oxide particles are immersed in the cerium oxide film-forming composition, and the cerium oxide film is formed by selectively coating the surface of the zinc oxide particles with cerium oxide at a constant temperature. The method of forming the cerium oxide film may be a method in which the raw material zinc oxide particles are added to a composition for forming a cerium oxide film which is prepared in advance to form a cerium oxide film, or the raw material zinc oxide particles may be suspended in advance. After the solvent is added, another raw material component is added to prepare a composition for forming a cerium oxide film, and a method of forming a cerium oxide film. In other words, the order of the raw material of the film-forming composition and the raw material zinc oxide particles is not particularly limited, and the film can be formed first. In these methods, after the suspension containing the raw material zinc oxide particles, water, an organic solvent and an alkali is prepared, the tetraalkoxy decane diluted with the organic solvent is dropped thereto at a constant rate to form a denseness. A good cerium oxide film is preferred and can be constructed in a continuous step that is industrially useful. Since the cerium oxide film is grown by selectively coating the surface of the zinc oxide particles, the film formation time can be increased to increase the film thickness. Of course, when the ruthenium acid in the composition for forming a cerium oxide film is mostly consumed by forming a film, the film formation rate is lowered, and by adding citric acid equivalent to the consumption amount in sequence, the film formation speed can be continuously applied. A cerium oxide film is formed. In particular, the raw material zinc oxide particles in the composition for forming a film for which ceric acid is added in accordance with the desired thickness of the cerium oxide film are kept for a predetermined period of time to form a cerium oxide film, which consumes citric acid, and oxidizes the formed coated cerium oxide. After the zinc fine particles are taken out of the system, the composition of -18-(15) 1310397 can be continuously used for the formation of the film of the next raw material oxidized particle by adding a decanoic acid corresponding to the consumption amount, and economicality can be constructed. Continuous steps of high productivity. For example, in the case where a suspension containing a raw material of zinc oxide particles, water, an organic solvent, and a base is prepared, and a tetraalkoxy oxime diluted with an organic solvent is dropped at a certain rate, it is diluted with an organic solvent. To a tetraalkoxy decane diluent corresponding to the desired thickness of the cerium oxide film, which is dropwise consumed at a constant rate of equilibrium with the hydrolysis rate, and the 'tetraalkoxy decane is completely consumed, thereby forming a desired film thickness and being dense. The cerium oxide film is obtained by taking out the formed cerium oxide-coated zinc oxide fine particles, and obtaining a high-purity product in which unreacted tetraalkoxy decane is not left. Of course, the solvent obtained by taking out the cerium oxide microparticles coated with cerium oxide can be recycled to the next film to form a step which is economical and productive. The temperature at which the cerium oxide film is formed is not particularly limited, but is preferably in the range of 10 to 100 ° C, more preferably in the range of 20 to 50 ° C. When the temperature is high, the film forming speed is increased, but if it is too high, the composition is too high. The components in the volatilization are difficult to maintain a certain composition of the solution, and if the temperature is too low, the film formation rate is slow and not practical. The pH of the composition for forming a cerium oxide film at the time of film formation is preferably alkaline in view of the denseness of the film. Further, since the solubility of zinc oxide is also changed depending on the pH, it is preferred to adjust the pH of the composition for forming a cerium oxide film by adjusting the amount of alkali added. However, in this case, 'the hydrolysis rate of the tetraalkyl decane is also changed by the change in the amount of the base added. Therefore, it is necessary to adjust the film formation temperature or the moisture content in the film-forming composition to make the hydrolysis rate suitable. . -19- (16) 1310397 After forming a cerium oxide film on zinc oxide particles, solid-liquid separation is carried out to separate the cerium oxide-coated zinc oxide particles. The separation method may employ a general separation method such as filtration, centrifugal deposition, or centrifugal separation. The zinc oxide fine particles of the coated cerium oxide having a low moisture content can be obtained by drying after solid-liquid separation. The drying method may be a general drying method such as natural drying, warm air drying, vacuum drying, spray drying or the like. The zinc oxide particles coated with cerium oxide of the present method do not need to be specially calcined, and may be calcined after use as needed. The ceria-coated cerium oxide microparticles of the cerium oxide microparticles obtained by the method are dense and practical cerium oxide coatings. In the present method, "compact" means that the formed cerium oxide film is high-density, uniform and free of pinholes or cracks, and "practical" means that the cerium oxide is bonded to the zinc oxide of the substrate (Si- O-Zn is strong, and peeling of the film is not caused, and the physical properties of the zinc oxide coated with cerium oxide are not easily changed. The oxidized particles of the coated cerium oxide of the present method are preferably coated with cerium oxide-coated zinc oxide which is surface-treated with a hydrophobicity-imparting agent. A method of performing surface treatment by oxidizing the coated cerium oxide with a hydrophobicity-imparting agent can be carried out by a known method. The method is, for example, a method in which the cerium oxide-coated zinc oxide particles are directly hydrophobized by a dry method or a spray method. In the dry method, an organic solution containing a hydrophobicity imparting agent or a hydrophobicity imparting agent by a spray method may be added to the above-mentioned coated cerium oxide-containing ultrafine particle mixed crystal stirred by a mixer such as a V-shaped mixer or a Han-So-mixer. On the oxide particles, continue to mix and evenly adhere to the surface of the powder and dry it, and it must be heated to make it adhere firmly to -20-(17) 1310397. Further, as the spraying method, a method of spraying a hydrophobicity-imparting agent or a solution thereof onto the coated cerium oxide-doped zinc oxide particles prepared at a high temperature may be used. In the wet method, the ultrafine particle mixed crystal oxide coated with cerium oxide may be dispersed in water or an organic solvent or a mixed solvent to obtain a dispersion liquid in which a hydrophobicity-imparting agent or a solution thereof, a reaction catalyst, etc. are added, and after stirring, The method of surface treatment is carried out. In this case, the powder of the coated ceria-containing zinc oxide fine particles which is hydrophobized on the surface can be obtained by drying after solid-liquid separation. The drying method may be a general drying method such as natural drying, warm air drying, vacuum drying, spray drying or the like. The powder of the cerium oxide-coated cerium oxide microparticles or the powder of the cerium oxide-coated zinc oxide fine particles hydrophobized on the surface may cause agglomeration of particles due to drying or calcination, and a step of reducing coarse particles is necessary. The method of reducing coarse particles is preferably dry classification. For example, it is possible to perform fine classification using a spoke classifier made by Nippon Engineering Co., Ltd. Although strong pulverization such as jet honing can effectively reduce agglomerated particles, it will destroy a part of the coated cerium oxide due to pulverization, and the new surface (zinc oxide surface) will be exposed due to the pulverization of the coarse zinc oxide surface treatment product. The formability or weather resistance of the organic polymer composition is not deteriorated. Further, in the wet standing classification using a solvent, it is not preferable because re-aggregation occurs in the solid-liquid separation/drying step after classification. The hydrophobicity-imparting agent used in the method is not particularly limited, and for example, a high-fat-21 such as a wax, a higher fatty acid triglyceride, a higher fatty acid, a higher fatty acid polyvalent metal salt, or a higher aliphatic metal salt of a higher aliphatic sulfate can be used. - (18) 1310397 Acids, higher alcohols or derivatives thereof, organic fluorides such as perfluorinated or partially fluorinated higher fatty acids and higher alcohols, anthrone oils, organoalkoxydecanes, organochlorostanes And organic hydrazine compounds such as decanes. It is preferred to use a higher fatty acid polyvalent metal salt, an anthrone oil, a decane coupling agent, or an alkoxy decane. The anthrone oil used in the method is not particularly limited, and examples thereof include dimethyl polysiloxane, methyl hydrogen diene polyoxyalkylene, methylphenyl polyoxyalkylene, and cyclic polydimethylene. Base oxane. Further, it is also possible to use a modified ketone oil such as an alkyl modification, a polyether modification, an amino modification, a thiol modification, an epoxy modification, or a fluorine modification. The chlorosilane to be used in the method is not particularly limited, and examples thereof include trimethylchlorodecane, dimethyldichlorodecane, methyltrichlorodecane, methyldichlorodecane, and dimethylvinyl chloride. Methylvinyl chloride, triphenylchlorodecane, methyldiphenylchlorodecane, diphenyldichlorodecane, methylphenyldichlorodecane and phenyltrichlorodecane. The taxane used in the method is not particularly limited, and examples thereof include hexamethyldioxane, hydrazine, Ν'-bis(trimethyldecane) urea, and N-trimethyldecane acetamide. Dimethyltrimethyldecylamine, diethyltrimethyldecylamine, and trimethyldecylimidazole. The organoalkoxydecane used in the method is not particularly limited, and may, for example, be ethylene trichlorodecane, ethylene tris(/5-methoxyethoxy)decane, ethylene trimethoxynonane or ethylene triethoxylate. Baseline, r-(methacryloxypropyl)trimethoxydecane, wan-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, r-glycidoxypropyltrimethoxy -22- (19) 1310397 decane, r-glycidylpropylmethyldiethoxydecane, n-/3 (aminoethyl)r-aminopropyltrimethoxydecane, N- /3 (Aminoethyl) 7-aminopropylmethyldiethoxy chopping, aminopropyl diethoxy sand, Ν-phenyl-7'-aminopropyltrimethoxy silicate, a decane coupling agent such as r - propyl propyl trimethoxy decane and r - chloropropyl trimethoxy decane, and methyl trimethoxy decane, dimethyl dimethoxy decane, trimethyl methoxy decane, Methyl triethoxy decane, dimethyl diethoxy decane, trimethyl ethoxy decane, methyl dimethoxy decane 'methyl diethoxy decane, dimethyl ethoxy decane, two Methyl vinyl Group Silane, dimethyl vinyl ethoxy Silane, Silane phenyltrimethoxysilane, phenyltriethoxysilane Silane, diphenyl methoxy. Alkane and diphenyldiethoxydecane. Further, a perfluorinated or partially fluorinated alkoxydecane having an alkyl group can also be used. In particular, it is preferred to use an alkyl alkoxy decane represented by the following formula: Formula: R1 ( R2n ) SiX3. n wherein R1 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is an alkoxy group having 1 to 4 carbon atoms, and η is 0 to 2 integer). The amount of the hydrophobicity-imparting agent to be coated is preferably such that the hydrophobicity-imparting agent can completely coat the surface of the coated cerium oxide-coated zinc oxide particles as a raw material. The amount can be calculated by the following formula: Minimum coating amount (g) = coated cerium oxide-containing ultrafine particle mixed crystal oxide -23- (20) 1310397 mass (g) x specific surface area (m2/g) Hydrophobicity-imparting agent Minimum coverage area (m2). If the amount of the hydrophobicity-imparting agent added is too large, it is uneconomical to precipitate to the surface of the ceria-coated ultrafine-particle mixed oxide particles. The addition amount of the hydrophobicity-imparting agent is related to the specific surface area of the ultrafine-particle mixed crystal oxide particles coated with cerium oxide, and cannot be arbitrarily, in general, the coated cerium oxide ultrafine particle mixed crystal oxide particles are 0. It is preferably 1 to 30% by mass or less, more preferably 1 to 20% by mass or less. If it is 0. Below 1% by mass, it is not preferable because sufficient hydrophobicity cannot be obtained. On the other hand, if it is more than 30% by mass, sufficient hydrophobicity can be obtained, but since the content of zinc oxide per unit weight is decreased, the ultraviolet shielding energy is lowered. The cerium oxide film of the cerium oxide-coated zinc oxide particles used in the method has a thickness of 〇_5 to l〇〇nm, which is 1. 0 to 50 nm is preferred, 1. 5 to 25 nm is better. The thickness of the cerium oxide film is 0. When the thickness is 5 nm or less, sufficient photocatalytic activity concealing effect cannot be obtained, and an organic polymer composition having stability may not be obtained, and the molded body or the structure may not be preferable. Further, when it exceeds 100 nm, it is not preferable to obtain an organic polymer composition, a shaped body or a structure having sufficient ultraviolet shielding energy. The thickness of the cerium oxide film is obtained by a transmission electron microscopy. The method is coated with cerium oxide zinc oxide fine particles having a primary particle diameter of from 1 to 200 nm, more preferably from 5 to 120 nm. When the primary particle diameter falls outside the above range, the organic polymer composition, the molded body, and the structure which have high ultraviolet shielding energy may not be obtained. In addition, the "primary particle" in this method is based on the definition of the 1979 issue of Japan's Kubo-Hei-24-(21) 1310397 Lang, "Powder", 55-66. The ratio of the absorption peak intensities of the infrared absorption spectrum of the coated cerium oxide microparticles obtained by the above method from 1 15 〇 to 125 〇 cm −1 and from 1 〇〇〇 to 1100 cm·1 ( I = I 1 /1 2; 11 is the absorption peak intensity (absorbance) of 1 1 50 0 to 1 2 5 0 -1 -1, and the absorption peak intensity of 12 is 1 000 to 1 100 cm·1 minus the baseline). 2 or more, preferably 0 _ 3 or more, and most preferably 〇·4 or more. Transmission of cerium oxide film coated with cerium oxide and zinc oxide The infrared absorption spectrum can be measured by the KBr powder method. Generally, the ratio of the absorption peak intensity of the infrared absorption spectrum of the infrared absorption spectrum of 1150 to 1250 0 cm-1 and 1 000 to 1100 enT1 is obtained by calcination by a sol-gel method or the like, or a cerium oxide film obtained by a CVD method. Less than 0. 2. Therefore, it is understood that I値 generally changes the hydrophilicity and oil absorption properties of the ceria film due to calcination, chemical bonds or functional groups. The refractive index of the cerium oxide layer of the cerium oxide-coated zinc oxide particles of the method is 1. 43 5 or more is better, 1. More than 440 is better. When the refractive index is less than 1 · 4 3 5, the denseness is lowered. Further, the cerium oxide film obtained by calcination by a general sol-gel method has a refractive index of less than 1.  4 3 5, low density and not practical. Here, in general, the density of the cerium oxide film is positively correlated with the refractive index. (for example, C.  JEFFERY BRINKER, SOL-GEL SCIENCE, 5 8 1 - 5 8 3, ACADEMIC PRESS (1 990 )). In the present method, "compact" means that the formed cerium oxide film is high-density 'uniform and free of perforations or cracks, and "practical" means bonding of cerium oxide and zinc oxide substrate (Si-Ο- Ζη bond) is firm, no peeling of the film, etc., and the physical properties of the zinc oxide coated with cerium oxide are not easily changed -25- (22) 1310397 rsfc.  The refractive index is measured by using a ruthenium dioxide film formed on a tantalum wafer immersed in a composition for forming a cerium oxide film, in the case of synthesizing zinc oxide coated with cerium oxide. That is, it is believed that the same cerium oxide film as that on the zinc oxide particles is formed on the wafer. The tortuosity of the ruthenium dioxide film on the ruthenium wafer can be measured by an ellipsometer (manufactured by ULVAC, LASSER ELLIPSOMETER ESM-1A). The cerium oxide-coated zinc oxide fine particles of the present method have a photocatalytic activity (i.e., initial oxygen consumption) measured by tetrahydronaphthalene auto-oxidation method of 60 Pa/min or less, more preferably 5 ÅPa/min or less. If the photocatalytic activity measured by the tetrahydronaphthalene auto-oxidation method exceeds 60 Pa/min, sufficient photocatalytic activity inhibition effect cannot be obtained, and it may be difficult to obtain sufficient durability. The tetrahydrogen naphthalene auto-oxidation method is described in "Sui Tian Xue, Titanium Dioxide _ Physical Properties and Application Technology, Technical Newspaper, pp. 1 96-119, 1991, Japan". The measurement conditions were temperature 40 ° C, tetrahydronaphthalene 20 ml, zinc oxide 0. 0 2 g. The photocatalytic activity of the zinc oxide microparticles coated with cerium oxide according to the method is the color fading speed of the sunset yell〇w method described in the examples, the lanthanide 1789 method, and the p-methoxycinnamic acid ethyl group. Determined by the hexyl ester method. The pigment fading speed (Δ ABS49q/hour) measured by the sunset yellow method of the coated cerium oxide-containing zinc oxide particles of the method is ο. 1 or less is preferable, and 〇·〇5 or less is more preferable. If the color fading speed exceeds 〇_1 ', the photocatalytic activity -26-(23) 1310397 is insufficiently inhibited, and sometimes sufficient durability cannot be obtained. In the present method, the decomposition rate of the organic ray-absorbing agent (= 葩 1 1 7 8 9 ) of the zinc oxide fine particles coated with cerium oxide by the lanthanum oxide 1 7 8 9 is preferably 0. 02 or less, and 0_01 or less. Better. The decomposition rate of the organic ultraviolet absorber measured by the lansole 1 7 8 9 method exceeds 0. 02, the inhibitory effect on the photocatalytic activity is insufficient, and sometimes it is not preferable to obtain sufficient durability. In the method, the decomposition rate of the organic ultraviolet absorber (=p-methoxycinnamate ethylhexyl ester) measured by the p-methoxy cinnamate ethylhexyl ester method is less than 5%. Preferably, 3% or less is better. When the decomposition rate of the organic ultraviolet absorber measured by the ethylhexyl methoxy-cinnamate method exceeds 5%, the effect of suppressing the photocatalytic activity is insufficient, and sufficient durability may not be obtained. Further, the zinc oxide powder coated with ceria is used, and the content of the above coarse particles can be measured by the following method. When the sample was a powder containing cerium oxide-coated zinc oxide fine particles coated with cerium oxide on the surface, 20 g of the sample was accurately weighed and placed in 1 800 ml of room temperature pure water, and sufficiently stirred. An appropriate amount (1 〇 ml) of a dispersing agent, for example, an aqueous solution of 10% sodium hexametaphosphate was added, and the mixture was dispersed by ultrasonic waves for 10 minutes. For the ultrasonic dispersion, for example, an ultrasonic homogenizer (type US-3 00T' output power 300W, transmission cycle number 20 kHz) manufactured by Nippon Seiki Co., Ltd. can be used. Then, the obtained suspension was placed in a micro-powder classifier (type PS-80) installed in Yokohama, RI, Japan, and the mesh was a high precision micro-screen of 5/m. 27- (24) 1310397 The device's ultrasonic vibrator, electromagnetic vibrator' and suction pump are wet precision graded. After the end of the classification, the powder on the sieve is collected by washing with water and mixed with pure water in a glass container. After it was placed in a 1 1 ot drier to evaporate water, the remaining residue was collected and weighed. The ratio of the residue in the 20 g of the sample used was a coarse particle of 5 # m or more. The sample is a powder containing coated cerium oxide-containing zinc oxide fine particles which is hydrophobized by surface-treated surface of the coated cerium oxide-coated zinc oxide fine particles coated with cerium oxide. In the above classification operation, the solvent other than the dispersant can be changed by changing the water to a mixed solvent of water and methanol. After the end of the classification, the powder on the sieve was air-dried, placed in a desiccator at 110 °c, and the remaining residue was collected and weighed. The ratio of the residue in 20 g of the sample used was 5 # m or more. The powder containing the cerium oxide-coated zinc oxide fine particles obtained as above has a content of 5/z m or more of coarse particles.  1% by mass or less is preferred, and 0. 05% by mass or less is more preferable. When the content of the coarse particles of 5 / m or more is more than 0.1% by mass, for example, the amount of the ultraviolet shielding effect is substantially exhibited, and the filaments are often broken when formed into a multifilament-like fine fiber, and the extremely thin blown film is formed. Perforations are generated and the stretch forming ratio of the strip shape cannot be increased. By using the above-mentioned combination of the coated cerium oxide-containing zinc oxide powder and the thermoplastic resin, it is possible to easily form a film or filament having sufficient ultraviolet ray shielding property without being deteriorated by the photocatalytic action. The zinc oxide powder containing the cerium oxide coated according to the present invention may further contain dioxin 28-(25) 1310397 titanium. Containing titanium dioxide can further enhance the UV protection. Here, the amount of the zinc oxide is preferably 2 parts by mass to 5 parts by mass, more preferably 2 parts by mass to 5 parts by mass, and most preferably 3 parts by mass to 5 parts by mass. When titanium dioxide is mixed to increase the ultraviolet defense energy, it is preferable to contain 2 parts by mass or more of titanium oxide, and if it exceeds 5 parts by mass, the white turbidity caused by titanium dioxide is increased, which is not suitable for some uses. The titanium dioxide to be contained is preferably a titanium dioxide coated with cerium oxide coated with cerium oxide in the same manner as the above-mentioned cerium oxide coated with cerium oxide. The method for producing the titanium dioxide coated with cerium oxide is not particularly limited, and a general method can be used. Any of various manufacturing methods such as high-temperature vapor phase oxidation of TiC 14 , gas phase hydrolysis of TiCl 4 , sulfuric acid method, and chlorine method can be used. The crystal form of titanium dioxide may be any of amorphous, rutile, anatase, and Butzkit, and may be a mixture thereof. However, it is preferable that the amount of impurities is as small as possible, and it is preferable that the aggregation is small in terms of controlling the secondary particle diameter. The titanium dioxide contained may also be an ultrafine particle mixed crystal oxide containing a mixed crystal having a titanium-oxygen-germanium bond present in the primary particles. The method for producing the ultrafine particle mixed crystal oxide containing the mixed crystal of the titanium-oxygen-oxime bond in the primary particles is not particularly limited. For example, it can be produced by the method shown in International Publication No. WO 01 /5 693 0. The ultrafine particle mixed oxide containing a titanium-oxygen-deuterium bonded mixed crystal in the primary particle has a BET specific surface area of A m 2 /g, and when the SiO 2 content is B mass %, B/A is generally 0. 02 to 0. 5, to 0. 05 to 0. 3 is better. If B/A is less than 〇. 〇2, the ultrafine particle mixed crystal oxidation in the organic polymer composition -29-(26) 1310397 The dispersibility of the substance is poor, and the weather resistance of the formed body is deteriorated. If it is larger than 0 · 5 , the surface of the particle is too much covered by the S i Ο 2 phase, and the effect of improving the ultraviolet shielding energy is not good. The ultrafine particle mixed crystal containing a titanium-oxygen-deuterium-bonded mixed crystal in the primary particles has a BET specific surface area of 10 to 200 m2/g, more preferably 15 to 100 m2/g. If it is more than 200 m2/g, it is difficult to produce efficiently. If it is less than 10 m2/g, the effect of improving the ultraviolet shielding energy is not good. Also, the average particle size is generally 〇·〇〇8#ηι to 〇. 15ym, better 0. 015/zm to 〇. The scope of l/im. If it is less than 〇. 〇〇8; zm is difficult to produce efficiently if it exceeds 0. At 1 5 μm, the improvement in UV shielding energy is not good. The ultrafine particle mixed crystal oxide may also have a core (c 〇re ) / shell (she 11 ) structure. In this case, the core is rich in the Ti 2 Ο 2 phase, and the shell is rich in the S i Ο 2 phase. good. In this case, the SiO 2 phase is in a state of being supported on a part of the surface of the particle, and may be a discontinuous load such as a dot shape or an island shape, or may be a continuous load such as a string shape, a mesh shape, or a porous shape, or may be continuous and discontinuous. Partial mixing exists. The coated cerium oxide-containing zinc oxide powder of the present invention can also be used as a cosmetic. In this case, it is possible to use a conventional raw material which is often blended, and a W/0 type or a 0/W type emulsified type "liquid form, solid form, gel form" or the like can be prepared by a general method. For example, it can be combined with quality raw materials (mica, talc 'kaolin, calcium carbonate, magnesium carbonate, phthalic anhydride, alumina, barium sulfate, etc.), white pigments (titanium dioxide, zinc oxide, etc.) and colored pigments (eg 'red iron oxide, yellow oxide Iron, black iron oxide, chromium oxide, group -30- (27) 1310397 cyan, indigo, carbon black, etc.), spherical powder (nylon powder, polymethyl methacrylate powder, etc.), oil (moving stone) Wax, squalane, castor oil, glyceryl diisostearate, glyceryl triisostearate, glycerol-3-ethylhexanoate, isopropyl myristate, glyceryl triisostearyl Acid ester, dimethyl polyxanthine, methyl phenyl polyoxalate, petrolatum, diisostearyl brewed maleate, refined lanolin, etc.), UV absorber (benzophenone, salicin) The acid-based, PABA-based, cinnamic acid-based, diphenylmethane-based, or pyridine-based acrylic acid-based emulsifier is not particularly limited as long as it has an anti-inflammatory component. The zinc oxide powder containing the coated cerium oxide used in the present invention has a high effect of suppressing the activity of the photocatalyst, and even if it is used together with the organic ultraviolet absorber, it can suppress the decomposition of the absorbent and can have a high ultraviolet shielding energy. The cosmetic material can maintain its effect for a long time. Further, when it is used together with an antioxidant having an antioxidant action, the photocatalytic activity of the titanium oxide coated with cerium oxide and the zinc oxide coated with cerium oxide can be further reduced by suppressing the amount of radicals generated by ultraviolet rays, thereby obtaining a dosage form A safe cosmetic with excellent stability and low phototoxicity. The blending amount of the zinc oxide powder coated with cerium oxide of the present invention is preferably 5 to 25 mass%, more preferably 5 to 20 mass%, based on the total amount of the cosmetic material. When the blending amount is 5% by mass or less, the ultraviolet ray-deficient effect is insufficient. When the amount of the zinc oxide powder containing the coated cerium oxide is 25% by mass or more, whitening and roughening are not applied when applied to the skin, and the feeling of use is poor. Not good. The zinc oxide powder containing the cerium oxide coated according to the present invention may also be mixed with a thermoplastic resin-31 - (28) 1310397 resin to obtain an organic polymer composition. The thermoplastic resin is not particularly limited, but is, for example, 'polyethylene, polypropylene, polystyrene, polyethylene terephthalate, AS resin, ABS resin, AES resin, polyvinylidene chloride, methacrylic resin, Polyvinyl chloride, polyamide, polycarbonate, polyallyl ester, polyimide, polyacetal, polyether ketone, polyether, I, polyphenylene sulfide, polyphenylene sulfide, and the like. The organic polymer composition contains the content of the cerium oxide-coated zinc oxide powder, which is generally 0. 01 to 80% by mass, preferably 0. 1 to 50% by mass, and particularly preferably 1 to 20% by mass. Further, as the concentrated dispersion, it is usually from 1 to 80% by mass, preferably from 1% to 40% by mass. The thermoplastic resin may be added with an antioxidant, an aging preventive agent, an ultraviolet absorber, a slip agent, a charge preventive agent, a surfactant, a calcium carbonate, a talc, etc. as a thermoplastic, a stabilizer, a foaming agent, and an expansion agent. Agents, conductive powders, conductive short fibers, deodorants, softeners, tackifiers, viscosity reducing agents, thinners, water repellents, oil repellents, crosslinkers, hardeners, etc., colorants or Fluorescent agent. However, when used for a film or a fine fiber, the additives, the coloring agent, and the fluorescent agent are preferably free of coarse particles or coarse fibers. These additives, colorants, phosphors, and the like can be kneaded into the thermoplastic resin, and can be added and formed during the molding process. An organic polymer composition comprising a zinc oxide powder coated with cerium oxide and a thermoplastic resin is obtained by mixing a zinc oxide powder containing cerium oxide and a thermoplastic resin. However, since the zinc oxide powder containing the coated ruthenium dioxide is a fine powder, it is not preferable to mix only the zinc oxide powder containing the coated -32-(29) 1310397 ruthenium with the thermoplastic resin, and it is preferable to knead in order to improve the uniformity. Additives, colorants, and phosphors can be added and scoured during mixing or kneading. The mixture of the zinc oxide powder containing the coated cerium oxide and the thermoplastic resin can be, for example, a mixer such as a V-shaped mixer or a Hansui mixer. Further, as the kneading, a continuous kneading machine such as a batch mixer such as a Banbury mixer, a single-axis extruder, a twin-shaft extruder, or a continuous mixer can be used. The organic polymer composition comprising the cerium oxide-coated zinc oxide powder and the thermoplastic resin may be used singly or as a color concentrate for use in the thermoplastic resin for dilution. The thermoplastic resin for dilution is not particularly limited, and examples thereof include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, AS resin, AB S resin, AES resin, and polyvinylidene chloride. Methacrylic resin, polyvinyl chloride, polyamine, polycarbonate, polyallyl ester, polyimide, polyacetal, polyether ketone, polyether mill, polyphenylene ether, polyphenylene sulfide, and the like. The organic polymer composition of the present invention can be used alone or as a concentrated color body for thermoplastic molding resins such as injection molding, hollow molding, extrusion molding, roll forming, flow forming, compression molding, melt blowing, and spunbond fabric. In a conventional molding method, a molded article such as a molded article such as a fiber, a yarn, a film, a sheet, a belt, or an injection molded article, or a hollow body such as a hollow fiber, a tube, or a bottle can be produced. Further, a molded body can be produced by a secondary molding method commonly used for thermoplastic resins such as vacuum forming, pressure forming, and laminated forming. A molded article such as a fiber, a wire, a film, a sheet, a ribbon, or an injection molded article composed of the organic polymer composition of the present invention, a hollow fiber, a hollow body such as a -33- (30) 1310397 tube, or a bottle, or the like It is not particularly limited as long as it is a thick formed body to a thin formed body. However, the composition of the present invention is particularly characterized by being capable of producing a thin shaped body which is generally difficult to obtain, and is most suitable for producing fine fibers or filaments, films and the like. These molded bodies may have a single-layer structure, or may have a multilayer structure structure. The molded body of the layer of the organic polymer composition of the present invention has high efficiency of ultraviolet shielding energy. The organic polymer composition of the present invention can be used as a molding index for a small extruder, either alone or as a complex color. For example, 'the color of the organic polymer composition is a small plastic mill made of a machine (stock), and the resin pressure rises when the resin is extruded immediately after the start of the kneading, which is not only expressed in the small plastic shape. It can also be used as a formability index when the organic polymer composition concentrate is directly diluted with a thermoplastic resin and molded into a thin fiber such as a blown film forming such as a blown film. When the increase in the pressure of the kneaded resin of the organic color concentrate is low, not only the formability of the composition concentrate in the small plastic mill is good, but also the perforation occurs during film formation, and the formation of fine fibers or the like is suppressed. Good formability can be obtained by breaking. For example, when the thermoplastic resin is an organic polymer color of polypropylene, the number of revolutions of the mesh type 20mm 0 extruder equipped with 100/630/100/80/60 mesh is rotated at 45 rpm, 230 (into 23 0 -23 When extruded at a temperature of 0 °C, the mixture is initially formed into a molded body, an organic polymer, a fine or a ribbon, and a plurality of layers are provided on the surface body for use as a shape for use in Toyo Seiki to quantify When the machine is used to dilute the film, or the polymer group polymer can suppress the filament, etc., and the composition is full of the full scraper □) -230- after the resin -34 - (31) 1310397 pressure, When the organic polymer composition is extruded at 3 kg, the resin pressure is preferably 5 MPa or less, more preferably 3 MPa or less. When the thermoplastic resin is a concentrated polymer of the organic polymer composition of polyamine, a full-scraper type 20 mm 0 extruder equipped with a mesh of 1 00/63 0/1 00/80/60 mesh is used. When extruded at a temperature of 45 rpm and 2 70 (inlet)-270-2 at 70-270 °C, the resin pressure at the beginning of the kneading is extruded with an organic polymer composition. The increase in the resin pressure at 3 kg is preferably 10 MPa or less, more preferably 5 MPa or less. a molded article such as a fiber, a wire, a film, a sheet, a ribbon, or an injection molded article, which is composed of the organic polymer composition of the present invention, a hollow body such as a hollow fiber, a tube or a bottle, and the like, wherein the fiber, the wire, the film, and the sheet In addition to being used alone, the ribbon may be co-extruded with other thermoplastic resins, integrally formed with the substrate, attached to the surface of the substrate, or formed into a surface layer composed of an organic polymer composition and a substrate. Multi-layer structure. The thickness of the film, sheet or ribbon is not particularly limited and is appropriately selected depending on the use thereof, and is generally 0. 0005 to 5. 0mm, preferably 0. 001 to 1. 0mm, preferably 0. 00 1 to o. Lmm. Further, the thickness of the fiber is not particularly limited and is appropriately selected depending on the use thereof, and is usually from 1 to 500 denier, preferably from 1 to 100 denier, and most preferably from 1 to 50 denier. a molded product such as a fiber, a film, a wire, a sheet, a ribbon, or an injection molded article composed of the organic polymer composition of the present invention, a hollow body such as a hollow fiber, a tube or a bottle, or the like, wherein the fiber, the film, the sheet or the belt The object may be attached to the surface of the substrate via an adhesive. As the adhesive, an adhesive such as an acrylate type, a polyvinyl alcohol type or a vinyl acetate type can be used. 35-(32) 1310397 Further, a molded product such as a fiber, a film, a wire, a sheet, a ribbon, or an injection molded article, and a hollow body such as a hollow fiber, a tube, or a bottle, which are composed of the organic polymer composition of the present invention, The fibers, films, sheets or ribbons may also be provided with a peelable protective film via an adhesive layer. As the protective film, a coated paper having a ruthenium resin as a release layer, a 2-axis extended polyethylene terephthalate film, or the like can be used. The protective film can be attached to any surface of the substrate which can be peeled off by such a structure in which an adhesive layer and a protective film are provided. The fiber, the film 'filament, the sheet, the ribbon, the molded article such as the injection molded article, the hollow body, the hollow body such as a tube or a bottle, and the like, the fiber, the film, the sheet, and the like, which are composed of the organic polymer composition of the present invention. Alternatively, the ribbon may be subjected to pattern printing or embossing of a concave-convex pattern to form a body shape. The material and shape of the substrate are not particularly limited as long as the ultraviolet shielding energy can be formed on the surface. The material of the substrate can be used, for example, metals such as iron, aluminum, and copper, ceramics such as glass and ceramics, inorganic materials such as gypsum, calcium citrate, and cement, polyvinyl chloride, polyester, polyolefin, polycarbonate, and polyamide. , acrylic resin, ABS resin, polystyrene, phenol resin, FRP and other plastics, wood, plywood, paper and other organic materials, glass fiber, carbon fiber, polyester fiber and other fibers. The molded article product such as a fiber, a silk, a film, a sheet, a ribbon, or an injection molded article which is composed of the organic polymer composition of the present invention can form a multilayered structure such as a hollow body such as a hollow fiber, a tube or a bottle. The shape of the substrate is not particularly limited, and may be any shape such as a film, a sheet, a sheet, a fiber, a nonwoven fabric, or a three-dimensional shape, and the size thereof is not particularly limited. -36- (33) 1310397 The molded body or multilayer structure described above may be used singly or as part of another structure. The structure is not particularly limited. For example, it may be composed of an inorganic material such as metal, concrete, glass, or ceramics, or may be an organic material such as paper, plastic, wood, or leather, or a combination thereof. Such items are, for example, packaging materials, building materials, machinery, vehicles, glass products, home appliances, agricultural materials, electronic equipment, tools, food utensils, bathroom products, toilet products, furniture, clothing, cloth products, fibers, leather products, paper products, Sports goods, bedding, containers, glasses, advertising boards, piping, wiring, metal parts, sanitary materials, automotive supplies, tents, stockings, socks, gloves, masks, undershirts, etc. The organic polymer composition containing the ceria-coated zinc oxide powder is excellent in formability and workability, and the molded article composed of the organic polymer composition is extremely excellent in weather resistance. In particular, the stockings, socks, sweatshirts, etc., which are formed by processing and processing such multifilament-type ultrafine fibers, or packaging materials and agricultural materials obtained by forming and processing extremely thin films, can exhibit excellent formability and workability. Weather resistance. Further, the formed and processed article of the present invention is characterized in that it does not exude an organic ultraviolet absorber or the like. Therefore, stockings, socks, undershirts, and the like have excellent durability against washing even after forming. The invention will be described in more detail below with reference to examples and comparative examples, but the invention is not limited thereto. The following evaluations were carried out in the following examples and comparative examples. -37- (34) 1310397 (Measurement of bismuth dioxide film thickness) The zinc oxide particles of the cerium oxide film were observed by a transmission electron microscope (JEM2〇1〇, an acceleration voltage of 20 0V manufactured by JEOL Ltd.). The thickness of the cerium oxide film on the surface of the particle (the substrate portion of the substrate which was coated and which had a shallow contrast was confirmed) was observed. (Average primary particle diameter) The zinc oxide fine particles of the cerium oxide film were observed by a transmission electron microscope (jEM2010 manufactured by JEOL Ltd., acceleration voltage of 200 V), and 100 particles were arbitrarily extracted to measure the particle diameter of each particle. Calculate the average particle size. (IR Spectrometry) The infrared absorption spectrum of the cerium oxide film of the zinc oxide fine particles of the cerium oxide film (FT -1 R - 8000 manufactured by Nikko Separation Co., Ltd.) is KB r method (light-emitting particles and KBr) The mixing ratio of each powder was measured by the luminescent particle/KBr mass ratio of 1/32). The absorbance of the absorption peak is calculated from the transmittance of the infrared absorption spectrum of 1150 to 1250 cm·1 and 1000 to 1 1 00 cnT1, and the ratio of the absorption peak intensity I is obtained (I = I 1 /1 2 ; 11 is 1 1 50 The absorbance of the absorption peak to USOcrrr1, 12 is the absorbance of the absorption peak of 1000 to 1100 cm·1). (Refractive Index Measurement) When a zinc oxide fine particle of a cerium oxide film is synthesized, a ruthenium dioxide film formed on a ruthenium wafer immersed in a system is used as an ellipsometer-38-(35) 1310397 (manufactured by ULVAC Corporation) ;LASSER ELLIPSOMETER ESM-1A) Determination. (Automated Oxidation of Tetrahydronaphthalene) "Tokino Learning, Titanium Dioxide, Physical Properties and Applied Technology, Technical Reporting Hall, pp. 1 96- 1 9 7 pages, 1991, Japan". The measurement conditions are temperature 4 〇 ° C 'tetrahydronaphthalene 20 ml, zinc oxide bismuth. 〇 2g. (Measurement of pigment fading speed • Falling yellow method) The obtained cerium oxide-coated zinc oxide fine particles and uncoated zinc oxide particles (raw material zinc oxide particles) and commercially available zinc oxide (Zn03 50, Sumitomo Osaka Cement Co., Ltd.) As a test substance, the dye fading speed was measured by the setting yellow method. First, the pigment drop-yellow-FCF (Wako Pure Chemical Co., Ltd.) was dissolved in 98% by mass of glycerin to have a pigment concentration of 〇·〇 2% by mass. Disperse the test substance to become 0. 0 6 7 mass%, irradiated with ultraviolet light (ultraviolet intensity 1. 65 mW/cm 2 ) of the dispersion. The absorbance of the sunset yellow-FCF maximum absorption wavelength of 490 nm was measured by a spectrophotometer (UV-160 manufactured by Shimadzu Corporation) at a light path of 1 mm, and the absorbance reduction rate and the absorbance reduction rate of the blank test (without adding zinc oxide) were calculated. The difference (△ ABS 4 9 〇 / hour). (Measurement of Decomposition Rate of Organic UV Absorbent 葩 丨 丨 丨 789 Method) -39- (36) 1310397 The obtained cerium oxide-coated zinc oxide fine particles and uncoated zinc oxide particles (raw zinc oxide particles) and the city Zinc oxide (Zn03 50, manufactured by Sumitomo Osaka Cement Co., Ltd.) was used as a test substance, and the decomposition rate of the organic ultraviolet absorber 葩17 was measured. That is, the test substance was dispersed in a polyethylene glycol 300 solution of 4-tert-butyl-4,-methoxybenzoquinone methane (Colasol 1789) (the concentration of the cable 1789 was 0 · 04 5 mass%) In each of them, 1% by mass of each slurry was separately prepared. Each slurry is 1. 2g was placed in a glass container and irradiated with ultraviolet light (ultraviolet intensity 1. After 1 hour, 1 g of the mixture was added, and 2 ml of isopropyl alcohol, 2 ml of hexane, and 3 ml of distilled water were added in this order. After stirring, the hexane phase was extracted with a hexane phase of 1 78 9 ' by a spectrophotometer (UV-160 manufactured by Shimadzu Corporation) to measure the absorbance (340 nm) of the light path of the hexane phase of 1 mm. The difference between the absorbance reduction rate at 340 nm and the absorbance reduction rate of the blank test (without adding zinc oxide) was obtained (Δ ABS 34 G / hour). (Measurement of decomposition rate of organic ultraviolet absorbers; p-methoxy cinnamate ethylhexyl ester method) The obtained cerium oxide-coated zinc oxide fine particles and uncoated zinc oxide particles (raw zinc oxide particles) are commercially available. Zinc oxide (Zn03 50, manufactured by Sumitomo Osaka Cement Co., Ltd.) was used as a test substance, and the decomposition rate of the organic ultraviolet absorber p-methoxycinnamate ethylhexyl ester was measured. Namely, the test substance was dispersed in a polyethylene glycol 3 00 solution of p-methoxycinnamic acid 2-ethylhexyl ester (p-methoxy cinnamic acid 2-ethylhexyl ester concentration was 0. In each of 05 mass%), each slurry of 〇33% by mass was prepared. Will -40- (37) 1310397 each slurry 1. 2 § Put into a glass container and irradiate with ultraviolet light (ultraviolet intensity l_65mW/cm2). After 90 minutes, add lg, and add isopropanol 2 m 1 , hexane 2 m 1 and distilled water 3 m 1 in sequence. After stirring, 2-ethylhexyl p-methoxycinnamate was extracted from the hexane phase, and the absorbance (300 nm) of the light path of the hexane phase was measured by a spectrophotometer (uv_1 60 manufactured by Shimadzu Corporation). The decomposition rate of p-methoxy cinnamic acid 2-ethylhexyl ester was determined from the difference between the absorbance reduction of 300 nm and the absorbance reduction of the blank test (without adding zinc oxide) (Zinc dissolution test) The zinc oxide powder containing the coated cerium oxide was evaluated for the dissolution of zinc ions against water as follows. The amount of glutinous glutinous rice is oxidized (including surface hydrophobized product) coated with oxidized sand, and the uncoated zinc oxide particles are dispersed in various p Η solutions to 5% by mass, and disturbed at 25 ° C. After 3 hours, the dispersion was sedimented by centrifugation, and it was measured by an atomic absorption spectrophotometer (Z-8200, manufactured by Hitachi, Ltd.). (Content of coarse particles of 5 /zm or more) When the sample is a powder containing zinc oxide particles coated with ceria coated with cerium oxide, the sample is properly weighed and placed at 丨8 〇〇m 1 at room temperature. In pure water, stir well. An appropriate amount (1 〇 ml) of a dispersing agent, for example, a sodium hexametaphosphate aqueous solution, was added thereto, and after stirring, the mixture was dispersed by ultrasonic waves for 1 minute. Ultrasonic dispersion can be used, for example, in Japan Seiki Co., Ltd., which has a -41 - (38) 1310397-limited ultrasonic homogenizer (type US-300T, output power 300W's transmission cycle number 20 kHz). Then, the obtained suspension was placed on a high-precision micro-screening net installed on a high-precision micro-screen of 5/m in the ultrafine powder classifier (type PS-80) of Yokohama, Japan, to be incorporated into the device. The ultrasonic vibrator, the electromagnetic vibrator, and the suction pump are subjected to wet precision classification. After the end of the classification, the powder on the sieve is collected by washing with water and mixed with pure water in a glass container. After it was evaporated in a 1 1 〇 t drier, the remaining residue was collected and weighed. The ratio of the residue in the sample of 20 g is a coarse particle of 5 // m or more. In the above classification operation, the sample is a powder containing coated surface-hydrophobic coated ceria-containing zinc oxide fine particles which is coated with ceria-coated cerium oxide-coated zinc oxide fine particles and surface-treated with a hydrophobicity-imparting agent. In the wet precision classification performed, a solvent other than the dispersant may be changed from water to a solution in which water and methanol are mixed in equal amounts. After the end of the classification, the powder on the sieve was air-dried and placed in a desiccator at 110 °c, and the remaining residue was collected and weighed. The ratio of the residue in 20 g of the sample used was 5 // m or more coarse particles. (Kneading resin pressure) An organic polymer composition containing a zinc oxide powder coated with ruthenium dioxide and a thermoplastic resin is used to measure the pressure of the kneaded resin using a small plastic mill manufactured by Toyo Seiki Co., Ltd. Formability. The mixing conditions of the small plastic mill are based on a full-scraper type 20mm 0 extruder equipped with a mesh screen of 1 00/630/1 00/80/60, with a number of revolutions at 45 rpm, and with a resin type. - (39) Temperature conditions for class 1310397. For the resin pressure immediately after the start of the kneading, the moldability is evaluated by the increase in the resin pressure when the organic polymer composition is extruded at 3 kg (the weathering resistance is suppressed by the photocatalytic action), and 20% of the coated cerium oxide is contained. The composition of the composition of the zinc oxide powder is added to the diluted resin, and the zinc oxide powder containing the coated bismuth is made 1%, and the thickness of the film forming mechanism of the 25 mmT die film is made by the central mechanical mechanism. 0/Zm film. The film was placed in a Sunshine super long weathermeter WEL-SUN-HCH type of a S g a tester (strand) for 180 hours, and subjected to photocatalytic weather resistance deterioration test. The evaluation of the weather resistance deterioration by photocatalytic activity is measured by the reflection/transmittance meter HR-100 manufactured by the (Color) Color Technology, and the turbidity before and after the Dawning Ultra-long-term Weathering Fastness Tester is measured. The change is assessed. The small change in turbidity is judged to be suppressed by the photocatalytic action. Example 1 will be 18. 25L deionized water, 22. 8L ethanol (produced by Pure Chemical Co., Ltd.) and 124ml of 25 mass% ammonia water (mixed in a 5〇L reactor manufactured by Dasheng Chemical Co., Ltd., i. 7 kg of raw material zinc oxide particles (high-purity zinc oxide UFZ manufactured by Titanium Co., Ltd. - primary particle diameter: 27 nm) was dispersed therein to prepare a suspension A. Following the long - term life of the compound polyoxidation system , the turbidity of the village is limited to TiO2 40 , and -43- (40) 1310397 1. 62L tetraethoxy decane (made by GE Toshiba ketone) and 1. Mix solution B with 26 L of ethanol. After stirring, the solution B was added to the suspension A at a constant rate of 9 hours and then allowed to stand for 12 hours. Film formation and ripening are carried out at 45 °C. The solid matter was then separated by centrifugation, dried under vacuum at 50 ° C for 12 hours, and then dried at 80 ° C for 12 hours under warm air. Subsequently, the cerium oxide-coated zinc oxide fine particles are obtained by jet milling. The transmission infrared absorption spectrum of the obtained coated ceria-zinc oxide was measured by KBr method, and it was observed that the absorption of Si-0-Si stretching vibration from 1 〇〇〇 to 1 200 CITT1 was not observed in the source of 2800 to 3,000 CHT1. From the absorption of 伸缩 stretching vibration, the film formed is identified as cerium oxide. In addition, the ratio of the primary particle diameter, the cerium oxide film thickness, the absorption peak intensity of the infrared absorption spectrum, the refractive index of the cerium oxide film, and the tetrahydrogenation The measurement results of the photocatalytic activity of the naphthalene auto-oxidation method are shown in Table 1. The pigment discoloration rate of the zinc oxide microparticles coated with cerium oxide is 0. 1 (AABS^o/hour) or less, the pigmentation is suppressed and reduced as compared with the uncoated and commercially available zinc oxide. The decomposition rate of the cerium oxide-coated zinc oxide particles is based on the decomposition rate of the organic ultraviolet absorber of the lanyard 1 78 9 method. 〇2 (△ ABS34()/hour) Below, the solubility of the ultraviolet absorber is remarkably lowered as compared with the uncoated product and the commercially available zinc oxide. The decomposition rate of the cerium oxide-coated zinc oxide fine particles is 5% or less, and the decomposability of the ultraviolet absorbing agent is lowered as compared with the uncoated product and the commercially available zinc oxide. -44 - (41) 1310397

Determination of 値 primary particle size (nm) 27 Silica sand film thickness (nm) 3 Infrared absorption peak intensity ratio I 値 二 二 二 film refractive index 1.443 tetrahydronaphthalene auto-oxidation activity (Pa / min) 3 9 Yttrium yellow color fading speed (△ABS490/hour) 0 葩 cable 1 789 method decomposition rate (ΛΑΒΒ〗 " / hour) 0.002 p-methoxycinnamic acid ethylhexyl ester decomposition rate (%) 0.5 at 9 7 Adding 3 parts by mass of dimethylpolysiloxane (KF96-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) in a mass fraction of zinc oxide coated with cerium oxide to a Hansu-type mixer (Mitsui Sanchi Mine ( The product) was thoroughly mixed, and then the solvent was removed by vacuum drying at 90 ° C, and then calcined at 200 ° C for 6 hours to obtain a surface-hydrophobized coated silica sand zinc oxide. The content of the coarse particles of 5 m m or more of the zinc oxide powder containing the coated cerium oxide was 1.6 mass%. Regarding the dissolution of zinc ions, the results are not shown in Table 2. The cerium oxide-coated zinc oxide of the present invention is compared with uncoated zinc oxide at various pHs. The dissolution of zinc ions is suppressed, and the amount of elution in pure water is as small as 0.5 ppm or less. Furthermore, by surface hydrophobization, the dissolution at each pH of -45-(42) 1310397 can be suppressed. Even when the organic polymer composition or the molded article thereof is sufficiently expected to be in contact with an acidic or alkaline solution, the effect of sufficiently preventing the elution of zinc ions is obtained. [Table 2] Dissolved d Zinc ion (ppm) Pure water (pH 6.4) 1% NH3 solution (pH 1 1.4) 0.0 1 % Nitric acid solution (pH 2_5) The zinc oxide particles coated with ceria of Example 1 <0.5 20 9 Surface-deuterated coated cerium oxide-coated zinc oxide particles of Example 1 <0.5 2 1 Uncoated raw material zinc oxide particles of Example 1 8 480 91 In addition, a spoke type classifier (Nippon Engineering Co., Ltd.) was used. The surface hydrophobized powder is subjected to dry precision classification. The zinc oxide powder containing the coated ceria was obtained, and the content of the coarse particles of 5 // m or more was 0.0 2% by mass. 80 parts of the thus obtained cerium oxide-containing zinc oxide powder and 80 parts of polypropylene (PW600N manufactured by Sunaroma Co., Ltd.) were obtained by a Kawada (super) honing machine at 60 rpm. Mixing for 3 minutes -46 - (43) 1310397 After the mixing with a 30 mm different-direction 2-axis extruder made in the Middle Ages, the organic polymer composition was obtained. The resulting organic polymer composition was subjected to a resin compaction at a temperature of 230 (human α) _23 〇 _ 23 〇 23 ° ° C, and the moldability was evaluated by a small plastic mill. As a result, as shown in Table 3, the tree and the _ & i were raised to a relatively low level of 1.3 MPa, and the formability was good. The resulting organic polymer composition was subjected to a photocatalytic weather resistance deterioration test by diluting with a PW6 00N manufactured by Sanaloma Co., Ltd. The film has a turbidity of 1 8.2 before being placed in the solar ultra-long-term weather fastness tester, and the film has a turbidity of 1 8.6 after leaving, and the turbidity change is relatively small to 0-4, and the weather resistance by photocatalytic action is very little deteriorated. From this, it is understood that the obtained cerium oxide-coated zinc oxide fine particles have little deterioration in weather resistance of polypropylene by photocatalytic action. Example 2 In the same manner as in Example 1, except that polyethylene (JH607C manufactured by Nippon Polyolefin Co., Ltd.) was used instead of polypropylene (PW60 0N manufactured by San Aroma), the same operation as in Example 1 was carried out. The organic polymer composition is a concentrated body. The obtained organic polymer composition color concentrate was evaluated for its moldability by a small plastic mill in the same manner as in Example 1. As a result, the resin pressure was increased to a relatively low 0.7 MPa, and the moldability was good. Further, it was diluted with polyethylene (JH607C manufactured by Nippon Polyolefin Co., Ltd.) to carry out a weathering resistance test by photocatalytic action, and as a result, the turbidity change -47-(44) 1310397 was considerably small as 〇·2, and it was resistant by photocatalytic action. Sexual deterioration is very small. From this, it is understood that the obtained cerium oxide-coated zinc oxide fine particles have little deterioration in weather resistance to polypropylene through photocatalyst. Example 3 In Example 1, except that polyacrylamide (manufactured by Yers (MS) Showa Denko Co., Ltd., A28GM) was used instead of polypropylene (PW600N manufactured by Sanalema), the examples and examples were carried out. 1 The same operation was carried out to obtain an organic polymer composition concentrate. The obtained organic polymer composition was a color concentrate except that the temperature condition was changed to 270 (inlet) -270-270-270 °C' and the examples! In the same manner, the formability was evaluated by a small plastic mill, and as a result, the resin pressure was increased to a relatively low 2.1 MPa, and the formability was good. Example 4 In the synthesis of the oxidized dry particles coated with cerium oxide of Example 1, except that cerium oxide particles (high-purity titanium dioxide F-4 made by Showa Qindanning Co., Ltd.; - sub-particle size of 30 nm) were used instead. 1 · 7 κ g raw material other than zinc oxide particles 'Titanium dioxide particles coated with cerium oxide were obtained by the same synthesis method. To 97 parts by mass of the obtained coated cerium oxide-containing titanium dioxide, 6 parts by mass of a dichloromethane solution of KD96-100CS Shin-Etsu Chemical Co., Ltd. was added to the Hansu-type mixer (Mitsui Sanchi) The mine (share) system is fully mixed and then at 90. (: After drying under vacuum to remove -48-(45) 1310397 solvent, the surface-hydrophobic coated cerium oxide-containing titanium dioxide is obtained by calcination at 200 ° C for 6 hours. The obtained titanium oxide powder containing coated cerium oxide is obtained. The content of the coarse particles of 5 M m or more was 1.5% by mass. Further, the surface hydrophobized powder was subjected to dry precision classification using a spoke type classifier (manufactured by Nippon Engineering Co., Ltd.). The titanium dioxide powder of bismuth has a content of coarse particles of 5/m or more and 0.02 mass%. Subsequently, 30 parts by mass of the graded coated cerium oxide-coated titanium oxide powder and the graded coated dioxide of Example 1 are oxidized. The zinc oxide powder of the cerium is mixed and homogenized to prepare a zinc oxide powder containing the coated cerium oxide. The zinc oxide powder containing the coated cerium oxide is obtained, and the content of the above coarse particles is 0.02% by mass. 20 parts of zinc oxide powder of bismuth and 80 parts of polypropylene (PW600N made by Amalgam) were mixed by a Kawada (super) honing machine at 600 rpm for 3 minutes, and then made by the Middle Ages. The organic polymer composition concentrated body was obtained by kneading in a different direction 2-axis extruder. The obtained organic polymer composition concentrated body was evaluated in the same manner as in Example 1 by a small plastic mill, and the resulting resin pressure was increased. The film composition of the obtained organic polymer composition was the same as that of Example 1, and the weather resistance deterioration test by photocatalytic activity was carried out, and the change in the turbidity of the film was as small as possible. '. 5 'The deterioration of the weather resistance by photocatalytic action is very small. From 49-(46) 1310397, it can be seen that the weathering resistance of the obtained cerium oxide-coated zinc oxide fine-particle-based polypropylene with photocatalytic activity is very small. Comparative Example 1 In the first embodiment, the same operation as in Example 1 was carried out except that the coated cerium oxide-containing zinc oxide powder was used instead of the classified cerium oxide-containing zinc oxide powder, and the organic polymer composition was obtained. The obtained organic polymer composition color concentrate was evaluated in the same manner as in Example 1 by a small plastic mill, and the resin pressure was increased to a considerable 8.6 MPa. The moldability was not good. However, the obtained organic polymer composition color concentrate was subjected to the photocatalytic degradation resistance test in the same manner as in Example 1. As a result, the change in the turbidity of the film was as small as 0.5, and the photocatalytic activity was resistant. It is understood that the weathering resistance of the obtained cerium oxide-coated zinc oxide fine-particle-based polypropylene by photocatalytic activity is extremely small. Comparative Example 2 In addition to the use of the coated cerium oxide-containing zinc oxide powder used in Comparative Example 1. The same procedure as in Example 2 was carried out to obtain an organic polymer composition concentrated body. The obtained organic polymer composition concentrated body was evaluated in the same manner as in Example 2 by a small plastic mill, and as a result, the resin pressure was increased. For a considerable 3.5 MPa, the formability is not good. However, the obtained organic polymer composition concentrate was operated in the same manner as in Example 2 -50(13) 1310397, and subjected to photocatalytic degradation resistance test. As a result, the change in film haze was as small as 0.3, and the photocatalytic action was resistant to weathering. Sexual deterioration is very small. From this, it is understood that the weathering resistance of the obtained cerium oxide-coated zinc oxide fine-particle-based polyethylene having a photocatalytic action is extremely small. Comparative Example 3 The same procedure as in Example 3 was carried out except that the coated cerium oxide-containing zinc oxide powder used in Comparative Example 1 was used, and an organic polymer composition concentrated body was obtained. The obtained organic polymer composition color concentrate was evaluated in the same manner as in Example 3 by a small plastic mill. As a result, the resin pressure was increased to 15 MPa, and the formability was poor. Comparative Example 4 In Example 1, in place of the use of zinc oxide particles (high-purity zinc oxide UFZ-4® manufactured by Showa Titanium Co., Ltd.; - sub-particle size 27 nm), the oxidation of the coated ceria-containing cerium oxide was replaced. Except for the zinc powder, the same operation as in Example 1 was carried out to obtain an organic polymer composition color concentrate. The organic polymer composition obtained was evaluated for its formability by a small plastic mill in the same manner as in Example 1. As a result, the resin pressure was increased to a considerable 4.2 MPa, and the formability was poor. Further, the obtained organic polymer composition was used in the same manner as in Example 1 to carry out a weathering resistance test by a photocatalytic action. As a result, the change in the turbidity of the film was as large as 8.2, and the weather resistance by the photocatalytic action was greatly deteriorated. From this, it is understood that the obtained cerium oxide-coated zinc oxide fine-particle polypropylene has a large weather resistance deterioration by photocatalyst _ -51 - (48) 1310397. Comparative Example 5 In Example 2, in place of the zinc oxide particles (high-purity zinc oxide UFZ-40 manufactured by Showa Titanium Co., Ltd.; - subgranularity: 27 nm), the zinc oxide containing coated cerium oxide was replaced. The same operation as in Example 2 was carried out, except for the powder, to obtain an organic polymer composition. The organic polymer composition obtained was evaluated for its formability by a small plastic mill in the same manner as in Example 2. As a result, the resin pressure was increased to a relatively high level of 6.5 MPa, and the formability was poor. Further, in the same manner as in Example 2, the obtained organic polymer composition concentrate was subjected to a photocatalytic deterioration test, and as a result, the change in the turbidity of the film was as large as 6.5, and the weather resistance by the photocatalytic action was greatly deteriorated. From this, it is understood that the weather resistance of the obtained cerium oxide-coated zinc oxide fine-particle-based polyethylene is greatly deteriorated by photocatalytic action. Comparative Example 6 An aqueous suspension (ZnO concentration: 50 g/L) of zinc oxide particles (high-purity zinc oxide UFZ-40 manufactured by Showa Titanium Co., Ltd.; sub-particle size: 27 nm) was heated to 80 ° C and stirred. An aqueous solution of zinc citrate having a zinc oxide content of 10% by weight based on SiO 2 was added. After aging for 1 minute, sulfuric acid was added thereto for 60 minutes while stirring, and the mixture was neutralized to pH 6.5. After the mixture was aged for 30 minutes, the obtained suspension was filtered, washed with water, and dried by heating at 130 ° C for 5 hours. The dried product thus obtained was pulverized by a jet mill to obtain a zinc oxide powder containing coated -52-(49) 1310397 ruthenium. The organic polymer composition concentrate was obtained by the same operation as in Example 1 except that the coated ceria-containing zinc oxide fine particles before the hydrophobization of Example 1 was used. The obtained organic polymer composition concentrated body was evaluated for its formability by a small plastic mill in the same manner as in Example 1. As a result, the resin pressure was increased to a relatively low cost of 2.2 MPa, and the formability was good. Further, the obtained organic polymer composition concentrate was operated in the same manner as in Example 1. The weather resistance deterioration test by photocatalytic activity was carried out, and as a result, the change in the turbidity of the film was as large as 3.5. The weather resistance of the photocatalytic action was deteriorated greatly. From this, it is understood that the weather resistance of the obtained cerium oxide-coated zinc oxide fine-particle-based polypropylene is greatly deteriorated by photocatalytic action. -53- (50)1310397

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-54- 1310397 (51) [Effect of the Invention] The present invention provides a zinc oxide powder containing coated cerium oxide, an organic polymer composition containing the powder, and a molded article thereof, wherein the powder is formed into a stomach shape The weather resistance does not deteriorate by the photocatalytic action, and the organic ultraviolet, the line absorbent oozes, the durability to the washing, and the powder of the film or the fine fiber having sufficient ultraviolet shielding energy are not generated, and the coarse particles of 5 m or more are 〇.1% by mass or less.

Claims (1)

1310397 Pick up, apply for patents η ώ Amendment _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a powder of cerium oxide-coated zinc oxide fine particles, wherein the primary particle diameter of the cerium oxide-coated zinc oxide fine particles is 1 to 2 〇〇 nm, the cerium oxide film thickness is 0.5 to 100 nm, and dry precision In the classification, the coarse particles of 5 // m or more are reduced to 0.1% by mass or less. 2. A zinc oxide powder containing coated ruthenium dioxide, which is coated with cerium oxide which is surface-treated with a surface of a cerium oxide-coated zinc oxide fine particle coated with cerium oxide. The powder of the zinc oxide fine particles is finely classified by a dry type, and the coarse particles of 5 μm or more are reduced to 0.1% by mass or less. 3. The zinc oxide powder containing the coated cerium oxide according to the second aspect of the patent application, wherein the hydrophobicity-imparting agent is one or more selected from the group consisting of an anthrone oil, an alkoxynonane, a decane coupling agent, and A hydrophobicity-imparting agent of a group of higher fatty acid salts. 4. The coated cerium oxide-containing zinc oxide powder according to claim 2 or 3, wherein the surface-hydrophobic coated cerium oxide-containing metal oxide fine particles have a primary particle diameter of 5 to 120 nm and are oxidized. The thickness of the enamel film is 0.5 to 25 nm. 5. The coated cerium oxide-containing zinc oxide powder according to claim 1 or 2, wherein the oxidized zinc oxide particles coated with cerium oxide are oxidized 1310397 矽 film at 1150 to 1250 cm -1 and 1000 to 1100 cm -1 The ratio of the absorption peak intensity of the infrared absorption spectrum is 1 (1 = 11/12; II is the absorption peak intensity of 1150 to 1250 CHT1, and 12 is the absorption peak intensity of 1000 to 1100 cm·1), and the ruthenium dioxide film is The refractive index is 1.435 or more. 6. The coated zinc oxide powder containing cerium oxide according to claim 1 or 2, the photocatalytic activity of the coated cerium oxide-containing zinc oxide powder measured by the tetrahydrogenonaphthalene auto-oxidation method is 60 Pa/ Minutes or less. 7. The pigment fading speed of the coated cerium oxide-containing zinc oxide powder measured by the Sunset yellow method, as claimed in claim 1 or 2 of the coated cerium oxide-containing zinc oxide powder. ABS49 〇 / hour) is 0 or less. 8. The oxidized coating containing cerium oxide according to claim 1 or 2; zinc powder, which is decomposed by the organic ultraviolet absorber measured by the Plasol method The speed (Δ ABS34G/hour) is 〇.〇1 or less. 9. If the coated cerium oxide-containing stomach 41: stomach 'powder', the cerium oxide-coated zinc oxide powder is measured by the p-methoxy benzoic acid Z-hexyl hexyl ester method. The organic ultraviolet absorber has a decomposition rate of 5% or less. 10. The coated cerium oxide powder containing the coated cerium oxide according to the first or second aspect of the patent application contains the oxidized zinc oxide powder containing ~~ oxidized tongs 43 -2- 1310397 η · as claimed in the first section The zinc oxide powder coated with silica sand contains 2 parts by mass to 5 parts by mass of titanium dioxide per part by mass of zinc oxide. 12. A zinc oxide powder containing coated silica sand as claimed in claim </ RTI> wherein at least a portion of the titanium dioxide is coated with silica sand. 13. The zinc oxide powder containing coated silica sand according to claim 12, wherein the titanium dioxide system contains a mixed crystal having a titanium-oxygen-oxime bond in a primary particle diameter. 14. The coated cerium oxide-containing zinc oxide powder according to claim 13, wherein the titanium dioxide has a BET specific surface area of Am2/g'Si〇2 content of B% by mass, Β/Α = 0·02 to 0.5. The zinc oxide-containing zinc oxide powder containing the titanium dioxide-based BET specific surface area of from 1 Å to 200 m 2 /g, as claimed in claim 13 or 14. 16. The coated zinc oxide powder containing cerium oxide according to claim 13 or 14, wherein the primary particle diameter of the titanium dioxide is from 0.008 μm to 0.15; 17. The coated cerium oxide-containing zinc oxide powder according to claim 13 or 14, wherein the titanium dioxide has a core/shell structure and is rich in a TiO2 phase in the core, and is rich in the shell Constructor containing Si〇2 phase. An organic polymer composition containing the coated zinc oxide powder -3-1310397 〇.01-80 mass%' and heat according to any one of claims 1 to 17 The plastic resin is 99.9 to 2% by mass. 1 9 · An organic polymer composition comprising 0.01 to 80% by mass of the zinc oxide powder containing the coated cerium oxide according to any one of claims 1 to 17, and selected from the group consisting of polyethylene and poly The thermoplastic resin of propylene and polystyrene 'polyamide, polyester, and polycarbonate is composed of 99.9 to 20% by mass. 20. The organic polymer composition of claim 18 or 19, which is obtained by molding a shaped body. The composition according to claim 20, wherein the molded body is selected from the group consisting of fibers, filaments, films, ribbons, sheets, hollow bodies, and multilayer structures. 22. The composition of claim 21, wherein the forming system is used for at least one selected from the group consisting of internal and external building materials, machinery, vehicle interior and exterior materials, glass products, home appliances, agricultural materials, electronic machines, tools, food containers, Bathroom supplies, toilet products, furniture, clothing, weaving, non-woven fabrics, cloth products, leather products, paper products, sporting goods, bedding, containers, glasses, advertising boards, piping, wiring, metal parts, sanitary materials, automotive supplies, tents Items such as outdoor items, stockings, socks, gloves, masks, and undershirts. 23. The coated cerium oxide-containing zinc oxide powder according to claim 1 or 2, which is used for a cosmetic.