JPH0867867A - Ultraviolet rays blocking material, ultraviolet rays blocking synthetic resin, ultraviolet rays blocking cosmetic and ultraviolet rays blocking coating film respectively using the same - Google Patents

Abstract

PURPOSE: To obtain an ultraviolet rays blocking material capable of absorbing ultraviolet rays having 200-400nm wavelength and readily being kneaded into synthetic resins, excellent in dispersibility and readily controlling color by carrying a cerium compound on inorganic porous fine particles. CONSTITUTION: This ultraviolet rays blocking material is obtained by carrying (B) a cerium compound and preferably further (C) a metal oxide on inorganic porous fine particles obtained preferably by an interfacial reaction method. Furthermore, though the size and the shape of the particles depend on uses, the size of particles are preferably 0.001-100μm, further preferably 0.05-50μm. As the component B, e.g. CeF3 , CeCl3 or CeO2 , etc., can be used and, as the component C, e.g. Fe2 O3 or ZnO can be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention shields ultraviolet rays contained in sunlight or the like that change substances such as synthetic resins or induce misreading of genetic information of cells of organisms to cause cancer. The present invention relates to an ultraviolet shielding material, a synthetic resin, a coating film, and a cosmetic product using the same.

[0002]

2. Description of the Related Art Generally, the surface of the earth is 200 nm or more in sunlight.
Ultraviolet light with a wavelength of 400 nm arrives. The average particle size is 0.005 for a conventional ultraviolet shielding material that absorbs the wavelength.
White titanium oxide, white zinc oxide or red iron oxide having an average particle size of 0.008 to 0.05
A yellow to orange ultrafine cerium oxide sol having a particle size of 0.1 to 5.0 μm and a slight yellow color containing 8% by weight of silicon dioxide, 5 to 24% by weight of cerium oxide and a pigment are obtained.
A white flaky or agglomerated particle silica-cerium oxide coated pigment has a slightly yellow to yellow color which is composed of zirconium oxide having an average particle diameter of 0.05 μm and containing about 35 to 49% by weight of zirconium oxide and 49 to 65% by weight of cerium oxide. Zirconium oxide-cerium oxide composite fine particles are commercially available.
Then, these ultraviolet shielding materials are mixed or added to synthetic resins, paints and cosmetics to produce ultraviolet shielding synthetic resins, ultraviolet shielding coating films, ultraviolet-cut cosmetics and the like.

[0003]

Therefore, various conventional ultraviolet shielding materials have various problems. That is, these conventional ultrafine particles of titanium oxide and ultrafine particles of zinc oxide are white, but have absorption wavelength regions of 350 nm or less and 37
It was 0 nm or less, and it was impossible to absorb all wavelength regions of ultraviolet rays. Also, although ultrafine iron oxide absorbs the entire wavelength range of ultraviolet rays, since it is iron oxide,
It has a red color, and when used in synthetic resins, paints and cosmetics, its color could not be adjusted arbitrarily, and it was used only in a limited number.

In the case of high concentration, the ultrafine cerium oxide sol absorbs all wavelength regions of ultraviolet rays, but since it is colored yellow to orange, when it is used in paints, it can be used in the same manner as iron oxide. Although it is difficult to adjust the color, the amount of addition is reduced to prevent coloring, but the absorption wavelength range of ultraviolet rays is reduced to 350 nm, and it is impossible to absorb the entire wavelength range. Further, when the ultrafine cerium oxide sol is subjected to a powdering treatment, there is a problem in that the particles agglomerate and the ability to absorb ultraviolet rays decreases. Further, since the ultrafine cerium oxide sol is in the form of a sol, it cannot be kneaded into a synthetic resin, and an ultraviolet shielding synthetic resin or the like could not be prepared.

Further, in the silica-cerium oxide coated pigment in which the surface of the core pigment is baked and coated with cerium oxide to prepare an ultraviolet shielding material, the cerium oxide is aggregated during coating and the ultraviolet absorbing ability is lowered. However, it was impossible to absorb the entire wavelength range of ultraviolet rays.

The zirconium oxide-cerium oxide composite particles also have both the ultraviolet reflection function of zirconium oxide and the ultraviolet absorption function of cerium oxide, but the degree of combination is low, and cerium oxide is originally used for the entire wavelength range of ultraviolet rays. What should be absorbed was as low as 350 nm or less.

As described above, the conventional one is colored when absorbing all wavelength regions of ultraviolet rays, and its use is limited or white one is absorbing all wavelength regions of ultraviolet rays. However, it is difficult to knead into a synthetic resin, and each has its advantages and disadvantages. Further, there is no ultraviolet shielding material capable of absorbing the entire wavelength region of ultraviolet rays while transmitting the visible light region.

[0008]

Therefore, the present invention absorbs ultraviolet rays having a wavelength of 200 to 400 nm reaching the surface of the earth, easily kneads into a synthetic resin, and has good dispersibility even when used in paints and cosmetics, It is intended to provide an ultraviolet shielding material whose color is easily adjusted, an ultraviolet shielding synthetic resin using the ultraviolet shielding material, an ultraviolet shielding coating film, and an ultraviolet shielding cosmetic.

Therefore, the problems of the conventional technique are solved as follows. That is, the problem can be solved by an ultraviolet shielding material in which a cerium compound is supported on inorganic porous fine particles or an ultraviolet shielding material in which a cerium compound and a metal oxide are supported on inorganic porous fine particles. Further, the ultraviolet shielding material of the present invention,
An ultraviolet-shielding synthetic resin, an ultraviolet-shielding cosmetic or an ultraviolet-shielding coating film can be obtained from a synthetic resin, a cosmetic raw material or a paint. The wavelength range of ultraviolet rays absorbed by the ultraviolet shielding material in the present invention is 200 nm to 400 nm, and the wavelength of visible light is longer than 400 nm and shorter than 800 nm.

It is desirable that the inorganic porous fine particles used for the ultraviolet shielding material of the present invention have excellent heat resistance, water resistance and corrosion resistance, and the shape, size, etc. are not limited, and are used. Those suitable for the above are preferably used, and natural or synthetic ones are used. For example, as the shape, a spherical shape can be used for cosmetics, an amorphous or spherical shape can be used for the synthetic resin, and a spherical shape can be used for the coating film. The size of the particles is 0.
Those having a thickness of 001 to 1000 μm can be used, and those having a thickness of 0.05 to 50 μm are particularly preferable. As the inorganic porous fine particles, the Chisso adsorption method (revised augmented powder physical property illustration edited by Japan Society of Powder Engineering and Japan Powder Engineering Society, published by Nikkei Technical Book Co., Ltd., date of issue: Showa 6
December 21, 2000, method described on pages 120 to 121) and mercury injection method (revised expanded powder physical property illustrated by Powder Engineering Society of Japan and Japan Powder Industrial Technology Association, published by Nikkei Technical Book Co., Ltd.)
Publication date: December 21, 1985, 121-124
The pore volume measured by the method described on page is 0.01
If it is cc / g or more, it is appropriately used.

Examples of the inorganic compound forming the inorganic porous fine particles used in the present invention include alkaline earth metal carbonates, silicates, phosphates, sulfates, metal oxides and metal hydroxides. , Other metal silicates, or other metal carbonates can be used. Specifically, the alkaline earth metal carbonates include calcium carbonate, barium carbonate, and magnesium carbonate, and the alkaline earth metal silicates include calcium silicate, barium silicate,
Examples thereof include magnesium silicate, examples of the alkaline earth metal phosphate include calcium phosphate, barium phosphate, magnesium phosphate, and examples of the alkaline earth metal sulfate include calcium sulfate, barium sulfate, magnesium sulfate, and the like. .

Further, metal oxides include silica, titanium oxide, iron oxide, cobalt oxide, zinc oxide, nickel oxide, manganese oxide, aluminum oxide, and metal hydroxides include iron hydroxide, nickel hydroxide, and hydroxide. Examples thereof include aluminum, calcium hydroxide, chromium hydroxide and the like.

Examples of the other metal silicates include zinc silicate and aluminum silicate, and examples of the other metal carbonates include zinc carbonate, aluminum carbonate, copper carbonate and nickel carbonate.

As the other inorganic porous fine particles, zeolite, diatomaceous earth and the like can be used.

Further, spherical inorganic porous fine particles disclosed in Japanese Examined Patent Publication No. 57-55454 can also be used. The method for producing the inorganic porous fine particles is as follows. A water-in-oil type emulsion (emulsion) is made with an agent and mixed with another aqueous solution of an inorganic compound to cause a precipitation reaction at the water drop interface to form an inorganic shell, and then a by-product or a surfactant. It is obtained by an interfacial reaction method that removes the like. The inorganic porous fine particles thus obtained are the solid inorganic hollow fine particles shown in FIG. 1 or the hollow inorganic porous fine particles shown in FIG.

For example, when silica is used as the inorganic compound, as an example, a water glass solution is first emulsified with a liquid paraffin solution of sorbitan monostearate and polyoxyethylene sorbitan monooleate to form a water-in-oil type. The emulsion is prepared and further added to an ammonium sulfate solution to cause a reaction, and the mixture is allowed to stand. Then, by filtering, washing and drying, hollow inorganic porous fine particles whose wall substance is hydrated silicic acid can be obtained. The inorganic porous fine particles of the present invention thus obtained have a particle diameter of 0.1 to 1000 μm and a pore volume of 0.01 to 5 cc.
/ G, pore size 20-600Å, specific area 100-80
A product of 0 m ² / g is obtained.

In addition, a substance contained in a clay mineral to form a card house or an intercalation compound may be used. Specific examples thereof include bentonite, activated bentonite, sodium bentonite, montmorillonite, acid-treated montmorillonite, activated clay, synthetic cement, synthetic amesite, synthetic frypontite, synthetic fryponta (na) ite / silica, smectite, hectite. , Laponite, Bidelite, Nontrolite,
Examples include saponite and vermiculite.

[0018] cerium compound is a compound containing cerium is a metal of lanthanide, specifically cerium fluoride (CeF _3), cerium chloride (CeCl ₃ or _{CeCl 3 · n H 2 O)} , cerium oxide (CeO ₂
Or CeO ₃ ) and cerium hydroxide (2Ce (OH) ₃
・ 3H ₂ O), cerium sulfate (Ce ₂ (SO ₄ ) ₃ or C
e (SO ₄ ) ₂ ), cerium oxalate (Ce ₂ (C
₂ O ₄ ) ₃ ), cerium acetate (Ce (C ₂ H
₃ O ₂ ) ₃ ), cerium nitrate (Ce ₂ (NO ₃ ) ₃ or C
e (NO ₃ ) ₄ ), ceric ammonium nitrate (Ce ₂ (N
_{O 3) 3 · 2NH 4 NO} 3), ceric ammon sulfate _{(Ce (NO 3) 4 ·} 2 (NH 4) 2 SO 4) and the like. A sol of these cerium compounds can also be used.

As the metal oxide, one obtained by oxidizing a metal having an ultraviolet absorbing ability is used, and specifically, iron oxide (Fe ₂ O ₃ ), zinc oxide (ZnO), titanium oxide (TiO ₂ ) and the like are used. Can be illustrated.

Further, as a method for supporting the cerium compound on the inorganic porous fine particles, the following method can be used. As the method, a cerium compound 4 is introduced into the void portion 2 or the hollow portion 3 of the inorganic porous fine particles 1 shown in FIG. 1 or 2 obtained by the above step under the equipment configuration shown in FIG. did. In this device, a vacuum chamber 7 provided with an exhaust valve 5 and a leak valve 6 and a tank 8 containing a solution of a cerium compound 4 are connected via an introduction valve 9, and inside the vacuum chamber 7. By depressurizing the inorganic porous fine particles 1, the solution of the cerium compound 4 under normal pressure was introduced into the voids 2 by utilizing the pressure difference. An example of the schematic process is shown below.

First, the inorganic porous fine particles 1 are set in the vacuum chamber 7, the exhaust valve 5 is opened while the leak valve 6 and the introduction valve 9 are closed, and the vacuum chamber 7 is depressurized to 10 to 10 ^-3 torr. To do. Next, the exhaust valve 5 is closed to end the exhaust of the vacuum chamber 7, and the introduction valve 9 is opened. At this time, since the tank 8 containing the solution of the cerium compound 4 is at atmospheric pressure, the cerium compound 4 is introduced into the vacuum chamber 7 due to the pressure difference. Since the voids 2 of the inorganic porous fine particles 1 are also depressurized by the exhaust in the vacuum chamber 7, the cerium compound 4 introduced into the vacuum chamber 7 penetrates into the voids 2 inside the inorganic porous fine particles 1. Subsequently, the leak valve 6 is opened to return the vacuum chamber 7 to atmospheric pressure, and then the excess solution of the cerium compound 4 is separated by filtration or the like to obtain inorganic porous fine particles carrying the cerium compound 4. In addition to the above, as a method of supporting the cerium compound, by mixing inorganic porous fine particles with a solution of the cerium compound, the cavities 2 or the hollow portions 3 shown in FIG. It can be supported.

Further, the inorganic porous fine particles carrying the cerium compound have a chamber temperature of 100 to 100 in the atmosphere.
By firing with a heating device or a firing device such as a 1000 ° C. muffle or oven, the carried cerium compound is oxidized to cerium oxide, and an ultraviolet shielding material having an ultraviolet absorbing ability is obtained. Alternatively, inorganic porous fine particles carrying a cerium compound may be added with an alkaline aqueous solution such as aqueous ammonia or an aqueous solution of caustic soda to form a hydroxide compound, or may be oxidized with an oxidizing agent such as hydrogen peroxide. Cerium compound 4 after supporting inorganic porous fine particles 1 used here
The content of is preferably 0.1 to 80% by weight, and particularly preferably 1 to 30% by weight. That is, if it is less than 0.1% by weight, the ultraviolet ray absorbing ability is insufficient and the ultraviolet ray shielding ability is lowered, and if it is more than 80% by weight, the cerium compound leaks out from the inorganic porous fine particles.
It is better to set it in the above range.

An example of a schematic sectional structure of the inorganic porous fine particles 1 carrying the cerium compound 4 thus produced is shown in FIG. In the example shown in the figure, the cerium compound 4 is carried in the non-hollow inorganic porous fine particles 1 whose wall substance is silicic acid anhydride, and the cerium compound from the numerous voids 2 ... Compound 4 can absorb ultraviolet rays. Further, the hollow portion 3 as shown in FIG.
It is also possible to have a state having.

Further, in such an ultraviolet shielding material, after a color material described later is carried in the hollow portion 3 of the hollow inorganic porous fine particles 1 as shown in FIG. 2, a cerium compound is placed in the void portion 2. It is also possible to produce a supported colored ultraviolet shielding material. As a method for supporting the color material, Japanese Patent Publication No. 5-3449 as proposed by the present applicant is proposed.
It can also be performed by the method disclosed in the publication.

Specific examples of the color material include the following. ◎ Inorganic pigment White pigment: Titanium oxide, zinc oxide, lithopone, zinc sulfide, zirconium oxide, barium metaborate, Puffunson white, manganese white, tungsten white, magnesium oxide, etc.

Black pigment: carbon black, iron black, titanium black,
Silica black, graphite, etc.

Gray pigment: zinc dust, zinc carbide, etc.

Red pigments: red iron oxide, cobalt red, molybdenum red, cobalt magnesia red, cuprous oxide, ferrocyanine copper red ultramarine and the like.

Yellow pigment: Ocher, yellow iron oxide, titanium yellow, barium yellow, strontium yellow, chrome titanium yellow, aureoline (cobalt yellow), tungsten yellow, vanadium yellow, nickel yellow, etc.

Green pigments: chrome green, chrome oxide, chrome hydroxide, zinc green, cobalt green, greenery, cobalt chrome green, Egyptian green, manganese green, pramen green, poly green, phosphate green, titanium green and the like.

Blue pigments: ultramarine blue, navy blue, cobalt blue, tungsten blue, molybdenum blue, egyptian blue, plemen blue, copper borate, lime blue, rock ultramarine blue and the like.

Purple pigment: Mars purple, manganese purple, cobalt purple, cobalt purple Nova, chromium chloride, copper purple, ultramarine purple and the like.

Metal powder pigments: aluminum powder, copper powder, bronze powder, stainless steel powder, nickel powder, silver powder, gold powder, etc.

Brown pigments: amber, iron oxide powder, Van Dyke tea, Prussian tea, manganese tea, copper tea, cobalt tea, ferrocyan copper tea and the like.

Pearl pigments: mica titanium, fish scale, bismuth oxychloride, iron oxide-treated mica titanium, navy blue-treated mica titanium, carbon black-treated mica titanium, carmine-treated mica titanium and the like.

Extender pigments: silica, silica white, calcium carbonate, barium carbonate, magnesium carbonate, magnesium silicate, calcium silicate, barium sulfate precipitating, baryta, white alumina, talc, gypsum, clay, satin white,
Bentonite, magnesia, slaked lime, strontium white, kaolin, mica, sericite, etc.

As the organic pigment, it is possible to use tar-based dyes, and for example, the following are listed as legal dye names. In red, red 2 and red 3
No. 102, Red No. 102 to Red No. 106, Red No. 201 to Red No. 208, Red No. 213 to Red No. 215, Red No. 218 to Red No. 223, Red No. 225 to Red No. 228, Red No. 2
No. 30-Red No. 232, Red No. 401, Red No. 404-
Red No. 405, red No. 501 to red No. 506, etc. can be exemplified.

For yellow, yellow 4, yellow 5, yellow 20
1-yellow 205, yellow 401-407 etc. can be illustrated.

Further, as the green color, green No. 3, green No. 201 to green No. 205, green No. 401 to green No. 402 and the like can be exemplified.

For blue, blue 1 to blue 2 and blue 20
No. 1 to blue No. 205, blue No. 403 to blue No. 404 and the like can be exemplified.

Other examples include purple No. 401 and black No. 401.

The content of the color material supported on the inorganic porous fine particles is preferably about 0.01 to 80% by weight, and particularly preferably 0.01 to 60% by weight. it can. That is, if the content of the coloring material is less than 0.01% by weight, it is difficult to adjust the color tone due to poor coloring property, and if the content is more than 80% by weight, it becomes difficult to carry the cerium compound and the ultraviolet absorption ability is increased. As the color material deteriorates and is regressed by ultraviolet rays,
It is desirable to set it in the above range. Further, in order to make it easy to knead into the resin, it is possible to treat with a silane coupling agent, a titanium coupling agent, or an aluminum coupling agent. In order to obtain biocompatibility, the surface of the particles can be coated with a material made of silicone, chitin, chitosan or the like.

As the synthetic resin used for the ultraviolet ray shielding synthetic resin, a thermosetting resin or a thermoplastic synthetic resin can be used. Specific examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furan resin, alkyd resin, epoxy resin, silicon resin,
Polyurethane can be exemplified. Specific examples of the thermoplastic resin include vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol, polystyrene, AS resin, ABS resin, methacrylic resin, polyethylene, polypropylene, fluororesin, polyamide,
Polyacetal resin, polycarbonate, polyphenylene oxide, polysulfone, celluloid, acetic acid fibrin plastic, silicone resin, polyacetal resin,
An unsaturated polyester resin etc. can be illustrated. Copolymers of the thermosetting resins and thermoplastic resins exemplified above can also be used. The content of the ultraviolet ray shielding material mixed with the synthetic resin is preferably 0.1 to 50% by weight, and particularly preferably 0.5 to 10% by weight.
Can be mixed. That is, when the content is less than 0.01% by weight, the amount of ultraviolet absorption decreases and the ultraviolet resistance of the synthetic resin decreases, and the synthetic resin deteriorates. Also, 50
If the content is more than weight%, the synthetic resin does not have a stickiness due to the ultraviolet shielding material and is easily disintegrated, so that the above range is preferable. With the content shown above, as a method for producing an ultraviolet shielding synthetic resin using a thermoplastic resin or a production method, an injection molding machine, an extrusion molding machine, together with pellets of the ultraviolet shielding material and the thermoplastic resin of the present invention,
The ultraviolet-shielding synthetic resin can be produced by molding in a mold heated to 100 to 300 ° C. such as a blow molding machine, a calender roll molding machine, a calender molding machine or a compression molding machine. When a thermosetting resin is used as a raw material, an ultraviolet-shielding synthetic resin can be produced by adding and mixing the raw material to the raw material and heating appropriately.

Examples of the UV-shielding cosmetics of the present invention include lotions, cream emulsions, foundations, white powder dusters, lipsticks, eyebrow cheek cosmetics, cosmetic oils and the like. Specific examples of the lotion include aftershaving lotion, general lotion, cologne, shaving lotion, hand lotion, suntan lotion, sunblock lotion and the like. As cream emulsions, aftershaving lotion,
Examples include cleansing cream, cold cream, shaving cream, milky lotion, vanishing cream, hand cream, sun cream, sunblock cream and the like. Specific examples of the foundations include cream foundations, liquid foundations, solid foundations and the like. Specific examples of the white powder dusting agents include cream powder, solid powder, powder powder, talcum powder, kneading powder, baby powder, body powder, and water powder. Examples of lipsticks include lipsticks and lip balms. Specific examples of eyebrow cheek cosmetics include eye cream, eye shadow, eyeliner, blusher, mascara, and eyebrow. Specific examples of the cosmetic oils include cosmetic oil and baby oil. The content of the ultraviolet ray shielding material mixed with the above-mentioned cosmetics is preferably about 0.1 to 50% by weight, particularly preferably 1 to 20%.
% Can be included. That is, if it is less than 0.1% by weight, the amount of ultraviolet ray absorption is reduced and it is impossible to prevent sunburn of the skin, etc. If it is contained in an amount of more than 50% by weight, it will be absorbed by the ultraviolet ray shielding material to the skin. Since the extensibility of is decreased, it is preferable to set it within the above range. That is, an ultraviolet-shielding cosmetic product can be produced or manufactured by mixing or emulsifying with the cosmetic raw materials described below.

As a cosmetic raw material for producing such cosmetics, those described in the "Cosmetic Raw Material Standard" of the Ministry of Health and Welfare are generally used. A specific example will be described below.
Oils and fats include olive oil, cacao butter, sesame oil, squalane, safflower oil, soybean oil and coconut oil, waxes include caderin wax, carnauba wax and lanolin, and fatty acids include
Examples thereof include oleic acid, oleic acid ester, stearic acid, stearic acid ester, palmitic acid, palmitic acid ester, myristic acid, myristic acid ester and the like. Further, liquid paraffin can be exemplified as the paraffin.

As the organic acid, ester compounds and metal salts can be used. Specific examples of the amino acid include aspartic acid, alanine, cystine, cysteine, serine, threonine and the like. Further, other organic acids include acetic acid, acetic acid ester, salicylic acid, salicylic acid ester, lactic acid, lactate, citric acid, citric acid anhydride, succinic acid, succinic acid ester, tartaric acid, sorbic acid, sorbic acid ester, oxalic acid, etc. Can be illustrated. Vitamins include pyridoxine hydrochloride, calcium pantothenate, biotin, vitamin A, β-carotene, sodium ascorbate, ascorbic acid, nicotinic acid amide,
Examples thereof include dl-α-tocopherol. Further, as the protein, casein, gelatin and the like can be used. Examples of the saccharide include sodium alginate, propylene glycol alginate, carrageenan, starch, sorbit, inosit, xylit, manit, nitrocell sauce, avia gum, sodium chondroitin sulfate and the like.

Examples of the surfactant include polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene compound, monooleic acid, monooleic acid ester, monolauric acid, monolauric acid ester, monostearic acid, monostearic acid ester, monopalmitin. Examples thereof include acids, monopalmitic acid esters, dipalmitic acid esters, castor oil, alkyl sulfates, sucrose fatty acid esters, soybean phospholipids and the like.

Further, examples of the chloride include zinc chloride, aluminum chloride, ferric chloride, potassium chloride and the like.

Examples of the silicic acid compound include calcium silicate, sodium silicate and silicic acid aldehyde.

Examples of the hydroxide compound include sodium hydroxide, calcium hydroxide, chromium hydroxide and the like.

Examples of the sulfuric acid compound include potassium aluminum sulfate, sodium sulfate, barium sulfate and the like.

Examples of the phosphoric acid compound include potassium dihydrogen phosphate, calcium hydrogen phosphate, sodium monohydrogen phosphate and the like.

In addition, glycerin, acetone, allantoin, sodium hydrogen sulfite, anhydrous sodium sulfite,
Almond oil, benzoic acid, sodium benzoate, isoctamol, liquid paraffin, paraffin, isopropanol, inosit, ethyl alcohol, anhydrous ethyl alcohol, edetic acid, edetate, diphenhydramine hydrochloride, eugenol, γ-oryzanol, carbon black, kaolin, calamine. , Licorice extract, canthariskitin, d-camphor, xylene, guaiazulene, coumarin, cresol, chloramine T, glycyrrhetinic acid, glycyrrhetinic acid compound, glycyrrhizinic acid, glycyrrhizinic acid compound, cyclohexane, citronellal, sodium oxalate, sodium bromate, bromine Compound, paraoxybenzoic acid, paraoxybenzoic acid compound,
Examples thereof include red iron oxide, bentonite, borax, mica, phosphorus roll, stalin, resorcin, rosin and vaseline.

Examples of natural dyes include flavonoids, carotenoids, quinones, porphyrins and the like.

As the pigment, those exemplified as the color material can be used.

The paint includes phenol resin paint, alkyd resin paint, aminoalumin resin paint, guanamine resin paint, vinyl chloride resin paint, butyral resin paint, styrene butadiene paint, chlorinated rubber paint, acrylic resin paint, epoxy resin paint, Unsaturated polyester resin paint,
Polyurethane resin paint, silicon resin paint, titanium resin paint, fluorine resin paint, vinyl acetate emulsion paint,
Examples thereof include styrene-butadiene-based emulsion paints and acrylic-based emulsion paints. An ultraviolet-shielding coating film can be prepared by mixing the ultraviolet-shielding material with this paint to form a coating film. The content of the ultraviolet shielding material mixed with the above-mentioned paint is preferably about 0.1 to 50% by weight, particularly preferably 1 to 2
It may contain 0% by weight. That is 0.1% by weight
If it is less than 50% by weight, the amount of ultraviolet absorption is reduced, the ultraviolet resistance of the coating film is reduced, and if it is contained in an amount of more than 50% by weight, the formation of the coating film is deteriorated by the ultraviolet shielding material.
It is desirable to set it in the above range.

[0057]

According to the ultraviolet shielding material of the present invention, by supporting the cerium compound on the inorganic porous fine particles, the ultraviolet rays penetrate into the voids of the inorganic porous fine particles and the ultraviolet rays are absorbed by the carried cerium compound. can do.
Further, the cerium compound in the inorganic porous fine particles can absorb ultraviolet rays by being mixed with the synthetic resin, the cosmetic raw material, and the paint.

[0058]

EXAMPLES Details of the present invention will be described based on examples. (Example 1) As Example 1, a spherical inorganic material of silica having a mean particle diameter of 5.0 μm, a mean pore volume of 0.9 cc / g, a mean pore diameter of 5 nm, and an ignition loss of 6% by weight of 60 g. 40 g of acetic acid-stabilized cerium oxide sol (trade name: Needral U15, manufactured by Taki Chemical Co., Ltd.) containing 15% by weight of cerium oxide in porous fine particles (trade name: Godball E-16C, manufactured by Suzuki Yushi Kogyo Co., Ltd.) ) Was carried. Then, this is baked for about 6 hours in a muffle furnace (trade name: FM-36 type, manufactured by Yamato Scientific Co., Ltd.) having an internal temperature of 400 ° C., and ultraviolet rays shielding 9.6 wt% of cerium oxide are carried. A material was produced.

(Embodiment 2) As Embodiment 2, Embodiment 1
The same operation as in Example 1 was performed, except that 60 g of acetic acid-stabilized cerium oxide sol (trade name: Ceria sol, manufactured by Anan Kasei Co., Ltd.) containing 11.3% by weight of cerium acetate was used. Then, an ultraviolet shielding material carrying 7.4% by weight of cerium oxide was prepared.

(Example 3) 60 g spherical inorganic porous material having a coating average particle diameter of 5.0 μm, an average pore volume of 0.9 cc / g, an average pore diameter of 5 nm, and a loss on ignition of 6% by weight. 40 g of cerium acetate solution containing 7.68 wt% of cerium oxide in fine particles (trade name: Godball B-6C, manufactured by Suzuki Yushi Kogyo Co., Ltd.) (trade name: cerium acetate solution, manufactured by Daiichi Rare Element Co., Ltd.) Was carried. Then, this is baked for about 6 hours in a muffle furnace (trade name: FM-36 type, manufactured by Yamato Scientific Co., Ltd.) with a chamber temperature of 400 ° C., and an ultraviolet shielding material carrying 5.1% by weight of cerium oxide. Was produced. 3 for the 60g UV shielding material
A cerium acetate solution containing 7.68% by weight of 0 g of cerium oxide was supported, and cerium oxide was supported under the same firing conditions as in Example 1. Then, 11.2 g of tetraethoxylane liquid and 4.4 g of this ultraviolet shielding material
Example 3 coated with silica and alumina to prevent the agglomeration by supporting 10.9% by weight of cerium oxide by carrying out firing under the same conditions and operations as in Example 1 by supporting the above-mentioned triisopropyl oxide aluminum liquid. As a result, an ultraviolet shielding material was prepared.

Example 4 In Example 4, silica was used as a raw material, the average particle diameter was 5.0 μm, and the average pore volume was 0.9.
cc / g, average pore size 5 nm, ignition loss 6% by weight 60
g spherical inorganic porous fine particles (trade name: God Ball E
-2C, manufactured by Suzuki Yushi Kogyo Co., Ltd.), 40 g of a cerium acetate solution containing 7.68% by weight of cerium oxide (trade name: cerium acetate solution, manufactured by Daiichi Rare Elements Co., Ltd.)
Was carried. Then, this is baked for about 6 hours in a muffle furnace (trade name: FM-36 type, manufactured by Yamato Scientific Co., Ltd.) having a chamber temperature of 400 ° C., and 5.1% by weight of cerium oxide.
An ultraviolet shielding material having good transmission of the carried visible light was produced.

Example 5 In Example 5, 20 g of a 6.78% cerium acetate aqueous solution (trade name: cerium acetate solution, manufactured by Daiichi Rare Element Co., Ltd.) and 20 g of a 5% zinc acetate aqueous solution (trade name: A mixed solution of zinc acetate and Wako Pure Chemical Industries, Ltd., was mixed with 70 g of ultrafine alumina Aluminium.
n Oxide C (manufactured by Japan Aerology Co., Ltd.) and supported, and fired under the same conditions as in Example 1,
An ultraviolet shielding material was produced.

Example 6 In Example 6, a mixed solution of 15 g of an aqueous 20.41% cerium nitrate solution and 20 g of an aqueous 5% ferric nitrate solution was used as an inorganic porous material made of calcium silicate. Fine particles (trade name: God Ball CAS,
(Supplied by Suzuki Yushi Kogyo Co., Ltd.) and supported, and baked under the same conditions as in Example 1 to prepare an ultraviolet shielding material.

Example 7 In Example 7, 20 g of a mixed solution of 20.41% cerium nitrate aqueous solution and 10 g of 5% zinc nitrate aqueous solution was mixed with 60 g of white carbon (trade name: Fineseal X70, Tokuyama). Soda Co., Ltd.) and montmorillonite (Murakami Clay Industry Co., Ltd.) were added and supported, and baked under the same conditions as in Example 1 to prepare an ultraviolet shielding material.

Example 8 In Example 8, a mixed solution of 10 g of a 10% cerium sulfate aqueous solution and 10 g of a 5% zinc sulfate aqueous solution was added to 60 g of sodium bentonite (manufactured by Murakami Clay Industry Co., Ltd.). Example 1 supported
Firing was performed under the same conditions as above to produce an ultraviolet shielding material.

Example 9 In Example 9, 20 g of a 2% cerium sulfate aqueous solution and 20 g of a 2% zinc sulfate aqueous solution were mixed with 5 g of Laponite G (trade name: Laponite G, Nihon Silica Co., Ltd.). Made by the company) and 5g of Laponite S
An ultraviolet shielding material was produced by adding and supporting it to a mixture (trade name: Laponite S, manufactured by Nippon Silica Co., Ltd.) and firing the mixture under the same conditions as in Example 1.

(Embodiment 10) The tenth embodiment includes 10
0g low density polyethylene (density: 0.914g / cm
³ , MI: 0.3) pellets and 20 g of the ultraviolet shielding material of Example 1 were put into a heating container of 100 to 130 ° C., mixed while being melted, and further adjusted to 190 ° C. The film was put into a molding machine to prepare a 200 μm-thick UV-shielding polyethylene film.

(Embodiment 11) The tenth embodiment includes 10
Add 0 g of water-soluble polyurethane resin coating (trade name: Neo Deluxe UW, manufactured by Kansai Paint Co., Ltd.) and 20 g of the ultraviolet shielding material of Example 1 and apply to a 1 mm thick plywood plate to apply 30 μm thick ultraviolet rays. A shielding coating film was prepared.

(Example 12) As Example 12, a cosmetic cream foundation prepared by using Example 4 was prepared according to the formulation shown in Table 1. That is, the production method is as follows: Purified water, triethanolamine, sorbit, paraoxybenzoic acid ester are mixed to prepare an aqueous phase,
Heat to 0 ° C. and add the UV blocking material of Example 4. Furthermore, stearic acid, lipophilic glyceryl monostearate, cetocytearyl alcohol, propylene glycol monolaurate, liquid paraffin, isopropyl myristate, and butyl paraoxybenzoate are mixed to prepare an oil phase, which is heated to 80 ° C. Then, the oil phase is added to the water phase with stirring to emulsify, and then 5 with stirring.
Cool to 0 ° C. and add perfume. And it cooled to room temperature and produced the cosmetic creamy foundation which is Example 12.

Comparative Example 1 As Comparative Example 1, silica containing 18% by weight of silicon dioxide and 24% by weight of cerium oxide-cerium oxide-coated talc (trade name: Cerigard-
T-3018, manufactured by Japan Inorganic Chemical Industry Co., Ltd.) was used as it was.

(Comparative Example 2) As Comparative Example 2, a product containing 42% by weight of zirconium oxide and 58% by weight of cerium oxide (trade name: CERACLAN III, manufactured by Toray Industries, Inc.) was used.

Comparative Example 3 As Comparative Example 3, an acetic acid-stabilized sol containing 15% by weight of cerium oxide (trade name: Needral U15, manufactured by Taki Chemical Co., Ltd.) was used.

(Comparative Example 4) In Comparative Example 4, ultrafine particle titanium oxide containing 90% by weight or more of rutile type titanium (trade name: MT-150W, manufactured by TAYCA Corporation) was used.

COMPARATIVE EXAMPLE 5 As Comparative Example 5, Example 1 was used.
The resin used for 0 was used as is.

Comparative Example 6 As Comparative Example 6, Example 1 was used.
The water-soluble polyurethane paint used in 1 was used as it was.

(Comparative Example 7) As Comparative Example 7, a cosmetic creamy foundation was prepared by adding inorganic porous fine particles having no UV-shielding ability as shown in Table 1.

[0077]

[Table 1]

In addition, Examples 1 to 3 and Comparative Example 1,
The ultraviolet shielding ability of Comparative Example 2 was measured. The measuring method is as follows: a spectrophotometer (trade name: UV-2200A, manufactured by Shimadzu Corporation) is used, and the amount of cerium oxide in the sample is adjusted to 1.9% by weight, and the mixture is kneaded with glycerin.
It was put in a 0 × 50 mm quartz glass cell and calculated from the reflectance. The results are shown in Fig. 4.

It is apparent from FIG. 4 that the embodiment has a superior ultraviolet absorbing ability.

Example 4 and Comparative Examples 1 to 3
The ultraviolet shielding ability was measured. That is, 200 nm
The transmittance at a wavelength of ˜800 nm was measured. The measurement method was as follows: A spectrophotometer (trade name: UV-2200A, manufactured by Shimadzu Corporation) was used, and the amount of cerium oxide in the sample was adjusted to 1.9% by weight and kneaded with glycerin to obtain 125 μm.
Quartz glass was sandwiched between the spacers and the transmitted light was measured and calculated from the transmittance. The results are shown in Fig. 5.

It is clear from FIG. 5 that Example 4 absorbs all the ultraviolet rays and has excellent transmittance in the visible rays.

Next, a resistance test by ultraviolet rays in Example 10 and Comparative Example 5 was conducted. The method is to use a sunshine carbon arc lamp as a light source and a sunshine long life weather meter (trade name: WEL-S
UN-HC, manufactured by Suga Test Instruments Co., Ltd.) 1500
Irradiation was carried out for a period of time, and the residual gloss ratio over the irradiation time was measured with a precision gloss meter (trade name: GM-26D, manufactured by Murakami Color Research Laboratory) according to JIS Z-8741. The results are shown in Fig. 6.

From FIG. 6, it is apparent that Example 10 containing the ultraviolet shielding material was resistant to ultraviolet rays.

Next, with respect to the ultraviolet shielding coating films of Example 11 and Comparative Example 6, the same ultraviolet resistance test as in Example 10 and Comparative Example 5 was conducted. The results are shown in Fig. 7.

From FIG. 7, it is apparent that the example 11 containing the ultraviolet shielding material had the ultraviolet resistance.

For Example 12 and Comparative Example 7, SPF (Sun Protection Factor) of Japan Cosmetic Industry Association was used.
It measured according to the measurement. The results are shown in Table 2.

[0087]

[Table 2]

As a result, as is clear from Table 2, Example 12
Had better UV absorption capacity.

[0089]

INDUSTRIAL APPLICABILITY The ultraviolet-shielding material of the present invention has various varieties in which the cerium compound is carried on the inorganic porous fine particles so that the ultraviolet light penetrates and the carried cerium compound absorbs all wavelengths of the ultraviolet light. It can be applied to things. In addition, since the inorganic porous fine particles can be adjusted to any color depending on the material, it is easy to adjust the color, and when mixed with a synthetic resin, a cosmetic raw material, or a paint, the cerium supported on the inorganic porous fine particles is used. Since the compound absorbs ultraviolet rays and prevents the synthetic resin from aging or deterioration due to ultraviolet rays and can be used for a long period of time, it is possible to save the labor and cost for replacement.
Further, it is possible to adjust the color of the ultraviolet-shielding coating film using the ultraviolet-shielding material of the present invention, and also to protect the coating material by absorbing ultraviolet rays, and to protect the coating site for a long period of time, so that it is cost effective. Will also be cheaper. Further, the cosmetics containing the ultraviolet ray shielding material absorb the ultraviolet rays which promote skin cancer and sunburn and shield the ultraviolet rays to the skin, so that the cosmetics can be safely out.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view showing an example of solid inorganic porous fine particles carrying a cerium compound of the present invention.

FIG. 2 is a sectional explanatory view showing an example of hollow inorganic porous fine particles carrying a cerium compound of the present invention.

FIG. 3 is an explanatory view showing an example of a method of injecting a cerium compound into the inorganic porous fine particles of the present invention.

FIG. 4 shows 200 to 80 of Examples 1 to 3 and Comparative Examples 1 and 2.
The graph which measured the reflectance in the wavelength of 0 nm

FIG. 5: 200 to 800 n of Example 4 and Comparative Examples 1 to 3
The graph which measured the transmittance in the wavelength of m.

FIG. 6 is a graph in which gloss remaining ratio is measured by a sunshine weather meter during irradiation time in Example 10 and Comparative Example 5.

FIG. 7 is a graph in which the residual gloss ratio is measured by a sunshine weather meter during irradiation time in Example 11 and Comparative Example 6.

[Explanation of symbols]

 1. Inorganic porous fine particles 2. Void 3. Hollow part 4. Cerium compound 5. Exhaust valve 6. Leak valve 7. Vacuum chamber 8. Tank 9. Introduction valve

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 3/28 KAG 5/09 KAR C09C 1/62 PBL 3/06 PBS C09D 5/00 PRB (72 ) Inventor Yasuhiro Kikuchi 2-3-1 Itakano, Higashiyodogawa-ku, Osaka, Suzuki Oil & Fat Industry Co., Ltd. (72) Shohei Kubota 2- 1-3, Itakano, Higashiyodogawa-ku, Osaka (72) Inventor Keisuke Hatano 2-3-1 Itakano, Higashiyodogawa-ku, Osaka-shi Suzuki Yushi Kogyo Co., Ltd.

Claims (6)

[Claims] 1. An ultraviolet shielding material, characterized in that a cerium compound is supported on inorganic porous fine particles. 2. An ultraviolet shielding material, characterized in that inorganic porous fine particles carry a cerium compound and a metal oxide. 3. The ultraviolet shielding material according to claim 1, wherein the inorganic porous fine particles are obtained by an interfacial reaction method. 4. An ultraviolet shielding synthetic resin comprising the ultraviolet shielding material according to claim 1, 2 or 3 and a synthetic resin. 5. An ultraviolet-shielding cosmetic comprising the ultraviolet-shielding material according to claim 1, 2 or 3 and a cosmetic raw material. 6. An ultraviolet-shielding coating film comprising the ultraviolet-shielding material according to claim 1, 2 or 3 and a paint.