JP3415716B2 - Ultraviolet ray shielding agent and skin external preparation having ultraviolet ray shielding effect - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technical field relating to an ultraviolet shielding agent having an excellent ultraviolet shielding effect, which contains a fine powder of tungsten oxide having an ultraviolet shielding effect, for example, a skin external preparation having an ultraviolet shielding effect. . More specifically, the present invention relates to an ultraviolet blocking agent capable of effectively blocking ultraviolet rays in a wide wavelength range by blending a tungsten oxide fine particle powder capable of effectively shielding both long-wavelength ultraviolet rays and medium-wavelength ultraviolet rays. It belongs to the technical field, and particularly when this ultraviolet blocker takes the form of a skin external preparation, it tends to be generally found in skin external preparations containing powders of metal oxides such as titanium oxide. It belongs to the technical field of an external preparation for skin that has no natural bluish white, has a light spread, and has a natural finish.

[0002]

2. Description of the Related Art In recent years, the adverse effect of ultraviolet rays in sunlight on the human body has become widely known, and countermeasures against it have been studied from various aspects. UV rays are dermatologically long-wavelength ultraviolet rays (UV-) of 320 to 400 nm.
A), medium wavelength ultraviolet rays (UV-B) of 290 to 320 nm and short wavelength ultraviolet rays (UV-C) of 290 nm or less. Of these ultraviolet rays, UV-C is the ultraviolet ray that has the most adverse effect on humans and other living organisms, but at present, most of it is absorbed and scattered by the ozone layer above the atmosphere and reaches the ground directly. (However, due to the recent depletion of the ozone layer, its protective effect diminishes, and there is concern that it will have an adverse effect on the human body.)

On the other hand, it is known that both UV-A and UV-B which reach the ground and are directly exposed to humans have various effects on the human body. These effects are overwhelmingly more adversely affecting the human body than beneficial effects such as promoting the production of vitamin D in the body. For example, UV-A is known to cause "immediate blackening", which is a blackening of the skin that occurs within minutes after exposure, and UV-B is known to cause "erythema" and "blisters". There is. Further, both UV-A and UV-B ultraviolet rays may have various adverse effects on the human body, such as promoting the generation of "spots" and "wrinkles" and being involved in the development of skin cancer. Are known.

Therefore, in order to prevent such adverse effects of ultraviolet rays on the human body, many ultraviolet protective agents have been developed to date. As existing UV-A protective agents, dibenzoylmethane derivatives, benzotriazole derivatives, benzophenone derivatives, anthranil derivatives, etc., as organic compound type ultraviolet absorbers; on the other hand, as inorganic compound type ultraviolet ray shielding agents, zinc oxide powder, oxidation Cerium powder. Zirconium oxide powder and the like are known. Existing UV-B
As the protective agent, as an organic compound-based ultraviolet absorber, a paraaminobenzoic acid derivative, a dimethylaminobenzoic acid derivative, a methoxycinnamic acid derivative, a salicylic acid derivative, a urocanic acid derivative, or the like; Titanium dioxide powder and the like are known.

However, organic compound type ultraviolet absorbers have not always been satisfactory in terms of stability to light and heat and safety to the skin. Also, U
The reality is that an organic compound-based UV absorber that absorbs both VA and UV-B UV rays effectively and in good balance is still under development. On the other hand, zinc oxide powder, which is a highly safe and stable inorganic compound-based UV-screening agent, has an excellent UV-A screening effect, but it blocks UV-A and UV-B UV rays. The effect is weak. On the contrary, in the titanium dioxide powder, the UV-B shielding effect is high, but the UV-A shielding effect is weak. Further, the external preparation for skin containing the titanium dioxide powder has a strong tendency to be accompanied by an unnatural bluish tinge when used, the spread of the makeup is heavy, and the cosmetic finish tends to be unnatural.

[0006]

SUMMARY OF THE INVENTION In view of the above technical situation, the present invention has an excellent ultraviolet shielding effect against ultraviolet rays in both UV-A and UV-B regions, and is safe and stable. Provide an excellent ultraviolet shielding agent, and further have an excellent ultraviolet shielding effect against ultraviolet rays in both the UV-A and UV-B regions in which this ultraviolet shielding agent is blended, and have safety and stability. It is an object of the present invention to provide an external preparation for skin which is excellent and has a natural finish and good usability.

In the inorganic compound type ultraviolet ray shielding agent which is the subject of the present invention, a slight light scattering ultraviolet ray shielding effect can be recognized, but most of the ultraviolet ray shielding effect is due to the band structure of the ultraviolet ray shielding agent itself. It depends on the absorption function of the resulting light. That is, the above-mentioned metal oxide currently used as a material for an inorganic compound-based ultraviolet shielding agent has a value of “forbidden band” which is an energy gap between the valence band and the conduction band in the molecule of the metal oxide. It is a metal oxide that absorbs light having the energy of. In consideration of blending the metal oxide powder into cosmetics, the powder surface area is increased to improve the ultraviolet shielding ability, and also from the viewpoint of preventing color separation and whitening, the powder is It is desirable that the particle size be as small as possible.

However, when the particle size is made small, the so-called "quantum confinement effect" in which the electronic state depends on the particle size, especially at a particle size of 100 nm or less, which is said to be ultrafine particles.
As a result, the forbidden band value increases and the minimum excitation energy by light increases. As a result, the absorption wavelength of light is shifted to the shorter wavelength side having larger energy, and the wavelength is longer in the external skin preparation containing ultrafine particles of titanium dioxide or zinc oxide, which is currently used as an ultraviolet shielding agent. The UV-A shielding effect tends to decrease. The present inventor positively captures the above-mentioned “quantum confinement effect” that occurs when making a metal oxide having a property of absorbing light, and makes it a fine particle to obtain a UV-B shielding ability and a UV-A. The above problems have been solved by focusing on finding a metal oxide having a band structure with excellent shielding ability and excellent safety and stability.

[0010]

As a result, the present inventors have found that
We focused on tungsten oxide, which has a smaller bandgap than titanium dioxide and zinc oxide and is excellent in safety and stability. That is, by effectively utilizing the above-mentioned "quantum confinement effect" that appears when the particles are made into ultrafine particles, a tungsten oxide that can effectively shield ultraviolet rays having a wavelength of 400 nm or less in a wide range. The present invention has been completed by discovering the fine particle powder of The present inventor provides the following invention in this specification.

According to a first aspect of the present invention, there is provided an ultraviolet ray shielding agent containing as an active ingredient a tungsten oxide (WO ₃ ) fine particle powder having an average particle size of 5 nm or more and 200 nm or less.

According to a second aspect of the present invention, there is provided an ultraviolet ray shielding agent, which comprises, as an active ingredient, tungsten oxide fine particle powder having an average particle size of 5 nm or more and 50 nm or less.

In claim 3, the surface of the tungsten oxide fine particle powder is coated with at least one elemental oxide selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide. The ultraviolet shielding agent according to claim 1 or 2, which is a fine powder of tungsten oxide.

In claim 4, the tungsten oxide fine particle powder is a tungsten oxide fine particle powder obtained by subjecting its surface to a hydrophobic treatment or a surface activity suppressing treatment.
An ultraviolet shielding agent according to any one of claims 1 to 3 is provided. The ultraviolet shielding agent according to any one of claims 1 to 4, wherein the tungsten oxide fine particle powder is a fine particle powder capable of blocking ultraviolet rays having a wavelength of 400 nm or less.

[0015] In the sixth aspect, there is provided the ultraviolet shielding agent according to any one of the first to fifth aspects, wherein the ultraviolet shielding agent is a skin external preparation. The ultraviolet shielding agent according to claim 6, wherein the content of the fine powder of tungsten oxide particles is 0.1 part by weight or more and 60.0 parts by weight or less of the total skin external preparation. The ultraviolet shielding agent according to claim 6, wherein the content of the tungsten oxide fine particle powder is 1.0 part by weight or more and 40.0 parts by weight or less of the entire skin external preparation.

In the present specification, an organic compound-based compound having a function of mainly absorbing ultraviolet rays is referred to as "ultraviolet absorber". In addition, a compound that has the effect of blocking and absorbing the ultraviolet rays of inorganic compounds is an "UV screening agent".
Say. Then, the concept combining the "ultraviolet absorber" and the "ultraviolet shielding agent" is called "ultraviolet protection agent" (including those already described).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. A. Regarding Tungsten Oxide Fine Particle Powder According to the Present Invention The tungsten oxide fine particle powder according to the present invention is a tungsten trioxide (WO ₃ ) fine particle powder having an average particle diameter of 5 nm or more and 200 nm or less (in the present specification). Is
It is also referred to as the “tungsten oxide fine particle powder of the present invention”. Usually, fine particle powder having an average particle diameter of 100 nm is referred to as ultrafine particle powder, but in the present specification, even when the average particle diameter of the tungsten fine particle powder is 100 nm or less, it is collectively referred to as tungsten oxide fine particle powder. ). Further, in the present specification, the average particle diameter of the fine particle powder means the arithmetic average diameter [Σnd
/ Σn (n: number of particles, d: particle diameter (diameter)).

The method for producing the tungsten oxide fine particle powder of the present invention is not particularly limited. That is, it can be manufactured by a vapor phase method, a liquid phase method, or other physical methods such as a high frequency induction heating method, an electron beam heating method, a laser beam heating method, and a sputtering method.
Here, the gas phase method and the liquid phase method, which are typical methods for producing the tungsten oxide fine particle powder of the present invention, will be briefly described.

For example, a low-boiling-point tungsten compound such as tungsten bromide or tungsten chloride is vaporized, and the low-boiling-point tungsten compound is reacted with oxygen at 800 ° C. or higher to produce a desired tungsten oxide fine particle powder. Can be carried out [gas phase method (gas phase reaction method)]. The particle size of the tungsten oxide particles can be reduced by increasing the reaction temperature, increasing the oxygen concentration in the reaction system, and decreasing the concentration of the low boiling point tungsten compound.

In addition, by adjusting the pH of an aqueous solution in which a water-soluble tungstate such as tungstic acid, sodium tungstate, potassium tungstate, etc. is dissolved, tungsten hydroxide is precipitated, and the desired tungsten is obtained by the firing method. Oxide fine particle powder can be produced [liquid phase method (hydrolysis method)].

Further, frozen droplets of an aqueous solution in which the above-mentioned water-soluble tungstate or the like is dissolved are formed at a low temperature, which is sublimated and then pyrolyzed to produce a desired tungsten oxide fine particle powder. Or the above water-soluble tungstate or the like is evaporated with hot air and further thermally decomposed,
Produce the desired tungsten oxide particulate powder;
The above water-soluble tungstate can be evaporated at a high temperature and at the same time pyrolyzed to produce a desired tungsten oxide fine particle powder [liquid phase method (homogeneous solvent evaporation method)].

In the liquid phase method, the particle size of the fine particle powder to be produced can be adjusted by adjusting the concentration of the above-mentioned aqueous solution of tungstate or the like. That is,
When the concentration of these aqueous solutions is made dilute, the particle size tends to be small, and conversely, when the concentration is high, the particle size tends to be large. Also, the particle size of the fine particle powder can be adjusted by adjusting the thermal decomposition temperature, the drying temperature, and the like.

Among these methods for producing the fine powder of tungsten oxide particles of the present invention, the hydrolysis method, which is one aspect of the liquid phase method, is easy to adjust the particle size and it is possible to obtain finer particles. Is easy, and a large amount of fine particles can be prepared by a single operation, which can be exemplified as a preferable production method. The above-described method for producing the tungsten oxide fine particle powder of the present invention is merely an example, and the present invention is not limited to these production methods.

The average particle diameter of the fine particles of the tungsten oxide fine particle powder of the present invention is 5 nm or more and 200 nm or less (diameter).
Is. If the average particle size exceeds 200 nm, the "quantum confinement effect" is weak, the UV-B shielding effect is reduced, the powder itself is slightly yellowish, and the ultraviolet shielding agent of the present invention containing the same This is not preferred because it tends to cause whitening and the like when using the external preparation for skin of one aspect. Further, it is not only difficult to isolate the above-mentioned tungsten oxide fine particle powder having an average particle diameter of less than 5 nm, but with this particle diameter, the "quantum confinement effect" becomes too strong, and the UV-A shielding effect is obtained. When it is used as an active ingredient of a skin external preparation to be described later, it tends to cause dispersion problems such as aggregation in the skin external preparation, which is not preferable.

The fine particles of the tungsten oxide fine particle powder of the present invention having an average particle diameter of 5 nm or more and 50 nm or less are
Due to the "quantum confinement effect", it has a particularly excellent UV-screening effect for both UV-A and UV-B, its production is relatively easy, and when it is used as an active ingredient of a skin external preparation described below. Usability is also good, and it is particularly preferable.

The average particle size of the tungsten oxide fine particle powder of the present invention is an arithmetic average size derived from the particle size (particle size distribution), and this particle size can be determined by a commonly known method. . For example, measurement of length and area of fine particles by electron micrograph, measurement of Stokes diameter of fine particles by centrifugal sedimentation method, measurement of specific surface area of fine particles by Knudsen method which is one of permeation method, BET method which is one of adsorption method, The particle size of the tungsten oxide fine particle powder of the present invention can be determined by measuring the specific surface area of the fine particles by the fluidization method or the liquid phase adsorption method, measuring the crystallite size by the X-ray diffraction method, or the like.

The tungsten oxide fine particle powder of the present invention is
In order to improve its dispersibility, powder stability, and suppress surface activity, the surface of the fine particles may be coated with an oxide of one or more elements selected from the group consisting of aluminum, zirconium and silicon. . This coating method can be performed using a generally known method. That is, the desired coated tungsten oxide fine particle powder of the present invention can be produced by dispersing uncoated tungsten oxide fine particle powder of the present invention in water and reacting the dispersion with a coating compound. . Examples of the coating compound include aluminum sulfate hexahydrate and the like when coated with aluminum; zirconium oxychloride octahydrate and the like when coated with zirconium; and silicon coated Examples thereof include sodium silicate and the like. For these coating steps,
The details will be described in Examples described later.

Further, the fine tungsten oxide particles of the present invention may be subjected to a silicone treatment, a fatty acid treatment, a metal soap treatment or the like as a hydrophobic treatment or a surface activity suppressing treatment. These hydrophobic treatment or surface activity suppression treatment method,
It can be performed using a generally known method. That is,
The desired coated tungsten oxide fine particle powder of the present invention can be produced by dispersing the uncoated tungsten oxide fine particle powder of the present invention in a solvent and adding the above-mentioned treatment components to this system. This processing step will be specifically described in Examples described later.

The tungsten oxide fine particle powder of the present invention which has been subjected to these hydrophobizing treatment or surface activity suppressing treatment has excellent water repellency or surface activity suppressing effect. In this manner, "tungsten oxide (WO ₃ ) fine particle powder having an average particle diameter of 5 nm or more and 200 nm or less" which is an active ingredient of the ultraviolet shielding agent of the present invention described below is provided.

B. Regarding the ultraviolet shielding agent of the present invention, the above-mentioned tungsten oxide fine particle powder of the present invention is used as an active ingredient of an ultraviolet shielding agent for protecting various adverse effects due to exposure to ultraviolet rays, for example, for external skin application for the purpose of shielding the human body from ultraviolet rays. It can be used as an active ingredient of an agent; as an ultraviolet ray shielding ingredient of a packaging material of a product which needs to prevent deterioration of cosmetics and foods due to ultraviolet rays as much as possible;

The form of these ultraviolet ray shielding agents can be appropriately selected depending on the individual specific purpose. For example,
The tungsten oxide fine particle powder of the present invention can be used as it is as the ultraviolet shielding agent of the present invention, or the tungsten oxide fine particle powder of the present invention can be blended as an active ingredient of the skin external preparation of the form described later. In particular, use as an active ingredient of the above-mentioned external preparation for skin is very preferable in order to make the best use of the characteristics of the tungsten oxide fine particle powder of the present invention.

C. As to the external preparation for skin of the present invention, as described above, it is particularly preferable to use the tungsten oxide fine particle powder of the present invention as an active ingredient of an external preparation for skin having the purpose of shielding the human body from ultraviolet rays. The external preparation for skin containing the above-mentioned tungsten oxide fine particle powder of the present invention (hereinafter, also referred to as the external preparation for skin of the present invention) is widely applicable to cosmetics, pharmaceuticals, quasi-drugs and the like applied to the outer skin. And its dosage form is also aqueous system, solubilization system, emulsion system, powder system, oil liquid system, gel system, ointment system, aerosol system, water-oil 2
A wide range of dosage forms can be used, such as a layer system and a water-oil-powder trilayer system.
In other words, basic cosmetics can be widely applied to the above-mentioned various dosage forms in the form of facial cleansers, lotions, milky lotions, creams, gels, essences (cosmetics), packs and masks. Further, makeup cosmetics can be widely applied to forms such as foundations and lipsticks.
Furthermore, as long as it is a drug or a quasi drug, it can be widely applied in the form of various ointments and the like. The dosage forms and forms that the external preparation for skin of the present invention can take are not limited to these dosage forms and forms.

The amount of the tungsten oxide fine particle powder of the present invention to be added to the skin external preparation is different from the specific dosage form of the skin external preparation to which the fine particle powder is added, and other specific purposes. Although it cannot be unconditionally specified depending on the balance with the components to be mixed, it is preferably 0.1 part by weight or more and 60.0 parts by weight or less, and 1.0 part by weight or more, 40. It is particularly preferable that the amount is 0 parts by weight or less.

If the total amount of the external preparation for skin is less than 0.1 parts by weight,
A sufficient ultraviolet ray shielding effect tends not to be obtained, and if the amount exceeds 60.0 parts by weight, usability tends to deteriorate, which is not preferable.

The external preparation for skin containing the fine powder of tungsten oxide of the present invention has a very excellent shielding effect against ultraviolet rays of both UV-A and UV-B. In addition, when powders of metal oxides such as titanium oxide are mixed and used, there is no unnatural bluish white that tends to be generally seen, yet the spread is light and the finish is natural. It has an amazing effect.

In the external preparation for skin of the present invention, the tungsten oxide fine particle powder of the present invention is used as a mixture with a pharmaceutically acceptable base (described later) according to the desired dosage form. As long as it is possible to exert the above-mentioned effects and the external preparation for skin is intended only for this effect, it is not particularly necessary to additionally mix other medicinal components.

However, for the purpose of imparting the effect that a skin external preparation will generally exhibit by adding other pharmaceutical active ingredients, it is not possible to add the other pharmaceutical active ingredient to the external skin preparation of the present invention. This is possible within a range that does not impair the intended effect of the present invention. For example, it is possible to further enhance the ultraviolet protection effect by blending it in the external preparation for skin in combination with other ultraviolet protection agents. That is, as UV-A absorbers, methyl anthranilate, anthranilic acid UV absorbers such as homomenthyl -N- acetyl anthranilate; 2, 4-dihydroxybenzophenone, 2, 2 ^'- dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 '
-Dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone benzophenone ultraviolet absorbers and the like; 2, 2'-hydroxy-5-methylphenyl benzotriazole, 2- (2 ^'- hydroxy-5'-tert - octylphenyl) benzotriazole, 2- ^(2' - hydroxy-5 '- benzotriazole ultraviolet absorbers such as methyl phenyl) benzotriazole; Ziani soil methane, ^4-methoxy-4' -
Tert -butyldibenzoylmethane (parsol A) and the like can be combined and blended.

As UV-B absorbers, para-aminobenzoic acid (hereinafter referred to as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl. PABA ethyl ester, N, N
A benzoic acid type ultraviolet absorber such as dimethyl PABA butyl ester and N, N-dimethyl PABA amyl ester;
Dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, methyl salicylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p
-Salicylic acid-based UV absorbers such as isopropanol phenyl salicylate; octyl cinnamate, ethyl-4
-Isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate , Isoamyl-p
-Methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β -Phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate,
Glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, octyl methoxycinnamate 3,
4,5-Trimethoxycinnamic acid-3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl, p-
Cinnamic acid-based UV absorbers such as dimethoxycinnamic acid monoethyl ester; 3- (4'-methylbenzylidene)-
camphor derivatives such as d, 1-camphor, 3-benzylidene-d, 1-camphor and 5- (3,3-dimethyl-2-norbornylidene) -3-penten-2-one;
Urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, dibenzalazine and the like may be combined and blended.

Further, as an ultraviolet shielding agent, titanium oxide (TiO ₂ ), talc (MgSiO ₂ ), carmine (F)
eO ₂ ), bentonite, kaolin, zinc oxide (Zn)
O) and the like can be combined and blended.

In order to impart a moisturizing effect, polyethylene glycol, dipropylene glycol, 1,3-
Moisturizing ingredients such as butylene glycol, glycerin, sorbitol, xylitol, maltitol, hyaluronic acid, chondroitin sulfate, sawara extract, peony extract and mucidin can be added.

In order to impart a whitening effect, vitamin C such as arbutin, kojic acid or ascorbic acid, ascorbic acid sulfuric acid ester (salt), ascorbic acid phosphoric acid ester (salt) and ascorbic acid dipalmitate.
A whitening ingredient such as type can be added.

Further, in order to impart a rough skin preventing effect,
Allantoin, Glycyrrhizic acid (salt), Glycyrrhetinic acid and its derivatives, Glutathione, Acylsarcosinic acid, Licorice extract component, Yellow extract component, Sikon extract component, Sawtooth grass extract component, Hilihari grass extract component, Aloe extract component, Rumex extract Ingredients, Kouhone extract, mallow extract, Touki extract, Horsetail extract, Yukinoshita extract, Arnica extract, Lily plant extract, Artemisia extract, Gardenia extract, etc. Anti-inflammatory ingredients; Citric acid, Tartaric acid , Orange, spruce, birch extract, hamamelis extract, odricho grass extract, white birch extract, rhubarb extract and other astringent components; vitamin A and its derivatives, vitamin B ₆ hydrochloride, vitamin B ₆
Tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ and its derivatives, vitamin B ₁₂ , vitamin B
Vitamin Bs such as ₁₅ and its derivatives, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E-acetate, vitamin E-nicotinate and other vitamin Es, vitamin Ds, vitamin H, pantothenic acid,
Vitamins such as pantothetin; carrot extract, lily extract component, loofah extract component, horse chestnut extract component, psyllium extract component, safflower extract component, natural product extract component such as Clara extract component, placenta extract component, etc. Can be blended.

Further, in order to impart a vasodilatory effect, a vasodilator component such as senburi extract component, senkyu extract component, sage extract component, cepharanthin, γ-oryzanol, and nicotinic acid benzyl ester may be added.

Further, in order to impart an antibacterial effect, an antibacterial component such as hinokitiol bisabolol and eucalyptol can be added.

Further, in order to impart a sebum suppressing effect, a sebum suppressing component such as ethinyl estradiol can be added. It should be noted that the above-listed medicinal components are not limited to other medicinal components that can be incorporated into the skin external preparation of the present invention. Further, the drug efficacy corresponding to the above-listed components is not limited to the above. For example, Vitamin C can be used as a whitening component and also as an antioxidant aid described later. Furthermore, in addition to the above-listed medicinal components alone being added to the skin external preparation of the present invention, two or more of the medicinal components described above may be added depending on the purpose.
It is also possible to combine them appropriately. In the external preparation for skin of the present invention, a well-known base component is widely used and blended in a range that does not impair the intended effect of the external preparation for skin of the present invention depending on the desired dosage form and form. You can

That is, powder components such as titanium dioxide, mica, talc, kaolin, titanium dioxide-coated mica; evening primrose oil, avocado oil, mink oil, macadamia nut oil,
Corn oil, rapeseed oil, castor oil, sunflower oil, cocoa oil, coconut oil, rice bran oil, olive oil, camellia oil,
Natural animal and vegetable oils and fats such as squalene; hydrocarbons such as liquid paraffin, paraffin, squalane, vaseline; waxes such as paraffin wax, lanolin, jojoba oil, whale wax, beeswax, candelilla wax, carnauba wax; cetanol, stearyl alcohol, Higher alcohols such as isostearyl alcohol, 2-octyldodecanol, and lanolin alcohol; lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid,
Higher fatty acids such as isostearic acid, oleic acid, linolenic acid, linoleic acid, oxystearic acid; isopropyl myristate, 2-octyldodecyl myristate,
Fatty acid esters such as isopropyl palmitate, isopropyl stearate, glycerol 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, cetyl 2-ethylhexanoate, diisostearyl malate and tetra-2-ethylhexane pentaslit; diethylene glycol Monopropyl ether, polyoxyethylene polyoxypropylene pentaerythritol ether,
Polar oils such as polyoxypropylene butyl ether and ethyl linoleate; silicone oils such as methyl polysiloxane and methyl phenyl polysiloxane; methyl cellulose, gum arabic, polyvinyl alcohol, montmorillonite, laponite, carboxyvinyl polymer, alkali-modified carboxyvinyl polymer, etc. Viscous agent: Organic solvent such as ethanol, 1,3-butylene glycol; Antioxidant or antioxidant aid such as butylhydroxytoluene, tocopherol, butylhydroxyanisole, gallic acid ester, phytic acid, malic acid; Benzoic acid, Antibacterial preservatives such as salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester (methylparaben, ethylparaben, butylparaben, etc.), hexachlorophene; sorbitan monolaurate Sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyethylene glycol monooleate, polyoxyethylene alkyl ether, polyglycol diester, lauroyl diethanol amide, fatty acid isopropanol amide, maltitol hydroxy aliphatic ether, alkylated polysaccharide , Nonionic surfactants such as alkyl glucoside, sugar ester and pantothenyl ethyl ether; cationic surfactants such as stearyl trimethyl ammonium chloride, benzalkonium chloride, lauryl amine oxide; sodium palmitate, sodium laurate, lauryl Potassium sulphate, alkylsulfuric acid triethanolamine ether,
Rohto oil, linear dodecylbenzene sulfate, polyoxyethylene hydrogenated castor oil maleic acid, anionic surfactants such as acylmethyl tauric acid; chelating agents such as sodium EDTA; menthol, peppermint oil, peppermint oil,
Camphor, thymol inositol, spinrantol,
A cooling agent such as methyl salicylate; a pigment; a fragrance; or purified water can be appropriately combined in the external preparation for skin of the present invention in accordance with the formulation according to the desired dosage form. The specific formulation of the external preparation for skin of the present invention will be described in Examples described later.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples and the like in its technical scope. A. Examples of Tungsten Oxide Fine Particle Powder of the Present Invention: [Example A-1] Production of Tungsten Oxide Fine Particle Powder of the Present Invention (1) As a dispersant, 3 l of 10 ^-5 mol / l sodium hexametaphosphate aqueous solution was used. The mixture was heated to 80 ° C. and the pH was adjusted to 7.0 with aqueous ammonia or hydrochloric acid. Then, while sufficiently stirring the system, 1 l of an aqueous solution in which 0.5 mol of tungstic acid (manufactured by Kanto Reagent Co., Ltd.) and 0.5 mol of ammonia were dissolved was first added in an amount of 50 ml at a dropping rate of 200 ml / hour or more. , After forming crystal nuclei in the solution, 10
The rest of the aqueous solution was added dropwise at a dropping rate of 0 ml / hour or less. At this time, the pH of the solution was maintained at 7.0 with hydrochloric acid.

After completion of the dropping, the system was aged at 80 ° C. for 60 hours, the aged powder dispersion was filtered, water was added again to the filtration residue, and the powder was sufficiently dispersed again. Let This operation of filtration and washing with water was repeated 3 times to remove soluble salts in the solution, and the filtration residue was sufficiently dispersed in acetone.
Allowed to dry for hours. After sufficiently crushing the obtained dried product,
Baking was performed at 500 ° C. for 2 hours to obtain a target powder.

As a result of subjecting this powder to X-ray diffraction, tungsten trioxide (W
It was confirmed that this powder was indeed tungsten trioxide (WO ₃ ), in agreement with O ₃ ). Moreover, when the obtained powder was observed with an electron microscope, the primary particle diameter was about 50.
It was confirmed to be nm.

(2) Coating treatment of the tungsten oxide fine particle powder of the present invention: 10 parts by weight of the surface of the powder coated with aluminum oxide. 10 parts by weight of the uncoated tungsten oxide fine particle powder of the present invention produced in the above (1) is 1000 parts by weight. Alkali oxide hexahydrate 1.3
2 parts and 1.58 parts of urea were added and dissolved, and the temperature was raised to 100 ° C. with sufficient stirring. Then, at 100 ℃ 4
Aluminum hydroxide was coated on the surface of the powder particles by performing a hydrolysis reaction of aluminum sulfate using a heating hydrolysis reaction of urea with stirring for a period of time. After completion of the reaction, washing with water and filtration were repeated 3 times to remove soluble salts, and then dispersed in 100 parts by weight of acetone and filtered to obtain 60 parts.
The sample dried in vacuum at 12 ° C. for 12 hours was baked at 300 ° C. for 3 hours to obtain 10.3 parts of the tungsten oxide fine particle powder of the present invention whose surface was coated with aluminum oxide.

Powder surface coating with zirconium oxide 10 parts by weight of the uncoated tungsten oxide fine particle powder of the present invention prepared in the above (1) is dispersed in 1000 parts by weight of water, and zirconium oxyhydrochloride octahydrate is added thereto. 0.78 parts of the product and 0.58 part of urea were added and dissolved, and the temperature was raised to 100 ° C. with sufficient stirring. After that, 100 ℃
By performing a hydrolysis reaction of aluminum sulfate using a heating hydrolysis reaction of urea for 4 hours with stirring,
The surface of the powder particles was coated with zirconium hydroxide. After completion of the reaction, washing with water and filtration were repeated 3 times to remove soluble salts, and then dispersed in 100 parts by weight of acetone and filtered.
The sample dried in vacuum at 0 ° C. for 12 hours was baked at 300 ° C. for 3 hours to obtain 10.3 parts of the tungsten oxide fine particle powder of the present invention whose surface was coated with zirconium oxide.

Powder surface coating with silicon oxide 10 parts by weight of the uncoated tungsten oxide fine particle powder of the present invention prepared in the above (1) and 2 parts by weight of sodium hydroxide are dissolved in 1000 parts by weight of water. , Disperse, and mix well with this sodium silicate 0.9
100 parts of an aqueous solution in which 1 part was dissolved was gradually added dropwise to the dispersion liquid. At this time, the pH of the dispersion was kept at 9 with hydrochloric acid. After completion of dropping, washing with water and filtration were repeated 3 times to remove soluble salts, and then dispersed in 100 parts by weight of acetone,
The sample was filtered and dried under vacuum at 60 ° C. for 12 hours to give 300
The tungsten oxide fine particle powder 1 of the present invention, the surface of which is coated with silicon oxide, by firing at 3 ° C. for 3 hours.
0.3 part was obtained.

(3) Hydrophobic treatment of the tungsten oxide fine particle powder of the present invention Silicone treated 2000 parts by weight of the uncoated tungsten oxide fine particle powder of the present invention prepared in the above (1) is added by 120 parts by weight of methyl hydrogen. A sample prepared by dissolving polysiloxane in 120 parts by weight of isopropanol was sufficiently dispersed in a Henschel mixer, dried at 100 ° C. for 10 hours, and then calcined at 200 ° C. for 2 hours to obtain a silicone-treated tungsten oxide of the present invention. 2100 parts of fine particle powder was obtained.

Fatty acid treatment 10 parts by weight of the uncoated tungsten oxide fine particle powder of the present invention prepared in the above (1) is dispersed in 1000 parts by weight of isopropanol, heated to 60 ° C., and then 0.3 parts by weight. 100 parts of an isopropanol solution in which 1 part of myristic acid was dissolved was gradually added dropwise with sufficient stirring.
Thereafter, the stirring state was maintained at 60 ° C. for 2 hours, filtration and dispersion in isopropanol were repeated to remove soluble salts, followed by drying at 80 ° C. for 12 hours, followed by pulverization with a small pulverizer, and fatty acid treatment of the present invention. 10.3 parts of tungsten oxide fine powder was obtained.

Metal soap treatment 10 parts by weight The uncoated tungsten oxide fine particle powder of the present invention prepared in the above (1) is dispersed in 1000 parts by weight of water, and 0.3 part by weight of sodium stearate is dissolved. Then, the mixture was heated to 80 ° C. with stirring and kept for 3 hours. Then, washing with water and filtration were repeated 3 times to remove soluble salts, then dispersed in 100 parts by weight of acetone, filtered, and vacuum dried at 60 ° C. for 12 hours to obtain a metal soap treated powder 1
0.3 part was obtained.

[Test Example A-1] Measurement of Absorption Spectrum 2 g of the tungsten oxide fine particle powder of the present invention produced by the above-mentioned method was filled in a powder measuring cell having a quartz glass as a window plate and manufactured by Hitachi U- Absorbance of the powder was measured with a 3410 spectrophotometer using an integrating sphere in the wavelength range of 240 to 700 nm.

FIG. 1 shows that ultrafine titanium dioxide P-25 (P-2), which is generally commercially available as an ultraviolet shielding agent.
5: made by Nippon Aerosil, particle diameter: 25 nm). From the results shown in FIG. 1, it was found that the ultrafine titanium dioxide P-25 (curve b in the figure) had about 3
Although the absorbance in the wavelength region of 30 nm or less is high, 330-
It was found that the absorbance in the wavelength region of 400 nm was low. Compared with this, the fine particle tungsten oxide of the present invention is 40
It was found that the absorbance was high over the entire ultraviolet region below 0 nm (curve a in the figure). From this, it was found that the particulate tungsten oxide of the present invention effectively shields UV-A and UV-B.

B. Example regarding the external preparation for skin of the present invention [Example B-1] Parts by weight of powdery foundation 1) Talc 15.0 2) Mica 20.0 3) Sericite 19.7 4) Fine particle tungsten oxide of the present invention ^* 10.0 5 ) Mica titanium 3.0 6) Zinc stearate 1.0 7) Red iron oxide 1.0 8) Yellow iron oxide 3.0 9) Black iron oxide 0.2 10) Nylon powder 10.0 11) Squalane 6.0 12 ) Lanolin acetate 1.0 13) Octyldodecyl myristate 2.0 14) Diisooctanoic acid neopentyl glycol 2.0 15) Sorbitan monooleate 0.5 16) Preservative proper amount 17) Antioxidant proper amount 18) Perfume proper amount *: manufactured by the manufacturing process described above. The same applies to the following examples.

<Manufacturing Method> 1) to 10) were mixed with a Henschel mixer, to which a mixture and dissolved of 11) to 18) were added, and the resulting mixture was further pulverized with a pulverizer. The crushed product was compression-molded in an aluminum inner plate to obtain a solid powdery foundation.

As a comparative example with the powdery foundation of Example B-1, a powdery foundation was prepared in which 10.0 parts by weight of ultrafine titanium dioxide was also added in place of the fine particle tungsten oxide of the present invention described in 4) above. (Comparative example B-1).

[Test Example B-1] <Examination of ultraviolet shielding ability> Example B-1 and Comparative Example B-1
0.1 g of the powdery foundation produced in 1. was evenly applied on a quartz plate in the range of 10 cm ² , and the transmittance was measured using an integrating sphere. Here, the transmittance of 350 nm is U
As a shielding function against V-A, a transmittance of 300 nm is UV-
The shielding ability for B was used.

The results are shown in Table 1.

[Table 1]

As shown in Table 1, the powdery foundation of the present invention produced in Example B-1 had a UV-A.
It has been found that it has a strong shielding ability against both B ultraviolet rays, especially UV-A. <Sensory Evaluation> The powdery foundations produced in Example B-1 and Comparative Example B-1 were subjected to a usage test using 10 panelists specialized in makeup while making comparisons.

The results are shown in Table 2.

[Table 2]

The symbols in the table are as follows: ⊚: 8 to 10 people are judged as good ◯: 6 to 7 people are judged to be good Δ: 3 to 5 people are judged to be good ×: 0 to 2 people are judged to be good Judgment As shown in Table 2, it was found that the powdery foundation of the present invention had no unnatural bluish white, light spread, and natural finish.

[0067]   [Example B-2] Oily foundation                                                   Parts by weight  1) Talc 12.8  2) Kaolin 10.0  3) Fine particle tungsten oxide of the present invention 15.0  4) Mica 10.0  5) Bengal 1.0  6) Yellow iron oxide 3.0  7) Black iron oxide 0.2  8) Solid paraffin 3.0  9) Microcrystalline Wax 6.0 10) Beeswax 2.0 11) Vaseline 12.0 12) Lanolin acetate 1.0 13) Squalane 6.0 14) Isopropyl palmitate 18.0 15) Antioxidant Appropriate amount 16) proper amount of fragrance

<Production method> 1) to 7) were mixed with a Henschel mixer and further pulverized with a pulsarizer. On the other hand, 8) ~ 1
2) was heated to 70 to 80 ° C. and dissolved and mixed. Further 13) to 15) were added to and mixed with this dissolution mixture. The mixed pulverized powders of 1) to 7) above were added to and mixed with the heat-mixed 8) to 15), and 16) was added thereto. This mixture was thoroughly mixed with a kneader and molded into an aluminum inner dish to produce the desired oily foundation.

[Test Example B-2] <Examination of UV-shielding ability> The UV-shielding ability of the oil-based foundation produced in this Example B-2 was measured by the above-mentioned Test Example B-
It examined by the procedure similar to 1. The results are shown below.

[0070] wavelength transmittance (%) 300nm 2.4 350nm 4.9 From the results, the present invention oily foundation, UV-
It was found to have a strong shielding ability against both A and B ultraviolet rays.

<Sensory Evaluation> With respect to the oily foundation of the present invention produced in Example B-2, a usage test was conducted in the same procedure as in Test Example B-1. As a result, the usability of each item was evaluated as ◎. That is, it was revealed that the oil-based foundation of the present invention had no unnatural bluish-white color, light spread, and natural finish.

[0071]   [Example B-3] Stick type foundation                                                 Parts by weight  1) Talc 10.0  2) Kaolin 5.8  3) Synthetic mica 10.0  4) Fine particle tungsten oxide of the present invention 20.0  5) Bengal 1.0  6) Yellow iron oxide 3.0  7) Black iron oxide 0.2  8) Solid paraffin 3.0  9) Microcrystalline Wax 7.0 10) Vaseline 15.0 11) Dimethyl polysiloxane 3.0 12) Squalane 5.0 13) Isopropyl palmitate 17.0 14) Antioxidant Appropriate amount 15) Fragrance suitable amount

<Production Method> 1) to 7) were mixed with a Henschel mixer, and the mixed powder was pulverized with a pulverizer. On the other hand, 8) to 14) were heated and mixed at 70 to 80 ° C. and sufficiently mixed. To this mixture, the mixed pulverized powder of 1) to 7) above and
15) was added, and the mixture was sufficiently kneaded with a TK mill, poured into a resin mold, and cooled to produce a stick foundation.

[Test Example B-3] <Study of ultraviolet ray shielding ability> The ultraviolet ray shielding ability of the stick foundation produced in this Example B-3 was measured by the same procedure as in the above-mentioned Test Example B-1. The results are shown below. Wavelength transmittance (%) 300 nm 1.4 350 nm 2.3 From these results, it was revealed that the stick foundation of the present invention has a strong ability to block both UV-A and B ultraviolet rays.

<Sensory Evaluation> With respect to the oily foundation of the present invention produced in Example B-3, a usage test was conducted in the same procedure as in Test Example B-1. As a result, the usability of each item was evaluated as ◎. That is, it was revealed that the stick foundation of the present invention had no unnatural bluish whiteness, had a light spread, and had a natural finish.

[0075]   [Example B-4] Emulsion type foundation                                                   Parts by weight  1) Synthetic sericite 3.5  2) Talc 4.0  3) Fine particle tungsten oxide of the present invention 8.0  4) Fine particle titanium dioxide 5.0  5) Bengal 0.4  6) Yellow iron oxide 0.8  7) Black iron oxide 0.2  8) Liquid paraffin 5.0  9) Decamethylcyclopentanesiloxane 12.0 10) Polyoxyethylene modified           Dimethyl polysiloxane 4.0 11) Purified water 50.1 12) Dispersant 0.1 13) 1,3-butylene glycol 5.0 14) Preservative Suitable amount 15) Stabilizer 2.0 16) proper amount of fragrance

<Production Method> 1) to 7) were mixed with a Henschel mixer, and this mixture was pulverized with a pervazer. On the other hand, 8) to 15) are heated to 70 to 80 ° C., thoroughly mixed, and the mixed pulverized product of 1) to 7) above and 16) are added to this mixture, and the mixture is emulsified with a TK homomixer to obtain the desired mixture. An emulsion type foundation was manufactured.

[Test Example B-4] <Study of Ultraviolet Ray Shielding Ability> The ultraviolet ray shielding ability of the emulsion type foundation produced in this Example B-4 was determined by the above Test Example B.
The procedure was similar to that for -1. The results are shown below. Wavelength transmittance (%) 300 nm 1.8 350 nm 3.4 From these results, the emulsion type foundation of the present invention is UV
-It was found that it has a strong shielding ability against both A and B ultraviolet rays.

<Sensory Evaluation> With respect to the emulsion type foundation of the present invention produced in Example B-4, a use test was conducted in the same procedure as in Test Example B-1. As a result, the usability of each item was evaluated as ◎. That is, the emulsion type foundation of the present invention has no unnatural blue-white,
It was found that it spreads lightly and the finish is natural.

[0079]   [Example B-5] O / W type cream                                                   Parts by weight  1) Purified water 52.5  2) Talc 5.0  3) 1,3-butylene glycol 8.5  4) Triethanolamine 2.0  5) Fine particle tungsten oxide of the present invention 5.0  6) Oxybenzone 2.0  7) Octyl paramethoxycinnamate 5.0  8) Squalane 5.0  9) Vaseline 5.0 10) Stearyl alcohol 3.0 11) Stearic acid 3.0 12) Glycerin monostearate 3.0 13) Polyethyl acrylate 1.0 14) Antioxidant Appropriate amount 15) Preservative Appropriate amount 15) Fragrance suitable amount

<Production Method> 1) to 5) and 6) to 16) were heated and dissolved at 70 to 80 ° C., respectively. Next, the heat-dissolved products of 6) to 16) were added to the heat-dissolved products of 1) to 5) that were sufficiently mixed, and the mixture was emulsified using a TK homomixer. This emulsion was cooled using a heat exchanger to produce the desired O / W cream.

[Test Example B-5] <Examination of UV-shielding ability> O produced in this Example B-5
The UV blocking ability of the / W cream was measured by the same procedure as in Test Example B-1. The results are shown below. Wavelength transmittance (%) 300 nm 2.6 350 nm 4.1 From these results, the O / W type cream of the present invention is UV-
It was found to have a strong shielding ability against both A and B ultraviolet rays.

<Sensory Evaluation> With respect to the O / W type cream of the present invention produced in Example B-5, a use test was conducted in Test Example B-.
The examination was conducted in the same procedure as 1st grade. As a result, the usability of each item was evaluated as ◎. That is, the present invention O /
W-type cream has no unnatural paleness, spreads lightly,
It turned out that the finish was natural.

Example 6 W / O type cream 1) Purified water 23.0 2) 1,3-butylene glycol 3.0 3) Octyl paramethoxycinnamate 5.0 4) Oxybenzone 3.0 5) 4-Methoxy- ^4' - tert -butyldibenzoylmethane 1.0 6) Fine particle tungsten oxide of the present invention (Silicone treated) 10.0 7) Hydrophobized synthetic mica 5.0 8) Squalane 48.0 9) Diisostearin Glycerin acid 2.0 10) Preservative proper amount 15) Perfume proper amount

<Production method> 1) and 2) and 3) to 11) were heated and dissolved at 70 to 80 ° C. Next, the heat-dissolved products of 3) to 11) were added to the heat-dissolved products of 1) and 2) that were sufficiently mixed, and the mixture was emulsified using a TK homomixer. This emulsion was cooled using a heat exchanger to produce the desired W / O cream.

[Test Example B-6] <Examination of ultraviolet ray shielding ability> W produced in this Example B-6
The UV shielding ability of the / O type cream was measured by the same procedure as in Test Example B-1. The results are shown below. Wavelength transmittance (%) 300 nm 2.2 350 nm 3.4 From these results, the W / O cream of the present invention is UV-
It was found to have a strong shielding ability against both A and B ultraviolet rays.

<Sensory Evaluation> With respect to the W / O type cream of the present invention produced in Example B-6, a use test was conducted in Test Example B-.
The examination was conducted in the same procedure as 1st grade. As a result, the usability of each item was evaluated as ◎. That is, the present invention W /
O-type cream has no unnatural paleness, spreads lightly,
It turned out that the finish was natural.

[0087]

INDUSTRIAL APPLICABILITY According to the present invention, an ultraviolet ray shielding agent which effectively shields ultraviolet rays having a wavelength of 400 nm or less (UV rays of both UV-A and B) and also an ultraviolet ray which is effective in shielding unnatural whiteness. There is provided a skin external preparation which is light, has a light spread, and has a natural finish.

[Brief description of drawings]

FIG. 1 is a curve diagram comparing the absorbances of the tungsten oxide fine particle powder of the present invention and ultrafine titanium dioxide in the wavelength range of 240 to 700 nm.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-100112 (JP, A) International Publication 97/030934 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/42 A61K 7/00

Claims (8)

(57) [Claims] 1. An ultraviolet shielding agent comprising a tungsten oxide (WO ₃ ) fine particle powder having an average particle diameter of 5 nm or more and 200 nm or less as an active ingredient. 2. An ultraviolet ray shielding agent comprising, as an active ingredient, a tungsten oxide fine particle powder having an average particle diameter of 5 nm or more and 50 nm or less. 3. A tungsten oxide in which a fine powder of tungsten oxide has a surface coated with one or more element oxides selected from the group consisting of aluminum oxide, zirconium oxide and silicon oxide. The ultraviolet shielding agent according to claim 1 or 2, which is a fine particle powder. 4. The tungsten oxide fine particle powder according to claim 1, wherein the tungsten oxide fine particle powder is a tungsten oxide fine particle powder whose surface is subjected to a hydrophobizing treatment or a surface activity suppressing treatment. UV blocking agent. 5. The ultraviolet shielding agent according to claim 1, wherein the tungsten oxide fine particle powder is a fine particle powder capable of blocking ultraviolet rays having a wavelength of 400 nm or less. 6. The ultraviolet shielding agent according to claim 1, which is an external preparation for skin. 7. The ultraviolet shielding agent according to claim 6, wherein the amount of the fine powder of tungsten oxide is 0.1 part by weight or more and 60.0 parts by weight or less based on the total weight of the external preparation for skin. 8. The ultraviolet shielding agent according to claim 6, wherein the content of the fine powder of tungsten oxide particles is 1.0 part by weight or more and 40.0 parts by weight or less based on the whole skin external preparation.