JP2008255067A - Antioxidant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antioxidant inhibiting peroxidation of sebum. <P>SOLUTION: It is found that the problems can be eliminated by using composite powder obtained by supporting a colloidized material of a platinum group element on an inorganic porous particle as the antioxidant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antioxidant that suppresses peroxidation of sebum.

  Sebum has an important role as a barrier function for maintaining the physiological function of the skin. On the other hand, when sebum peroxide is generated by peroxidation of sebum, it changes into a skin irritant and may cause rough skin, pimples, acne and the like. It is well known that excessive production of lipid peroxides in sebum inhibits the normal function of sweat glands and sebaceous glands. In particular, squalene in sebum is susceptible to oxidation by oxygen and ultraviolet rays, and is a stimulating substance. It will become.

  For skin external preparations containing an oily component, antioxidants such as tocopherol, dibutylhydroxytoluene and butylhydroxyanisole are often used for the purpose of preventing oxidation of the external preparation itself. When this antioxidant is applied to the skin, it also partially suppresses peroxidation of sebum components. This is also one of the functions of the external preparation for skin.

  However, in the case of anti-oxidants used in the past, there are few that are satisfactory in terms of sufficient anti-oxidation and sustainability when anti-peroxidation of sebum is expected. Yes.

  As a document on this subject, what provides an “antioxidant” that prevents peroxidation of sebum secreted into the skin by active oxygen and prevents skin aging (see Patent Document 1), leaves of Asenyaku and young branches By using a mixture of the above extract and ion-exchanged water obtained by treating purified water with a 0.2 to 0.8 μm membrane filter (hereinafter referred to as membrane-treated ion-exchanged water), the oxidation of sebum is suppressed, A skin external preparation (see Patent Document 2) excellent in prevention of acne and pimples, and a buckwheat oil composition prevent peroxidation of sebum caused by ultraviolet rays alone or in a cosmetic preparation containing a lipid emulsion (see Patent Document 3) ), Peroxidation inhibitor of oxidizable sebum component containing chanoki or its extract, oxidizable sebum component containing chanoki or its extract and plant superoxide dismutase The peroxide inhibitor, acne, in particular to provide excellent cosmetic prevention or improvement of adult acne and skin roughness (see Patent Document 4), etc. is disclosed. In these cases, there are no examples of pursuing its sustainability.

JP-A-6-24937 JP-A-8-127524 Japanese National Patent Publication No. 9-507063 JP 2004-10505 A

  Conventionally, it has been known that colloids of platinum group elements typified by platinum nanocolloids have excellent active oxygen scavenging ability. As a literature on colloidal products of platinum group elements, foods containing a colloidal solution of platinum group elements effective for preventing diseases, promoting vitality of the human body, and promoting health by efficiently eliminating active oxygen (Patent Document 5) The active oxygen generated in the living body, characterized by mixing platinum and palladium in colloidal form, and treating and preventing a disease caused by the active oxygen (see Patent Document 6), platinum Anti-inflammatory analgesic patch (see Patent Document 7), characterized by using a colloid of a group element, a drug having a medicinal component of anti-inflammatory analgesia and a component that generates far-infrared rays, and protecting the skin and activating the stratum corneum For the purpose of achieving this, active oxygen species contained in a liquid such as blood can be obtained by attaching platinum nanoparticles to a cosmetic (see Patent Document 8) in which a platinum colloid is dispersed in a base, and a resin substrate. A removable active oxygen species removing material (see Patent Document 9) and the like are disclosed.

  With regard to platinum nanocolloids, formulation into health foods and cosmetics in recent years has begun to be studied. The colloidalized platinum group element is a material that is expected to have superior antioxidant ability compared to conventional antioxidants, but there is still room for research in practical aspects. In particular, when used in actual preparations, the antioxidant ability is influenced by the interaction with the preparation system, and there remains a problem in terms of substantially sufficient inhibitory effect and sustainability.

JP 11-346715 A Japanese Patent Laid-Open No. 11-60493 JP 2001-114671 A JP 2001-122723 A JP 2006-290840 A

  In the present invention, a platinum group colloidal product was used as an antioxidant substance, and a method for maintaining the high antioxidant power on the skin was intensively studied.

  As a result of researches to solve the above problems, the present inventor has used these composite powders obtained by supporting a colloidal product of a platinum group element on inorganic porous particles as an antioxidant. It has been found that the problems can be solved, and the present invention has been completed.

  The antioxidant comprising the composite powder in which the inorganic porous particles of the present invention carry a colloidal product of a platinum group element has not only an excellent antioxidant ability but also maintains its action. Therefore, it is possible to achieve a superior performance that enables high-concentration blending in the preparation and that the effect thereof has sufficient sustainability.

  An embodiment of the present invention will be described.

  As the platinum group element used in the present invention, ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like, which are the elements of the fifth to sixth periods of the eighth to tenth groups, can be used. Platinum is more preferable. By making these ultrafine to nanosize (nm) and making them in a colloidal state, the electric double layer generated on the surface of the colloidal particles acts more than buoyancy and can maintain dispersion.

  The inorganic porous particles used as the matrix of the composite powder carrying the platinum group colloidal product used in the present invention are selected from silicic anhydride (silica), alumina, titanium dioxide, hydroxyapatite particles or a mixture thereof. It is preferred that In particular, silicic acid anhydride is particularly preferable from the viewpoint of durability of antioxidant capacity. The inorganic porous particles are preferably spherical particles from the viewpoint of usability. In addition, spherical silicic acid anhydride has a hollow type and a non-hollow type, and either can be used.

The 3~15μm The average grain size of the inorganic porous particles, specific surface area can be used particles in the range of 200~750m ² / g, an average particle diameter of 5 to 10 [mu] m, a specific surface area 250~500m ² / g The range of particles is preferred in terms of durability of antioxidant capacity.

  As a method for supporting the colloidalized platinum group element on the inorganic porous particles, for example, the inorganic porous powder is immersed in a colloid solution containing the substance, and after a certain period of time has passed, A method may be mentioned in which a dry powder is taken out of the solution and dried.

  Furthermore, the surface of the antioxidant containing the composite powder in which colloids of platinum group elements are supported on inorganic porous particles is selected from dimethylpolysiloxane, trimethylsiloxysilicate, methylhydrogenpolysiloxane or dimethylhydrogenpolysiloxane. By subjecting the surface treatment agent to a hydrophobic treatment, the persistence on the skin is improved, and as a result, its antioxidant ability and durability can be maintained.

  When the antioxidant of the present invention is used for a skin external preparation, the preferred range is not particularly limited as the ratio of the antioxidant to the skin external preparation.

  Next, a test for evaluating the action of the antioxidant of the present invention and a prescription example of a skin external preparation containing the same will be described in more detail. The technical scope of the present invention is not limited by these. Antioxidant action was tested with lipid peroxide production inhibitory action.

[sample]
Sample A (product of the present invention): 0.02 mg / mL platinum nanocolloid-supported silicic acid dispersion sample B: 0.05 mass%, 25 ppm platinum nanocolloid dispersion
[Inhibition of lipid peroxide production]
(A) Test method 0.1 mL of each sample of A and B was added to a 4.9 mL linolenic acid solution, and UV for 3 hours and 5 hours (UVB, 3 hours: 13.5 J / cm ² , 5 hours: 22.3 J / Cm ² ), 0.3 mL of the reaction solution was dispensed into a stoppered test tube, and 3 mL of 0.05N hydrochloric acid was added. 1 ml of thiobarbitur (TBA) reagent was added thereto and mixed, and then boiled for 30 minutes. After rapidly cooling to room temperature in an ice-cold water bath, 4 mL of a methanol-butanol solution was added and extracted with shaking. Centrifugation is performed at 2500 rpm for 10 min, 150 μL of butanol layer (upper layer) is dispensed on a microplate, the absorbance at 535 nm is measured, and the amount of the produced lipid peroxide is measured.
Lipid peroxide production of each sample using the relative value when the amount of lipid peroxide generated in the control is 100 (water is used) that is irradiated with ultraviolet rays without adding an antioxidant. The inhibitory action was evaluated. A significance probability of less than 5% (p <0.05) is represented by * and a significance probability of less than 1% (p <0.01) is represented by ** with respect to the significance probability p value in the t-test.
(B) Test results Table 1 shows the test results.

From the results of Table 1, only sample A showed a significant lipid peroxide production-inhibiting action after 3 hours of UV irradiation. Samples A and B both showed significant inhibition of lipid peroxide formation when irradiated with ultraviolet light for 5 hours. Compared to the sample B platinum nanocolloid, the sample A of the present invention, which is a platinum nanocolloid supported anhydrous Silicic acid showed stronger inhibitory action. Further, it was found that the platinum nanocolloid-supported silicic acid sample A of the sample A according to the present invention has a more stable action of inhibiting the formation of lipid peroxide.
From the above results, it was confirmed that the antioxidant of Sample A, which is a product of the present invention, exhibits excellent antioxidant ability and has stable antioxidant ability over time.

  Next, about the sample A and B, it confirmed about the stability at the time of mix | blending with a skin external preparation. Samples A and B were blended as the antioxidants 1 to 3 in the formulations of Examples 1 to 3 described below, and the changes after 24 hours at 50 ° C. were observed. The results are shown in Table 2. In the table, ◎ indicates that there was no change, and Δ indicates that changes with time such as aggregation were observed.

  In the results of Table 2, when Sample B was blended with an external preparation, it was unstable and some aggregation, sedimentation, and the like were observed. It was confirmed that Sample A, which is the product of the present invention, can be blended stably regardless of the external preparation system. For this reason, regarding the sample in which aggregation was observed in Sample B, it was confirmed by sampling that the lipid peroxide production inhibitory action varied, and that stable antioxidant ability could not be obtained.

  Next, the formulation of an external preparation for skin containing the antioxidant of the present invention is shown by the following examples, but the present invention is not limited to these.

[Example 1] Emulsion (1) Squalane 10.0 (mass%)
(2) Methylphenylpolysiloxane 4.0
(3) Hydrogenated palm kernel oil 0.5
(4) Hydrogenated soybean phospholipid 0.1
(5) Polystearic acid polyoxyethylene sorbitan (20E.O.)
1.3
(6) Sorbitan monostearate 1.0
(7) Glycerin 4.0
(8) Methyl paraoxybenzoate 0.1
(9) Carboxyvinyl polymer 0.15
(10) The balance to be purified water 100 (11) Arginine (1% by mass aqueous solution) 20.0
(12) * Antioxidant 1 5.0 of the present invention
Production method: The oil phase components (1) to (6) are heated and dissolved at 80 ° C. On the other hand, the aqueous phase components (7) to (10) are dissolved by heating at 80 ° C. The oil phase component is added to this while stirring and uniformly emulsified with a homogenizer. After emulsification, start cooling and add (11) and (12) sequentially and mix uniformly.
* Antioxidant 1 of the present invention: Hydrophobized platinum nanocolloid supported non-hollow silica

[Example 2] Cosmetic liquid (1) Purified water 100 balance (mass%)
(2) Glycerin 10.0
(3) Sucrose fatty acid ester 1.3
(4) Carboxyvinyl polymer (1% by weight aqueous solution) 17.5
(5) Sodium alginate (1% by weight aqueous solution) 15.0
(6) Polyglyceryl monolaurate 1.0
(7) Macadamia nut oil fatty acid phytosteryl 3.0
(8) N-lauroyl-L-glutamate di (phytosteryl-2-octyldodecyl) 2.0
(9) Hardened palm oil 2.0
(10) Squalane (from olive) 1.0
(11) Behenyl alcohol 0.75
(12) Beeswax 1.0
(13) Jojoba oil 1.0
(14) 1,3-butylene glycol 10.0
(15) L-arginine (10% by mass aqueous solution) 2.0
(16) * Antioxidant 2 of the present invention 3.5
Production method: The aqueous phase components (1) to (6) are mixed and dissolved by heating at 75 ° C. On the other hand, the oil phase components (7) to (13) are mixed and dissolved by heating at 75 ° C. Next, the oil phase component is added to the aqueous phase component and preliminary emulsification is performed, followed by uniform emulsification with a homomixer. Cooling is started after completion of emulsification, and (14) to (16) are added at 50 ° C. and mixed uniformly.
* Antioxidant 2 of the present invention: Hydrophobized platinum nanocolloid supported hollow silica

[Example 3] Aqueous gel (1) Carboxyvinyl polymer 0.5 (mass%)
(2) The balance made into purified water 100 (3) Sodium hydroxide (10 mass% aqueous solution) 0.5
(4) Ethanol 10.0
(5) Methyl paraoxybenzoate 0.1
(6) Fragrance 0.1
(7) * Antioxidant 3 3.0 of the present invention
(8) Polyoxyethylene (60E.O.) hydrogenated castor oil 1.0
Manufacturing method: (1) is added to (2), and after stirring uniformly, (3) is added. After stirring uniformly, (5) previously dissolved in (4) is added. After stirring uniformly, the previously mixed (6) to (8) are added and stirred and mixed uniformly.
* Antioxidant 3 of the present invention: platinum nanocolloid supported non-hollow alumina

  The skin external preparation containing the antioxidant according to the present invention also showed excellent antioxidant properties in Examples 1 to 3 described above, and was confirmed to persist for a long time even when applied to the skin.

Claims (5)

An antioxidant comprising a composite powder in which a colloidalized platinum group element is supported on inorganic porous particles. The antioxidant according to claim 1, wherein the inorganic porous particles have an average particle diameter of 5 to 10 µm and a specific surface area in the range of 250 to 500 m ² / g. The antioxidant according to claim 1 or 2, wherein the inorganic porous particles are silicic anhydride. The surface of the antioxidant is further subjected to a hydrophobic treatment with a surface treatment agent selected from dimethylpolysiloxane, trimethylsiloxysilicic acid, methylhydrogenpolysiloxane or dimethylhydrogenpolysiloxane. The antioxidant of any one of -3. A skin external preparation comprising the antioxidant according to any one of claims 1 to 4.