JP5020122B2 - Topical skin preparation - Google Patents

Description

  The present invention relates to an external preparation for skin containing a carotenoid and a platinum group metal colloid, and more particularly to an external preparation for skin whose stability of carotenoid is improved by a platinum group metal colloid.

Although it is known that the ingredients blended in cosmetics originally have useful effects on the skin such as anti-aging and prevention / improvement of spots such as polyphenols such as catechin and carotenoids such as astaxanthin Because of its low oxidative stability, there are many cases in which it is difficult to stably blend it into the preparation. For this reason, ingenuity has been made such as combined use with an antioxidant such as ascorbic acid and encapsulation of an active ingredient. (See Patent Document 1).
As for carotenoids, since they are oxidized and faded by light, anti-fading measures such as blending of antioxidants and use of light-shielding containers have been taken, but they are not sufficient. In addition, many antioxidants that can be used in combination with carotenoids are oil-soluble, and water-based dosage forms such as lotions can be blended in only a small amount, so that they may not sufficiently act on carotenoids. Further, the blended antioxidant itself may be deteriorated by oxygen and discolored (discolored or colored) over time, so that the antioxidant effect may not be maintained for a long period of time, and the carotenoid's original effect could not be sufficiently exhibited.
On the other hand, it is known that certain types of platinum group metal colloids including platinum colloid have an antioxidant ability (see Patent Documents 2 and 3).
JP-A-1-215263 JP-A-53-109878 JP 2001-114671 A

  However, the discoloration and coloring mechanisms are complex, so the appropriate methods for suppressing them vary from material to material, and it is difficult to find stabilization methods and stabilizers suitable for each material. There has been a demand for stabilization methods and stabilizers suitable for carotenoids such as astaxanthin, which are known to have useful effects.

In view of this situation, the present inventor has intensively studied to solve the above problems, and as a result, by combining a carotenoid including astaxanthin and a platinum group metal colloid, the carotenoid is prevented from fading due to light and has a significant effect on stability. The present invention has been completed.
That is, the present invention includes the following components (A) and (B);
(A) Carotenoid (B) An external preparation for skin characterized by containing a platinum group metal colloid is provided.
The carotenoid of component (A) is one or more selected from the group consisting of astaxanthin, lycopene, β-carotene, zeaxanthin, lutein, canthaxanthin, cryptoxanthine, violaxanthin, capsanthin, fucoxanthin and derivatives thereof. The above-mentioned skin external preparation is provided. And the said external preparation for skin is provided with the said component (B) which is a platinum colloid.

  Since the external preparation for skin of the present invention can effectively exert the effect of carotenoids on the skin by improving the stability of carotenoids such as astaxanthin, it prevents carotenoids from aging, improves rough skin, and prevents and improves spots. Useful.

Examples of the carotenoid of component (A) blended in the external preparation for skin of the present invention include astaxanthin, lycopene, β-carotene, zeaxanthin, lutein, canthaxanthin, cryptoxanthine, violaxanthin, capsanthin, fucoxanthin and their derivatives. .
Examples of the derivatives include esters with amino acids such as glycine and alanine, esters with carboxylic acids such as acetic acid and citric acid, and salts thereof, esters with inorganic acids such as phosphoric acid and sulfuric acid, and salts thereof, or eicosapentaene. Monoesters selected from fatty acids such as highly unsaturated fatty acids such as acid and docosahexaenoic acid, unsaturated fatty acids such as oleic acid and linoleic acid, saturated fatty acids such as palmitic acid and stearic acid, and the like or different And glycosides such as glucoside.
These may be chemically synthesized products, or may be extracted from natural products such as plants, animals, microorganisms, etc. The type, production area, and production method of the raw materials are not particularly limited, and may be one or two. More than one species can be blended.

Further, among the above carotenoids, a particularly preferred carotenoid is astaxanthin, and astaxanthin, for example, those extracted from natural products such as krill, salmon, trout, cypress, red yeast, Haematococcus algae, and synthetic products can be used. .
As an extraction solvent for obtaining a carotenoid such as astaxanthin from a natural product, for example, an organic solvent such as acetone, ether, chloroform and alcohol (ethanol, methanol, etc.) can be used, and a mixed solution thereof can also be used. it can. Alternatively, supercritical carbon dioxide may be used.

  For example, extract by adding extraction solvent to krill family krill (Euphausia similis GO), separate this extract to obtain an astaxanthin extract extract, then distill the extraction solvent from this extract, and hydrogenate as necessary It can be obtained by conducting a chemical reaction such as hydrolysis or hydrolysis, and finally deodorizing and purifying using means such as molecular distillation or column chromatography or high performance liquid chromatography (HPLC).

The amount of the carotenoid component (A) in the external preparation for skin of the present invention is not particularly limited, but is preferably 0.0001 to 5% by mass (hereinafter simply referred to as “%”), more preferably 0.0001. ~ 1%. When an extract is used, the concentration of the extract is not limited as long as the amount of solute is within the above range.

  On the other hand, the platinum group metal colloid of the component (B) blended in the present invention refers to a state in which platinum group metal particles are dispersed in a liquid phase, and the platinum group metal includes ruthenium, osmium, rhodium, A generic term for transition metals consisting of iridium, palladium, and platinum. In the present invention, among these, rhodium and platinum are preferable and platinum is most preferable from the viewpoint of the stability of the carotenoid of component (A). The platinum group metal colloid of the component (B) of the present invention may be a kind of metal colloid selected from platinum group metals, or a colloid of two or more kinds of metals. Metal species colloids are preferred, and platinum or rhodium colloids are preferred.

  In order to bring the platinum group metal into a stable colloidal state, the metal particles preferably have a large specific surface area and excellent surface reactivity. The particle size of the platinum group metal particles is not particularly limited as long as it can be in a colloidal state, but is preferably a nano unit. Specifically, the particle size is preferably 1 to 5 nm, more preferably 1 to 3 nm, and particularly preferably 1.5 to 2.5 nm. The particle size distribution of the particles is preferably narrow. Specifically, the particle size of 90% by number or more of colloidal particles preferably falls within the range of 0.1 to 10 nm, and falls within the range of 1 to 3 nm. Is more preferable. The average particle size of the colloidal particles can be determined by observing with a transmission electron microscope.

  The main component of the liquid phase in which the platinum group metal particles are dispersed is preferably water, and may contain an organic solvent as long as the colloidal state is not destabilized. Examples of the organic solvent include alcohols such as methanol and ethyl alcohol; polyhydric alcohols such as glycerin, diglycerin, 1,3-butylene glycol and dipropylene glycol.

  Various methods for producing metal colloids or metal particles are known (for example, JP-B-57-43125, JP-A-59-120249, JP-A-9-225317, JP-A-10-176207). JP, 2001-79382, JP, 2001-122723, etc.) and those skilled in the art can prepare easily by referring to these methods. For example, a chemical method called a precipitation method or a metal salt reduction reaction method, or a physical method called a combustion method can be used. In the present invention, metal colloids and metal particles prepared by any method may be used, but metal colloids prepared by a metal salt reduction reaction method are used from the viewpoint of ease of production and quality, or the above-mentioned method. It is preferable to prepare and use the metal particles obtained by the above method as a colloid.

  In the metal salt reduction reaction method, for example, an aqueous solution or organic solvent solution of a water-soluble or organic solvent-soluble metal salt or metal complex is prepared, and after adding a water-soluble polymer to this solution, the pH is adjusted as necessary. The metal particles can be obtained by reduction by heating under reflux in an inert atmosphere. The type of the water-soluble or organic solvent-soluble salt of the metal is not particularly limited. For example, acetate, chloride, sulfate, nitrate, sulfonate, or phosphate can be used. It may be used.

  The type of water-soluble polymer used in the metal salt reduction reaction method is not particularly limited. For example, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylate, cyclodextrin, amylopectin, or methylcellulose can be used. A combination of the above may also be used. Preferably, polyvinylpyrrolidone and polyacrylate can be used, and more preferably, polyacrylate can be used. Further, various surfactants such as anionic, cationic, amphoteric or nonionic surfactants can be used instead of or together with the water-soluble polymer. When the reduction is performed using alcohol or glycol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, n-amyl alcohol, ethylene glycol or the like is used. These water-soluble polymers and surfactants are coordinated to platinum group metals after the formation of metal particles in the liquid phase, improving the solvophilicity of the metals, and in colloidal state as protective colloid agents. Contributes to stabilization.

  The metal particles produced in the liquid phase by the metal salt reduction reaction method may be used for the preparation of a skin whitening agent and other skin external preparations such as cosmetics containing them without being separated from the liquid phase. Good. For example, metal particles are produced in the liquid phase by a metal salt reduction reaction method, and if necessary, an appropriate purification step (for example, a step of distilling off the organic solvent used in the step of the metal salt reduction reaction method). Thereafter, by adding an arbitrary amount of water or removing an arbitrary amount of water, it is possible to prepare a whitening agent, a skin external preparation or the like comprising a stable colloid. If desired, a surfactant, a dispersing agent or the like that contributes to stabilization of the colloidal state may be added.

  The compounding amount of the platinum group metal colloid of the component (B) of the present invention varies depending on the dosage form of the external preparation, the purpose of use, etc., but in general, the concentration of the platinum group metal is preferably in the final composition. 0.1 nmol / L to 1 mmol / L, more preferably 10 nmol / L to 10 μmol / L. Within this range, the colloid can be blended stably and an excellent medicinal effect can be exhibited.

  The topical skin preparation of the present invention contains components that are usually used in preparations such as cosmetics, quasi-drugs, and external pharmaceuticals, that is, water (purified water), as long as the effects of the present invention are not impaired as necessary. , Hot spring water, deep layer water, etc.), oil agent, surfactant, metal soap, gelling agent, powder, alcohol, water-soluble polymer, film forming agent, resin, UV protection agent, inclusion compound, antibacterial agent, Perfume, deodorant, salt, pH adjuster, refresher, animal / microbe-derived extract, plant extract, blood circulation promoter, astringent, antiseborrheic agent, whitening agent, anti-inflammatory agent, active oxygen scavenger, Cell activators, humectants, chelating agents, keratolytic agents, enzymes, hormones, vitamins and the like can be added.

  Examples of the formulation of the external preparation for skin of the present invention are not particularly limited. For example, makeup cosmetics such as emulsions, creams, lotions, cosmetics, packs, cleaning agents, foundations, blushers, lipsticks, hair nourishing agents, Any form of hair cosmetics such as hair tonics, shampoos and rinses, dispersions, ointments, liquids, aerosols, patches, poultices, liniments and the like may be used.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative reference example are given and this invention is demonstrated further more concretely, the scope of the present invention is not limited to these.

[Production Example 1: Preparation of platinum colloid]
Poly (sodium polyacrylate) (0.31 g manufactured by Aldrich Co.) was placed in a 100 mL two-necked eggplant type flask connected with an Allen cooler and a three-way cock, and dissolved in 23 mL of distilled water. This solution was stirred for 10 minutes, in addition chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O, Wako Pure Chemical Industries, Ltd.) 1.66 × ^{10 -2} M solution dissolved in distilled water to a (2 mL) Stir for 30 minutes. The reaction system was purged with nitrogen, 25 mL of special grade ethanol was added, and the mixture was refluxed at 100 ° C. for 2 hours while maintaining a nitrogen atmosphere. The UV-visible light absorption spectrum of the reaction solution was measured to confirm the disappearance of the platinum ion peak and the saturation of the peak due to the scattering characteristic of the metal solid, and the reduction reaction was completed. The organic solvent was distilled off under reduced pressure to prepare a platinum colloid liquid (average particle size 2.4 ± 0.7 nm). The platinum concentration of the obtained platinum colloid was 1 mmol / L.

Example 1 (Invention Products 1 and 2, Comparative Products 1 and 2): Lotion <Astaxanthin anti-fading effect (stabilization effect) test>
A lotion was prepared according to the formulation and manufacturing method shown in Table 1 below, and stored at room temperature for 2 weeks.
By the following evaluation method, the astaxanthin residual rate was calculated | required from the quantity of astaxanthin before and behind a test, and the fading prevention effect (stabilization effect) of astaxanthin was evaluated from the value. The results are also shown in Table 1.

(Manufacturing method)
The prescription ingredients shown in Table 1 were mixed and dissolved to obtain a skin lotion.

(Evaluation method)
For each sample, the absorbance at 470 nm, which is a characteristic absorption wavelength of astaxanthin, was measured at the beginning of preparation (before the test) and after being left in a room with a fluorescent lamp for 2 weeks (after the test). Further, the value was determined as the anti-fading effect (stabilizing effect) of astaxanthin according to the following criteria.
Astaxanthin residual rate = (absorbance after test / absorbance before test) × 100 (%)

(Criteria)
◎: Astaxanthin residual rate is 90% or more ○: Astaxanthin residual rate is 60% or more and less than 90% Δ: Astaxanthin residual rate is 30% or more and less than 60% ×: Astaxanthin residual rate is less than 30%

  As is clear from Table 1, it can be seen that the platinum colloid is very excellent in the effect of suppressing the decrease in the residual rate of astaxanthin. The effect is extremely high compared to the compound containing ascorbic acid known as an antioxidant instead of platinum colloid (Comparative Product 2), and the platinum colloid has the effect of stabilizing astaxanthin in a very small amount. I understood.

Comparative Reference Example (Comparative Products 3 to 5): Lotion <Catechin Coloring Prevention Effect (Stabilization Effect) Test>
In order to show the specificity of the stabilization effect of platinum colloid on astaxanthin as a comparison data, instead of astaxanthin, catechin, which is a kind of polyphenol that is also difficult to be formulated and is highly colored over time, is used to oxidize catechin. The effect of platinum colloid on coloring by reaction was confirmed.
The method of confirmation is to prepare lotion with the formulation and manufacturing method shown in Table 2 below, store at 50 ° C for 1 week, and evaluate the anti-catechin coloring effect (stabilization effect) from the absorbance change before and after each sample test. did. The results are also shown in Table 2.

(Evaluation method)
The absorbance at 470 nm was measured at the beginning of preparation of each sample shown in Table 2 (before the test) and when stored for 1 week at 50 ° C. (after the test), and the difference was determined. The smaller the change in absorbance, the smaller the degree of coloring.

(Criteria)
○: Absorbance change is 0
Δ: Absorbance change is less than 0.01 ×: Absorbance change is 0.01 or more

  Then, as can be seen from Table 2, the platinum colloid, which showed a remarkable effect on the stabilization of astaxanthin, was surprisingly ineffective at stabilizing the catechin (preventing coloring) and promoted the coloring. have done.

As described above, from the results of Tables 1 and 2, it was found that the action of platinum colloid is specific and remarkable for carotenoids such as astaxanthin.

Example 2: Toner lotion (component) (%)
(1) Glycerin 5
(2) 1,3-butylene glycol 6.5
(3) Polyoxyethylene (20E.O.) sorbitan 1.2
Monolaurate (4) Ethyl alcohol 12
(5) Astaxanthin * 1 0.001
(6) Sodium ascorbyl phosphate 0.5
(7) Ascorbic acid glucoside 2
(8) Lactic acid 0.05
(9) Sodium lactate 0.1
(10) Platinum colloid * 2 0.05
(11) Collagen 1
(12) Methyl paraoxybenzoate 0.05
(13) Perfume appropriate amount (14) Purified water remaining

(Manufacturing method)
A. Components (3) to (5) and (12) and (13) are mixed and dissolved.
B. Components (1), (2), (6) to (11) and (14) are mixed and dissolved.
C. A and B were mixed and uniformed to obtain a skin lotion.

  The lotion prepared in Example 2 is extremely stable without discoloration, odor, precipitation, and the like, and when applied to the skin, there is an effect required for a lotion formulated with astaxanthin, that is, a fresh moisturizing feeling, continuously. By applying, it was effective in suppressing or improving spots and dullness.

Example 3: Emulsion (component) (%)
(1) Polyoxyethylene (10E.O.) sorbitan 1
Monostearate (2) Polyoxyethylene (60EO) Sorbit 0.5
Tetraoleate (3) Glyceryl monostearate 1
(4) Stearic acid 0.5
(5) Behenyl alcohol 0.5
(6) Squalane 8
(7) Haematococcus alga extract * 3 0.1
(8) Ethyl alcohol 5
(9) Licorice extract 0.01
(10) Dipotassium glycyrrhizinate 0.1
(11) Platinum colloid * 2 0.2
(12) Purified water Residual amount (13) Methyl paraoxybenzoate 0.1
(14) Carboxyvinyl polymer 0.2
(15) Sodium hydroxide 0.1
(16) Hyaluronic acid 0.1
(17) Zinc oxide 3
(18) Perfume appropriate amount * 3 Containing 5% astaxanthin

(Manufacturing method)
A. Ingredients (12)-(14) are heated and mixed and maintained at 70 ° C.
B. Ingredients (1) to (9) are heated and mixed and maintained at 70 ° C.
C. A is added to B, mixed and uniformly emulsified.
D. After cooling C, add (10) and (11) and mix uniformly.
E. (15) was added to D, the mixture was sufficiently stirred, (16) to (18) were further added, and mixed uniformly to obtain an emulsion.

  The emulsion prepared in Example 3 has no discoloration and odor and is very stable, and when applied to the skin, the smooth feel and emollient effect required for emulsions containing carotenoids can be obtained and applied continuously. Therefore, it was excellent in the effect of suppressing or improving wrinkle formation and skin hardening.

Example 4: Cream (ingredient) (%)
(1) Cetostearyl alcohol 3
(2) Glycerin fatty acid ester 2
(3) Polyoxyethylene monooleate (20) sorbitan 1
(4) Sorbitan monostearate 1
(5) N-stearoyl-N-methyltaurine sodium 0.5
(6) Vaseline 5
(7) Dimethylpolysiloxane (100 mPa · s) 3
(8) Glyceryl tri-2-ethylhexanoate 20
(9) Astaxanthin solution * 4 0.05
(10) Ellagic acid 0.05
(11) Lactic acid (50% aqueous solution) 1
(12) Dipropylene glycol 10
(13) Arbutin 3
(14) Sodium citrate 0.5
(15) Platinum colloid * 2 0.5
(16) Ascorbyl magnesium phosphate 0.1
(17) Titanium oxide 0.1
(18) Fragrance appropriate amount (19) Edetate disodium 0.03
(20) Ethyl paraoxybenzoate 0.05
(21) Purified water remaining * 4 Containing 5% astaxanthin

(Manufacturing method)
A. Ingredients (1) to (10) are heated and mixed and maintained at 70 ° C.
B. Ingredients (11) to (16) and (19) to (21) are heat mixed and maintained at 70 ° C.
C. A is added to B, mixed and uniformly emulsified.
D. After cooling C, (17) and (18) were added and mixed uniformly to obtain a cream.

  The cream prepared in Example 4 is stable without discoloration, odor, separation, etc. When applied to the skin, the smooth feel and moisturizing feeling required for cosmetics and creams containing carotenoids can be obtained and applied continuously. By doing so, it was effective in suppressing or improving spots, dullness and the like.

Example 5: Sunscreen emulsion (component) (%)
(1) Polyoxyalkylene-modified organopolysiloxane 1
(2) Dimethylpolysiloxane (100 mPa · s) 5
(3) Octamethylcyclotetrasiloxane 20
(4) Isotridecyl isononanoate 5
(5) Paramethoxycinnamic acid-2-ethylhexyl 5
(6) Fine particle titanium oxide 10
(7) Fine zinc oxide 10
(8) Zirconium oxide 5
(9) Polystyrene powder 3
(10) Trimethylsiloxysilicic acid
/ Cyclopentasiloxane solution 0.5
(11) Haematococcus alga extract * 3 0.01
(12) Propyl paraoxybenzoate 0.1
(13) Dipropylene glycol 3
(14) Ethyl alcohol 10
(15) Purified water remaining amount (16) Salt 0.2
(17) Platinum colloid * 2 0.01
(18) Perfume appropriate amount

(Manufacturing method)
A. Components (1) to (10) are mixed and dispersed.
B. Components (11) to (16) are mixed and dissolved.
C. Add B to A and emulsify uniformly.
D. Components (17) and (18) were added to C to obtain a sunscreen emulsion.

  The sunscreen emulsion prepared in Example 5 is extremely stable without discoloration, odor, separation, etc., and when applied to the skin, the carotenoid effect is exerted to protect the skin from ultraviolet rays during the day, and to prevent stains, dullness, etc. It was excellent in the effect of suppressing or reducing.

Claims (3)

The following components (A) and (B);
(A) Carotenoid (B) A skin external preparation characterized by containing a platinum group metal colloid. The component (A) carotenoid is one or more selected from the group consisting of astaxanthin, lycopene, β-carotene, zeaxanthin, lutein, canthaxanthin, cryptoxanthin, violaxanthin, capsanthin, fucoxanthin and derivatives thereof. The skin external preparation according to claim 1, wherein the preparation is externally applied. The skin external preparation according to claim 1 or 2, wherein the component (B) is a platinum colloid.