JP2013189397A - Skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin cosmetic in which an antioxidant itself is hardly deteriorated with the passage of time, and retinol or a retinol derivative has remarkably excellent oxidation stability.SOLUTION: This cosmetic contains (a) retinol or a retinol derivative, (b) a 0.001-0.8 mass% phenol-based antioxidant, (c) 0.001-0.8 mass% acetoxy tetramethylbutyl phenyl tetramethylbutyl benzofuranone, and (d) an oil whose IOB is ≥0.1 in an organic conceptual diagram; wherein the blending ratio (mass ratio) between (b) the phenol-based antioxidant and (c) acetoxy tetramethylbutyl phenyl tetramethylbutyl benzofuranone is 1:10 to 10:1.

Description

  The present invention relates to a skin cosmetic such as an emulsion containing retinol or a retinol derivative and having excellent storage stability.

  Anti-aging is one of the major goals of skin care cosmetics. Among them, wrinkles are the most important skin aging phenomenon from a cosmetic point of view. In recent years, retinoids have attracted attention as cosmetic drugs having an effect of improving skin wrinkles, and the application of retinoic acid and retinol, which are one of retinoids, to skin cosmetics has been studied. It is known that these act on keratinocytes to express hyaluronic acid synthesis promoting effect and exert wrinkle improving effect by increasing stratum corneum moisture. In particular, retinol is superior as a cosmetic drug because it has a milder effect than retinoic acid and does not exhibit strong side effects. However, retinol is very unstable and is easily oxidized under the influence of heat, light, oxygen, etc. (Non-Patent Document 1).

  In order to prevent deterioration due to oxidation, retinol is generally used in combination with an antioxidant. Among these, phenolic antioxidants such as tocopherol and dibutylhydroxytoluene (BHT) are often used because they exhibit an excellent antioxidant effect even in a small amount (Non-patent Document 2). In fact, cosmetics using these phenolic antioxidants in combination with retinol have also been proposed (Patent Document 1).

  However, phenolic antioxidants such as tocopherol and dibutylhydroxytoluene are liable to be oxidized per se, resulting in a problem that the antioxidant effect is weakened over time, discoloration is caused, and a strange odor is generated. In addition, when a large amount is blended in anticipation of the reduction of the antioxidant effect over time, there is a problem that it is deposited when stored at a low temperature.

  Thus, there is still a need for a skin cosmetic excellent in storage stability that can suppress oxidation of retinol or a retinol derivative, which has an effect of eliminating wrinkles and improving wrinkles, and can also suppress deterioration of the antioxidant itself over time. ing.

JP 2002-167320 A

"New Cosmetics" 2nd edition, Takeo Mitsui, 2001, published by Nanzan Hall, pages 170-171 "New Cosmetics" 2nd edition, Takeo Mitsui, 2001, published by Nanzan Hall, pages 162-163

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a skin cosmetic in which the antioxidant itself is hardly deteriorated with time and the oxidation stability of retinol or a retinol derivative is remarkably excellent.

As a result of intensive studies, the present inventors have determined that a skin cosmetic containing retinol or a retinol derivative contains a phenolic antioxidant such as tocopherol or dibutylhydroxytoluene, and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone. By blending, the oxidation stability of retinol or a retinol derivative can be remarkably improved, and at the same time, the phenolic antioxidant itself can be prevented from being discolored over time and the generation of a strange odor, thereby completing the present invention. It came. It should be noted that acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone known as an antioxidant is combined with a phenolic antioxidant in a specific blending amount and blending ratio, so that these are used alone. In addition, an excellent stabilizing effect is exhibited.
In addition, phenolic antioxidants and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone are poorly compatible with some oils and may precipitate during storage, but can be stabilized by adding a certain polar oil. It was also found that it can be dissolved.

That is, the present invention
(A) retinol or a retinol derivative,
(B) 0.001 to 0.8% by mass of a phenolic antioxidant,
(C) 0.001-0.8 mass% of acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone, and (d) an oil whose IOB in the organic conceptual diagram is 0.1 or more, (b) phenolic oxidation The gist of the present invention is a skin cosmetic wherein the blending ratio (mass ratio) of the inhibitor and (c) acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone is 1:10 to 10: 1.

  According to the skin cosmetics of the present invention, aged hydroxytetramethylbutylphenyltetramethylbutylbenzofuranone can suppress deterioration of the phenolic antioxidant over time. For this reason, these two components work together to produce a synergistic antioxidant effect, keep retinol or retinol derivatives more stable, and maintain the wrinkle disappearance / improving effect of retinol or retinol derivatives over a long period of time. Can do. Also, since acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone and phenolic antioxidants cooperate as described above to produce a synergistic stabilizing effect, the total amount of antioxidants can be reduced. In particular, it is possible to suppress the precipitation of antioxidants, which tend to occur particularly at low temperatures, and at the same time to suppress discoloration and off-flavors due to their own deterioration.

  The skin cosmetic of the present invention comprises (a) retinol or a retinol derivative, (b) a phenolic antioxidant, (c) acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone, and (d) an IOB in an organic conceptual diagram. Is characterized by containing an oil content of 0.1 or more in a specific amount and blending ratio. Hereinafter, the present invention will be described in detail.

<(A) Retinol or retinol derivative>
The retinol or retinol derivative is not particularly limited as long as it can be used in the fields of cosmetics, pharmaceuticals, quasi drugs and the like. The retinol derivative has a wrinkle disappearance / improving effect similar to that of retinol, and examples thereof include retinol acetate and retinol palmitate.

  Retinol or a retinol derivative can mix | blend 1 type (s) or 2 or more types. The amount of retinol or retinol derivative is not particularly limited, but is generally 0.001 to 10.0% by mass, preferably 0.005 to 1.0%, based on the total amount of the skin cosmetic. It is 0.01 mass%, More preferably, it is 0.01-0.5 mass%. If it is less than 0.001% by mass, it is difficult to sufficiently exhibit the wrinkle disappearance / improvement effect. It is difficult to recognize, and it tends to irritate the skin.

<(B) Phenolic antioxidant>
Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and polymeric phenolic antioxidants. Specifically, monophenol antioxidants such as dibutylhydroxytoluene, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert) -Butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) and other bisphenol antioxidants, tetrakis- [methylene-3- (3 '-, 5'-di-tert-butyl-) 4′-hydroxyphenyl) propionate] methane, and high-molecular phenolic antioxidants such as α-tocopherol. Of these, dibutylhydroxytoluene (BHT) is preferred because the effect of preventing deterioration by acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone is high.

  0.001-0.8 mass% is preferable with respect to the skin cosmetics whole quantity, and, as for the addition amount of a phenolic antioxidant, 0.01-0.5 mass% is more preferable, 0.01-0.1 More preferred is mass%. If it is 0.001 mass% or more, the oxidation of a retinol or a retinol derivative can fully be suppressed. On the other hand, when it mixes more than 0.8 mass%, there exists a tendency which precipitates at the time of storage or becomes a cause of generation | occurrence | production of discoloration and a strange odor.

<(C) Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone>
Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone is an antioxidant having the following structure.
As a commercially available product, a product sold as “TINOGARD LO1 (registered trademark)” by BASF can be used.

  The amount of acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone added is preferably 0.001 to 0.8 mass%, more preferably 0.01 to 0.5 mass%, and more preferably 0.001 mass% with respect to the total amount of the skin cosmetic. 01-0.1 mass% is further more preferable. If it is 0.001 mass% or more, the time-dependent deterioration of a phenolic antioxidant can fully be suppressed, As a result, retinol or a retinol derivative can be hold | maintained more stably. On the other hand, when it mix | blends more than 0.8 mass%, there exists a tendency to precipitate at the time of storage.

<(B) Compounding ratio of phenolic antioxidant and (c) acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone>
In order to bring out the synergistic antioxidant effect of phenolic antioxidant and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone, and to achieve better storage stability than when these are used alone, these two components are used as described above. In addition to blending in a predetermined amount, it is necessary to use at a predetermined blending ratio. That is, the blending ratio (mass ratio) of phenolic antioxidant: acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone needs to be 1:10 to 10: 1 and should be 1: 2 to 2: 1. More preferred. If the blending ratio is out of the range, the synergistic effect of these two components may not be sufficiently obtained.

<(D) Oil whose IOB is 0.1 or more in the organic conceptual diagram>
The organic conceptual diagram was proposed by Satoshi Fujita, and details thereof are described in “Pharmaceutical Bulletin”, vol. 2,2, pp. 163-173 (1954), “Area of Chemistry” vol. 11, 10, pp. 719-725 (1957), "Fragrance Journal", vol. 50. pp. 79-82 (1981). In other words, the source of all organic compounds is methane (CH ₄ ), all other compounds are all regarded as derivatives of methane, and the number of carbon atoms, substituents, and bonding modes (difference in single bond, double bond, triple bond) ), Set a certain numerical value for each ring, etc., add the scores to find the organic and inorganic values, and plot them on a diagram with the organic value on the X axis and the inorganic value on the Y axis. It will be. The organic conceptual diagram is also shown in “Organic Conceptual Diagram-Basics and Applications” (written by Yoshio Koda, Sankyo Publishing, 1984).
The IOB in the organic conceptual diagram is an abbreviation of Inorganic / Organic Balance, and the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, “inorganic value (IV) / organic property Value (OV) ".

Examples of oils having an IOB of 0.1 or more include 2-ethylhexyl 2-ethylhexanoate (IOB = 0.2), tripropylene glycoline neopentanoate (IOB = 0.52), and isodecylbenzoate (IOB = 0.0). 23), propylene glycol dicaprylate (IOB = 0.32), isononyl isononanoate (IOB = 0.2), cetyl 2-ethylhexanoate (IOB = 0.52), glyceryl tri-2-ethylhexanoate (IOB = 0.36), pentaerythritol tetra-2-ethylhexanoate (IOB = 0.35), di-2-ethylhexyl succinate (IOB = 0.32), and the like, but are not limited thereto.
In the present invention, one or two or more oil components having an IOB of 0.1 or more can be arbitrarily selected and used.

  The content of oil having an IOB of 0.1 or more is 50% by mass or more, more preferably 60% by mass or more, based on the total oil phase contained in the skin cosmetic. If it is less than 50.0 mass%, sufficient stability cannot be obtained, and a phenolic antioxidant or acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone may precipitate. Moreover, if it is this range, it will be hard to produce a sticky feeling and the refreshing feeling of use can be given.

  The oil phase may contain an oil component having an IOB of less than 0.1, that is, a non-polar oil component such as liquid paraffin, isoparaffin, isohexadecane, isododecane, squalane, squalene, hydrogenated polyisobutene and the like. However, since the phenolic antioxidant and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone are difficult to dissolve in these nonpolar oils, it is necessary to limit the amount of the skin cosmetic so as not to be unstable.

  The skin cosmetics according to the present invention are various components that are usually blended in the field of cosmetics and quasi-drugs, for example, surfactants, emulsifiers, powder components, solids, as long as the effects of the present invention are not impaired. Fats and oils, humectants, thickeners, sequestering agents, pigments, pH adjusters, skin nutrients, vitamins, preservatives, fragrances and the like can be appropriately blended as necessary.

  The skin cosmetic according to the present invention can be produced according to a conventionally used method. For example, an oil phase component and an aqueous phase component are separately mixed to prepare an oil phase and an aqueous phase, respectively, and the aqueous phase and the oil phase are mixed and emulsified with a homomixer or the like.

  The use of the skin cosmetic according to the present invention is not particularly limited, but it can be applied to various products such as facial or body emulsions, creams, and cosmetics.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited by these Examples. Unless otherwise specified, the blending amount indicates mass%.

Prior to this example, the evaluation method used in this example will be described.
[Storage stability (odor) test]
The test sample was put in a 50 ° C. constant temperature bath, and after 4 weeks, it was determined by sensory evaluation according to the following evaluation criteria.
(Evaluation criteria)
◎: No off-flavor is felt, and there is no problem even if it is not scented or flavored.
○: Almost no strange odor is felt.
Δ: A slight odor is felt.
X: A clear off-flavor is felt, and even if it is scented or scented, it can be used.

[Storage stability (appearance) test]
The test sample was placed in a thermostatic bath at 50 ° C., and after 4 weeks, the appearance was visually observed and judged according to the following evaluation criteria.
(Evaluation criteria)
○: No discoloration is observed.
Δ: Some discoloration is observed.
X: Clear discoloration is recognized.

(Examples 1-6 and Comparative Examples 1-6)
A skin cosmetic having the composition shown in Table 1 below was prepared, and this was used as a test sample, and the storage stability was evaluated for odor and appearance according to the above evaluation criteria. The evaluation results are also shown.

Note) * 1: “TINOGARD LO1 (registered trademark)” manufactured by BASF

  As shown in Table 1, a composition containing both dibutylhydroxytoluene and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone in a predetermined amount and mixing ratio provides sufficient storage stability with respect to odor and appearance. (Examples 1-4). On the other hand, in the composition not containing any one or both of these two components, retinol and, when contained, a strange odor and discoloration due to oxidation of dibutylhydroxytoluene were observed (Comparative Examples 1 to 3). ). In particular, as is clear from the comparison between Example 1 and Comparative Examples 2 and 3, when both of the two components are included, the storage is superior to the case where either one is included in a larger amount than the total amount of the two components. Stability was obtained. From this, it can be seen that these two components cooperate with each other and exhibit an excellent antioxidant effect synergistically. Moreover, when these 2 components were included excessively, although generation | occurrence | production of a strange odor was not recognized, the external appearance was impaired by discoloration (comparative example 4).

  Further, even when both dibutylhydroxytoluene and acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone are contained, if the blending ratio is outside the range of 1:10 to 10: 1, synergistic oxidation It was confirmed that the prevention effect was not fully exhibited (Examples 5-6, Comparative Examples 5-6).

  Below, the other formulation example of the skin cosmetics which concern on this invention is given. Also according to these formulation examples, good storage stability was obtained in the same manner as in the above Examples.

Formulation Example 1 (cream):
Compounding ingredients Compounding amount (% by mass)
2-ethylhexyl 2-ethylhexanoate 8
Liquid paraffin 3
Dimethylpolysiloxane 2
Tetra-2-ethylhexanoic acid pentaerythrit 4
Stearyl alcohol 3
Behenyl alcohol 2
Glycerin 5
Dipropylene glycol 4
Trehalose 1
Polyisoethylene glyceryl monoisostearate 2
Polyoxyethylene glyceryl monostearate 1
Lipophilic glyceryl monostearate 2
Citric acid 0.02
Sodium citrate 0.08
Potassium hydroxide 0.04
Retinol palmitate (1 million units) 0.25
Tocopherol acetate 0.1
P-Hydroxybenzoate appropriate amount phenoxyethanol appropriate amount edetate trisodium 0.05
4-t-butyl-4′-methoxydibenzoylmethane 0.01
2-Ethylhexyl paramethoxycinnamate 0.1
BHT 0.05
Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone
0.05
β-carotene 0.01
Carboxyvinyl polymer 0.1
Purified water Residual fragrance Appropriate amount

Formulation Example 2 (Cream):
Compounding ingredients Compounding amount (% by mass)
Dimethylpolysiloxane 3.0
Decamethylcyclopentasiloxane 18.0
Isononyl isononanoate 5.0
Polyoxyethylene / methylpolysiloxane copolymer 1.0
Decamethylcyclopentasiloxane blend of cross-linked polymethylsiloxane (Dow Corning 9040 Silicone Elastomer Blend ^TM : Dow Corning) 5.0
Retinol 0.2
P-Hydroxybenzoate Equivalent amount Trimethylsiloxysilicate 2.0
Ethanol 2.0
Glycerin 3.0
Dipropylene glycol 5.0
Polyethylene glycol 6000 5.0
Sodium hexametaphosphate 0.05
Tocopherol acetate 0.1
BHT 0.1
Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone
0.05
Fennel extract 0.1
Hamelis extract 0.1
Yeast extract 1
Edetate trisodium 0.05
Yellow iron oxide appropriate amount dimethyl distearyl ammonium hectorite 1.5
Polyvinyl alcohol 0.1
Hydroxyethyl cellulose 0.1
Perfume Appropriate amount of purified water

Formulation Example 3 (Emulsion):
Compounding ingredients Compounding amount (% by mass)
Dimethylpolysiloxane 2
Glyceryl tri-2-ethylhexanoate 4
Octyl palmitate 2
Sunflower oil 1
Squalane 2
Retinol acetate 0.2
Ethanol 5
Glycerin 6
1,3-butylene glycol 5
Polyoxyethylene methyl glucoside 3
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.05
Hydroxypropyl-β-cyclodextrin 0.1
Dipotassium glycyrrhizinate 0.05
Loquat leaf extract 0.1
Fennel extract 0.1
Yeast extract 0.1
Lavender oil 0.1
BHT 0.05
Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone
0.1
Giant extract 0.1
Xanthan gum 0.1
Carboxyvinyl polymer 0.1
Acrylic acid / alkyl methacrylate copolymer 0.1
Bengala Appropriate amount Yellow iron oxide Appropriate amount Paraben Appropriate amount Purified water Residual

Formulation Example 4 (Emulsion):
Compounding ingredients Compounding amount (% by mass)
Liquid paraffin 2
Vaseline 1
Retinol 0.1
Behenyl alcohol 1.5
Glycerin 5
Dipropylene glycol 7
Polyethylene glycol 1500 2
Isostearic acid 0.5
Stearic acid 0.5
Behenic acid 0.5
Tetra-2-ethylhexanoic acid pentaerythrit 4
Cetyl 2-ethylhexanoate 3
Glycerol monostearate 1
Polyoxyethylene glyceryl monostearate 1
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.05
Stearyl glycyrrhetinate 0.05
Royal Jelly Extract 0.1
Yeast extract 0.1
Tocopherol acetate 0.1
BHT 0.05
Acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone
0.05
Acetylated sodium hyaluronate 0.1
Edetate trisodium 0.05
Carboxyvinyl polymer 0.15
Paraben Appropriate amount Purified water Residual flavoring Appropriate amount

Claims (3)

(A) retinol or a retinol derivative,
(B) 0.001 to 0.8% by mass of a phenolic antioxidant,
(C) 0.001-0.8 mass% of acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone, and (d) an oil whose IOB in the organic conceptual diagram is 0.1 or more, (b) phenolic oxidation A skin cosmetic wherein the blending ratio (mass ratio) of the inhibitor and (c) acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone is 1:10 to 10: 1.   The skin cosmetic according to claim 1, wherein the phenolic antioxidant is dibutylhydroxytoluene.   The skin cosmetic according to claim 1 or 2, wherein the blending ratio of (b) phenolic antioxidant and (c) acetoxytetramethylbutylphenyltetramethylbutylbenzofuranone is in the range of 1: 2 to 2: 1. .