JP6001902B2 - Composition containing ascorbic acid derivative - Google Patents

Description

  The present invention relates to a composition containing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate. The composition of the present invention is particularly useful as a cosmetic or an external preparation for skin, and is particularly suitable for a form requiring transparency.

  Higher fatty acid esters of ascorbic acid-2-phosphate, which is a vitamin C derivative, are used in various cosmetics and skin external preparations as amphiphilic components having functions such as whitening, anti-inflammatory, and anti-aging. Yes. Several techniques have been investigated to improve the stability of this component over time.

  Patent Document 1 describes a skin external preparation characterized by containing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate and a polyhydric alcohol. According to this, ascorbic acid- It is stated that even when a salt of a higher fatty acid ester of 2-phosphate is formulated as an external preparation for skin, turbidity and precipitation can be prevented over time. Patent Document 2 contains a fatty acid ester of L-ascorbic acid-2-phosphate and / or a salt thereof, a liquid oil having an IOB value of 0.07 to 0.65, a surfactant, and water. An oil-in-water composition is described, and according to this, hydrolysis of a fatty acid ester of L-ascorbic acid-2-phosphate which is an active ingredient and / or a salt thereof in the oil-in-water composition is suppressed. It is stated that stable blending is possible. Furthermore, in Patent Document 3, a composition containing a specific ascorbic acid-2-phosphate derivative, a nonionic surfactant and water is prepared, and this is mixed with a divalent or higher metal salt or an aqueous solution thereof. The composition characterized by having prepared by this is described, and it is stated that according to this, the stability of the ascorbic acid derivative can be remarkably improved. Further, Patent Document 4 is not related to an ascorbic acid ester, but relates to the blending of a retinoid having a common oil-soluble property, which includes at least a retinoid and a lipid bilayer film composed of hydrogenated phospholipid. A retinoid stabilizing composition characterized by containing retinoid-encapsulated particles encapsulating a hydrophobic antioxidant is described. Further, it is described that such a retinoid stabilizing composition can provide an aqueous preparation having excellent stability with time, non-stickiness and fresh feeling.

JP 2005-336156 (Patent 0467328) JP2009-249325 JP2007-320858 JP 2009-256268 A

  In the conventional method, the ascorbic acid derivative is not sufficiently stable over time, and problems such as discoloration and precipitation are apparent particularly in skin lotions that are aqueous liquids and require transparency.

Degradation of the higher fatty acid ester salt of ascorbic acid-2-phosphate is accelerated at high and low temperatures, and yellowing, white turbidity and precipitation occur. Yellowing was due to discoloration of ascorbic acid, a degradation product, and white turbidity / precipitation was thought to be due to higher fatty acids. Therefore, these problems can be reduced if decomposition is appropriately suppressed.
The present inventors diligently studied a method for stabilizing a salt of a higher fatty acid ester of ascorbic acid-2-phosphate in the form of a lotion. As a result, it has been found that yellowing and clouding / precipitation can be suppressed by using a specific amino acid or a specific sulfur-containing compound in combination, and the present invention has been completed.

The present invention provides the following.
[1] The following components (A) to (F);
(A) Salt of higher fatty acid ester of ascorbic acid-2-phosphate (B) One or two or more kinds of sulfur selected from pyrosulfite, sulfite, bisulfite, dithionate and thiosulfate Containing antioxidant compound (C) amino acid having two or more nitrogen atoms in the molecule (D) ethylenediaminetetraacetic acid, or a salt thereof (E) 1,2-alkanediol, and / or glycerin (F) water A composition having a pH of 6.0 to 8.0 at 25 ° C.
[2] The composition according to [1], wherein component (B) is pyrosulfite or thiosulfate.
[3] The composition according to [1] or [2], wherein the component (C) is arginine and / or histidine.
[4] The composition according to any one of [1] to [3], wherein the component (E) is 1,2-pentanediol.
[5] The composition according to any one of [1] to [4], wherein the amount of component (E) is 3 to 15% by mass.
[6] The blending mass ratio of components (B), (C), (D) and (E) to component (A) is as follows:
(B) / (A) = 0.001 to 0.2
(C) / (A) = 0.02-1
(D) / (A) = 0.02-1
(E) / (A) = 2.5-50
The composition according to any one of [1] to [5].
[7] The composition according to any one of [1] to [6], which is a transparent liquid.
[8] The composition according to any one of [1] to [7], wherein the composition is a cosmetic or an external preparation for skin.

According to the present invention, the stability of a salt of a higher fatty acid ester of ascorbic acid-2-phosphate is improved.
According to the present invention, it is possible to obtain a colorless and transparent composition that hardly causes yellowing, white turbidity, and precipitation at low and high temperatures.

The composition of the present invention contains the following components (A) to (F):
(A) a salt of a higher fatty acid ester of ascorbic acid-2-phosphate;
(B) a sulfur-containing antioxidant compound selected from pyrosulfite, sulfite, bisulfite, dithionite and thiosulfate (C) an amino acid having two or more nitrogen atoms in the molecule;
(D) Ethylenediaminetetraacetic acid, or a salt thereof (E) 1,2-alkanediol, and / or glycerin (F) water In the present invention, when the numerical range is represented by “X to Y”, it is particularly described. Except for X and Y at both ends. The term “salt” with respect to the component of the present invention refers to a salt acceptable as a cosmetic or an external preparation for skin unless otherwise specified, and includes sodium salt, potassium salt, magnesium salt, or Zinc salts and the like are included.

[Component (A)]
The composition of the present invention comprises a salt of a higher fatty acid ester of ascorbic acid-2-phosphate. In the present invention, “a salt of a higher fatty acid ester of ascorbic acid-2-phosphate” refers to a phosphoric acid ester-bonded to the hydroxyl group at the 2-position of ascorbic acid, and the hydroxyl group at the 6-position, unless otherwise specified. A compound in which a higher fatty acid is ester-bonded, wherein a phosphate residue ester-bonded to the hydroxyl group at the 2-position forms a salt.

  The ester-linked higher fatty acid residue is preferably an aliphatic carboxylic acid residue having 10 to 20 carbon atoms, and more preferably lauric acid, myristic acid, palmitic acid, stearic acid, 2-hexyldecanoic acid or isostearic acid. More preferably, it is a residue of palmitic acid.

  Examples of the salt are not particularly limited as long as they are acceptable as cosmetics or skin external preparations. Examples include salts of alkali metals, alkaline earth metals, tertiary amines, and the like. Preferred examples include the sodium salt, potassium salt, magnesium salt, or zinc salt described above.

A preferable example of a salt of a higher fatty acid ester of ascorbyl 2-phosphate used in the present invention is a salt of ascorbyl palmitate, more specifically, a sodium salt or magnesium salt of ascorbyl palmitate. is there. An example of a salt of a higher fatty acid ester of ascorbic acid-2-phosphate that is particularly preferably used in the present invention is trisodium ascorbyl phosphate (chemical name: L-ascorbic acid-2-phosphate -6-palmitin). It is trisodium acid (trisodium L-ascorbyl 2-phosphate 6-palmitate ).

  In the present invention, as a salt of a higher fatty acid ester of ascorbic acid-2-phosphate, only one type may be used, or two or more types may be used in combination.

  The salt of higher fatty acid ester of ascorbic acid-2-phosphate is obtained by adding lipophilicity to the water-soluble ascorbic acid derivative by further introducing a higher fatty acid residue into the phosphate ester of ascorbic acid. It is medium. Compared to existing ascorbic acid derivatives, it has superior skin permeability, promotes collagen synthesis in the skin, and can be expected to have an anti-aging effect.

  The compounding amount of the salt of the higher fatty acid ester of ascorbic acid-2-phosphate in the composition of the present invention is 0.03 to 10% by mass (hereinafter sometimes simply referred to as “%”), and is a preferable compounding. The amount is 0.1 to 2%, and a more preferable blending amount is 0.3 to 1%. If it is this range, since effects, such as whitening, are also excellent and stability with time is also excellent, it is preferable.

[Component (B)]
The composition of the present invention comprises one or more sulfur-containing antioxidant compounds selected from pyrosulfite, sulfite, bisulfite, dithionite and thiosulfate. The component (B) of the present invention can exhibit an antioxidant action, and can prevent oxidative degradation of the component (A).

  As a component (B), 1 type (s) or 2 or more types can be used as needed, It is preferable to use at least pyrosulfite or thiosulfate, and it is more preferable to use sodium pyrosulfite or sodium thiosulfate. .

  The compounding quantity of the component (B) in the composition of this invention can be 0.0005 to 1%, a preferable compounding quantity is 0.001 to 0.4%, and a more preferable compounding quantity is 0.003 to 0. .2%. If it is this range, since temporal stability is more excellent, it is preferable.

  Furthermore, regarding a content mass ratio with a component (A), it can be set as (B) / (A) = 0.002-0.8, and it is preferable to set it as 0.0005-0.4, and. It is more preferable to set it to 001-0.2. If it is this range, it can fully contribute to stabilization of (A).

[Component (C)]
The composition of the present invention contains an amino acid containing two or more nitrogen atoms in the molecule. An amino acid containing two or more nitrogen atoms in the molecule can be selected from arginine, glutamine, tryptophan, histidine, lysine, glycylglycine, and asparagine. According to the study by the present inventors, when glycine, which is an amino acid having only one nitrogen atom in the molecule, is used instead of component (C), precipitation occurs at low temperature, yellowing and cloudiness at high temperature. Tended to occur. In the present invention, “high temperature” means 50 ° C. or higher unless otherwise specified, and “low temperature” in the present invention means 5 ° C. or lower unless otherwise specified. The stability at a high temperature and the stability at a low temperature can be evaluated by performing the presence or absence of discoloration, the presence or absence of precipitation, and a sensory test when stored at the temperature for several days to several months, for example, one month.

  Among the components (C), particularly preferred for use in the present invention is an amino acid containing 3 or more nitrogen atoms selected from arginine and histidine. As a component (C), 1 type (s) or 2 or more types can be used as needed.

  Although the compounding quantity of the component (C) of this invention is not specifically limited, It can be 0.005 to 1%, A preferable compounding quantity is 0.01 to 0.4%, and is more preferable. The blending amount is 0.06 to 0.2%.

  Furthermore, regarding a content mass ratio with a component (A), it can be set as (C) / (A) = 0.005-4, it is preferable to set it as 0.01-2, and 0.02-1 More preferably. If it is this range, it can fully contribute to stabilization of (A).

[Component (D)]
The composition of the present invention comprises ethylenediaminetetraacetic acid (EDTA) or a salt thereof. Component (D) acts as a chelating agent. According to the study by the present inventors, when etidronic acid was used in place of the EDTA salt, no change in color tone was observed at both high and low temperatures, but precipitation tended to occur. . Therefore, in the present invention, as component (D), EDTA or a salt thereof will be suitable. EDTA or a salt thereof is considered to be beneficial in that the pH is neutral and the chelating ability is high and the coordination number is large. Diethylenetriaminepentaacetic acid pentasodium, which is often used in the same manner as EDTA (or its salt), is more likely to exhibit chelating ability in the alkaline region of pH, and glycine exhibits chelating ability in the neutral region. It is considered that EDTA having a higher order is superior in chelating ability.

  When a salt of EDTA is used as component (D), it is not particularly limited as long as it can be used in cosmetics or skin external preparations. For example, a sodium or potassium salt of EDTA is preferably used. It may be used alone or in combination as required.

  Although the compounding quantity of the component (D) of this invention is not specifically limited, It can be 0.005-0.8%, A preferable compounding quantity is 0.01-0.4%, A more preferable blending amount is 0.06 to 0.2%. Furthermore, regarding a content mass ratio with a component (A), it can be set to (D) / (A) = 0.005-4, It is more preferable to set it as 0.01-2, 0.02-1 More preferably. Such a range is particularly suitable when disodium ethylenediaminetetraacetate used in the examples, but when EDTA itself or other salts are used as component (D) of the present invention, An amount (molar equivalent) corresponding to the disodium salt can be used.

[Component (E)]
The composition of the present invention comprises 1,2-alkanediol and / or glycerin. The component (E) is considered to have an effect of increasing the solubility of the component (A) and making it less likely to cause white turbidity / precipitation. When 1,3-butylene glycol (BG), propylene glycol, dipropylene glycol (DPG), or diglycerin is used instead of the specific component (E), the stability at low temperatures tends to be inferior. there were. A particularly preferred example of 1,2-alkanediol is 1,2-pentanediol (pentylene glycol). (E) As a component, you may use 1 type or in mixture as needed.

Although the compounding quantity of the component (E) of this invention is not specifically limited, It can be set to 2-20%, A preferable compounding quantity is 3-15%, A more preferable compounding quantity is 4-10. %.
Furthermore, regarding the content mass ratio with a component (A), it can be set as (E) / (A) = 0.5-70, It is more preferable to set it as 1-60, It is set as 2.5-50. More preferably.

[Component (F)]
In the composition of the present invention, water is used as a solvent for dissolving the component (A) and other components. Water can give a fresh feel to the skin during and after use.

  As water, purified water can be used. The blending amount of water is not particularly limited and can be appropriately blended according to the amount of other components. However, the preferable blending amount is 75 to 97%, and the more preferable blending amount is 80 to 96%.

[PH]
The skin external preparation of this invention is adjusted to pH 6.0-8.0. A pH adjuster may be used. When the pH exceeds 8, the stability at high temperature tends to be inferior, and when the pH is less than 6.0, the stability at low temperature tends to be inferior. The pH adjuster used for pH adjustment is not particularly limited as long as it can adjust the pH of the composition to 6.0 to 8.0 and is acceptable as a component for external use on the skin. Examples of pH adjusters that can be used in the present invention include citrate, phosphate, and tartrate. In addition, when mentioning pH by this invention, it is a value at the time of 25 degreeC except the case where it describes especially.

[Other ingredients]
In the composition of the present invention, various components to be blended in a normal cosmetic or skin external preparation within a range not impeding the effects of the present invention, specifically, oils, alcohols, powders, soluble polymers, A film forming agent, a surfactant, an organically modified clay mineral, a resin, an ultraviolet absorber, an antiseptic, an antibacterial agent, a fragrance, a refreshing agent, an antioxidant, and the like can be added.

  If it is a comparatively small amount, an oil agent can be mix | blended with the composition of this invention. The oil can soften the skin and can exert an emollient feeling on the skin.

  In the composition of the present invention, a cosmetic agent for the purpose of whitening, anti-oxidation and the like, which is blended in normal cosmetics or skin external preparations, can be blended within a range not impairing the effects of the present invention.

  Examples of whitening agents include arbutin, vitamin C and its derivatives, hawthorn extract, Inchinkou (Kawara mugwort) extract, licorice extract, Clara extract, wheat extract, saicin extract, rice and rice bran extract, black Examples include currant extract, Ibukitorano extract, Neubara (Agetsu) extract, Ezocogi extract, Sakuhakuhi extract, Toki extract, coffee extract, pearl barley (Yokuinin) extract and the like.

  Antioxidants include coenzyme Q10, alpha lipoic acid, vitamin E and derivatives thereof, carotenoids, dibutylhydroxytoluene, butylhydroxyanisole, rutin and derivatives thereof, glutathione and derivatives thereof, superoxide dismutase, mannitol, caquette extract, geno shoco Extract, Peonies extract, Superoxide Dismutase, Ginkgo biloba extract, Scarab (Ogon) extract, Mikaika (Maikai, Hermanus) extract, Tormentilla extract, Grape extract, Yashajitsu (Yasha) extract, Yukinoshita extract, Examples include rosemary (mannenro) extract, tea extract (Oolong tea, black tea, green tea, etc.) and the like.

  Furthermore, the composition of the present invention can be blended with an electrolyte that has been difficult to be blended stably into an emulsion. Specifically, for example, amino acids other than the component (C) described above (for example, glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, hydroxyproline, thyroxine, methionine, cystine, cysteine, Water-soluble derivatives of amino acids such as aspartic acid and glutamic acid) and trimethylglycine and N-acetyl-glutamic acid, hydroxyacetic acid, lactic acid, β-hydroxypropionic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, α-hydroxyiso Sodium such as caproic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, malic acid, tartronic acid, citric acid, tartaric acid, pyrrolidone carboxylic acid salt Potassium salt, triethanolamine salt, ammonium salt, dipotassium glycyrrhizinate, urea, L-ascorbic acid-2-sodium phosphate, L-ascorbic acid-2-magnesium phosphate, ascorbic acid glucoside, phenylbenzimidazole sulfonate, Examples include hydroxymethoxybenzophenone sulfonate. The blending amount of the electrolyte is more preferably 0.1% to 5% from the viewpoint of cosmetic effects and stability at high temperatures.

[Production method, others]
For production of the composition of the present invention, conventional methods known to those skilled in the art can be used. Although not particularly limited, for example, the component (A) is dissolved in the component (F) in advance, and the other components are mixed and dissolved therein.

  In the composition of the present invention, discoloration and precipitation due to decomposition of the component (A) are suppressed, but may be inherently transparent, translucent, or a certain degree of turbidity. You may have. Whether or not it is transparent and the degree of transparency can be appropriately determined by those skilled in the art based on existing methods and criteria applied to lotions. For example, regarding transparency, a judgment standard of about 4 to 5 levels is provided, and can be judged visually by a trained expert. Transparency can also be expressed by transmittance (a value representing the intensity ratio of incident light and transmitted light irradiated to the liquid to be determined as a percentage). The transparent or translucent transmittance is preferably 70% or more at a wavelength of 700 nm.

  Although the property of the composition of this invention is not specifically limited, In order to enjoy the effect of this invention more, it is preferable that it is liquid. In addition, the liquid in this invention refers to the viscosity value of 1-3000 mPa * s at 25 degreeC, and is a property which has sufficient fluidity | liquidity. The viscosity here is measured using a B-type rotational viscometer (Toshiba System Co., Ltd., Bismetron viscometer VDA2).

  The composition of the present invention is suitable for use as a cosmetic or external preparation for skin, and the composition of the present invention can be added to form a cosmetic or external preparation for skin. The amount of the composition when used by adding to a cosmetic or a skin external preparation is not particularly limited, but can be, for example, 0.1 to 70% with respect to the total amount of the cosmetic or skin external preparation, It is preferable to set it as 0.5 to 60%, and it is more preferable to set it as 1.0 to 50%. It is because it can mix | blend stably if it is this range.

  The present invention is suitable for cosmetics. The form of the cosmetic is not particularly limited, and examples thereof include skin care cosmetics such as lotion, cosmetic liquid, massage fee, and pack fee, and base cosmetics. Moreover, the usage method includes a method of using by hand and fingers, a method of using it by impregnating a nonwoven fabric and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

Examples 1 to 18 and Comparative Examples 1 to 17: Lotion Toner lotions having the formulations shown in Tables 1 and 2 below were prepared by the following production methods, and the stability at high and low temperatures was evaluated by the following methods. The results are also shown in Table 1 and Table 2. In addition, all Examples and Comparative Examples except Comparative Example 16 were colorless and transparent in production.

[Preparation method]
A: No. No. 22 component is No. Dissolve in 23.
B: Other ingredients and A were mixed and dissolved to obtain a skin lotion.

[Evaluation method]
Each sample was stored at 50 ° C. or 5 ° C. for 1 month, and then visually evaluated by a cosmetics evaluation specialist for the presence or absence of discoloration (yellowing, cloudiness) and precipitation according to the following.
Stability ◎: No discoloration or precipitation is observed at all ○: Discoloration or precipitation is slightly observed but is at a satisfactory level Δ: Discoloration or precipitation is observed, which is a problem in quality as a cosmetic material ×: Discoloration or Severe precipitation

Example 19: Cosmetic liquid (liquid)
(Ingredient) (%)
1. Polyoxyethylene isostearate (50 mol)
Hardened castor oil 0.5
2. Ubiquinone 0.02
3. Glyceryl trioctanoate 0.03
4). Di-2-ethylhexyl succinate 0.03
5. Di-2-ethylhexanoic acid neopentyl glycol 0.05
6). 6. Purified water remaining amount Xanthan gum 0.05
8). Purified water 10.0
9. Ascorbyl palmitate trisodium 1.0
10. Edetate disodium 0.1
11 Sodium lactate 0.5
12 Sodium dithionite 0.1
13. Glycylglycine 0.1
14 Citric acid 3Na 0.28
15. Monohydrogen phosphate 2Na 0.02
16.1,2-Pentanediol 10.0
17. Glycerin 5.0
18. Ethanol 3.0
19. Water-soluble collagen 0.01
19. Methyl paraoxybenzoate 0.1
20. Fragrance 0.01

(Production method)
A. Ingredients 1-5 are uniformly dissolved.
B. Component 7 is added to component 6 heated to 70 ° C., mixed and stirred, and cooled to room temperature.
C. Add A to B and mix uniformly.
D. While stirring C, ingredients 8 to 20 are added and mixed uniformly.
E. D was filled into a container to obtain a serum.

  The cosmetic liquid of Example 19 was a cosmetic liquid excellent in stability at high and low temperatures.

Example 20: Sheet-form cosmetic (component) (%)
1. Ethanol 10.0
2. Tetra 2-ethylhexanoic acid pentaerythritol 0.01
3. Polyoxyethylene (40 mol) hydrogenated castor oil 0.01
4). Polyoxyethylene (60 mol) hydrogenated castor oil 0.01
5. Sorbitan sesquioleate 0.01
6). Triceteares-4-phosphate (Note 1) 0.01
7). PPG-9 Diglyceryl (Note 2) 1.0
8.1,3-Butylene glycol 5.0
9. Ascorbyl palmitate trisodium 2.0
10. Sodium pyrosulfite 0.01
11 Arginine 0.1
12 Edetate disodium 0.3
13. Citric acid 3Na 0.28
14 Monohydrogen phosphate 2Na 0.02
15.1,2-Pentanediol 8.0
16. Sodium hyaluronate 0.01
17. Tranexamic acid 2.0
18. Carboxyvinyl polymer (Note 3) 0.2
19. Sodium hydroxide 0.06
20. Purified water remaining amount 21. Phenoxyethanol 0.1
22. Fragrance 0.01
(Note 1) HOSTAPHAT KW340D (manufactured by Clariant Japan)
(Note 2) SY-DP9 (Sakamoto Pharmaceutical Co., Ltd.)
(Note 3) CARBOPOL 980 (manufactured by LUBRIZOL ADVANCED MATERIALS)

(Production method)
A: Components 1 to 6 are mixed and dissolved.
B: Components 7 to 22 are added to A, and this is impregnated into the nonwoven fabric.
C: B was sealed and filled in an aluminum laminate bag-like container to obtain a sheet-like cosmetic.

  The cosmetic liquid of Example 19 was a cosmetic liquid excellent in stability at high and low temperatures.

Claims (7)

The following components (A) to (F);
(A) Salt of higher fatty acid ester of ascorbic acid-2-phosphate (B) Sulfur-containing antioxidant compound (C) selected from pyrosulfite, sulfite, bisulfite, dithionate and thiosulfate An amino acid having two or more nitrogen atoms in the molecule (D) ethylenediaminetetraacetic acid or a salt thereof (E) 1,2-alkanediol (excluding propylene glycol) and / or glycerin (F) water was blended. A composition having a pH of 6.0 to 8.0 at 25 ° C,
The blending mass ratio of components (B), (C), (D) and (E) to component (A) is as follows:
(B) / (A) = 0.001 to 0.2
(C) / (A) = 0.02-1
(D) / (A) = 0.02-1
(E) / (A) = 2.5-50
A composition.   The composition according to claim 1, wherein component (B) is pyrosulfite or thiosulfate.   The composition according to claim 1 or 2, wherein component (C) is arginine and / or histidine.   The composition according to any one of claims 1 to 3, wherein the component (E) is 1,2-pentanediol.   The composition of any one of Claims 1-4 whose compounding quantity of a component (E) is 3-15 mass%.   The composition according to any one of claims 1 to 5, which is a transparent liquid.   The composition according to any one of claims 1 to 6, which is a cosmetic or an external preparation for skin.