JP2005531568A - Cosmetic composition containing a salt of malonic acid - Google Patents

Abstract

There is provided a cosmetic composition comprising a salt of malonic acid as an active ingredient in a cosmetically acceptable carrier. The composition exhibits a deflection value greater than 1 in the pig skin test.

Description

  The present invention relates to cosmetic compositions containing salts of malonic acid and the use of these compositions to control signs of skin aging.

  Smooth, soft and supple skin has an outstanding cosmetic appeal and is also a characteristic of the normal working of the epidermis. Human skin ages with aging, and wrinkles are formed by wrinkles on the epidermis, and wrinkles and wrinkles. These indicate that the figure loses youth and tells the transition to old age. Excessive amounts of sunlight will accelerate the transition process. Also, after being exposed to a cold climate or excessive contact with a detergent or solvent, the outer layer of the epidermis known as the stratum corneum becomes dry and easily peeled off. As a result, the skin loses moisture and the skin begins to lose characteristics such as smoothness, softness, and flexibility.

  Skin softeners such as fats, phospholipids and sterols have been used in the past to soften wrinkled or dry skin. These emollients are only partially effective as treatments for unhealthy skin.

  The use of hydroxycarboxylic acids to enhance the quality of human skin has been known for some time. There is no doubt that α-hydroxy carboxylic acids are much more effective than ordinary emollients.

  U.S. Pat. No. 4,424,234 (Alderson et al.) Describes α-hydroxycaproic acid and α-hydroxycaprylic acid in a composition having a pH value of less than 7, usually 2 to 4 or A skin treatment composition containing the mixture is disclosed. Yu and Van Scott have been widely patented in this field. For example, US Pat. No. 4,105,782 reports amine or ammonium salts of α-hydroxy carboxylic acids in the treatment of acne or dandruff. U.S. Pat. No. 4,105,783 and U.S. Pat. No. 4,197,316 suggest that these compounds can be used to treat dry skin. U.S. Pat. No. 4,234,599 discloses the use of [alpha] -hydroxy carboxylic acids, their esters or amine salts for the treatment of keratosis. More recently, US Pat. No. 5,091,171 focuses on the effectiveness of these compounds in age-related blemishes, wrinkles and age-related skin changes.

  Hydroxycarboxylic acids are considered to be very promising therapeutically, but this substance has been found to irritate the skin after repeated external application. Inflammation can range from sensory inflammation, such as a tingling, tingling, and tingling sensation, to clinical symptoms such as redness and skin peeling. The cause of such inflammation is related to a decrease in the pH of the stratum corneum of human skin. Low pH has been suggested to cause disruption of cell-cell junctions of keratinocytes, resulting in undesirable skin reactions, especially for certain people with sensitive skin.

  Organic acids other than functionalized α-hydroxy acids are disclosed in cosmetic literature. For example, US Pat. No. 5,641,495 (Jokura et al.) Discloses dicarboxylic acids and dicarboxylic acid salts in combination with ceramides or pseudoceramides. The examples illustrate the sodium and potassium salts of succinic acid. Low molecular weight dicarboxylic acids such as malonic acid may also be used. Although this system can perform excellent wetting and is rarely irritated, it has been suggested that this system combats the signs of aging that result in loss of skin smoothness, softness and tenderness. Absent. Improvements in these areas are consumer demands that have not yet been realized.

  Thus, the advantages of the present invention are cosmetic compositions that are effective to suppress signs of aging and can even eliminate this, especially for improving skin smoothness, softness and softness. It is to provide a novel cosmetic ingredient.

According to the first object of the present invention,
(I) about 0.0001 to about 30% by weight of a salt of malonic acid;
(Ii) about 1 to about 99.9% by weight of a cosmetically acceptable carrier;
A cosmetic composition is provided, wherein the composition exhibits a deflection value greater than 1 in a pig skin test.
Furthermore,
(I) about 0.0001 to about 30% by weight of a salt of malonic acid;
(Ii) about 1 to about 99.9% by weight of a cosmetically acceptable carrier;
Providing a cosmetic composition comprising: a cosmetic composition wherein the composition exhibits a deflection value greater than 1 in a pig skin test;
Applying the cosmetic composition to the skin;
There is provided a method of suppressing signs of aging including

  We have now found that the salt of malonic acid is at least as effective as α-hydroxy carboxylic acid to combat signs of skin aging. Most specifically, the salt of malonic acid showed significant activity in improving skin smoothness, softness and flexibility.

  A feature of the invention is the use of a malonate salt that gives the composition a positive deflection value of at least 1, preferably at least 1.1 compared to water in the Porcine Skin Test. It is. In this test, a thermomechanical analyzer is used, a 20 cm load is applied to a 1 cm diameter disc-shaped pig skin, and the direct deflection is recorded in mm. Use water as a control. Skin samples are measured before treatment and 24 hours after one, two and three treatments. In these treatments, 150 μl of each composition is applied to the skin and maintained for 5 minutes, then removed without rinsing. Then, it is dried at 21 ° C. and a relative humidity of less than 10%.

  In data conversion, the ratio of the warp value after applying the test composition three times to the warp value of the water standard is determined. This ratio is defined as the deflection value.

Various types of counter cations for malonate anions can be used to form salts.
The malonate salt has the general formulas (I) and (II):

によって表されるような半中和マロン酸または全中和マロン酸またはそれらの混合物でよく、式中のＸはカチオン性の対イオンを表す。

May be semi-neutralized malonic acid or fully neutralized malonic acid or mixtures thereof as represented by wherein X represents a cationic counterion.

  Suitable cationic counter ions are alkali metal ions and alkaline earth metal ions. Representative examples include cations of lithium, sodium, potassium, magnesium, calcium, ammonium, and combinations thereof.

  Not only inorganic cations but also organic cations can be used. Particularly useful cations are quaternized nitrogen cations having 1 to 1,000, preferably 1 to 20, and optimally 3 to 12 carbon atoms. Their representatives are triethanolamine, diethanolamine, propanolamine, monoethanolamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine. , Cyclopentylamine, norbornylamine, octylamine, ethylhexylamine, nonylamine, decylamine, pyrrolidone, amino acids (lysine, arginine, alanine, glutamine, histidine, glycine), 2-amino-2-methyl-1-propanol, dimethylethanol With cations derived from amines such as amines, polyethylenimine, tris (hydroxymethyl) aminomethane and combinations thereof. That.

  Most preferred are cations derived from ammonia, dimethylethanolamine, tris (hydroxymethyl) aminomethane. Typical malonate salts derived from these preferred materials are ammonium malonate, diammonium malonate, dimethylethanolammonium malonate, bis (dimethylethanolammonium) malonate, tris (hydroxymethyl) methaneammonium malonate, and di- [Tris (hydroxymethyl) methaneammonium] malonate.

  The amount of malonate is about 0.0001 to about 30% by weight of the cosmetic composition, preferably about 0.1 to about 15%, more preferably about 0.5 to about 10%, optimally It may range from about 1 to about 8% by weight.

  The present invention may use salt I, salt II or a mixture of these salts as active ingredients. When the mixture is present, the molar ratio of monosalt I to disalt II is from about 1000: 1 to about 1: 1000, preferably from about 10: 1 to about 1: 500, more preferably from about 2: 1 to about 1. : 200, optimally in the range of about 1: 1 to about 1:20.

  The composition of the present invention will also contain a cosmetically acceptable carrier. The amount of carrier can range from 1% to 99.9%, preferably from about 70% to about 95%, optimally from about 80% to about 90%. Useful carriers include water, emollients, fatty acids, fatty alcohols, humectants, thickeners and combinations thereof. The carrier can be aqueous, anhydrous or an emulsion. Preferably, the composition is an aqueous, especially water and oil, W / O or O / W type or triple W / O / W type emulsion. When water is present, the amount will range from about 5 to about 95% by weight, preferably from about 20 to about 70% by weight, optimally from about 35 to about 60% by weight.

  The emollient material will act as a cosmetically acceptable carrier. These may be in the form of silicone oils, synthetic esters and hydrocarbons. The amount of emollient can be any value ranging from about 0.1 to about 95% by weight, preferably from about 1 to about 50% by weight.

  Silicone oils can be classified into volatile and non-volatile varieties. As used herein, the term “volatile” means a material that has a measurable vapor pressure at ambient temperature. The volatile silicone oil is preferably selected from cyclic (cyclomethicone) or linear polydimethylsiloxanes containing 3 to 9, preferably 4 to 5, silicon atoms.

Nonvolatile silicone oils useful as an emollient material are polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. Essentially non-volatile polyalkylsiloxanes useful in the present invention include, for example, polydimethylsiloxanes having viscosities from about 5 × 10 ⁻⁶ to 0.1 m ² / sec at 25 ° C. Preferred non-volatile emollients useful in the compositions of the present invention include polydimethylsiloxanes having viscosities from about 1 × 10 ⁻⁵ to about 4 × 10 ⁻⁴ m ² / sec at 25 ° C.

  Another class of non-volatile silicones are emulsifying and non-emulsifying silicone elastomers. Representative of this type are dimethicone / vinyl dimethicone crosspolymers available as Dow Corning 9040, General Electric SFE 839 and Shin-Etsu KSG-18. Silicone waxes such as Silwax WS-L (dimethicone copolyol laurate) may also be useful.

Suitable ester emollients are listed below.
(1) Alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms. Examples include isoarachidyl neopentanoate, isononyl isonanonoate, oleyl myristate, oleyl stearate and oleyl oleate.
(2) Ether-esters such as fatty acid esters of ethoxylated fatty alcohols.
(3) Polyhydric alcohol ester. Ethylene glycol mono- and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol (200-6000) mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol 2000 monooleate, polypropylene Glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty esters, ethoxylated glyceryl mono-stearate, 1,3-butylene glycol monostearate, 1, 3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene Rubitan fatty acid ester is a suitable polyhydric alcohol esters. Pentaerythritol, neopentyl glycol esters of trimethylolpropane and C ₁ -C ₃₀ alcohols are particularly useful.
(4) Wax esters such as beeswax, spermaceti and tribehenine wax.
(5) A sterol ester whose representative example is cholesterol fatty acid ester.
(6) Sugar esters of fatty acids such as sucrose polybehenate and sucrose polycottonsedate.

Hydrocarbons which are suitable cosmetically acceptable carriers include petrolatum, mineral oil, C _{11 to} C ₁₃ isoparaffins, polyalphaolefins, especially isohexadecane commercially available as Permethyl 101A from Presperse Inc.

  Fatty acids having 10 to 30 carbon atoms are also suitable as cosmetically acceptable carriers. Representative of this type are pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, ricinoleic acid, arachidic acid, behenic acid and erucic acid.

  Fatty alcohols having 10 to 30 carbon atoms are another useful class of cosmetically acceptable carriers. Representatives of this type are stearyl alcohol, lauryl alcohol, myristyl alcohol and cetyl alcohol.

  Polyhydric alcohol type humectants can be used as cosmetically acceptable carriers. Typical polyhydric alcohols include glycerol, polyalkylene glycols, more preferably alkylene polyols and their derivatives such as propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol and their derivatives, sorbitol, hydroxypropyl Sorbitol, hexylene glycol, 1,3-butylene glycol, isoprene glycol, 1,2,6-hexanetriol, ethoxylated glycerol, propoxylated glycerol and mixtures thereof. The amount of humectant may be any value in the range of 0.5 to 50%, preferably 1 to 15% by weight of the composition.

  Thickeners can be used as part of the cosmetically acceptable carrier of the composition of the present invention. Typical thickeners include cross-linked acrylates (eg Carbopol 982®), hydrophobically modified acrylates (eg Carbopol 1382®), cellulosic derivatives and natural gums. Useful cellulosic derivatives include sodium carboxymethylcellulose, hydroxypropylmethocellulose, hydroxypropylcellulose, hydroxyethylcellulose, ethylcellulose and hydroxymethylcellulose. Natural gums suitable for the present invention include guar gum, xanthan gum, sclerotium, carrageenan, pectin and combinations of these gums.

  Inorganics, especially clays such as bentonite and hectorite, fumed silica, and silicates such as magnesium aluminum silicate (Veegum®) can also be used as thickeners.

  The amount of thickener may range from 0.0001 to 10% by weight, usually from 0.001 to 1% by weight, optimally from 0.01 to 0.5% by weight.

  The cosmetic composition of the present invention may be in any form. These forms include lotions, creams, roll-on formulations, sticks, mousses, aerosols and non-aerosol sprays, and formulations applied to fabrics (eg nonwovens).

  Surfactants may also be present in the cosmetic composition of the present invention. When present, the total concentration may range from about 0.1 to about 40%, preferably from about 1 to about 20%, optimally from about 1 to about 5% by weight of the composition. . The surfactant may be selected from anionic, nonionic, cationic and amphoteric surfactants.

Particularly preferred nonionic surfactants are those having a C _{10 to} C ₂₀ fatty alcohol or acid hydrophobe condensed with 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobic group; C _{2 to} C ₁₀ alkylphenols condensed with 2 to 20 moles of alkylene oxide; mono- and di-fatty acid esters of ethylene glycol; fatty acid monoglycerides; sorbitan, mono- and di-C _{8 to} C ₂₀ fatty acids; and polyoxy Ethylene sorbitan and combinations thereof. Alkyl polyglycosides and sugar fatty amides (eg methyl gluconamides) are also suitable nonionic surfactants.

Preferred anionic surfactants include soap, alkyl ether sulfates and sulfonates, alkyl sulfates and sulfonates, alkylbenzene sulfonates, alkyl and dialkyl sulfosuccinates, C ₈ -C ₂₀ acyl isethionates, C ₈ -C ₂₀ alkyl ether phosphates _include C 8 _{-C 20} sarcosinates and combinations thereof.

  The composition of the present invention may also contain a sunscreen active. Particularly preferred are materials such as ethylhexyl p-methoxycinnamate, available as Parsol MCX®, avobenzone, available as Parsol 1789®, and benzophenone-3 known as oxybenzone. Inorganic sunscreen actives such as ultrafine titanium dioxide, zinc oxide, polyethylene and various other polymers may be used. When present, the amount of sunscreen may generally range from 0.1 to 30%, preferably from 2 to 20%, optimally from 4 to 10%.

  It is desirable to include a preservative in the cosmetic composition of the present invention to protect against the growth of potentially harmful microorganisms. A traditional preservative suitable for the composition of the present invention is an alkyl ester of para-hydroxybenzoic acid. Other more preservatives that have been used more recently are hydantoin derivatives, propionates and various quaternary ammonium compounds. Cosmetic chemists are familiar with the appropriate preservatives and can select preservatives that pass the preservative challenge test and provide stability to the product without making any modifications.

  Particularly preferred preservatives are phenoxyethanol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate and benzyl alcohol. The preservative must be selected considering the use of the composition and the potential for incompatibility between the preservative and the other ingredients in the emulsion. Preservatives are preferably used in amounts ranging from 0.01 to 2% by weight of the composition.

The composition of the present invention may contain vitamins. Typical vitamins are vitamin A (retinol), vitamin B ₂ , vitamin B ₆ , vitamin C, vitamin E and biotin. Derivatives of vitamins may be used. For example, vitamin C derivatives include ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glycoside. Derivatives of vitamin E include tocopheryl acetate, tocopheryl palmitate and tocopheryl linoleate. DL-panthenol and its derivatives may also be used. When vitamins are present in the composition of the present invention, the total amount may range from 0.001 to 10% by weight, preferably from 0.01 to 1% by weight, optimally from 0.1 to 0.5% by weight. .

  Another class of useful substances are enzymes such as oxidases, proteases, lipases, and combinations thereof. Superoxide dismutase, commercially available as Biocell SOD from Brooks Company, USA is particularly preferred.

  The composition of the present invention may contain a skin lightening compound. Representative substances are placenta extract, lactic acid, niacinamide, arbutin, kojic acid, ferulic acid, resorcinol, and derivatives such as 4-substituted resorcinol and combinations thereof. The amount of these components may range from about 0.1 to about 10% by weight of the composition, preferably from about 0.5 to about 2%.

An exfoliation promoter may also be present. Representative are α-hydroxycarboxylic acid and β-hydroxycarboxylic acid. The term “acid” includes not only the free acids, but also their salts and their C ₁ -C ₃₀ alkyl or aryl esters and lactones. By removing water, a cyclic or linear lactone structure is formed to produce a lactone. Typical acids are glycolic acid, lactic acid and malic acid. Salicylic acid is representative of β-hydroxycarboxylic acid. When these materials are present, the amount can range from about 0.1 to about 15% by weight of the composition.

  Depending on the case, various plant extracts may be included in the composition of the present invention. Representatives are green tea, chamomile, licorice extracts and combinations thereof. The extract may be water-soluble or water-insoluble, and each is carried in a hydrophilic or hydrophobic solvent. Water and ethanol are preferred extraction solvents.

  Materials such as lipoic acid, retinoxytrimethylsilane (available from Clariant Corp. under the trademark Silcare 1M-75), dehydroepiandrosterone (DHEA), and combinations thereof may also be included. Ceramides (Ceramide 1, Ceramide 3, Ceramide 3B and Ceramide 6, etc.) and pseudoceramides that may be used in many compositions of the present invention may be excluded. The amount of these materials can range from about 0.000001 to about 10% by weight, preferably from about 0.0001 to about 1% by weight.

  Dyes, flavorings, opacifiers and abrasives can also be included in the compositions of the present invention. Each of these materials may range from about 0.05 to about 5% by weight, preferably 0.1 to 3% by weight.

  The meaning of the term “comprising” includes elements not specified but not limited to only those elements described thereafter, regardless of their functional significance. In other words, the steps, elements or options described need not be exhaustive. When the terms “including” or “having” are used, these terms are always meant to be equivalent to “including” as defined above.

  Understand that all numerical values in this specification indicating the amount of material are modified with the term “about” except in the Examples and Comparative Examples, or where otherwise expressly indicated. I want to be.

  The following examples more fully illustrate the embodiments of this invention. All parts, percentages and proportions set forth herein and in the claims are by weight unless otherwise indicated.

(Example 1)
A typical cosmetic cream of the present invention is shown in Table I below.

(Example 2)
A water-in-oil topical liquid makeup foundation using the malonate salt of the present invention is shown in Table II below.

(Example 3)
This example shows a skin cream containing the malonate salt of the present invention.

(Example 4)
Representative of the powdery cosmetic composition of the present invention is the formulation of Table IV.

(Example 5)
The relatively anhydrous compositions of the present invention are shown in Table V.

(Example 6)
An aerosol packaged foam cleanser suitable for the present invention is shown in Table VI.

  An aerosol is prepared using 92% by weight of the concentrate of Table VI and 8% propellant. The propellant is a combination of dimethyl ether, isobutane and propane.

(Example 7)
Also, an adhesive cosmetic patch may be formulated according to the present invention. An adhesive hydrogel is prepared by mixing 30 grams of 2-acrylamido-2-methylpropanesulfonic acid monomer with 5 grams of a 1% aqueous solution of methylene-bis-acrylamide in 20 grams of distilled water. The solution is then activated with 0.4% magnesium persulfate catalyst. Shortly after mixing the catalyst into the hydrogel solution, 0.1 grams of ammonium malonate in 5 ml of water is added. The resulting solution is coated onto a 50/50 blend of polypropylene and hydrophilic polyester and allowed to solidify. The resulting adhered hydrogel is placed in a hot air oven and heated at 40 ° C. for 24 hours. The final water content of the hydrogel is 50%. A polystyrene back layer is applied over the adhesive hydrogel.

(Example 8)
A disposable single-use body wipe product according to the present invention is described. A non-woven wipe sheet of 70/30 polyester / rayon is produced with a weight of 1.8 g and dimensions of 15 cm × 20 cm. This wipe sheet is impregnated with the composition shown in Table VII below.

Example 9
Various carboxylates were evaluated for their response in the pig skin test. The Perkin-Elmer thermomechanical analyzer Model TMS-1 was used to operate the apparatus with a 20 gram load placed in the center of a 1 cm diameter disc shaped pig skin. Skin curvature was recorded directly in mm. Sample size was 6 skin pieces per treatment. Water was used as a control. Measurements were taken before drying and 24 hours after the first, second and third treatment. For each treatment, 150 μl of the test material solution was applied to the skin and maintained for 5 minutes and then removed without rinsing. Drying conditions were 21 ° C. and humidity of less than 10%. The results are recorded in Table VIII below.

  From these results it is clear that the malonate salt significantly increased skin flexibility. In contrast, succinate and glycolate salts significantly enhanced skin stiffness. The effects of glycolate and succinate were statistically similar. These results indicate that malonate salts and compositions containing these salts can improve smoothness, softness and flexibility.

  Table IX records the deflection values measured for cosmetic cream formulations having the composition detailed in Table I (using various active ingredients in Phase D). The deflection value of the cream containing the malonate salt was higher than that of either the base cream or the cream containing the glycolate salt. This result indicates that the use of malonate resulted in a smoother, softer and more flexible skin.

  The above description and examples illustrate selected embodiments of the present invention. While variations and modifications based on these will be suggested to those skilled in the art, all such variations and modifications are encompassed within the spirit and scope of the present invention.

Claims (8)

(I) about 0.0001 to about 30% by weight of a salt of malonic acid;
(Ii) about 1 to about 99.9% by weight of a cosmetically acceptable carrier;
A cosmetic composition comprising a cosmetic composition, wherein the composition exhibits a deflection value greater than 1 in a pig skin test.   The composition of claim 1, wherein the malonic acid is present as a semi-neutralized acid and a total neutralized acid in a molar ratio ranging from about 1000: 1 to about 1: 1000, respectively.   The composition of claim 2, wherein the molar ratio ranges from about 2: 1 to about 1: 200.   The salt of claim 1 having a cationic counterion for malonate, wherein the counterion is an inorganic cation selected from lithium, sodium, potassium, magnesium, calcium, ammonium, and combinations thereof. The composition according to any one of the above.   The cationic counter ion for the malonate is polyethyleneimine, triethanolamine, diethanolamine, propanolamine, monoethanolamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, isopropanol. Pentylamine, hexylamine, cyclohexylamine, cyclopentylamine, norbornylamine, octylamine, ethylhexylamine, nonylamine, decylamine, pyrrolidone, amino acids (lysine, arginine, alanine, glutamine, histidine, glycine), 2-amino-2- Consists of methyl-1-propanol, dimethylethanolamine, tris (hydroxymethyl) aminomethane and combinations thereof A composition according to claim 1, any one of 2 to 4 selected from the loop is an organic cation having a 1,000 carbon atoms.   A cosmetic sticking or wiping product comprising the cosmetic composition according to any one of claims 1 to 5. (I) about 0.0001 to about 30% by weight of a salt of malonic acid;
(Ii) about 1 to about 99.9% by weight of a cosmetically acceptable carrier;
Providing a cosmetic composition comprising: a cosmetic composition wherein the composition exhibits a deflection value greater than 1 in a pig skin test;
Applying the cosmetic composition to the skin;
A method of suppressing signs of aging including:   7. The method of claim 6, wherein the signs of aging to be suppressed are smoothness, softness and flexibility.