WO1995005159A1 - Hydroxyalcanoates acyles et leurs utilisations - Google Patents

Hydroxyalcanoates acyles et leurs utilisations Download PDF

Info

Publication number
WO1995005159A1
WO1995005159A1 PCT/EP1994/002666 EP9402666W WO9505159A1 WO 1995005159 A1 WO1995005159 A1 WO 1995005159A1 EP 9402666 W EP9402666 W EP 9402666W WO 9505159 A1 WO9505159 A1 WO 9505159A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
skin
derivative
composition according
hydroxyalkanoate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1994/002666
Other languages
English (en)
Inventor
Paul Anthony Bowser
Ailsa Pauline Hilary Grieverson
Desmond Bernard Hagan
Ian Richard Scott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever NV
Original Assignee
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB939316847A external-priority patent/GB9316847D0/en
Priority claimed from GB939316924A external-priority patent/GB9316924D0/en
Priority claimed from GB939316935A external-priority patent/GB9316935D0/en
Application filed by Unilever NV filed Critical Unilever NV
Priority to AU76122/94A priority Critical patent/AU7612294A/en
Publication of WO1995005159A1 publication Critical patent/WO1995005159A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/002—Aftershave preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/007—Preparations for dry skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations

Definitions

  • the invention relates to the topical use of hydroxy alkanoate derivatives for improving the condition of human skin, particularly for moisturising the skin, hair, nails and other epithelial tissues, including the mucosae, also for reducing skin drying and for delaying the appearance of or eliminating wrinkles and fine lines on the skin.
  • the invention also relates to a method for the delivery to the epidermis of a hydroxyalkanoate for moisturising the skin, hair and nail and to compositions for topical use to achieve this benefit.
  • Human skin consists essentially of two layers: the inner dermis and the outer epidermis, the former functioning mainly as a mechanical support for the latter.
  • the epidermis which can be as little as 0.06 mm thick in the case of the eye lid to as much as 0.8 mm on the foot, itself comprises four or five layers, namely:
  • the Stratum Spinosum the prickle cell layer which represents the first morphologically distinct stage in the differentiation of epidermal cells. It consists of numerous evenly spaced intercellular bridges - tonofilaments - each with a central thickening. The margins of several of these thickenings accounts for the appearance of desmosomes . The tonofilaments form the earliest precursor of keratin.
  • the Stratum Granulosum the granular layer immediately above the prickle cell layer, which contains basophilic granules of keratohyalin. Also present in the Stratum Granulosum are the bridges (desmosomes and tono filaments seen in the prickle cell layers) , but their close apposition renders them less visible.
  • the Stratum Lucidum seen especially in the epidermis of the hand and foot, comprises cells which are of even thickness and essentially non-nuclear.
  • the Stratum Corneum which lies above the Stratum Lucidum (when present) , forms the outermost layer of the epidermis.
  • the Stratum Corneum is composed of dead, flat, fully keratinized cells which lie on top of one another to a depth of from 0.02 to 0.8 mm.
  • the Stratum corneum also possesses lipid materials which effectively form a waterproof barrier to the external surface of the skin.
  • Beneath the epidermis is the dermis which is composed of collagen, usually accompanied by elastin and reticulin. These materials are fibrous proteins embedded in a mucopolysaccharide ground substance.
  • Several cellular types, together with nervous and vascular networks, are found in the dermis, together with specialised appendages, including sweat glands, hair follicles with associated sebaceous glands.
  • a soft, supple and flexible skin has a marked cosmetic appeal and these characteristics are attributes of normal functioning epidermis, particularly with respect to the young human subject.
  • the outer layer of the epidermis i.e. the stratum corneum, can however become dry and flaky following exposure to adverse climatic conditions, or by excessive contact with detergents or solvents which results in a loss of skin moisture. Consequently, the skin can lose its soft, supple and flexible characteristics.
  • Emollients such as fats, phospholipids and stearols, have in the past been used to soften dry skin, but this can leave the skin greasy and unattractive.
  • topical application to the skin of classical humectants does not alleviate this problem, as these compounds are not particularly skin substantive and are generally rinsed from the skin during washing.
  • sodium stearoyl lactylate may be used in oil-in-water cosmetic creams as the emulsifier to impart body, lubricity and opalescence to the cream. It is alleged that its absorption to the skin may enhance its softening action.
  • PCA PCA sodium.salt, sodium lactate and lactic acid can be used as effective humectants to hold moisture in the skin.
  • EP 0 530 866 (Unilever) concerns novel sulfoxy alkanoate surfactants which it is believed are broken down by enzymes naturally present in the skin, or are naturally hydrolysed upon contact with the skin to yield "Benefit Reagents” e.g. Hydroxy acid and/or Fatty Alcohol.
  • EP 0 442 708 discloses cosmetic compositions containing 2-hydroxy alkanoic acids. Due to the presence of these acids in compositions, several benefits are imparted to the skin, such .as an increase in the elasticity of the skin, particularly of the stratum corneum. Similarly, EP 0 007 785 (Unilever) discloses cosmetic compositions comprising 2-hydroxy alkanoic acids, which also give various skin benefits when topically applied to the skin.
  • cream or lotion formulations containing lactic acid when applied topically to the skin, can improve the flexibility and texture of the skin, and it is believed that lactate contributed to this effect.
  • lactate contributed to this effect.
  • the invention is accordingly concerned with the generation in situ in the epidermis of hydroxy alkanoic acids and the topical use of their corresponding acyl or alkyl derivatives to achieve this end.
  • one aspect of the invention provides the use of an effective amount of at least 0.001% by weight based on the total composition of a hydroxy alkanoate derivative having the structure (1) :
  • R 1 [O-CH C] m OR 3 (1) 0 where R x represents H- or C j . .O j . ⁇ -C-
  • R 3 represents H- , C x H y O z N w - or a metallic, ammonium or alkanolammonium, counterion, p is an integer from 2 to 22, q is an integer from 5 to 45, x is an integer of from 1 to 20, y is an integer of from 3 to 41, z is O, or an integer of from 1 to 10, w is O, or an integer of from 1 to 5, and m is an integer of from 1 to 5 provided that when R 1 is H- , then R 3 is C x H y O z N w - , or when
  • R ⁇ is H- or a countenon, then R is C X H 0 2 N w C-
  • compositions intended for topical application to human skin; said compositions otherwise comprising a cosmetically acceptable vehicle.
  • the invention also provides a method for delivering to the epidermis a 2-hydroxy alkanoate having the structure (2) :
  • composition comprising the corresponding hydroxy alkanoaate derivative having the structure (1) :
  • composition in contact with the skin for at least 10 seconds to permit the hydroxy alkanoate derivative to penetrate through the stratum corneum to reach the lower strata of the epidermis, and
  • composition suitable for topical application to the skin, hair, nails, mucosae and other epithelial tissue, which composition comprises:
  • hydroxyalkanoate derivative possessing the ability of penetrating the stratum corneum and hydrolysing by enzymic cleavage within the epidermis to yield the corresponding hydroxyalkanoate having the structure (2) :
  • R 1 is an acyl group of the above mentioned general formulae O O
  • the value of x is preferably at least 5 A value of at least 9, for instance 9 to 13, is more preferred.
  • C p H q - represents an alkyl group, especially a straight chain alkyl group.
  • the value of q must of course be 2p+l.
  • C p H is alkenyl, such as straight chain alkenyl .
  • the vehicle includes water.
  • Certain preferred compositions include water-immiscible oil and/or water-soluble organic solvent such as ethanol.
  • the amount of oil does not usually exceed 50% by weight of the composition, neither does the amount of water-soluble solvent, although in total these non-water materials may provide more than 50% by weight of the composition.
  • the invention may be applied in the context of a composition which is applied to skin, especially the face, and either left there or at least not removed immediately.
  • compositions frequently include some oil or oily material or organic solvent which is water soluble.
  • topical application of the hydroxyalkanoate derivatives can also improve the skin surface in other respects by eliminating or by preventing the development of, or at least slowing, skin surfaces changes.
  • changes include, fine lines, wrinkles, blemishes, blotches, nodules, atrophy, pigmented spots, lesions, elastoic changes characterised by leathery, coarse, rough, dry and yellowish skin, photo-damages skin, loss of elasticity and other changes associated with ageing.
  • the hydroxyalkanoate derivatives can also have marked antiaging benefits to the skin.
  • the topical application of the hydroxyalkanoate derivatives can also be used for the treatment of spots, pimples and acne, especially for the inhibition of Propionibacterium acnes, which is believed to be a causative organism in the development of acne comedones.
  • Topical application of the hydroxyalkanoate derivatives can also be used in the treatment of dandruff on the scalp, again in view of the ability of these derivatives to inhibit microorganisms implicated in the development of dandruff.
  • Hydroxy alkanoate derivatives for use in accordance with the invention are chosen from those having the structure (1) as herein defined, and are generally acyl or alkyl derivatives. Acyl derivatives are particularly preferred.
  • acyl derivatives of hydroxy alkanoates include:
  • R 1 in structure (1) represents the acyl group: O
  • R 3 represents -H, or an alkali metal, an alkaline earth metal, ammonium or an alkanolammonium counterion. Specific examples are the sodium, potassium, calcium, ammonium or triethanolammonium salts or free acids of :
  • n-propionyl derivative of 2-hydroxyoctanoate i.e. 2- (n-propionyloxy) octanoate
  • R 1 in Structure (1) represents the acyl group:
  • C p H g represents an alkyl group in the series CH 3 CH 2 - to CH 3 (CH 2 ) 19 -
  • C x H y represents a branched chain alkyl group m is 1 to 5, and
  • R represents -H, an alkali metal, an alkaline earth metal, ammonium or an alkanolammonium counterion.
  • R 1 in structure (1) represents the acyl group:
  • C p H represents an alkyl group in the series CH 3 CH 2 - to CH 3 ( CH 2 ) 19 - m is 1 to 5
  • R 3 represents -H, or an alkali metal, an alkaline earth metal, ammonium or alkanolammonium counterion.
  • R 1 is an acyl group
  • References includes US-A-4058540, preparations given in EP-A-54435 and Taylor et al, Tetrahedron letters £0 . 5285 (19) .
  • a route for the preparation of such compounds comprises: i) forming an acyl chloride by reacting an alkanoic acid with oxalyl chloride, thus:
  • R 1 in structure (1) represents -H
  • R 3 represents C X H -
  • m is 1.
  • the 2-hydroxyalkanoic acids are well known compounds. Their alkyl esters can be made by conventional esterification techniques.
  • the amount of hydroxyalkanoate derivative to be employed in accordance with the invention as an effective amount will normally be from 0.001 to 50%, preferably at least 0.1%, e.g. from 0.1 to 30%, and most preferably at least 0.5%, e.g. from 0.5 to 20% by weight of the composition.
  • composition for use in accordance with the invention can either be employed as a "leave-on” product, in which case it is intended to be applied to the skin and left in place, or it can be employed as a "rinse- off” or “wipe-off” product, usually for cleansing the skin, in which case it will normally be rinsed or wiped from the skin shortly after application, e.g., after washing.
  • the most preferred amount of hydroxyalkanoate derivative will be from 0.1 to 2%, whereas, for “rinse-off” or “wipe-off” products, the corresponding preferred amount will be from 0.1 to 20% or more, in both instances expressed in terms of percentage by weight of the composition.
  • a significant form of this invention is therefore a cleansing composition containing from 5 to 40% by weight of an acyl derivative of a hydroxyalkanoate, having the above structure (1) in which R 3 represents -H or a metallic, ammonium or alkanolammonium counterion, while R 1
  • O 0 represents C y iyO ⁇ -C- , preferably C X H C- .
  • Such a cleansing composition generally also contains water.
  • the invention provides a method for cleaning the skin or the hair which comprises the steps of (i) applying to the skin or hair cleansing composition as specified above;
  • hydroxyalkanoate derivatives as herein described, will in use normally be applied to human skin in the form of a composition that also comprises a cosmetically acceptable vehicle, that is intended to facilitate the distribution of the hydroxyalkanoate derivative on and over the skin surface at an appropriate concentration.
  • composition can thus be solid, semi-solid or liquid in nature, dependent upon the choice of vehicle.
  • vehicle itself can be inert or it can possess beneficial physiological properties of its own.
  • a vehicle for this purpose presents a wide range of possibilities depending on the required product form of the composition. Suitable vehicles can be classified as described hereinafter.
  • Vehicles are therefore substances that can act as diluents, dispersants, or solvents for the hydroxy alkanoate derivative which ensures that it can be applied to and distributed evenly over the skin at an appropriate concentration.
  • the vehicle is preferably one which can aid penetration of the hydroxy alkanoate derivative deep into the epidermis, to enable it more readily to influence the condition of the skin.
  • compositions according to the invention can include water as a vehicle, and/or at least one cosmetically acceptable vehicle other than water.
  • Vehicles other than water can include liquid or solid emollients, solvents, humectants, thickeners and powders. Examples of each of these types of vehicle, which can be used singly or as mixtures of one or more vehicles, are as follows:
  • Emollients such as stearyl alcohol, glyceryl monoricinoleate, mink oil, cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, di-n-butyl sebacate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, butyl stearate, polyethylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil, cotton seed oil, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, evening primrose oil, soybean oil,
  • Propellants for aerosols such as propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide;
  • Solvents such as ethyl alcohol, methylene chloride, isopropanol, acetone, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran;
  • Powders such as chalk, talc, fullers earth, kaolin, starch, gums, colloidal silica sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminium silicate, organically modified montmorillonite clay, hydrated aluminium silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethyl cellulose, ethylene glycol monostearate, ethylene glycol distearate;
  • the cosmetically acceptable vehicle will usually form from 10 to 99.99%, preferably from 10 to 99% and most preferably from 50 to 99% by weight of the composition, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
  • composition for use according to the invention can also optionally comprise a penetration enhancer which can potentiate the benefit of the hydroxy alkanoate derivative by improving its delivery through the stratum corneum to its site of action deep in the epidermis.
  • a penetration enhancer which can potentiate the benefit of the hydroxy alkanoate derivative by improving its delivery through the stratum corneum to its site of action deep in the epidermis.
  • the penetration enhancer can accordingly function in a variety of ways. It can for example, improve the distribution of the hydroxy alkanoate derivative on the skin surface, or it can increase its partition into the stratum corneum and beyond from the composition when applied topically, so aiding its passage to a lower level within the epidermis. Other mechanisms enhancing the benefit of the hydroxy alkanoate derivative may also be involved.
  • penetration enhancers examples include
  • the amount of penetration enhancer when employed in accordance with the invention, will normally be from 0.1 to 50%, preferably from 0.5 to 25% and most preferably from 0.5 to 10% by weight of the composition.
  • composition according to the invention can optionally comprise one or more oils or other materials having the properties of an oil.
  • a composition in accordance with the invention may be formulated as an emulsion having both aqueous and oil phases. This applies particularly to leave-on products which are frequently formulated as emulsions.
  • an oil or oily material will normally be present, together with an emulsifier to provide either a water-in-oil emulsion or an oil-in-water emulsion, depending largely on the average hydrophilic-lipophilic balance (HLB) of the emulsifier employed.
  • HLB hydrophilic-lipophilic balance
  • suitable oils include mineral oils and vegetable oils, silicone oils and oily materials such as those already proposed herein as emollients.
  • the quantity of oil, if present, is often at least 5% by weight, often remains a minority of the composition, in other words 5 to 50% by weight. Preferred are at least 10% and/or not more than 30% by weight.
  • the oil or oily material when present for the purposes for forming an emulsion, may form up to 90%, e.g. preferably from 10 to 80% by volume of the composition.
  • composition according to the invention can also optionally comprise one or more emulsifiers the choice of which will normally determine whether a water-in-oil or and oil-in-water emulsion is formed.
  • emulsifiers the choice of which will normally determine whether a water-in-oil or and oil-in-water emulsion is formed.
  • Duplex emulsions ie water-in-oil-in-water or oil-in-water-in-oil, can also be formed.
  • the chosen emulsifier or emulsifiers should normally have an average HLB value of from 1 to 6. "When an oil-in-water emulsion is required, a chosen emulsifier or emulsifiers should have an average HLB value of >6.
  • Suitable emulsifiers are set below in Table 1 in which the chemical name of the emulsifiers is given together with an example of a trade name as commercially available, and the average HLB value.
  • Sorbitan trioleate Arlacel 85 1.8 Sorbitan tristearate Span 65 2.1 Glycerol monooleate Aldo MD 2.7
  • Glycerol monostearate Atmul 84S 2.8 Glycerol monolaurate Aldo MC 3.3 Sorbitan sesquioleate Sorbitan monooleate Sorbitan monostearate Cetyl dimethicone copolyol Poloxyethylene (2) stearyl ether Poloxyethylene sorbitol beeswax derivative PEG 200 dilaurate Sorbitan monopalmitate Polyoxyethylene (3.5) nonyl phenol PEG 200 monostearate
  • the amount of emulsifier or mixtures thereof, to be incorporated in the composition of the invention, when appropriate is from 1 to 50%, preferably from 2 to 20% and most preferably from 2 to 10% by weight of the composition.
  • composition for use according to the invention optionally can also comprise a retinoid, such as retinoic acid or retinol (Vitamin A) and/or derivative thereof, further to enhance the benefits to skin.
  • a retinoid such as retinoic acid or retinol (Vitamin A) and/or derivative thereof, further to enhance the benefits to skin.
  • examples of derivatives of retinol include:
  • the amount of retinoid, when present in the composition according to the invention is from 0.01 to 10% and preferably 0.1 to 5% by weight of the composition.
  • the composition for use according to the invention optionally can also comprise a tocopherol (vitamin E group) , as an antioxidant for the composition, and to limit oxidative damage to skin.
  • the vitamin E group comprises ⁇ .-tocopherol, j ⁇ -tocopherol, ⁇ -tocopherol and ⁇ - tocopherol.
  • the composition according to the invention optionally can also comprise a tocopheryl ester, such as tocopheryl acetate.
  • the amount of a tocopherol, or ester thereof, when present in the composition according to the invention is from
  • composition 0.0001 to 20%, preferably from 0.0001 to 10% by weight of the composition.
  • composition of the invention can also comprise water, usually up to 90%, preferably from 5 to 80% by volume. Water can function as the cosmetically acceptable vehicle.
  • the vehicle contains water, or aqueous ethanol, in an amount which is a majority of the composition, that is to say over 50%. If ethanol is present, the amount will generally remain a minority of the composition, such as from 10 to 50%. Even when ethanol is included, the quantity of water will generally be substantial, amounting to a majority of the composition or nearly so, such as at least 40% of the composition.
  • a composition for use in accordance with the invention may contain one or more surfactants notably at least 1% thereof, in addition to the hydroxy alkanoate derivatives, which are cosmetically acceptable and suitable for topical application to the skin. This applies particularly when the composition is a cleansing composition containing an acyl derivative of hydroxyalkanoate as surfactant.
  • Such compositions may contain a co-surfactant, for example in an amount up to 30% by weight of the composition, preferably from 5% or 10% to 25% or 20% by weight.
  • a co-surfactant may assist in providing a good lather when the composition is used. Examples of possible skin cleansing surfactants are now given.
  • composition of the invention can comprise soap or a non-soap anionic surfactant which is preferably chosen from alkyl sulphate, alkyl ether sulphate, alkyl sulphonate, alkyl aryl sulphonate, olefin sulphonate, acyl sarcosinate, acyl tauride, acyl isethionate, nonoalkyl sulphosuccinate, dialkylsulphosuccinate, N-acylated a- amino acid, alkyl carboxylate, monoalkyl phosphate and dialkyl phosphate.
  • a non-soap anionic surfactant which is preferably chosen from alkyl sulphate, alkyl ether sulphate, alkyl sulphonate, alkyl aryl sulphonate, olefin sulphonate, acyl sarcosinate, acyl tauride, acyl isethionat
  • anionic surfactants include:
  • alkyl sulphates such as sodium lauryl sulphate [eg. EMPICOL CX available from Albright & Wilson] , and triethanolaminde lauryl sulphate [e.g. EMPICOL TL40/T, available from Albright & Wilson] .
  • alkylether sulphates such as sodium lauryl ether sulphate [eg. EMPICOL ESB70, available from Albright & Wilson] .
  • alkyl sulphonates such as sodium alkane (C 13 _ 18 ) sulphonate [eg. HOSTAPUR SAS 30, available from Hoechst]
  • alkylaryl sulphonates such as sodium alkyl benzene sulphonate [eg. TEEPOL CM44, available from Shell] .
  • olefin sulphonates such as sodium olefin sulphonate (C 5 _ 18 ) [eg. HOSTAPUR OS, available from Hoechst] .
  • R 3 is chosen from C 6 _ 14 alkyl
  • M is a counterion chosen from alkali metals, ammonium and substituted ammonium such as alkanolammonium.
  • acyl sarcosinate having the structure (51) is sodium lauryl sarcosinate [eg. HAMPOSYL L-95, available from Grace] .
  • acyl taurides having the structure (52) :
  • R 4 is chosen from C 8 _ 18 alkyl
  • acyl tauride having the structure (52) is coconut methyl taurine [eg. FENOPEN TC 42, available from International Spaicalty Products] .
  • acyl isethionates having the structure (53 ) :
  • R 5 is chosen from C 8 _ 18 alkyl.
  • acyl isethionate having the structure (53) is sodium acyl isethionate [eg. JORDAPON Cl, available from Jordon] .
  • R >6 is chosen from C 10 _ 20 alkyl.
  • Examples of monoalkyl sulphosuccinates having the structure (54) include:
  • sodium lauryl sulphosuccinate eg. EMPICOL SLL, available from Albright & Wilson
  • magnesium alkyl sulphosuccinate eg. ELFANOL 616 Mg, available from AKZO.
  • sodium lauryl ethoxysulphosuccinate eg. EMPICOL SDD, available from Albright & Wilson
  • EMPICOL SDD sodium lauryl ethoxysulphosuccinate
  • coconut monoethanolamide ethoxysulphosuccinate eg. EMPICOL SGG
  • disodium lauryl polyglvcolether sulphosuccinate eg. SURTAGENE S30, available from CHEM-Y
  • polvethyleneglycol sulphosuccinate eg. REWOPOL SBFA 30, available from REWO] .
  • dialkyl sulphosuccinates having the structure (55) :
  • R 7 and R 8 are the same or different, and are chosen from C 6 _ 14 alkyl.
  • dialkyl sulphosuccinate having the structure (55) is sodium dilauryl sulphosuccinate [eg. EMCOL 4500, available from Witco] .
  • R 9 is chosen from C 6 _ 16 alkyl
  • n 1 or 2.
  • acyl lactylate having the structure (56) is decanoyl lactylate [eg. PATIONIC 122a, available from Patterson, CJ] .
  • N-acylated o.-amino acids such as sodium lauroyl glutamate [eg. ACYLGLUTAMATE LS-11, available from Ajinomoto Co. Inc] .
  • alkyl ether carboxylates such as C 12 . 14 0 (EO) 4 OCH 2 C0 2 Na [eg . AKYPO RLM 38 , available from Akzo] monoalkyl phosphates and dialkyl phosphates, such as dioctyl phosphate.
  • composition of the invention can also comprise a cationic surfactant.
  • Suitable cationic surfactants are those with the structure (57) :
  • R 1 , R 2 , R 3 and R 4 each represents alkyl or aryl groups, and X represents al halogen counterion.
  • Preferred cationic surfactants in accordance with structure (57) include:
  • Hexadecyl trimethyl ammonium chloride such as Arquad 16, available from Akzo.
  • Dihydrogenated tallow dimethyl ammonium chloride such as Arquad 2HT, available from Akzo.
  • Dodecyl benzyl dimethyl ammonium bromide such as Amoxyl BR 1244, available from Seppic.
  • Cocoamidopropyl trimethyl ammonium chloride such as Empigen CSC, available from Albright & Wilson.
  • Amphoteric surfactant
  • composition of the invention can also comprise an amphoteric surfactant .
  • Suitable amphoteric surfactants are derivatives of aliphatic quaternary ammonium, phosphonium arid sulphonium compounds, wherein the aliphatic radicals contain from 8 to 18 carbon atoms, and may be straight chain or branched, and further contain an anionic water-solubilising group, such as carboxyl, sulphonate, sulphate, phosphate or phosphonate.
  • Preferred amphoteric surfactants include:
  • Alkyl betaines having the structure (58) :
  • R 1 is C ⁇ - ⁇ alkyl
  • alkyl betaine having the structure (58) is lauryldimethyl betaine [eg. EMPIGEN BB, available from Albright & Wilson] .
  • Alkylamidopropyl betaines having the structure (59) :
  • alkylamidopropyl betaine having the structure (59) is cocamidopropy betaine [eg. TEGOBETAIN L7, available from Goldschmidt) .
  • Alkylamphoglvcinates or Alkylamphopropjonates having the structure (60)
  • R 11 is chosen from H, CH 2 COO " and (CH 2 ) 2 COO ⁇
  • R 111 is chosen from CH 2 COO " and (CH 2 ) 2 COO ⁇
  • Suitable examples of compounds (60) are cocoamphoglycinate (available from GAF) , and cocoamphopropionate.
  • Sultaines having the structure (61) : .
  • R 2 is chosen from C 12 _ 16 alkyl alkylamido groups.
  • sultaine having the structure (61) is cocamidopropylhydroxysultaine [eg. CYCLOTERIC BET-CS, available from Alcolac) .
  • amphoteric surfactant are lauryl dimethyl betaine and cocamidopropyl betaine.
  • amphoteric surfactants can contribute to the foaming of the skin cleansing composition, while ameliorating the harshness of the anionic surfactant.
  • composition of the invention can also comprise alkoxylated or glycosidic nonionic surfactant having an HLB of 8 or more. Above this value nonionics generally form clear isotropic solutions in combination with the other surfactants in the ranges defined above.
  • Preferred nonionic surfactants are polyoxyethylene alkyl esters and polyoxyethylene alkyl ethers and alkyl polyglycosides .
  • a suitable example of a polyoxyethylene alkyl ester is that having the CTFA designation Polysorbate 80 which is a mixture of oleate esters of sorbitol and sorbitol anhydrides, condensed with approximately 20 moles of ethylene oxide. Also suitable is Polysorbate 20 which is a mixture of laurate esters or sorbitol and sorbitol anhydrides condensed with approximately 20 moles of ethylene oxide.
  • Polysorbate 80 and Polysorbate 20 are available commercially as TWEEN 80 and TWEEN 20 respectively, from ICI Americas.
  • compositions of the invention are also suitable for use in the compositions of the invention.
  • polyethylene glycol ether of C 9 _ 1]L alcohol with an average of 8 ethoxy units which is available commercially as NONIDET LE-8T or as SYNPERONIC 91-8T
  • polyethylene glycol ether of C 12 _ 15 alcohol with an average of 9 ethoxy units which is available commercially as DOBANOL 25-9.
  • alkyl polyglycosides include the glycosides of glucose or glucose oligomers where the alkyl chain can be C 8 . 16 and the average number of glucose units is 1 to 2.
  • a suitable example is ORAMIX NS 10 which is the glucoside of C 10 _ 12 fatty alcohol with an average of about 1.5 glucose units.
  • high molecular weight silicone surfactants such as a high molecular weight polymer of dimethyl polysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight from 10,000 to 50,000.
  • the dimethyl polysiloxane polymer is conveniently provided as a dispersion in a volatile siloxane, the dispersion comprising, for example, from 1 to 20% by volume of the polymer and from 80 to 99% by volume of the volatile siloxane.
  • the dispersion consists of a 10% by volume of the polymer dispersed in the volatile siloxane.
  • Examples of the volatile siloxanes in which the polysiloxane polymer can be dispersed include polydimethyl siloxane (pentamer and/or hexamer) .
  • a particularly preferred silicone surfactant is cyclomethicone and dimethicone copolyol, such as DC 3225C Formulation Aid available from DOW CORNING.
  • Another is laurylmethicone copolyol, such as DC Q2-5200, also available from Dow Corning.-
  • the amount of silicone surfactant, when present in the composition will normally be up to 25%, preferably from 0.5 to 15% by weight of the emulsion.
  • Examples of other cosmetic adjuncts which can optionally be employed in the composition for use according to the invention include preservatives, such as para-hydroxy benzoate esters; antioxidants, such as butyl hydroxy toluene; humectants, such as glycerol, sorbitol, 2- pyrrolidone-5-carboxylate, dibutylphthalate, gelatin, polyethylene, glycol, preferably PEG 200-600; buffers, such as lactic acid together with a base such as triethanolamine or sodium hydroxide; ceramides of synthetic, animal or plant origin; pseudoceramides; phospholipids; vitamins, such as 1,25 dihydroxy cholecalciferol; waxes, such as beeswax, ozokerite wax, paraffin wax, plant extracts, such as Aloe vera, cornflower, witch hazel, elderflower, cucumber, thickeners; activity enhancers; colourants; perfumes; and sunscreen materials such as ultrafine titanium dioxide and organic sunscreens such as p
  • the hydroxy alklanoate derivative is combined with ceramides, pseudoceramides, polyol fatty acid polyesters, sterols, particularly cholesterol, galactosyldiacyl-glycerols, glycosphingolipids, fatty acids and esters thereof and mixtures thereof and other ingredients, such as mevalonic acid, hexadecylsuccinic acid monobehenyl ester ethoxylate (7.3 EO) and/or derivatives thereof to produce a liposomal dispersion.
  • ceramides pseudoceramides
  • polyol fatty acid polyesters particularly cholesterol, galactosyldiacyl-glycerols, glycosphingolipids, fatty acids and esters thereof and mixtures thereof and other ingredients, such as mevalonic acid, hexadecylsuccinic acid monobehenyl ester ethoxylate (7.3 EO) and/or derivatives thereof to produce a liposomal dispersion.
  • a further preferred composition may also contain in combination with the hydroxy alkanoate derivative and optional additional ingredients disclosed above, an organic acid component chosen from hydroxy alkanoic acids, such as alpha, beta and omega hydroxyacids, especially glycolic acid, lactic acid, citric acid, tartaric acid, tartronic acid and 2-hydroxyoctanoic acid, and keto alkanoic acids, esters thereof and mixtures thereof.
  • hydroxy alkanoic acids such as alpha, beta and omega hydroxyacids, especially glycolic acid, lactic acid, citric acid, tartaric acid, tartronic acid and 2-hydroxyoctanoic acid, and keto alkanoic acids, esters thereof and mixtures thereof.
  • Cosmetic adjuncts can form the balance of the composition
  • composition of the invention will normally have a pH value of from 4 to 9, preferably from 4.5 to 8.5.
  • the pH can be adjusted as necessary by the addition of an alkali or acid as a pH adjustant, and/or by the addition of a buffer, such as a citrate buffer or a phosphate buffer.
  • composition for use in accordance with the invention is preferably preserved against microbial attack in such a manner that it will enjoy an extended shelf life following manufacture and prior to sale and use. Ideally the composition will have an indefinite shelf life.
  • composition according to the invention can be preserved by sterilisation to remove or kill substantially all viable microbial contaminants. This can be achieved for example by irradiation using a lethal dose of gamma rays, by heat sterilisation or by ultrafiltration using techniques that are well established in the pharmaceutical industry.
  • composition according to the invention can also be preserved by including in it a chemical preservative which functions to prevent the growth of or kill bacteria, fungi or other microorganisms .
  • chemical preservatives include ethanol, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, sodium propionate and the methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid.
  • the amount of chemical preservative that can be incorporated in the composition according to the invention will generally be from 0.05 to 5%, preferably from 0.1 to 2% by weight, the amount chosen being sufficient to arrest microbial proliferation.
  • composition according to the invention can also be preserved by the inclusion of a water activity depressant such as glycerol, propylene glycol, sorbitol, sugars and salts, for examples alkali metal halides sulphates and carboxylates .
  • a water activity depressant such as glycerol, propylene glycol, sorbitol, sugars and salts, for examples alkali metal halides sulphates and carboxylates .
  • a water activity depressant sufficient should be incorporated in the composition according to the invention to reduce the water activity ( ⁇ . w ) from 1 to ⁇ 0.9, preferably to ⁇ 0.85 and most preferably ⁇ 0.8, the lowest of these values being that at which yeasts, moulds and fungi will not proliferate.
  • the invention also provides a process for preparing a composition according to the invention which comprises the steps of mixing an effective amount of an hydroxy alkanoate derivative, as herein defined, together with a cosmetically acceptable carrier for the derivative.
  • composition of the invention can be formulated as liquids, for example as a lotion, shampoo, milk or cream for use in conjunction with an a'pplicator such as roll- ball applicator, or a spray device such as an aerosol can containing propellant, or a container fitted with a pump to disperse the liquid product.
  • a'pplicator such as roll- ball applicator
  • a spray device such as an aerosol can containing propellant
  • a container fitted with a pump to disperse the liquid product Alternatively, the compositions of the invention can be solid or semi-solid, for example sticks, creams or gels, for use in conjunction with a suitable applicator or simply a tube, bottle or lidded jar, or as a liquid-impregnated fabric such as a tissue wipe.
  • the invention accordingly also provides a closed container containing a composition as herein defined. USE OF THE COMPOSITION
  • acyl (and/or alkyl) derivatives of hydroxyalkanoate when applied to the stratum corneum, will penetrate into the epidermis or cutaneous appendages, such as eccrine, apocrine and sebaceous glands, where hydrolysis by endogenous skin or microbial esterases will cleave the molecule to release in situ the corresponding hydroxy alkanoate, together with the fatty acid or fatty alcohol that forms the residue of the applied hydroxy alkanoate derivative.
  • the composition as applied to the skin surface can either be a "leave-on” product or a “rinse- off” or “wipe-off” product.
  • a leave-on product such as a cream or lotion
  • it can be applied to the skin from a ' suitable container and spread over a desired area of skin, such as the face and neck, shoulders, arms and legs, and then rubbed in using the hands and fingers, or using an applicator.
  • the hydroxyalkanoate derivative being lipophilic in nature, will penetrate into and through the stratum corneum, by virtue of the lipid materials that normally reside in that region close to the skin surface.
  • esterases are encountered that hydrolyse the hydroxy alkanoate derivative to release the desired hydroxyalkanoate.
  • composition for use in accordance with the invention is a "rinse-off" product
  • it will generally function as a skin cleanser.
  • a suitable amount for example 5 to 10 ml of the skin cleanser comprising the hydroxy alkanoate derivative, which can itself have surfactant properties, but is preferably accompanied by a co-surfactant, is applied to the skin and formed into a lather in the presence of water.
  • surplus product is generally rinsed from the skin and the skin is then dried.
  • the rinse-off product can also be used for washing the hair or for cleansing the entire body surface, for example in the shower.
  • hydroxyalkanoate derivative in accordance with this invention might be included as part of a composition for washing dishes by hand, thereby to enhance its mildness.
  • the composition When the composition is a wipe-off product, it will also generally function as a skin cleanser, especially for removing make-up.
  • a suitable amount for example 0.5 to 5ml of the skin cleanser comprising the hydroxy alkanoate derivative can be applied to the skin, particularly where make-up is to be removed, and rubbed-in.
  • the area of treated skin can then be wiped with a cloth, tissue or with cotton wool to remove surplus of the composition together with make-up that has been loosened from the skin.
  • both “rinse-off” and “leave-on” products in accordance with the invention and those that are used as part of the normal shaving process, namely as a pre-shave product, or as an after-shave product .
  • Both products in use are intended to moisturise or otherwise condition the skin, prior to or after shaving, so as to enhance the shaving process, and this can be achieved by delivery to the epidermis of an hydroxy alkanoate, in the manner described hereinbefore.
  • Shaving treatment products such as these can be employed either by men to remove unwanted facial hair or beard, or by women to remove unwanted hair from other parts of the body surface, particularly the legs. Wherever such products are used, they possess the ability to enhance the moisturisation of the skin, so improving its condition after the shaving process.
  • men's shaving products are used regularly, they can serve to provide regular delivery of hydroxyalkanoate to the skin.
  • after-shave products contain as a cosmetically acceptable vehicle, more than about 85% by weight of ethanol and water.
  • shaving products can contain other cosmetic adjuncts such as glycerine, perfume, perfume solubilisers to promote product clarity, vitamins and derivatives thereof such as vitamin E acetate and Vitamin A palmitate, thickeners such as Carbopol 980, triethanolamine and other adjuncts as conventionally used in pre- or after-shave products.
  • other cosmetic adjuncts such as glycerine, perfume, perfume solubilisers to promote product clarity, vitamins and derivatives thereof such as vitamin E acetate and Vitamin A palmitate, thickeners such as Carbopol 980, triethanolamine and other adjuncts as conventionally used in pre- or after-shave products.
  • Example 1 Synthesis of 2- (stearoyl) octanoic acid Stearic acid was dissolved under reflux in sodium-dried diethyl ether and oxalyl chloride added and further refluxed for 2 hours to complete the reaction to stearoyl chloride. Excess ether and oxalyl chloride were first removed by warm distillation, and then,last traces of oxalyl chloride were removed by pumping under vacuum.
  • 2-hydroxy octanoic acid was dissolved in pyridine (potassium hydroxide dried) and chloroform (ethanol free, anhydrous sodium sulphate/Al 2 ) 3 column dried) and then stearoyl chloride added rapidly to the 2-hydroxy octanoic acid solution and shaken vigorously. The reaction vessel was left for 60 hours with occasional shaking.
  • reaction mixture was then dissolved in diethyl ether and transferred to a separating funnel at -10°C.
  • the ether solution was washed free of pyridine/salts with four aliquots of 0.5N hydrochloric acid cooled to 0°C.
  • the ether solution was then washed with three aliquots of ice cold distilled water before drying over anhydrous sodium sulphate.
  • Example 2 The product was extracted as in Example 1, then its solution in a small volume of ether was neutralised to pH 7 with sodium hydroxide solution at 0°C. The solution was frozen and freeze dried.
  • the above preparation was also carried out using 14 C radiolabelled 2-hydroxyoctanoic acid.
  • the resulting radiolabeled 2- (decanoyloxy) octanoic acid had a specific activity of about 2.5 ⁇ Ci. mg "1 , which is about 900mCi. mole -1 . It was neutralised to its sodium salt and diluted to an aqueous solution with a concentration of 55.6mM, corresponding to 2.0 % by weight.
  • Three pieces of full thickness skin, taken from pig ear, were cut to 4 x 4cm and pinned out on a polystyrene foam support. 30 ⁇ l aliquots of the above solution were applied to four of the test pieces with a pipette and spread over the entire surface using the pipette tip. The fifth piece was left untreated.
  • the first test piece was swabbed with dry cotton wool to remove excess liquid.
  • Each strip of tape was placed in a scintillation vial with lml of phosphate buffer (pH 7) .
  • the plate was eluted with 80:20:2 hexane:ether:acetic acid mixture.
  • the spots on the plate were detected and quantified by their emitted radiation.
  • Each lane on the plate displayed two spots, one corresponding to hydrolysis products of the octanoate and a second spot corresponding to the substituted octanoate itself.
  • the results (mean of five repeats) were: % of Total label
  • the dodecanoyl derivative of 2-hydroxy dodecanoic acid incorporating 14 C radiolabel, was prepared in analogous manner to the preceding example. It had specific activity of 4.17 ⁇ Ci. mg " It was neutralised to its sodium salt of formula:
  • the final line in the table shows the amount of radiolabel removed onto the cotton wool used to remove liquid from the pig skin before taking tape strips.
  • Glyceryl monostearate 1.75 Candelilla Wax 1.00
  • the above formulation can be modified by replacing the ester of 2-hydroxyalkanoic acid with an equal amount of sodium 2-decyloxyoctanoate.
  • the above formulation can be modified by replacing the ester of 2-hydroxyalkanoic acid with an equal amount of sodium 2-octyloxyhexanoate.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Emergency Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)

Abstract

Une composition destinée à une application topique comprend un dérivé d'hydroxyalcanoate de la structure (I), dans laquelle R1 représente H- ou acyle, R2 représente alkyle contenant au moins 2 atomes de carbone, R3 représente H-, alkyle, alkyle substitué ou interrompu ou un contre-ion d'alcanolammonium d'ammonium ou métallique. Ce dérivé d'hydroxyalcanoate pénètre profondément dans la peau et subit un clivage sous l'action des enzymes de la peau afin de libérer l'hydroxyalcanoate correspondant, ce qui produit un effet bénéfique sur la peau.
PCT/EP1994/002666 1993-08-13 1994-08-10 Hydroxyalcanoates acyles et leurs utilisations Ceased WO1995005159A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU76122/94A AU7612294A (en) 1993-08-13 1994-08-10 Acylated hydroxyalkanoates and their uses

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB9316935.7 1993-08-13
GB9316847.4 1993-08-13
GB939316847A GB9316847D0 (en) 1993-08-13 1993-08-13 Cosmetic composition
GB939316924A GB9316924D0 (en) 1993-08-13 1993-08-13 Cosmetic composition
GB939316935A GB9316935D0 (en) 1993-08-13 1993-08-13 Cleansing composition
GB9316924.1 1993-08-13

Publications (1)

Publication Number Publication Date
WO1995005159A1 true WO1995005159A1 (fr) 1995-02-23

Family

ID=27266811

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002666 Ceased WO1995005159A1 (fr) 1993-08-13 1994-08-10 Hydroxyalcanoates acyles et leurs utilisations

Country Status (2)

Country Link
AU (1) AU7612294A (fr)
WO (1) WO1995005159A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998017316A1 (fr) * 1996-10-18 1998-04-30 Cellegy Pharmaceuticals Inc. Puissants stimulateurs de penetration transdermique
EP0747041A3 (fr) * 1995-06-07 1999-05-06 Unilever Plc Composition cosmétique contenant du pétrolatum
US10188736B2 (en) 2013-09-30 2019-01-29 Enza Biotech Ab Surfactant composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105783A (en) * 1975-07-23 1978-08-08 Yu Ruey J Therapeutic treatment of dry skin
EP0007785A2 (fr) * 1978-07-24 1980-02-06 Unilever Plc Compositions de traitement de la peau, procédé pour leur préparation et applicateur contenant lesdites compositions
EP0261812A1 (fr) * 1986-08-29 1988-03-30 Unilever Plc Composition cosmétique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105783A (en) * 1975-07-23 1978-08-08 Yu Ruey J Therapeutic treatment of dry skin
EP0007785A2 (fr) * 1978-07-24 1980-02-06 Unilever Plc Compositions de traitement de la peau, procédé pour leur préparation et applicateur contenant lesdites compositions
EP0261812A1 (fr) * 1986-08-29 1988-03-30 Unilever Plc Composition cosmétique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747041A3 (fr) * 1995-06-07 1999-05-06 Unilever Plc Composition cosmétique contenant du pétrolatum
WO1998017316A1 (fr) * 1996-10-18 1998-04-30 Cellegy Pharmaceuticals Inc. Puissants stimulateurs de penetration transdermique
US10188736B2 (en) 2013-09-30 2019-01-29 Enza Biotech Ab Surfactant composition
US10857232B2 (en) 2013-09-30 2020-12-08 Enza Biotech Ab Surfactant composition

Also Published As

Publication number Publication date
AU7612294A (en) 1995-03-14

Similar Documents

Publication Publication Date Title
TW568789B (en) Compositions containing hydroxy acids or retinoids
US5885595A (en) Cosmetic composition with a retinol fatty acid ester
EP0435483B1 (fr) Composition cosmétique
EP0793481B1 (fr) Composition cosmetique contenant des derives d'hydroxy-alcanoate
US5961992A (en) Benefit agent compositions comprising mixtures of alpha-hydroxy esters
US5078991A (en) Topical composition
JP2000327558A (ja) 細胞更新速度を増大させる方法
CA2099188C (fr) Utilisation d'une composition cosmetique
JPH07316012A (ja) 皮膚の表面層と深層とに同時に作用する美容組成物及びその用途
JP2886591B2 (ja) 化粧料
AU652969B2 (en) Cosmetic composition
AU687594B2 (en) Product for topical application containing a lipase and a hydroxy acid precursor
CA2166468C (fr) Compositions de nettoyage renfermant un alcanoate comme agent de conditionnement
JPH10298136A (ja) 新規なサリチル酸誘導体及びその化粧用及び／または皮膚用組成物における使用
CA2243715C (fr) Procede pour reduire les matieres grasses produites par la peau
US20020006420A1 (en) Use of a 2-amino-alkane polyol as agent for treating skin ageing signs
NZ329890A (en) Cosmetic topical composition containing a ceramide derivative
EP0542549A1 (fr) Utilisation d'une composition cosmétique
US20020018792A1 (en) Skin care anti-sebum compositions containing 3,4,4-trichlorocarbanilide
Abamba Skin preparations
MXPA99011655A (en) Benefit agent compositions comprising mixtures of alpha-hydroxy esters

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK ES FI GB GE HU JP KE KG KP KR KZ LK LT LU LV MD MG MN MW NL NO NZ PL PT RO RU SD SE SI SK TJ TT UA UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase