EP0555250A1 - Cosmetic composition - Google Patents

Cosmetic composition

Info

Publication number
EP0555250A1
EP0555250A1 EP91918089A EP91918089A EP0555250A1 EP 0555250 A1 EP0555250 A1 EP 0555250A1 EP 91918089 A EP91918089 A EP 91918089A EP 91918089 A EP91918089 A EP 91918089A EP 0555250 A1 EP0555250 A1 EP 0555250A1
Authority
EP
European Patent Office
Prior art keywords
phosphorylated
pseudoceramide
group
sulphated
carbon atoms
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.)
Withdrawn
Application number
EP91918089A
Other languages
German (de)
French (fr)
Inventor
Peter Critchley
Susan Edith Kirsch
Anthony Vincent Rawlings
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 PLC
Unilever NV
Original Assignee
Unilever PLC
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 GB909022926A external-priority patent/GB9022926D0/en
Priority claimed from GB909027706A external-priority patent/GB9027706D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0555250A1 publication Critical patent/EP0555250A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/10—Phosphatides, e.g. lecithin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
    • 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
    • A61K8/68—Sphingolipids, e.g. ceramides, cerebrosides, gangliosides
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
    • C07C305/06—Hydrogenosulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • 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

Definitions

  • the invention relates to modified pseudoceramides
  • compositions for topical application to human skin, hair or nails.
  • ceramides present within the intercellular lipid lamellae of the stratum corneum play an important role in the production and maintenance of the water permeability barrier of the skin. Ceramides, or substances closely related to them, have been disclosed as components of skin care compositions.
  • Kao Corporation in EP 227 994 and EP 282 816 disclose the use of synthetic ceramides, which are similar to their to their natural counterparts found in skin.
  • Unilever in EP 97 059 disclose ⁇ -O-linoleoyl ceramides and emphasize their role in the water barrier function of the skin.
  • pseudoceramides that is synthetic analogues of naturally occuring ceramides which resemble in the key properties the natural substances, and which have been modified by phosphorylation and/or sulphation. Accordingly, when these modified pseudoceramides are applied topically to the skin, together with a suitable cosmetically acceptable vehicle, they will readily penetrate the stratum corneum without permanently disrupting it, and after
  • R represents the group:
  • OR 2 R 1 represents a linear or branched, saturated or unsaturated, hydroxylated or
  • A represents H or the group:
  • R 2 & R 3 individually represent H, a sugar
  • R 4 represents a linear or branched
  • non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms or the group Y-O-(C a H b )- ;
  • R 5 represents a linear or branched, saturated or unsaturated, hydroxylated or non- hydroxylated, phosphorylated or non- phosphorylated, sulphated or non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms;
  • P i represents a is an integer of from 7 to 49
  • b is an integer of from 10 to 98
  • c is 0, or an integer of from 1 to 4
  • n 0 or 1
  • X 1 , X 2 & X 3 individually represent H, a C 1 to 5
  • alkyl group or a C 1 to 5 hydroxyalkyl group
  • Y represents H or a residue of a C 14 to C 22 fatty acid having the structure (3):
  • y is an integer of from 20 to 40
  • z is O, or an integer of from 1 to 4; provided that at least one out of R 2 & R 3 is either a phosphate residue or a sulphate residue.
  • the invention provides a class of modified
  • pseudoceramides having the general structure (1) or (2) as hereinbefore defined.
  • the group R 1 of the structure (1) above may preferably be aliphatic hydrocarbon group of 1 to 33 carbon atoms, more preferably 8 to 28 carbon atoms, yet more preferably 12 to 22 carbon atoms.
  • the group R 4 is preferably an aliphatic hydrocarbon group of 8 to 49 carbon atoms, more preferably 11 to 29 carbon If
  • R 4 C is acyl of 12 to 30 carbon atoms.
  • the group R 4 may be derived from a hydroxylated aliphatic group and may be sulphated or phosphorylated through reaction with the hydroxyl group(s).
  • the group R 5 is preferably aliphatic hydrocarbon of up to 28 carbon atoms, especially 8 to 28 carbon atoms, more preferably 12 to 22 carbon atoms. Also, with reference to structure (1), the value of "a” is preferably an integer of from 24 to 30 and the value of "b” is preferably an integer of from 44 to 60. Also, with reference to structure (1), the group Y
  • modified pseudoceramides according to the invention can be synthesised using a conventional method involving phosphorylation and/or sulphation. Examples of
  • phosphorylation comprise the treatment of pseudoceramide with one of the following: (i) phosphorus pentoxide - (P 2 O 5 ),
  • Examples of sulphation comprise the treatment of
  • pseudoceramide with one of the following: (i) chlorosulphonic acid,
  • phosphorylation will preferably be of formula
  • Phosphorylation or, as the case may be, sulphation will preferably be carried out under conditions where any hydroxyl group present in the starting material can react. This then leads to (at least some) formation of product compounds in which neither R 2 nor R 3 is H. It can also convert hydroxyl groups present as substituents on R 1 , R 4 or R 5 into phosphate or sulphate groups. There may be sulphation or phosphorylation of all free hydroxyl groups in the starting material. Such uncontrolled sulphation or phosphorylation is acceptable because it is intended that the sulphate or phosphate groups will be removed in vivo by naturally occurring enzymes.
  • the sulphated pseudoceramide having the structure (16) is prepared from N-(2-hydroxy-3-hexadecyloxypropyl)
  • the invention also provides a composition for topical application to human skin which comprises: i. an effective amount of a modified pseudoceramide or mixture of modified pseudoceramides having the structure (1); and ii. a cosmetically acceptable vehicle for the modified pseudoceramide.
  • composition according to the invention comprises in its simplest form a special modified pseudoceramide or a mixture of pseudoceramides and a vehicle therefor to enable the modified pseudoceramide(s) to be dispersed onto the skin and distributed thereon.
  • composition according to the invention comprises an effective amount of a modified pseudoceramide, or a mixture thereof, having the structure (l) as herein defined.
  • Preferred examples of the modified pseudoceramide having the structure (1) are those having the structure (4) to (24), as herein defined.
  • the amount of the modified pseudoceramide, or a mixture thereof present in the composition according to the invention is from 0.00001 to 50%, preferably from 0.001 to 20% and most preferably from 0.1 to 10% by weight.
  • the Cosmetically Acceptable Vehicle is from 0.00001 to 50%, preferably from 0.001 to 20% and most preferably from 0.1 to 10% by weight.
  • composition according to the invention also comprises a cosmetically acceptable vehicle to act as a dilutant, dispersant or carrier for the modified pseudoceramide in the composition, so as to facilitate its distribution when the composition is applied to the skin and/or hair.
  • Vehicles other than water can include liquid or solid emollients, solvents, humectants, thickeners and powders.
  • Emollients such as stearyl alcohol, glyceryl monoricinoleate, glyceryl monostearate, 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
  • lanolin cocoa butter, corn oil, cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, evening primrose oil, soybean oil, sunflower seed oil, avocado oil, olive oil, sesame seed oil, coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petroleum jelly, mineral oil, butyl myristate, isostearic acid, palmitatic acid, isopropyl linoleate, lauryl
  • lactate myristyl lactate, decyl oleate, myristyl
  • Propellants such as trichlorofluoromethane
  • dichlorodifluoromethane dichlorotetrafluoroethane, monochlorodifluoromethane, trichlorotrifluoroethane, 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
  • silicate fumed silica
  • carboxyvinyl polymer sodium carboxymethyl cellulose
  • ethylene glycol monostearate
  • the cosmetically acceptable vehicle will usually form from 10 to 99.9%, preferably from 50 to 99% by weight of the emulsion, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
  • an emulsion in which case 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-lyophilic balance (HLB) of the emulsifier employed.
  • HLB hydrophilic-lyophilic balance
  • composition according to the invention can optionally comprise one or more oils or other materials having the properties of an oil.
  • suitable oils include mineral oil and
  • oils vegetable oils, and oil materials, such as those already proposed herein as emollients.
  • Other oils or oily materials include silicone oils, both volatile and non-volatile, such as polydimethyl siloxanes.
  • the oil or oily material when present for the purposes for forming an emulsion, will normally form up to 90%, 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.
  • the chosen emulsifier or emulsifiers should normally have an average HLB value of from 1 to 6.
  • 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. Table 1
  • 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 Arlacel 83 3.7 Sorbitan monooleate Arlacel 80 4.3 Sorbitan monostearate Arlacel 60 4.7 Poloxyethylene (2)
  • 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 of the invention can also comprise water, usually up to 98%, preferably from 5 to 80% by volume.
  • composition of the invention can also optionally comprise a high molecular weight silicone surfactant which can also act as an emulsifier, in place of or in addition to the optional emulsifier (s) already mentioned.
  • a high molecular weight silicone surfactant which can also act as an emulsifier, in place of or in addition to the optional emulsifier (s) already mentioned.
  • the silicone surfactant is a high molecular weight polymer of dimethyl polysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight of from 10,000 to 50,000 and having the structure:
  • CH 3 a has a value of from 9 to 115
  • b has a value of from 0 to 50
  • x has a value of from 133 to 673
  • y has a value of from 25 to 0.25.
  • the dimethyl polysiloxane polymer is one in which: a has a value of from 10 to 114
  • b has a value of from 0 to 49
  • x has a value of from 388 to 402
  • y has a value of from 15 to 0.75 one of groups R' and R" being lauryl, and the other having a molcular weight of from 1000 to 5000.
  • a particularly preferred dimethyl polysiloxane polymer is one in which: a has the value 14
  • y has the value 1.25
  • 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.
  • 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.
  • silicone surfactant when present in the composition will normally be up to 25%, preferably from 0.5 to 15% by weight of the emulsion.
  • adjuncts examples include preservatives, such as para-hydroxy benzoate esters; antioxidants, such 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 triethanolamine or sodium hydroxide
  • surfactants such as glycerol ethers and other pseudoceramides of synthetic, animal or plant origin
  • phospholipids such as beeswax, ozokerite wax, paraffin wax, plant extracts, such as Aloe vera, cornflower, witch hazel, elderflower, cucumber; thickeners; activity enhancers; colourants;
  • sunscreen materials such as ultrafine titanium dioxide and organic sunscreens such as
  • p-aminobenzoic acid and esters thereof ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate and butyl methoxydibenzoylmethane, and mixtures thereof.
  • pseudoceramide is combined with conventional ceramides, unmodified pseudoceramides, cholesterol, cholesterol fatty acids, fatty acids, triglycerides, cerebroside,
  • the modified pseudoceramide is dissolved in squalene or squalane, optionally together with conventional ceramides and/or pseudoceramides, and formulated with volatile and
  • non-volatile silicones to produce an anhydrous or nearly anhydrous single phase system.
  • Cosmetic adjuncts can form the balance of the composition.
  • composition according to the invention is intended primarily as a product for topical application to human skin, especially as an agent for reducing the permeability to water of the skin, particularly when the skin is dry or damaged, in order to reduce moisture loss and generally to enhance the quality of skin.
  • the composition can also be applied to hair and nails.
  • the modified pseudoceramides according to the invention have surfactant properties and can therefore also be used, in the form of a composition as herein defined, for cleansing the surface of the human body.
  • the composition can be used to cleanse the skin to remove make up or can be employed in a shampoo for cleansing the hair.
  • a small quantity of the composition for example from 1 to 5ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device.
  • the topical skin, hair or nail treatment composition of the invention can be formulated as a lotion having a viscosity of from 4,000 to 10,000 mPas, a fluid cream having a viscosity of from 10,000 to 20,000 mPas or a cream having a viscosity of from 20,000 to 100,000 mPas, or above.
  • the composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer.
  • a lotion or fluid cream can be packaged in a bottle or a roll-ball applicator or a propellant-driven aerosol device or a container fitted with a pump suitable for finger operation.
  • the composition When the composition is a cream, it can simply be stored in a non-deformable bottle or squeeze container, such as a tube or a lidded jar.
  • the invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined.
  • Example 1 The invention is illustrated by the following examples.
  • Example 1 The invention is illustrated by the following examples.
  • This example illustrates a high internal phase
  • a high internal phase water-in-oil emulsion having the following formulation was prepared:
  • Example 2 This example also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes: i. liquid paraffin replaced the fully hydrogenated
  • Example 2 also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes:
  • the phosphorylated pseudoceramide had the structure (6).
  • This example illustrates an oil-in-water cream containing an ester of the invention.
  • Alfol 16RD is cetyl alcohol
  • This example also illustrates an oil-in-water emulsion in accordance with the invention, in which the formulation of example 4 was prepared but with the following change: the modified pseudoceramide was phosphorylated and had the structure (8), as herein defined.
  • This example illustrates an alcoholic lotion containing an amide of the invention.
  • the lotion had the following formulation: % w/w Phosphorylated pseudoceramide
  • This example illustrates an alcoholic lotion containing an amide of the invention.
  • the lotion had the following formulations: % w/w Phosphorylated pseudoceramide
  • compositions according to the invention represent lotions which can be used in the treatment of dry skin: % w/w
  • compositions according to the invention represent lotions which can be used in the treatment of dry skin:
  • Example 13 This example illustrates a high internal phase
  • a high internal phase water-in-oil emulsion having the following formulation was prepared:
  • Example 2 also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes: i. liquid paraffin replaced the fully hydrogenated
  • Example 2 also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes:
  • the phosphorylated pseudoceramide had the structure (22).
  • This example illustrates an oil-in-water cream containing an ester of the invention.
  • Alfol 16RD is cetyl alcohol
  • Example 18 also illustrates an oil-in-water emulsion containing an ester of the invention, in which the formulation of example 4 was prepared but with the following change: the sulphated pseudoceramide was that having structure (24), as herein defined.
  • Example 18 the sulphated pseudoceramide was that having structure (24), as herein defined.
  • Example 19 also illustrates an oil-in-water emulsion in accordance with the invention, in which the formulation of example 4 was prepared but with the following changes: the modified pseudoceramide was phosphorylated and had the structure (4) as herein defined.
  • Example 19
  • This example illustrates an alcoholic lotion containing an amide of the invention.
  • the lotion had the following formulation: % w/w
  • This example illustrates an alcoholic lotion containing an amide of the invention which is suitable for application to nails.
  • the lotion had the following formulations :
  • compositions according to the invention represent lotions which can be used in the treatment of dry, unmanageable hair. % w/w
  • compositions according to the invention represent lotions which can be used in the treatment of dry skin, hair or nails: % w/w
  • Example 24 The oil-in-water emulsion of Example 24 was prepared, but the sulphated pseudoceramide (7) was replaced with the phosphorylated pseudoceramide (18) or the phosphorylated pseudoceramide (20).
  • Example 26 The water-in-oil emulsion of Example 1 was prepared, but the phosphorylated pseudoceramide (14) was replaced with the sulphated pseudoceramide (21).

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Abstract

On décrit des pseudocéramides modifiés ainsi que leur synthèse et des compositions les contenant, destinés à une application topique à la peau, les cheveux ou les ongles humains. Les pseudocéramides modifiés présentent la structure suivante (I) ou (II) qui peut se résumer approximativement comme suit: R1, R4, R5 représentent un hydrocarbure aliphatique, A représente H ou un groupe aliphatique terminé par OR3, et R2 et/ou R3 représentent phosphate ou sulfate. La présence de phosphate ou de sulfate facilite l'absorption par la peau, après quoi le phosphate ou le sulfate est enlevé par des enzymes naturellement présentes in vivo.Modified pseudoceramides as well as their synthesis and compositions containing them, intended for topical application to human skin, hair or nails are described. The modified pseudoceramides have the following structure (I) or (II) which can be summarized approximately as follows: R1, R4, R5 represent an aliphatic hydrocarbon, A represents H or an aliphatic group terminated by OR3, and R2 and / or R3 represent phosphate or sulfate. The presence of phosphate or sulfate facilitates absorption through the skin, after which the phosphate or sulfate is removed by enzymes naturally present in vivo.

Description

COSMETIC COMPOSITION
FIELD OF THE INVENTION
The invention relates to modified pseudoceramides,
their synthesis and use in compositions for topical application to human skin, hair or nails.
BACKGROUND TO THE INVENTION AND PRIOR ART It is generally understood that ceramides present within the intercellular lipid lamellae of the stratum corneum play an important role in the production and maintenance of the water permeability barrier of the skin. Ceramides, or substances closely related to them, have been disclosed as components of skin care compositions. In particular, Kao Corporation in EP 227 994 and EP 282 816 disclose the use of synthetic ceramides, which are similar to their to their natural counterparts found in skin. Also, Unilever in EP 97 059 disclose ω -O-linoleoyl ceramides and emphasize their role in the water barrier function of the skin.
It is believed that one of the causes of dry skin and ageing skin is a reduction in the amount of lipid
contained within these intercellular lipid lamellae. It is therefore desirable to be able successfully to replace these depleted lipids via the topical route.
One of the problems associated with the topical
application of skin and hair care products containing ceramides or their synthetic analogues, is devising a suitable method for delivering them effectively to the lipid lamellae, without causing permanent disruption of the stratum corneum. It is accordingly apparent that permanently disrupted stratum corneum is unable to retain molecules of this sort, as they are simply washed out again when the stratum corneum (skin) is contacted with water.
This problem has not successfully been solved to date. Kao Corporation have reported in GB 2 178 312, EP 227 994 and EP 282 816, that co-surfactants such as glyceryl ethers assist synthetic ceramide to penetrate into the stratum corneum. However, these co-surfactants tend to disrupt the stratum corneum, so that when penetration occurs allowing the synthetic ceramide access to the lipid lamellae, there is nothing to prevent them being washed out again on contact with water.
We have solved this problem by using modified
pseudoceramides, that is synthetic analogues of naturally occuring ceramides which resemble in the key properties the natural substances, and which have been modified by phosphorylation and/or sulphation. Accordingly, when these modified pseudoceramides are applied topically to the skin, together with a suitable cosmetically acceptable vehicle, they will readily penetrate the stratum corneum without permanently disrupting it, and after
demodification with phosphatases or sulphatases which occur naturally in skin and which will cleave off the phosphate or sulphate groups respectively, the unmodified pseudoceramide structures will remain locked in the desired location within the stratum corneum. Since the phosphate and/or sulphate groups, which facilitate
delivery, have been removed once the pseudoceramide is in position, it is then not be possible subseguently to wash the pseudoceramide from the skin, so ensuring that it is available to effect repair in situ of lipid lamellae which have become damaged under dry skin conditions. SUMMARY OF THE INVENTION
We have modified pseudoceramides by phosphorylation or sulphation to assist their penetration into the lipid lamellae of the stratum corneum. Once located within the lipid lamellae, naturally-occurring phosphatases and sulphatases will cleave off the phosphate or sulphate groups respectively, to leave the pseudoceramides lodged firmly within the stratum corneum. DEFINITION OF THE INVENTION
Accordingly, the invention provides modified
pseudoceramides having the structure (1): (1)
where R represents the group:
R4-C- , or the group
R5-O-CH2CH CH2- ;
OR2 R1 represents a linear or branched, saturated or unsaturated, hydroxylated or
non-hydroxylated, phosphorylated or non-phosphorylated, sulphated or non-sulphated aliphatic hydrocarbon having from 1 to 49 carbon atoms; A represents H or the group:
(2) R2 & R3 individually represent H, a sugar
residue, a phosphate residue (Pi), or a sulphate residue (SO3 Θ); R4 represents a linear or branched,
saturated or unsaturated, hydroxylated or non-hydroxylated, phosphorylated or non-phosphorylated, sulphated or
non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms or the group Y-O-(CaHb)- ;
R5 represents a linear or branched, saturated or unsaturated, hydroxylated or non- hydroxylated, phosphorylated or non- phosphorylated, sulphated or non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms;
P i represents a is an integer of from 7 to 49
b is an integer of from 10 to 98
c is 0, or an integer of from 1 to 4
n is 0 or 1
X1, X2 & X3 individually represent H, a C1 to 5
alkyl group or a C1 to 5 hydroxyalkyl group
Y represents H or a residue of a C14 to C22 fatty acid having the structure (3):
-C-(CxHyZz)CH3 (3) where Z is -OH, -OPi, -OSO3 Θ or an epoxy oxygen x is an integer of from 12 to 20
y is an integer of from 20 to 40
z is O, or an integer of from 1 to 4; provided that at least one out of R2 & R3 is either a phosphate residue or a sulphate residue. DISCLOSURE OF THE INVENTION
The Modified Pseudoceramide
The invention provides a class of modified
pseudoceramides having the general structure (1) or (2) as hereinbefore defined.
The group R1 of the structure (1) above may preferably be aliphatic hydrocarbon group of 1 to 33 carbon atoms, more preferably 8 to 28 carbon atoms, yet more preferably 12 to 22 carbon atoms.
The group R4 is preferably an aliphatic hydrocarbon group of 8 to 49 carbon atoms, more preferably 11 to 29 carbon If
atoms (so that R4 C is acyl of 12 to 30 carbon atoms). The group R4 may be derived from a hydroxylated aliphatic group and may be sulphated or phosphorylated through reaction with the hydroxyl group(s).
The group R5 is preferably aliphatic hydrocarbon of up to 28 carbon atoms, especially 8 to 28 carbon atoms, more preferably 12 to 22 carbon atoms. Also, with reference to structure (1), the value of "a" is preferably an integer of from 24 to 30 and the value of "b" is preferably an integer of from 44 to 60. Also, with reference to structure (1), the group Y
preferably represents a straight chain saturated C16-18 fatty acid residue or a straight chain all cis n-6,9 di-unsaturated C16-18 fatty acid residue. Specific examples of these modified pseudoceramides and related structures are those having the structures
(4)-(20):
N-(2-hydroxy-3-hexadecyloxypropyl)-N-(2-phosphoethyl) hexadecamide having the structure (4):
(4)
N-(2-hydroxyoctadecyl)-N-(2-sulphoethyl)hexadecamide having the structure (5):
(5)
N-(2-hydroxy-3-hexadecyloxypropyl)-N-(2-phosphoethyl)- ω -o-linoleoyl docosamide having the structure (6):
(6) linoleoyl-O-( N-(2-hydroxy-3-hexadecyloxypropyl)-N-(2-sulphoethyl)- ω)-O-linoleoyl hexadecamide having the structure (7):
(7) linoleoyl-O-(CH
N-(2-hydroxyoctadecyl)-N-(2-phosphoethyl)-ω-O-linoleoyl- hexadecamide having the structure (8):
(8) linoleoyl-O-(CH2)15 N-(2-hydroxy-3-nonyloxypropyl)-N-(2-sulphoethyl)decamide having the structure (9):
(9)
N-(2-hydroxy-3-tritriacontyloxypropyl)-N-(2-phosphoethyl) pentacosamide having the structure (10):
(10)
N-(2-hydroxy-3-hexadecyloxypropyl)-N-(3-methyl-4- phosphobutyl)hexadecamide having the structure (11) :
(11)
N-(2-phospho-3-hexadecyloxypropyl)-N-(2-phosphoethyl) hexadecamide having the structure (12):
(12)
N-(2-0-glucopyranosyl-3-hexadecyloxypropyl)-N-(2- phosphoethyl)hexadecamide having the structure (13):
(13)
N-(2-phospho-3-hexadecyloxypropyl)-N-(2-hydroxyethyl)- hexadecamide having the structure (14):
(14)
N-(2-sulphooctadecyl)-N-(2-hydroxyethyl)hexadecamide having the structure (15):
(15)
N-(2-sulpho-3-hexadecyloxypropyl)-N-(2-sulphoethyl)- hexadecamide having the structure (16):
(16)
N-(2-sulpho-3-hexadecyloxypropyl)-N-(2-phosphoethyl)- hexadecamide having the structure (17):
(17)
N-(2-phospho-3-hexadecyloxypropyl)-N-(2-phosphoethyl)-2- phosphohexadecamide having the structure (18):
N-(2-sulpho-3-tritriacontyloxypropyl)-N-(2-sulphoethyl)-2- sulphopentacosamide having the structure (19):
N-(2-phospho-3-hexadecyloxypropyl)-N-(2-phosphoethyl)- linoleamide having the structure (20):
CH3 (CH2 )4 CH=CHCH2CH=CH(C
N-(2-sulpho-3-pentadecyloxypropyl)-N-(2-sulphoethyl)- linoleamide having the structure (21):
CH3 (CH2 )4CH=CHCH2CH=CH( 2-Phosphoethanolamine-N-bis-(2-phospho-3- hexadecyloxypropyl) having the structure (22) :
(22)
2-phosphoethanolamine-N-bis-(2-sulpho-3- hexadecyloxypropyl) having the structure (23) :
(23)
Di-(2-sulpho-3-hexadecyloxypropyl)amine having the structure (24):
(24)
SYNTHESIS OF THE MODIFIED PSEUDOCERAMIDES
The modified pseudoceramides according to the invention can be synthesised using a conventional method involving phosphorylation and/or sulphation. Examples of
phosphorylation comprise the treatment of pseudoceramide with one of the following: (i) phosphorus pentoxide - (P2O5),
(ii) polyphosphonic acid,
(iii) phosphorus oxychloride, (POCl3), followed by hydrolysis, or
(iv) phosphorus trichloride (PCl3) followed by:
(a) oxidation using, for example,
chlorine, and then
(b) hydrolysis.
Examples of sulphation comprise the treatment of
pseudoceramide with one of the following: (i) chlorosulphonic acid,
(ii) thionylchloride, (SOCl2), or
(iii) fuming sulphuric acid The material which is subjected to sulphation or
phosphorylation will preferably be of formula
in which A is H or a group
- ( CH2 )c
and other characteristics are as set out above.
Phosphorylation or, as the case may be, sulphation will preferably be carried out under conditions where any hydroxyl group present in the starting material can react. This then leads to (at least some) formation of product compounds in which neither R2 nor R3 is H. It can also convert hydroxyl groups present as substituents on R1, R4 or R5 into phosphate or sulphate groups. There may be sulphation or phosphorylation of all free hydroxyl groups in the starting material. Such uncontrolled sulphation or phosphorylation is acceptable because it is intended that the sulphate or phosphate groups will be removed in vivo by naturally occurring enzymes. SPECIFIC EXAMPLES OF THE SYNTHESIS
Synthesis of N-(2-phospho-3-hexadecyloxypropyl)-N- ( 2-phosphoethyl)-hexadecamide (12) The phosphorylated pseudoceramide having the structure (12) is prepared from N-(2-hydroxy-3-hexadecyloxypropyl) -N-(2-hydroxyethyl)-hexadecamide, having the structure (25), in accordance with the following scheme:
(25)
(12)
Synthesis of N-(2-sulpho-3-hexadecyloxypropyl)-N- (2-sulphoethyl) hexadecamide (16)
The sulphated pseudoceramide having the structure (16) is prepared from N-(2-hydroxy-3-hexadecyloxypropyl)
-N-(2-hydroxyethyl)-hexadecamide, having the structure (25), in accordance with the following scheme:
(25)
3
(16)
DEFINITION OF COMPOSITIONS OF THE INVENTION
The invention also provides a composition for topical application to human skin which comprises: i. an effective amount of a modified pseudoceramide or mixture of modified pseudoceramides having the structure (1); and ii. a cosmetically acceptable vehicle for the modified pseudoceramide.
DISCLOSURE OF THE COMPOSITION The composition according to the invention comprises in its simplest form a special modified pseudoceramide or a mixture of pseudoceramides and a vehicle therefor to enable the modified pseudoceramide(s) to be dispersed onto the skin and distributed thereon.
The Modified Pseudoceramide
The composition according to the invention comprises an effective amount of a modified pseudoceramide, or a mixture thereof, having the structure (l) as herein defined.
Preferred examples of the modified pseudoceramide having the structure (1) are those having the structure (4) to (24), as herein defined.
The amount of the modified pseudoceramide, or a mixture thereof present in the composition according to the invention is from 0.00001 to 50%, preferably from 0.001 to 20% and most preferably from 0.1 to 10% by weight. The Cosmetically Acceptable Vehicle
The composition according to the invention also comprises a cosmetically acceptable vehicle to act as a dilutant, dispersant or carrier for the modified pseudoceramide in the composition, so as to facilitate its distribution when the composition is applied to the skin and/or hair.
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, glyceryl monostearate, 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, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, evening primrose oil, soybean oil, sunflower seed oil, avocado oil, olive oil, sesame seed oil, coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petroleum jelly, mineral oil, butyl myristate, isostearic acid, palmitatic acid, isopropyl linoleate, lauryl
lactate, myristyl lactate, decyl oleate, myristyl
myristate;
Propellants, such as trichlorofluoromethane,
dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, trichlorotrifluoroethane, 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.
The cosmetically acceptable vehicle will usually form from 10 to 99.9%, preferably from 50 to 99% by weight of the emulsion, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
OPTIONAL SKIN BENEFIT MATERIALS AND COSMETIC ADJUNCTS A particularly convenient form of the composition
according to the invention is an emulsion, in which case 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-lyophilic balance (HLB) of the emulsifier employed. Oil or oily material
The composition according to the invention can optionally comprise one or more oils or other materials having the properties of an oil.
Examples of suitable oils include mineral oil and
vegetable oils, and oil materials, such as those already proposed herein as emollients. Other oils or oily materials include silicone oils, both volatile and non-volatile, such as polydimethyl siloxanes.
The oil or oily material, when present for the purposes for forming an emulsion, will normally form up to 90%, preferably from 10 to 80% by volume of the composition.
Emulsifier
The 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.
When a water-in-oil emulsion is required, 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. Examples of 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. Table 1
Chemical Name Trade Name HLB Value of Emulsifier
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 Arlacel 83 3.7 Sorbitan monooleate Arlacel 80 4.3 Sorbitan monostearate Arlacel 60 4.7 Poloxyethylene (2)
stearyl ether Brij 72 4.9
Poloxyethylene sorbitol
beeswax derivative G-1702 5 PEG 200 dilaurate Emerest 2622 6.3 Sorbitan monopalmitate Arlacel 40 6.7 Polyoxyethylene (3.5)
nonyl phenol Emulgen 903 7.8 PEG 200 monostearate Tegester PEG
200 MS 8.5
Sorbitan monolaurate Arlacel 200 8.6 PEG 400 dioleate Tegester PEG
400-DO 8.8
Polyoxyethylene (5)
monostearate Ethofat 60-16 9.0 Polyoxyethylene (4) sorbitan
monostearate Tween 61 9.6
Polyoxyethylene (4) lauryl
ether Brij 30 9.7 Polyoxyethylene (5) sorbitan
monooleate Tween 81 10.0 PEG 300 monooleate Neutronyx 834 10.4 Polyoxyethylene (20)
sorbitan tristearate Tween 65 10.5 Polyoxyethylene (20)
sorbitan trioleate Tween 85 11.0 Polyoxyethylene (8)
monostearate Myrj 45 11.1 PEG 400 monooleate Emerest 2646 11.7 PEG 400 monostearate Tegester PEG 400 11.9 Polyoxyethylene 10
monooleate Ethofat 0/20 12.2
Polyoxyethylene (10)
stearyl ether Brij 76 12.4 Polyoxyethylene (10)
cetyl ether Brij 56 12.9 Polyoxyethylene (9.3)
octyl phenol Triton X-100 13.0 Polyoxyethylene (4)
sorbitan monolaurate Tween 21 13.3 PEG 600 monooleate Emerest 2660 13.7 PEG 1000 dilaurate Kessco 13.9
Polyoxyethylene sorbitol
lanolin derivative G-1441 14.0 Polyoxyethylene (12)
lauryl ether Ethosperse LA -12 14.4 PEG 1500 dioleate Pegosperse 1500 14.6
Polyoxyethylene (14)
laurate Arosurf HFL-714 14.8 Polyoxyethylene (20)
sorbitan monostearate Tween 14.9 Polyoxyethylene 20 sorbitan
monooleate Tween 80 15.0 Polyoxyethylene (20)
stearyl ether Brij 78 15.3 Polyoxyethylene (20)
sorbitan monopalmitate Tween 40 15.6 Polyoxyethylene (20) cetyl
ether Brij 58 15.7 Polyoxyethylene (25)
oxypropylene G-2162 16.0 monostearate
Polyoxyethylene (20)
sorbitol monolaurate Tween 20 16.7 Polyoxyethylene (23)
lauryl ether Brij 35 16.9 Polyoxyethylene (50)
monostearate Myrj 53 17.9 PEG 4000 monostearate Pegosperse 4000
MS 18.7
The foregoing list of emulsifiers is not intended to be limiting and merely exemplifies selected emulsifiers which are suitable for use in accordance with the invention.
It is to be understood that two or more emulsifiers can be employed if desired.
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.
Water
The composition of the invention can also comprise water, usually up to 98%, preferably from 5 to 80% by volume. Silicone Surfactant
The composition of the invention can also optionally comprise a high molecular weight silicone surfactant which can also act as an emulsifier, in place of or in addition to the optional emulsifier (s) already mentioned.
The silicone surfactant is a high molecular weight polymer of dimethyl polysiloxane with polyoxyethylene and/or polyoxypropylene side chains having a molecular weight of from 10,000 to 50,000 and having the structure:
where the groups R' and R" are each
chosen from -H, C1-18 alkyl and
- [CH2CH2O]a[CH2CHO]bH
CH3 a has a value of from 9 to 115,
b has a value of from 0 to 50,
x has a value of from 133 to 673,
y has a value of from 25 to 0.25.
Preferably, the dimethyl polysiloxane polymer is one in which: a has a value of from 10 to 114
b has a value of from 0 to 49
x has a value of from 388 to 402
y has a value of from 15 to 0.75 one of groups R' and R" being lauryl, and the other having a molcular weight of from 1000 to 5000.
A particularly preferred dimethyl polysiloxane polymer is one in which: a has the value 14
b has the value 13
x has the value 249
y has the value 1.25
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. Ideally, 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. Other Cosmetic Adjuncts
Examples of conventional adjuncts which can optionally be employed include preservatives, such as para-hydroxy benzoate esters; antioxidants, such 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; surfactants, such as glycerol ethers and other pseudoceramides of synthetic, animal or plant origin; phospholipids; 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-aminobenzoic acid and esters thereof, ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate and butyl methoxydibenzoylmethane, and mixtures thereof.
In a further preferred composition, the modified
pseudoceramide is combined with conventional ceramides, unmodified pseudoceramides, cholesterol, cholesterol fatty acids, fatty acids, triglycerides, cerebroside,
phospholipid and other ingredients well known to those skilled in the art to produce a liposomal dispersion.
In yet another preferred composition, the modified pseudoceramide is dissolved in squalene or squalane, optionally together with conventional ceramides and/or pseudoceramides, and formulated with volatile and
non-volatile silicones to produce an anhydrous or nearly anhydrous single phase system. Cosmetic adjuncts can form the balance of the composition.
Use of the Composition
The composition according to the invention is intended primarily as a product for topical application to human skin, especially as an agent for reducing the permeability to water of the skin, particularly when the skin is dry or damaged, in order to reduce moisture loss and generally to enhance the quality of skin. The composition can also be applied to hair and nails.
The modified pseudoceramides according to the invention have surfactant properties and can therefore also be used, in the form of a composition as herein defined, for cleansing the surface of the human body. In particular the composition can be used to cleanse the skin to remove make up or can be employed in a shampoo for cleansing the hair. In use, a small quantity of the composition, for example from 1 to 5ml, is applied to exposed areas of the skin, from a suitable container or applicator and, if necessary, it is then spread over and/or rubbed into the skin using the hand or fingers or a suitable device. PRODUCT FORM AND PACKAGING
The topical skin, hair or nail treatment composition of the invention can be formulated as a lotion having a viscosity of from 4,000 to 10,000 mPas, a fluid cream having a viscosity of from 10,000 to 20,000 mPas or a cream having a viscosity of from 20,000 to 100,000 mPas, or above. The composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer.
For example, a lotion or fluid cream can be packaged in a bottle or a roll-ball applicator or a propellant-driven aerosol device or a container fitted with a pump suitable for finger operation. When the composition is a cream, it can simply be stored in a non-deformable bottle or squeeze container, such as a tube or a lidded jar.
The invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined.
EXAMPLES
The invention is illustrated by the following examples. Example 1
This example illustrates a high internal phase
water-in-oil emulsion in accordance with the invention.
A high internal phase water-in-oil emulsion having the following formulation was prepared:
% w/w Fully hydrogenated coconut oil 3.9
Phosphorylated pseudoceramide
having the structure (14) 0. 1
Brij 92* 5
Bentone 38 0. 5
Preservative 0. 3
MgSO47H2O 0. 3
Butylated hydroxy toluene 0. 01
Perfume qs
Water to 100
*Brij 92 is polyoxyethylene (2) oleyl ether
Example 2 This example also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes: i. liquid paraffin replaced the fully hydrogenated
coconut oil, and ii. the sulphated pseudoceramide had the structure (5). Example 3
This example also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes:
The phosphorylated pseudoceramide had the structure (6).
Example 4
This example illustrates an oil-in-water cream containing an ester of the invention.
An oil-in-water cream emulsion having the following formulation was prepared:
% w/w
Mineral oil 4
Sulphated pseudoceramide
having the structure (7) 0.1
Brij 56* 4
Alfol 16RD* 4
Triethanolamine 0.75
Butane-1,3-diol 3
Xanthan gum 0.3
Preservative 0.4
Perfume qs
Butylated hydroxy toluene 0.01
Water to 100
*Brij 56 is cetyl alcohol POE (10)
Alfol 16RD is cetyl alcohol Example 5
This example also illustrates an oil-in-water emulsion in accordance with the invention, in which the formulation of example 4 was prepared but with the following change: the modified pseudoceramide was phosphorylated and had the structure (8), as herein defined.
Example 6
This example also illustrates an oil-in-water emulsion in accordance with the invention, in which the formulation of example 4 was prepared but with the following changes: sulphated pseudoceramide was that having the
structure (9) as herein defined.
Example 7
This example illustrates an alcoholic lotion containing an amide of the invention.
The lotion had the following formulation: % w/w Phosphorylated pseudoceramide
having the structure (10) 0.2
Ethanol 40
Perfume qs
Butylated hydroxy toluene 0.01
Water to 100 Example 8
This example illustrates an alcoholic lotion containing an amide of the invention.
The lotion had the following formulations: % w/w Phosphorylated pseudoceramide
having the structure (11) 0.2
Dimethylsulphoxide 10
Ethanol 40
Antioxidant 0.1
Perfume qs
Water to 100
Examples 9 and 10 The following compositions according to the invention represent lotions which can be used in the treatment of dry skin: % w/w
9 10
Phosphorylated pseudoceramide
having the structure (12) 1.5 -
Phosphorylated pseudoceramide
having the structure (1133)) - 0 .5
Perfume 0. 1 0. 1
Hydroxyethyl cellulose 0. 4 0. 4
Absolute ethanol 25 25 p-methyl benzoate 0.2 0.2 Sterilised demineralised water to 100 to 100 Examples 11 and 12
The following compositions according to the invention represent lotions which can be used in the treatment of dry skin:
% w/w
11 12 The phosphorylated pseudoceramide
having the structure (14) 0.08 - The sulphated pseudoceramide
having the structure (15) - 0.15 Ethanol 10 10 Perfume 0.5 0.5
Distilled water to 100 to 100
Example 13 This example illustrates a high internal phase
water-in-oil emulsion in accordance with the invention.
A high internal phase water-in-oil emulsion having the following formulation was prepared:
% w/w
Fully hydrogenated coconut oil 3.9
sulphated pseudoceramide
having the structure (16) 0.1
Brij 92* 5
Bentone 38 0.5
Preservative 0.3
MgSO47H2O 0.3
Butylated hydroxy toluene 0.01
Perfume qs
Water to 100
*Brij 92 is polyoxyethylene (2) oleyl ether
Example 14
This example also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes: i. liquid paraffin replaced the fully hydrogenated
coconut oil, and ii. the phosphorylated and sulphated pseudoceramide had the structure (17). Example 15
This example also illustrates a high internal phase water-in-oil emulsion in accordance with the invention in which the formulation of Example 1 was prepared but with the following changes:
The phosphorylated pseudoceramide had the structure (22).
Example 16
This example illustrates an oil-in-water cream containing an ester of the invention.
An oil-in-water cream emulsion having the following formulation was prepared:
% w/w
Mineral oil 4
Phosphorylated and sulphated
pseudoceramide having
the structure (23) 0.1
Brij 56* 4
Alfol 16RD* 4
Triethanolamine 0.75 Butane-1,3-diol 3
Xanthan gum 0.3
Preservative 0.4
Perfume qs
Butylated hydroxy toluene 0.01 Water to 100
*Brij 56 is cetyl alcohol POE (10)
Alfol 16RD is cetyl alcohol Example 17
This example also illustrates an oil-in-water emulsion containing an ester of the invention, in which the formulation of example 4 was prepared but with the following change: the sulphated pseudoceramide was that having structure (24), as herein defined. Example 18
This example also illustrates an oil-in-water emulsion in accordance with the invention, in which the formulation of example 4 was prepared but with the following changes: the modified pseudoceramide was phosphorylated and had the structure (4) as herein defined. Example 19
This example illustrates an alcoholic lotion containing an amide of the invention. The lotion had the following formulation: % w/w
Sulphated pseudoceramide
having the structure (5) 0.2
Ethanol 40
Perfume qs
Butylated hydroxy toluene 0.01
Water to 100
Example 20
This example illustrates an alcoholic lotion containing an amide of the invention which is suitable for application to nails.
The lotion had the following formulations :
% w/w
Phosphorylated pseudoceramide
having the structure (6) 0.2
Dimethylsulphoxide 10
Ethanol 40
Antioxidant 0.1
Perfume qs
Water to 100
Examples 21 and 22
The following compositions according to the invention represent lotions which can be used in the treatment of dry, unmanageable hair. % w/w
21 22 Sulphated pseudoceramide
having the structure (7) 1.5 - Phosphorylated pseudoceramide
having the structure (8) - 0. 5 Perfume 0. 1 0. 1 Hydroxyethyl cellulose 0. 4 0. 4 Absolute ethanol 25 25 p-methyl benzoate 0. 2 0.2 Sterilised demineralised water to 100 to 100 Examples 23 and 24
The following compositions according to the invention represent lotions which can be used in the treatment of dry skin, hair or nails: % w/w
21 24
The sulphated pseudoceramide
having the structure (9) 0.08 -
The phosphorylated pseudoceramide
having the structure (10) - 0. 15
Ethanol 10 10
Perfume 0.5 0.5 Distilled water to 100 to 100 Example 25
The oil-in-water emulsion of Example 24 was prepared, but the sulphated pseudoceramide (7) was replaced with the phosphorylated pseudoceramide (18) or the phosphorylated pseudoceramide (20).
Example 26 The water-in-oil emulsion of Example 1 was prepared, but the phosphorylated pseudoceramide (14) was replaced with the sulphated pseudoceramide (21).

Claims

CLAIMS 1. Modified pseudoceramides having the structure (1):
(1)
A where R represents the group:
group ;
R1 represents a linear or branched, saturated or unsaturated, hydroxylated or
non-hydroxylated, phosphorylated or non-phosphorylated, sulphated or
non-sulphated aliphatic hydrocarbon having from 1 to 49 carbon atoms; A represents H or the group:
(2) R2 & R3 individually represent H, a sugar
residue, a phosphate residue (Pi), or a sulphate residue (SO3 Θ);
R4 represents a linear or branched,
saturated or unsaturated, hydroxylated or non-hydroxylated, phosphorylated or non-phosphorylated, sulphated or non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms or the group Y-O-(CaHb)- ; R5 represents a linear or branched,
saturated or unsaturated, hydroxylated or non-hyroxylated, phosphorylated or non-phosphorylated, sulphated or non- sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms; Pi represents
a is an integer of from 7 to 49
b is an integer of from 10 to 98
c is O, or an integer of from 1 to 4
d is O or 1
n is 0 or 1
X1, X2 & X3 individually represent H, a C1 to 5 alkyl group or a C1 to 5 hydroxyalkyl group
Y represents H or a residue of a C14 to C22 fatty acid having the structure (3):
-C-(CxHyZz)CH3 ( 3 ) where Z is -OH, -OPi, -OSO3 Θor an epoxy oxygen
x is an integer of from 12 to 20
y is an integer of from 20 to 40
z is 0, or an integer of from 1 to 4; provided that at least one out of R2 & R3 is either a phosphate residue or a sulphate residue.
2. A compound according to claim 1 wherein R1 contains 1 to 33 carbon atoms and R5 contains 1 to 28 carbon atoms.
3. A compound according to claim 2 wherein R1 contains 8 to 33 carbon atoms, R4 contains 8 to 49 carbon atoms and
R5 contains 8 to 28 carbon atoms.
4. A compound according to claim 1, claim 2 or claim 3 wherein R4 is phosphorylated or sulphated.
5. A compound according to any one of claims 1 to 4 wherein neither R2 nor R3 represents H.
6. A process for synthesising a modified pseudoceramide according to any one of claims 1 to 5 which comprises the step of phosphorylation and/or sulphation of
pseudoceramide having the structure (1):
(1)
where R represents the group: O
R4-C- , or the group
R5-O-CH2CH CH2- ;
OR2 R1 represents a linear or branched, saturated or urisaturated, hydroxylated or
non-hydroxylated, phosphorylated or
non-phosphorylated, sulphated or
non-sulphated aliphatic hydrocarbon having from 1 to 49 carbon atoms;
A represents H or the group:
(2)
R2 & R3 individually represent H or a sugar
residue provided that at least one of
R2 and R3 is H; R4 represents a linear or branched,
saturated or unsaturated, hydroxylated or non-hydroxylated,
norr-phosphorylated,
non-sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms or the group Y-O-(CaHb)- ; R5 represents a linear or branched,
saturated or unsaturated, hydroxylated or non-hyroxylated,
non-phosphorylated, non- sulphated aliphatic hydrocarbon group having from 1 to 49 carbon atoms; and Pi, a, b, c, d, n, X1, X2, X3 and Y are as defined in claim 1.
7. A composition suitable for topical application to skin, hair or nails, which comprises: i. an amount of from 0.0001 to 20% by weight of the
modified pseudoceramide according to any one of claims 1 to 5 and ii. a cosmetically acceptable vehicle for the modified pseudoceramide.
8. The use of at least 0.0001% by weight of a modified pseudoceramide according to any one of claims 1 to 5 as an agent for skin water barrier repair, in a topical
composition comprising a major proportion of a cosmetically acceptable vehicle for the modified pseudoceramide.
9. The use of at least 0.0001% by weight of a modified pseudoceramide according to any one of claims 1 to 5 as an agent for improving nails or as an agent for improving hair.
10. A method for the treatment of skin, hair or nails which comprises topical application thereto of a
composition according to claim 7.
EP91918089A 1990-10-22 1991-10-21 Cosmetic composition Withdrawn EP0555250A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9022926 1990-10-22
GB909022926A GB9022926D0 (en) 1990-10-22 1990-10-22 Cosmetic composition
GB9027706 1990-12-20
GB909027706A GB9027706D0 (en) 1990-12-20 1990-12-20 Cosmetic composition

Publications (1)

Publication Number Publication Date
EP0555250A1 true EP0555250A1 (en) 1993-08-18

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Country Status (7)

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EP (1) EP0555250A1 (en)
JP (1) JPH06504265A (en)
KR (1) KR930702360A (en)
AU (1) AU8734391A (en)
BR (1) BR9107032A (en)
CA (1) CA2094500A1 (en)
WO (1) WO1992006982A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993005763A1 (en) * 1991-09-24 1993-04-01 Kao Corporation Composition for external skin care
GB9124360D0 (en) * 1991-11-15 1992-01-08 Unilever Plc Cosmetic compositions
CA2099188C (en) * 1992-07-24 2005-12-13 Paul A. Bowser Use of a cosmetic composition
FR2718960B1 (en) * 1994-04-22 1996-06-07 Oreal Compositions for the treatment and protection of hair, based on ceramide and polymers with cationic groups.
FR2747567B1 (en) * 1996-04-22 1998-05-22 Oreal USE OF CERAMIDE FOR THE TREATMENT OF NAILS
KR19980034991A (en) 1996-11-11 1998-08-05 안용찬 Non-natural ceramide-related compounds and external skin preparations containing them
CN104530117B (en) * 2014-11-21 2017-05-24 何彦波 Tall oil acid diethanolamide phosphate ester, and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US4534899A (en) * 1981-07-20 1985-08-13 Lipid Specialties, Inc. Synthetic phospholipid compounds
JPS59187787A (en) * 1983-04-11 1984-10-24 Meito Sangyo Kk Production of sphingolipid derivative using enzymic method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9206982A1 *

Also Published As

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BR9107032A (en) 1994-01-25
JPH06504265A (en) 1994-05-19
AU8734391A (en) 1992-05-20
WO1992006982A1 (en) 1992-04-30
CA2094500A1 (en) 1992-04-23
KR930702360A (en) 1993-09-08

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