WO1997022329A1

WO1997022329A1 - Cosmetic hair treatment method

Info

Publication number: WO1997022329A1
Application number: PCT/EP1996/005008
Authority: WO
Inventors: Walter Thomas Gibson; Preyesh Parmar; Caroline Riches; Gillian Elizabeth Westgate
Original assignee: Unilever Plc; Unilever N.V.
Priority date: 1995-12-16
Filing date: 1996-11-11
Publication date: 1997-06-26
Also published as: EP0866684B1; AR005070A1; AU7571896A; DE69614565D1; DE69614565T2; ES2162113T3; EP0866684A1; GB9525775D0

Abstract

A cosmetic method for imparting body and volume to human hair comprising increasing the diameter of the hair fibre by supplementation of the hair root with a composition comprising between 0.01 and 10 % by weight cysteine, or a derivative thereof, wherein the cysteine or derivative thereof is delivered to the hair root by topical application of the composition to the hair and/or the scalp.

Description

COSMETIC HAIR TREATMENT METHOD

This invention relates to methods of cosmetic treatment of human hair to enhance the mechanical properties of the hair fibre. In particular the invention relates to the delivery of a composition comprising cysteine to the hair to

supplement the hair roots and to cause the hair fibre to become thicker, so increasing hair body and volume.

Cysteine is an amino acid which has been recognised as linked with the growth of human hair For example, JP 58162511 describes an oral preparation for the growth and generation of hair which is prepared from L-cysteine and other amino acids RO 99940 describes a lotion for combatting scurf and regenerating hair comprising a blend of cysteine and

methionine with inorganic sulphates and herb extracts. DE 1617477 describes a hair tonic which is said to stimulate hair roots to produce new growth which comprises 0.3%

cysteine mixed with an array of other substances including vitamins, hormones, other amino acids and salicylic acid. JP 56087514 mentions that cystine or cysteine have attracted attention as promoters for the growth of hair but may cause problems due to lack of oxidation stability. Dithioglycollic acid is taught as a suitable replacement.

Many formulations have been proposed over the years for the promotion of the growth of human hair or the curing or prevention of baldness However, there is no discussion in the prior art of an effect on the mechanical properties of the existing hair fibre as such.

Increasing hair diameter leads to concomitant increases in hair bending stiffness and tensile strength For example, the former parameter can be represented as an index calculated on the basis of the 2nd moment of area of the hair's transverse section (a concept used in the engineering industry to predict the relative bending resistance of different structures), hence the relationship to diameter. Increasing hair bending stiffness and tensile strength leads to an increase in the way the hair "stands-off" from the scalp, the property known as "root lift". Related to this is the consumer's perception of improved fullness, body and volume. The diameter of the hair has been reported by

Tolgysi J. Soc. Cosm. Chem. 7. 571-578 (1976) to have a

particularly strong effect on hair body.

Consequently, there exists a need for substances which may be topically supplied to the human hair or scalp to increase the diameter of a thinning hair, or to maintain the fibre

diameter at its maximum potential.

Fratini et al (J. Invest Dermatol 102: 178-185, 1994) have shown that the abomasal or intravenous infusion of either cysteine or methionine into sheep consuming roughage-based (i.e. nutritionally poor) diets stimulates wool growth and increased the sulphur content of the "new" wool. Cysteine infusion usually leads to an increase in wool growth rate and an increase in fibre diameter of 5-10% , typically 1-3um.

Surprisingly, we have found that the levels of cysteine in plucked human hair roots are very low or undetectable in comparison with other amino acids, and that this deficiency is apparent irrespective of the subject's state of nutrition. We have further established, from in vitro studies using isolated human hair follicles, that the administration to the hair follicle of a composition comprising cysteine has a thickening effect on the hair fibre. It is unexpected that the mechanical properties of the normal human hair fibre would be critically dependent on supplementation with

cysteine, since in the studies on sheep discussed above, the animals were initially underfed in order for the effect of cysteine or methionine supplementation to become apparent. Moreover, the cysteine or methionine was supplied to the sheep by endogenous delivery rather than exogenous

application. Furthermore, the wool fibre comprises only one cuticle cell fibre layer (human hair comprises 8-10) and is designed to be shed and regenerated every year.

Accordingly, the present invention provides a cosmetic method for imparting body and volume to human hair comprising increasing the diameter of the hair fibre by supplementation of the hair root with a composition comprising between 0.01 to 10% by weight cysteine or a derivative thereof, wherein the cysteine or derivative thereof is delivered to the hair root by topical application of the composition to the hair and/or the scalp.

Cysteine can be incorporated into a composition for topical application to the hair and/or scalp, for imparting body and volume to human hair.

A convenient source of the cysteine is a protein hydrolysate. Protein hydrolysates are a source of amino acids in both free and peptide form. Preferably, the amino acids are more than 50% free. The hydrolysate must have a significant cysteine content. Preferably, at least 2% of the amino acids in the hydrolysate are cysteine/cystine. The use of hydrolysates reduces the odour problems sometimes encountered with the sulphur containing amino acids and may reduce the extent of stimulation of dandruff and other foreign organisms on the scalp or in the region of the hair root. Furthermore, there appears to be benefit from use of a hydrolysate which is greater than the contribution expected, in terms of hair nutrition, from the individual amino acids. It is also possible, and may sometimes be more convenient, to employ simple derivatives of cysteine, such as salts, preferably hydrosalts. A particularly preferred example of a hydrosalt is a

hydrohalide, especially the hydrochloride derivative.

It is further possible to employ other derivatives of

cysteine including acyl, ester and peptide derivatives.

These too may be used as salts or hydrosalts.

Examples are derivatives of cysteine having the structure (1): SR₁

(CH₂)

CHNHR²

COOR³ where R¹ is chosen from: (i) H-,

(ii) R³COO-CH(NHR²)-(CH₂) -and,

(iii) R³COO-CH(NHR²)-(CH₂) -S-; and where R³ is chosen from:

(i) H-,

(ii) C_xH_y-, and

(iii) C_xH_yCO-;

(iv) amino acid residues, or substituted amino acid

residues where any free -NH₂ group is modified to form a -NHCOC_xH_y or a -NHC_xH_y group, and/or any free -COOH group is substituted to form a COOR³ group,

(v) peptide residues comprising from 2 to 8 amino acid

residues or substituted amino acid residues, which are substituted as defined in (iv) above; the amino acid residues or substituted amino acid residues, as herein defined, being derived from one or more of the following amino acids:

L-α-alanine

L-β-alanine

L- arginine

L- γ - amino butyric acid

L- aspartic acid

L- citrulline

L- cysteine

L- cystine

L- 3,4-dihydroxyphenylalanine (DOPA)

L- glutamine

L- glutamic acid

L- glycine

L- histidine

L- homoserine

L- hydroxylysine

L- hydroxyproline

L- isoleucine

L- leucine

L- lysine

L- methionine

L- ornithine

L- phenylalanine

L- proline

L- serine L- threonine

L- N,N,N-trimethyl glycine (betaine)

L- tryptophan

L- tyrosine, and

L- valine; and where R³ is chosen from :

(l) H⁺

(ii) alkali metal cations chosen from Na⁴ , K⁺ and Li⁺,

(m) NH₄ ⁺ or alkanolammonium ions, and

(iv) C_xH_y -; where x is an integer of from 1 to 22 and

y is an integer of from 3 to 45

Preferred examples of cysteine derivatives where the group R² is an amino acid residue are the dipeptide's: L- α-alanylcysteine

L- β-alanylcysteine

L- asparaginylcysteine

L- citrulinylcysteine

L- cysteinylcysteine

L- 3,4-dihydroxyphenylalanlycysteine

L- cystinylcysteine

L- glutaminylcysteine

L- glutamylcysteine

L- methionylcysteine, and

L- tyrosinylcysteine

Preferred examples of cysteine derivatives where the group R² is a peptide residue are the tripeptide's: L- α-alanylmethionylcysteine

L- methionylglutaminylcysteine

L- citrulinylglutamylcysteine

Preferred examples of cysteine derivatives where the group R² is an acyl group are N-alkanoyl derivatives in which the alkanoyl moiety has an alkyl chain length of from 3 to 20 carbon atoms, preferably from 4 to 10 carbon atoms, e.g. N-butanoylcysteine, N-hexanoylcysteine and N-octanoylcysteine.

Preferred examples of cysteine derivatives where the group R³ is an alkyl group are those in which the alkyl group is straight chain and of from 1 to 20 carbon atoms, preferably from 1 to 4 carbon atoms, e.g. methylcysteine, ethylcysteine and n-propylcysteine.

The total amount of cysteine or cysteine derivative present in the composition for use in the method according to the invention is between 0.01 and 10% by weight, which upper limit is influenced by solubility considerations. Preferably the cysteine or derivative thereof is used at a level of between 0.05 and 5% by weight, most preferably between 0.1 and 0.5% by weight. The cysteine solution utilised in the formulation of

compositions for use in the method of the invention is suitably of a concentration between 0.04 mMolar and 6 mMolar, preferably m. The composition for use in the method according to the invention can be formulated as a shampoo and will then accordingly comprise one or more surfactant which are

cosmetically acceptable and suitable for topical application to the hair. Preferred surfactants, which may be used singularly or in combination, are selected from anionic, nonionic, amphoteric and zwitterionic surfactants, and mixtures thereof. Suitable anionic surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl lsethionates, alkyl succinates, alkyl sulphosuccinates, N-alkoyl

sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium, magnesium, ammonium and mono-, di- and

triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule.

Examples of suitable anionic surfactants include sodium oleyl succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl lsethionate, sodium lauroyl lsethionate and sodium N- lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl

sulphate, triethanolamine monolauryl phosphate, sodium lauryl ether sulphate 1 EO, 2EO and 3EO, ammonium lauryl sulphate and ammonium lauryl ether sulphate 1EO, 2EO and 3EO.

Nonionic surfactants suitable for use in compositions for use in the invention may include condensation products of aliphatic (C₈ - C₁₈) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups. Other suitable nonionics include mono- or di-alkyl alkanolamides. Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide.

Further suitable nonionic surfactants are the alkyl

polyglycosides (APG's). Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APG's are defined by the following formula:

RO - (G)_n wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.

R may represent a mean alkyl chain length of from about C₅ to about C₂₀. Preferably R represents a mean alkyl chain length of from about C₈ to about C₁₂. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C₅ or C₆ monosaccharide residues, and is preferably a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose. The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Preferably, the value of n lies in the range of from about 1.1 to about 2. Most preferably the value of n lies in the range of from about 1.3 to about 1.5.

Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those

materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel. Amphoteric and zwitterionic surfactants suitable for use in compositions for use in the invention may include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl

carboxyglycinates, alkyl amphopropionates,

alkyllamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Examples include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate.

The surfactant(s) may be present in compositions for use in the invention in a total amount of from about 1 to about 40% by weight, preferably from about 2 to about 30% by weight.

Compositions for use in the invention may also contain one or more hair conditioning agents, as are well known in the art. Such conditioning agents may include cationic surfactants, cationic polymers, volatile or non-volatile silicones and other materials which are known in the art as having

desirable hair conditioning properties.

Such compositions may optionally include a deposition polymer to aid deposition of the conditioning agent(s) onto the hair. Suitable deposition polymers include cationic guar gum derivatives, cationic polyacrylamides and cationic guar gum derivatives, cationic polyacrylamides and cationic cellulose ether derivatives. Particularly preferred are those cationic guar gum derivatives given the CTFA designation guar

hydroxypropyl trimonium chloride, available commercially for example as JAGUAR C13S.

As further optional components for inclusion in compositions for use in the invention, in addition to water, may be mentioned the following conventional adjunct materials known for use in cosmetic compositions: suspending agents,

thickeners, pearlescing agents, opacifiers, salts, perfumes, buffering agents, colouring agents, emollients, moisturisers, foam stabilisers, sunscreen materials, antimicrobial agents, preservatives, natural oils and extracts, propellants.

The composition for use in the invention can be formulated as a shampoo or hair conditioner, or as a liquid or gel, or 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 container to suit its viscosity and intended use by the consumer. For example, a shampoo, conditioner, liquid, gel, lotion or fluid cream can be packaged in a bottle or a sachet 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.

The invention further provides the use of cysteine, or a derivative thereof, in a cosmetic method for imparting body and volume to human hair as above described.

The compositions for use in the invention are primarily intended for topical application to the hair and/or scalp of the human subject to impart body and volume to the hair by increasing hair diameter. The amount of the composition and the frequency of application to the hair and/or scalp can vary widely, depending on personal needs, but it is suggested as an example that topical application of from 0.1 to 5g daily containing from 0.01 to 10% by weight cysteine or a

derivative thereof over the period of at least six months will in most cases result in an increase in hair diameter and hence an improvement in hair body and volume.

The invention will now be illustrated by the following non-limiting Examples, in which:

Figure 1 is a graph showing cumulative hair growth

(mm) with time for different

concentrations of cysteine;

Figure 2 is a graph showing the up-take of

cysteine by hair follicles as a function of cysteine concentration;

Figure 3 is a graph showing the effect of cysteine

reversal on cumulative hair growth (mm) with time;

Figure 4 is a graph showing the effect of cysteine

concentration on the diameter (μm) of

hair fibres;

Figure 5 is a graph showing the ratio of in vitro

to in vivo hair diameter for different

concentrations of cysteine; and Figure 6 is a graph showing the influence of

cysteine availability on hair fibre

diameter. EXAMPLES

Eyaluation of Efficacy of Cysteine using the In Vitro Hair Follicle Growth Test The effect of cysteine on hair diameter was assessed using an in vitro test which uses isolated human hair follicles in a culture medium.

Example 1

Growth of Human Hair In Vitro is dependent upon the

Concentration of Cysteine in the Medium

Human hair follicles were isolated from scalp skin by the methods described by Philpott et al J Cell Science 97 463- 471, 1990. Follicles isolated in this way are undamaged and are capable of growth in vitro for several days at rates comparable with those described for hair growth in vivo.

Follicles isolated in this way were cultured as described by Westgate et al Br. J. Dermatol 129 372-379, 1993 in a

completely defined culture medium called Williams E medium (obtainable from ICN FLOW), the latter supplemented with antibiotics, glutamine, hydrocortisone and Insulin. In this example the concentration of cysteine + cystine (referred to as half cystine) was varied and the daily rate of growth of follicles measured. The results are shown in Table 1, and Figure 1 and demonstrates that growth increases with cysteine concentration in the medium. Example 2

Incorporation of cysteine into human hair in vitro is

concentration dependent

Follicles were isolated as described in Example 1 and

cultured for 5 hours in the presence of a range of

concentrations of cysteine, a small proportion of which was radiolabelled. After 5 hours the follicles were transferred to normal supplemented Williams E medium to "chase" the radioactivity into the fibre being grown in the follicle, for 48 hours. The hair fibre was isolated from each follicle using a combination of detergent and enzyme and the 'naked' fibre dissolved and subjected to liquid scintillation

counting. Results are shown in Figure 2 and Table 2.

Example 3

Addition of Cysteine can increase the growth rate of human hair in vitro

Human hair follicles were isolated as described in Example 1 and placed into culture in Williams E medium formulated to contain a lower concentration of cysteine. Follicles were cultured for 2 days in this medium then transferred to medium containing a higher amount of cysteine. Results are shown in Table 3 and Figure 3 and demonstrate that the follicles can respond to an increase in the concentration of cysteine in the medium by increasing their growth rate.

Example 4

The diameter of human hair fibres grown in vitro is dependent on the concentration of cysteine used in the medium

Follicles were isolated as described in Example 1 and placed into culture in supplemented Williams E medium containing a range of concentrations of cysteine. Following several days of culture (7-11), follicles were removed from the medium and the fibres isolated from the follicles as described above. The diameter of the fibres was measured using a modified Laser Scan Micrometer (Mitotoyu) coupled to a moving jig which was capable of rotating the fibre through 180° and moving the fibre through the laser beam at intervals of

0.2mm. Each isolated fibre contained a small part which was formally grown in vivo, the diameter of this "in vivo" end of the fibre. The diameter of the fibre grown in vitro was measured at intervals of 0.2mm along the fibre. For

estimation of the effect of different media concentrations of cysteine on diameter, the average in vitro diameter was compared across the treatment concentrations of cysteine and the ratio of in vitro diameter to in vivo diameter was calculated. Results are shown in Table 4 and Figures 4 and 5 and

demonstrate that the diameter of the fibres is dependent on the concentration of cysteine available to the follicles.

Example 5

Addition of cysteine can increase the diameter of human hair in vitro

Follicles were isolated as described in Example 1 and

cultured as described in Example 3. Fibres were isolated and diameter measured as described in Example 4. The results show that the diameter of the fibre has decreased from the in vivo diameter when placed in a lower concentration of cysteine (9.0μM) and increased again when placed in the higher concentration (495.0μM).

The change in diameter was calculated by taking, firstly the diameter at the narrowest part of the fibre for each of the three treatments and secondly the diameter of the fibre during growth after addition of cysteine - deemed to be the in vitro diameter, and taking the ratio of these to the in vivo diameter. The results are shown in Figure 6 and

demonstrate that in follicles where the cysteine

concentration was reversed, the fibre diameter was similarly reversed.

The following examples 6 and 7 illustrate shampoos for use in washing the hair and scalp, and for increasing hair body and volume.

(1) 15,000 cS dimethiconol, added as microemulsion ex Dow Corning

(2) is a 60% silicone emulsion polymer, mol wt 300,000

(3) is a copolymer of a carboxylic acid containing monomer and acrylic esters ex Goodrich.

Claims

1. A cosmetic method for imparting body and volume to human hair comprising increasing the diameter of the hair fibre by supplementation of the hair root with a composition comprising between 0.01 and 10% by weight cysteine, or a derivative thereof, wherein the cysteine or derivative thereof is delivered to the hair root by topical application of the composition to the hair and/or the scalp.

2. A method according to claim 1 in which the cysteine is used at a level of between 0.1 and 0.5% by weight of the composition.

3. A method according to any preceding claim in which the source of the cysteine is a protein hydrolysate.

4. A method according to any preceding claim in which the cysteine is delivered to the hair or scalp from a liquid base.

5. A method according to any preceding claim in which the composition is applied to the hair in a vehicle which contains a preservative and which is suitable to remain in contact with the hair and scalp for several hours.

6. A method according to any preceding claim in which the composition is in the form of a lotion that may be applied and left on overnight.

7. A method according to any preceding claim in which the vehicle is a liquid, gel or paste and includes shampoos, conditioners, hair sprays, styling gels and lotions.

8. The use of cysteine, or a derivative thereof, in a cosmetic method for imparting body and volume to human hair according to any one of claims 1 to 6.