WO2005077319A2

WO2005077319A2 - Hair treatment compositions comprising a protein disulfide isomerase

Info

Publication number: WO2005077319A2
Application number: PCT/EP2005/001062
Authority: WO
Inventors: Richard Skinner; Laxmikant Tiwari; Christina Vrettou
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2004-02-12
Filing date: 2005-02-02
Publication date: 2005-08-25
Also published as: TW200538157A; WO2005077319A3; AR047963A1

Abstract

The invention provides a hair treatment composition such as a shampoo or conditioner suitable for topical application to style hair and in particular to lengthening the hair. The composition comprises a protein disulphide isomerase or mimic thereof.

Description

HAIR TREATMENT COMPOSITIONS

FIELD OF THE INVENTION

The invention relates to hair treatment compositions. The compositions are particularly suitable for application to style hair and in particular to lengthen it.

BACKGROUND AND PRIOR ART

Many people desire their hair to appear long, straight and shiny. To achieve this straightening devices are sold that mechanically lengthen and straighten the hair, such devices are disclosed in EP 0 511 892.

The present application discloses formulations and processes for lengthening hair.

DESCRIPTION OF THE INVENTION

In a first aspect, the present invention provides a hair treatment composition comprising 0.001 to 20 wt% of the total composition of a protein disulphide isomerase or mimic thereof.

The invention also relates to a hair treatment composition comprising a surfactant or a propellant or mixtures thereof and a protein disulphide isomerase or mimic thereof. A further aspect of the invention is the use of a protein disulphide isomerase or mimic thereof for styling hair, in particular lengthening.

The invention also relates to a method of treating hair by applying to the hair a composition comprising protein disulphide isomerase or mimic thereof

Detailed Description of the Invention

The present invention is based on the finding that protein disulphide isomerase or mimics thereof are particularly useful in styling hair, especially lengthening hair.

In the context of the present invention a mimic is defined as a compound that has the same action on disulphide bonds as a protein disulphide isomerase. Preferably the mimic has at least 5% of the activity of the enzyme it mimics when used to treat a suitable proteinaceous substrate. The activity can be expressed as micromoles of substrate converted per minute per microgram of enzyme or mimic. More preferably it has at least 15% of the activity of the enzyme it mimics. Methods of measuring the activity of a mimic are well known. Any suitable metho.d described in the literature for measuring the mimics activity may be used.

A mimic may have the same amino acid sequence as its parent active site or it may be similar and have the same "key" action. It is preferable if the hair treatment composition is of formula I

Formula I

wherein each R is independently selected from Cι-C₄ alkyl groups, H, carboxylic acids, sulphonic acid groups or hydroxyl groups and each R¹¹ is independently selected from Cι-C₄ groups or H.

It is preferable if at least one of the R¹ group of formula 1 is hydrogen, preferably each R¹ with the formula is a hydrogen group.

It is preferable if at least one of the R¹¹ group of formula 1 is hydrogen, preferably each R¹¹ within the formula is a hydrogen group. In a most preferred every R¹ and R¹¹ group is hydrogen, a commercially available compound of this type is known as (+) -trans-1, 2-bis (2-mercaptoacetamido) cyclohexane, known commercially as vectrase.

In one aspect the total amount protein disulphide isomerase or mimic thereof is generally from 0.001 to 20 wt%, preferably from 0.1 to 10 wt%, more preferably from 0.5 to 5 wt%.

Product Form

The final product form of hair treatment compositions according to the invention may suitably be, for example, shampoos, conditioners, sprays, mousses, gels, waxes or lotions. Particularly preferred product forms are shampoos, post-wash conditioners (leave-in and rinse-off) and hair treatment products such as hair essences.

Shampoo compositions preferably comprise one or more cleansing surfactants, which are cosmetically acceptable and suitable for topical application to the hair. Further surfactants may be present as emulsifiers.

Suitable cleansing surfactants are selected from anionic, amphoteric and zwitterionic surfactants and mixtures thereof. The cleansing surfactant may be the same surfactant as the emulsifier, or may be different. Anionic Cleansing Surfactant

Shampoo compositions according to the invention will typically comprise one or more anionic cleansing surfactants, which are cosmetically acceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkyl 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.

Typical anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl sulpho succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium cocoyl isethionate, sodium lauryl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate (n)EO, (where n ranges from 1 to 3) , ammonium lauryl sulphate and ammonium lauryl ether sulphate (n) EO, (where n ranges from 1 to 3) . The total amount of anionic cleansing surfactant in shampoo compositions of the invention is generally from 5 to 30, preferably from 6 to 20, more preferably from 8 to 16 wt%.

Co-surfactant

The shampoo composition can optionally include co- surfactants, preferably an amphoteric or zwitterionic surfactant, which can be included in an amount ranging from 0 to about 8, preferably from 1 to 4 wt%.

Examples of amphoteric and zwitterionic surfactants include, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines) , alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate.

Another preferred co-surfactant is a nonionic surfactant, which can be included in an amount ranging from 0 to 8, preferably from 2 to 5 wt%.

For example, representative nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (Cs - Cι₈) 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.

Further nonionic surfactants which can be included in shampoo compositions of the invention are the alkyl polyglycosides (APGs) . 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 APGs are defined by the following formula:

RO - (G)„

wherein R is a branched or straight chain C₅ to C₂o alkylor alkenyl group, G is a saccharide group and n is from 1 to 10.

Other sugar-derived nonionic surfactants which can be included in shampoo compositions of the invention include the C₁₀-C₁8 N-alkyl (Cι-C₆) polyhydroxy fatty acid amides, such as the Cι₂-Cχ₈ N-methyl glucamides, as described for example in WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as Cι₀-Cι₈ N- (3-methoxypropyl) glucamide.

The shampoo composition can also optionally include one or more cationic co-surfactants included in an amount ranging from 0.01 to 10, more preferably from 0.05 to 5, most preferably from 0.05 to 2 wt% . Useful cationic surfactants are described hereinbelow in relation to conditioner compositions .

The total amount of surfactant (including any co-surfactant, and/or any emulsifier) in shampoo compositions of the invention is generally from 5 to 50, preferably from 5 to 30, more preferably from 10 to 25 wt%.

Cationic Polymer

A cationic polymer is a preferred ingredient in shampoo compositions of the invention, for enhancing conditioning performance of the shampoo.

Suitable cationic nitrogen polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition

The cationic conditioning polymer will generally be present in compositions of the invention at levels of from 0.01 to 5, preferably from 0.05 to 1, more preferably from 0.08 to 0.5 wt%.

Conditioning Surfactant

Conditioner compositions usually comprise one or more conditioning surfactants, which are cosmetically acceptable and suitable for topical application to the hair.

Suitable conditioning surfactants are selected from cationic surfactants, used singly or in admixture.

Cationic surfactants useful in compositions of the invention contain amino or quaternary ammonium hydrophilic moieties, which are positively charged when, dissolved in the aqueous composition of the present invention. The most preferred cationic surfactants for conditioner compositions of the present invention are monoalkyl quaternary ammonium compounds in which the alkyl chain length is Cι_δ to C₂₂.

Examples of suitable cationic surfactants include quaternary ammonium compounds, particularly trimethyl quaternary compounds .

Preferred quaternary ammonium compounds include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride (BTAC) , cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chloride and salts of these where the chloride is replaced by halogen, (e.g. , bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, or alkylsulphate. Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in hair conditioners of the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Salts of primary, secondary, and tertiary fatty amines are also suitable cationic surfactants.

In the conditioners of the invention, the level of cationic surfactant is preferably from 0.01 to 10, more preferably 0.05 to 5, most preferably 0.1 to 2 wt% of the total composition.

Fatty Materials

Conditioner compositions of the invention preferably additionally comprise fatty materials. By "fatty material" is meant a fatty alcohol, an alkoxylated fatty alcohol, a fatty acid or a mixture thereof.

(Or propoxylated) fatty alcohols having from about 12 to about 18 carbon atoms in the alkyl chain can be used in place of, or in addition to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof.

The level of fatty alcohol material in conditioners of the invention is suitably from 0.01 to 15, preferably from 0.1 to 10, and more preferably from 0.1 to 5 wt%. The weight ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably from 4:1 to 1:8, optimally from 1:1 to 1:7, for example 1:3. Suspending Agents

In a preferred embodiment, the hair treatment composition, especially if it is a shampoo composition, further comprises from 0.1 to 5 wt% of a suspending agent.

Silicone Conditioning Agents

The compositions of the invention can contain, emulsified droplets of a silicone-conditioning agent, for enhancing conditioning performance.

Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly shampoos and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol . Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31188.

A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino function.

The total amount of silicone is preferably from 0.01 to 10

%wt of the total composition more preferably from 0.3 to 5, most preferably 0.5 to 3 wt% is a suitable level. (ii) Non-silicone Oily Conditioning Components

Compositions according to the present invention may also comprise a dispersed, non-volatile, water-insoluble oily conditioning agent.

By "insoluble" is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1% (w/w) , at 25°C.

Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof.

Adjuvants

The compositions of the present invention may also contain adjuvants suitable for hair care. Generally such ingredients are included individually at a level of up to 2, preferably up to 1 wt% of the total composition.

Suitable hair care adjuvants, include amino acids, sugars and ceramides.

Styling Polymers

The hair styling polymer if present is preferably present in the compositions of the invention in an amount of from 0.001% to 10% by weight, more preferably from 0.1% to 10% by weight, such as from 1% to 8% by weight. Hair styling polymers are well known. Suitable hair styling polymers include commercially available polymers that contain moieties that render the polymers cationic, anionic, amphoteric or nonionic in nature. Suitable hair styling polymers include, for example, block and graft copolymers. The polymers may be synthetic or naturally derived.

Examples of anionic hair styling polymers are: copolymers of vinyl acetate and crotonic acid; terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate; copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50% esterified with a saturated alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol; acrylic copolymers containing acrylic acid or methacrylic acid as the anionic radical-containing moiety with other monomers such as: esters of acrylic or methacrylic acid with one or more saturated alcohols having from 1 to 22 carbon atoms (such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t- butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, n-hexyl acrylate, n-octyl acrylate, lauryl methacrylate and behenyl acrylate) ; glycols having from 1 to 6 carbon atoms (such as hydroxypropyl methacrylate and hydroxyethyl acrylate) ; styrene; vinyl caprolactam; vinyl acetate; acrylamide; alkyl acrylamides and methacrylamides having 1 to 8 carbon atoms in the alkyl group (such as methacrylamide, t-butyl acrylamide and n-octyl acrylamide) ; and other compatible unsaturated monomers. The additional styling polymer may also contain grafted silicone, such as polydimethylsiloxane .

Specific examples of suitable anionic hair styling polymers are:

RESYN® 28-2930 available from National Starch (vinyl acetate/crotonic acid/vinyl neodecanoate copolymer) ;

ULTRAHOLD® 8 available from BASF (CTFA designation Acrylates/acrylamide copolymer) ; the GANTREZ®ES series available from ISP Corporation esterified copolymers of methyl vinyl ether and maleic anhydride) .

Other suitable anionic hair styling polymers include carboxylated polyurethanes. Carboxylated polyurethane resins are linear, hydroxyl-terminated copolymers having pendant carboxyl groups. They may be ethoxylated and/or propoxylated at least at one terminal end. The carboxyl group can be a carboxylic acid group or an ester group, wherein the alkyl moiety of the ester group contains one to three carbon atoms. The carboxylated polyurethane resin can also be a copolymer of polyvinylpyrrolidone and a polyurethane, having a CTFA designation PVP/polycarbamyl polyglycol ester. Suitable carboxylated polyurethane resins are disclosed in EP-A- 0619111 and US Patent No. 5,000,955. Other suitable hydrophilic polyurethanes are disclosed in US Patent Nos. 3,822,238; 4,156,066; 4,156,067; 4,255,550; and 4,743,673.

Amphoteric hair styling polymers which can contain cationic groups derived from monomers such as t-butyl aminoethyl methacrylate as well as carboxyl groups derived from monomers such as acrylic acid or methacrylic acid can also be used in the present invention. One specific example of an amphoteric hair styling polymer is Amphomer® (Octylacrylamide/ acrylates/butylaminoethyl methacrylate copolymer) sold by the National Starch and Chemical Corporation.

Examples of nonionic hair styling polymers are homopolymers of N- vinylpyrrolidone and copolymers of N-vinylpyrrolidone with compatible nonionic monomers such as vinyl acetate. Nonionic polymers containing N- vinylpyrrolidone in various weight average molecular weights are available commercially from ISP Corporation - specific examples of such materials are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 630,000 sold under the name PVP K- 90 and are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 1,000,000 sold under the name of PVP K-120.

Other suitable nonionic hair styling polymers are cross- linked silicone resins or gums. Specific examples include rigid silicone polymers such as those described in EP-A- 0240350 and cross-linked silicone gums such as those described in WO 96/31188. Examples of cationic hair styling polymers are copolymers of amino-functional acrylate monomers such as lower alkyl aminoalkyl acrylate, or methacrylate monomers such as dimethylaminoethyl methacrylate, with compatible monomers such as N-vinylpyrrolidone, vinyl caprolactam, alkyl methacrylates (such as methyl methacrylate and ethyl methacrylate) and alkyl acrylates (such as ethyl acrylate and n-butyl acrylate) .

Specific examples of suitable cationic polymers are: copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, available from ISP Corporation as Copolymer 845, Copolymer 937 and Copolymer 958; copolymers of N-vinylpyrrolidone and dimethylaminopropylacrylamide or methacrylamide, available from ISP Corporation as Styleze® CC10;

copolymers of N-vinylpyrrolidine and dimethylaminoethyl methacrylate; copolymers of vinylcaprolactam, N-vinylpyrrolidone and dimethylaminoethylmethacrylate;

Polyquaternium-4 (a copolymer of diallyldimonium chloride and hydroxyethylcellulose) ;

Polyquaternium-11 (formed by the reaction of diethyl sulphate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate) , available from ISP as Gafquat® 734, 755 and 755N, and from BASF as Luviquat® PQ11; Polyquaternium-16 (formed from methylvinylimidazolium chloride and vinylpyrrolidone) , available from BASF as Luviquat® FC 370, FC 550, FC 905 and HM-552;

Polyquaternium-46 (prepared by the reaction of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulphate) , available from BASF as Luviquat®Hold.

Examples of suitable naturally-derived polymers include shellac, alginates, gelatins, pectins, cellulose derivatives and chitosan or salts and derivatives thereof. Commercially available examples include Kytamer® (ex Amerchol) and Amaze® (ex National Starch) .

Also suitable for use as additional styling polymers in the compositions of the invention are the ionic copolymers described in WO 93/03703, the polysiloxane-grafted polymers disclosed in WO 93/23446, the silicone-containing polycarboxylic acid copolymers described in WO 95/00106 or WO 95/32703, the thermoplastic elastomeric copolymers described in WO 95/01383, WO 95/06078, WO 95/06079 and WO 95/01384, the silicone grafted adhesive polymers disclosed in WO 95/04518 or WO 95/05800, the silicone macro-grafted copolymers taught in WO 96/21417, the silicone macromers of WO 96/32918, the adhesive polymers of WO 98/48770 or WO - II

98/48771 or WO 98/48772 or WO 98/48776, the graft polymers of WO 98/51261 and the grafted copolymers described in WO 98/51755.

The invention will now be further illustrated by the following, non-limiting Examples.

EXAMPLES

Reaction Conditions

40mg of L-cystine was added 5ml of HPLC grade water. This solution was ultrasonicated for 15 min and then filtered through a 0.45μm PVDF syringe filter (ca. 0.2mg/ml Yalkovsky, S.H., Dannenfelser, RM, 1992). A solution of (+) -trans-1, 2-bis (2- mercaptoacetamido) cyclohexane was prepared as ImM in methanol. 200μl of the (+) -trans-1, 2-bis (2- mercaptoacetamido) cyclohexane solution was added to 1.5ml of the saturated L-cystine solution. The mixture was thoroughly mixed using a whirlie mixer and immediately analysed for cystine and cysteine levels. Samples were taken every five minutes up to 1 hour as described below.

Capillary Electrophoresis (CE) Instrument Settings Capillary: 8cm x 50μm i.d. (ca.40cm after detection cell) Carrier Electrolyte: 50mM Sodium Tetraborate in water Applied voltage: -17kV Sample introduction: lOmBar for 10 sec at the anode Capillary temperature: 40°C

Detection : UV at 200nm (Response time: 0.1s)

The electrophoregram showed that (+) -trans-1, 2-bis (2- mercaptoacetamido) cyclohexane was acting by reducing the

Cystine, causing the formation of cysteine. This conversion of amino acids with the hair follicle is known to cause hair to lengthen

By measuring the area underneath each peak the concentration of each reaction component could be calculated.

The areas under the cystine and cysteine peaks are shown in the Table 1 below:

Table 1.

Conversion of Cystine to Cysteine with time

The following formulation was prepared:

Examples A, B, 2, 3 and 4 were used to measure the straightening effect on a switch of hair using the following procedure: 20 strands of hair within a lg switch of curly hair were physically uncurled until straight and the their length recorded, the average length was calculated. 6g of product was applied to the lg switch of hair and the treated hair wrapped in cling film and held straight for 14 hours. The switch was washed with a 12 wt% solution of SLES 2EO and 2wt% CAPB, combed straight and allowed to dry naturally. The length of 20 fibres was measured and the average length calculated. The results below show the latter measurement as a percentage of the former measurement.

Carbopol 980 (ex Noveon INC)

The above Examples demonstrate that (+-trans-l, ,2- bis (mercaptoacetamido) cyclohexane straightens both Caucasion and African hair.

Claims

A hair treatment composition comprising 0.001 to 20 wt% of the total composition of a protein disulphide isomerase or mimic thereof.

A hair treatment composition according to claim 1 in which the protein disulphide isomerase or mimic thereof is a compound of formula I

Formula I wherein each R¹ is independently selected from Cι-C₄ alkyl groups, H, carboxylic acids, sulphonic acid groups or hydroxyl groups and each R¹¹ is independently selected from C₁-C₄ groups or H.

3. A hair treatment comprising a surfactant or a propellant or mixtures thereof and a protein disulphide isomerase or mimic thereof.

4. A hair treatment according to claim 3 in which the protein disulphide isomerase or mimic thereof is a compound of formula I

Fomula I wherein each R¹ is independently selected from Cι-C alkyl groups, H, carboxylic acids, sulphonic acid groups or hydroxyl groups and each R¹¹ is independently selected from C₁-C4 groups or H.

5. A hair care composition according to any preceding claim in which each R¹ is a hydrogen group.

6. A hair care composition according to any preceding claim in which each R¹¹ is a hydrogen group.

7. A hair treatment composition according to any preceding claim in which the total amount of protein disulphide isomerase or mimic thereof is from 0.1 to 10 wt% of the total formulation.

8. A hair treatment composition according to any preceding claim which comprises a cationic or silicone based conditioning agent.

9. A hair treatment composition according to any preceding claim which further comprises a styling agent.

10. A hair treatment composition according to any preceding claim which comprises an aqueous base.

11. A method of treating hair by applying to the hair a protein disulphide isomerase or mimic thereof.

12. Use of a a protein disulphide isomerase or mimic thereof for lengthening the hair