AU2012230351A1 - Peptide-based hair colorants - Google Patents

Abstract

Dye composition comprising a peptide dye, said peptide dye comprising a peptide covalently bound to a negatively charged reactive dye; in which the peptide dye is obtainable by reacting a peptide containing a primary amine, secondary amine, OH, SH group or mixtures with a negatively charged reactive dye.

Description

WO 2012/126987 PCT/EP2012/055085 PEPTIDE -BASED HAIR COLORANTS The present invention relates to a hair care composition comprising a dye and a method for dying the hair using said composition. 5 Background W02006/028503 (Dupont) discloses hair binding peptides covalently bound to certain dyes. The linkage is done via carboxylic acid, alcohol, amine or aldehyde 10 groups which must be present on the dye. FR 2 456 764 (L'Or6al) discloses quaternary amine polymer linked to dyes for the colouration of hair. The dyes used do not carry negatively charged substituents. 15 US 4 228 259 (L'Or6al) discloses a dye for keratinic material comprises a water soluble cationic polymer. W02008/009579 (Ciba) and W02009/090121 to W02009/090125 (BASF) disclose cationic dyes covalently linked to polymers for the colouration of hair. 20 Co-pending Unilever application no. PCT/CN2010/071156 discloses hair dye compositions comprising a positively charged polymer covalently bound to a negatively charged reactive dye. 25 Despite the prior art there remains a need for simpler routes to binding dyes to hair binding peptides.

WO 2012/126987 PCT/EP2012/055085 -2 Description of the Invention The present invention provides a dye composition comprising a peptide dye, said peptide dye comprising a peptide covalently bound to a negatively charged 5 reactive dye; in which the peptide dye is obtainable by reacting a peptide containing a primary amine, secondary amine, OH, SH group or mixtures with a negatively charged reactive dye. In a second aspect the invention provides a method of colouring the hair by 10 application of the above described composition to the hair. Detailed description of the invention In the context of the present application the term "MB 50 " refers to the 15 concentration of the binding peptide that gives a signal that is 50% of the maximum signal obtained in an ELISA-based binding assay. The MB 50 provides an indication of the strength of the binding interaction or affinity of the components of the complex. The lower the value of MB 50 , the stronger the interaction of the peptide with its corresponding substrate. 20 The term "binding affinity" refers to the strength of the interaction of a binding peptide with its respective substrate. The binding affinity is defined herein in terms of the MB 50 value, determined in an ELISA-based binding assay. 25 The composition can be used to dye any material, preferably it is used to dye keratinous material, more preferably it is a hair dye composition.

WO 2012/126987 PCT/EP2012/055085 -3 Dye Peptide The composition of the invention comprises a dye-peptide comprising a peptide covalently bound to a negatively charged reactive dye. 5 In the context of this invention dye peptide and peptide dye can be used interchangeably. A hydrolysed reactive dyes is one in which the reactive groups has reacted with 10 the hydroxide anion, HO-, rather than the polymer. A reactive dye that has two reactive groups, where one reactive group has reacted with the peptide to form a covalent bond and one reactive group has reacted with HO-, is not classed as a hydrolysed reactive dye in the context of the invention. 15 Equally a reactive dye that has three reactive groups where one or two reactive groups have reacted with the peptide to form covalent bonds and one or two reactive groups have reacted with HO-, is not classed as a hydrolysed reactive dye in the context of the reaction. 20 A hydrolysed dye has no covalent bond to the peptide. The composition of the invention preferably comprise less than 1 00ppm of hydrolysed reactive dye per 1 0000ppm of dye peptide., more preferably less than 50ppm, most preferably less than 5ppm. Most preferably hydrolysed reactive dyes 25 are not present in the composition. Such dyes may be removed by dialysis or careful control of the reactions conditions. It is found that the absence of hydrolysed dye reduced the staining on textiles.

WO 2012/126987 PCT/EP2012/055085 -4 A reactive dye that has two reactive groups, where one has reacted with the peptide to form a covalently bond and one has reacted with HO-, is not classed as a hydrolysed dye in the context of the invention. 5 Preferably the composition comprises from 0.01 to 15wt% of dye peptide in the total composition, more preferably from 0.2 to 1 Owt% most preferably from 0.5 to 3wt% of the dye peptide. Reactive dye 10 Reactive dyes are described in Industrial Dyes (K.Hunger ed, Wiley VCH 2003). Many Reactive dyes are listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). 15 Reactive groups are preferably selected from heterocyclic reactive groups and, a sulfooxyethylsulfonyl reactive group (-SO 2

CH

2

CH

2

OSO

3 Na). The sulfooxyethylsulfonyl reactive group converts to a vinyl sulfone in alkali. 20 The heterocyclic reactive groups are preferably nitrogen contains aromatic rings bound to a halogen or an ammonium group or a quaternary ammonium group, which react with NH 2 or NH groups of the peptides to form covalent bonds. The halogen is preferred, most preferably Cl or F. 25 Preferably the reactive dye contains more than one reactive group, preferably two or three. Preferably, the reactive dye comprises a reactive group selected from dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, WO 2012/126987 PCT/EP2012/055085 -5 vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and trichloropyrimidine. With the exception of copper phthalocyanine based dyes the dye does not 5 comprise a metal complex dyes , preferably the dye does not comprise a based azo metal complex dye. The reactive group may be linked to the dye chromophore via an alkyl spacer for example: dye-NH-CH 2

CH

2 -reactive group. 10 Especially preferred heterocylic reactive groups are RN R 0 1 N Y, X N N X 0NN R1 r 1 O, IaN C N N X ,,N XN C H CI H N1 Z1 X N Cl; CI 15 Wherein R 1 is selected from H or alkyl, preferably H. X is selected from F or Cl When X = Cl, Z 1 is selected from -Cl, -NR 2

R

3 , -OR 2 , -SO 3 Na When X=F, Z 1 is selected from -NR 2

R

3

R

2 and R 3 are independently selected from H, alkyl and aryl groups. Aryl groups 20 are preferably phenyl and are preferably substituted by -SO 3 Na or SO 2

CH

2

CH

2

OSO

3 Na. Alkyl groups are preferably methyl or ethyl. The phenyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups 25 include -CH 3 , -C 2

H

5 , and -OCH 3 WO 2012/126987 PCT/EP2012/055085 -6 The alkyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups include -CH 3 , -C 2

H

5 , -OH, -OCH 3 , -OC 2

H

4 0H. 5 Most preferred heterocylic reactive groups are selected from CI CI N N N --SOO2CH2CH2OSO3Na N 4 N N N N N H H and H H Where n=1 or 2, preferably 1. 10 Preferably the reactive dye contains more than one reactive group, preferably two or three. Preferably, the reactive dye comprises a chromophore selected from azo, 15 anthraquinone, phthalocyanine, formazan and triphendioaxazine. Where the dye is an azo dye it is preferred that the azo dye is not an azo-metal complex dye. Preferably, the reaction of the peptide and the reactive dye to form the dye 20 peptides, takes place in water at alkaline pH, preferable pH=1 0 to 11.5, at temperature of 40-1 OC for 0.5 to 3 hours after the dye is added to the solution. Thereafter the solution is cooled to room temperature and neutralised to pH=7 within 1 to 2 hours. The total level of peptide in the reaction solution is preferable 2 to 50, more preferably from 5 to 20wt%. These conditions minimise the 25 production of hydrolysed dye. Examples of reactive dyes include reactive black 5, reactive blue 19, reactive red 2, reactive blue 171, reactive blue 269, reactive blue 11, reactive yellow 17, WO 2012/126987 PCT/EP2012/055085 -7 reactive, reactive orange 4, reactive orange 16, reactive green 19, reactive brown 2, reactive brown 50. Reactive blue dyes are preferably selected from anthraquinone, mono azo, bis 5 azo, triphenodioxazine, and phthalocyanine, more preferably anthraquinone, bis azo, and triphenodioxazine, most preferably bis-azo and triphenodioxazine. A preferred blue bis-azo dye is of the form N N 6N 10 NaO 3 S SO 3 Na Where one or both of the A and B rings are substituted by a reactive group. The A and B rings may be further substituted by sulphonate groups (SO 3 Na). The A and B rings may be further substituted with suitable uncharged organic 15 groups, preferably with a molecular weight lower than 200. Preferred uncharged organic groups are -CH 3 , -C 2

H

5 , and -OCH 3 A preferred blue anthraquinone dye is of the form O NH 2 SO 3 Na O HNO 20 Where the C ring is substituted by a reactive group. The dye may be further substituted with sulphonate groups (SO 3 Na) and suitable uncharged organic WO 2012/126987 PCT/EP2012/055085 -8 groups, preferably with a molecular weight lower than 200. Preferred uncharged organic groups are-CH 3 , -C 2

H

5 , and -OCH 3 . A preferred blue triphenodioxazine dye is of the form 5 CI CI Where the D and E rings are substituted by a reactive groups. Preferably the D and E rings are further substituted by sulphonate groups (SO 3 Na). 10 Examples of reactive blue dyes are reactive blue 2, reactive blue 4, reactive blue 5, reactive blue 7, reactive blue 15, reactive blue 19, reactive blue 27, reactive blue 29, reactive blue 49, reactive blue 50, reactive blue 74, reactive blue 94, reactive blue 246, reactive blue 247, reactive blue 247, reactive blue 166, reactive 15 blue 109, reactive blue 187, reactive blue 213, reactive blue 225, reactive blue 238, reactive blue 256. Further structures are exemplified below:

SO

3 Na NaO 3 S

SO

3 Na HN NH 0 NH 2 N NH SO 3 Na N N CIN NaO3S SO3Na CI N ),N6 H C1 CI H ~c~SO 3 Na NaO 3 S NaO 3

SOH

2

CH

2

CO

2 S NH 0 NH 2 N SO 2

CH

2

CH

2

OSO

3 Na N 5 N NaO 3 S SO 3 Na WO 2012/126987 PCT/EP2012/055085 -9 CI I NaO 3 S S3Na NaO 3 H N N N N ' Ol -N SO3Na NaO3 & N N SO3Na CI CI Reactive Red dyes are preferably selected from mono-azo and bis-azo dyes. 5 A preferred reactive red azo dye is of the form P 'J NH 0 HN NaO 3 S SO 3 Na Where the F ring is optionally extended to form a naphthyl group and is optionally 10 substituted by groups selected from sulphonate groups (SO 3 Na) and a reactive group. G is selected from a reactive group, H, or alky group. A reactive group must be present on the dye. 15 Examples of reactive red dyes are reactive red 2, reactive red 3, reactive red 4, reactive red 8, reactive red 9, reactive red 12, reactive red 13, reactive red 17, reactive red 22 ,reactive red 24, reactive red 29, reactive red 33 reactive red 139, reactive red 198 and reactive red 141. 20 Reactive yellow and orange dyes are preferably selected from mono-azo dyes. Examples of reactive yellow and orange dyes are reactive yellow 1, reactive yellow 2, reactive yellow 3, reactive yellow 16, reactive yellow 17, reactive yellow WO 2012/126987 PCT/EP2012/055085 -10 25 , reactive yellow 39, reactive orange 107, reactive yellow 176 and reactive yellow 135. Combination of reactive dyes may be used to obtain a wide colour palette with use 5 of a limited number of dyes. Preferably a trichromate system consisting of a mixture of three reactive dyes. Preferably the trichromate system contains a combination of a reactive blue or a reactive black dye, a reactive red and a reactive yellow dye. For example reactive black 5, reactive yellow 176 and reactive red 239; reactive blue 176, reactive yellow 176 and reactive red 141. 10 Preferably, each peptide molecule should be covalently bound to at least one dye molecule, preferably more than two. To avoid differential build up on multiple treatments, if more than one colour is 15 present, for example a reactive red and a reactive blue, they are preferably bound to the same peptide backbone. Preferably, the dye peptide is obtainable by reacting the peptide with from 0.1 to 20wt% of reactive dye, most preferably from 1 to 1 Owt%. 20 Peptide The peptide comprises a free -SH, -OH, -NH or -NH 2 group for reaction with the dye. More preferably, the peptide contains at least one -NH or -NH 2 group. 25 Peptides of the invention have preferably from 5 to 50 amino acids, more preferably from 10 to 25. Preferably, at least one of the amino acid is selected from arginine or lysine, more 30 preferably lysine. Most preferably the peptide contains 2 to 3 lysine groups.

WO 2012/126987 PCT/EP2012/055085 - 11 When polyamine is referred to as being covalently bound to a reactive dye one skilled in the art will understand that the reactive group is no longer present in the dye peptide. This is exemplified below for three reactive groups: o O H 2 N-peptide 0 NHpeptide || H 2

H

2 || || H 2 I dye-S-C -C -OSO 3 Na -: dye-S-C=CH 2 3 dye-S-C -CH 2 11 alkali 11 H alkali 11 o 0 0 CI NHpeptide H N H 2 N-peptide H N dye-N N ki dye-N N N__ alkali CI CI F NHpeptide H N H 2 N-peptide H N dye-N N al dye-N N N__ alkaliN 5 NHPh NHPh The peptide-based hair colorants of the present invention are obtainable by coupling a hair-binding peptide (HBP) with a negatively charged reactive dye (D). 10 Preferably, each peptide molecule should be covalently bound to one dye molecule. Any peptide may be used. The peptide is preferably a hair-binding peptide. The 15 hair-binding peptide part of the peptide-based hair colorant binds strongly to the hair, thus keeping the colouring agent attached to the hair for a long lasting hair colouring effect. Preferred peptides and their synthesis are disclosed in W02006/028503. The hair-binding peptides include, but are not limited to, hair-binding peptides selected by the screening methods 20 described in WO/2006/028503, WO/2006/094093 and WO/2006/094094. Preferably the peptide comprises at least 80%, preferably 90%, most preferably 100% of the amino acid sequence homology selected from hair binding peptides WO 2012/126987 PCT/EP2012/055085 -12 disclosed W02006/028503. Of particular interest are those disclosed in W02006/028503 SEQ ID NOs:5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41,42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 64 5 66, 69, and 70. For bleached hair, the fingernail-binding peptide, given as SEQ ID NO:60, may also be used Composition 10 Unless specified otherwise, all wt% values quoted hereinafter are percentages by weight based on total weight of the hair treatment composition. Where the composition is a hair conditioning composition it will preferably further comprise a conditioning active such as fatty alcohol and/or fatty acid and/or fatty 15 ester and/or fatty amide, and/or a cationic surfactant and/or silicone to improve the feel of the hair. It is preferred if the compositions are formulated in an aqueous base. 20 Preferably, the composition has a pH of from 2 to 11, more preferably from 3 to 9. The pH may be controlled by the use of common buffers and/or alakalis such as NaOH, NH 4 0H and/or acid such as HCI.

WO 2012/126987 PCT/EP2012/055085 -13 Product Form Compositions of the present invention are formulated into hair colouring compositions which may take a variety of forms, including, for example, mousses, 5 gels, lotions, creams, sprays and tonics. These product forms are well known in the art. The preferred product is a lotion, cream, spray, aerosol mousse or gel. 10 This invention is particularly relevant for dying human hair. Method of application The method of application is to apply the composition to the hair preferably to wet 15 hair, the composition is preferably left on the hair for up to 60 minutes, more preferably up to 30 minutes before it is removed by rinsing. EXAMPLES 20 The invention will now be illustrated by the following non-limiting Examples. Example 1 Peptides with the sequences 25 (a) Thr Asp Met Gln Ala Pro Thr Lys Ser Tyr Ser Asn (b) Trp His Asp Lys Pro Gln Asn Ser Ser Lys Ser Thr (c) Gly Pro His Asp Thr Ser Gly Gly Val Arg Pro Asn Leu His His Thr Ser Lys Lys Glu Lys Arg Glu Asn Arg Lys Val Pro Phe Tyr Ser His Ser Val Thr Ser Arg Gly Asn 30 Val WO 2012/126987 PCT/EP2012/055085 -14 are prepared according to W02006/028503. Peptide (a) is added to demineralise water such that the peptide:water weight 5 ratio is 20:1 To this was added the bis-azo dye with structure:

,S

3 Na Na3Sc3L

SO

3 Na HN NH 0 NH 2 N NH SO 3 Na N NCI NaO 3 S SO 3 Na CIN N The mol ratio of peptide: reactive dye is 2:1. The solution is heated to 343 K and 10 mixed for 45 minutes before the addition of 100g/L of soda ash. The solution is stirred for a further 45 minutes at 343K, before cooling and adjusting the pH to 7 using 2M HCl. Preferably the composition contains from 0.2 to 10wt% of the total composition of the dye polymer, more preferably from 0.5 to 3wt%. 15 The experiment is repeated for peptide (b) and (c) except al :1 mix of the following dyes was used: NaO 3

SOH

2

CH

2

CO

2 S NH 0 HN N N SO 3 Na H NaO 3 S SO 3 Na I NaO 3 S H3Na NaO 3 S H H N N N N N N N O N SO 3 Na NaO 3 S / f N

SO

3 Na CI CI 20 When applied to bleached blond hair a blue/black colour is achieved.

Claims (10)

1. Dye composition comprising a peptide dye, said peptide dye comprising a peptide covalently bound to a negatively charged reactive dye; in which the 5 peptide dye is obtainable by reacting a peptide containing a primary amine, secondary amine, OH, SH group or mixtures with a negatively charged reactive dye.

2. Dye composition according to claim 1 in which the peptide comprises at 10 least one amino acid having a side chain comprising an amino group.

3. Dye composition according to any preceding claim in which the peptide comprises at least one amino acids selected from arginine or lysine, preferably lysine. 15

4. Dye composition according to any preceding claim in which the peptide comprises at least 80%, preferably 90%, most preferably 100% of the amino acid sequence homology selected from the group consisting of (a)Thr Asp Met Gln Ala Pro Thr Lys Ser Tyr Ser Asn 20 (b) Trp His Asp Lys Pro Gln Asn Ser Ser Lys Ser Thr (c) Gly Pro His Asp Thr Ser Ser Gly Gly Val Arg Pro Asn Leu His His Thr Ser Lys Lys Glu Lys Arg Glu Asn Arg Lys Val Pro Phe Tyr Ser His Ser Val Thr Ser Arg Gly Asn Val 25

5. Dye composition according to any one of claims 1 to 4 in which the hair binding peptide is from 7 to 25 amino acids and has a binding affinity for hair, measured as MB 50 equal to or less than 10-5 M. WO 2012/126987 PCT/EP2012/055085 -16

6. Dye composition according to any preceding claim in which the composition comprises less than 1 00ppm of a hydrolysed reactive dye per 1 0000ppm of dye peptide. 5

7. Dye composition according to any preceding claim comprising from 0.2 to 10% by weight of the total composition of hair dye peptide.

8. Dye composition according to any preceding claim wherein the reactive dye comprises a reactive group selected from dichlorotriazinyl, 10 difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and trichloropyrimidine.

9. Composition according to any preceding claim that is a hair dye 15 composition.

10. Method for dying hair comprising the steps of applying to the hair a composition as described in any one of the previous claims. eolf-seql.txt SEQUENCE LISTING <110> Unilever plc Unilever nv <120> Composition <130> G3151 <160> 3 <170> PatentIn version 3.5 <210> 1 <211> 12 <212> PRT <213> Artificial Sequence <220> <223> Hair deposition peptide <400> 1 Thr Asp Met Gln Ala Pro Thr Lys Ser Tyr Ser Asn 1 5 10 <210> 2 <211> 12 <212> PRT <213> Artificial Sequence <220> <223> Hair deposition peptide <400> 2 Trp His Asp Lys Pro Gln Asn Ser Ser Lys Ser Thr 1 5 10 <210> 3 <211> 40 <212> PRT <213> Artificial Sequence <220> <223> Hair deposition peptide <400> 3 Gly Pro His Asp Thr Ser Gly Gly Val Arg Pro Asn Leu His His Thr 1 5 10 15 Ser Lys Lys Glu Lys Arg Glu Asn Arg Lys Val Pro Phe Tyr Ser His 20 25 30 Ser Val Thr Ser Arg Gly Asn Val 35 40 Page 1