Title of Invention

A TWO COMPONENT HAIR/SKIN COLOURING SYSTEM

Abstract A two component hair/skin colouring system comprising: a. a cationic polymer 0.0005 to 0.05 % by wt. ; and b. a synergistic mixture of a natural phenol (weight range 50 - 500 mg/100 ml) and unripe tamarind extract (0.5-5.0 gm/100 ml) in a ratio 1:100 to 1:10 in a buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition metal ion (Fe2+, Fe3+, Cu 2+).
Full Text FORM -2
THE PATENTS ACT, 19
(39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
A TWO COMPONNENT HAIR/SKIN COLOURING SYSTEM
HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the nature of the invention and the manner in which it is to be performed.



GRANTED

19-10-2001

Technical Field:
The present invention relates to compositions for changing the colour of keratinic fibers especially human hair. The composition can also be used to increase the colour of human skin. The composition is especially useful to obtain a range of desired colours on hair.
Background and Prior art:
Melanins are naturally occurring pigments present in hair and skin and are synthesised in the melanocytes in presence of the enzyme tyrosinase. Two different melanins are found in human hair, the blonde, brown and black hair contain eumelanin while Pheomelanin is found in red hair. The enzyme tyrosinase catalyses the hydroxylation of tyrosine to 3,4-dihydroxyphenylalanine (DOPA) and its subsequent oxidation to dopachrome which further undergoes a series of complex reactions to form eumelanins and pheomelanins.
Cosmetic purposes has made the alteration of colouration of hair very popular. The discovery of synthetic hair dyes simplified the process of dyeing hair and gave much more reliable and versatile results in comparison the natural dyes. The

preference to use natural materials is very high although this process has a lot of inconveniences and problems.
Aqueous hair dyeing compositions produced by reaction between DOPA and/or a salt thereof with an inorganic oxidant such as soluble ammonium, sodium and potassium salts of ferricyanide and potassium permanganate in a buffered system
with a pH range of 6 to 10, is reported (US 5279618, Clairol Inc.).

US 5603734 reports a method of permanently colouring hair by applying at least one catechol, a persulphate oxidising agent and a buffering system to provide a pH 7 to 11.

Use of quaternary amines along with compositions reported for colouring hair is known to improve the feel and combability of the hair after treatment (US 4402700).
A novel natural hair colouring process described (Brown et.al., J of Soc. of Cos. Chemists, 48, 1997) relates to a process of converting DOPA on hair to 5,6-dihydroxyindole by careful selection of the oxidant. This indole is a precursor of black eumelanin and it is readily polymerised in situ to dye the hair black. They have also found that incorporation of sulfur-containing nucleophiles such as cysteine and other thiols into the above process produces a wide range of shades on hair.
The prior art relates to the use of inorganic oxidants for the production of melanin on hair and the synthetic hair colourants are toxic and cause allergic reactions in many people.
It has now been found that it is possible to colour hair using a colouring system comprising a cationic polymer and a synergistic mixture of natural plant extract and a phenol and a metal ion. The use of the polymer along with aforesaid components mixture will help in improved deposition of the colour on the hair and also give other benefits like feel and combability etc. It is also possible to generate a wide range of shades by the use of the mixture according to the invention. The product will be safe as the composition is natural based. Since this product increases melanin synthesis, it could also be used on skin to increase skin colour and in tanning preparations.
Tamarindus is a monotypic genus of trees of the family Leguminosae represented by T.indica, indigenous to tropical Africa and South India, It is widely cultivated in the tropics and sub-tropics. The fruit of the tree is the most useful part which contains a sweetish, acidic pulp and hence used for souring of food products. It

has now been found that a synergistic combination of the extract from the unripe fruits of this tree and a natural phenol can act as a hair dye.
Description of the Invention:

According to one aspect the present invention relates to a two component
hair/skin'colouring system comprising:
a. a cationic polymer 0.0005 to 0.05 % by wt.; and
b. a synergistic mixture of a natural phenol (weight range 50 - 500 mg/100
ml) and unripe tamarind extract (0.5-5.0 gm/100 ml) in a ratio 1:100 to 1:10
in a buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition metal ion (Fe2+, Fe3+, Cu2+).
According to another aspect the present invention there is provided a method for

dyeing hair comprising the steps of:
a) mixing a natural phenol, unripe tamarind extract and ferric chloride in a buffered system with a pH range of 4-10
b) applying an aqueous solution of the cationic polymer on to the hair
c) later applying the mixture described in (a)
d) allowing the said mixture to permanently colour the hair by remaining in contact with the hair for 8 - 16 hrs. Alternately step (d) can also be performed by intermittent applications of the mixture for 20 min time periods. Here at least 4-6 applications are recommended for best results.
The process of the invention may conveniently be practiced by providing pre-measured amounts of the reactants in separate containers packed in a kit form. It would be simple for the user to mix the components and subsequently spread the

material on the hair to be dyed. This being a very simple operation can be carried out by anyone and does not require any professional expertise.
According to a further aspect of the invention there is provides/a hair/skin colouring kit, comprising
a) a kit housing ;
b) a cationic polymer 0.0005 to 0.05 % by wt.; and
c) a synergistic mixture of a natural phenol (weight range 50 - 500 mg/100 ml) and unripe tamarind extract (0.5-5.0 gm/100 ml) in a ratio 1:100 to 1:10 in a buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition metal ion (Fe2+, Fe3+, Cu 2+); and
d) instruction manual containing guidance for applying the components (b) and (c) to hair and/o'r skin
The instruction manual may be provided by way of a printed instructions on the body of the kit or separately. The kit is in the form of the container including a cardboard box or the like having the components (b) and (c) above provided in two separate enclosures.
Detailed description of the invention:
The hair/skin colouring Composition of the present invention comprises an aqueous composition comprising a natural phenol and an extract from the unripe fruits of the plant Tamanndus indica. The dyeing of the hair is permanent and by the manipulation of the ingredients a range of colours can be achieved. By "permanent" one means that the colour is not removable by shampooing with standard surfactant based cosmetic shampoos.


Natural Phenol:
A wide variety of naturally occurring compounds having one or more phenolic hydroxyl groups, such as, for example, Catechol or DOPA species, can be utilized in the invention. It may include DOPA or its homologues, analogs or derivatives. It may be chosen from, for example, cysteinyl dopa, alpha alkyl dopa having 1-4, preferably 1 to 2 carbon atoms in the alkyl group, epinephrine, and dopa alkyl esters. Suitable soluble acid salts of dopa are selected from hydrochloride or sulphate salts. The suitable basic salts are the alkali metal salts or alkaline earth metal salts and sodium and potassium salts are preferred. Natural extracts of plants containing high levels (e.g., greater than 1% by weight, preferably greater than 10% by weight, more preferably greater than 50 % by weight) of dopa and other catechols can also be used.
Buffering Agent:
The critical pH to be maintained is between 4 to 10 and preferably a pH between 5-8. Buffers suitable for use in this invention are preferably phosphate or acetate. Others such as carbonates, bicarbonates, borates, TRIS hydroxymethyl aminomethane may also be used.
Plant extract:
The synergistic combination of the extract from the unripe fruits of the tree Tamarindus indica and a natural phenol act as a hair dye. The other parts of the plant such as leaf, flowers, ripe fruits were not found to be useful to have this effect.


Cationic polymers:
The cationic polymer used here is preferably polyethylenimine. A wide variety of cationic polymers are known in the art and can be effectively utilized for the process of the invention. Some of these include polymers of dialkyl/trialkyl ammonium alkyl(meth)acrylate, polysaccharides or ethers or esters of polysaccharides with ammonium side groups, especially guar, cellulose and starch derivatives, polymeric adducts of ethylene oxide with ammonium groups, quaternary ethylenimine polymers, poly (dimethylaminoethyl methacrylate) or copolymers of the same with other acrylates, quaternized poly 1-vinylimidazole, etc.
Optional Ingredients:
Various optional ingredients such as thickeners, organic solvents, surface-active agents, pH adjusting agents, antioxidants, perfumes etc may be employed in the composition.
The organic solvents are included in the composition as co-solvents to assist dissolution of the components of the composition. The level of the organic solvent is preferably 1-10% by weight. Suitable solvents are mono and poly hydric alcohols such as ethyl alcohol, isopropyl alcohol, propylene glycol, benzyl alcohol etc.
Surfactants employed in the composition can be anionic, cationic, nonionic, amphoteric or zwitterionic. To mention a few examples they may be selected from higher alkylbenzene sulphonates, alkylnaphthalene sulphonates, sulphonated esters of alcohols and poly basic acids, taurates, fatty alcohol sulphates, sulphates of branched chain or secondary alcohols, salts of fatty acids or fatty acid mixtures, N-oxyalkylated fatty acid alkanolamides, and others. The surface


active agents may be selected from those given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch. The levels may be from about 0.05 to 15% by weight. The anionic and nonionic surfactants are used as emulsifiers and the cationic surfactants are useful as conditioning agents.
A thickening agent may also be incorporated to increase the viscosity of the formulation. This will enable easy application of the composition on the hair. Thickening agents are selected from sodium alginate, gums, or cellulose derivatives. The quantity to be incorporated will be in the range 0.1 to 20% by weight and the preferred viscosity of the formulation is in the range 100 cps to 10,000 cps.
Certain metal ions such as copper, zinc, nickel, cobalt and iron when present in the composition are known to enhance colour development.
In practice the process of the present invention is conducted at room temperature for a period of up to an hour. Elevated temperatures may be used by the use of a hair dryer. At the end of the dyeing process the hair is washed using a conventional shampoo.
The product can be formulated either in the form of a gel or as a liquid. The invention will now be demonstrated by the following non-limiting examples. In the examples and throughout this specification, all percentages are by weight unless otherwise indicated.


EXAMPLES: Example 1:
Demonstration of the substantivitv of the dve:
Samples of white hair (20-25 strands) were bunched together and dipped in solutions containing polyethyleneimine (PEI), a cationic polymer (solution A) for 20 min and the dye solution comprising DOPA, catechol, FeCI3, and tamarind extract in proportions as shown in Table 1 (solution B), overnight at room temperature. After an overnight incubation the hair were removed, washed twice with shampoo and dried. The colour of the hair was then recorded.
Table 1

Test Conditions Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
Solution A (PEI) 0.00125% ~ 0.00125% 0.00125% — 0.00125%
Solution B:
Dopa 100 mg 100 mg 100 mg — ~ —
Catechol ~ — — 100 mg 100 mg 100 mg
FeCI3 15 mg 15 mg 15 mg 15 mg 15 mg 15 mg
Tamarind Ext. 1 gm 1 gm ~ 1 gm 1 gm ~
Buffer or water To 100 ml To 100 ml To 100 ml To 100 ml To 100 ml To 100 ml
Results Hair was evenly coated black and the dye was stable to repeated shampooing Hair was coated black but the dye was not substantive and was washed off easily Hair was coated black but were very patchy and not evenly coated Hairs were evenly coated black and the dye was stable to repeated shampooing Hair was coated black but the dye was not substantive and was washed off easily Hair was coated black but were very patchy and not evenly coated
It was seen that a pre-rinse in Solution A and the tamarind extract was essential for substantivity of colour.


Example 2:
Demonstration of variations in colour obtained:
By varying the concentrations of catechol, tamarind extract and the pH of the solution, it was possible to get different colours as presented in Table 2.
Table 2

Cone. of catechol 5mg 5mg 10 mg 0.1 mg 0.1 mg
PH 6.8 8.0 8.0 8.0 8.0
Cone, of TE 10mg 10 mg 10 mg 10 mg 25 mg
Water to make up volume to 1 ml 1 ml 1 ml 1 ml 1 ml
Colour obtained Red Green Brown Grey / brown Brown
EXAMPLE 3:
Demonstration of the effect of unripe tamarind extract.
Spectrophotometer readings showing the formation of dopachrome (O.D. 475 nm) only with raw fruit extract and not with ripe fruit extract are as follows.
Table 3

O.D at 475 nm at 5 min O.D at 475 nm at 15 min
Raw fruit 1.338 1.737
Ripe fruit 0.045 0.069
The data presented in Table 3 shows that only when raw fruit is used significant amount of melanin was generated but not when ripe tamarind fruit was used.


WE CLAIM:

1. A two component hair/skin colouring system comprising:
a. a cationic polymer 0.0005 to 0.05 % by wt. ; and
b. a synergistic mixture of a natural phenol (weight range 50 - 500 mg/100 ml)
and unripe tamarind extract (0.5-5.0 gm/100 ml) in a ratio 1:100 to 1:10 in a
buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition
metal ion (Fe2+, Fe3+, Cu 2+).
2. A composition according to Claim 1 wherein the natural phenol comprises catechol and/or DOPA and/or homologues, analogues or derivatives of these compounds.
3. A composition according to Claim 1 or Claim 2 wherein the natural phenol comprises a DOPA species selected from the group consisting of: cysteinyl dopa, alpha alkyl dopa having 1-4, preferably 1 to 2 carbon atoms in the alkyl group, epinephrine and dopa alkyl esters having 1 to 6 carbon atoms in the alkyl group.
4. A composition according to any one of Claims 1 to 3 wherein the natural phenol comprises a DOPA species present as a soluble acid salt selected from hydrochloride and sulfate salts.
5. A composition according to any one of Claims 1 to 3 wherein the natural phenol comprises a DOPA species present as a basic salt selected from alkali and alkaline earth metal salts.
6. A composition according to any one of Claims 1 to 5 wherein the natural phenol comprises a natural plant extract comprising DOPA and/or other catechols.


7. A composition according to anyone of claims 1 to 6 wherein the composition further comprises a transition metal ion selected from the group consisting of: copper, zinc, nickel, cobalt and iron.
8. A composition according to anyone of claims 1 to 7 wherein (a) is separate from (b) in a two part system.
9. A composition according to claim 1 wherein the buffer system has a pH range of from 5 to 8.
10. A composition according to anyone of claims 1 to 9 wherein the unripe tamarind extract is derived from the unripe fruits of the tree Tamarindus indica.
11. A composition according to anyone of claims 1 to 10 wherein the cationic polymer is selected from the group consisting of: polyethylenimine; polymers of dialkyl/trialkyl ammonium alkyl (meth) acrylate; polysaccharides or ethers or esters of polysaccharides with ammonium side groups, especially guar, cellulose and starch derivatives; polymeric adducts of ethylene oxide with ammonium groups, quaternary ethyleneimine polymers; poly (dimethylaminoethyl methacrylate) or copolymers of the same with other acrylates, and quaternized poly 1-vinylimidazole.
}2. A hair/skin colouring kit having the two componenthair/skin colouring system as claimed in claim 1 comprising:
a. a kit housing;
b. said two component hair / skin colouring system, and
c. instruction manual containing guidance for applying the components of said hair
and/or skin colouring system,


buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition
metal ion (Fe2+, Fe3+, cu 2+);
d) instruction manual containing guidance for applying the components (b) and (c) to hair ana/or skin.
13. A kit according to Claim 12 wherein the natural phenol, comprises catechol

and/or DOPA and/or homologues, analogues or derivatives of these compounds.
14.A kit according to Claim 12 or Claim 13 wherein the natural phenol comprises a DOPA species selected from the group consisting of: cysteinyl dopa, alpha alkyl dopa having 1-4, preferably 1 to 2 carbon atoms in the alkyl group, epinephrine and dopa alkyl esters having 1 to 6 carbon atoms in the alkyl group.
15. A kit according to any one of Claims 12 to 14 wherein the natural phenol comprises a DOPA species present as a soluble acid salt selected from hydrochloride and sulfate salts.
16.A kit according to any one of Claims 12 to 14 wherein the natural phenol comprises a DOPA species present as a basic salt selected from alkali and alkaline earth metal salts.
17. A kit ccording to any one of Claims 12 to 16 wherein the natural phenol comprises a natural plant extract comprising DOPA and/or other catechols.
18. A kit according to any one of Claims 12 to 17 wherein the composition further comprises a transition metal ion selected from the group consisting of: copper, zinc, nickel, cobalt and iron.


19. A kit according to anyone of claims 12 to 18 wherein (b) is separated from (c) by a separator means in the kit.
20. A kit according to claim 12 wherein the buffer system has a pH range of from 5 to 8.
21. A kit according to anyone of claims 12 to 20 wherein the unripe tamarind extract is derived from the unripe fruits of the tree Tamarindus indica.
22. A-kit accoVding to anyone of claims 12 to 21 wherein the cationic polymer is selected from the group consisting of: polyethylenimine; polymers of dialkyl/trialkyl ammonium alkyl (meth) acrylate, polysaccharides or ethers or esters of polysaccharides with ammonium side groups, especially guar, cellulose and starch derivatives; polymeric adducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers, poly (dimethylaminoethyl methacrylate) or copolymers of the same with other acrylates; and quaternized poly 1-vinylimidazole.
23. A-method for dyeing hair using the two components hair/skin colouring system as claimed in claim 1 comprising the steps of:
i) obtaining said synergistic mix of a natural phenol (weight range 50 - 500 mg/100 ml) and unripe tamarind extract (0.5-5.0 gm/100 ml) in a ratio 1:100 to 1:10 in a buffered system with a pH range of 4-10 containing 1 - 20 mg of a transition metal ion (Fe2+, Fe3+, Cu2+);
ii) applying an aqueous solution of said cationic polymer on to the hair ;
iii) after step (ii) applying the mix obtained in (i) on to the hair ; and
iv) allowing the said mixture to remain in contact with the hair for a sufficient time to permanently colour the hair.


24.A-colouring_component for colouring hair/skin as herein described and exemplified.
Dated 19tn day of October 2001,
Hindustan Lever Limited
(S Venkatramani) Patents Manager

Documents:

940-mum-2000-cancelled pages(19-10-2001).pdf

940-mum-2000-claims(granted)-(19-10-2001).doc

940-mum-2000-claims(granted)-(19-10-2001).pdf

940-MUM-2000-CORRESPONDENCE(8-2-2012).pdf

940-mum-2000-correspondence(ipo)-(8-12-2005).pdf

940-mum-2000-correspondence1(19-10-2001).pdf

940-mum-2000-correspondence2(9-5-2005).pdf

940-mum-2000-form 1(20-10-2000).pdf

940-mum-2000-form 19(23-6-2003).pdf

940-mum-2000-form 2(granted)-(19-10-2001).doc

940-mum-2000-form 2(granted)-(19-10-2001).pdf

940-mum-2000-form 3(19-10-2001).pdf

940-mum-2000-form 5(19-10-2001).pdf

940-mum-2000-petition under rule 138(2-8-2004).pdf

940-mum-2000-power of attorney(29-7-2007).pdf


Patent Number 197736
Indian Patent Application Number 940/MUM/2000
PG Journal Number 41/2007
Publication Date 12-Oct-2007
Grant Date 08-Dec-2005
Date of Filing 20-Oct-2000
Name of Patentee HINDUSTAN LEVER LIMITED
Applicant Address HINDUSTAN LEVER HOUSE 165/166,BACKBAY RECLAMATION, MUMBAI 400 020, MAHARASHTRA, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 RAMAN GOVINDARAJAN D-6 GOLDEN ENCLAVE, AIRPORT ROAD, BANGALORE-560 017, KARNATAKA, INDIA.
2 MANI INDU 12 GOLF MANOR APARTMENTS, WIND TUNNEL ROAD, MURUGESHPALYA, BANGALORE - 560 017, KARNATAKA, INDIA.
3 BHAGYALAKSHMI KRITHIVASAN 6, KALAKATEESWARA NILAYA, VINAYAKA LAYOUT, IMMADIHALLI, MAIN ROAD, WHITEFIELD, BANGALORE 560 066, KARNATAKA, INDIA.
4 PAWAR SAMBHAJIRAO HEMANT C/O DEPARTMENT OF OPHTHAMOLOGY AND VISUAL SCIENCES, WASHINGTON UNIVERSITY SCHOOL OF MEDICINE, 660 SOUTH EUCLID AVE. ST.LOUIS, MO 63110-1093, UNITED STATES OF AMERICA.
PCT International Classification Number A61K7/13
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA