A process for coloring keratin fibers using a composition comprising indican, henna powder, hydrolase and oxidase enzymes, and water.

Abstract

The present invention relates to a process for coloring keratin fibers using a composition C comprising: (i) indican of formula (I) and / or a powder containing it; (ii) henna powder; (iii) at least one exogenous enzyme of the hydrolase type; (iv) at least one exogenous enzyme of the oxidase type; and (v) water.

Description

Title of the invention: A method for coloring keratin fibers using a composition comprising indican, henna powder, hydrolase and oxidase enzymes, and water

[0001] The present invention relates to a method for coloring keratin fibers using a composition comprising indican and / or a powder containing it, henna powder, at least one exogenous hydrolase-type enzyme, at least one exogenous oxidase-type enzyme and water. technical field

[0002] Two main modes of staining keratin fibers are known, in particular human keratin fibers, and in particular hair.

[0003] The first, called oxidation or permanent coloring, consists of using one or more oxidation dye precursors, more particularly one or more oxidation bases possibly associated with one or more couplers.

[0004] The second coloring method, called direct or semi-permanent coloring, involves the application of direct dyes, which are colored and coloring molecules with an affinity for fibers. Given the nature of the molecules used, they remain mostly on the surface of the fiber and penetrate relatively little into the fiber, compared to the small precursor molecules of oxidation dyes. The main advantage of this type of coloring is that it does not require an oxidizing agent, which limits fiber degradation.

[0005] One of the best-known natural dyes is that derived from the henna plant.

[0006] Henna is made up of leaves of shrubs of the genus Lawsonia of the family Lythraceae which is based on the principle of coloring by the active ingredient lawsone: 2-hydroxy-1,4-naphthoquinone.

[0007] Another well-known natural colorant is indigo (see Ullmann's Encyclopedia of Industrial Chemistry, "hair preparation", item 5.2.3, 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; 10.1002 / 14356007.al2 57Lpub2).

[0008] However, the colouring resulting from the combination of henna powder and indican, corresponding to the precursor of indigo and / or natural powder containing it such as indigo powder from crushed indigo leaves, generally leads to grey-green colours that evolve very over time.

[0009] The resulting hair colors are weak, dull, with a significant and unsightly color change. This change is often observed during the first week after coloring, making this technology unpredictable.

[0010] In addition, this coloring requires large quantities of powder and water.

[0011] In addition, colonic visibility on keratin fibers generally requires a long application time of more than 45 minutes, usually from 1 hour to 24 hours.

[0012] These points make the technology unattractive because its use and rinsing are very difficult.

[0013] Moreover, hair colored by this combination is particularly difficult to detangle.

[0014] The process responsible for the coloring is an enzymatic process for both henna powder and indican and / or a natural powder containing it, involving in particular endogenous enzymes of the hydrolase type, i.e. naturally present in these powders.

[0015] Indeed, through a first enzymatic deglucosylation reaction of the derivatives of 1,4-dihydroxynaphthalene-2-glucoside and 2,4-dihydroxynaphthalene-1-glucoside present in henna powder, hydrolawsone is obtained. Then, its oxidation with oxygen leads to the production of lawsone, which imparts an intense orange to coppery color.

[0016] Furthermore, via a first enzymatic deglucosylation reaction of indican, indoxyl is obtained which by oxidation with oxygen or via a second enzymatic reaction is transformed into indigo allowing to deliver a blue-violet colouring.

[0017] However, this enzymatic process is long, requires the use of hot water, and large quantities of ingredients and the resulting color changes over time.

[0018] There is therefore a need to develop coloring processes from the combination of henna powder and indican and / or powder containing them, allowing to improve the kinetics of the enzymatic process, and therefore of coloring and consequently to significantly increase the visibility of the coloring in short application times, i.e. a fast coloring with a good color rise, while obtaining intense natural shades, stable and without changing over time.

[0019] Furthermore, the formulation of environmentally friendly cosmetic products, that is to say whose design and development take into account environmental issues, is becoming a major concern to help meet planetary challenges.

[0020] It is therefore essential to propose more sustainable cosmetic processes that make it possible to respond to these environmental challenges.

[0021] The present invention is specifically designed to meet all or part of these needs. Description of the invention

[0022] The present invention relates to a method for coloring keratin fibers using a composition C comprising: (i) of the following formula (I) indican: and / or a powder containing it; (ii) henna powder; (iii) at least one exogenous hydrolase-type enzyme; (iv) at least one exogenous oxidase-type enzyme; and (v) water.

[0023] The process according to the invention makes it possible to obtain an intense, chromatic and rapid coloration of keratin fibers with a good rise in color and without color change over time.

[0024] Other objects, features, aspects and advantages of the invention will become even clearer upon reading the description and examples that follow.

[0025] The expression "at least one" means one or more.

[0026] Unless otherwise indicated, the bounds of a range of values ​​are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

[0027] By the expression "greater than" and respectively the expression "less than" in the context of the present invention, we mean an open interval that is strictly greater than, respectively strictly less than, and therefore that the bounds are not included.

[0028] For the purposes of this application, "keratin fibers" means in particular human keratin fibers such as hair, eyelashes, eyebrows, and body hair, preferably hair, eyebrows and eyelashes, even more preferably hair.

[0029] For the purposes of the present invention, "hair" means the hair on the head. This term does not include body hair, eyebrows, or eyelashes. Formula Indican (I) and / or powder containing it

[0030] As previously stated, composition C implemented in the process according to the invention comprises indican of the following formula (I): and / or a powder containing it.

[0031] Indican, an uncoloured material, is a precursor of indigo.

[0032] Indican is found naturally in certain plants, particularly in indigiferous plants, notably in indigo leaves.

[0033] Preferably, as indigo-bearing plants in which indican is found, numerous species from the genera can be cited:

[0034] - Indigofera such as Indigofera tinctoria, Indigo suffruticosa, Indigofera articulata, Indigofera arrecta, Indigofera gerardiana, Indigofera argentea, Indigofera indica, Indigofera longiracemosa;

[0035] - Isatis such as Isatis tinctoria',

[0036] - Polygonum or Persicaria such as Polygonum tinctorium (Persicaria tinctoria);

[0037] - Wrightia such as Wrightia tinctoria;

[0038] - Calanthe such as Calanthe veratrifolia; and

[0039] - Baphicacanthus such as Baphicacanthus cusia.

[0040] Indigo leaves are preferably dried and ground into powder before being introduced into composition C applied in the process according to the invention.

[0041] Thus, preferably, indican is introduced into composition C in powder form.

[0042] Advantageously, the powder containing indican of formula (I) comprises indigo powder, preferably indigo powder from indigo-bearing plant(s), in particular leaves of indigo-bearing plant(s), more preferably of the genus Indigofera, and more particularly Indigofera tinctoria, and better, the powder containing indican of formula (I) is indigo powder, preferably indigo powder from indigo-bearing plant(s), in particular leaves of indigo-bearing plant(s), more preferably of the genus Indigofera, and more particularly Indigofera tinctoria.

[0043] According to the invention, the powder containing indican of formula (I) is different from an indican extract of formula (I).

[0044] By "indican extract of formula (I)", we mean a product of maceration in at least one aqueous and / or organic solvent of indigo-bearing plants.

[0045] The formation of indigo from indican is the result of an enzymatic process.

[0046] A first enzymatic deglucosylation reaction (RE1) of indican of formula (I) leads to indoxyl of the following formula (II):

[0047] This enzymatic reaction also produces a glucose residue.

[0048] Then, the indoxyl of formula (II) can undergo a second oxidative enzymatic reaction (RE2) to form the indigo of formula (III) as follows:

[0049] Advantageously, the total content of formula indican (I) ranges from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 0.7 to 10% by weight, even more preferably from 0.8 to 9% by weight, better from 0.9 to 8% by weight relative to the total weight of the powder containing it.

[0050] Advantageously, the total powder content containing indican of formula (I) ranges from 0.1 to 50% by weight, preferably from 0.5 to 45% by weight, more preferably from 1 to 40% by weight, even more preferably from 3 to 35% by weight, better from 5 to 30% by weight relative to the total weight of composition C.

[0051] Advantageously, the total indican content of formula (I) ranges from 0.0001 to 10% by weight, preferably from 0.0015 to 6.75% by weight, more preferably from 0.007 to 4% by weight, even more preferably from 0.024 to 3.15% by weight, and better still from 0.045 to 2.4% by weight relative to the total weight of composition C. Henna powder

[0052] As previously stated, composition C implemented in the process according to the invention comprises henna powder.

[0053] By "henna powder" is meant a pure natural product derived from henna plants, reduced by grinding or other mechanical means, into fine particles.

[0054] According to the invention, henna powder is different from henna extract.

[0055] By "henna extract" is meant a product of maceration in at least one aqueous and / or organic solvent.

[0056] Henna powder is obtained from Lawsonia inermis leaves, preferably reduced to fine particles by mechanical grinding.

[0057] The leaves of Lawsonia mermzs comprise henosides, notably 1,4-dihydronaphthalene-2-glucoside and 2,4-dihydronaphthalene-1-glucoside.

[0058] The formation of lawsone (2-hydroxy-l,4-naphthoquinone), the molecule responsible for the orange / copper colour of henna coloring, can be catalyzed by enzymatic reactions, from the henosides present in the leaves of Lawsonia inermis.

[0059] A first enzymatic deglucosylation reaction (RET) of 1,4-dihydronaphthalene-2-glucoside and 2,4-dihydronaphthalene-l-glucoside leads to the obtaining of hydrolawsone and a glucose residue.

[0060] Then, a second oxidative enzymatic reaction (RE2') leads to the production of lawsone.

[0061] Advantageously, the total henna powder content ranges from 0.1 to 50% by weight, preferably from 0.5 to 45% by weight, more preferably from 1 to 40% by weight, even more preferably from 3 to 35% by weight, better from 5 to 30% by weight relative to the total weight of composition C. Exogenous hydrolase-type enzyme

[0062] As previously stated, composition C implemented in the process according to the invention comprises at least one exogenous hydrolase-type enzyme (iii).

[0063] For the purposes of this invention, "exogenous enzyme" means an enzyme introduced externally into the medium, i.e., added in addition to the enzymes that may be naturally present in the indican-containing powder or in the henna powder used in the process according to the invention. The exogenous enzyme may be the same as, or different from, those that may be naturally present in, the indican-containing powder or in the henna powder used in the process according to the invention.

[0064] By "hydrolase-type enzyme", for the purposes of the present invention, means an enzyme which catalyzes the breaking of chemical bonds by the addition of a water molecule and which are classified under the EC 3 nomenclature of the IUBMB (International Union of Biochemistry and Molecular Biology, iubmb.org).

[0065] Exogenous hydrolase-type enzymes are involved in the RE1 and RE1' enzymatic reactions as described above.

[0066] They are used in particular within the framework of the invention in the deglucosylation process (RE1') of henoside compounds present in the leaves of Lawsonia inermis, in hydrolawsone, more particularly in the deglucosylation of henosides 1,4-dihydroxynaphthalene-2-glucoside and 2,4-dihydroxynaphthalene-l-glucoside in hydrolawsone.

[0067] In addition, these enzymes are used in the process of deglucosylation of indican (RE1) present in indigo leaves, into indoxyl.

[0068] Advantageously, the exogenous hydrolase-type enzyme(s) (iii) are chosen from glycosylases (EC 3.2), preferably from glycosidases (EC 3.2.1), more preferably from beta-glucosidases (EC 3.2.1.21), cellulases (EC 3.2.1.4), and mixtures thereof.

[0069] The glycosidases of the invention are glycoside hydrolase enzymes that catalyze the hydrolysis of glycosidic bonds by releasing at least one glycosidic compound.

[0070] Glycosidases within the meaning of the present invention can be in solid form, in particular powder, in solution or immobilized on a solid support.

[0071] By "solid support" carrying one or more enzymes is meant a "matrix" on which one or more enzymes have been immobilized; said enzymes have retained their catalytic functions. Said enzymes are immobilized on the support by chemical or physical immobilization methods, and remain in a defined space within which they can be used repeatedly or continuously.

[0072] Methods for immobilizing said enzymes can be cited as classical methods known to those skilled in the art (see for example "Enzyme immobilization: an overview on techniques and support materials, 3 Biotech"; 3(1): 1-9 (2013 Feb), Doctoral thesis, Ecole Nat. Sup. Chimie Montpellier, H. Jarrar, "Enzymatic bioelectrodes for applications in biosensors and biofuel cells" (16 / 12 / 2011) in particular chap. 1.7), such as adsorption, crosslinking, covalent grafting, encapsulation, recognition by affinity / bioaffinity such as antigen / antibody type recognition.

[0073] The matrices used are those known to those skilled in the art. These include i) organic polymers such as agarose, cellulose, dextran, polymers such as polyvinyl chloride, acrylates, nylons, polystyrene; ii) inorganic materials: silica in the form of microporous glass beads and silica gel; and iii) hybrids of the two previous matrices i) and ii) such as agarose-acryl amide and polymer-coated silica.

[0074] Preferably, the matrix is ​​different from polysaccharides or polysaccharide derivatives.

[0075] For the purposes of this invention, "polysaccharide derivatives" means a compound obtained by chemical modification of a polysaccharide, and comprising at least two monosaccharides linked together by O-glycosidic bonds within the structure of said compound.

[0076] The glycosidase enzyme(s) may be of plant, animal, fungal (yeasts, molds, fungi) or bacterial origin.

[0077] Glycosidases can also be obtained by biotechnology.

[0078] Beta-glucosidases carry out hydrolysis of the -O-glucoside bond into beta-glucoside of a monosaccharide or oligosaccharide comprising a glucose portion.

[0079] These enzymes are known as gentiobiase, cellobiase, emulsin, elaterase, aryl-beta-glucosidase, beta-D-glucosidase, beta-glucoside glucohydrolase, arbutinase, amygdalinase, p-nitrophenyl beta-glucosidase, primeverosidase, amygdalase, linamarase, salicilinase, and beta-1,6-glucosidase (EC 3.2.1.21). The latter are also known as Amygdalin beta-glucosidase, Prunasin beta-glucosidase, Vicianin beta-glucosidase, Glucosylceramidase, and cellulase-type enzymes produced primarily by fungi, bacteria, and protozoa that catalyze the hydrolysis of cellulose.

[0080] Examples of glycosidases include:

[0081] - the cellulase(s) marketed under the name "Cellulase from Trichoderma reesei”, for example by the company Sigma-Aldrich.

[0082] - beta-glucosidases marketed by DuPont under the names MULTIFECT® CX 15L and Optimase CX 15L; naturally sourced glucosidases such as almond beta-glucosidases, in particular sweet almond beta-glucosidase; almond beta-glucosidase marketed by the Aldrich company under the name 49290 “beta-glucosidase from almonds” lyophilized powder,

[0083] - and mixtures thereof.

[0084] Advantageously, the total content of exogenous hydrolase (iii) enzyme(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better still from 0.0025% to 0.1% by weight relative to the total weight of composition C

[0085] Advantageously, the total glycosylase content(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

[0086] Preferably, the total glycosidase content(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C. Exogenous oxidase-type enzyme

[0087] As previously stated, composition C implemented in the process according to the invention comprises at least one exogenous oxidase-type enzyme (iv).

[0088] By "oxidase-type enzyme", for the purposes of the present invention, means an oxidoreductase enzyme which catalyzes redox reactions involving the transfer of electrons, preferably 4 electrons, from a given substrate to molecular oxygen (O2), leading to the formation of oxidized products and reactive oxygen derivatives and which are classified under the EC 1 nomenclature of the IUBMB (International Union of Biochemistry and Molecular Biology, iubmb.org).

[0089] Exogenous oxidase-type enzymes are involved in the RE2 and RE2' enzymatic reactions as described above.

[0090] They are notably used in the context of the invention in the process of oxidizing hydrolawsone to lawsone (RE2'), which is responsible for the orange color of henna powder.

[0091] In addition, they are also used in the oxidation process of indoxyl to indigo (RE2), which is responsible for the blue-violet color.

[0092] Advantageously, the exogenous oxidase-type enzyme(s) (iv) are selected from polyphenol oxidases (EC 1.10.3), preferably from laccases (EC 1.10.3.2), tyrosinases (EC 1.10.3.1), and mixtures thereof, more preferably from laccases.

[0093] These laccases can in particular be chosen from laccases of plant origin, animal origin, fungal origin (yeasts, molds, fungi) or bacterial origin, the organisms of origin being able to be mono- or multicellular.

[0094] Laccases can also be obtained by biotechnology.

[0095] Among the plant-derived laccases that can be used according to the invention, we can mention the laccases produced by plants carrying out chlorophyll synthesis such as those indicated in patent application FR-A-2 694 018.

[0096] Among the laccases of fungal origin, possibly obtained by biotechnology, usable according to the invention, we can mention the laccase(s) from Polyporus versicolor, Rhizoctonia praticola and Rhus vernicifera as described for example in patent applications FR-A-2 112 549 and EP-A-504005; the laccases described in patent applications WO95 / 07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998 and WO97 / 19999.

[0097] Oxidase-type enzymes as defined in the present invention may be in solid form, in particular as a powder, in solution, or immobilized on a solid support

[0098] Among exogenous oxidase-type enzymes, examples include those sold under the trade names "Laccase from Trametes versicolor", "Laccase from Agaricus bisporus" or "Laccase from Aspergillus sp", " Laccase from Rhus vemicifera”, “Tyrosinase from mushroom”, for example by the company Sigma-Aldrich.

[0099] Thanks to exogenous hydrolase-type enzymes and exogenous oxidase-type enzymes, respectively involved in the enzymatic reactions of deglucosylation and oxidation, the kinetics of said enzymatic reactions are significantly increased, advantageously leading to the formation of lawsone and indigo, reducing the exposure time and thus significantly increasing the intensity and visibility of the coloration while limiting the color change over time.

[0100] Advantageously, the total content of exogenous oxidase (iv) type enzyme(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

[0101] Advantageously, the total content of polyphenol(s) oxidase(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

[0102] Advantageously, the total laccase content(s) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

[0103] Advantageously, the total content of exogenous hydrolase (iii) and oxidase (iv) type enzymes ranges from 0.0002% to 20% by weight, preferably from 0.0005% to 10% by weight, more preferably from 0.001% to 2% by weight, even more preferably from 0.002% to 1% by weight, and better from 0.005% to 0.2% by weight relative to the total weight of composition C.

[0104] Advantageously, if only one supported exogenous enzyme is implemented (either the oxidase or the hydrolase), the weight ratio between the total content of exogenous hydrolase-type enzymes (iii) and the total content of exogenous oxidase-type enzymes (iv) in composition C ranges from 0.1 to 100, preferably from 0.5 to 50, more preferably from 0.7 to 20, even more preferably from 0.8 to 12, better said weight ratio is equal to 10.

[0105] Advantageously, if neither of the exogenous enzymes (hydrolase and oxidase) is implemented in supported form, or if both types of enzymes are implemented in supported form, the weight ratio between the total content of exogenous hydrolase-type enzymes (iii) and the total content of exogenous oxidase-type enzymes (iv) in composition C ranges from 0.1 to 10, preferably from 0.5 to 5, plus preferably from 0.7 to 2, even more preferably from 0.8 to 1.2, better said weight ratio is equal to 1.

[0106] For the purposes of this invention, "supported enzyme" means an enzyme immobilized on a solid support. Water

[0107] Composition C implemented in the process according to the invention comprises water.

[0108] Advantageously, the total water content (v) ranges from 30 to 95% by weight, preferably from 35 to 90% by weight, more preferably from 40 to 85% by weight relative to the total weight of composition C.

[0109] Advantageously, composition C implemented in the process according to the invention may further comprise at least cysteine ​​and / or isatin, in particular as additional agent(s). Additives

[0110] Composition C implemented in the process according to the invention may further comprise additives commonly used in cosmetics, such as, for example, antifoaming agents, thickening agents, moisturizing agents, clays, mineral fillers, UV filters, perfumes, anionic, cationic, nonionic or amphoteric surfactants, vitamins, preservatives, silicones, waxes, mordants, and mixtures thereof. These additives may be present in said composition C in an amount ranging from 0 to 20% by weight relative to the total weight of composition C.

[0111] The person skilled in the art shall take care to choose these possible additives and their quantities so that they do not impair the properties of composition C.

[0112] Preferably, composition C implemented in the process according to the invention comprises a total content of mordanting agent(s) selected from organic or mineral salts of iron, aluminum, titanium, calcium, manganese, copper, zinc, strontium, and mixtures of these salts, of less than 1% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight relative to the weight of composition C.

[0113] More preferably, the composition C implemented in the process according to the invention is free of mordanting agent(s) selected from organic or mineral salts of iron, aluminum, titanium, calcium, manganese, copper, zinc, strontium, and mixtures of these salts. Process

[0114] Composition C can be applied to wet or dry hair, in rinsed or unrinsed mode.

[0115] Advantageously, the application of composition C is carried out between 20°C and 50°C, preferably between 20°C and 45°C.

[0116] Composition C may optionally be applied to the keratin fibers after the application of a shampoo and rinsing with water.

[0117] Preferably, the application of composition C is carried out after the application of shampoo and then rinsing with water.

[0118] After the application of composition C, and after possibly combing, said composition C can be left in place on the keratin fibers.

[0119] Advantageously, composition C is left on the keratin fibers for a period of less than or equal to 45 minutes, preferably less than or equal to 30 minutes, more preferably from 1 minute to 30 minutes, even more preferably from 5 minutes to 30 minutes.

[0120] When composition C is left on the keratin fibers, said keratin fibers can be covered occlusively, for example with plastic film or a cap.

[0121] After application of composition C, the keratin fibers can be rinsed with water and / or undergo one or more shampoos.

[0122] Preferably, the keratin fibers are rinsed with water and then possibly undergo one or more shampoos after the application of composition C.

[0123] The keratin fibers can then be rinsed with water after the application of shampoo.

[0124] After applying composition C to the keratin fibers, the keratin fibers can be dried. The keratin fibers can be air-dried or dried using a drying device such as a helmet, a hairdryer, or a climazon. When the drying step is carried out with a helmet or a hairdryer, the drying temperature is above 40°C.

[0125] Preferably, if the keratin fibers are dried after the application of composition C, they are dried, in addition to the supply of heat, with an airflow.

[0126] Advantageously, the process according to the invention does not include a denaturation step, such as denaturation by heating, and / or separation of endogenous enzymes from the henna powder and / or the powder containing indican.

[0127] Indeed, henna powder and / or powder containing indican as described above may contain endogenous enzymes, i.e. enzymes naturally present in said henna powder and / or in said powder containing indican.

[0128] The denaturation step can for example be implemented by heating, in particular at a temperature ranging from 60°C to 200°C.

[0129] The separation step can for example be implemented by extraction using a solvent.

[0130] The present invention will now be described more specifically by means of examples, which are in no way limiting to the scope of the invention. However, the examples allow for the support of specific features, variants, and preferred embodiments of the invention. Examples

[0131] Compositions A to L, as described in the tables below, have been prepared: quantities are expressed in g of raw material as is, unless otherwise stated.

[0132] [Tables 1] ABC Composition: Lawsonia inermis Leaf Powder - Origin: Morocco (1) 0.10 0.10 0.10 Indican (I) (2) 0.0120 0.0120 0.0120 Glucosidase (3) 0.25 0.25 0.25 Oxidase (4) 0.25 - - Oxidase (5) - 0.25 - Oxidase (6) - - 0.25 Water 1.90 1.90 1.90

[0133] (1) sold by Natural Origins

[0134] (2) sold by Sigma Aldrich under reference 13750

[0135] (3) aqueous solution at 50 mg / mL of “Cellulase from Trichoderma reesei”

[0136] (4) aqueous solution at 50 mg / mL of “Laccase from Trametes versicolor”

[0137] (5) aqueous solution at 50 mg / mL of “Laccase from Agaricus bisporus”

[0138] (6) 50 mg / mL aqueous solution of "Laccase from Aspergillus sp"

[0139] [Tables2] Compositions DEF Laws onia inermis leaf powder - Origin Mar oc (1) 0.25 0.25 0.25 Formula Indican (I)(2) 0.009375 0.009375 0.009375 Glucosidase (3) 0.25 0.25 0.25 Oxidase (4) 0.25 - - Oxidase (5) - 0.25 - Oxidase (6) - - 0.25 Water 1.75 1.75 1.75

[0140] [Tables 3] Compositions GHI Lawsonia inermis Leaf Powder - Origin Morocco (1) 0.40 0.40 0.40 Formula Indican (I)(2) 0.003 0.03 0.03 Glucosidase (3) 0.25 0.25 0.25 Oxidase (4) 0.25 - - Oxidase (5) - 0.25 - Oxidase (6) - - 0.25 Water 1.60 1.60 1.60

[0141] [Tables 4] JKL Compositions Laws onia inermis leaf powder - Origin Morocco (1) 0.05 0.05 0.05 Indican of formula (I)(2) 0.0135 0.0135 0.0135 Glucosidase (3) 0.25 0.25 0.25 Oxidase (4) 0.25 - - Oxidase(5) - 0.25 - Oxidase (6) - - 0.25 Water 2.00 2.00 2.00

[0142] Compositions A to L were prepared by mixing henna powder with indican of formula (I), then with water at 19°C. Then, the mixture was vigorously stirred for 30 seconds until a homogeneous mixture was obtained.

[0143] Glucosidase-type and oxidase-type enzymes were then added to the mixture.

[0144] The mixture was homogenized with a wooden spoon, or a "maryse" type spatula in order to make a poultice.

[0145] The resulting poultice was applied to strands of natural Caucasian hair with 90% white hair (BN) of 0.5g, on both sides of the strands.

[0146] Then, the wicks were left to rest for 30 minutes at 33°C under transparent plastic film.

[0147] After the processing time, the strands were rinsed with water until the colouring composition was completely removed, then they underwent shampooing according to the protocol described below.

[0148] Then, the strands were rinsed with water and dried with a hairdryer. Shampoo Protocol#:

[0149] The colored hair strands were combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The hair strands were then squeezed dry between two fingers.

[0150] A standard shampoo (Garnier Ultra Doux) was applied evenly to the colored strands at a rate of 0.4g of standard shampoo per gram of strands, gently massaging the strands of hair along their length (6 passes) for 15 seconds, from root to tip.

[0151] The hair strands were then placed in a watch glass and left to rest for 1 minute.

[0152] Next, the hair strands were rinsed with water by passing the strand between the fingers (15 passes). The hair strands were then squeezed dry between two fingers. Results

[0153] The rise in strand colouring was evaluated in the CIE L*a*b* system using a Konica Minolta CM2600d spectrophotometer (illuminant D65).

[0154] In this L*a*b* system, L* represents the intensity of the color, a* indicates the green / red color axis and b* the blue / yellow color axis.

[0155] The color uptake is assessed by the color difference AE between the uncolored and colored strands. The greater the AE value, the greater the color uptake.

[0156] The value of AE is calculated according to the following equation:

[0157]

[0158] In this equation, L*, a* and b* represent the values ​​measured after hair coloring, and Lo*, a0* and b0* represent the values ​​measured before hair coloring.

[0159] The measurements were taken after 10 minutes of exposure and then after 30 minutes.

[0160] The results are summarized in Table 5 below:

[0161] [Tables5] Color Composition Driving time L* a* b* AE before staining - 58.58 (Lo*) 0.98 (a0*) - A 10 min 53.36 -6.58 11.67 9.50 30 min 1.5.41 B 10 min 53.82 -3.25 16.21 6.71 30 min 46.65 -5.41 16.30 13.71 C 10 min 55.31 -3.01 13.42 5.20 min 30 min 57.713 D 56.06 2.77 21.07 7.63 30 min 48.86 2.69 20.32 11.67 E 10 55.71 4.24 21.27 8.39 30 min 47.98 0.99 110 F 18.4 5.74 30 min 48.31 4.31 24.19 14.78 G 10 min 52.81 5.55 20.04 9.46 30 min 50.03 10.39 28.57 19.27 1.37 H 9.12 30 min 49.46 12.71 27.4 19.95 I 10 min 57.87 5.36 20.01 7.40 30 min 50.76 13.71 31.14 22.67 J 30 min 40.4 -10.49 3.65 23.90 K 10 min 51.21 -9.96 9.81 13.87 30 min 46.99 -12.79 9.89 18.48 L 10 min 53.17 -7.8 5.56 13.38 30 min 41.29 -10.31 0.86 24.52

[0162] It is clear from the table above that the hair strands colored using the processes according to the invention exhibit good color rise, with rapid coloring.

Claims

Demands

1. A process for coloring keratin fibers employing a composition C comprising: (i) indican of the following formula (I): À X .0^ ûz V' A en .-A and / or a powder containing it; (ii) henna powder; (iii) at least one exogenous hydrolase-type enzyme; (iv) at least one exogenous oxidase-type enzyme; and (v) water.

2. A process according to claim 1, characterized in that the indican-containing powder of formula (I) comprises indigo powder, preferably indigo powder derived from indigo-bearing plant(s), in particular from the leaves of indigo-bearing plant(s), more preferably of the genus Indigofera, and more particularly Indigofera tinctoria and better, the indican-containing powder of formula (I) is indigo powder, preferably indigo powder derived from indigo-bearing plant(s), in particular from the leaves of indigo-bearing plant(s), more preferably of the genus Indigofera, and more particularly Indigofera tinctoria.

3. A process according to claim 1 or 2, characterized in that the total indican content ranges from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, more preferably from 0.7 to 10% by weight, even more preferably from 0.8 to 9% by weight, better from 0.9 to 8% by weight relative to the total weight of the powder containing it.

4. A process according to any one of the preceding claims, characterized in that the total powder content containing indican ranges from 0.1 to 50% by weight, preferably from 0.5 to 45% by weight, more preferably from 1 to 40% by weight, even more preferably from 3 to 35% by weight, better from 5 to 30% by weight relative to the total weight of composition C.

5. A process according to any one of the preceding claims, characterized in that the total indican content ranges from 0.0001 to 10% by weight, preferably from 0.0015 to 6.75% by weight, more preferably from 0.007 to 4% by weight, even more preferably from 0.024 to 3.15% by weight, and better still from 0.045 to 2.4% by weight relative to the total weight of composition C.

6. A process according to any one of the preceding claims, characterized in that the total henna powder content ranges from 0.1 to 50% by weight, preferably from 0.5 to 45% by weight, more preferably from 1 to 40% by weight, even more preferably from 3 to 35% by weight, better from 5 to 30% by weight relative to the total weight of composition C.

7. A method according to any one of the preceding claims, characterized in that the exogenous hydrolase-type enzyme(s) (iii) are selected from glycosylases, preferably from glycosidases, more preferably from beta-glucosidases, cellulases and mixtures thereof.

8. A process according to any one of the preceding claims, characterized in that the total content of exogenous hydrolase-type enzyme(s) (iii) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

9. A method according to any one of the preceding claims, characterized in that the exogenous oxidase-type enzyme(s) (iv) are selected from polyphenol oxidases, preferably from laccases, tyrosinases and mixtures thereof, more preferably from laccases.

10. A process according to any one of the preceding claims, characterized in that the total content of exogenous oxidase-type enzyme(s) (iv) ranges from 0.0001% to 10% by weight, preferably from 0.00025% to 5% by weight, more preferably from 0.0005% to 1% by weight, even more preferably from 0.001% to 0.5% by weight, and better from 0.0025% to 0.1% by weight relative to the total weight of composition C.

11. A method according to any one of the preceding claims, characterized in that the total content of exogenous enzymes of type hydrolase (iii) and oxidase type (iv) ranges from 0.0002% to 20% by weight, preferably from 0.0005% to 10% by weight, more preferably from 0.001% to 2% by weight, even more preferably from 0.002% to 1% by weight, and better from 0.005% to 0.2% by weight relative to the total weight of composition C.

12. A process according to any one of the preceding claims, characterized in that the total water content (v) ranges from 30 to 95% by weight, preferably from 35 to 90% by weight, more preferably from 40 to 85% by weight relative to the total weight of composition C.

13. A method according to any one of the preceding claims, characterized in that composition C is left on the keratin fibers for a period of less than or equal to 45 minutes, preferably less than or equal to 30 minutes, more preferably from 1 minute to 30 minutes, even more preferably from 5 minutes to 30 minutes.