WO2024042025A1

WO2024042025A1 - Hair dyes leading to an increase of the colour resistance of dyed hair

Info

Publication number: WO2024042025A1
Application number: PCT/EP2023/072911
Authority: WO
Inventors: Désirée Sarah HAAG; Christine Mendrok-Edinger
Original assignee: Dsm Ip Assets B.V.
Priority date: 2022-08-22
Filing date: 2023-08-21
Publication date: 2024-02-29
Also published as: CN119744161A; EP4577178A1; KR20250053146A

Abstract

The present invention relates to hair dye compositions comprising a specific mixture of branched and linear saturated C15-C19 alkanes, an ester of a fatty acid and dextrin. It has been shown that these hair dye compositions lead to a significant increase of colour resistance of dyed hair.

Description

HAIR DYES LEADING TO AN INCREASE OF THE COLOUR RESISTANCE OF DYED HAIR

TECHNICAL FIELD

The present invention relates to the field of cosmetic compositions, particularly to the field of cosmetic compositions for the dyeing of hair.

Background of the invention

The hair colouration is a specific field of cosmetics. The hair colouration is a common procedure particularly among women and is performed by using hair dyes.

Hair dyes are classified, according to colour resistance, into temporary, semipermanent, demipermanent and permanent. The first two are based on molecules which are already coloured. Temporary dyes act through dye deposition on cuticles, but semipermanent may penetrate a little into the cortex and so the colour resists up to typically six washes. Demipermanent and permanent hair dyes are based on colour precursors, called oxidation dyes, and the final shade is developed by their interactions with an oxidizing agent, but they differ from the alkalizing agent used. In oxidation systems, there is an intense diffusion of the molecules into the cortex, what promotes a longer colour resistance.

Washing of hair, particularly by shampoos, leads to a fading of the colour. A semipermanent hair dye is washed out after typically 4-6 shampooing. Although, due to the chemical fixation, a permanent dye persists for a significantly longer time to water, respectively to shampoos, also the colour resistance of permanent hair dyes is not perfect.

Because the customer desires to have a constant hair colour and appearance over an extended period, an increase of the colour resistance of a hair dye is a strong desire in the market field of hair colouration. Summary of the invention

Therefore, the problem to be solved by the present invention is to offer a product which increases the colour resistance of a hair dye which is applied to the hair.

Surprisingly, it has been found that this problem can be solved by a hair dye composition according to claim 1 .

It has been observed that the colour of dyed hair resists much longer to the negative washing-out effect of shampoos and water when the dyed hair is treated with a hair composition which comprises a specific mixture of branched and linear saturated C15-C19 alkanes, an ester of a fatty acid.

Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.

Detailed description of the invention

In a first aspect, the present invention relates to a hair dye composition comprising

- a mixture of branched and linear saturated C15-C19 alkanes; and

- an ester of a fatty acid and dextrin; wherein the amount of branched saturated C15-C19 alkane in said mixture of branched and linear saturated C15-C19 alkanes is more than 80 % by weight, preferably more that 90 % by weight, most preferred more than 92 % by weight, in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

In the present document, a “C_x-y-alkyl” group is an alkyl group comprising x to y carbon atoms, i.e. , for example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example -CH(CH3)-CH2-CH3 is considered as a C4-alkyl group.

In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label. The term "UV filter" in the present document stands for a substance that absorbs ultraviolet light (=UV light), i.e. electromagnetic radiation of the wavelength between 280 and 400 nm. IIV(A) filters are UV filters that absorb UV(A) light, i.e. electromagnetic radiation of the wavelength between 315 and 400 nm. UV(B) filters are UV filters that absorb UV(B) light, i.e. electromagnetic radiation of the wavelength between 280 and 315 nm.

A liquid organic UV filter is liquid at ambient temperature (i.e. 25°C).

A solid organic UV filter is solid at ambient temperature (i.e. 25°C).

A "mixture of branched and linear saturated C15-C19 alkanes" in the present document means that said mixture comprises different alkanes each of them only having 15, 16, 17, 18 or 19 carbon atoms but does not comprise any alkanes having less carbons. Therefore, such a mixture does not contain for example dodecane or isododecane. Said mixture comprises both branched and linear C15-C19 alkanes.

The term "shampoo" as used in the present document relates to a hair care composition used for cleansing of hair, i.e. the removal of oils, dirt, skin particles, dandruff, environmental pollutants and other contaminant particles that gradually build up in hair. The term shampoo also encompasses conditioning shampoos. The shampoo preparations according to the invention are applied to the hair and then rinsed away with water and are well known to a person skilled in the art.

The term "hair conditioner" refers in the present document to a hair care composition which are applied after washing the hair with cleansing compositions, such as a shampoo. The conditioners leave the hair more soft and pliable, facilitates combing and impart other positive attributes to the hair. Such hair conditioners can be leave in or rinse off products and are well known to a person skilled in the art.

White is not regarded as “colour” in the present document.

The term "colour resistance" refer to the resistance of a dye to be washed out by water, respectively by a cleansing product, typically a shampoo, of the dyed hair. An increase in colour resistance, therefore, means that the removal of the hair dye from the dyed hair by washing/shampooing is reduced. The term “hair dye composition” refers to a composition which can dye hair, particular human hair. It, however, does not relate to coloured cosmetic compositions which comprise pigments, particularly inorganic pigments such as iron oxide or carbon black.

Mixture of branched and linear saturated C15-C19 alkanes

The hair dye composition comprises a mixture of branched and linear saturated C15-C19 alkanes.

Particular suitable mixtures of C15-C19 alkanes are particularly the ones disclosed in WO 2016/185046, WO 2017/046177, WO 2018/109353 A1 and WO 2018/109354 A1 and WO 2018/172228 A1 .

Preferably, the mixture of branched and linear saturated C15-C19 alkanes has a content of carbon of biological origin being greater or equal to 90% with respect of the total weight of the mixture of branched and linear saturated C15- C19 alkanes. The biological origin of chemicals is very advantageous as such material has a high degree of sustainability. High sustainable products or compositions are highly demanded in the market.

The determination of the content of biomaterial or content of biocarbon is given pursuant to standards ASTM D 6866-12, method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7 026-04). Standard ASTM D 6866 concerns "Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis", while standard ASTM D 7 026 concerns ’’Sampling and Reporting of Results for Determination of Biobased Content of Materials via Carbon Isotope Analysis". The second standard mentions the first in its first paragraph. The first standard describes a test of measurement of the ratio ¹⁴C/¹²C of a sample and compares it with the ratio ¹⁴C/¹²C of a sample renewable reference of origin 100%, to give a relative percentage of C of origin renewable in the sample. The standard is based on the same concepts that the dating with ¹⁴C.

It is further preferred that the composition has no or a very small amount (less than 100 ppm, particularly less than 30 ppm) of aromatic hydrocarbons with respect to the total weight of the mixture of branched and linear saturated CI SCI 9 alkanes. The mixture of branched and linear saturated C15-C19 alkanes is particularly produced by catalytic hydrogenation of hydrocarbon biomass feedstock, such as described in detail in WO 2016/185046, particular the one disclosed as example 3 of WO 2016/185046.

It is preferred that the amount of linear saturated C15-C19 alkanes in said mixture of branched and linear saturated C15-C19 alkanes is less than 10 % by weight, preferably less than 8 % by weight, most preferred more than 5 % by weight, in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of C15 is less than 3 %, particularly less than 1 %, preferably less than 0.05 %, by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is preferred that the mixture of branched and linear saturated C15-C19 alkanes is a mixture of branched and linear saturated C16-C19 alkanes.

It is further preferred that the amount of branched saturated C16-C18 alkane is more than 90% by weight, preferably more than 95 % by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of C15 alkanes is less than 5 %, particularly less than 2%, by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of branched saturated C17-C18 alkane is more than 85% by weight, preferably more than 92 % by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of C17 alkanes is more between 15 and 20 % by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of branched saturated C18 alkane is more than 50% by weight, preferably more than 60 % by weight, even more preferably more than 70 % by weight, relative to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

It is further preferred that the amount of C18 alkanes is particularly between 70 and 75 % by weight in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

In other words, the mixture of branched and linear saturated C15-C19 alkanes consist preferably mainly of C18 alkane(s), most preferably mainly of branched C18 alkane(s).

As the hair dye composition comprises a mixture of branched and linear saturated C15-C19 alkanes, said composition does not comprise any lower alkanes, i.e. it does particularly not comprise any C12 alkanes and particularly does not comprise any C12 or C13 or C14 alkanes.

It is further preferred that the mixture of C15-C19 alkanes has at 20°C, a viscosity of 3-15 mPa s, particularly between 6 and 12 mPa s.

It is further preferred that the mixture of C15-C19 alkanes has at 20°C a refractive index of between 1 .40 and 1 .48, particularly of between 1 .42 and 1 .45, most preferably between 1 .43 and 1.44.

It is further preferred that the mixture of C15-C19 alkanes is the mixtures of C15-C19 alkanes as commercialized as EMOGREEN™ L19 by SEPPIC.

The amount of the mixture of branched and linear saturated C15-C19 alkanes is in the range of between 0.015 and 12.0 % by weight, particularly between 0.5 and 11 .0 % by weight, preferably between 1 .0 and 10.0 % by weight, more preferably between 1 .5 and 8.0 % by weight, even more preferably between 2.0 and 6.0 % by weight, based on the weight of the hair dye composition.

Ester of a fatty acid and dextrin

The hair dye composition further comprises an ester of a fatty acid and dextrin.

Dextrin is an oligomer of D-glucose. Its structure can be represented simplified by the following structure

Dextrins have different average degrees of glycopolymerization which leads to different molecular weights.

In the present invention, the dextrin of said ester of a fatty acid and dextrin has preferably an average degree of glycopolymerization of between 3 and 20, particularly between 8 and 16.

It is preferred that the fatty acid of said ester of a fatty acid and dextrin is a C14-C18 fatty acid, particularly a linear C14-C18 fatty acid, most preferably palmitic acid.

As particular suitable ester of a fatty acid and dextrin is a dextrin palmitate as commercialized as Rheopearl® KL2 by Chiba Flour Milling.

Dextrin has several hydroxyl groups which can be esterified.

It is preferred that said ester of a fatty acid and dextrin has an average number of esterified hydroxyl groups of more than 2.5, preferably between 2.5 and 3.5, more preferably between 2.5 and 3.4, most preferably between 2.5 and 3.2, per glucose unit.

In other words, preferably the majority of all the hydroxyl groups of the dextrin are esterified.

It is further preferred that said ester of a fatty acid and dextrin has a molecular weight M_n of between 8'000 and 16'000 Da, preferably between 9'000 and 13'000 Da, more preferably between 10'000 and 11'500 Da.

The molecular weight Mn is determined in Dalton (Da) particularly by SEC/GPC using polystyrene as standard.

Both fatty acid and dextrin have biological origin. The biological origin of chemicals is very advantageous as such material or products thereof have a high degree of sustainability. High sustainable products or compositions are highly demanded in the market.

The amount of the ester of a fatty acid and dextrin is preferably in the range of between 0.01 and 15 % by weight, particularly between 0.1 and 12 % by weight, preferably between 0.2 and 8 % by weight, more preferably between 0.6 and 7 % by weight, even more preferably between 0.8 and 6 % by weight, most preferably between 1 .3 and 4 % by weight, based on the weight of the hair dye composition.

In the said hair dye composition, the ratio of the weight of said ester of a fatty acid and dextrin to the weight of said mixture of branched and linear saturated C15-C19 alkanes is preferably less than 1 , preferably in the range of 0.5 to 0.8, most preferred in the range of 0.55 - 0.70.

In other words, the composition comprises preferably more, by weight, of the C15-C19 alkanes than of the ester of a fatty acid and dextrin.

Hair Dyes

Principally, the invention relates to any hair dyes known to the person skilled in the art. The hair dye composition comprises either a hair dye or precursor(s) of a hair dye.

Semipermanent Hair Dyes

In a preferred embodiment, the hair dye is a semipermanent hair dye.

The semipermanent hair dye is advantageous in that it is very easy for application and suitable for regular use and is a way of colouring the hair particularly mild to the hair and the skin as they are not using an oxidizing agent. The number of different shades of hair colours, however, is somehow more limited. Furthermore, semipermanent hair dyes are less suitable to colour gray or white hair. Finally semipermanent hair dyes cannot be used to obtain a lighter shade of the actual hair colour, which limits the possibilities of colouration for people having a natural dark or black hair colour. Semipermanent hair dyes typically include compounds having a chromophore system that is common in dye chemistry such as nitro, azo, anthraquinone, triphenylmethane, triarylmethane, and azomethane, which may be used as disperse dyes, nitro dyes, cationic (basic) dyes, anionic (acidic) dyes and metal complex dyes (as disclosed indicated in Ullmann's Encyclopedia of Industrial Chemistry Vol A 12, page 586, 5th, completely revised edition, 1989). Of particular interest are e.g. anthraquinone dyes, especially those containing a dialkylaminoalkylamino (DAAA) group. Specific examples include the following compounds available under the trademark ARIANOR® from Warner Jenkinson Ltd.: ARIANOR Straw Yellow, ARIANOR Mahogany, ARIANOR Steel Blue, ARIANOR Madder Red, ARIANOR Ebony and ARIANOR Sienna Brown. Furthermore, very suitable anthraquinone dyes are anthraquinone having a quaternary ammonium side chain.

Specific examples for nitro dyes are compounds selected from the group consisting of 2-((2-nitrophenyl)amino)ethan-1-ol (CAS: 4926-55-0), 4-((2- hydroxyethyl)amino)-3-nitrophenol (CAS: 92952-81-3), 2-((4-amino-2- nitrophenyl)amino)ethan-1-ol (CAS: 2871-04), N,N'-Bis(2-hydroxyethyl)-2-nitro-p- phenylenediamine (CAS: 84041-77-0) and 2,2'-((4-((2-Hydroxyethyl)amino)-3- nitrophenyl)imino)bisethanol) (CAS: 33229-34-4), 2-nitro-p-phenylenediamine (CAS: 5307-14-2) and 4-nitro-o-phenylenediamine (CAS: 99-56-9).

Semipermanent hair dyes are commercially available in a great variety of chemistry and colours. Particularly suitable as semipermanent hair dyes are those implemented in the commercial product lines selected from the group consisting of Revlon® Professional Nutri Color™ Filters from Revlon®, John Freida Violet Crush for Blondes from Kao Brands, Revolution Haircare Tones for Brunettes from Revlon®, Good Dye Young from Good Dye Young, Wella Color by You from Coty and Syoss Color Glow from Schwarzkopf & Henkel. Permanent Hair Dyes

In another preferred embodiment, the hair dye is a permanent hair dye.

The permanent hair dye is advantageous over the other types of hair dyes in that it offers the highest colour resistance of hair dyes, has an excellent colour coverage, particularly also for white or gray hair, and offers the broadest variety of colours and shades available. Permanent hair dyes, however, are rather aggressive, due to the chemical oxidation and fixation process.

Typically, a permanent hair dye is produced by a permanent hair colouring composition. Hence, in his embodiment, the hair dye composition comprises at least three components by which the permanent dye is formed:

(1) a primary intermediate agent,

(2) a coupling agent, and

(3) an oxidant.

The process of permanent hair dye formation is typically performed under basic conditions by the use of an alkalizing agent.

The mechanism of oxidation involves three steps:

1 ) Oxidation of the primary intermediate;

2) Reaction of this with a coupling agent; and

3) Oxidation of the resulting compound by an oxidizing agent to give the final dye.

Oxidizing agents are usually hydrogen peroxide, and the alkaline environment is usually provided by ammonia. The combination of hydrogen peroxide and ammonia causes the natural hair to be lightened, providing a "blank canvas" for the dye. Ammonia opens the hair shaft pores so that the dye can actually diffuse inside the fiber. These dye intermediate and coupling agent can undergo oxidation and coupling reaction to form high molecular weight products, which are trapped in the hair matrix and cannot be readily removed through washing. Primary intermediate agent

Primary intermediate agents are well known for use in hair colour, and include ortho or para substituted aminophenols or phenylenediamines, particularly para-phenylenediamines of the formula:

wherein R¹¹ and R¹² are each independently hydrogen, Ci-6-alkyl, or C1-6- alkyl substituted with one or more hydroxy, methoxy, methylsulphonylamino, aminocarbonyl, furfuryl, unsubstituted phenyl, or amino substituted phenyl groups; and

R¹³, R¹⁴, R¹⁵ and R¹⁶ are each independently hydrogen, Ci-6-alkyl, C1-6- alkoxy, halogen, or Ci-e-alkyl substituted with one or more hydroxy or amino groups.

Preferred primary intermediate agent are selected from the group consisting of para-phenylenediamine, 2-methyl-1 ,4-diaminobenzene, 2,6-dimethyl- 1 ,4-diaminobenzene, 2,5-dimethyl-1 ,4-diaminobenzene, 2,3-dimethyl-1 ,4- diaminobenzene, 2-chloro-1 ,4-diaminobenzene, 2-methoxy-1 ,4-diaminobenzene, 1 -phenylamino-4-aminobenzene, 1 -dimethylamino-4-aminobenzene, 1 - diethylamino-4-aminobenzene, 1 -bis(beta-hydroxyethyl)amino-4-aminobenzene, 1 -methoxyethylamino-4-aminobenzene, 2-hydroxymethyl-1 ,4-diaminobenzene, 2- hydroxyethyl-1 ,4-diaminobenzene, 2-isopropyl-1 ,4-diaminobenzene, 1 -hydroxy- propylamino-4-aminobenzene, 2,6-dimethyl-3-methoxy-1 ,4-diaminobenzene, 1 - amino-4-hydroxybenzene, 1 -hydroxyethyl 4,5-diamino pyrazole, 6-methoxy-2- methylamino-3-aminopyridine and derivatives thereof, and acid or basic salts thereof. Particularly preferred primary intermediate agent are p-phenylenediamine, p-aminophenol, o-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2,5- diaminotoluene, their salts and mixtures thereof.

Colour Coupling agents

The colour coupling agent is particularly selected from the group consisting of m-aminophenol, 2,4-diaminotoluene, 4-amino, 2-hydroxytoluene, phenyl methyl pyrazolone, (3-methyl-1 -phenyl-5-pyrazolone), 3,4-methylenedioxyphenol, 3,4-methylenedioxy-1 -[(beta-hydroxyethyl)amino]benzene, 1 -methoxy-2-amino-4- [(beta-hydroxyethyl)amino]benzene, 1 -hydroxy-3-(dimethylamino)benzene, 6- methyl-1-hydroxy-3[(beta-hydroxyethyl)amino]benzene, 2,4-dichloro-1 -hydroxy-3- am inobenzene, 1 -hydroxy-3-(diethylam ino)benzene, 1 -hydroxy-2-methyl-3-am ino- benzene, 2-chloro-6-methyl-1 -hydroxy-3-aminobenzene, 1 ,3-diaminobenzene, 6- methoxy- 1 ,3-diaminobenzene, 6-hydroxyethoxy-1 ,3-diaminobenzene, 6-methoxy- 5-ethyl-1 ,3-diaminobenzene, 6-ethoxy-1 ,3-diaminobenzene, 1-bis(beta-hydroxy- ethyl)amino-3-aminobenzene, 2-methyl-1 ,3-diaminobenzene, 6-methoxy-1-amino- 3-[(beta-hydroxyethyl)amino]-benzene, 6-(beta-aminoethoxy)-1 ,3-diamino- benzene, 6-(beta-hydroxyethoxy)-1 -amino-3-(methylamino)benzene, 6-carboxy- methoxy-1 ,3-diaminobenzene, 6-ethoxy-1-bis(beta-hydroxyethyl)amino-3-am inobenzene, 6-hydroxyethyl-1 ,3-diaminobenzene, 1 -hydroxy-2-isopropyl-5-methyl- benzene, 1 ,3-dihydroxybenzene, 2-chloro-1 ,3-dihydroxybenzene, 2-methyl-1 ,3- dihydroxybenzene, 4-chloro-1 ,3-dihydroxybenzene, 5,6-dichloro-2-methyl-1 ,3- dihydroxybenzene, 1 -hydroxy-3-amino-benzene, 1 -hydroxy-3-(carbamoylmethyl- amino)benzene, 6-hydroxybenzomorpholine, 4-methyl-2,6-dihydroxypyridine, 2,6- dihydroxypyridine, 2,6-diaminopyridine, 6-aminobenzomorpholine, 1-phenyl-3- methyl-5-pyrazolone, 1 -hydroxynaphthalene, 1 ,7-dihydroxynaphthalene, 1 ,5- dihydroxynaphthalene, 5-amino-2-methyl phenol, 4-amino-2-hydroxytoluene, 2- amino-3-hydroxytoluene, 2-amino-5-hydroxytoluene, 4-hydroxyindole, 4-hydroxy- indoline, 6-hydroxyindole, 6-hydroxyindoline, 2,4-diaminophenoxyethanol, 1- naphthol, 2-naphthol, phenol, catechol, m-amino phenol, m-phenylenediamine, phenol which is substituted on the amino group or benzene ring with at least one alkyl, hydroxyalkyl, alkylamino group; catechol which is substituted on the amino group or benzene ring with at least one alkyl, hydroxyalkyl, alkylamino group; m- amino phenol which is substituted on the amino group or benzene ring with at least one alkyl, hydroxyalkyl, alkylamino group; m-phenylenediamine, which is substituted on the amino group or benzene ring with at least one alkyl, hydroxyalkyl, alkylamino group; and mixtures thereof.

Preferred coupling agents are selected from the group consisting of resorcinol, 1 -naphthol, 2-methylresorcinol, 4-amino-2-hydroxy toluene, m-amino- phenol, 2,4-diaminophenoxyethanol, 3-methyl-1-phenyl-5-pyrazolone, their salts, or mixtures.

Alkalizing agents

Preferably, the permanent hair colouring composition comprises an alkalizing agent. The term "alkalizing agent" means an ingredient that is capable of imparting alkalinity (e. g. a pH of greater than 7) to the oxidative composition. Preferred alkalizing agents are ammonium hydroxide, metal hydroxides, alkanolamines, sodium silicate, metal carbonates, sodium metasilicate, and mixtures thereof. Suitable metal hydroxides and carbonates include alkali metal and alkaline earth metal hydroxides or carbonates. Examples of such metal hydroxides are hydroxides of sodium, potassium, lithium, calcium, magnesium or. A particularly preferred alkaline earth metal hydroxide is sodium hydroxide. Preferably the alkanolamine is selected from the group consisting of mono-, di-, and trialkanolamines such as monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), 2-aminobutanol, aminoethyl propanediol, aminomethyl propanediol, bis-hydroxyethyl tromethamine (=bis(2-hydroxyethyl)amino-tris- (hydroxymethyl)methane), diethyl ethanolamine, diisopropanolamine, dimethylaminomethylpropanol, dimethyl MEA (=2-(dimethylamino)-ethan-1-ol), isopropanolamine, methylethanolamine, mixed isopropanolamines, triisopro- panolamine, tromethamine (=tris(hydroxymethyl)aminomethane) and mixtures thereof. A particularly preferred alkanolamine is monoethanolamine (MEA). Most preferred are dye mixtures that contain ammonium hydroxide as alkalizing agent in combination with a second alkalizing agent such as an alkanolamine.

Permanent hair colouring compositions are commercially available in a great variety of chemistry and colours. Particularly suitable as permanent hair dyes are those obtained from the commercial product lines selected from the group consisting of Schwarzkopf Brilliance from Schwarzkopf, Schwarzkopf got2b Edelmetall from Schwarzkopf & Henkel, L’ Oreal Preference Vivid Colors from L’ Oreal, Revlon © Total Color™ from Revlon, Schwarzkopf Brilliance Gem Collection from Schwarzkopf & Henkel, Wella Professional Koleston Perfect Pure Naturals from Wella, Wella Koleston from Coty, Beautycolor Bela&Cor from Bonyplus, Miracle System from Josh Wood Colour, Garnier Nutrisse Ultra Creme Permanent Hair Dye from L’Oreal and Hello!! Bubble Foam Color - Mise en Scene from Amorepacific.

The hair dye composition may comprise further ingredients the person skilled in the art knows for hair dye compositions form his/her knowledge. A few examples for such additional ingredients are selected from the group consisting of water, alcohols, particularly C10-22 alcohols, silicone oils, salts, particularly sodium chloride, fragrances, oils, particularly natural, plant oils, surfactants, preferably anionic surfactants or a nonionic surfactants or a amphoteric or zwitterionic surfactants, particularly alkylsulfates, alkylethersulfates, alkylsulfonates or alkylarylsulfonates, stabilizers, and thickeners, particularly celluloses or hydroxyethylcelluloses.

It is preferred that the hair dye is either a permanent hair dye or a semipermanent hair dye.

Hair Dy Kit

Due to the necessary chemical reaction between primary intermediate agent, coupling agent, and oxidant to form the permanent hair dye the hair dye composition is stored in the different compartments prior to the use resp. application of the hair dye composition.

Therefore, in a further aspect, the invention relates to a hair dye kit 1 comprising the hair dye composition 2, as described above in great detail, which is localized inside of a package 3.

As discussed above in one embodiment the hair dye of the hair dye composition comprises

- a semipermanent hair dye

- the mixture of branched and linear saturated C15-C19 alkanes; and

- the ester of a fatty acid and dextrin.

These parts of the hair dye compositions as well as their preferred embodiments have been already discussed above in great detail.

In this embodiment, the complete hair dye composition is preferably stored before its use in a single compartment package.

Figure 1 shows schematically such a hair dye kit 1 which has one compartment 4. The compartment is preferably so that the hair dye composition 2, which is localized inside the compartment, is protected from the environment and prevents the composition from leaking. The compartment is, hence, particularly preferred tight against water and/or humidity and/or other liquid fluids, and/or oxygen and/or light and/or protects the composition from heat. The compartment 3 is preferably made out of polymer, metal, metal alloy or composite, particularly metal coated polymer foil or metal and/or metal coated cardboard. The compartment preferably comprises means for filling and/or emptying 8, such as for example a lid or seal or cap or latch or cap, particularly a screwing cap, or any means to define a predefined breaking point or zone. The compartment may be flexible or solid. In this embodiment, the compartment 4 may also be regarded as a package 3 for the hair dye composition 2. As discussed above, in another preferred embodiment, the hair dye of the hair dye composition is a permanent hair dye composition and that the hair dye kit 1 comprises

- the mixture of branched and linear saturated C15-C19 alkanes; and

- the ester of a fatty acid and dextrin; and

- a primary intermediate agent, and

- a coupling agent; and

- an oxidant.

In this embodiment the hair dye kit 1 is preferably a hair dye kit 1 in which the package 3 consists of at least two different closed compartments 4 wherein the mixture of branched and linear saturated C15-C19 alkanes, the ester of a fatty acid and dextrin; and the primary intermediate agent are localized in a first compartment 4a and oxidant is localized in second compartment 4b.

Figure 2 shows schematically such a hair dye kit 1 which has a package 3 with different compartments.

The compartments 4, 4a, 4b can have loose compartments, i.e. that the individual compartments are not fixed to each other by fixing means. This can be realized for example by the use of individual bags or bottles as compartments.

It this case, it is preferred that these compartments are enclosed in a package 3 which might represent for example a transport or sale packaging. It is preferred that such a packaging is a covering box, particularly made of cardboard, preferably coated cardboard, or polymer. On this covering board, information such as trade name, instructions or any other information, which is typically printed on the outer surface of a commercial product packing, is preferably provided.

The different compartments 4, 4a, 4b, 4c can be all made out the same material or of different material. The size, respectively the inner space (content), of the individual compartments 4, 4a, 4b 4c are preferably chosen so that the respective amount of the respective parts of the hair composition corresponds to the amount needed in the final hair dye product.

Preferably, the following parts of a permanent hair dye composition

- the mixture of branched and linear saturated C15-C19 alkanes; and

- the ester of a fatty acid and dextrin; and

- a primary intermediate agent, and

- a coupling agent; are contained in the first compartment 4a whereas the oxidant is contained in the second compartment 4b.

In one of the preferred embodiments, the volume of inner space of one of the compartments is chosen so that the complete amount of hair dye composition can be filled in said compartment.

An example for such an embodiment is schematically represented in figure 4. In this example, a few components of the hair dye composition 2, particularly the mixture of branched and linear saturated C15-C19 alkanes; and

- the ester of a fatty acid and dextrin; and

- a primary intermediate agent, and

- a coupling agent; are stored in a first compartment 4a.

In the second compartment 4b, the rest of the hair dye composition 2, particularly an oxidant, are stored. The second compartment 4b is only partially filled with the respective parts of the hair dye composition so that compartment has sufficient remaining (empty) volume capacity inside of the second compartment 4b to take up the parts of the hair dye composition 2 stored in the first compartment 4a. The second compartment 4b has preferably means for filling and/or emptying 8, as shown in figure 4, preferably a screwing cap. The ingredients of the hair dye composition 2 are storage stable for an extended time, particularly for several months. Figure 5a shows the situation when the package 3 of the kit, is removed, and the second compartment 4b is opened, particularly by applying the means for filling and/or emptying 8, as shown in figure 3, preferably by removing the screwing cap.

The first compartment 4a, which is for example a sealed polymer bag or a bottle made of polymer, also opened, for example by cutting the walls of the first compartment by a pair of scissors or puncturing to allow accessing the parts of the hair dye composition stored in the first compartment 4a. These parts of the hair dye composition are added to the part of the hair dye composition stored in the second compartment 4b.

Figure 5b shows the situation of figure 5a after complete filling the content of the first compartment in to the second compartment. The complete hair dye composition is within the second compartment 4b. By closing the means for filling and/or emptying 8, preferably by remounting the screwing cap, the different components may be easily mixed, for example by shaking, before the permanent hair dye is formed by the ingredients so that the permanent hair dye composition is ready for use. At this moment in time, the means for filling and/or emptying 8, can be used again, preferably by removing the screwing cap, to allow the composition to leave the second compartment 4b and to be applied to hair.

The different compartments may also be connected to each other. In this case they are typically connected by means to define a predefined breaking point or zone. Such means can be obtained particularly by moulding of thin layers of polymers and/or by weakening the material linking the compartments by holes, particularly by a row of lines, which allow the destruction of the link between the compartments by for example ripping forces.

Figure 6 shows a schematic representation of such a typical hair dye kit which has two compartments with a linking zone with a predefined breaking point or zone. The first compartment 4a and the second compartment 4b are connected to each other by means of a predefined breaking point or zone 7. In this area the thickness of material is typically reduced and/or comprises holes 6, as shown in figure 6. The material thickness and/or number and size of holes is typically chosen so that the two compartments 4a and 4b are held together. By exerting a specific force to this area, the linkage is broken so that the two compartments can be taken apart. This force is typically applied by a ripping action exerted by the hand of the consumer or hairdresser or by cutting action by a pair of scissors or a knife. This embodiment has the advantage that during storage and transport the two compartments are not moved loosely within the package 3 and can be easily separated at the time of use allowing an easy handling of the two compartments.

Figures

Figure 1 shows a schematic representation of a hair dye kit which has one compartment.

Figure 2 shows a schematic representation of a hair dye kit which has two compartments.

Figure 3 shows a schematic representation of a hair dye kit which has three compartments.

Figure 4 shows a schematic representation of a hair dye kit which has two compartments of which one compartment provides sufficient inner space to enclose the whole hair dyeing composition.

Figure 5 shows a schematic representation of a hair dye kit of figure 4 before (figure 5a) and after mixing (figure 5b).

Figure 6 shows a schematic representation of a hair dye kit which has two compartments with a linking zone with a predefined breaking point or zone. List of reference signs

1 Hair Dye Kit

1 Hair dye composition

2 Package

3 Compartment

4a First Compartment

4b Second Compartment

4c Third compartment

4 Linking zone

5 Hole

6 Predefined breaking point or zone

7 Means for filling and/or emptying

Resistance of hair dye applied on hair

The hair dye composition is applied to hair, particular to human hair. It has been observed that the hair dye composition, as described above in great detail, leads to an increased colour resistance of a hair dye which is applied to hair.

Colours are difficult to describe. One of the methods is the representation of colour by the so-called Lab colour space. Currently the mostly used Lab method is the CIE-L*a*b*as proposed by CIE in 1976. In this representation the parameters “L”, resp. “L*”, is lightness, and the parameters “a”, resp. “a*”, and “b”, resp. “b*”, are colour-opponent dimensions. The parameter L, resp. L*, has a value between 0 and 100, parameters a and b, resp. a* and b*, have a value between - 100 and 100.

Changes in colour are, hence, defined by a change of L, resp. L*, (= AL resp. AL*), a, resp. a*, (= Aa resp. Aa*), and/or b, resp. b*, (= Ab resp. Ab*) values.

Despite the background theory is rather complex, a decrease of value of L, resp. L* leads to a sensation of a darker colour. An increase of the value a, resp. a* leads to a sensation of enhancing of the red colour component. An increase of the value b, resp. b* leads to a sensation of enhancing of the yellow colour component. A colour change is usually not only a change of an individual parameter L, a or b, resp. L*, a* or b*, but a change of more than one of these parameters simultaneously.

Hence, there has been the colour difference defined which is expressed by AE, resp. AE*, according to the following formula

Assessing the advantage of this invention is best realized by comparing the measured colour of dyed hair before and after shampooing and/or washing cycles.

As mentioned, it has been observed that the hair dye composition, as described above in great detail, leads to an increased colour resistance of a hair dye which is applied to hair.

Hence, in a further aspect, the present invention relates to the use of a mixture of branched and linear saturated C15-C19 alkanes in combination with an ester of a fatty acid and dextrin in a hair dye for increasing the colour resistance of a hair dye which is applied to hair.

More specifically, the hair dye is in a one preferred embodiment a semipermanent hair dye and in another preferred embodiment a permanent hair dye.

In a further aspect, the invention relates to a method of dyeing hair comprising the steps of a) applying a hair dye composition as shown above in great detail to hair b) washing the dyed hair.

Typically, step b) takes only place after a certain time of waiting after step a). In this time of typically 5 to 60 minutes, particularly 30 - 45 minutes, between step a) and b) the hair dye has the chance to better coat and/or penetrate the hair.

Particularly in case where the hair dye is a permanent dye, it is advised that the hair dye composition is thoroughly mixed to allow that the ingredients of the hair dye composition are homogenously distributed and that certain parts of the ingredients, such as primary intermediate agent, coupling agent and oxidant, are enabled to react to form the permanent hair dye, before the final hair dye composition is applied to the hair in step a). It is, furthermore, preferred that the hair is treated with a conditioner.

Hence, it is preferred that after step b) a step c) followed by step d) is performed in the above method c) applying a hair conditioner to the dyed and washed hair resulting from steps a) and b); d) washing the conditioned dyed hair resulting from step c).

Hair conditioners, as well as their compositions, are well known to the person skilled in the art.

Examples

The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

Experimental series 1 : semipermanent hair dye

Dyeing of hair by semipermanent hair dyes

Hair tresses (Kerling Nr. 826204 KT dicht, Euro-hair, remis extra bleached, color 10/0, length: 120 mm) have been dyed according to the instruction provided in the package of the semipermanent hair dye Revelon Professional® Nutri Color™ Filters 200 Violet ("200 Viole ) or Revelon Professional® Nutri Color™ Filters 190 Blau (“190 Blau”) or Revelon Professional® Nutri Color™ Filters 740 Light Copper (^’740 Light Copper¹’) using the hair dyeing composition according to table 1 .

Revelon Professional® Nutri Color™ Filters 190 Blau comprises the semipermanent hair dye HC blue No. 16 (=dimethyl-[3-[[4-(methylamino)-9,10-dioxo- anthracen-1-yl]amino]propyl]-propylazanium bromide).

Revelon Professional® Nutri Color™ Filters 200 Violet comprises the semipermanent hair dyes HC blue No. 16 and Basic Violet 2 (=4-[(4-amino-3- methylphenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]-2- methylaniline hydrochloride).

Revelon Professional® Nutri Color™ Filters 740 Light Copper comprises the semipermanent hair dyes Basic Brown 17 (=[8-[(4-Amino-2-nitrophenyl)azo]-7- hydroxy-2-naphthyl]trimethylammoniumchlorid) and Basic Red 76 (=[7-Hydroxy-8- [(2-methoxyphenyl)azo]-2-naphthyl]trimethylammoniumchlorid).

The hair dye composition has been prepared by admixing dextrin palmitate, and/or C15-C19 alkane and/or water at 70°C under stirring in a beaker to the undiluted commercial hair dye (i.e. 190 Blau or 200 Violet or 740 Light Copper). The compositions of table 1 have been cooled under stirring to room temperature before further use.

Each hair tress has been treated with 1 ml of the respective hair dyeing composition for 5 minutes. The tress has been rinsed for 30 seconds with warm water (38°C) and dried at room temperature overnight. 3 tresses have been prepared per sample.

Table 1 . Hair dye compositions (amounts in % by weight).

⁷ comprises semipermanent hair dye HC blue No. 16 (=dimethyl-[3-[[4-(methylamino)-9,10- dioxo-^,anthracen-1 -yl]amino]propyl]-propylazanium bromide)

² comprises semipermanent hair dyes HC blue No. 16 and Basic Violet 2 (=4-[(4-amino-3- methylphenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]-2-methylaniline hydrochloride).

³ comprises semipermanent hair dyes Basic Brown 17 (=[8-[(4-Amino-2-nitrophenyl)azo]-7- hydroxy-2-naphthyl]trimethylammoniumchlorid) and Basic Red 76 (=[7-Hydroxy-8-[(2- methoxyphenyl)azo]-2-naphthyl]trimethylammoniumchlorid)

⁴ Dextrin Palmitate: Mn=11'300-11'500 Da, determined by SEC/GPC.

⁵ EMOGREEN™ L19

Shampooing of hair dyed by semipermanent hair dye

For each shampooing/washing cycle the dyed tresses have been washed with 0.5 ml of a shampoo of the composition according to table 2 per hair tress for 30 seconds, and then rinsed for 30 seconds with warm water (38°C). This procedure has been repeated 4 times so that the tresses have been shampooed/washed 5 times in total for each shampooing/washing cycle. At the end of each shampooing/washing cycle the tresses have been dried at room temperature overnight.

Table 2 Composition of shampoo.

‘amounts in % by weight.

Color measuring

The L*a*b*-values of the hair tresses have been measured before the first (i.e.

“after 0 cycles") and after the respective shampooing/washing cycles (i.e. “after 1 cycle", “after 2 cycles" etc.), using a Konica Minolta-CM 600d color measurement device. The respective 3 tresses have been positioned next to each other and the L*a*b*-values have been 25 times measured and their average has been reported in tables 3, 5 and 7. The changes in colour indicated as AL*, Aa*, Ab* and AE* in tables 4, 6 and 8 are calculated from the color measurements of the initial values and after the respective shampooing/washing cycles.

Table 3. Measurement of L*a*b* values of hair dyed with dyes of table 1 based on semi-permanent dye Revelon Professional® Nutri

Color™ Filters 190 Blau.

Table 4. Changes in L*a*b* values of table 3 compared to the values after 0 cycles. ^Changes in AE* values versus Ref.1

Table 5. Measurement of L*a*b* values of hair dyed with dyes of table 1 based on semi-permanent dye Revelon Professional® Nutri Color™ Filters 200 Violet.

Table 6. Changes in L*a*b* values of table 5 compared to the values after 0 cycles. ^Changes in AE* values versus

Ref.4

Table 7. Measurement of L*a*b* values of hair dyed with dyes of table 1 based on semi-permanent dye Revelon Professional® Nutri Color™ Filters 740 Light Copper. i o

00

Table 8. Changes in L*a*b* values of table 7 compared to the values after 0 cycles. ^Changes in AE* values versus

Ref.7

Experimental series 2: Dyeing of hair by permanent hair dyes

Dyeing of hair by permanent hair dyes

Hair tresses (Kerling Nr. 826204 KT dicht, Euro-hair, remis extra bleached, color 10/0, length: 120 mm) have been dyed according to the instruction provided in the package of the permanent hair dyes Igora Royal permanent color cream 0-89 red violet or Igora Royal Metallics 5-26 Lightbrown Ash Chocolate using the respective hair dye composition of table 9.

Table 9. Permanent hair dye compositions (amounts in % by weight).

¹ CP Igora red represents the color part of the two compartment package of the commercial product Igora Royal permanent color cream 0-89 red violet. The color part comprises 1 -Hydroxyethyl 4,5-Diamino Pyrazole Sulfate (primary intermediate) and 1- Naphthol (coupling agent).

² CP Igora LB represents the color part of the two compartment package of the commercial product Igora Royal Metallics 5-26 Lightbrown Ash Chocolate comprises toluene-2,5-diamine sulfate, 6-methoxy-2-methylamino-3-aminopyridine, 1 -hydroxyethyl 4,5- diamino pyrazole sulfate (primary intermediates); resorcinol, m- aminophenol, 2-methylresorcinol, 4-amino-2-hydroxy toluene (coupling agents).

³ Dextrin Palmitate: Mn=11'300-11'500 Da, determined by SEC/GPC.

⁴ EMOGREEN™ L19 The hair dye compositions have been prepared by admixing the respective amounts, given in table 9, of dextrin palmitate, and/or C15-C19 alkane and/or water at 70°C under stirring in a beaker to the undiluted color cream part of the commercial hair dye (i.e. CP Igora red or CP Igora LB) (comprising primary intermediate agents and coupling agents). The compositions of table 9 have been cooled under stirring to room temperature before further use. Then the so prepared compositions have been mixed with the respective developer part (comprising hydrogen peroxide as oxidant) of the commercial hair dye according to the instruction provided with the commercial hair dye in a plastic hairdresser bowl and mixed with a hair color brush. The mixed solution was then let to rest for 5 minutes.

Each hair tress has been then treated with 1 ml of the respective hair dyeing composition prepared as described. After 30 minutes of exposure time the tresses have been rinsed with warm water (38°C) until the water ran clear. Then the tresses have been dried over night at room temperature. The tresses have been cut in switches of 1 .0 cm width. For each test 3 tresses have been prepared.

The color of the dyed tresses has been measured to get the initial L*, a* b* values value (i.e. “after 0 cycles") using the color measuring method as described below “Color measuring”.

Shampooinq/Washinq of hair dyed by permanent hair dye

For each shampooing/washing cycle the dyed tresses have been washed with 0.5 ml of a shampoo of the composition according to table 2 per hair tress for 30 seconds, and then rinsed for 30 seconds with warm water (38°C). This procedure has been repeated 10 times so that the tresses have been shampooed/washed 10 times in total for each shampooing/washing cycle. At the end of each shampooing/washing cycle the tresses have been dried at room temperature overnight.

Color measuring

The L*a*b*-values of the hair tresses have been measured before the first (i.e. “after 0 cycles") and after the respective shampooing/washing cycles (i.e. “after 1 cycle", “after 2 cycles" etc.) respectively, using a Konica Minolta-CM 600d color measurement device. The respective 3 tresses have been positioned next to each other and the L*a*b*-values have been 25 times measured and their average has been reported in tables 10 and 12. The changes in colour indicated as AL*, Aa*, Ab* and AE* in tables 11 and 13 are calculated from the color measurements of the initial values and after the respective shampooing/washing cycles.

Table 10. Measurement of L*a*b* values of hair dyed with permanent dyes according to table 9 based on CP Igora red.

T able 11 . Changes in L*a*b* values of table 10 compared to the values after 0 cycles. ^Changes in AE* values versus Ref.10

Table 12. Measurement of L*a*b* values of hair dyed with permanent dyes according to table 9 based on CP Igora LB.

Table 13. Changes in L*a*b* values of table 12 compared to the values after 0 cycles. ^Changes in AE* values versus Ref.13

The results of tables 3 - 8 and 10 - 13 show that the inventive hair dye compositions (i.e. 1, 2, 3, 4 and 5) show significantly higher colour resistance of dyed hair as compared to the comparative hair compositions (i.e. Ref.1 - Ref. 15) with semipermanent or permanent hair dyes, respectively.

Such an increase of higher colour resistance is very advantageous to the endcustomer as the hair colour remains visually more or less constant for a longer period of time and, as a result thereof, extends the time until a next hair coloration is needed.

Claims

1 . A hair dye composition comprising

- a mixture of branched and linear saturated C15-C19 alkanes; and

2. The hair dye composition according to claim 1 , characterized in that the amount of linear saturated C15-C19 alkanes in said mixture of branched and linear saturated C15-C19 alkanes is less than 10 % by weight, preferably less than 8 % by weight, most preferred more than 5 % by weight, in respect to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

3. The hair dye composition according to claim 1 or 2, characterized in that the amount of branched saturated C18 alkane is more than 50% by weight, preferably more than 60 % by weight, even more preferably more than 70 % by weight, relative to the weight of said mixture of branched and linear saturated C15-C19 alkanes.

4. The hair dye composition according to any of the preceding claims characterized in that said ester of a fatty acid and dextrin has an average number of esterified hydroxyl groups of more than 2.5, preferably between 2.5 and 3.5, more preferably between 2.5 and 3.4, most preferably between 2.5 and 3.2, per glucose unit.

5. The hair dye composition according to any of the preceding claims characterized in that said ester of a fatty acid and dextrin has a molecular weight M_n of between 8'000 and 16'000 Da, preferably between 9'000 and 13'000 Da, more preferably between 10'000 and 11'500 Da. The hair dye composition according to any of the preceding claims characterized in that the hair dye composition is a permanent hair dye. The hair dye composition according to any of the preceding claims 1 to 5 characterized in that the hair dye composition is a semipermanent hair dye. The hair dye composition according to any of the preceding claims characterized in that the amount of the mixture of branched and linear saturated C15-C19 alkanes is in the range of between 0.015 and 12.0 % by weight, particularly between 0.5 and 11 .0 % by weight, preferably between

1 .0 and 10.0 % by weight, more preferably between 1 .5 and 8.0 % by weight, even more preferably between 2.0 and 6.0 % by weight, based on the weight of the hair dye composition. The hair dye composition according to any of the preceding claims characterized in that the amount of the ester of a fatty acid and dextrin is in the range of between 0.01 and 15 % by weight, particularly between 0.1 and 12 % by weight, preferably between 0.2 and 8 % by weight, more preferably between 0.6 and 7 % by weight, even more preferably between 1 .3 and 4 % by weight, based on the weight of the hair dye composition. . A hair dye kit (1 ) comprising the hair dye composition (2) according to any of the preceding claims 1 to 9 localized inside of a package (3). . The hair dye kit (1 ) according to claim 10 characterized in that the hair dye is a permanent hair dye and comprises

- the mixture of branched and linear saturated C15-C19 alkanes; and

- the ester of a fatty acid and dextrin; and

- a primary intermediate agent, and

- a coupling agent; and

- an oxidant. The hair dye kit (1) according to claim 11 characterized in that the package

(3) consists of at least two different closed compartments (4) wherein the mixture of branched and linear saturated C15-C19 alkanes, the ester of a fatty acid and dextrin; and the primary intermediate agent are localized in a first compartment (4a); and that the oxidant is localized in second compartment (4b). Use of a mixture of branched and linear saturated C15-C19 alkanes in combination with an ester of a fatty acid and dextrin in a hair dye for increasing the colour resistance of a hair dye which is applied to hair. The use according to claim 13, characterized in that the hair dye is a permanent hair dye. Method of dyeing hair comprising the steps of a) applying a hair dye composition according of the preceding claims 1 to 9 to hair b) washing the dyed hair.