EP1067900A1 - Packaged hair colouring composition - Google Patents

Abstract

Packaged hair colouring composition comprising a stable aqueous hair colouring composition comprising a compound of formula (I), wherein D is a chromophore; X and Y are independently selected from halogen and -SR', provided that at least one of X and Y is -SR', wherein R' is selected from H, C1-C4 alkyl, (CH2)nCOOH, (CH2)nCONH2, (CH2)nSO3H, (CH2)nCOOM, (CH2)nPO3H, (CH2)nOH, (CH2)nSSO3-, (CH2)nNR'2, (CH2)nN+R'3, PhSSO3-, PhSO¿3?H, PhPO3H, PhNR'2, PhN?+R'¿3, -CN, SO3-, (CH2)2CH(SH)R'(CH2)3COOH, -CH2CHOHCH2SH, and formulas (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), -CH2CH2NH2; n is an integer in the range of 1 to 4 wherein within the same molecule n is not necessarily the same integer; and M is a cation of alkaline earth metal, alkali metal, NH4+ or NR'¿3?+; L is a linking moiety; Z is selected from pyrimidine or triazine; R'' is C1-C4 alkyl; and a package for said hair colouring composition. The packaged hair colouring compositions of the present invention provide improved wash fastness of dye on hair, less colour fade over time, improved consumer acceptance in terms of providing a single packaged hair dye composition and improved product stability.

Description

Packaged Hair Colouring Composition

Technical Field

This invention relates to a packaged hair colouring composition comprising a reactive

dye compound comprising a chromophore and a nitrogen-containing heterocycle comprising at least one thio-substituent.

Background of the Invention

The desire to alter the color of human hair is not a facet of modern times. Since the days of the Roman Empire the color of human hair has been routinely altered to accommodate the changes of fashion and style. However the attainment of precise

initial colors which are retained by the hair for a desirable period has remained a more

elusive goal. The difficulties in the development of hair coloring compositions which

can deliver precise long-lasting colors are in part due to the inherent structure of the hair itself and in part due to the necessary conditions of effective hair coloration processes.

In general, the condition and structure of human hair is not regular along the length

of the hair shaft. Human hair is subject to various chemical and mechanical

treatments such as combing, brushing, shampooing, heating, perming as well as 2

exposure to the sun. As such, the hair at the ends of the hair shaft will generally

exhibit greater signs of damage relative to the new growth close to the scalp. This damage can lead to inconsistent coloration when the hair is dyed due to irregular

uptake of the hair coloring agents along the length of the hair shaft.

Once the hair has been colored there is a desire for the color to be resistant to fading,

as occasioned by the actions of washing (also known as wash fastness), perspiration,

hair spray and other exterior factors such as the action of the sun, and further that the

color be retained in a consistent manner for a predictable period of time. Additionally

damage to the hair that can lead to irregular dye uptake as discussed above, can lead

to increased fading of the damaged portions of the hair and consequently, irregular levels of color fade over time. An additional difficulty commonly associated with the

dyeing of human hair is the need for dye systems which avoid any adverse effect on

the hair and skin of the user, such as brittle hair, or, irritation of the skin, or, staining

(coloring) of the skin.

Thus, it would be desirable to develop a hair coloring composition which exhibits

reduced fade, provides improved resistance to wash out during a regular cleansing

regimen, can deliver substantially consistent hair color results throughout the hair,

which has reduced irritant effect on the skin , which has reduced staining on the skin,

which has reduced adverse effects on the hair of the user and also to develop a convenient and easy-to-use method for the delivery of such a hair coloring composition to the hair. Over the years significant effort has been directed towards the elimination of many of

the problems associated with the dyeing of human hair Various approaches to hair

dyeing have been developed, these include, oxidative dyes, direct action dyes, natural dyes, metallic dyes and reactive dyes.

GB-A-0,951,021 (Turner-Hall Corporation) relates to methods and compositions for

dyeing keratinous fibres by attaching a dyestuff molecule to a particular site thereof

through true covalent bonds The method comprises reducing some of the disulfide linkages of the cystine in the fibers to sulfhydryl groups while breaking hydrogen

bonds by applying to the fibers in alkaline aqueous solution a reducing agent for

breaking disulfide linkages of keratinous fibres and a hydrogen bond breaker for

keratinous fibres and bonding a water-soluble fibre reactive dye compound such as a

dichlorotriazine dye to the sulfhydryl groups by applying an aqueous solution of the

fibre reactive dye. Thioglycolic acid is disclosed as a reducing agent

US-A-3,415,606 discloses a method for dyeing human hair comprising the steps of

treating said hair with an effective amount of mercaptan and then treating the hair

with a dichlorotriazine fibre reactive dye

"The Reaction Mechanism of Fibre Reactive Dyestuffs with Hair Keratin", Albert

Shansky, American Perfumer and Cosmetics, November 1966, and "Dyeing of

Human Hair with Fibre Reactive Dyestuffs", Albert Shansky, Cosmetics and

Toiletries, November 1976, disclose a method of coloring hair comprising treating 4

the hair for five minutes with a reducing-H bond breaking solution (containing

thioglycolate, alkali, lithium bromide and urea) followed by rinsing the hair and then

treating the hair with a dichlorotriazine fibre reactive dye

Dyes and Pigments 14, 1990, pages 239-263, "Synthesis and Application of Reactive Dyes with Heterocyclic Reactive Systems" discloses fibre reactive dyes containing chlorotriazine heterocycles with thio substituents

Reactive dye hair coloring agents can be used to deliver a variety of hair colors to the

hair However substantial improvement is needed in the areas of color saturation,

color development, precise initial color consistency, improved wash fastness,

improved hair condition and levels of hair damage

Thus there is a need for reactive dye hair coloring compounds and compositions

which effectively dye the hair but avoid or reduce damage to the hair, which can

color the hair effectively and avoid or reduce irritation and/or staining to the skin of the user

It has surprisingly been found that the packaged hair colouring compositions of the

present invention comprising a nitrogen-containing heterocycle selected from

pyrimidine or triazine, substituted with at least one thio-deπvative, provides

improvements in colour saturation, colour development, colour consistence, wash

fastness, hair condition, and reduction in hair damage and skin irritation In addition, conventional, reactive dye hair coloring compositions typically comprise

at least two separately packaged components, which are generally, reducing agent

and reactive dye hair coloring agents. These separately packaged components are

admixed just prior to application to the hair. Such an admixing step can be messy

and inconvenient to the user. Typically, such coloring compositions need to be used soon after admixing due to degradation of the resulting coloring composition. As

such, excess admixed coloring composition is disposed of after application of the

required amount to the hair. It has been found that the reactive dyes of the present

invention can be incorporated in a singly packaged mixture with improved stability

versus conventional reactive dye systems. The singly packaged coloring compositions of the present invention are suitable for use in a multi-application

format (i.e. the consumer can use a single package for several color applications over

a period of time). It has also been found that the reactive dye compounds and

compositions herein are stable over time, and can be stored as such.

All percentages are by weight of the final compositions in the form intended to be

used unless specified otherwise.

Summary of the Invention

According to the present invention there is provided packaged hair colouring composition comprising a stable aqueous hair colouring composition

comprising a compound of formula (I):

wherein D is a chromophore;

X and Y are independently selected from halogen and -SR', provided that at

least one of X and Y is -SR', wherein R' is selected from H, C 1 -C4 alkyl,

(CH2)_nCOOH, (CH2)_nCONH₂, (CH2)_nSO₃H, (CH₂)_nCOOM,

(CH₂)_nPO₃H, (CH₂)_nOH, (CH₂)_nSSO₃ ^', (CH₂)_nNR"₂, (CH₂)_nN⁺R"₃, PhSSO3^", PhSO₃H, PhPO₃H, PhNR"2, PhN⁺R"₃, -CN, SO3^", (CH2)2CH(SH)R"(CH2)3COOH, -CH2CHOHCH2SH, and

NH

^■C ^

NH,

NH₂

/

^■H₂C CH

COOH -HC COOH

CHo COOH

=CH

COOHC IOOH

CH₃

C COOH

H

OH

-C COOH

CH, H C- ^■(CH₂)_n-

CH- -CO- "(CH₂)_n- ^■SH

CH, -o- -CO- "(CH₂)_n- ^•SH

HoC- -(CH₂)_n-

CH- ^■CO- ^•(CH₂)_n- ^■SR"

CH, ^■O CO (CH₂)_n SR"

H n₍H₂C) O- "(CH₂)_n-

CH, "(CH₂)_n-

CH -O CO (CH₂)_n SH CH₂- - (CH₂)_n-

CH, -CO- ^■ (CH₂)_n- ^■SR"

CH₂CH₂CH CH₂CH₂CH₂COOH

SR"

-CH₂CH₂NH2_.

n is an integer in the range of 1 to 4 wherein within the same molecule n is not necessarily the same integer; and M is a cation of alkaline earth metal, alkali

metal, NH4⁺ or NR" ⁺ _;

L is a linking moiety;

Z is selected from pyrimidine or triazine;

R" is C1-C4 alkyl; 10

and a package for said hair colouring composition.

The packaged hair colouring compositions of the present invention provide improved

wash fastness of dye on hair, less colour fade over time, improved consumer

acceptance in terms of providing a single packaged hair dye composition and improved product stability.

Detailed Description of the Invention

The packaged hair colouring composition of the present invention comprises a hair

colouring composition comprising a reactive dye compound and a package for said

hair colouring composition.

Any suitable packaging for delivering the reactive dye compounds and compositions

described herein can be used. Examples of suitable packaging include bottle, pump-

foamer, and the like.

The hair colouring composition comprises a reactive dye which comprises a nitrogen-

containing heterocycle, a chromophore moiety, a linking group to link the nitrogen- containing heterocycle to the chromophore.

The reactive dye compounds used herein have the formula (I) 11

wherein D is a chromophore;

X and Y are independently selected from halogen and -SR', provided that at

least one of X and Y is -SR', wherein R' is selected from H, C 1 -C4 alkyl,

(CH2)_nCOOH, (CH2)_nCONH2, (CH2)_nSO₃H, (CH2)nCOOM,

(CH₂)_nPO₃H, (CH₂)_nOH, (CH₂)_nSSO₃ ^", (CH₂)_nNR"2, (CH₂)_nN⁺R"₃, PhSSO₃ ^", PhSO H, PhPO H, PhNR"2, PhN⁺R"₃, -CN, SO ^", (CH2)2CH(SH)R"(CH2)3COOH, -CH2CHOHCH2SH, and

NH

^■cr?

NH, .

NH₂

/

-H₂C CH

\

COOH 12

-HC COOH

CH₂ COOH

:CH

COOHCOOH

CH₃

C COOH

H

OH

C COOH

CH-, 13

H,C- ^■(CH₂)_n-

CH- -CO (CH₂)_n SH

CH, -CO- "(CH₂)_n- ^■SH

O

H,C- "(CH₂)_n-

CH- -CO- " (CH₂)_n- ^■SR"

CH, -O- -CO- ^•<CH₂)_n- ^■ SR"

H n₍H₂C) O- ^■ (CH₂)_n-

CH, ^■O C (CH₂)_n-

CH₂ O CO (CH₂)_n SH 14

CH, ^■O- ^■ (CH₂)n^"

CH, -CO- ^•(CH₂)_n- -SR"

-CH₂CH₂CH CH₂CH₂CH₂COOH

SR"

-CH2CH2NH2

n is an integer in the range of 1 to 4 wherein within the same molecule n is not

necessarily the same integer, and M is a cation of alkaline earth metal, alkali

metal, NH4⁺ or NR"₃ ⁺

L is a linking moiety,

Z is selected from pyrmidine or triazine,

R" is C1-C4 alkyl,

and esters and salts thereof 15

Chromophore Moiety

Any chromophore moieties suitable for use for dying substrates can be used in the

present invention. The term chromophore as used herein means any photoactive

compound and includes any coloured or non-coloured light absorbing species, eg. fluorescent brighteners, UV absorbers, IR absorbing dyes.

Suitable chromophore moieties for use in the dye compounds herein include the

radicals of monoazo, disazo or polyazo dyes or of heavy metal complex azo dye

derived therefrom or of an anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye.

Suitable chromophore moieties for use in the dye compounds herein include those

disclosed in EP-A-0,735,107 (Ciba-Geigy), incorporated herein by reference,

including the radicals described therein which contain substituents customary for

organic dyes, such as sulphonate substituents which enhance the water-soluble properties of the dye compound.

Most preferred chromophore D groups for use herein are polysulphonated azo

chromophores such as those present in Levafix (RTM) dyes commercially available

from Dystar. 16

Nitrogen Containing Heterocycle

The nitrogen containing heterocycle herein is selected from pyrimidine or triazine, preferably triazine.

The nitrogen containing heterocycle has at least one thio substituent SR' wherein R'

is selected from H, C1-C4 alkyl, (CH2)_nCOOH, (CH2)_nCONH2, (CH2)_nSO₃H,

(CH )_nCOOM, (CH₂)_nPO₃H, (CH₂)_nOH, (CH₂)_nSSO₃ ^", (CH₂)_nNR"2, (CH2)_nN⁺R"₃, PhSSO₃ ^", PhSO₃H, PhPO H, PhNR"2, PhN⁺R" , -CN, SO3^", (CH2)2CH(SH)R"(CH2)₃COOH, -CH2CHOHCH2SH, and

NH

-C

^' NH .

NH₂

/

-H₂C CH

COOH 17 HC COOH

CH₂ COOH

:CH

COOHCOOH

CH₃

^•C COOH

H

OH

-C COOH

CH,

18

O

H,C- ^■(CH₂)_n-

CH- -CO- "(CH₂)_n- ^■SH

CH, ^■CO- "(CH₂)_n- -SH

H,C- -(CH₂)_n-

CH- ^■O- -CO- "(CH₂)_n- ^■SR"

CH, -CO (CH₂)_n SR"

H n₍H₂C) O- "(CH₂)_n-

CH, ^■(CH₂)_n-

CH₂ O CO (CH₂)_n SH 19

CH, "(CH₂)_n-

CH, -co- ^■(CH₂)_n- ^■SR"

CH₂CH₂CH CH₂CH₂CH₂COOH

SR"

-CH2CH2NH2_.

n is an integer in the range of 1 to 4 wherein within the same molecule n is not

necessarily the same integer; and M is a cation of alkaline earth metal, alkali

metal, NH4⁺ or NR"₃ ⁺ _.

Preferred R' groups for use herein are CH2COOH, CH2CH2OH and (COOH) CH2CH2(COOH), preferably CH2COOH.

The nitrogen-containing heterocycle may be substituted by two SR' groups or by one

SR' group and one halogen group, preferably by two SR' groups.

Linking Moiety 20

The compounds herein further comprise a linking moiety to link each nitrogen-

containing heterocycle to each chromophore moiety. Any linking moieties suitable

for use in dyeing substrates can be used in the present invention. Preferably the

linking moiety is selected from NR, NRC=O, C(O)NR, NRSO2 and -SO2NR wherein R is H or C1-C4 alkyl which can be substituted by halogen, preferably fluorine or chlorine, hydroxyl, cyano, C1-C4 alkoxy, C2-C5 alkoxycarbonyl,

carboxyl, sulfamoyl, sulfo or sulfato. When the heterocycle is quinoxaline or

phthalazine, a preferred linking moiety is NRC=O, where R is H or C 1 -C4 alkyl,

more preferably where R is H or CH₃, especially H.

In general, dyes having the formula (I) can be prepared by reacting suitable

precursors of the dye of formula (I) with one another, at least one of which contains a

group D-L-Z, wherein D, L and Z are as defined above, at least one of which

contains an S group (wherein R is as defined above).

For example, dye compounds of the invention having a formula (1) wherein Z is a

triazine heterocycle can be prepared by reacting one mole of dichlorotriazine dye,

such as those commercially available from BASF under the tradename Procion

(RTM), with a one mole of a suitable reactant containing an SR¹ group.

Dye compounds of the invention having a formula (I) wherein Z is a pyrimidine

heterocycle can be prepared by reacting a difluoromonochloro pyrimidine dye such as

those commercially available from Clariant under the tradenames Drimalan F (RTM)

and Drimarene R or K (RTM), or a trichloropyrimidine dye such as those 21

commercially available from Clariant under the tradename Drimarene X, with a suitable reactant containing an SR' group

The reactions of the starting dye compounds with the reactant containing an SR' group are generally carried out at a pH of from about 7 to about 10, and at a temperature of about 0-5 C

The dye compounds herein can be incorporated into dye compositions together with

suitable carrier materials which are selected depending on what type of substrate is

being dyed Such carrier materials will be well known to those skilled in the art

Any carrier materials suitable for use in hair dye compositions can be used herein

The compositions of the present invention comprise from about 0 01% to about 10%,

preferably from about 0 1% to about 5%, especially from about 0 1% to about 3% by

weight of one or more reactive dye compounds having the formula (1) The types

and levels of dyes used in each composition will depend upon the desired hair shade

A preferred ingredient in the hair dye compositions herein is a reducing agent Any

reducing agents suitable for use in hair dye compositions may be used herein Some

typical reducing agents for use herein are listed in GB-A-951,021 and GB-A-

589,956, incorporated herein by reference Examples of suitable reducing agents include thioglycolic acid, thiolactic acid, dihydrolipoate, thioglycerol,

mercaptopropionic acid, sodium bisulfite, ammonium bisulfide, zinc formaldehyde 22

sulfoxylate, sodium formaldehyde sulfoxylate, sodium metabisulfite, potassium borohydride, pegylated thiols and hydroquinone. Particularly suitable for use herein

are pegylated thiols.

Another preferred ingredient herein is a hydrogen bond breaker. Any hydrogen bond

breaker suitable for use in a hair dye composition can be used herein. Suitable

examples include lithium bromide, urea, resorcinol, catechol, dihydroxyacetone,

formamide, potassium chloride and magnesium chloride. Particularly preferred for

use herein is urea.

The coloring compositions of the present invention have a pH in the range of from

about 7 to about 11 , preferably from about 9 to about 10.5. In order to maintain

such a pH the compositions may contain one or more optional buffering agents.

Examples of alkaline buffering agents are ammonium hydroxide, ethylamine,

dipropylamine, triethylamine and alkanediamines such as 1,3-diaminopropane,

anhydrous alkaline alkanolamines such as, mono or di- ethanolamine, preferably those

which are completely substituted on the amine group such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine or a heterocyclic amine such as

morpholine as well as the hydroxides of alkali metals, such as sodium and potassium

hydroxide, hydroxides of alkali earth metals, such as magnesium and calcium

hydroxide, basic amino acids such as L-argenine, lysine, alanine, leucine, iso-leucine,

oxylysine and histidine and alkanolamines such as dimethylaminoethanol and

aminoalkylpropanediol and mixtures thereof. Also suitable for use herein are 23

compounds that form HCO₃ ^" by dissociation in water (hereinafter referred to as 'ion forming compounds'). Examples of suitable ion forming compounds are Na2CO₃,

NaHCO₃, K₂CO₃, (NH4)₂CO₃, NH₄HCO₃, CaCO₃ and Ca(HCO₃) and mixtures

thereof.

Preferred buffering agents for use herein are ammonium hydroxide, and sodium hydroxide.

The coloring compositions of the present invention may additionally include a

thickener at a level of from about 0.05% to about 20%, preferably from about 0 1%

to about 10%), more preferably from about 0.5% to about 5% by weight Thickening

agents suitable for use in the compositions herein are selected from oleic acid, cetyl

alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, synthetic

thickeners such as Carbopol, Aculyn and Acrosyl and mixtures thereof Preferred

thickeners for use herein are Aculyn 22 (RTM), steareth-20 methacrylate copolymer,

Aculyn 44 (RTM) ,polyurethane resin and Acusol 830 (RTM), acrylates copolymer

which are available from Rohm and Haas, Philadelphia, PA, USA Additional

thickening agents suitable for use herein include sodium alginate or gum arabic, or

cellulose derivatives, such as methyl cellulose or the sodium salt of carboxymethylcellulose or acrylic polymers

Water is the preferred diluent for the compositions according to the present

invention. However, the compositions according to the present invention may

include one or more solvents as additional diluent materials Generally, solvents 24

suitable for use in the coloring compositions of the present invention are selected to

be miscible with water and innocuous to the skin Solvents suitable for use as additional diluents herein include C]-C20 mono- or polyhydric alcohols and their ethers, glycerine, with monohydric and dihydric alcohols and their ethers preferred. In these compounds, alcoholic residues containing 2 to 10 carbon atoms are

preferred. Thus, a preferred group includes ethanol, isopropanol, n-propanol,

butanol, propylene glycol, ethylene glycol monoethyl ether, and mixtures thereof

Water is the preferred principal diluent in the compositions according to the present

invention. Principal diluent, as defined herein, means, that the level of water present is higher than the total level of any other diluents

The diluent is present at a level preferably of from about 5% to about 99.98%,

preferably from about 15% to about 99.5%, more preferably at least from about 30%

to about 99%), and especially from about 50% to about 98% by weight of the

compositions herein.

The compositions of the present invention can additionally contain a surfactant

system. Suitable surfactants for inclusion in the compositions of the invention

generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and

can be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants

and mixtures thereof.

(i) Anionic Surfactants 25

Anionic surfactants suitable for inclusion in the compositions of the invention include alkyl sulphates, ethoxylated alkyl sulphates, alkyl glyceryl ether sulfonates, methyl

acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl ethoxy carboxylates, alkyl phosphate esters, ethoxylated

alkyl phosphate esters, alkyl sulphates, acyl sarcosinates and fatty acid/protein

condensates, and mixtures thereof Alkyl and/or acyl chain lengths for these

surfactants are C12-C22, preferably C^-Cj g more preferably C 12 14

(ii) Nonionic Surfactants

The compositions of the invention can also comprise water-soluble nonionic

surfactant(s). Surfactants of this class include C 12 14 fatty acid mono-and

diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide

surfactants having the general formula below

O Rr

Re C — N — Z.

The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide

surfactants according to the above formula are those in which Rg is C5-C_{3 ]}

hydrocarbyl, preferably Cβ-CjQ hydrocarbyl, including straight-chain and branched

chain alkyl and alkenyl, or mixtures thereof and R9 is typically hydrogen, C j -Cg alkyl

or hydroxyalkyl, preferably methyl, or a group of formula -R ^O-R² wherein R' is 26

C2-Cg hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C2-C4 alkylene, R² is Cj-Cg straight-chain, branched-chain

and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is preferably C 1-C4

alkyl, especially methyl, or phenyl. Z2 is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3

hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof Z2

preferably will be derived from a reducing sugar in a reductive amination reaction,

most preferably Z2 is a glycityl moiety. Suitable reducing sugars include glucose,

fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.

As raw materials, high dextrose corn syrup, high fructose corn syrup, and high

maltose corn syrup can be utilised as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z2. It should be understood that it is by no means intended to exclude other suitable raw materials. Z2 preferably

will be selected from the group consisting of -CH2-(CHOH)_n-CH2OH, -

CH(CH₂OH)-(CHOH)_n.₁-CH₂H, CH₂(CHOH)2(CHOR')CHOH)-CH2OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or polysaccharide,

and alkoxylated derivatives thereof. As noted, most preferred are glycityls wherein n is 4, particularly -CH₂-(CHOH)₄-CH₂OH.

The most preferred polyhydroxy fatty acid amide has the formula

Rg(CO)N(CH₃)CH2(CHOH)₄CH₂OH wherein Rg is a C6-C 19 straight chain alkyl

or alkenyl group. In compounds of the above formula, Rg-CO-N< can be, for 27

example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmiamide, tallowamide, etc.

Suitable oil derived nonionic surfactants for use herein include water soluble

vegetable and animal-derived emollients such as triglycerides with a

polyethyleneglycol chain inserted, ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives One preferred class of

oil-derived nonionic surfactants for use herein have the general formula below

RCOCH₂CH (OH) CH₂ (OCH₂CH₂ ) _nOH

wherein n is from about 5 to about 200, preferably from about 20 to about 100, more

preferably from about 30 to about 85, and wherein R comprises an aliphatic radical

having on average from about 5 to 20 carbon atoms, preferably from about 7 to 18

carbon atoms

Suitable ethoxylated oils and fats of this class include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl

palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and

glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn

oil, preferably glyceryl tallowate and glyceryl cocoate 28

Preferred for use herein are polyethyleneglycol based polyethoxylated Co-C 15 fatty

alcohol nonionic surfactants containing an average of from about 5 to about 50 ethyleneoxy moieties per mole of surfactant.

Suitable polyethylene glycol based polyethoxylated C9-C15 fatty alcohols suitable for

use herein include C9-C11 Pareth-3, C9-C11 Pareth-4, C9-C1 1 Pareth-5, C9-C1 1

Pareth-6, Cg-Cj 1 Pareth-7, C9-C1 1 Pareth-8, C 1 1 -C 15 Pareth-3, C _j J -C J S Pareth-4,

C11-C15 Pareth-5, C1 1-C 15 Pareth-6, Ci ]-C _{1 5} Pareth-7, C n -C _{1 5} Pareth-8, C \ \ ~ C15 Pareth-9, C1 1-C15 Pareth-10, Cπ -C ₁₅ Pareth-1 1, C _π -C ι ₅ Pareth- 12, C n - C15 Pareth-13 and Cj 1-C15 Pareth-14. PEG 40 hydrogenated castor oil is

commercially available under the tradename Cremophor (RTM) from BASF. PEG 7

glyceryl cocoate and PEG 20 glyceryl laurate are commercially available from Henkel

under the tradenames Cetiol (RTM) HE and Lamacit (RTM) GML 20 respectively. C9-C11 Pareth-8 is commercially available from Shell Ltd under the tradename Dobanol (RTM) 91-8. Particulary preferred for use herein are polyethylene glycol

ethers of ceteryl alcohol such as Ceteareth 25 which is available from BASF under

the trade name Cremaphor A25.

Also suitable for use herein are nonionic surfactants derived from composite

vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii

Kotschy) and derivatives thereof. Similarly, ethoxylated derivatives of Mango,

Cocoa and Illipe butter may be used in compositions according to the invention.

Although these are classified as ethoxylated nonionic surfactants it is understood that

a certain proportion may remain as non-ethoxylated vegetable oil or fat. 29

Other suitable oil-derived nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn

oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil,

safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed

oil.

(iii) Amphoteric Surfactants

Amphoteric surfactants suitable for use in the compositions of the invention include

(a) imidazolinium surfactants of formula (VII)

C₂ H ₄ OR₂

CH ₂ Z

R . N

+

N -

wherein R] is C7-C22 alkyl or alkenyl, R2 is hydrogen or CH2Z, each Z is independently CO2M or CH2CO2M, and M is H, alkali metal,

alkaline earth metal, ammonium or alkanolammonium, and/or

ammonium derivatives of formula (VIII) 30

C₂H₄OH R₁CONH(CH₂) ₂N⁺CH₂Z R₂

wherein Ri , R2 and Z are as defined above;

(b) aminoalkanoates of formula (IX)

RιNH(CH2)_nCO₂M

iminodialkanoates of formula (X)

R₁N[(CH₂)_mCO₂M]₂

and iminopolyalkanoates of formula (XI)

Rl-[N(CH₂)p]_qN[CH₂CO₂M]2

CH₂CO₂M

wherein n, m, p, and q are numbers from l to 4, and R] and M are

independently selected from the groups specified above; and

(c) mixtures thereof. 31

Suitable amphoteric surfactants of type (a) are marketed under the trade name

Miranol and Empigen and are understood to comprise a complex mixture of species

Traditionally, the Miranols have been described as having the general formula (VII), although the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non- cyclic structure (VIII) while the 4th Edition indicates yet another structural isomer in

which R2 is O-linked rather than N-linked In practice, a complex mixture of cyclic

and non-cyclic species is likely to exist and both definitions are given here for sake of

completeness Preferred for use herein, however, are the non-cyclic species

Examples of suitable amphoteric surfactants of type (a) include compounds of formula XII and/or XIII in which K\ is CgHj (especially iso-capryl), C9H19 and

C1 1H23 alkyl Especially preferred are the compounds in which Rj is C9H]9, Z is

CO2M and R2 is H, the compounds in which Rj is C] ]H2₃, Z is CO2M and R2 is

CH2CO2M; and the compounds in which R] is C ] _] H2 , Z is CO2M and R2 is H

In CTFA nomenclature, materials suitable for use in the present invention include

cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, and especially

cocoamphoacetate and cocoamphodiacetate (otherwise referred to as

cocoamphocarboxyglycinate) Specific commercial products include those sold under the trade names of Ampholak 7TX (sodium carboxy methyl tallow polypropyl

amine), Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol H2M Cone

Miranol C2M Cone. N.P , Miranol C2M Cone O P , Miranol C2M SF, Miranol CM

Special (Rhδne-Poulenc), Alkateric 2CIB (Alkaril Chemicals), Amphoterge W-2 32

(Lonza, Inc ); Monateric CDX-38, Monateric CSH-32 (Mona Industries), Rewoteric AM-2C (Rewo Chemical Group), and Schercotic MS-2 (Scher Chemicals) Further

examples of amphoteric surfactants suitable for use herein include Octoxynol-1 (RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM), polyoxyethylene

(4) nonylphenyl ether and Nonoxynol-9, polyoxyethylene (9) nonylphenyl ether

It will be understood that a number of commercially-available amphoteric surfactants

of this type are manufactured and sold in the form of electroneutral complexes with,

for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants,

especially those of the sulfated Cg-Cjg alcohol, Cg-Cjg ethoxylated alcohol or Cg-

Ci g acyl glyceride types Note also that the concentrations and weight ratios of the

amphoteric surfactants are based herein on the uncomplexed forms of the surfactants,

any anionic surfactant counterions being considered as part of the overall anionic

surfactant component content.

Examples of preferred amphoteric surfactants of type (b) include N-alkyl

polytrimethylene poly-, carboxymethylamines sold under the trade names Ampholak

X07 and Ampholak 7CX by Berol Nobel and also salts, especially the

triethanolammonium salts and salts of N-lauryl-beta-amino propionic acid and N-

lauryl-imino-dipropionic acid. Such materials are sold under the trade name Deriphat

by Henkel and Mirataine by Rhδne-Poulenc

(iv) Zwitterionic Surfactants 33

Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines of the formula R5R0R7N ^" (CH2)_nCO2M and amido betaines of the formula (XII) below

R<

R₅CON (CH₂ ) _mN (CH₂ ) _nC0₂M

R-

wherein R5 is C] 1-C22 al yl or alkenyl, Rg and R7 are independently C | -C alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m

are each numbers from 1 to 4 Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine,

laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine (RTM)

Water-soluble auxiliary sultaine surfactants suitable for inclusion in the compositions

of the present invention include alkyl sultaines of the formula (XIII) below

R₂

R₁ CON(CH2)_mN⁺(CH₂)nCH(OH)CH₂SO3-M⁺

R<: 34

wherein Rj is C7 to C22 alkyl or alkenyl, R2 and R are independently C \ to C alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and

m and n are numbers from 1 to 4 Preferred for use herein is coco amido

propylhydroxy sultaine.

Water-soluble auxiliary amine oxide surfactants suitable for inclusion in the

compositions of the present invention include alkyl amine oxide R5R6R7NO and

amido amine oxides of the formula (XIV) below

Rt

R₅CON(CH₂)_mN O

R 7

wherein R5 is C\ to C22 alkyl or alkenyl, Rg and R7 are independently Cj to C₃

alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and

m is a number from 1 to 4 Preferred amine oxides include cocoamidopropylamine

oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide

The hair coloring compositions of the present invention may, in addition to the

essential reactive hair coloring agents, optionally include other dye materials

Optional other dyes suitable for use in the hair coloring compositions and processes 35

according to the present invention include both semi-permanent, temporary and other

dyes

Suitable optional dyes for use herein include oxidative dyes Any oxidative dye suitable for use in dyeing hair can be used in the compositions herein, for example those mentioned in WO98/27945, incorporated herein by reference in its entirety

Non-oxidative dyes as defined herein include the so-called 'direct action dyes',

metallic dyes, metal chelate dyes, fibre reactive dyes and other synthetic and natural

dyes Various types of non-oxidative dyes are detailed in 'Chemical and Physical Behaviour of Human Hair' 3rd Ed by Clarence Robbins (pp250-259), 'The Chemistry

and Manufacture of Cosmetics' Volume IV 2nd Ed Maison G De Navarre at

chapter 45 by G S Kass (pp841-920), 'cosmetics Science and Technology' 2nd Ed ,

Vol. II Balsam Sagarin, Chapter 23 by F E Wall (pp 279-343), 'The Science of Hair

Care' edited by C Zviak, Chapter 7 (pp 235-261 ) and 'Hair Dyes', J C Johnson, Noyes Data Corp , Park Ridge, U S A (1973), (pp 3-91 and 1 13- 139)

A number of additional optional materials can be added to the coloring compositions

herein described each at a level of from about 0 001% to about 5%, preferably from

about 0 01%) to about 3%, more preferably from about 0 05% to about 2% by weight

of composition Such materials include proteins and polypeptides and derivatives

thereof, water-soluble or solubilizable preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA,

Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate 36

and bisabalol, benzoic acid, sodium benzoate and 2-phenoxyethanol, antioxidants such as sodium sulphite, hydroquinone, sodium bisulphite, sodium metabisulphite,

sodium dithionite, erythrobic acid and other mercaptans; dye removers such as oxalic

acid, sulphated castor oil, salicylic acid and sodium thiosulphate, H2O2 stabilisers such as tin compounds such as sodium stannate, stannic hydroxide and stannous

octoate, acetanilide, phenacetin colloidal silica such as magnesium silicate,

oxyquinoline sulphate, sodium phosphate, and tetrasodium pyrophosphate, and p-

hydroxybenzoates; moisturising agents such as hyaluronic acid, chitin , and starch-

grafted sodium polyacrylates such as Sanwet (RTM) IM- 1000, IM- 1500 and IM-

2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and

described in US-A-4,076,663 as well as methyl cellulose, starch, higher fatty

alcohols, paraffin oils, fatty acids and the like; solvents ; anti-bacterial agents such as

Oxeco (phenoxy isopropanol); low temperature phase modifiers such as ammonium ion sources (e.g. NH4 Cl); viscosity control agents such as magnesium sulfate and

other electrolytes, quaternary amine compounds such as distearyl-, dilauryl-, di-

hydrogenated beef tallow-, dimethyl ammonium chloride, dicetyldiethyl

ammoniumethylsulphate, ditallowdimethyl ammonium methylsulphate, disoya

dimethyl ammonium chloride and dicoco dimethyl ammonium chloride, hair conditioning agents such as silicones, higher alcohols, cationic polymers and the like,

enzyme stabilisers such as water soluble sources of calcium or borate species,

colouring agents; Tiθ2 and Tiθ2-coated mica, perfumes and perfume solubilizers,

and zeolites such as Valfour BV400 and derivatives thereof and Ca²⁺/Mg²⁺

sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates,

amino polyphosphonates etc and water softening agents such as sodium citrate 37

The present invention is represented by the following non-limiting examples. In the examples, all concentrations are on a 100% active basis and all percentages are by

weight unless otherwise stated and the abbreviations have the following designations.

Examples

Example 1

Synthesis of Monothioglycolatotriazine dye using Procion (RTM) dyes as starting

materials

The monothioglycolato triazine dye is prepared using the synthesis route as illustrated

in Diagram 1.

38

N. -Cl N , ,SCH₂COOH

-HN- D HN- thioglycolic acid <

N N

^N^/ 0-5°C, pH7.5-8 / N Cl^"

Cl Cl

In the reaction scheme D is a chromophore and varies depending on which starting

dye is used. In the present example a variety of Procion (RTM) dyes commercially

available from BASF are used as starting materials, in particular, Procion Red MX-

8B, Procion Yellow MX-8G and Procion Blue MX-2G

Synthesis of monochloromonothioglycolato triazine dye

An aqueous dye solution (0. lmol/lOOml, pH 7.5) of a purified Procion (RTM)

dichlorotriazine dye is prepared. To this solution, a 0. Imol solution of

Mercaptoacetic acid is added by slow dripping at a temperature of between 0 and 5° 39

C. After the addition of mercaptoacetic acid, the pH of the system is adjusted to 8

using sodium carbonate and HCl. The reaction is then allowed to proceed, at 0~5°C and pH8, for 5-8 hours. For each individual dye, the required reaction time is

different (7-8 hours for Procion Red MX-8B, -6 hours for Procion Yellow MX-8G

and -5 hours for Procion Blue MX-2G). During the synthesis, a rapid pH drop is observed which can adjusted to pH 8 using buffering agents. The end-of-reaction

point, for this part of the synthesis, is indicated by the pH of the reaction system

remaining constant for more than 5 minutes. At this point, the dye monochloro¬

monothioglycolato triazine is obtained. At the end of the synthesis, the pH of the

system is reduced to below pH 2. The solid monochloromonothioglycolato triazine

dye compounds are then obtained following precipitation and filtration.

Example 2

Synthesis of monothioethanoltriazine dye

The monothioethanol triazine dye is prepared using the synthesis route as illustrated in Diagram 2.

40

N. XI N . ,SCH₂CH₂OH

D- ^■HN- < D- ^■HN- ^ thioethanol

N N

^N _>/ ^N PH 7-7.5, 0-5°C + cr

^^

Cl Cl

Diagram 2

In the reaction scheme D is a chromophore and varies depending on which starting

dye is used. In the present example Procion (RTM) Red MX-8G is used as the

starting material, but other suitable dichlorotriazine dye compounds can also be used

as starting materials such as Procion Yellow MX-8G and Procion Blue MX-2G

0.1 mole of Procion Red MX-8G dye is dissolved in 150 ml of distilled water and

added to a flask. The flask is placed in an ice-water bath. 0 1 moles of thioethanol is 41

then added drop-wise, to the reaction mixture under stirring. The total addition time

is one hour. The pH of the reaction scheme is maintained at pH 7-7.5 and the

temperature of the reaction system 0-5°C during addition of thioethanol. The

reaction is then allowed to proceed at 0-5°C and pH 7.5-8 (which is corrected using sodium carbonate and HCl) for 5 hours. The endpoint of the reaction is indicated by

the pH remaining constant for more than 5 minutes. At this point, the

monochloromonothioethanol triazine dye is obtained. Using 6N HCl, the pH of the

system is then reduced to below pH2 to terminate the reaction. KCl (35%> of the

total solution) is then added to the reaction mixture in order to precipitate the dye. Filtration using Whatman filter paper follows. The precipitate is then washed with

acetone for 4-5 times (50ml of acetone used each time) to obtain the final dye

product.

Example 3

Synthesis of monothiosuccinate triazine dye

The monothiosuccinate triazine dye is prepared using the synthesis route as illustrated

in Diagram 3. 42

. N. ,CI N, ,TSA

^■HN- -HN- thiosuccinic acid < ►

N pH 7.5, 0-5°C N + cr

^/^N

Cl Cl

Diagram 3

In the reaction scheme D is a chromophore and varies depending on which starting

dye is used. In the present example Procion (RTM) Red MX-8G is used as the

starting material, but other suitable dichlorotriazine dye compounds can also be used as starting materials, such as Procion (RTM) Yellow MX-8G and Procion (RTM) 43

Blue MX-2G. In the above reaction scheme TSA denotes thiosuccinate attached to the ring via its sulphur atom.

0.1 moles of pure Procion Red MX-8G dye and 150ml of distilled water are introduced into a 400ml flask. The flask is placed in an ice-water bath. 0.1 moles of

thiosuccinic acid is then added dropwise with stirring. The addition time is 1-1.5

hours. The pH of the reaction system is maintained at pH7.5 and the temperature of

the reaction system is 0-5°C throughout the addition of thiosuccinic acid.

The reaction is then allowed to proceed, at 0-5°C and pH7.5-8 (which is corrected

using sodium carbonate and HCl) for 6 hours. The endpoint of the reaction for this

part of the synthesis is indicated by the pH of the reaction system remaining constant

for more than 5 minutes. At this point, the dye monochloromonothiosuccinate

triazine dye is obtained. Using 6N HCl, the pH of the system is then reduced to

below pH 2 to terminate the reaction. KCl (35% of the total solution) is then added

to the reaction mixture in order to precipitate the dye. Filtration using Whatman

paper follows. The precipitate is then washed with acetone for 4-5 times (50ml of

acetone is used each time) to obtain the final dye product.

Example 4

Synthesis of mono-5-chloro-4-thioglycolato pyrimidine dye 44

The mono-5-chloromono4-thioglycolato pyrimidine dye is prepared using the synthesis route as illustrated in Diagram 4.

N. N .

^■HN- < D- ^■HN- < mercaptoacetic_ acid

N pH 9.8-10, 0-5°C N + F-

Cl ^' Cl

SCH₂COOH

Diagram 4 45

In the reaction scheme D is a chromophore and varies depending on which starting dye is used. In the present example Drimalan (RTM) Red FB dye commercially available from Clariant is used as starting material. However, Drimalan Red FB can

be substituted for any suitable difluoromonochloro pyrimidine dye such as those

commercially available under the tradename Drimalan and Drimarene dyes, in

particular, Drimalan Red FB, Drimalan Yellow F-R, Drimalan Blue F-G, Drimalan

Blue F-B, Drimalan Yellow F-3GL, Drimalan Black F-B, Drimarene Golden Yellow

R-G2R, Drimarene Blue R-GL, Drimarene Brill Red R-8B, and Drimarene Brill Red

K-4BL. In the above reaction scheme TGA denotes a thioglycolato moiety.

0.1 moles of Drimalan Red F-B dye and distilled water are introduced into a flask.

The flask is then placed in an ice- water bath. 0.1 moles of mercaptoacetic acid is

then added dropwise to the reaction mixture with stirring. The total addition time is

1-1.5 hours. The pH of the reaction mixture is maintained at pH 9.8-10 and at a

temperature of 0-5°C throughout the addition of mercaptoacetic acid.

The reaction is then allowed to proceed at 5°C and pH 9.8- 10 (which is corrected

using sodium carbonate and HCl) for 15 hours. The end-of-reaction point for this

part of the synthesis is indicated by the pH of the reaction system remaining constant for more than 5 minutes. At this point, the mono-5-chloro-2-fluoro-mono-4-

thioglycolato pyrimidine dye is obtained. Using 6N HCl the pH of the system is then

reduced to below pH2 to terminate the reaction. KCl (≡35% of the total solution) is

then added to the reaction mixture in order to precipitate the dye. Filtration using

Whatman filter paper follows. The precipitate is then washed with acetone for 4-5 46

times (..-50ml of acetone used each time) to obtain the mono-5-chloro-2-fluoro- mono-4-thioglycolato pyrimidine dye.

Example 5

Dye solutions can be made up using compounds prepared according to Example 1

and packaged in a suitable bottle-type package.

Auburn Dye

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80

Dye prepared according to 0.23

Example 1 using Procion Red MX-

8B

Dye prepared according to 0.42

Example 1 using Procion Yellow

MX-GR 47

Dye prepared according to 0.35 Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 80% 9.26

Triethanolamine 99% 50.74

Ammonium Hydroxide 29% 9.00

Water to 100

Light Brown Dye

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80

Dye prepared according to 0.010

Example 1 using Procion Red MX-

8B

Dye prepared according to 0.226

Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0.678

Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 80% 9.26 48

Triethanolamine 99% 50 74

Ammonium Hydroxide 29%> 9 00

Water to 100

Champagne Blonde

Ingredients %

Urea 10 00

Cocamidopropyl Betaine 0 80

Dye prepared according to 0 023 Example 1 using Procion Red MX- 8B

Dye prepared according to 0 465 Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0 512 Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 80% 9 26

Triethanolamine 99% 50 74

Ammonium Hydroxide 29% 9 00

Water to 100 49

Auburn Dye

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80

Dye prepared according to 0.23

Example 1 using Procion Red MX-

8B

Dye prepared according to 0.42

Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0.35

Example 1 using Procion Blue MX-2G, 125

Thioglycolic Acid 99% 7.48

Ammonium Hydroxide 29% 1 1.48

Water to 100

Light Brown Dye

Ingredients % 50

Urea 10.00

Cocamidopropyl Betaine 0.80

Dye prepared according to 0.010 Example 1 using Procion Red MX-

8B

Dye prepared according to 0.226

Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0.678 Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 99% 7.48

Ammonium Hydroxide 29% 1 1.48

Water to 100

Champagne Blonde

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80 51

Dye prepared according to 0.023 Example 1 using Procion Red MX-

8B

Dye prepared according to 0.465 Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0.678

Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 99% 7.48

Ammonium Hydroxide 29% 1 1.48

Water to 100

Auburn Dye

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80 52

Dye prepared according to 0.23 Example 1 using Procion Red MX-

8B

Dye prepared according to 0.42

Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0 35

Example 1 using Procion Blue

MX-2G, 125

Thioglycolic Acid 99% 7 48

Sodium Hydroxide 47% 8 38

Water to 100

Light Brown Dye

Ingredients %

Urea 10 00

Cocamidopropyl Betaine 0 80

Dye prepared according to 0 010

Example 1 using Procion Red MX-

8B 53

Dye prepared according to 0.226 Example 1 using Procion Yellow

MX-GR

Dye prepared according to 0.678 Example 1 using Procion Blue MX-2G, 125

Thioglycolic Acid 99% 7.48

Sodium Hydroxide 47% 8.38

Water to 100

Champagne Blonde

Ingredients %

Urea 10.00

Cocamidopropyl Betaine 0.80

Dye prepared according to 0.023 Example 1 using Procion Red MX-

8B

Dye prepared according to 0.465

Example 1 using Procion Yellow

MX-GR 54

Dye prepared according to 0.512 Example 1 using Procion Blue MX-2G, 125

Thioglycolic Acid 99% 7.48

Sodium Hydroxide 47% 8.38

Water to 100

Any of the compounds prepared according to Examples 1 to 4 can be substituted for

the compounds in the dye compositions above.

In particular, the packaged hair colouring compositions of the examples provide improvements in terms of consumer acceptance since no admixing of ingredients is necessary before dyeing, and improved wash fastness.

Claims

55WHAT IS CLAIMED IS:

1. Packaged hair colouring composition comprising a stable aqueous hair colouring composition comprising a compound of formula (I):

wherein D is a chromophore;

X and Y are independently selected from halogen and -SR', provided that at

least one of X and Y is -SR', wherein R' is selected from H, C 1-C4 alkyl,

(CH2)_nCOOH, (CH2)_nCONH2, (CH2)_nSO₃H, (CH2)_nCOOM,

(CH₂)_nPO₃H, (CH₂)_nOH, (CH₂)_nSSO₃-, (CH₂)_nNR"₂, (CH₂)_nN⁺R"₃, PI1SSO3^", PhSO H, PhPO H, PhNR"2, PhN⁺R"₃, -CN, SO₃ ^",

(CH2)2CH(SH)R"(CH2)3COOH, -CH2CHOHCH2SH, and

NH

-C <?

^'NH₂. 56

NH,

/

-H,C- -CH

\

COOH

-HC COOH

CH₂ COOH

=rCH

COOHC IOOH

CH₃

C COOH

H 57

OH

-C COOH

CH-,

O

H,C- " (CH₂)_n-

CH- ^ΓûáCO (CH₂)_n SH

CH, ^ΓÇóCO- "(CH₂)_n- ^ΓûáSH

H,C- "(CH₂)_n-

CH- -O- ^ΓûáCO (CH₂)_n- SR"

CH, "CO (CH₂)_n SR"

H n₍H₂C) O C (CH₂)_n- 58

O

CH, -(CH₂)_n-

CH, ^ΓûáCO- " (CH₂)_n- ^ΓûáSH

O

CH₂ O C II (CH₂)_n

CH₂ O CO (CH₂)_n SR"

CH₂CH₂CH CH₂CH₂CH₂COOH

SR"

-CH2CH2NH2_.

n is an integer in the range of 1 to 4 wherein within the same molecule n is not

necessarily the same integer; and M is a cation of alkaline earth metal, alkali

metal, H4⁺ or NR"₃ ⁺ _;

L is a linking moiety; 59

Z is selected from pyrimidine or triazine;

R" is C1-C4 alkyl;

and a package for said hair colouring composition.

2. Packaged hair colouring composition according to Claim 1 wherein Z is

triazine.

3. Packaged hair colouring composition according to Claim 1 or 2 wherein both

X and Y are -SR'.

4. Packaged hair colouring composition according to any of Claims 1 to 3

wherein R' is CH2COOH.

5. Packaged hair colouring composition according to any of Claims 1 to 4

wherein L is selected from L is selected from NR, NRC=O, C(O)NR, NRSO2

and -SO2NR wherein R is H or C 1-C4 alkyl which can be substituted by

halogen, preferably fluorine or chlorine, hydroxyl, cyano, C 1 -C4 alkoxy, C2-

C5 alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato.

6. Packaged hair colouring composition according to any of Claims 1 to 5 wherein L is NR. 60

7. A reactive dye compound according to Claim 6 wherein R is selected from C1-C4 alkyl or H, preferably H.

8. A hair colouring composition comprising:

(a) a purified reactive dye compound in particulate form having the formula (I):

wherein D is a chromophore;

X and Y are independently selected from halogen and -SR', provided that at

least one of X and Y is -SR', wherein R' is selected from H, C1-C4 alkyl,

(CH2)_nCOOH, (CH₂)nCONH , (CH₂)_nSO₃H, (CH2)_nCOOM,

(CH₂)nPO₃H, (CH₂)_nOH, (CH₂)nSSO:f, (CH₂)_nNR" , (CH₂)_nN⁺R"₃,

PhSSO ^", PhSO₃H, PhPO₃H, PhNR"2, PhN⁺R"₃, -CN, SO₃ ^",

(CH2)2CH(SH)R"(CH2)3COOH, -CH2CHOHCH2SH, and 61

NH

^

NH,

NH₂

/

-H,C- -CH

\

COOH

^ΓûáHC COOH

C IH₂ COOH

=z:CH

COOHC IOOH

CH₃

C COOH

H 62

OH

C I COOH

C IH₃

H,C- ^Γûá (CH₂)_n-

CH- ^ΓÇóO- ^ΓûáCO- ^Γûá(CH₂)_n- -SH

CH, ^ΓûáCO- "(CH₂)_n- ^ΓûáSH

H C- "(CH₂)_n-

CH- ^ΓûáCO (CH₂)_n SR"

CH, -CO (CH₂)_n SR"

O

H n₍H₂C) O C (CH₂)_n- 63

O

CH₂- ^Γûá(CH₂)_n-

CH, -CO- ^Γûá(CH₂)_n- ^ΓûáSH

O

CH₂ O C II (CH₂)_n-

CH₂ O CO (CH₂)_n SR"

CH₂CH₂CH CH₂CH₂CH₂COOH

SR"

-CH2CH2NΗ2.

n is an integer in the range of I to 4 wherein within the same molecule n is not

necessarily the same integer; and M is a cation of alkaline earth metal, alkali

metal, NH4⁺ or NR"₃ ⁺- 64

L is a linking moiety;

Z is selected from pyrimidine or triazine;

R" is C1-C4 alkyl; and

(b) a solvent.

9. A hair colouring composition according to Claim 8 wherein the solvent

comprises water.