WO2001062221A1 - Pretraitement applique avant des compositions de coloration de cheveux, et procedes - Google Patents

Pretraitement applique avant des compositions de coloration de cheveux, et procedes Download PDF

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Publication number
WO2001062221A1
WO2001062221A1 PCT/US2001/005598 US0105598W WO0162221A1 WO 2001062221 A1 WO2001062221 A1 WO 2001062221A1 US 0105598 W US0105598 W US 0105598W WO 0162221 A1 WO0162221 A1 WO 0162221A1
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WIPO (PCT)
Prior art keywords
hair
composition
color
pretreatment
color altering
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PCT/US2001/005598
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English (en)
Inventor
Dominic Pratt
Louis Carlos Dias
Matthew Underwood
Delyth Angharad James
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU2001243210A priority Critical patent/AU2001243210A1/en
Publication of WO2001062221A1 publication Critical patent/WO2001062221A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers

Definitions

  • This invention relates to hair coloring compositions and methods, more particularly to decreasing the extent of damage to hair during the application of hair color altering compositions by pretreating hair prior to altering the color of the hair.
  • the problems associated with coloring hair are numerous, including the delivery of precise colors to the hair, increasing the retention time of color in the hair, damage imparted to the hair during the coloring process, inconsistent coloration of the hair due to irregular uptake of hair coloring agents along the length of the hair shaft and adverse effects on the hair and skin of the user, such as brittle hair, irritation of the skin, staining and lachrymatory effects. It would be highly desirable to develop a system for increasing color uptake and color retention on the hair whilst decreasing damage to the hair and reducing other adverse effects to the user.
  • Oxidative hair coloring agents and peroxygen oxidising agents can be used to deliver a variety of hair colors to the hair. However substantial improvement is desirable in the areas of improved color saturation, improved color development, precise initial color consistency, improved wash fastness, improved hair condition and lower levels of hair damage.
  • hair coloring compositions containing oxidative hair coloring agents are formulated at high pH (from about pH 9 to about pH 12) and commonly contain, in addition to the oxidative hair coloring agents and an inorganic peroxygen oxidising agent, peroxide activating agents and a variety of additional cosmetic agents.
  • the hair coloring compositions also commonly contain coloring agent and peroxygen oxidising agent stabilising agents.
  • HSA hair swelling agent
  • HSAs enhance the coloring process by swelling the hair fibres to aid the diffusion of the peroxygen oxidising agent and the oxidative hair coloring agents into the hair. This enables faster, more thorough dye oxidisation and hair coloring.
  • HSA aqueous (alkaline) solution containing a source of ammonia, such as ammonium hydroxide.
  • a source of ammonia such as ammonium hydroxide.
  • ammonia can cause skin irritation and in addition has an undesirable odour and can cause lachrymatory effects.
  • hair coloring methods which deliver a combination of improved hair coloring attributes, such as longer lasting color (reduced fade), initial color generation, increased color uptake and color consistency across hair types (ie. Such as hair of varying age and condition i.e. virgin (untreated), grey, permed, bleached etc).
  • hair coloring methods which provide a combination of lower levels of skin irritation and/or skin staining versus conventional systems, reduced damage to the hair fibres and reduced staining of skin and an acceptable odor.
  • Color development means the change in the hair color, expressed in terms of Delta E ( ⁇ E).
  • US 5,100,436 discloses aqueous solutions of transition metal ions used to catalyze the oxidative dyeing of virgin hair. Specifically the process involves using transition metal ions complexed with dipyridyl or o-phenanthroline chelating agents as an aqueous pretreatment for hair. Subsequently to the application of the pretreatment composition an oxidative dyeing mixture is applied to the hair. The pretreatment is rinsed off the hair prior to the application of the oxidative dyeing mixture.
  • GB 1 ,469,265 discloses a process for coloring hair, comprising treating the hair with an acid dye in aqueous solution subsequent to the application of a water-soluble composition comprising a cationic polymer selected from water-soluble acid salts.
  • the pH range for the compositions of this invention are from 2.5 to 7.0. The presence of a pH differential between the first and second treatment compositions is not disclosed.
  • JP 4069324 discloses the use of non-oxidative hair coloring agents having a pH of 2.5 to 7.5 in conjunction with pretreatment compositions. o Thus none of these disclosures is concerned with the problem addressed by the present invention which is the provision of methods for coloring hair using the effective oxidative coloring systems but reducing hair damage and other undesirable effects, at the same time as maintaining or even improving color uptake and/or retention.
  • 5 EP-B- 435,012 describes the use of HCO 3 " generating compounds in hair dyeing compositions. This is used in combination with an alkali, hydrogen peroxide and coloring agents.
  • the pH of the final treatment composition applied to the hair is in the range 6.5 - 7.9.
  • the components which form this composition are provided separately and premixed prior to o simultaneous application of all the components to the hair.
  • the present invention provides, in a first aspect, a method of altering hair color comprising the steps of.
  • the method of the present invention enables the amount- of time such damaging components spend on the hair to be lowered compared to hair color altering methods that do not include a pretreatment, by including these in the 25 pretreatment composition.
  • Pretreatment has surprisingly also been found to increase the efficacy of oxidising agent/oxidative coloring agent based systems.
  • wash fade This process is known as wash fade and can be measured over a period of time, usually in terms of number of washes of the colored hair. Fluorescence studies have shown that the application of a coloring composition without a pretreatment composition leads to a certain degree of fade. In pretreated hair, in contrast, we have observed that color is less easily removed from the hair, resulting in less fade.
  • Damage to hair is measured in terms of concentration levels of cysteic 5 acid in the hair.
  • the damaging components in the color altering composition for example the oxidising agent, can cause scission of cysteine bonds in the hair. This can cause production of cysteic acid, the levels of which can be measured and correlated to the amount of damage inflicted on the hair.
  • concentration of cysteic acid is generally measured by spectrophotometric i o methods, discussed in greater detail below.
  • the present invention can decrease damage compared to commercial high pH hair coloring methods which do not include a pretreatment step but instead include a simultaneous application of all components.
  • the present invention provides an increased ability to color the hair 15 compared to a hair color altering treatment having a pH of 1 to 7 which is applied without a pretreatment but instead includes an application of all components.
  • the hair to be treated may be 'living', i.e. on a living body or may be
  • the pretreatment composition is applied to the hair prior to the color altering composition.
  • the 5 pretreatment composition may be removed, for example by rinsing, prior to application of the color altering composition, although in preferred embodiments and in the first aspect of the invention the pretreatment composition is not removed before application of the color altering composition.
  • An essential feature of the present invention is the provision of a two
  • the first step involves the pretreatment of the hair with a composition having a pH in the range of 1 to 13, preferably 6 to 13, more preferably 7.5 to 12, more preferably 8 to 10, most preferably 8.5 to 9.5 and especially 8.7 to 9.2.
  • a further essential feature of the present invention is that the pretreatment composition has a higher pH than that of the color altering composition.
  • the difference in pH of the two compositions is greater than 0.5 pH units, preferably greater than 1 pH unit, more preferably greater than 2 or 3 pH units.
  • a most preferred embodiment of the present invention provides a pretreatment composition having a pH in the range 8.5 to 9.5 and a color altering composition having a pH of no greater than 6, more preferably no greater . than 5.5.
  • the pretreatment composition is not a color altering composition and is substantially free of any oxidative or non-oxidative hair coloring agents and oxidising agents. That is, any oxidative or non-oxidative hair coloring agents, or oxidising agents that are present in the pretreatment composition are present in an amount of less than 2%, preferably less than 1 %, more preferably less than 0.5%, most preferably less than 0.1%.
  • the pretreatment composition generally comprises an alkalising agent.
  • an alkalising agent such as an organic or inorganic base selected from sodium hydroxide, ammonia, potassium hydroxide, piperidine, an alkylamine, such as mono-, di- or tri-methylamine, mono-, di- or tri-ethylamine, mono-, di- or tri-propylamine, mono-, di- or tri-butylamine, mono-, di- or tri-isopropylamine, isobutylamine, tert-butylamine, an amylamine, myristylamine or laurylamine, ethylenediamine, an alkanolamine, such as mono-, di- or tri-etha ⁇ olamine, mono-, di- or tri-propanolami ⁇ e, mono-, di- or tri-isopropanolamine or 2-amino-2-methylpropanol, 2-amino-2-methylpropane-1 ,3-diol, an alky
  • the alkalising agent has the effect of swelling the hair and aiding in the solubilisation of melanin, which aids in improving color uptake. We find that the swelling of the hair using the pretreatment composition of the present invention causes little damage to the hair.
  • the alkalising agent is a salt which, upon dissolution, produces HCO 3 ' ions
  • the alkalising agent is selected from ammonium carbonate, ammonium carbamate and ammonium hydrogen carbonate, most preferably ammonium carbonate.
  • the alkalising agent is included at a concentration (by weight) of from about 0.01 % to about 10%, more preferably from about 0.1 % to about 5%, and especially from about 1.5% to about 5.5% based on total pretreatment composition.
  • the pretreatment is applied directly to the hair and is left in place for between 30 seconds and 20 minutes, preferably 1-10 minutes, more preferably 2-6 minutes, most preferably 3-5 minutes application of the color altering composition without prior removal of the pretreatment composition.
  • the pretreatment composition may comprise a number of other components in addition to the ammonium carbonate/ammonium hydrogen carbonate or other alkalising. agent, as follows: Solvents/Diluents
  • the alkalising agent is generally prepared and presented as an aqueous solution, preferably containing from 5 - 99.5% water, more preferably 10 - 96% water.
  • the pretreatment composition may comprise an organic solvent, preferably 0.1 - 50% of an organic solvent, more preferably 0.2 - 10%.
  • organic solvents suitable for use as additional diluents herein include C 1 -C 20 mono- or polyhydric alcohols and their ethers andglycerine, with monohydric and dihydric alcohols and their ethers preferred. In these compounds, alcoholic residues containing 2 to 10 carbon atoms are preferred.
  • preferred solvents include ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol mo ⁇ oethyl ether, and mixtures thereof.
  • Principal diluent means the solvent in the composition which is present at a higher levels than the total level of all other diluents.
  • Water is the preferred principal diluent in the compositions according to the present invention and it is most preferred that water is substantially the only diluent.
  • the pretreatment composition may also comprise a surfactant system.
  • a surfactant system generally 0.05 - 10% of a surfactant is used, more preferably 0.1 - 2%, most preferably 0.2 - 0.5%.
  • 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 anio ⁇ ic, cationic, nonionic, amphoteric, zwitte onic surfactants and mixtures thereof, (i) Anionic Surfactants
  • Anionic surfactants suitable for inclusion in the pretreatment composition includes 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 C 12 -C 22) preferably C 12 - C 18 more preferably C 12
  • the pretreatment composition of the invention can also comprise water- soluble nonionic surfacta ⁇ t(s).
  • Surfactants of this class include C 12 -C 14 fatty acid mono-and diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide surfactants having the general formula below.
  • N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to the above formula are those in which R 8 is C 5 - C 31 hydrocarbyl, preferably C 6 -C 19 hydrocarbyl, including straight-chain and branched chain alkyl and alkenyl, or mixtures thereof and R 9 is typically hydrogen, 0,-Cs alkyl or hydroxyalkyl, preferably methyl, or a group of formula -R'-O-R 2 wherein R 1 is C 2 -C 8 hydrocarbyl including straight-chain, branched- chain and cyclic (including aryl), and is preferably C 2 -C d alkylene, R 2 is C,-C a straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is preferably C r C 4 alkyl, especially methyl, or phenyl.
  • Z 2 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.
  • Z 2 preferably will be derived from a reducing sugar in a reductive amination reaction, most preferably Z 2 is a glycid moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • 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 Z 2 . It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z 2 preferably will be selected from the group consisting of -C H 2 -( C H O H ) n -C H 2 O H , -C H ( C H 2 O H )-( C H O H) n -1 -C H 2 H , CH 2 (CHOH) 2 (CHOR , )(CHOH)-CH 2 OH, 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 -CH 2 -(CHOH) 4 -CH 2 OH.
  • the most preferred polyhydroxy fatty acid amide has the formula R 8 (CO)N(CH 3 )CH 2 (CHOH) 4 CH 2 OH wherein R ⁇ is a C 3 -C 19 straight chain alkyl or alkenyl group.
  • R 8 -CO-N ⁇ can be, for 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 polyethyle ⁇ eglycol chain inserted; ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives.
  • water soluble vegetable and animal-derived emollients such as triglycerides with a polyethyle ⁇ eglycol chain inserted
  • ethoxylated mono and di-glycerides ethoxylated lanolins
  • ethoxylated butter derivatives ethoxylated butter derivatives.
  • One preferred class of oil-derived nonionic surfactants for use herein have the general formula below:
  • 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,0 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 derived5 from thglycerides, such as palm oil, almond oil, and corn oil, preferably glyceryl tallowate and glyceryl cocoate.
  • Preferred for use in the pretreatment composition are polyethyleneglycol based polyethoxylated C 9 -C, s fatty alcohol nonionic surfactants containing an average of from about 5 to about 50 ethyleneoxy o moieties per mole of surfactant.
  • Suitable polyethylene glycol based polyethoxylated C 9 -C 15 fatty alcohols suitable for use herein include C 9 -C 1 t Pareth-3, Cs-C ⁇ Pareth-4, C 9 - Cn Pareth-5, Cg-C,, Pareth-6, Pareth-7, Cg-C,, Pareth-8, C ⁇ r C 15 Pareth-3, C ⁇ C 15 Pareth-4, C ⁇ -C ⁇ Pareth-5, C ⁇ -C ⁇ Pareth-6, C ⁇ C 1s 5 Pareth-7, C ⁇ r C 15 Pareth-8, C ⁇ -C-s Pareth-9, C ⁇ -C ⁇ Pareth-10, C ⁇ r C 15
  • Pareth-11 C ⁇ C 15 Pareth-12, C -C l5 Pareth-13 and C -C 15 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 o (RTM) HE and Lamacit (RTM) GML 20 respectively.
  • C 8 -C Conduct 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.
  • nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof.
  • ethoxylated derivatives of Mango, Cocoa and lllipe 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.
  • 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.
  • Amphoteric 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, sa
  • Amphoteric surfactants suitable for use in the compositions of the invention include:
  • R 1 is C 7 -C 22 alkyl or alkenyl
  • R 2 is hydrogen or CH 2 Z
  • each Z is independently C0 2 M or CH 2 CO 2 M
  • M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (VIII)
  • Suitable amphoteric surfactants of type (a) are marketed under the 0 trade name Miranol and Empigen and are understood to comprise a complex mixture of species.
  • 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 R 2 is O-linked ratherS than N-ltnked.
  • CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclic structure (VIII) while the 4th Edition indicates yet another structural isomer in which R 2 is O-linked ratherS than N-ltnked.
  • 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.
  • amphoteric surfactants of type (a) include o compounds of formula Xll and/or Xlll in which R 1 is C g H 17 (especially iso- capryl), C 9 H 19 and C ⁇ H ⁇ alkyl. Especially preferred are the compounds in which R n is C 9 H 19 , Z is CO 2 M and R 2 is H; the compounds in which R 1 is C H 23 , Z is CO 2 M and R 2 is CH 2 CO 2 M; and the compounds in which R 1 is CnHa, Z is CO 2 M and R 2 is H.
  • 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 (Rhone-Poulenc);
  • Alkateric 2C1B (A ⁇ karil Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mo ⁇ a Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals).
  • amphoteric surfactants suitable for use herein include Octoxynol-1 (RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) no ⁇ ylphenyl ether and Nonoxynol-9, polyoxyethylene (9) nonylphenyl ether.
  • 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 C a - C 18 alcohol, C 8 -C 18 ethoxylated alcohol or C e -C 1 ⁇ acyl glyceride types.
  • 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.
  • amphoteric surfactants of type (b) include N- alkyl polytrimethylene poly-, carboxymethyiamines sold under the Irade 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 Rh ⁇ ne-Poulenc. (iv) Zwitterionic Surfactants
  • Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the compositions of the present invention include alkyl betaines of the formula R 5 R 6 RV (CH 2 ) awkwardCO 2 M and amido betaines of the formula (Xll) below:
  • R 5 is alkyl
  • M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium
  • 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 pretreatment composition includes alkyl sultaines of the formula (Xlll) below: ( Xl M )
  • R 1 is C 7 to C 22 alkyl or alkenyl
  • R 2 and R 3 are independently C, to C 3 alkyl
  • M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium
  • 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 R 5 R 6 R 7 NO and amido amine oxides of the formula (XIV) below:
  • R 5 is C ⁇ to C 22 alkyl or alkenyl
  • R 5 and R 7 are independently C-, to C 3 alkyl
  • M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium
  • m is a number from 1 to 4.
  • Preferred amine oxides include cocoamidopropyiamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide, (v) Cationic Surfactants
  • Cationic surfactants suitable for inclusion in the compositions of the present invention include Polyquatemium-4 (Celquat H-100;L200-supplier National Starch); Polyquaternium-10 (Celquat SC-240C; SC-230 M-supplier National Starch); (UCARE polymer series--JR-125, JR-400, LR-400, LR-30M, LK, supplier Amerchol); Polyquaternium-11 (Gafquat 734; 755N-suppIier ISP); Polyquaternium-16 (Luviquat FC 370; FC550; FC905; HM-552 supplier by BASF); PVP/Dimethylaminoethylmethacrylate (Copolymer 845; 937; 958-lSP supplier); Vinyl Caprolactam/PVP/Dimethylarnin ⁇ eihy) Methacrylate copolymer (Gaffix VC-713; H2OLD EP-1 -supplier ISP); Chitosan (Kyt
  • Preferred cationic polymers are Polyquater ⁇ ium-4; Polyquatemium-10; Polyquatemium-11 ; Polyquatemium- 6; PVP/Dimethylaminoeth Vinyl Caprolactam/PVP/Dimethylaminoethyl Methacrylate copolymer; and, Chitosan. 5
  • PVP/Dimethylaminoeth Vinyl Caprolactam/PVP/Dimethylaminoethyl Methacrylate copolymer and, Chitosan.
  • a number of additional optional materials can be added to the pretreatment composition, 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 l o polypeptides " and derivatives thereof; water-soluble or solubilizable preservatives such as DMDM Hydantoin, Germalf 115, methyl, ethyl, pr ⁇ pyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate and bisabalol, benzoic acid, sodium benzoate and 2-phenoxyethanol; a ⁇ tioxidants such as
  • viscosity control agents such as magnesium sulfate and other electrolytes; o quaternary amine compounds such as distearyl-, dilauryl-, di-hydrogenated beef tallow- dimethyl ammonium chloride, dicetyldiethyl ammoniumethylsuiphate, ditallowdimethyl ammonium methylsulphate, disoya 13 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; coloring agents; TiO 2 and TiO 2 -coated mica; perfumes and perfume solubilizers; and zeolites such as Valfour BV400 and derivatives thereof and Ca 2 */Mg 2* sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates etc. and water softening agents such as
  • Another essential feature of the present invention is the provision of a second, hair coloring or bleaching step, which involves treating the hair with a color altering composition having a pH less than that of the pretreatment composition.
  • the initial high pH (immediately after the application of the color altering composition). has the effect of promoting the reaction of the coloring and/or bleaching components of the color altering composition but as the pH decreases, damage to the hair is limited (damage is increased under high pH conditions).
  • the color altering composition generally contains one or more coloring agents. Coloring agents are components which apply a color to the hair.
  • the coloring agents may be oxidative or non-oxidative or a combination of these, but are preferably oxidative.
  • the color altering composition usually also contains an oxidising agent, and optional additional components which may or may not be active ingredients.
  • the color altering composition may contain, in addition to a mixture of active oxidising agents and one or more coloring agents, other ingredients such as oxidising aids, sequestrants, stabilisers, thickeners, buffers, carriers, surfactants, solvents, antioxida ⁇ ts, polymers, and conditioners,
  • the color altering composition can be a hair lightening composition.
  • Such compositions can contain one or more coloring agents that produce colors which are lighter than the initial hair color, preferably with an oxidising agent. They may contain no coloring components at all but simply an oxidising agent to lighten the hair. In general, however, they contain at least some coloring agent.
  • the color altering compositions utilised in the present invention preferably have a pH in the range of from about 1 to 9, more preferably about 1.5 to about 7, more preferably from about 2 to about 6, in particular from about 2.5 to about 5.8 and especially from about 3.5 to about 5.5.
  • Several different pH modifiers can be used to adjust the pH of the o color altering composition utilised in the present method.
  • This pH adjustment can be effected by using well known acidifying agents in the field of treating keratinous fibres, and in particular human hair, such as inorganic and organic acids such as hydrochloric acid, tartaric acid, citric acid, succinic acid, phosphoric acid and carboxylic or sulphonic acids5 such as ascorbic acid, acetic acid, lactic acid, sulphuric acid, formic acid, ammonium sulphate and sodium dihydrogenphosphate /phosphoric acid, disodium hydrogenphosphate /phosphoric acid, potassium chloride /hydrochloric acid, potassium dihydrogen phthalate/ hydrochloric acid, sodium citrate / hydrochloric acid, potassium dihydrogen citrate /hydrochloric o acid, potassium dihydrogencitrate/ citric acid, sodium citrate / citric acid, sodium tartarate/ tartaric acid, sodium lactate/ lactic acid, sodium acetate/ acetic acid, disodium hydrogenphosphate/ citric acid and sodium chloride/
  • alkaline buffering agents are ammonium hydroxide,5 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 dimethylami ⁇ oethano), polyalkylene polyamines such as diethylenetriamine or a heterocyclic amine such as morpholine as well as o 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-argeni ⁇ e, lysine, ala ⁇ ine, leucine, iso-leuci ⁇ e, oxylysine and histidine and alka ⁇ olamines such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof.
  • the method of altering hair color utilizes a color altering composition having a pH in the range 1 to 6, " preferably less than 6.
  • the pretreatment composition may remain on the hair during application of the color altering composition, although, in a preferred embodiment the pretreatment is rinsed from the hair prior to application of the color altering composition.
  • compositions used in the methods according to the present invention may be provided as kits comprising of a number of separate components.
  • the kits comprise at least two components. It is essential that the pretreatment composition is presented separately from the color altering composition.
  • the pretreatment composition may be presented in a form selected from foams, aerosol foams / mousses, conditioners, shampoos, tonics, aqueous sprays and gels. Most preferably the pretreatment composition is presented as a foam.
  • a preferred kit comprises two components.
  • the first component is presented separately (ie. not attached) from the second and comprises the pretreatment composition.
  • the second component comprises a color altering composition containing an oxidative hair coloring agent and oxidising composition, preferably containing a peroxygen bleach oxidising agent.
  • the color altering compositions be in a form which is easy and convenient to prepare and use by the consumer, since the oxidising agent must remain in contact with the hair for a certain period of time and not run or drip off of the hair, possibly causing eye or skin irritation.
  • the color altering compositions of the present invention can be provided as a single pack or as a kit comprising separately packaged components. This latter feature allows one to maintain stability of the coloring composition. This also allows the hair color altering composition components to either be mixed by the user immediately prior to application to the hair, or mixed and stored for future use, or mixed and part of the 5 mixture used and the remainder stored for future use. Color altering components can be delivered from a single package having multi- compartments to keep each component separate until it is mixed. Suitable single packages having multiple compartments include those disclosed in WO99/26508, WO99/26509, WO99/26510, WO99/265 1 and WO99/26596o and these are the preferred packaging used for the present invention. In another embodiment, the packaging may comprise a multi- compartment, aerosol packaging or a delaminati ⁇ g bottle packaging.
  • the color altering compositions according to the present invention may be provided to the consumer in the form of a single components package.
  • a single pack comprises a single solution containing the oxidising agent, and the hair coloring agent.
  • the single solution is applied directly to the hair by the consumer subsequent to the application of the pretreatment composition, thereby providing a simple, fast, easy to use, 'no- mess' hair coloring system.
  • a further advantage of such a single o component system is that it can be stored and re-used i.e., a single package may contain enough coloring composition for several applications over time.
  • the oxidative hair coloring agent and oxidising agents are preferably kept apart from one another until application to the hair is undertaken. This may be accomplished by the provision of a 5 compartmentalised packaging.
  • This packaging contains the oxidative hair coloring agent and oxidising composition but does not allow the compositions to contact each other until the compositions are mixed. Mixing is usually undertaken by the user immediately prior to application to the hair.
  • the components can also be mixed and the resulting composition o can be stored for future use or part of the resulting composition can be used and the rest of the composition stored for future use.
  • the kit comprises instructions for use of the compositions disclosed herein. These include instructions to carry out any of the steps described above.
  • the color altering compositions used in the methods of the invention may comprise an oxidising agent, which may be an inorganic or organic oxidising agent.
  • the oxidising agent is preferably present at a level of from about 0.01 % to about 10%, preferably from about 0.01 % to about 6%, more preferably from about 1 % to about 4% by weight of composition.
  • the color altering compositions utilised in the present invention comprise from about 0.0003 moles (per 100g of composition) to less than about 0.09 moles (per 100g of composition) of an inorganic peroxygen based oxidising agent.
  • a preferred oxidising agent for use herein is an inorganic peroxygen oxidising agent.
  • the inorganic peroxygen oxidising agent should be safe and effective for use in the methods herein.
  • the inorganic peroxygen oxidising agents suitable for use herein will be soluble in the compositions used in the o methods according to the present invention when in liquid form or in the form intended to be used.
  • inorganic peroxygen oxidising agents suitable for use herein will be water-soluble.
  • Water soluble oxidising agents as defined herein means agents which have a solubility to the extent of about 10g in 1000ml of deionised water at 25°C ("Chemistry" C. E. Mortimer. 5 5th Edn. ⁇ 277).
  • the inorganic peroxygen oxidising agents useful herein are generally inorganic peroxygen materials capable of yielding peroxide in an aqueous solution.
  • Inorganic peroxygen oxidising agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides such as sodium o periodate, sodium perbromate and sodium peroxide, and inorganic perhydrate salt oxidising compounds, such as the alkali metal salts of perborates, percarbonates, perphosphates, persilicates, persulphates and the like. These inorganic perhydrate salts may be incorporated as monohydrates, tetrahydrates etc. Mixtures of two or more of such inorganic peroxygen oxidising agents can be used if desired. While alkali metal bromates and iodates are suitable for use herein the bromates are preferred. Highly preferred for use in the compositions used in the methods according to the present invention is hydrogen peroxide.
  • the inorganic peroxygen oxidising agent is present at a level of from about 0.01% to less than about 6%, preferably from about 0.01 % to about 4%, more preferably from about 1 % to about 4%, more preferably from about 2% to about 3% by weight of color composition.
  • Preformed organic peroxyacid is present at a level of from about 0.01% to less than about 6%, preferably from about 0.01 % to about 4%, more preferably from about 1 % to about 4%, more preferably from about 2% to about 3% by weight of color composition.
  • the color altering compositions used in the methods according to the present invention may instead or in addition to the inorganic peroxygen oxidising agent(s), comprise one or more preformed organic peroxyacid oxidising agents.
  • Suitable organic peroxyacid oxidising agents for use in the coloring compositions according to the present invention have the general formula:
  • R is selected from saturated or unsaturated, substituted or unsubstituted, straight or branched chain, alkyl, aryl or alkaryl groups with from 1 to 14 carbon atoms.
  • a class of organic peroxyacid compounds suitable for use herein are the amide substituted compounds of the following general formulae: or
  • R 1 is, a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having from 1 to 14 carbon atoms
  • R 2 is, a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having from 1 to 14 carbon atoms
  • R 5 is H or, a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having from 1 to 10 carbon atoms.
  • Amide substituted organic0 peroxyacid compounds of this type are described in EP-A-0, 170,386.
  • organic peroxyacid oxidising agents include peracetic, pernanoic, nonylamidoperoxycaproic acid (NAPCA), perbenzoic, m- chloroperbenzoic, di-peroxy-isophtha!ic, mono-peroxyphthalic, peroxylauric, hexanesulphonyl peroxy propionic, N,N-phthaloylamino peroxycaproic,5 mo ⁇ oper succinic, nonanoyloxybenzoic, dodecanedioyl-monoperoxybenzoic, nonylamide of peroxyadipic acid, diacyl and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid and derivatives thereof. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- o phthaloylaminoper
  • the preformed organic peroxyacid oxidising agents should be safe and effective for use in the compositions herein.
  • the preformed organic peroxyacid oxidising agents suitable for use herein will be soluble in5 the compositions according to the present invention when in liquid form and in the form intended to be used.
  • organic peroxyacid oxidising agents suitable for use herein will be water-soluble.
  • Water-soluble preformed organic peroxyacid oxidising agents as defined herein means agents which have a solubility to the extent of about 10g in 1000ml of o deionised water at 25°C ("Chemistry" C. E. Mortimer. 5th Edn. ⁇ 277).
  • the preferred peroxyacid materials suitable for use herein are selected from peracetic and pernanoic acids and mixtures thereof.
  • the preformed organic peroxyacid oxidising agent, where present, is preferably present at a level of from about 0.01 % to about 8%, more preferably from about 0.1 % to about 6%, most preferably from about 0.2% to about 4%, and especially from about 0.3% to about 3% by weight of the hair coloring composition.
  • the weight ratio of the inorganic peroxygen oxidising agent to the preformed organic peroxy acid is preferably in the range of from about 0.0125:1 to about 500: 1 , more preferably from about 0.0125:1 to about 50:1.
  • the color altering compositions according to the present invention may optionally comprise additional organic peroxides such as urea peroxide, melami ⁇ e peroxide and mixtures thereof.
  • additional organic peroxides such as urea peroxide, melami ⁇ e peroxide and mixtures thereof.
  • the level of organic peroxide, where present, is from about 0.01% to about 3%, preferably from about 0.01% to about 2%, more preferably from about 0.1% to about 1.5% and most preferably from about 0.2% to about 1% by weight of composition.
  • the color altering compositions utilized in the present invention include as an essential feature an oxidative or non-oxidative hair coloring agent. Such hair coloring agents are used in combination with the oxidising agent to formulate permanent, demi-permanent, semi-permanent or temporary hair coloring compositions. Most preferably the coloring altering compositions comprise an oxidative hair coloring agent, and contain substantially no non-oxidative hair coloring agents.
  • Permanent hair coloring compositions as defined herein are compositions which once applied to the hair are substantially resistant to wash-out.
  • Demi-permanent hair coloring compositions as defined herein are compositions which are substantially removed from the hair after up to 24 washes.
  • Semi-permanent hair coloring compositions as defined herein are compositions which once applied to the hair are substantially removed from the hair after up to 10 washes.
  • Temporary hair coloring compositions as defined herein are compositions which once applied to the hair are substantially removed from the hair after up to 2 washes.
  • a preferred hair coloring agent herein is an oxidative hair coloring agent.
  • concentration of each oxidative hair coloring agent in the coloring compositions according to the present invention is preferably from about 0.001 % to about 3% by weight, more preferably from about 0.01 % tos about 2% by weight.
  • the total combined level of oxidative hair coloring agents in the compositions according to the present invention is from about 0.001 % to about 5%, preferably from about 0.01 % to about 4%, more preferably from about 0.1 % to about 3%, most preferably from about 0.1 % to about 2% by o weight.
  • oxidative hair coloring agents can be used in the compositions according to the present invention.
  • oxidative hair coloring agents consist essentially of at least two components, which are collectively referred to as dye forming5 intermediates (or precursors).
  • Dye forming intermediates can react in the presence of a suitable oxidant to form a colored molecule.
  • the dye forming intermediates used in oxidative hair colorants include: aromatic diamines, aminophenols, various heterocycles, phenols, napthols and their various derivatives. These dye forming intermediates cano be broadly classified as; primary intermediates and secondary intermediates.
  • Primary intermediates which are also known as oxidative dye precursors, are chemical compounds which become activated upon oxidation and can then react with each other and/or with couplers to form colored dye complexes.
  • the secondary intermediates also known as color modifiers or couplers, are generally colorless molecules which can form colors in the presence of activated precursors/primary intermediates, and are used with other intermediates to generate specific color effects or to stabilise the color.
  • Primary intermediates suitable for use in the compositions and processes herein include: aromatic diami ⁇ es, polyhydric phenols, amino phenols and derivatives of these aromatic compounds (e.g., N-substituted derivatives of the amines, and ethers of the phenols). Such primary intermediates are generally colorless molecules prior to oxidation.
  • the process by which color is generated from these primary intermediates and secondary coupler compounds generally includes a stepwise sequence whereby the primary intermediate can become activated (by oxidation), and then enjoins with a coupler to give a dimeric, conjugated colored species, which in turn can enjoin with another 'activated' primary intermediate to produce a trimeric conjugated colored molecule.
  • oxidative dye primary intermediates include those monomeric materials which, on oxidation, form oligomers or polymers having extended conjugated systems of electrons in their molecular structure. Because of the new electronic structure, the resultant oligomers and polymers exhibit a shift in their electronic spectra to the visible range and appear colored.
  • oxidative primary intermediates capable of forming colored polymers include materials such as aniline, which has a single functional group and which, on oxidation, forms a series of conjugated imines and quinoid dinners, trimers, etc. ranging in color from green to black.
  • Oxidative dyes known in the art can be used in the compositions according to the present invention.
  • a representative list of primary intermediates and secondary couplers suitable for use herein is found in Sagarin, "Cosmetic Science and Technology”," Interscie ⁇ ce, Special Ed. Vol. 2 pages 308 to 310. It is to be understood that the primary intermediates detailed below are only by way of example and are not intended to limit the compositions and processes herein.
  • the typical aromatic diami ⁇ es, polyhydric phenols, amino phenols, and derivatives thereof, described above as primary intermediates can also have additional substituents on the aromatic ring, e.g. halogen, aldehyde, carboxylic acid, nitro, sulfonic acid and substituted and unsubstituted hydrocarbon groups, as well as additional substituents on the amino nitrogen and on the phenolic oxygen, e.g. substituted and unsubstituted alkyl and aryl groups.
  • Suitable aromatic diamines amino phenols, polyhydric phenols and derivatives thereof, respectively, are compounds having the general formulas (I), (II) and (III) below:
  • Y is hydrogen, halogen, (e.g. fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,
  • R ⁇ R 2 , R 3 and R 4 are the same or different from each other 5 and are selected from the group consisting of hydrogen, C, to C 4 alkyl or alkenyl and C ⁇ to C 9 aryl, alkaryl or aralkyl, and R s is hydrogen, C 1 to C 4 unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from those designated as Y, above, or C 6 to C 9 unsubstituted or substituted aryl, alkaryl or aralkyl wherein the substituents are selected from o those defined as Y, above.
  • the precursors of formula (I) are amines, they can be used herein in the form of peroxide-compatible salts, as noted, wherein X represents peroxide-compatible anions of the type herein before detailed.
  • the general formula of the salt indicated is to be understood to encompass those salts having mono-, di-, and tri-negative anions.
  • formula (I) compounds are: o-phenylenediami ⁇ e, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, 2- iodo-p-phenylenediamine, 4-nitro-o-phenylenediamine, 2-nitro-p- phenylenediamine, 1 ,3,5-triaminobenzene, 2-hydroxy-p-phenyle ⁇ ediami ⁇ e, 2,4-diaminobenzoic acid, sodium 2,4-diaminobe ⁇ oate, calcium di-2,4- 0 diaminobenzoate, ammonium 2,4-diaminobenzoate, trimethylammonium 2,4- diaminobenzoate, tri-(2-hydr ⁇ xyethyl)ammonium 2,4-diaminobenzoate, 2,4- diaminobenzaldehyde carbonate, 2,4-diami ⁇ obenzen
  • R 1 and R 2 can be the same or different from each other and are the same as in formula (I)
  • R s is the same as in formula (1)
  • R 6 is hydrogen or C, to C 4 substituted or unsubstituted alkyl or alkenyl wherein the substituents are selected from those defined as Y in formula (I).
  • formula (II) compounds are: o-aminophenol, m-ami ⁇ ophenol, p-aminophenol, 2-iodo-p-aminophenol, 2- nitro-p-aminophenol, 3,4-dihydroxya ⁇ ili ⁇ e, 3,4-diami ⁇ ophenol, chloroacetate, 2 ⁇ hydroxy-4-aminobenzoic acid, 2-hydroxy-4- aminobenzaldehyde, 3-ami ⁇ o-4-hydroxybenzenesulfonic acid, N,N- diisopropyl-p-aminophenol, N-methyl-N-(1 -propenyl)-p-aminophenol, N- phenyl-N-benzyl-p-aminophenol sulphate, N-methyl-N-(3-ethylphenyl)-p- aminophenol, 2-nitro-5-ethyl-p-amino ⁇ he ⁇ ol, 2-nitro-5-(2-bromoethyl)- ⁇ - aminophenol
  • R 1 and R 2 can be the same or different from each other and are the same as in formula (I)
  • R 5 is the same as in formula (I)
  • R 6 is hydrogen or C, to C 4 substituted or unsubstituted alkyl or alkenyl wherein the substituents are selected from those defined as Y in formula (t).
  • formula (III) compounds are: o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol), p-hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxy ⁇ henol, 4-(2-chloroethoxy) phenol, 4-(2-propenoxy) phenol, 4-(3-chloro-2-propenoxy) phenol, 2-chloro- 4-hydroxyphenol (2-chlorohydroquinone), 2-nitro-4-hydroxyphenol(2- nitrohydroquinone), 2-amino-4-hydroxyphenol, 1 ,2,3-trihydroxybenzene (pyrogallol), 2,4-dihydroxybenzaldehyde, 3,4-dihydoxybenzoic acid, 2,4- dihydroxybenzenesulfonic acid, 3-ethyl-4-hydroxyphenol, 3-(2-nitroethyl)-4- hydroxyphenol, 3-(2-propenyl)-4-hydroxyphenol, 3-(3-chloro ⁇ 2-propenyl)-4-
  • Secondary coupling compounds which are suitable for inclusion in the coloring compositions and processes herein before described include certain aromatic amines and phenols and derivatives thereof which do not produce color singly, but which modify the color, shade or intensity of the colors developed by the primary oxidized dye intermediates.
  • Polyhydric alcohols are also suitable for use as couplers herein.
  • aromatic amines and phenols and derivatives described above as couplers can also have additional substituents on the aromatic ring, e.g., halogen, aldehyde, carboxylic acid, nitro, sulfonyl and substituted and unsubstituted by hydrocarbon groups, as well as additional substituents on the amino nitrogen, or phenolic oxygen, e.g. substituted and unsubstituted alkyl and aryl groups.
  • peroxide-compatible salts thereof are suitable for use herein.
  • aromatic amines examples include phenols and derivatives thereof.
  • aromatic amines examples include phenols and derivatives thereof.
  • Z is hydrogen, C, to C 3 alkyl, halogen (e.g. fluorine, chlorine, bromine or iodine) nitro,
  • R 1 and R 2 are the same or different and are selected from the group consisting of hydrogen, C, to C 4 alkyl or alkenyl and G 6 to C 9 aryl, alkaryl or aralkyl and R 7 is hydrogen, C, to C 4 unsubstituted or substituted alkyl or alkenyl wherein the substituents are selected from those designated as Z above or C 6 to C 9 unsubstituted or substituted aryl, alkaryl or aralkyl wherein the substituents are selected from those defined as Z above and 5 wherein X is as defined in formula (I).
  • formula (IV) compounds are: aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline, p-ami ⁇ obenzaldehyde, p-aminobenzoic acid, sodium-p-aminobenzoate, lithium-p-ami ⁇ obenzoate, calcium di-p-aminobenzoate, ammonium-p-aminobenzoate, i o trimethylamrnonium-p-aminobenzoate, tri(2-hydroxyethyl)-p-ami ⁇ obenzoate, p-aminobenzenesulfonic acid, potassium p-aminoben ⁇ enesulfonate, N- methylaniline, N-propyl-N-phenylaniline, N-methyl-N-2-propenylaniline, N- benzylaniline, N-(2-ethylphenyl)aniline, 4-methylaniline, 4-(2- bromoethyl
  • formula (V) compounds are: phenol, p-chlorophenol, p-nitrophenol, p-hydroxybenzaldehyde, p- hydroxybenzoic acid, p-hydroxybenzenesulfo ⁇ ic acid, ethylphenyl ether, 2- 30 chloroethylphenyl ether, 2-nitroethylphenyl ether, phenoxyacetaldehyde, phe ⁇ oxyacetic acid, 3-phenoxy-1 -propene, 3-phenoxy-2-nitro-1 -propene, 3- phenoxy-2-bromo-1 -propene, 4-propylphenol, 4-(3-bromopropyl) ⁇ henol, 2- (2- ⁇ itroethyl)phenol, (4-hydroxyphenyl)acetaldehyde, (4- hydroxyphenyl)acetic acid, 4-(2-propenyl) ⁇ henol, 4-phenylphenol, 4- benzylphenol, 4-(3-fluoro-2-
  • Additional primary intermediates suitable for use herein include catechol species and in particular catechol "dopa” species which includes dopa itself as well as homologs, analogs and derivatives of DOPA.
  • suitable cachetol species include cysteinyl dopa, alpha alkyl dopa having 1 to 4 , preferably 1 to 2 carbon atoms in the alkyl group, epinephrine and dopa alkyl esters having 1 to 6 , preferably 1 to 2 carbon atoms in the alkyl group.
  • R ⁇ R 2 and R 3 which may be the same or different, are electron donor or acceptor substutue ⁇ ts selected from H, lower (C ⁇ Ce) alkyl, OH, OR, COOR, NHCOR, CN, COOH, Halogen, NO 2 , CF 3 , SO 3 H or NR 4 R S , with the proviso that only one of the R ⁇ R 2 or R 3 can be CN, COOH, halogen, NO 2l CF 3 or SO 3 H:
  • R 4 and R 5 which may be the same or different, are H, lower (C C s ) alkyl or substituted lower (C,-C 6 ) alkyl in which the substituent may be OH, OR, NHCOR 6 , NHCONH 2 , NHCO 2 R 6 , NHCSNH 2 , CN, COOH, SO 3 H, SO 2 NR 6 , SO 2 R s or CO 2
  • oxidative hair coloring agents of the formula:
  • oxidative hair coloring agents are generally referred to as photographic dyes and include those disclosed in WO98/52519, WO98/52520, WO98/52521, WO98/52522, WO98/52523, and can be used in the present invention.
  • Pyrazoloazole type couplers may also be used in the color altering compositions of the present invention.
  • Such compounds have the general structure below wherein 2 , Z b , and Z ⁇ are individually selected from carbon or nitrogen, which may optionally have substituents.
  • R and R 2 are individually selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, amine, alkyl substituted with one of more nitrogen or sulfur atom, alkenyl substituted with one of more nitrogen or sulfur atom, alkynyl substituted with one of more nitrogen or sulfur atom, aryl substituted with one of more nitrogen or sulfur atom, alkaryl substituted with one of more nitrogen or sulfur atom, aralkyl substituted with one of more nitrogen or sulfur atom, and halogens.
  • Z a , Z b , and Z c have substituents, they are preferably selected from the same groups as defined for R, and R 2 .
  • the primary intermediates can be used herein alone or in combination with other primary intermediates, and one or more can be used in combination with one or more couplers. The choice of primary intermediates and couplers will be determined by the color, shade and intensity of coloration which is desired.
  • low intensity colors such as natural blond to light brown hair shades generally comprise from about 0.001 % to about 5%, preferably from about 0.1 % to about 2%, more preferably from about 0.2% to about 1 % by weight of coloring composition of total oxidative dyeing agents and may be achieved by the combination of primary intermediates such as 1 ,4- diamino-benzene, 2,5-diamino toluene, 2,5-diamino-anisole, 4-aminophenol,
  • 2,5-diamino-benzyl alcohol and 2-(2',5'-diamino)phenyl-ethanol with couplers such as resorcinol, 2-methyl resorcinol or -chloro resorcinol.
  • couplers such as, 5-amino-2-methyl phenol and 1 ,3-diamino-benze ⁇ e derivatives such as 2,4-diamino-anisole at levels of from about 0.5% to about 1 % of total dyeing agents can lead to medium intensity red colors.
  • High intensity colors such as blue to blue-violet hair shades can be produced by the combination of the above primary intermediates with couplers such as 1 ,3-diamino-benzene or its derivatives such as 2,5- diamino-toluene at levels of from about 1 % to about 6% by weight of composition of total dyeing agents.
  • Black hair colors can be obtained by combining the aforementioned primary intermediates with couplers such as 1 ,3-diaminobenzene or its derivatives
  • Particularly preferred oxidative dyes ustilised in the compositions used in the present invention include para-phenylene diamine, para- aminophenol, 2-amino-3-hydroxy pyridine, resorcinol, 4-amino-2-hydroxy toluene, meta-phenylene diamine, meta-aminophenol [N,N bis (2- hydroxyethyl)p-phenyIenediamine], ⁇ -naphthol, 2,5-diaminotoluene sulphate and ortho-aminophenol.
  • the coloring altering compositions utilised in the present invention may, in addition to an oxidative hair coloring agent, include non-oxidative and other dye materials.
  • Optional non-oxidative and other dyes suitable for use in the hair coloring compositions and processes according to the present invention include both semi-permanent, temporary and other dyes.
  • 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,
  • Direct action dyes which do not require an oxidative effect in order to develop the color, are also designated hair tints and have long been known in the art. They are usually applied to the hair in a base matrix which includes surfactant material. Direct action dyes include nitro dyes such as the derivatives of nitroamino benzene or nitroaminophe ⁇ ol; disperse dyes such as nitroaryl amines, aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinone dyes; basic dyes such as Acridine Orange C.l. 46005. Nitrodyes are added to dyeing compositions to enhance color of colorant and to add suitable aesthetic color to the dye mixture prior to application.
  • direct action dyes include the Arianor dyes basic brown 17, C.I.(color index) - no. 12,251 ; basic red 76, C.l. - 12,245; basic brown 16, C.l. - 12,250; basic yellow 57, C.l. - 12,719 and basic blue 99, C.l. - 56,059 and further direct action dyes such as acid yellow 1 , C.l. - 10,316 (D&C yellow no.7); acid yellow 9, C.l. - 13,015; basic violet C.l. - 45,170; disperse yellow 3, C.l. - 11 ,855; basic yellow 57, C. l. - 12,719; disperse yellow 1 , C.l.
  • Fibre reactive dyes include the Procion (RTM), Drimare ⁇ e (RTM), Cibacron (RTM), Levafix (RTM) and Remazol (RTM) dyes available from ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst respectively.
  • Natural dyes and vegetable dyes as defined herein include henna (Lawsonia alba), camomile (Mat ⁇ ca ⁇ a chamomila orAnthemis nobilis), indigo, logwood and walnut hull extract.
  • Temporary hair dyes are generally comprised of dye molecules which are too large to diffuse into the hair shaft and which act on the exterior of .the hair. They are usually applied via a leave-in procedure in which the dye solution is allowed to dry on the hair surface. As such these dyes are typically less resistant to the effects of washing and cleaning the hair with surface active agents and are washed off of the hair with relative ease. Any temporary hair dye may suitably be used in the compositions of the invention and examples of preferred temporary hair dyes are illustrated below.
  • Semi-permanent hair dyes are dyes which are generally smaller in size and effect to temporary hair rinses but are generally larger than permanent (oxidative) dyes.
  • semi-permanent dyes act in a similar manner to oxidative dyes in that they have the potential to diffuse into the hair shaft.
  • semi-permanent dyes are generally smaller in size than the aforementioned conjugated oxidative dye molecules and as such are pre-disposed to gradual diffusion out of the hair again. Simple hair washing and cleaning action will encourage this process and in general semipermanent dyes are largely washed out of the hair after about 5 to 8 washes. Any semi-permanent dye system may be suitably used in the compositions of the present invention.
  • Suitable semi-permanent dyes for use in the compositions of the present invention are HC Blue 2, HC Yellow 4, HC Red 3, Disperse Violet 4, Disperse Black 9, HC Blue 7, HC Yellow 2, Disperse Blue 3, Disperse violet 1 and mixtures thereof. Examples of semi-permanent dyes are illustrated below:
  • Typical semi-permanent dye systems incorporate mixtures of both large and small color molecules. As the size of the hair is not uniform from root to tip the small molecules will diffuse both at the root and tip, but will not be retained within the tip, while the larger molecules will be generally only be able to diffuse into the ends of the hair. This combination of dye molecule size is used to help give consistent color results from the root to the tip of the hair both during the initial dyeing process and during subsequent washing. Catalyst
  • the color altering compositions used herein may optionally contain a transition metal containing catalyst for the inorganic peroxygen oxidising agents and the, optional, preformed peroxy acid oxidising agent(s).
  • One suitable type of catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra
  • Suitable catalysts include the manganese-based complexes disclosed in US-A-5,246,621 and US-A-5,244,594. Preferred examples of these catalysts include MnlV 2 ( ⁇ -O)3(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2-(PF 6 ) 2 , Mnlll 2 ( ⁇ -O)1 ( ⁇ -OAc)2(1 ,4,7 ⁇ trimethyl-1 ,4,7- triazacyclononane)2-(CIO 4 ) 2 , MnlV 4 ( ⁇ -O)6(1 ,4,7-triazacyclononane)4- (CIO 4 ) 2 , MnlllMnlV 4 ( ⁇ -O)1 ( ⁇ -0Ac)2-(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2-(CIO 4 ) 3 , and mixtures thereof.
  • ligands suitable for use herein include 1,5,9- trimethyl-1 ,5,9-triazacyclododecane, 2-methyl-1 ,4,7-triazacyclononane, 2- methyl-1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl-1 ,4,7-triazacyclo ⁇ onane, and mixtures thereof.
  • binuclear Mn complexed with tetra-N-de ⁇ tate and bi-N-dentate ligands including N 4 Mnlll( ⁇ -O) 2 MnlVN 4 )+and [Bi ⁇ y 2 Mnlll( ⁇ -O) 2 MnlVbipy 2 ]-(CIO 4 ) 3 .
  • the color altering compositions utilised in the invention may contain as an optional component a heavy metal ion sequestrant.
  • Heavy metal ion sequestrants are components which act to sequester (chelate or scavenge) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • sequestering agents are valuable in hair coloring compositions as herein described for the delivery of controlled oxidising action as well as for the provision of good storage stability of the hair coloring products.
  • Heavy metal ion sequestrants are generally present at a level of from about 0.005% to about 20%, preferably from about 0.01 % to about 10%, more preferably from about 0.05% to about 2% by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methyle ⁇ e phosphonate) and hydroxy- ethylene-1 ,1-diphosphonate.
  • Preferred biodegradable non-phosphorous heavy metal ion sequestrants suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • ethylenediami ⁇ e-N,N'-disuccinic acid see US-A-4,704,233, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • EP-A-516,102 The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N- carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • the -alani ⁇ e-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • 510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.
  • Dipicolinic acid and 2-phosphonobutane-1 ,2,4-tricarboxylic acid are also suitable.
  • Glycinamide-N.N'-disuccinic acid (GADS) ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • the heavy metal ion sequestering agents utilised in the present invention may be used in their alkali or alkaline earth metal salts.
  • Heavy metal ion sequestering agents for use herein include (a) sodium stannate, etidronic acid, and pe ⁇ tasodium pentatate, (b) sodium stannate, disodium pyrophosphate, sodium pentatate, ⁇ sodium stannate, disodium pyrophosphate and EDTA, (d) sodium stannate, etidronic acid and EDTA and (e) sodium stannate, disodium pyrophosphate and etidronic acid, Peroxide stabilising agents
  • the color altering compositions of the present invention may additionally comprise an alkoxylated benzoic acid or a salt thereof which acts as a peroxide stabilising agent
  • said alkoxylated benzoic acid or a salt thereof is selected from the group consisting of a monoalkoxy benzoic acid, or a salt thereof, a dialkoxy benzoic acid, or a salt thereof, a trialkoxy benzoic acid, or a salt thereof; and mixtures thereof.
  • the alkoxylated benzoic acid or the salt thereof is a trimethoxy benzoic acid or a salt thereof (TMBA).
  • TMBA trimethoxy benzoic acid or a salt thereof
  • the alkoxylated benzoic acid or the salt thereof is selected from the group consisting of 3,4,5,- trimethoxy benzoic acid, a salt 4 S thereof, 2,3,4- trimethoxy benzoic acid, a salt thereof, 2,4,5- trimethoxy benzoic acid, a salt thereof and mixtures thereof.
  • said alkoxylated benzoic acid is 3,4,5,- trimethoxy benzoic acid.
  • Suitable monoalkoxy benzoic acids or salts thereof are commercially available from Aldrich, in particular m-methoxy benzoic acid is commercially available from Aldrich.
  • Suitable trimethoxy benzoic acids or salts thereof are commercially available from Aldrich and Merck.
  • the color altering composition utilised in the present invention comprises from 0.001 % to 5%, preferably from 0.005% to 2.5% and more preferably from 0.01 % to 1.0% by weight of the total composition of said alkoxylated benzoic acid or a salt thereof.
  • an alkoxylated benzoic acid or a salt thereof acts as a radical scavenger in the color altering composition of the present invention.
  • the presence of an alkoxylated benzoic acid or a salt thereof, the color altering compositions significantly increases the immediate chemical stability and particularly the chemical stability upon storage of the peroxygen bleaching agents comprised in the color altering compositions utilised in the present invention.
  • the color altering compositions utilised in 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, Diluent
  • Water is the preferred diluent for the color altering compositions 5 utilised in the present invention.
  • the compositions according to the present invention may include one or more solvents as additional diluent materials.
  • solvents suitable for use in the coloring compositions are selected to be miscible with water and innocuous to the skin.
  • Solvents suitable for use as additional diluents herein include C 1 -C 20 mono- or0 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.
  • a preferred group includes ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, and mixtures thereof.
  • Water is the5 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 o from about 30% to about 99%, and especially from about 50% to about 98% by weight of the compositions herein.
  • a further additional material useful in the color altering compositions according to the present invention is one or more enzymes.
  • Suitable enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • o Peroxidases are haemoproteins specific for peroxide, but using a wide range of substances as donors. Catalase which decomposes peroxide, is included here in view of the fact that it is generally similar in structure and properties and is able to bring about certain oxidations by H 2 O 2 .
  • H 2 O 2 The decomposition of H 2 O 2 can be regarded as the oxidation of one molecule by the other. It is widespread in aerobic cells and may have some more important function.
  • the coenzyme peroxidases are not haemoproteins and one at least is a flavoprotein. Other flavoproteins such as xanthine oxidase will also use H 2 O 2 among other acceptors, and the coenzyme peroxidases resemble these rather than the classical peroxidases in not being specific for H 2 O 2 .
  • Suitable peroxidases for the compositions of the present invention include horseradish peroxidase, Japanese radish peroxidase, cov s milk peroxidase, rat liver peroxidase, linginase and haloperoxidase such as chloro- and bromo-peroxidase.
  • Enzymes are optionally incorporated at levels sufficient to provide up to about 50 mg by weight, more typically about 0.01 mg to about 10 mg of active enzyme per gramm of the hair treatment composition of the invention. Stated otherwise the peroxidase enzyme may be incorporated into the compositions in accordance with the invention at a level of from about 0.0001 % to about 5%, preferably from about 0.001 % to about 1 %, more preferably from about 0.01 % to about 1 % active enzyme by weight of the composition.
  • protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Amylases include amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0,0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp.. Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Asperqillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • the color altering compositions utilised herein can additionally contain a surfactant system which may be any of those discussed above as being suitable for the pretreatment composition.
  • a number of additional optional materials can be added to the color altering compositions herein described. These may be selected from the same materials as defined as optional materials for use in the pretreatment compositions.
  • the equipment used to measure both the initial color and color change on substrates (hair / skin) dyed with the low pH coloring compositions of the present invention is a Hunter Colorquest spectrophotometer.
  • the value used to express the degree of color change on any particular substrate is ⁇ E.
  • ⁇ E as defined herein, is represented by a factual sum of L, a, and b values such that:
  • 'a' is a measure of the red and green quotients (color hues) such that positive equates to red and negative equates to green
  • 'b' is a measure of the yellow and blue quotients (color hues) such that positive equates to yellow and negative equates to blue.
  • Spectrophotometric measurements can be carried out on the Hunter Labscan Colorimeter which is full scanning spectrocolorimeter with a wavelength of from 400-700 nanometers which records the color of test hair switches (tresses) in terms of 'L ⁇ 'a' and 'b' values.
  • the machine is set to: mode - 0/45; port size - 1 inch; view size - 1 inch; light - D65; field of view - 10°; UV lamp/filter - none.
  • the hair is placed in a sample holder designed to hold the hair in a uniform orientation during measurement. Equivalent colorimeters can be used, but it must be ensured that the hair does not move during measurement. The hair must be spread to cover the 1 inch port during color measurement.
  • Dots are placed on the switch holder to guide the positioning of the holder at the port. The dots are lined up with a mark on the port and readings are taken at each spot. 8 measurements are run per switch, 4 on each side, and 1 switch is run per treatment. Standard Hair Switch
  • compositions according to the present invention can be used to color hair of all colors, types and condition, For the purposes of illustration a number of test hair switch types have been tested herein. These standard hair switches can be measured in terms of their approximate L, a, b values. Virgin Yak 82 -1 12
  • a 4 gramme switch of about 8 inch long hair is hung over a suitable container.
  • the pretreatment composition is then applied to the hair, massaged into the hair and left in place for 5 minutes (1.5 grammes of pretreatment composition per gramme of hair).
  • the test coloring product is then prepared (i.e. , where applicable the separate bottle components are mixed together) and about 2 grammes of product is applied directly to the test hair switch without removal of the pretreatment compostion.
  • the colorant is massaged through the hair switch for up to about 1 minute and then left on the hair switch for up to about 30 minutes.
  • the colored hair switch is then cleansed and dried. Drying can be effected either naturally (without heat assistance) or using a drier.
  • the color development (initial color) of the colored, cleansed, dried test hair switch can then be assessed using the Hunter Colorquest spectrophotometer.
  • the pH of the pretreatment formulations 1 and 2 is in the range 8.8 to
  • AHT 4-amino-2-hydroxytoluene
  • Pretreatment Formulation 1 is applied to untreated Yak switch for 5 minutes followed by color altering formulation for 30mins at 30°C.
  • Pretreatment formulation 1 was applied to the hair for 5 minutes then dye formulation III was applied to the hairfor 30mins at 30°C. On drying, the cysteic acid content was measured using FTIR (Fourier Transform Infra Red) and the ⁇ E measured using UV/vis as discussed above. The process was repeated for 2, 3 and 4 cycles. A second set of results were generated without the pretreatment.
  • FTIR Fastier Transform Infra Red
  • Switches were dyed with formulations I, II and IV with and without 2% ammonium carbonate pretreatment (Pretreatmentformulation l). Switches were then put through 40 shampoo washing cycles and the loss of color measured.

Abstract

L'invention concerne un procédé permettant de modifier la couleur des cheveux, qui consiste a) à appliquer sur les cheveux à colorer une composition de prétraitement possédant un pH de 1 à 13, ladite composition de prétraitement étant sensiblement exempte d'agents de modification de couleur de cheveux; et b) à appliquer sur les cheveux, dans une étape ultérieure, une composition de modification de couleur possédant un pH de 1 à 13, le pH de la composition de prétraitement étant plus élevé que le pH de la composition de modification de couleur. On ne rince pas la composition de prétraitement avant l'application de la composition de modification de couleur.
PCT/US2001/005598 2000-02-24 2001-02-22 Pretraitement applique avant des compositions de coloration de cheveux, et procedes WO2001062221A1 (fr)

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FR2852839A1 (fr) * 2003-03-25 2004-10-01 Oreal Compositions reductrices pour la decoloration ou la deformation permanente de fibres keratiniques comprenant des acides polycarboxyliques et leurs sels comme agents complexants
US6835213B2 (en) 2002-10-23 2004-12-28 The Procter & Gamble Company Compounds for hair coloring compositions
WO2006060565A2 (fr) * 2004-12-02 2006-06-08 The Procter & Gamble Company Compositions de coloration capillaire a taux eleve de carbonate et/ou d'oxydant
WO2006060570A2 (fr) * 2004-12-02 2006-06-08 The Procter & Gamble Company Compositions de teintures capillaires
EP1669106A1 (fr) * 2004-12-02 2006-06-14 The Procter and Gamble Company Composition colorante capillaire contenant une teneur elevée de carbonate et / ou oxidante.
EP1671619A1 (fr) * 2004-12-02 2006-06-21 The Procter and Gamble Company Compositions de coloration capillaire
US7267696B2 (en) 2003-03-25 2007-09-11 L'oreal S.A. Composition for dyeing keratinous fibers, comprising a hydroxycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
US7303588B2 (en) 2003-03-25 2007-12-04 L'oreal S.A. Composition for dyeing keratinous fibers, comprising at least one polycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
EP1982748A2 (fr) 2005-03-11 2008-10-22 The Procter & Gamble Nouvelles compositions de colorant de cheveux à utiliser dans la coloration capillaire oxydative
WO2013071192A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et méthodes pouvant modifier l'aspect des cheveux
WO2013071191A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et méthodes pouvant modifier l'aspect des cheveux
WO2013071182A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et procédés pour modifier l'aspect de cheveux
WO2014074812A1 (fr) * 2012-11-09 2014-05-15 L'oreal Procédés pour modifier la couleur et l'aspect de cheveux
US20150265513A1 (en) * 2012-11-09 2015-09-24 Michael DeGeorge Methods for altering the color and appearance of hair
US9565915B2 (en) * 2011-11-09 2017-02-14 L'oreal Compositions and methods for altering the appearance of hair
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
EP3287120A1 (fr) * 2016-08-24 2018-02-28 Noxell Corporation Procédé de coloration des cheveux
US20180055750A1 (en) * 2016-08-24 2018-03-01 The Procter & Gamble Company Method for treating hair
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US6835213B2 (en) 2002-10-23 2004-12-28 The Procter & Gamble Company Compounds for hair coloring compositions
FR2852839A1 (fr) * 2003-03-25 2004-10-01 Oreal Compositions reductrices pour la decoloration ou la deformation permanente de fibres keratiniques comprenant des acides polycarboxyliques et leurs sels comme agents complexants
EP1473022A2 (fr) * 2003-03-25 2004-11-03 L'oreal Compositions réductrices pour la décoloration ou la déformation permanente de fibres kératiniques comprenant des acides polycarboxyliques et leurs sels comme agents complexants
EP1473022A3 (fr) * 2003-03-25 2005-08-24 L'oreal Compositions réductrices pour la décoloration ou la déformation permanente de fibres kératiniques comprenant des acides polycarboxyliques et leurs sels comme agents complexants
US7303588B2 (en) 2003-03-25 2007-12-04 L'oreal S.A. Composition for dyeing keratinous fibers, comprising at least one polycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
US7267696B2 (en) 2003-03-25 2007-09-11 L'oreal S.A. Composition for dyeing keratinous fibers, comprising a hydroxycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
EP1669106A1 (fr) * 2004-12-02 2006-06-14 The Procter and Gamble Company Composition colorante capillaire contenant une teneur elevée de carbonate et / ou oxidante.
EP1671619A1 (fr) * 2004-12-02 2006-06-21 The Procter and Gamble Company Compositions de coloration capillaire
WO2006060570A3 (fr) * 2004-12-02 2006-07-27 Procter & Gamble Compositions de teintures capillaires
WO2006060565A3 (fr) * 2004-12-02 2006-08-03 Procter & Gamble Compositions de coloration capillaire a taux eleve de carbonate et/ou d'oxydant
WO2006060570A2 (fr) * 2004-12-02 2006-06-08 The Procter & Gamble Company Compositions de teintures capillaires
WO2006060565A2 (fr) * 2004-12-02 2006-06-08 The Procter & Gamble Company Compositions de coloration capillaire a taux eleve de carbonate et/ou d'oxydant
EP1982748A2 (fr) 2005-03-11 2008-10-22 The Procter & Gamble Nouvelles compositions de colorant de cheveux à utiliser dans la coloration capillaire oxydative
EP1982749A2 (fr) 2005-03-11 2008-10-22 The Procter and Gamble Company Nouvelles compositions de colorant de cheveux à utiliser dans la coloration capillaire oxydative
EP2775991A1 (fr) * 2011-11-09 2014-09-17 L'Oréal Compositions et méthodes pouvant modifier l'aspect des cheveux
US20140311517A1 (en) * 2011-11-09 2014-10-23 L'oreal Compositions and methods for altering the appearance of hair
WO2013071182A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et procédés pour modifier l'aspect de cheveux
US9565916B2 (en) * 2011-11-09 2017-02-14 L'oreal Compositions and methods for altering the appearance of hair
CN104023695A (zh) * 2011-11-09 2014-09-03 欧莱雅 一种改变头发外观的组合物及方法
CN104039296A (zh) * 2011-11-09 2014-09-10 欧莱雅 一种改变头发外观的组合物及方法
WO2013071192A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et méthodes pouvant modifier l'aspect des cheveux
CN104066423A (zh) * 2011-11-09 2014-09-24 欧莱雅 一种改变头发外观的组合物及方法
US20140305464A1 (en) * 2011-11-09 2014-10-16 L'oreal Compositions and methods for altering the appearance of hair
US9565915B2 (en) * 2011-11-09 2017-02-14 L'oreal Compositions and methods for altering the appearance of hair
EP2775991A4 (fr) * 2011-11-09 2015-08-12 Oréal L Compositions et méthodes pouvant modifier l'aspect des cheveux
EP2775992A4 (fr) * 2011-11-09 2015-08-26 Oréal L Compositions et procédés pour modifier l'aspect des cheveux
EP2787962A4 (fr) * 2011-11-09 2015-12-02 Oréal L Compositions et procédés pour modifier l'aspect de cheveux
WO2013071191A1 (fr) * 2011-11-09 2013-05-16 L'oreal Compositions et méthodes pouvant modifier l'aspect des cheveux
US9578944B2 (en) * 2011-11-09 2017-02-28 L'oreal Compositions and methods for altering the appearance of hair
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10723974B2 (en) 2012-09-10 2020-07-28 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US20150290093A1 (en) * 2012-11-09 2015-10-15 Lisa Salvemini Methods for altering the color and appearance of hair
US9474700B2 (en) * 2012-11-09 2016-10-25 L'oreal Methods for altering the color and appearance of hair
US9566221B2 (en) 2012-11-09 2017-02-14 L'oreal Methods for altering the color and appearance of hair
EP2916916A4 (fr) * 2012-11-09 2016-06-22 Oréal L Procédés pour modifier la couleur et l'aspect de cheveux
CN105007984A (zh) * 2012-11-09 2015-10-28 欧莱雅 用于改变头发颜色和外观的方法
US20150265513A1 (en) * 2012-11-09 2015-09-24 Michael DeGeorge Methods for altering the color and appearance of hair
WO2014074812A1 (fr) * 2012-11-09 2014-05-15 L'oreal Procédés pour modifier la couleur et l'aspect de cheveux
US20190143150A1 (en) * 2016-04-25 2019-05-16 Noxell Corporation Method for colouring hair including pretreatment
EP3287120A1 (fr) * 2016-08-24 2018-02-28 Noxell Corporation Procédé de coloration des cheveux
US20180055750A1 (en) * 2016-08-24 2018-03-01 The Procter & Gamble Company Method for treating hair
CN113693953A (zh) * 2021-08-14 2021-11-26 广州市丝露杰精细化工有限公司 一种酸性倒膜烫护发一体式烫发膏及其制备方法

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