WO2005018589A1

WO2005018589A1 - Hair colouring composition

Info

Publication number: WO2005018589A1
Application number: PCT/EP2004/008662
Authority: WO
Inventors: Margie Ann Fowler; Jitendra Patel
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2003-08-22
Filing date: 2004-07-30
Publication date: 2005-03-03
Also published as: TW200513270A; AR045286A1

Abstract

A hair dye composition comprising: i) an oxidative hair dye intermediate; and ii) 0.0001 to 0.099 wt % of the total composition of an organic antioxidant, wherein the desired shade of the hair is reached often more than one application of the composition.

Description

HAIR COLOURING COMPOSITION

FIELD OF THE INVENTION

The present invention relates to a method for the gradual permanent colouring of hair.

BACKGROUND AND PRIOR ART

WO02/074266 discloses a method of dying the hair by treating the hair with consecutive applications of dye, such that the desired shade is achieved over a period of days or weeks. The dyes described in this application are permanent dyes and comprise a .dye solution and a developer solution.

Unlike more conventional systems the dyes disclosed in WO 02/074266 need to react quickly so that they can dye the hair in about 5 minutes, but the formulation also needs to be stable on storage.

Organic antioxidants have been used in the past in hair dyes, however we have found that very low levels of antioxidants can prevent oxidation of the composition on storage yet allow on application the oxidative dye intermediate to rapidly dye the hair. DESCRIPTION OF THE INVENTION

In a first aspect, the present relates to a hair dye composition comprising: i) an oxidative hair dye intermediate; and ii) 0.0001 to 0.099 wt% of the total composition of an organic antioxidant.

A further aspect of the invention relates to a method of gradually dying the hair by applying to the hair the composition described above.

The invention also relates to the use of the composition described above for dying the hair, wherein the desired shade of the hair is reached after more than one application of the composition.

By the term "gradually" is meant more than one application of the composition is required to achieve the desired colour change of hair treated with the composition. In most instances the composition is added once a day or whenever the consumer washes their hair.

Unless indicated otherwise, all percentages used herein are percentages by weight of active material based on the weight of the respective composition.

DETAILED DESCRIPTION OF THE INVENTION

Compositions of the invention preferably comprise a two part dye formulation that is mixed together immediately before application to the hair. Most conveniently the composition comes in a container comprising two separate compartments, one containing the hair colouring agent the other containing a peroxygen compound. In the present invention the antioxidant is combined with the at least one oxidative dye intermediate in the hair colouring compartment.

Oxidative Hair Dye Intermediate

The oxidative dye intermediates suitable for use with compositions of the present invention can be divided into two groups: primary intermediates and couplers.

Primary intermediates:

Suitable primary intermediates include the aromatic diamines, the diaminophenols, the aminophenols with amino or hydroxy groups para or ortho to each other.

Couplers : .

Suitable couplers include the m-diamines, the m-aminophenols and the polyphenols.

A representative list of oxidative dye precursors suitable for use herein is found in Sagarin, "Cosmetic Science and Technology"," Interscience, Special Edition, Volume 2, pages 308 to 310.

It is highly preferred if the compositions of the present invention comprise a primary intermediate. Suitable primary intermediates include p-aminophenol, N, NBis (2-hydroxyethyl) - p_phenylenenediamine sulphate, tolune-2, 5-diamine sulphate, 2-nitro p-phenylenediamine sulphate, particularly preferred is p-phenylenediamine. Mixtures of these primary intermediates are also preferred.

Couplers for use with the invention include 4-amino-2- hydroxytouene, m-aminophenol, 2-methylresocinol, 1-napthol, p-phenyldiamine, resorcinol, 1-phenyl 3-methyl pyrozolone, m-phenlenediamine, 4-amino-m-cresol, 1, napthol It is especially preferred if mixtures of various combinations of the above are used.

In the most preferred form the composition has both resorcinol and p-phenylenediamine present. In many preferred formulations other couplers and primary intermediates are also present.

The total level of oxidative dye intermediate (coupler and primary intermediate) within the formulation is preferably from 0.05 t 5 wt% of the total composition.

The hair colouring compositions of the present invention may, in addition to the essential oxidative hair-colouring agents, optionally include non-oxidative and other dye materials .

Antioxidants

Suitable organic antioxidants for use with the present invention are disclosed in the International Cosmetic Ingredient Dictionary and Handbook under the heading antioxidants. Naturally only organic materials within those listed are classified as organic antioxidants.

Preferred antioxidants are selected from the group consisting of ascorbic acid, isomer of ascorbic acid, salts ' of ascorbic acid and mixtures thereof. Particularly preferred is erythorbic acid.

The level of organic antioxidant is from 0.0001 to 0.099 wt % of the total formulation, more preferably 0.0005 to 0.05 wt%, most preferably from 0.001 to 0.01 wt%.

It is advantageous if an inorganic antioxidant is present. Suitable inorganic antioxidants are listed in the Ingredient Dictionary and Handbook under the heading Antioxidants or Reducing Agents.

Sodium metabisulphite is a particularly preferred inorganic antioxidant.

The level of inorganic antioxidant is preferably from 0.01 to 1 wt: most preferably from 0.05 to 0. 3 wt% of the total composition.

The weight ratio of inorganic antioxidant to organic antioxidant is preferably from 50:1 to 2:1, more preferably from 40:1 to 5:1 and most preferably from 30:1 to 10:1. Buffering Agents/pH Modifiers

The colouring compositions of the present invention have a preferred pH in the range of from about 7.5 to about 12, more preferably from about 8 to about 10 at 25°C.

Standard pH modifiers or buffering agents can be used to adjust the pH of the final composition or any constituent part thereof.

Preferred for use, as a buffering agent for the colouring compositions according to the present invention is ammonium hydroxide and/or sodium hydroxide.

Preferred levels of ammonium hydroxide are from 2 to 5 wt% of the total formulation.

Preferred levels of sodium hydroxide are from 0.1 to 5-wt% of the total formulation.

Fatty Alcohols and Thickeners

Fatty alcohols and thickeners may be included in compositions of the invention. These alcohols can be used alone, or in admixture with each other. The alcohol may preferably be present at from about 0.5 to about 10 weight percent of the composition, and more preferably at from about 2 to about 5 weight percent. Fatty chain lengths of from about 11 to about 18 carbons and mixtures thereof are also useful.

Thickening agents suitable for use in the compositions herein may also be 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. Additional thickening agents suitable for use herein include sodium alginate or gum arabic, or cellulose derivatives, such as methylcellulose or the sodium salt of carboxymethylcellulose or acrylic polymers .

Fatty alcohols of the above discussed carbon chain lengths which are ethoxylated to contain an average of one or two moles of ethylene oxide per mole of fatty alcohol can be used in place of the fatty alcohols themselves.

Volatile Silicones

Volatile silicones may also be employed in the compositions of the invention. The volatile silicone oil is often described as a volatile polyorganosiloxane, and is a liquid material having a measurable vapour pressure at ambient conditions (about 20 to 25° C). Typically the vapour pressure of volatile silicones lies in the range of from 1 or 10 Pa to 2 kPa at 25 °C. Volatile polyorganosiloxanes can be linear or cyclic or mixtures thereof. Non-Volatile Silicones

Non-volatile silicones may be included in compositions of the invention. Nonvolatile silicone oils include polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers. The essentially non-volatile polyalkyl siloxanes useful herein include, for example, polydimethyl siloxanes with viscosities of from about 5 to about 25 million centistokes at 25 °C. Among the preferred non-volatile silicones useful in the present compositions are the polydimethyl siloxanes having viscosities from aboutlO to about 400 centistokes at 25°C.

Cationic Conditioning Agent

The conditioning compositions of this invention also contain at least a water-soluble or water-dispersible quaternary nitrogen-containing conditioning agent that is also sometimes referred to herein as a cationic compound. A long chain fatty alcohol is also present in more preferred compositions, and a tertiary amidoamine is additionally present in particularly preferred compositions.

The quaternary nitrogen-containing conditioning agents are preferably present at from about 0.5 to about 5 percent by weight of the composition as an active ingredient. More preferably, the quaternary nitrogen-containing conditioning agent is present at from about 2 to about 3 weight percent, as an active ingredient. The class of quaternary nitrogen-containing conditioning agents useful herein contain one quaternary nitrogen atom having (a) two long aliphatic chains and (b) two identical or different short chain alkyl groups having one or two carbon atoms, each bonded to the quaternary nitrogen atom. The two long chains each contain about 12 to about 18 carbon atoms.

Illustrative conditioning agents include distearyldimethylammonium chloride, dicetyldimonium chloride, dimethyldi- (hydrogenated tallow) ammonium chloride and dilauryldimethylammonium chloride.

Surfactant Materials

The compositions of the present invention can additionally contain a surfactant system. It is preferred if the compositions of the invention are used as shampoos or conditioners, conditioners are particularly preferred. Both conditioner and shampoo-based compositions can include cationic, nonionic or zwitterionic surfactants.

OPTIONAL INGREDIENTS

The compositions of the present invention can comprise a wide range of optional ingredients. Examples of these functional classes include: anticaking agents, binders, biological additives, bulking agents, chelating agents, chemical additives, colourants, cosmetic astringents, cosmetic biocides, denaturants, drug astringents, emulsifiers, film formers, fragrance components, humectants, thickeners, opacifying agents, plasticizers, preservatives, propellants, reducing agents, solvents, foam boosters, hydrotropes, solubilizing agents, suspending agents (nonsurfactant) , sunscreen agents, ultraviolet light absorbers, and viscosity increasing agents (aqueous and nonaqueous) . Examples of other functional classes of materials useful herein that are well known to one of ordinary skill in the art include solubilizing agents, sequestrants, and the like.

Other optional ingredients include organic acids. A nonexclusive list of examples of organic acids which can be used as the proton donating agent are adipic acid, tartaric acid, citric acid, maleic acid, malic acid, succinic acid, glycolic acid, glutaric acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, polyacrylic acid, their salts, and mixtures thereof. Non-exclusive lists of examples of mineral acid for use herein are hydrochloric, phosphoric, sulfuric and mixtures thereof.

Method of Use

It has been have found that daily hair care products can achieve durable desired hair colour. As noted above, the hair care product preferably comprises of two parts.

Part A: Dye intermediates normally at an alkaline pH Part B: Hydrogen peroxide normally at an acidic pH

Part A is mixed with part B and applied to hair. Part A and part B of the present invention must be kept apart until just before use. By varying the concentration of the actives and the treatment time, the amount of colour on hair could be varied while minimising hair damage. To make the product more convenient and fool proof, part A and B can be packaged in dual dispensing systems where both parts are mixed out side of the package when dispensed which is then applied to the wet hair as a conditioner or shampoo. Depending upon the amount of colour desired, the treatment time could be varied from two minutes or longer.

Such conditioner or shampoo treatments would add colour to hair gradually without damage due to lower contact time. Each subsequent treatment would add colour until the desired shade is obtained. Depending upon the concentration of the actives and contact time, a desired shade may be reached in six to eight treatments. We have found that since any one treatment does not exceed the threshold of irreversible damage, the total damage resulting from multiple treatments is lower than the damage from a single conventional treatment. Such a process gives the user control on the amount of colour deposited on her hair, and also the option to discontinue further applications if the colour delivered is not to her liking. She also has the option to switch to another COLOUR shade immediately without having to wait the six to eight weeks that is recommended for conventional treatments.

In general the method of use is to shampoo the hair as usual using a conventional shampoo. The composition of the invention (part A and part B) is mixed in the palm of the hand and applied to the hair like a conventional conditioner. The hands are then rinsed. The product is left in the hair for about 2 to 5 minutes. Finally the hair is rinsed thoroughly.

This process is repeated over a period of days until the desired colour is reached.

The invention will now be illustrated with aid of the following Examples. A number illustrates Examples of the invention, and comparative Examples are illustrated by a letter.

The following examples, which were made, are shown as illustrations only and are not intended to limit the scope of the invention.

The colour conditioner consists of two parts, a dye phase and a developer phase. The two phases are mixed at a one to one ratio before use.

The formulation was prepared under nitrogen atmosphere. Citric acid, stearamidopropyl dimethylamine, dicetyldimonium chloride, stearyl alcohol and ceteareth-20, and cetyl alcohol were added to water at 85°C, mixed and heated for 30 minutes. The batch was cooled to 57 °C and added to a pre- mix of water and EDTA, a pre-mix of antioxidants, dyes and water were added at a temperature of 49 °C, the remaining ingredients were added at 38 °C.

Phosphoric acid, sodium stannate, stearamidopropyl dimethylamine, dicetyldimonium chloride, stearyl alcohol, and Ceteareth-20, cetyl were added to water at 85°C, mixed and heated for 30 minutes. The batch was cooled to 57 °C and added to a pre-mix of water, potassium chloride and EDTA. the mixture was further cooled to 38 °C and hydrogen peroxide, silicones and DMDM hydantoin were added.

Experiment #1

The dye phase formulations (Examples A and 1) were exposed at room temp and digital pictures were taken at set time intervals to show the difference in appearance of the product due to air oxidation.

Example A had a colour change over a period of 30 minutes, Example 1 did not show this change.

Experiment #2

1 gram virgin white hair tresses were washed and excess water removed. The wet hair tresses were treated with following formulas; Example A 1 part of Formula A +1 part of Formula 3 Example 1 1 part of Formula 1+ 1 part of Formula 3 Example 2 1 part of Formula 2 + 1 part of Formula 3 Example B 1 part of Formula B + 1 part of Formula 3

These Examples were left on the hair tresses for 2 minutes and then rinsed off thoroughly. The hair tresses were air- dried and L* a* b* and DE* readings taken on the Macbeth coloureye to show the colour deposition differences. The results are given in table 1 below.

The Macbeth coloureye is a colourimeter that reads the tristimulus values of L* a* b*, lightness, redness, yellowness, and total colour. Four rotated measurements per swatch are taken then averaged. Each measurement on a hair swatch is taken on the same side. • Δ L* is a measure of change in lightness (higher values indicate a greater increase in lightness) , • Δ a* is a measure of change in redness (higher values are greater change in redness) , and • Δ b* is a measure of yellowness (higher values are greater change in yellowness) . • Δ E* is total colour difference and is based on the differences for all three colour parameters (L*, a*, b*) . ΔE= A/ [(ΔL)² + (Δa)² + (Δb)² ]

ΔE indicates the colour change and higher delta E means bigger colour change.

Table: 1: L* a* b* and ΔE*

The above chart shows the change in colour ΔE after 2-min. applications of all four prototypes. From the ΔE number one can conclude that formula A 1 and 2 provided similar colour to the hair. Formula B provides much lower colour to the hair.

Claims

1. A hair dye composition comprising: i) an oxidative hair dye intermediate; and ii) 0.0001 to 0.099 wt% of the total composition of an organic antioxidant.

2. A hair dye composition according to claim 1 in which the level of organic antioxidant is from 0.003 to 0.05 wt% of the total formulation.

3. A hair dye composition according to any preceding claim in which the organic antioxidant is selected from the group consisting of ascorbic acid, isomer of ascorbic acid, salts of ascorbic acid and mixtures thereof.

4. A hair dye composition according to claim 3 in which the organic antioxidant is erythorbic acid.

5. A hair dye composition according to any preceding claim which further comprises an inorganic antioxidant.

6. A hair dye composition according to any preceding claim in which the weight ratio of inorganic antioxidant to organic antioxidant is from 40:1 to 5:1

7. A hair dye composition according to claim 5 or claim 6 in which the level of inorganic antioxidant is from 0.05 to 0. 3 wt% of the total composition.

8. A hair dye composition according to any one of claims 5 to 7 in which the inorganic acid is sodium metabisulphite .

9. A hair dye composition according to any preceding claim in which the oxidative dye intermediate comprises p- phenylene diamine and resorcinol

10. A hair dye composition according to any preceding claim which further comprises 2 to 5 wt% of ammonium hydroxide .

11. A hair dye composition according to any preceding claim which further comprises 0.1 to 5 wt% of Sodium hydroxide.

12. A method of gradually dying the hair by applying to the hair a composition according to any preceding claim

13. Use of a composition according to any preceding claim for dying the hair, wherein the desired shade of the hair is reached after more than one application of the composition.