WO1998052520A1 - Hair colouring methods - Google Patents
Hair colouring methods Download PDFInfo
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- WO1998052520A1 WO1998052520A1 PCT/US1998/010498 US9810498W WO9852520A1 WO 1998052520 A1 WO1998052520 A1 WO 1998052520A1 US 9810498 W US9810498 W US 9810498W WO 9852520 A1 WO9852520 A1 WO 9852520A1
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- Prior art keywords
- hair
- compounds
- coupler
- colouring
- couplers
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- 0 C*N(**)c(cc1)ccc1N Chemical compound C*N(**)c(cc1)ccc1N 0.000 description 7
- ZGCZUXLVQJELGB-UHFFFAOYSA-N CC(CC1=O)N(C)N1c1ccccc1 Chemical compound CC(CC1=O)N(C)N1c1ccccc1 ZGCZUXLVQJELGB-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
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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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
-
- 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
Definitions
- This invention relates to new methods for colouring hair.
- Methods are well known for providing various colours to hair by dyeing, either for changing a natural hair colour/and or for colouring grey hair. These methods generally comprise applying to the hair various aromatic compounds, commonly known as developers (also known as precursors or primary intermediates) , together with various other aromatic compounds, commonly known as couplers. These are referred to as oxidative hair colouring agents because they require an oxidising agent for formation of colour.
- the developers are generally 1, 4-disubstituted benzene compounds, most commonly 1,4-diaminobenzene compounds, and the couplers can also be disubstituted benzene compounds, such as 1, 3-disubstituted benzene compounds.
- the range of structures of couplers is much more varied than that of developers.
- the compounds are subjected to oxidising conditions under which the developers and couplers react to form colour. It is generally believed that this occurs by means of a stepwise sequence in which developer molecules are activated by oxidation and react with couplers to form reactive dimers. These then continue reacting to form coloured trimers, which do not react further.
- Standard products normally include several different developers and several different couplers, for instance up to 5 developers and 5 or more couplers. It is generally accepted that 10 to 12 different compounds are required to achieve the full range of colours. It is also known to apply these colouring agents in different ways so as to obtain varying degrees of permanence of the final colour produced.
- Compositions and methods for colouring hair are normally placed into one of four categories. According to this categorisation, coloration may be permanent, demi-permanent, semi-permanent or temporary.
- Permanent coloration is that which once applied to the hair is substantially resistant to wash-out, ie it does not wash out after at least 30 washes.
- Demi-permanent coloration is that which is substantially removed from the hair after about 24 washes.
- Coloration of this general type is sometimes described as "tone on tone” coloration.
- Semi-permanent coloration is substantially removed from the hair after about 10 washes and has undergone some change after about 5 washes.
- Temporary coloration is generally substantially removed from the hair after about two washes. Temporary colouring materials are usually not of the oxidative type.
- Demi-permanent coloration is an important aim for the consumer. Generally variations in permanence can be obtained with known systems by varying the time for which the colouring agents and oxidising agents are left on the hair before rinsing. However, using the standard oxidative hair colouring agents discussed above, it is normally necessary to leave the components on the hair for at least
- a further disadvantage is that developers can react with each other as well as with couplers and the reactive dimers can react with developers and couplers.
- the reaction chemistry is undefined and it is not possible to predict with any precision the compounds which will be present in the hair at the end of the colour-forming reaction.
- the exact composition of the coloured molecules formed in the hair can vary from process to process according to the prevailing conditions. Therefore the colours eventually obtained can vary between applications.
- GB 1,025,916 discloses certain developers and couplers of different types. It describes developers which are N,N- disubstituted phenylene dia ine derivatives. Three classes of coupler are described. Some phenol-based couplers are said to provide a blue colour, some R-C0-CH 2 -C0R derivatives are said to provide a yellow colour and some pyrazolone derivatives are said to provide a red colour.
- GB 1,025,916 describes mixing pairs of couplers, for instance red with blue, blue with yellow, etc so as to obtain shades between the colours which would be obtained with either of the couplers used individually. It describes various examples of dyeing hair using the disclosed developers and couplers. In some examples developer is applied and left for a period of time, followed by application of coupler, which is also left for a period of time and is then followed by application of oxidising agent. The majority of the examples describe first mixing developer, coupler and hydrogen peroxide as oxidising agent and then applying the mixture to the hair.
- the combined materials are left on the hair for 20 minutes before rinsing.
- the various components are applied sequentially, the first is left on for 20 minutes before rinsing, so that some material remains.
- the second component is then applied and left on the hair for 20 minutes, in the presence of the first component, before rinsing.
- a hair colouring composition comprising
- Z is an active leaving group
- X is an active leaving group or a non-leaving substituent such that in the presence of an oxidising agent the or each developer reacts with the or each coupler substantially only at the positions having the active leaving group Z and, if X is an active leaving group, X, and (iii) oxidising agent, applying components (i) , (ii) and (iii) to the hair to be coloured, and allowing the components (i) , (ii) and (iii) to remain together on the hair for not more than 15 minutes, and rinsing the hair.
- the method is preferably such that the colour applied to the hair is demi-permanent, ie.
- the hair after 10 washes it remains in the hair after 10 washes but is substantially removed from the hair after 24 washes.
- it is such that it may undergo noticeable change after two or three washes (as is normal for most hair colourings) but does not change significantly for the next five or seven washes, i.e. between three and eight or ten washes.
- the developer is an amino aromatic compound which has a structure such that it is capable of being oxidised by an oxidising agent.
- the structure is also such that the oxidised developer is capable of undergoing electrophilic attack by one other molecule.
- the structure of the developer is such that it reacts substantially only at one position, which is normally an amine.
- Suitable developers of this type include aminoaromatic systems in which there is only one primary amine group, at which reaction occurs, other amine and other reactive groups being protected by blocking substituents.
- couplers of type (C) having an additional active leaving group X, also react at the X position to give a single resulting coloured trimer. In this case also only one type of final coloured molecule is produced from that coupler.
- the defined developer also reacts only at one position.
- the coloured molecules formed have significantly reduced water-solubility in the hair in comparison with the trimers formed in standard oxidative colouring systems, which assists in achieving increased wash fastness .
- the method of the invention provides demi-permanent coloration, ie coloration which remains on the hair after about 10 washes, but is substantially removed from the hair after about 24 washes.
- demi-permanent coloration can be defined in terms of the ⁇ E fade test described below.
- the method of the invention provides coloration of a red shade (of hue value in the range from about 25 to about 70) which has a ⁇ E fade value less than about 5.0, preferably less than about 4.5, more preferably less than about 4.0 after 10 washes.
- a red shade delivered according to the method of the invention and having hue value in the range of from about 25 to about 70 gives a ⁇ E fade of at least about 5, preferably at least about 6, more preferably at least about 7 or 8.
- it may give a ⁇ E fade of at least about 10 or 12 after 20 washes and ⁇ E fade may even be at least 15 or 20 after 24 washes.
- ⁇ E fade values for prepermed, prebleached, light brown hair which has been coloured a brown or black shade (of hue value less than about 25) by the method of the invention are generally less than about 2.3, preferably less than about 2.0, more preferably less than about 1.7 after 10 washes.
- the change in hair colour, % ⁇ E, after 10 washes is preferably less than about 5%, more preferably less than about 4.5%, most preferably less than about 4%, and in particular less than about 3%.
- ⁇ E fade values after 24 washes are often at least about 12 or 15 and may even be at least about 20.
- ⁇ E fade results for prepermed, prebleached light brown hair which has been coloured a light brown shade (of hue value in the range of from about 70 to about 110) by the method of the invention are generally less than about 2.6, preferably less than about 2.3 after 10 washes.
- the change in colour % ⁇ E, after 10 washes is less than about 15%, preferably less than about 12%, more preferably less than about 10%, and in particular less than about 8%.
- the ⁇ E fade value is often at least about 2.6, for instance at least about 3 or 4.
- the ⁇ E fade value after 20 washes is at least about 6 or 8 , preferably at least about 10 or 12. It may be as great as at least about 15 or 20.
- developer, (ii) couplers and (iii) oxidising agent are applied to the hair. They may be applied substantially simultaneously, that is they may for instance be mixed and applied to the hair together. Alternatively, within the term “substantially simultaneously” we also include application of one or more components followed by application of one or more other components after not more than 5 minutes. In the method of the invention the components can also be applied sequentially. For instance the developer and couplers may be applied to the hair and left for a period of time, for instance from above 5 to 25 minutes. Excess of these components may be rinsed off the hair, leaving the necessary level on the hair. This is followed by application of the oxidising agent, which then remains on the hair for not more than 15 minutes. It is essential in the invention that the period of time during which all three components are present on the hair is not more than 15 minutes. After this period the hair is rinsed.
- the three components are present together on the hair for not more than 15 minutes. This time is short in comparison with the application times which are required for compounds currently available which obtain the same degree of wash fastness. Times significantly above 15 minutes will reduce the convenience to the consumer of the method.
- the three components are present together on the hair for not more than 10 minutes, more preferably not more than 7 or 5 or not more than 4.5 minutes, and can give good results even when present for not more than 2.5 or 3 minutes.
- the components are present together on the hair for at least 30 seconds, often at least 1 minute. Contact times of 2 or 3 minutes or more may be suitable. The contact time during which all three components are present on the hair should be sufficiently long to give the component time to become substantive on the hair and for the colour to develop to the required degree of wash fastness.
- coupler molecules are used.
- Some suitable coupler molecules (A) , (B) and (C) are known from the field of photography, as are some suitable developers. When they have reacted with a developer molecule the couplers (A) give a cyan colour, the couplers (B) give a yellow colour and the couplers (C) give a magenta colour.
- Each coupler contains a moiety of a specific formula which is such that it has an active leaving group Z at a defined site.
- an active leaving group we mean any group which can be removed (under the conditions prevailing during the hair-dyeing process) so that the developer reacts at that position in the coupler molecule.
- the bond formed between the coupler and developer molecule is thus formed at the site of the active leaving group.
- active leaving groups are H, PhO, Cl, Br, alkoxy (RO) such as phenoxy PhO, and RS- in which R is alkyl or aryl, but any leaving group which leaves during the reaction so as to allow coupling between developer and coupler is suitable.
- X is an active leaving group it may be any of those listed above for Z.
- Couplers (A) give a cyan colour.
- the particular shade or intensity of colour can be varied by varying the substituents of the phenol or naphthol molecule. It has an active leaving group para to the OH group. This may be an active proton, ie the aromatic ring is unsubstituted in the para position and other substituents on the ring are not such as to reduce the reactivity at this position.
- couplers (A) have the formula I, as follows:
- Z is H or another active leaving group.
- Z is H.
- R 1 , R 2 ' R 3 and R 4 are, independently, H, OH, -C0 2 H,
- -C0 2 R F, Cl, Br, -CN, -N0 2 -, CF 3 , cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -NH 2 , -NHR, -NHCOR, -NR 2 , -NHCOR, -R » NHCOR, -CONHR, R'CONHR, -R'OH, -S0 2 R, S0 2 NHR, -R'S0 2 R, -R'S0 2 NHR, -S0 3 H, -OR, -R'OR or -COR, in any of which R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl, and R' is alkylene, alkenylene, cycloalkylene, cycloalkenylene, arylene, alkarylene or
- R 1 and R 2 may together form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl group.
- Substituting groups include OH, -OR, Cl, Br, F, -C0 2 H, -C0 2 R, -NH 2 and -COR.
- alkyl and alkenyl are usually C ⁇ g, often C ⁇ , cycloalkyl and cycloalkenyl are usually C 5 _ 8 , often C 5 , aryl or ar- is usually phenyl or naphthyl and the alk-moiety in alkaryl is usually C_ 6 , often C 1 -. 4 .
- R 1 , R 2 , R 3 or R 4 is alkyl it is selected from methyl, ethyl, n-propyl, i- propyl and t-butyl.
- R is alkyl it is preferably one of these groups and when R' is alkylene it is preferably derived from one of these groups.
- Coupler (A) is a naphthol derivative of the formula II, as follows:
- R 3 and R 4 are preferably H and the developer is ⁇ -naphthol.
- Suitable couplers (A) thus have the formula III or IV, as follows:
- Coupler (A) can be a naphthol having no solubilising substituents (other than Z) , in particular no -COOH or -OH substituents. Naphthols are preferably unsubstituted.
- couplers of this formula II in particular when R 3 and R 4 are H, and especially when Z is H, have a particularly advantageous combination of properties for improving wash fastness whilst allowing rapid colouring, when the hair to be coloured has been damaged, for instance by perming or bleaching.
- their molecules have a structure such that as monomers they are small enough to diffuse easily into the hair shaft (which, when damaged, is rather porous) but as dimers they are trapped within the hair shaft. Further, their water-solubility is low enough that they are not easily washed out during subsequent hair treatment processes.
- Preferred couplers have the formula I in which R 1 , R 2 , R 3 and R 4 are independently selected from OH, H, methyl, ethyl, n-propyl, i-propyl, t-butyl, NH 2 , -C0 2 H, and -COR.
- R 1 , R 2 , R 3 and R 4 are independently selected from OH, H, methyl, ethyl, n-propyl, i-propyl, t-butyl, NH 2 , -C0 2 H, and -COR.
- Z is H.
- a preferred coupler of this preferred type is 3-amino phenol . We find that these preferred couplers show particularly good performance on damaged hair. They demonstrate good colour uptake and good wash fastness.
- Z is any active leaving group. Suitable examples are H, PhO, Cl and Br but any other groups which react similarly (under the conditions of the hair-dyeing reaction) may be used. If Z is PhO, Cl or Br the reactivity of the coupler can tend to be increased in comparison with couplers in which Z is H.
- the defined groups may also contain any non-interfering substituent, that is any group which does not hinder the coupling reaction between developer and coupler.
- phenyl and naphthyl groups may be substituted.
- Suitable non-interfering substituents include C0 2 H, CH 3 , S0 2 NHCH 3 , S0 3 H, C ⁇ _ 3 alkyl such as ethyl or propyl and CONHR in which R is preferably Cj_ 3 alkyl.
- Alkyl and CONHR substituents have the advantage that the solubility of the final coloured molecule is reduced.
- Phenyl groups may contain one or more substituents which are the same or different. If phenyl groups are substituted, mono substitution is preferred. Preferably the groups are unsubstituted unless otherwise stated.
- Yellow couplers (B) contain the 1,3-diketone group
- R 5 and R 6 are, independently, H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R' CONHR, -ROH, -R'S0 2 R, -R'C0 2 NHR, -NHCOR, -NR 2 , -NHR, -NH 2 -R'OR and -OR.
- R can be H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl and R 1 is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene. Substituted versions of any of these can be used. Suitable substituents include OH, -OR, Cl, Br, F, -C0 2 H, -C0 2 R, -NH 2 and -COR.
- At least one of R 5 and R 6 contains an aryl group.
- Some couplers (B) are of the formula VI as follows:
- R can be for instance methyl, phenyl, t-butyl or N(CH 3 ) CH 2 CH 2 OH.
- R 5 may also be phenyl.
- the N-phenyl does not contain solubilising substituents.
- the N-phenyl is unsubstituted.
- the R 5 phenyl is free of solubilising substituents, in particular free of -COOH and -OH substituents and is most preferably unsubstituted.
- couplers of the formula VI have a particularly advantageous combination of properties for improving wash fastness whilst allowing rapid colouring, in particular for damaged hair.
- their molecules have a structure such that as monomers they are small enough to diffuse easily into the porous, damaged hair shaft but as dimers they are trapped within the hair shaft. Further, their solubility is such that they are not easily washed out during subsequent hair treatment processes.
- R 5 is methyl, ethyl, n-propyl, i-propyl, t-butyl or phenyl (especially methyl) and R 6 is NR 2 in which the R groups are the same or different and can be R as discussed above, in particular methyl, ethyl, n-propyl, i-propyl, t-butyl or phenyl (especially ethyl) .
- R 5 and R 6 are, independently, short chain (C ⁇ ) alkyl such as methyl, ethyl, i-propyl, n-propyl or t-butyl or short chain (C ⁇ ) alkoxy, such as methoxy or ethoxy.
- R 5 is C- 4 alkyl (especially methyl) and R 6 is C ⁇ alkyl (especially methyl) or C ⁇ alkoxy (especially methoxy) .
- alkyl groups can advantageously be hydroxylated, to produce for instance hydroxymethyl (usually 2-hydroxyethyl) , hydroxyethyl, hydroxypropyl or hydroxybutyl .
- Couplers (B) of these latter types are particularly advantageous for the coloration of undamaged as well as damaged hair. On undamaged hair they show fast colour uptake without loss of wash fastness. They also show good wash fastness on damaged hair.
- Z may be any of the leaving groups indicated for Z in coupler (A) above.
- Z is H.
- the defined groups may also contain any non-interfering substituent, that is any group which does not hinder the coupling reaction between developer and coupler.
- phenyl and naphthyl groups may be substituted.
- Suitable non-interfering substituents include C0 2 H, CH 3 , S0 2 NHCH 3 , S0 3 H, C ⁇ - 3 alkyl such as ethyl or propyl and CONHR in which R is preferably C ⁇ alkyl.
- Alkyl and CONHR substituents have the advantage that the solubility of the final coloured molecule is reduced.
- Phenyl groups may contain one or more substituents which are the same or different. If phenyl groups are substituted, mono substitution is preferred. Preferably the groups are unsubstituted unless otherwise stated.
- Couplers (C) are pyrazolone derivatives, that is they contain the group
- Z is an active leaving group and X is an active leaving group or a non-leaving substituent.
- X is a non-leaving substituent and they are of the formula VII, as follows:
- R may be H, -OH, -C0 2 H, -C0 2 R, F, Cl, Br, -CN, -N0 2 , CF 3 , alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -NH 2 , -NHR, -NR 2 , -NHCOR, -R 1 NHCOR, -CONHR, -R 1 CONHR, -R'OH, -S0 2 R, -S0 2 NHR, -R*S0 2 R, -R*S0 2 NHR, -S0 3 H, -OR, -R'OR or -COR.
- R 8 can be H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R'CONHR, -R'OH, -R » S0 2 R, -R'S0 2 NHR or -R'OR.
- R is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl
- R' is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene (or substituted versions of any of these) .
- Suitable substituting groups include OH, -OR, Cl, Br, F, -C0 2 H, -C0 2 R, -NH 2 , and -COR.
- R 7 can be H or methyl. It may alternatively be -NHR or -NHCOR in which R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or aralkyl.
- R 7 is H, lower (C ⁇ ) alkyl such as methyl, ethyl, n-propyl, i-propyl or t-butyl, or substituted or unsubstitited phenyl, in particular H, methyl or ethylphenyl .
- R 8 is advantageously H, lower (C : _ 4 ) alkyl such as methyl, ethyl, n-propyl, i-propyl or t-butyl, or substituted or unsubstituted phenyl.
- it is phenyl, it can be preferred that it is a phenyl free of solubilising substituents, in particular -COOH and -OH substituents.
- m- S0 3 H and p-S0 3 H substituents can be used.
- R 8 When R 8 is phenyl it can preferably be unsubstituted.
- R 8 can also preferably be H, phenyl
- couplers of these latter formulae have a particularly advantageous combination of properties for improving wash fastness whilst allowing rapid colouring, especiallyon undamaged hair.
- their molecules have a structure such that as monomers they are small enough to diffuse easily into the undamaged hair shaft but as dimers they are trapped within the hair shaft. Further, their solubility is such that they are not easily washed out during subsequent hair treatment processes.
- Suitable couplers (C) have the formula VIII, as follows:
- R 9 is preferably
- Z may be any of the leaving groups indicated for Z in couplers (A) and (B) above.
- the listed groups may also contain any non-interfering substituent, that is any group which does not hinder the coupling reaction between developer and coupler.
- phenyl and naphthyl groups may be substituted.
- Suitable non-interfering substituents include C0 2 H, CH 3 , S0 2 , NHCH 3 , S0 3 H, Ci. 3 alkyl such as ethyl or propyl and CONHR in which R is preferably C ⁇ alkyl.
- Alkyl and CONHR substituents have the advantage that the solubility of the final coloured molecule is reduced.
- Phenyl groups may contain one or more substituents which are the same or different. if phenyl groups are substituted, mono substitution is preferred. Preferably groups are unsubstituted unless otherwise stated.
- couplers (A) include -naphthol, 3-aminophenol and the compounds having the following structural formulae:
- couplers (B) include benzoylacetanilide, acetoacetanilide, N,N-diethyl and N,N- dimethyl acetoacetamide and the compounds of the formulae
- couplers (C) include the pyrazolone of structural formula:
- couplers discussed above may also be used in the salt form, for instance sulphate, phosphate and hydrochloride, particularly sulphate or hydrochloride.
- Compounds containing free amine groups are preferably used in the form of their salt.
- the salt form of such compounds forms a powder and is often more stable than the free base form.
- the solubility of the couplers and their structure should be selected so that they are sufficiently soluble to be formulated into a suitable application form, which may be aqueous, and of solubility and size such that they can diffuse sufficiently rapidly into the hair shaft.
- a suitable application form which may be aqueous, and of solubility and size such that they can diffuse sufficiently rapidly into the hair shaft.
- the final coloured molecule produced must be of size and solubility that it does not easily wash out of the hair shaft. Again, we find that larger, more insoluble coloured molecules give better wash fastness in damaged hair and smaller, more soluble molecules give good wash fastness in undamaged hair.
- the method of the invention may use any one, or more, of the couplers (A) , (B) and (C) in combination with the defined developer and the oxidising agent.
- a particular advantage of the use of these particular couplers is that it is possible to obtain the full range of colours using just three specific types of coupler and one type of developer.
- the method uses at least two out of the three types of coupler. More preferably it uses at least one coupler (B) and/or (C) and most preferably it uses at least one coupler of each type (A) , (B) and (C) .
- couplers to be supplied in the form of a mixture having the required amounts of each type of coupler to develop whichever colour is desired.
- coupler materials separately packaged so that the consumer can control the eventual colour which is obtained by mixing the correct amounts of each coupler to form the composition.
- coupler is present in the composition in a total amount of from 0.001% to 5 or 10% by weight based on total weight of composition applied to the hair.
- total amounts of coupler are at least 0.01 wt%, often at least 0.1 or 1%.
- they are not more than 6% and in some preferred processes not more than 3%, for instance not more than 2.5%.
- Couplers of types (A) and (C) can be used in particularly low amounts.
- couplers of type (A) may be used in amounts, by weight based on total weight of composition applied to the hair, of from 0.001 to 1%, preferably 0.004 or 0.005 to 0.5%, for instance not more than 0.05 wt%.
- Couplers of type (C) can be used in amounts of from for instance 0.01 to 2 or 4%, preferably 0.03 to 2 or 3%, and in some preferred cpmpositions not more than 1 or 0.5%.
- Couplers of type (B) are often used in larger amounts, for instance from 0.05 to 3 or 4wt%, for instance up to 5 or 6% and in some preferred compositions 0.1 to 2 or 3wt%.
- the developer is an amino aromatic compound capable of being oxidised and undergoing a single electrophilic attack in the oxidised state.
- it may be an aromatic system containing a single primary amine substituent.
- the developer is such that it reacts substantially at only one position (normally the amine position) .
- the structure of the developer may be such that it is possible that it reacts with other developer molecules, but it reacts preferentially with coupler molecules.
- the structure of the developer is such that it undergoes substantially no reaction with other developer molecules.
- Suitable developers include o-nitro and p-nitro - naphthyla ines of the formulae
- Suitable developers include o- and p- nitrophenylamines H 2 N-Ph-N0 2/ N,N-disubstituted o-phenylene diamines and, N,N-disubstituted p-phenylene diamines.
- the developer can be an N,N-disubstituted p-phenylene diamine.
- These developers have an amine group protected by disubstitution and react only at the primary amine group. In this case it normally has the formula IX, as follows:
- R 10 and R 11 are each independently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, -R'NHCOR, -R' CONHR, -R'OH, -R'S0 2 R, -R'S0 2 NHR OR -R'OR in which R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, and R' is alkylene, cycloalkylene, alkenylene, cycloalkenylene, arylene, alkarylene or aralkylene, or substituted versions of any of these.
- Suitable substituting groups include OH, -OR, Cl, Br, F, - C0 2 H, -C0 2 R, -OR and -COR.
- R 10 and R 11 may together form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring.
- R 10 and R 11 are, independently, C,_ alkyl, preferably -CH 3( -CH 2 CH 3 or i-propyl; C ⁇ hydroxyalkyl, preferably -CH 2 CH 2 OH; alkylene alkoxy, preferably ethylmethoxy (-CH 2 CH 2 OCH 2 ) ; or R 12 S0 2 NHR 12 or R 12 NHS0 2 R 12 in which R 12 is Cj. 3 alkyl, for instance -CH 2 CH 2 S0 2 NHCH 3 or -CH 2 CH 2 NHS0 2 CH 3 .
- Particularly preferred developers of the above formula IX are those in which R 10 and R 11 are both -CH 2 CH 3 or R 10 is -CH 2 CH 3 and R 11 is -CH 2 CH 2 NHS0 2 CH 3 .
- the latter R 11 substituent is believed to contribute to dermatological compatibility.
- R 10 is ethyl and R 11 is hydroxyethyl ; or R 10 is ethyl and R 11 is -CH 2 CH 2 OCH 3 ; or R 10 is selected from H, methyl, ethyl, and propyl and R 11 is selected from methyl, ethyl and propyl.
- the developer may be selected from compounds having the general formula X:
- the group Y is a blocking group which ensures that reaction (under the conditions of dyeing the hair) takes place only at the primary amine group.
- the group Y for instance can be -NR 10 R (as in formula IX above) .
- Other suitable Y groups include -N0 2 , -C0 2 H, -C0 2 R, -COR and OH.
- R is as defined above for formula IX.
- the blocking group Y is in the ortho position relative to the amino group, giving the following formula XI.
- the group Y is positioned so that the developer undergoes only one reaction, at the primary amine group, under the conditions of the reaction.
- R 13 , R 14 , R 15 and R 16 can each be, independently, any of the groups listed for R 1 to R 4 above.
- R 13 and R 14 together and/or R 15 and R 16 together, may form a substituted or unsubstituted cycloalkyl, cycloalkenyl or aryl ring.
- R 13 to R 16 are, independently, H, methyl, ethyl, n-propyl, i-propyl, F, Cl, OH, -C0 2 H, -C0 2 R or -COR.
- the listed groups may also contain any non-interfering substituent, that is any group which does not hinder the coupling reaction between developer and coupler.
- phenyl and naphthyl groups may be substituted.
- Suitable non-interfering substituents include C0 2 H, CH 3 , S0 2 NHCH 3 , S0 3 H, C ⁇ - 3 alkyl such as ethyl or propyl and CONHR in which R is preferably C ⁇ 3 alkyl.
- Alkyl and CONHR substituents have the advantage that the solubility of the final coloured molecule is reduced.
- Phenyl groups may contain one or more substituents which are the same or different. If phenyl groups are substituted, mono substitution is preferred. Preferably the groups are unsubstituted unless otherwise stated.
- a preferred developer has the following formula XII, as follows:
- Examples of further preferred developers which are particularly suitable for coloration of undamaged hair, are 2 , 6-dichloro-p-aminophenol, 2-chloro-p-aminophenol, 3- chloro-p-aminophenol, 2, 3-dichloro-p-aminophenol and 3,5- methyl-p-aminophenol .
- the derivatives above include salts, for instance sulphate, phosphate and hydrochloride, particularly sulphate or hydrochloride. Salts are normally formed with the amine groups.
- the preferred developer in which R 10 is -CH 2 CH 3 and R 11 is CH 2 CH 2 NHS0 2 CH 3 is often provided in salt form as a stable powder (more stable than the free base form) .
- this salt forms such that it contains 3 moles of salt molecule to 2 moles of the free base molecule.
- a further useful salt is the hydrochloride salt of developers such as 2 , 6-dichloro-p-aminophenol.
- Developer is often included in the composition in amounts of from 0.01 to 5 or 7% by weight based on total composition applied to the hair. Preferred amounts of developer are from 0.3 to 2 or 4%, preferably 0.4 to 1.5 or 3%.
- solubility properties can be important.
- the developer and coupler compounds themselves should have solubility such that they can be formulated in appropriate concentrations.
- solubility For application at high pH preferably have solubility of at least 10, more preferably at least 15 and most preferably at least 20g/100 ml deionised water at pH about 10 and 25°C. They may have solubility at least 25g/100 ml, and even up to 50 or 80 g/100 ml, but normally not more than 30g/l00 ml.
- the developer and coupler compounds are also generally such that the solubility of the final coloured dimer (or trimer if produced) is low under normal hair conditions and, especially, conditions of washing.
- solubility (at pH about 8) of the final coloured molecule is preferably below 5 g/100 ml deionised water at 25°C, in particular below 2 or 1 g/100 ml and most preferably below 0.5 g/100 ml or even below 0.2 g/100 ml.
- compositions which are to be applied at high pH for instance above pH 10
- an indication of solubility can sometimes be given by pKa.
- one or more of the developers and couplers, in particular the developers has an ionisable group which is substantially ionised at a pH of above 9, preferably above pH 10, this is an indicator of solubility at about pH 10.
- the final coloured molecule and at the pH in the hair shaft which is usually about pH 5.5 to 6) it becomes non-ionised. This gives an indication that under normal conditions it has reduced solubility.
- An advantage of the invention is that the full range of colours can be achieved using a very small number of compounds, in contrast to standard oxidative dyeing systems.
- oxidative colouring agents can be classed as "oxidative" colouring agents, since they require the presence of an oxidising agent to initiate their reaction.
- the composition contains less than 0.1 wt%, especially less than 0.08 wt% and in particular less than 0.05 wt% and even substantially no oxidative dye materials which are capable of undergoing reaction more than once (under the oxidising conditions of the dyeing reaction) .
- a preferred composition comprises not more than 0.1 wt% of any oxidative colouring agent which can react with itself under the conditions of hair dyeing. Preferably it comprises not more than 0.08 wt% or 0.05 wt% of any such agent. More preferably the total amount of such agents does not exceed these values.
- colouring agents such as vegetable dyes can be included, but it is preferred that no non-oxidative dyes are present and indeed preferably no other colouring components are included than the developer (i) as defined and couplers (A) , (B) and (C) . That is, in the hair dye composition the colouring components consist essentially of developer (i) and couplers (A), (B) and/or (C) . Trivial amounts of other colouring components can of course be included provided they do not significantly influence the final colour. Preferably these are the only oxidative colouring agents applied to the hair and no oxidative colouring agents are applied which are not of the types (i) , (A) , (B) and (C) , preferably the formulae I to X.
- colouring agents such as vegetable dyes can be included but it is preferred that no non-oxidative dyes are present and indeed preferably no other colouring components are applied than the developer (i) as defined and couplers (A), (B) and (C) . That is, in the method of the invention the colouring components consist essentially of developer (i) and couplers (A) , (B) and/or (C) . Trivial amounts of other colouring components can of course be applied provided they do not significantly influence the final colour.
- an oxidising agent which is applied to the hair. This oxidising agent is normally included in the composition just before it is applied to the hair. Normally the composition of the invention will be supplied in at least two individual packages such as bottles, the oxidising agent being included in one package and the developers and couplers being included in another.
- a preferred oxidising agent is hydrogen peroxide.
- Other oxidising agents which may be used include other inorganic peroxygen oxidising agents, preformed organic peroxyacid oxidising agents and other organic peroxides such as urea peroxide, melamine peroxide, and mixtures of any of these.
- Suitable oxidising agents are preferably water- soluble, that is they have a solubility of at least about lOg in 1,000 ml of deionised water at 25°C ("Chemistry" C.E. Mortimer, 5th Edition, page 277).
- Suitable inorganic alkali metal peroxides other than hydrogen peroxide include sodium periodate, sodium perbromate and sodium peroxide, and inorganic perhydrate salt oxidising compounds such as the alkali metal salts of perborates, percarbonates, perphosphates, persilicates, and persulphates.
- 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.
- Alkali metal bromates and iodates are suitable, bromates being preferred.
- Another suitable inorganic oxidising agent is chlorite.
- Amounts of inorganic peroxygen oxidising agent which can be used in the composition are normally from 0.0003 mol 0.2 mol per lOOg of composition, preferably up to 0.1 mol/lOOg.
- Suitable preformed organic peroxyacid oxidising agents have the general formula R 30 C(O)OOH, in which R 30 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.
- One class of organic peroxyacid compounds suitable for use in the invention is that of the amide substituted compounds of the following general formulae XII and XIV:
- R 30 is a saturated or unsaturated alkyl or alkaryl group or an aryl group, having from 1 to 14 carbon atoms
- R 32 is a saturated or unsaturated alkyl or alkaryl group, or an aryl group, having from 1 to 14 carbon atoms
- R 31 is H or a saturated or an unsaturated alkyl or alkaryl group, or an aryl group, having from 1 to 10 carbon atoms.
- Amide substituted organic peroxyacid compounds of this type are described in EP-A-170, 386.
- organic peroxyacid oxidising agents include peracetic, pernanoic, nonylamidoperoxycaproic acid (NAPCA) , perbenzoic, m-chloroperbenzoic, di-peroxy- isophthalic, mono-peroxyphthalic, peroxylauric, hexanesulphonyl peroxy propionic, N,N-phthaloylamino peroxycaproic, monoper 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-phthaloylaminoperoxicaproic acid
- Preferred peroxyacid materials are selected from peracetic and pernanoic acids and mixtures thereof.
- Suitable amounts of preformed organic peroxyacid oxidising agents are from about 0.0001 to 0.1 mol per lOOg of compositions, preferably from about 0.001 to 0.05 mol, more preferably from about 0.003 to 0.04 mol, especially from about 0.004 to 0.03 mol/lOOg.
- 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 colouring 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.
- suitable amounts are 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.
- An advantage of the systems of the invention is that very low levels of oxidising agent can be used if desired. Such systems are described in more detail in our copending application number 9710756.9 filed today.
- the colouring compositions of the invention have pH above 6.1 or 6.5, preferably above pH 7 , in particular above pH 8 or 9. A pH of from 9 to 12 is often suitable.
- the systems of the invention can also be incorporated into low pH (eg pH 1 to 6) hair colouring systems described in our copending application number GB9626713.3.
- the materials for use in the method of the invention may be supplied in the manner standard for known oxidative colouring systems. For instance, the developers and couplers may be supplied in one package, with the oxidising agent being supplied in another package. The contents of the two packages can be mixed and applied to the hair together or applied separately, as discussed above.
- the composition applied to the hair may comprise ammonia, for instance in an amount of at least 0.01 wt%, preferably at least 0.05 wt% or 0.1 wt%.
- the developers, couplers, oxidising agent, and any other materials to be applied to the hair as components of the composition of the invention may be provided in any suitable physical form.
- a preferred physical form is liquid.
- the liquid may be of low viscosity, for instance it may be water thin, or it may be of higher viscosity.
- the material may be suspended in a gel network.
- the gel may be solid or of low viscosity.
- the materials for colouring the hair are often formulated so that when they are mixed to form a composition for application to the hair they form a product of cream-like consistency, which is convenient for application to the hair.
- the final composition which is applied to the hair is often in the form of an emulsion.
- Each individual material may be supplied in a form such that the composition containing it has a pH of above or below 7. For instance it may be from pH 1 to 11.
- the carrier may have a pH of above 6.1 or 6.5 or even above 7, for instance from pH 8 or 9 to pH 10 or 11.
- a pH as supplied of from 1 to 6 can assist in improving stability of the components.
- the materials may be provided such that the pH of the final composition when mixed for application to the hair has a pH below 7 even though one of the components used to form it has a pH of above 7.
- Alcohols such as ethanol in amounts of from for instance 5 to 10 or 25% may be included to aid solubility of the developers and, particularly, the couplers in a water-based carrier.
- the conditions of the reaction are normally those conventionally applied for dyeing hair.
- the temperature is normally from 10 to 45°C, often 20 to 35°C.
- pH can be low (eg below 7 or 6) but is often high, for instance above 6.1 or 6.5, usually above 7 or 8 or 9 or even above 10.
- the hair colouring kit of the second aspect of the invention is a particularly convenient way of supplying the components for use in the method of the invention.
- the materials used and the method steps specified in the instructions may have any of the features defined for the method of the invention.
- any other conventional components of hair colouring compositions may be applied to the hair, for instance as described in our copending application 9626713.3.
- compositions can contain various optional ingredients as follows.
- the only oxidative dye materials in the composition are materials (i) and (ii) discussed above.
- the compositions may optionally contain minor amounts of other oxidative dye materials. These may include those described in our copending application PCT/US97/22719, filed 9 December 1997.
- 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 coloured.
- oxidative primary intermediates capable of forming coloured polymers include materials such as aniline, which has a single functional group and which, on oxidation, forms a series of conjugated imines and quinoid dimers, trimers, etc. ranging in colour from green to black.
- Non-oxidative and other dyes The hair colouring compositions used in the present invention may, in addition to the essential oxidative hair colouring agents (i) and (ii) and optional oxidative dyes, optionally include non-oxidative and other dye materials.
- non-oxidative and other dyes suitable for use in the hair colouring 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.
- 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 nitroaminophenol; disperse dyes such as nitroaryl amines, aminoanthraquinones or azo dyes; anthraquinone dyes, naphthoquinone dyes; basic dyes such as Acridine Orange C.I. 46005.
- Nitro dyes are added to dyeing compositions to enhance colour of colorant and to add suitable aesthetic colour 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.I. - 12,245; basic brown 16, C.I. -12,250; basic yellow 57, C.I. - 12,719 and basic blue 99, C.I. - 56,059 and further direct action dyes such as acid yellow 1, C.I. - 10,316 (D&C yellow no.7); acid yellow 9, C.I. - 13,015; basic violet C.I. - 45,170; disperse yellow 3, C.I. - 11,855; basic yellow 57, C.I. - 12,719; disperse yellow 1, C.I.
- Fibre reactive dyes include the Procion (RTM) , Drimarene (RTM) , Cibacron (RTM) , Levafix (RTM) and Re azol (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 (Matricaria chamomila or Anthe is 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 the hair with relative ease.
- Temporary hair dye can 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 predisposed to gradual diffusion out of the hair again. Simple hair washing and cleaning action will encourage this process and in general semi-permanent dyes are largely washed out of the hair after about 5 to 8 washes.
- a semipermanent dye system can be included 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:
- Red Typical semi-permanent dye systems incorporate mixtures of both large and small colour 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. Buffering Agents
- compositions may contain one or more optional buffering agents and/or hair swelling agents (HSAs) .
- HSAs hair swelling agents
- 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 acids 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 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/glycine/hydrochloric acid
- alkaline buffering agents are ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as 1, 3-diaminopropane, anhydrous alkaline alkanolamines such as mono or di-ethanolamine, preferably those which are completely substituted on the amine group such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine or a heterocyclic amine such as orpholine as well as the hydroxides of alkali metals, such as sodium and potassium hydroxide, hydroxides of alkali earth metals, such as magnesium and calcium hydroxide, basic amino acids such as L-arginine, lysine, alanine, leucine, iso-leucine, oxylysine and histidine and alkanolamines such as dimethylaminoethanol and aminoalkylpropanediol and mixtures thereof.
- anhydrous alkaline alkanolamines such as mono
- ion forming compounds compounds that form HC0 3 " by dissociation in water
- suitable ion forming compounds are Na 2 C0 3 , NaHC0 3 , K 2 C0 3 , (NH4) 2 C0 3 , NH 4 HC0 3 , CaC0 3 and Ca(HC0 3 ) and mixtures thereof. These are suitable for buffering to high pH.
- buffering agents to low pH
- organic and inorganic acids having a first pKa below pH 6, and their conjugate bases.
- first pKa means the negative logarithm (to the base 10) of the equilibrium constant, K, where K is the acid dissociation constant.
- Suitable organic and inorganic acids for use herein are: aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic, salicylic, formic, benzoic, malic, lactic, malonic, oxalic, citric, phosphoric acid and mixtures thereof.
- Particularly preferred are acetic, succinic, salicylic and phosphoric acids and mixtures thereof.
- the colouring compositions herein may optionally contain a catalyst for any inorganic peroxygen oxidising agents and the optional preformed peroxy acid oxidising agent (s) .
- Thickeners 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) , acrylate copolymers 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 compositions according to 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 of the present invention are selected to be miscible with water and innocuous to the skin.
- Solvents suitable for use as additional diluents herein include C ⁇ C 20 mono- or polyhydric alcohols and their ethers, glycerine, with monohydric and dihydric alcohols and their ethers preferred. In these compounds, alcoholic residues containing 2 to 10 carbon atoms are preferred.
- a preferred group includes ethanol, isopropanol, n-propanol, butanol, propylene glycol, ethylene glycol monoethyl ether, 1, 2-hexanediol, butoxyethanol , benzyl alcohol, and mixtures thereof.
- Water is the preferred principal diluent in the compositions according to the present invention. Principal diluent, as defined herein, means, that the level of that diluent present is higher than the total level of any other diluents.
- the diluent is present at a level preferably of from about 5% to about 99.98%, preferably from about 15% to about 99.5%, more preferably at least from about 30% to about 99%, and especially from about 50% to about 98% by weight of the compositions herein.
- a further additional material useful in the hair coloring compositions according to the present invention is one or more enzymes.
- Suitable enzymatic materials include the commercially available Upases, 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.
- 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 0 2 The decomposition of H 2 0 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 0 2 among other acceptors, and the coenzyme peroxidases resemble these rather than the classical peroxidases in not being specific for H 2 0 2 .
- Suitable peroxidases for the compositions of the present invention include horseradish peroxidase, Japanese radish peroxidase, cow'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 O.Olmg to about 10 mg of active enzyme per gram 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, for example, -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. , Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomonas 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 Aspergillus 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.
- compositions of the present invention can additionally contain a surfactant system.
- Suitable surfactants for inclusion in the compositions of the invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and can be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof, (i) Anionic Surfactants
- Anionic surfactants suitable for inclusion in the compositions of the invention include alkyl sulphates, ethoxylated alkyl sulphates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N- acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl ethoxy carboxylates,
- compositions of the invention can also comprise water-soluble nonionic surfactant (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.
- the preferred 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, Cj-Cg 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 4 alkylene, R 2 is C : -C 8 straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl , and is preferably C ⁇ -C 4 alkyl, especially methyl, or phenyl.
- Z 2 is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 hydroxyls (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 a ination reaction, and most preferably Z 2 is a glycityl moiety.
- Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
- Z 2 preferably will be selected from the group consisting of -CH 2 -(CH0H) n -CH 2 0H, -CH(CH 2 OH)-(CHOH) n .
- n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof.
- R' is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof.
- 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 8 is a C6-C19 straight chain alkyl or alkenyl group.
- R8 -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 polyethyleneglycol chain inserted; ethoxylated mono- and diglycerides, polyethoxylated lanolins and ethoxylated butter derivatives.
- water soluble vegetable and animal-derived emollients such as triglycerides with a polyethyleneglycol chain inserted
- ethoxylated mono- and diglycerides ethoxylated mono- and diglycerides
- polyethoxylated lanolins polyethoxylated 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, preferably from about 7 to 18 carbon atoms.
- Suitable ethoxylated oils and fats of this class include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn oil, preferably glyceryl tallowate and glyceryl cocoate.
- Preferred for use herein are polyethyleneglycol based polyethoxylated C 9 -C 15 fatty alcohol nonionic surfactants containing an average of from about 5 to about 50 ethyleneoxy moieties per mole of surfactant.
- Suitable polyethylene glycol based polyethoxylated C 9 - C 15 fatty alcohols suitable for use herein include C 9 -C n Pareth-3, C 9 -C n Pareth-4 , C 9 -C n Pareth-5, C 9 -C n Pareth-6, C 9 -C u Pareth-7, C 9 -C Pareth-8, C n -C 15 Pareth-3 , C n -C 15 Pareth-4, C n -C 15 Pareth-5, C u -C l5 Pareth-6, C n -C 15 Pareth-7, C n-Ci 5 Pareth-8, C -C 15 Pareth-9 , C n -C 15 Pareth-10, C n -C 15 Pareth-11, C n -C 15 Pareth-12 , C u -C 15 Pareth-13 and C n -C 15 Pareth-14.
- PEG 40 hydrogenated castor oil is commercially available under the tradename Cremophor (RTM) from BASF.
- RTM Cremophor
- PEG 7 glyceryl cocoate and PEG 20 glyceryl laurate are commercially available from Henkel under the tradenames Cetiol (RTM) HE and Lamacit (RTM) GML 20 respectively.
- C 9 - C u Pareth-8 is commercially available from Shell Ltd under the tradename Dobanol (RTM) 91-8.
- Particularly 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.
- Nonoxynol surfactants may also be used. Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof. Similarly, ethoxylated derivatives of Mango, Cocoa and Illipe butter may be used in compositions according to the invention. Although these are classified as ethoxylated nonionic surfactants it is understood that a certain proportion may remain as non-ethoxylated vegetable oil or fat.
- 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 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 C0 2 M
- M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of the formula (2)
- n, m, p, and q are numbers from 1 to 4, and R 1 and M are independently selected from the groups specified above;
- Suitable amphoteric surfactants of type (a) are marketed under the trade name Miranol and Empigen and are understood to comprise a complex mixture of species.
- Miranol and Empigen are marketed under the trade name Miranol and Empigen and are understood to comprise a complex mixture of species.
- 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 compounds of formula (1) and/or (2) in which R x is C 8 H :7 (especially iso-capryl) , C 9 H 19 and C H 23 alkyl. Especially preferred are the compounds in which R 1 is C 9 H 19 , Z is C0 2 M and R 2 is H; the compounds in which R 1 is C n H 23 , Z is C0 2 M and R 2 is CH 2 C0 2 M; and the compounds in which R 1 is C n H 23 , Z is C0 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.
- Miranol C2M SF Miranol CM Special (Rh ⁇ ne-Poulenc) ; Alkateric 2CIB (Alkaril Chemicals) ; Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona 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) nonylphenyl 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 8 -C 18 alcohol, C 8 -C 18 ethoxylated alcohol or C 8 -C 18 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-, carboxymethyla ines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts, especially the triethanolammonium salts and salts of N-lauryl-beta- amino propionic acid and N-lauryl-imino-dipropionic acid. Such materials are sold under the trade name Deriphat by Henkel and Mirataine by 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 R 7 N + (CH 2 ) n C0 2 M and a ido betaines of the formula (6) below:
- R 5 is C n -C 22 alkyl or alkenyl
- R 6 and R 7 are independently C ⁇ -C 3 alkyl
- M is H
- n, m are each numbers from 1 to 4.
- Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine, laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine (RTM) .
- Water-soluble auxiliary sultaine surfactants suitable for inclusion in the compositions of the present invention include alkyl sultaines of the formula (7) below:
- R wherein 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 and m and n are numbers from 1 to 4.
- Preferred for use herein is coco amido propylhydroxy sultaine.
- Water-soluble auxiliary amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide R 5 R 6 R 7 NO and amido amine oxides of the formula (8) below:
- R 5 is C to C 22 alkyl or alkenyl
- R 6 and R 7 are independently C x 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 cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.
- a number of additional optional materials can be added to the coloring compositions herein described, each at a level of from about 0.001% to about 5%, preferably from about 0.01% to about 3%, more preferably from about 0.05% to about 2% by weight of composition.
- Such materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives; natural preservatives such as benzyl alcohol, potassium sorbate and bisabalol, benzoic acid, sodium benzoate and 2- phenoxyethanol; dye removers such as oxalic acid, sulphated castor oil, salicylic acid and sodium thiosulphate; H 2 0 2 stabilisers; moisturising agents such as hyaluronic acid, chitin , and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in US-A-4
- viscosity control agents such as magnesium sulfate and other electrolytes; quaternary amine compounds such as distearyl-, dilauryl-, di-hydrogenated beef tallow-, dimethyl ammonium chloride, dicetyldiethyl ammoniu ethylsulphate, ditallowdimethyl ammonium methylsulphate, disoya dimethyl ammonium chloride and dicoco dimethyl ammonium chloride; hair conditioning agents such as silicones, higher alcohols, cationic polymers and the like; enzyme stabilisers such as water soluble sources of calcium or borate species; colouring agents; Ti0 2 and Ti0 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 soften
- the equipment used to measure both the initial colour and colour change of substrates (hair/skin) dyed with the low pH colouring compositions of the present invention is a Hunter Colourquest spectrophotometer.
- the value used to express the degree of colour change on any particular substrate is Delta E ( ⁇ E) .
- Hunter Colourquest measurements can be carried out on the Hunter Labscan Colourimeter which is a full scanning spectrocolorimeter with a wavelength of from 400-700 nanometers which records the colour 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 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 colour 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.
- compositions according to the present invention can be used to colour hair of all colours, types and condition.
- various test hair switches can be tested. Two of these standard hair switches can be measured in terms of their approximate L, a, b values.
- the colourant is massaged through the hair switch for the desired period, which can be up to about 1 minute and then left on the hair switch for the desired period.
- the coloured hair switch is then cleansed (according to the shampoo protocol IV below) and dried. Drying can be effected either naturally (without heat assistance) or using a drier.
- the colour development (initial colour) of the coloured, cleansed, dried test hair switch can then be assessed using the Hunter Colourquest spectrophotometer.
- the preferred initial shade of the coloured hair will have a hue value (arc tangent of (b/a) ) in the range of from about 25 to about 70, more preferably from about 30 to about 65, most preferably from about 35 to about 60 and wherein the initial colour intensity (L) is greater than about 10 and less than about 70, preferably greater than about 15 and less than about 65 more preferably greater than about 20 and less than about 60.
- the preferred initial shade of the coloured hair will have a hue value (arc tangent of (b/a)) of less than about 25, preferably less 55 than about 20 and the initial colour intensity (L) will be greater than about 1 and less than about 50, preferably greater than about 5 and less than about 45.
- the preferred initial shade of the coloured hair will have a hue value (arc tangent of (b/a) ) in the range of from about 70 up to about 110 and wherein the initial colour intensity (L) will be greater than about 20 and less than about 95, preferably greater than about 25 and less than about 90.
- a significant colour change, as delivered via the colouring compositions according to the present invention often means a colour change on permed and bleached hair in terms of Delta E which is preferably greater than about 5 or 8, preferably greater than about 10, more preferably greater than about 12 , most preferably greater than about 15 and especially greater than about 20.
- Delta E is preferably greater than about 5 or 8, preferably greater than about 10, more preferably greater than about 12 , most preferably greater than about 15 and especially greater than about 20.
- a 4 gramme, 8 inch test switch (or a 2 gramme, 4 inch test switch) of coloured hair is clamped over a suitable container and rinsed thoroughly for about 10 seconds using warm water (at about 100°F at about 1.5 gallons/minute pressure).
- Shampoo about 0.1 ml non-conditioning shampoo per gramme hair
- the shampoo and lathering process is then repeated with a final 60 second rinse. Excess water can be removed (squeezed) from the test switch using the fingers.
- test switch is then dried either naturally, or using a pre-heated dryer box at about 140°F (for about 30 minutes) .
- the coloured, cleansed, dried test hair switch can then be colour assessed (Delta E fade) .
- each different switch to be assessed should be tested in water at equivalent temperature, pressure level and hardness level.
- V Perming Protocol The following method is used to perm hair which is usually subsequently to be bleached.
- a 4 gram switch of about 8 inch long hair is hung over a suitable container.
- Perming solution supplied under the trade name "Zotos” is applied to the hair so as to saturate it totally.
- the switches are then resaturated.
- the switches are then laid on a plastic tray for 20 minutes and subsequently rinsed for 1 1/2 to 2 minutes with tap water at 37°C.
- the switches are squeezed dry and towelled dry.
- the switches are then hung over the container again and commercially available "Zotos" neutraliser is applied so as to saturate them. They are then laid in the plastic tray for 5 minutes and subsequently rinsed for 1 1/2 to 2 minutes in tap water at 37°C.
- the switches are then shampooed twice and left to dry.
- the prepermed switches are dried for 20 minutes and hung over the edge of the container. A maximum of 9 or 10 switches at once are treated.
- the commercially available bleach from Clairol, "Born Blonde (with chamomile) " is mixed according to the instructions and 10 grams of the material is applied to each switch and massaged in thoroughly. Each switch is wrapped loosely in clingfilm and left for 30 minutes. It is subsequently rinsed for 2 minutes in tap water at 37°C. It is then shampooed once.
- formulation 1 can be used in a method according to the invention for producing demi-permanent hair coloration.
- the following components are used in formulation 1 as colouring components:
- composition of formulation 1 is as follows;
- the pH of formulation 1 is from 9 to 10.
- Formula I was applied and left for 2 minutes followed by peroxide solution which was left for 2 minutes and provided 0.34% H 2 0 2 (based on total ingredients added to the hair) .
- Formula II was applied and left for 2 minutes. All tests were carried out on permed and bleached light brown hair. Results were as follows:
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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AU75909/98A AU7590998A (en) | 1997-05-23 | 1998-05-22 | Hair colouring methods |
CA002290566A CA2290566A1 (en) | 1997-05-23 | 1998-05-22 | Hair colouring methods |
EP98923675A EP1006989A4 (en) | 1997-05-23 | 1998-05-22 | Hair colouring methods |
JP55067798A JP2001504861A (en) | 1997-05-23 | 1998-05-22 | Hair dyeing method |
BR9809462-9A BR9809462A (en) | 1997-05-23 | 1998-05-22 | Process and set for coloring hair |
Applications Claiming Priority (10)
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GBGB9710759.3A GB9710759D0 (en) | 1997-05-23 | 1997-05-23 | Hair colouring compositions and thier use |
GB9710754.4 | 1997-05-23 | ||
GB9710756.9 | 1997-05-23 | ||
GB9710757.7 | 1997-05-23 | ||
GB9710761.9 | 1997-05-23 | ||
GBGB9710756.9A GB9710756D0 (en) | 1997-05-23 | 1997-05-23 | Hair colouring compositions and thier use |
GBGB9710757.7A GB9710757D0 (en) | 1997-05-23 | 1997-05-23 | Hair colouring methods |
GBGB9710761.9A GB9710761D0 (en) | 1997-05-23 | 1997-05-23 | Hair colouring compositions and their use |
GB9710759.3 | 1997-05-23 | ||
GBGB9710754.4A GB9710754D0 (en) | 1997-05-23 | 1997-05-23 | Hair colouring compositions and their use |
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PCT/US1998/010499 WO1998052521A1 (en) | 1997-05-23 | 1998-05-22 | Hair colouring compositions and their use |
PCT/US1998/010503 WO1998052523A1 (en) | 1997-05-23 | 1998-05-22 | Hair colouring compositions and their use |
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PCT/US1998/010499 WO1998052521A1 (en) | 1997-05-23 | 1998-05-22 | Hair colouring compositions and their use |
PCT/US1998/010503 WO1998052523A1 (en) | 1997-05-23 | 1998-05-22 | Hair colouring compositions and their use |
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EP (5) | EP1006989A4 (en) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001076546A2 (en) * | 2000-04-07 | 2001-10-18 | The Procter & Gamble Company | Method for colouring hair |
US7066967B2 (en) * | 2001-07-24 | 2006-06-27 | The Procter & Gamble Company | Hair coloring compositions and their use |
Families Citing this family (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6074438A (en) * | 1998-03-03 | 2000-06-13 | Bristol-Myers Squibb Co. | Hair dyeing compositions containing 2-chloro- and 2,6-dichloro-4-aminophenol and phenylpyrazolones |
DE19828205C1 (en) * | 1998-06-25 | 1999-11-25 | Goldwell Gmbh | Oxidation hair dyeing system giving e.g. blue and violet colors with peroxide |
FR2805159B1 (en) | 2000-02-23 | 2005-06-10 | Oreal | COMPOSITIONS FOR KERATIN FIBER OXIDATION DYE COMPRISING N- (2-HYDROXYBENZENE) -CARBAMATE OR N- (2-HYDROXYBENZENE) -UREE AS A COUPLER, AND METHODS OF DYING |
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EP2378918B1 (en) | 2009-01-16 | 2013-01-02 | The Procter & Gamble Company | Apparatus for modifying keratinous surfaces |
US9745543B2 (en) | 2012-09-10 | 2017-08-29 | Ecolab Usa Inc. | Stable liquid manual dishwashing compositions containing enzymes |
ES2824105T3 (en) * | 2014-05-16 | 2021-05-11 | Olaplex Inc | Keratin Treatment Methods and Formulations |
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KR20200073260A (en) * | 2017-10-18 | 2020-06-23 | 노오쓰웨스턴유니버시티 | Graphene-based multifunctional cosmetic composition |
US10918183B2 (en) * | 2017-12-21 | 2021-02-16 | L'oreal | Hair color cartridge and compositions for use in the hair color cartridge |
CA3121202A1 (en) | 2018-11-30 | 2020-06-04 | Nuvation Bio Inc. | Pyrrole and pyrazole compounds and methods of use thereof |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4094635A (en) * | 1976-09-09 | 1978-06-13 | L'oreal | Meta-aminophenol sulfonamides as couplers in hair dye compositions |
US5006127A (en) * | 1986-08-21 | 1991-04-09 | Goldwell Gmbh | Agent for the oxidative dyeing of hair, method for the preparation of the agent and use of the agent |
US5584889A (en) * | 1993-12-27 | 1996-12-17 | Clairol Incorporated | Oxidative hair dyeing process with dihydroxybenzenes and aminoethanethiols |
US5603734A (en) * | 1993-12-27 | 1997-02-18 | Clairol Incorporated | Hair dyeing with persulfate oxidants and catechols |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL284202A (en) * | 1961-10-26 | 1900-01-01 | ||
FR1403633A (en) * | 1963-08-01 | 1965-06-25 | Oreal | New hair dye solution |
LU77994A1 (en) * | 1977-08-19 | 1979-05-23 | Oreal | TINCTORIAL COMPOSITIONS BASED ON OXIDIZING COLORANTS CONTAINING AN ALKANOIC ACID (2,5-DIHYDROXYPHENYL) OR ONE OF ITS SALTS AS AN ANTI-OXIDANT AND PROCESS OF PREPARATION |
US4252534A (en) * | 1978-10-19 | 1981-02-24 | Ciba-Geigy Corporation | Dyeing assistants and their use in dyeing synthetic fibre material |
FR2508055A1 (en) * | 1981-06-18 | 1982-12-24 | Oreal | USE OF ALKYL DERIVATIVES OF HYDROQUINONE AS ANTIOXIDANT AGENT IN TINCTORIAL OXIDATION COMPOSITIONS |
JPH0413612A (en) * | 1990-04-27 | 1992-01-17 | Kao Corp | Dyeing agent composition of keratinous fiber |
US5279619A (en) * | 1990-05-31 | 1994-01-18 | L'oreal | Process for dyeing keratinous fibers with 2,4-diamino-1,3-dimethoxybenzene at an acid ph and compositions employed |
US5352372A (en) * | 1993-02-02 | 1994-10-04 | Sequa Chemicals, Inc. | Textile resins with reduced free formaldehyde |
US5344463A (en) * | 1993-05-17 | 1994-09-06 | Clairol, Inc. | Hair dye compositions and methods utilizing 2-substituted-1-naphthol couplers |
JPH07267831A (en) * | 1994-03-28 | 1995-10-17 | Hoyu Co Ltd | Hair dye composition |
FR2720633B1 (en) * | 1994-06-06 | 1996-07-05 | Oreal | Keratin fiber oxidation dyeing composition comprising 2- (BETHA-hydroxyethyl) paraphenylenediamine, 2-methylresorcin and 3-aminophenol, and dyeing process using such a composition. |
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1998
- 1998-05-22 AU AU75913/98A patent/AU7591398A/en not_active Abandoned
- 1998-05-22 KR KR1019997010887A patent/KR20010012919A/en not_active Application Discontinuation
- 1998-05-22 WO PCT/US1998/010490 patent/WO1998052519A1/en not_active Application Discontinuation
- 1998-05-22 EP EP98923675A patent/EP1006989A4/en not_active Withdrawn
- 1998-05-22 CN CN98806740A patent/CN1261777A/en active Pending
- 1998-05-22 WO PCT/US1998/010502 patent/WO1998052522A1/en not_active Application Discontinuation
- 1998-05-22 EP EP98923679A patent/EP1003466A4/en not_active Withdrawn
- 1998-05-22 KR KR1019997010868A patent/KR20010012901A/en not_active Application Discontinuation
- 1998-05-22 AU AU75909/98A patent/AU7590998A/en not_active Abandoned
- 1998-05-22 CA CA002290565A patent/CA2290565A1/en not_active Abandoned
- 1998-05-22 EP EP98923676A patent/EP1006990A4/en not_active Withdrawn
- 1998-05-22 EP EP98923669A patent/EP1011618A1/en not_active Withdrawn
- 1998-05-22 CN CN98807354A patent/CN1264286A/en active Pending
- 1998-05-22 CA CA002290604A patent/CA2290604A1/en not_active Abandoned
- 1998-05-22 AU AU75910/98A patent/AU7591098A/en not_active Abandoned
- 1998-05-22 CA CA002290605A patent/CA2290605A1/en not_active Abandoned
- 1998-05-22 US US09/424,474 patent/US20020088062A1/en not_active Abandoned
- 1998-05-22 CA CA002290566A patent/CA2290566A1/en not_active Abandoned
- 1998-05-22 WO PCT/US1998/010499 patent/WO1998052521A1/en not_active Application Discontinuation
- 1998-05-22 CA CA002290603A patent/CA2290603A1/en not_active Abandoned
- 1998-05-22 JP JP55067798A patent/JP2001504861A/en not_active Ceased
- 1998-05-22 AU AU76921/98A patent/AU744937B2/en not_active Ceased
- 1998-05-22 BR BR9809464-5A patent/BR9809464A/en not_active IP Right Cessation
- 1998-05-22 AU AU75903/98A patent/AU7590398A/en not_active Abandoned
- 1998-05-22 WO PCT/US1998/010503 patent/WO1998052523A1/en not_active Application Discontinuation
- 1998-05-22 JP JP55068098A patent/JP2001507374A/en not_active Ceased
- 1998-05-22 JP JP55067098A patent/JP2001504860A/en not_active Ceased
- 1998-05-22 ID IDW991440A patent/ID27324A/en unknown
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- 1998-05-22 CN CN98807167A patent/CN1263457A/en active Pending
- 1998-05-22 JP JP55067998A patent/JP2001504863A/en active Pending
- 1998-05-22 KR KR1019997010867A patent/KR20010012900A/en not_active Application Discontinuation
- 1998-05-22 US US09/424,473 patent/US20020124329A1/en not_active Abandoned
- 1998-05-22 HU HU0001230A patent/HUP0001230A3/en unknown
- 1998-05-22 WO PCT/US1998/010498 patent/WO1998052520A1/en not_active Application Discontinuation
- 1998-05-22 JP JP55067898A patent/JP2001504862A/en not_active Ceased
- 1998-05-22 CN CN98806917A patent/CN1261778A/en active Pending
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- 1998-05-22 BR BR9809463-7A patent/BR9809463A/en not_active IP Right Cessation
- 1998-05-22 EP EP98924846A patent/EP0989841A1/en not_active Withdrawn
- 1998-05-22 CN CN98807353A patent/CN1264285A/en active Pending
- 1998-05-25 PE PE1998000415A patent/PE91099A1/en not_active Application Discontinuation
- 1998-05-25 PE PE1998000416A patent/PE90899A1/en not_active Application Discontinuation
- 1998-05-25 PE PE1998000417A patent/PE90999A1/en not_active Application Discontinuation
- 1998-05-26 CO CO98029442A patent/CO4930328A1/en unknown
- 1998-05-26 CO CO98029445A patent/CO4940353A1/en unknown
- 1998-05-26 AR ARP980102418A patent/AR012225A1/en unknown
- 1998-05-26 CO CO98029441A patent/CO4940356A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4094635A (en) * | 1976-09-09 | 1978-06-13 | L'oreal | Meta-aminophenol sulfonamides as couplers in hair dye compositions |
US5006127A (en) * | 1986-08-21 | 1991-04-09 | Goldwell Gmbh | Agent for the oxidative dyeing of hair, method for the preparation of the agent and use of the agent |
US5584889A (en) * | 1993-12-27 | 1996-12-17 | Clairol Incorporated | Oxidative hair dyeing process with dihydroxybenzenes and aminoethanethiols |
US5603734A (en) * | 1993-12-27 | 1997-02-18 | Clairol Incorporated | Hair dyeing with persulfate oxidants and catechols |
Non-Patent Citations (1)
Title |
---|
See also references of EP1006989A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001076546A2 (en) * | 2000-04-07 | 2001-10-18 | The Procter & Gamble Company | Method for colouring hair |
WO2001076546A3 (en) * | 2000-04-07 | 2002-02-07 | Procter & Gamble | Method for colouring hair |
US7066967B2 (en) * | 2001-07-24 | 2006-06-27 | The Procter & Gamble Company | Hair coloring compositions and their use |
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