111111
`
`1111111111111111111111111111111111111111111111111111111111111
`US007481846B2
`
`c12) United States Patent
`Marsh et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 7,481,846 B2
`*Jan. 27,2009
`
`(54) METHOD OF RAPID HAIR DYEING
`
`(75)
`
`Inventors: Jennifer Mary Marsh,
`Henley-on-Thames (GB); Graham Neil
`McKelvey, Famborough (GB); Andrew
`David Wyrko, Egham (GB)
`
`(73) Assignee: The Procter & Gamble Company,
`Cincinnati, OH (US)
`
`( *) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 345 days.
`
`This patent is subject to a terminal dis(cid:173)
`claimer.
`
`(21) Appl. No.: 11/233,277
`
`(22) Filed:
`
`Sep.22,2005
`
`(65)
`
`Prior Publication Data
`
`US 2006/0064823 AI
`
`Mar. 30, 2006
`
`(30)
`
`Foreign Application Priority Data
`
`6,540,791 B1 * 4/2003 Dias .............................. 8/405
`6,669,933 B2
`12/2003 Duffer
`6,703,004 B2
`3/2004 Narasimhan
`2003/0154561 A1
`8/2003 Patel
`2004/0055095 A1 * 3/2004 McKelvey et a!.
`4/2004 Plos
`2004/0078906 A1
`2004/0098814 A1
`5/2004 Au
`2004/0098816 A1
`5/2004 Au
`
`............. 8/405
`
`FOREIGN PATENT DOCUMENTS
`
`EP
`EP
`FR
`wo
`wo
`wo
`wo
`
`0435012 A1
`1106166 A2
`1592939 A
`WO-O 1128508 A1
`WO-O 1/76546 A2
`WO 200289754 A1 *
`W0-2004/014328 A1
`
`7/1991
`6/2001
`6/1970
`4/2001
`10/2001
`1112002
`2/2004
`
`OTHER PUBLICATIONS
`
`PCT, Search Report, PCT/US2005/034007, Sep. 28, 2006.
`* cited by examiner
`Primary Examiner-Eisa B Elhilo
`(74) Attorney, Agent, or Firm-Melissa Krasovec; Marianne
`Dressman; Tara M. Rosnell
`
`Sep.24,2004
`
`(EP)
`
`.................................. 04255824
`
`(57)
`
`ABSTRACT
`
`(51)
`
`Int. Cl.
`A61Q 5110
`(2006.01)
`(52) U.S. Cl. ....................... 8/405; 8/426; 8/435; 8/619;
`8/620; 8/107; 8/111; 132/202; 132/208
`(58) Field of Classification Search ..................... 8/405,
`8/426,435,619,620, 107, 111; 132/202,
`132/208
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`5,525,123 A
`
`6/1996 Lorenz
`
`The present invention relates to a method of hair coloring and
`bleaching compositions providing a composition comprising
`i) at least one source of peroxymonocarbonate ions, ii) at least
`one alkalizing agent, preferably a source of ammonium ions,
`and iii) at least one radical scavenger, wherein said composi(cid:173)
`tionhas a pH of up to 9.5, andapplyingthe composition to the
`hair and retaining on the hair for a period of less than 20
`minutes, which provide a high level oflift and lightening and
`the required dye deposition and grey coverage whilst reduc(cid:173)
`ing the concentration of peroxide, the annnonia odor and
`reducing the hair fiber damage.
`
`11 Claims, No Drawings
`
`1
`
`

`

`US 7,481,846 B2
`
`1
`METHOD OF RAPID HAIR DYEING
`
`FIELD OF THE INVENTION
`
`The present invention relates to a method of rapid bleach(cid:173)
`ing and colouration of keratinous fibres.
`
`BACKGROUND OF THE INVENTION
`
`The permanent alteration of the colour ofkeratinous fibres,
`in particular human hair, by the application of hair dyes is
`well known. In order to provide the consumer with the hair
`colour and the intensity of colour desired, a very complex
`chemical process is utilized. Permanent hair dyeing formula(cid:173)
`tions typically comprise oxidative hair dye precursors, which
`can diffuse into the hair through the cuticle and into the cortex
`where they can then react with each other and suitable oxid(cid:173)
`ising agents to form the end dye molecules. Due to the large
`size of these resultant molecules they are unable to readily
`diffuse out of the hair during subsequent washing with water 20
`and/or detergents; hence delivering the consumer-desired
`permanency of colour. The reaction typically takes place in an
`aggressive environment at approximately pH 10 in the pres(cid:173)
`ence of an alkalizing agent and in the presence of an oxidizing
`agent. Moreover, the consumer repeats this process regularly
`in order to maintain the desired hair colour shade and the
`intensity of colour and to ensure continual, even coverage of
`the hair including coverage of new hair growth.
`However, despite the fact that commercial hair dyeing
`products have been available for many years, the products still
`exhibit a number of consumer-related deficiencies. In particu(cid:173)
`lar, the application ofhair dye products is still a relatively time
`consuming process and it may take the consumer over an hour
`to mix, apply, wait for the colour to develop and remove the
`product; before drying and restyling. Since for most consum(cid:173)
`ers the hair dyeing process is a regular part of their beauty
`routine it would be highly desirable if the time required to dye
`the hair could be reduced whilst still meeting all of the other
`requirements of; ease of application, low odour, and espe(cid:173)
`cially of course the delivery of the required hair colour, par- 40
`ticularly for consumers requiring significant changes and/or
`levels of lift in the resultant colour.
`A number of attempts have been described in the literature
`to reduce the application time required to dye hair, for
`example by the use of oxidative hair dye or bleach composi(cid:173)
`tions comprising carbonate. For example;
`W001/28508 describes hair dyeing and bleaching compo(cid:173)
`sitions comprising an oxidising agent, hair colouring agents
`and ammonium carbonate and or carbamate which provides
`improved bleaching and colouring with reduced odour and
`hair damage without the need for buffering agents, pH modi(cid:173)
`tiers or hair swelling agents. The compositions are applied to
`the hair for a time period of from 1 to 60 minutes.
`FR1592939 describes a hair dyeing composition compris(cid:173)
`ing oxidative dyes, ammonium carbonate and hydrogen per(cid:173)
`oxide at pH 7-9 which provides effective dyeing in a fairly
`short period of time.
`EP435012 describes hair-dyeing compositions, which
`require a short dyeing time, create little damage to hair, and no
`irritating odour after dyeing comprising a carbonate source, a
`non odour generating alkali hydrogen peroxide and a buffer
`solution. Similarly, EP1106166 describes hair dye composi(cid:173)
`tions comprising ammonia, carbonate (other than ammonia
`salt), transition metal salt and chelating agent which do not
`give off an irritating odour, have low skin irritation and can
`change the hair colour into a lighter tone in a short time.
`
`2
`W004/014328 describes one step hair colouring composi(cid:173)
`tions comprising peroxide oxidizing agents, specific oxidiz(cid:173)
`ing agents and at least one water soluble carbonate releasing
`salts which more effectively deliver colour wherein the com(cid:173)
`position is applied for a period offrom 2 to 60 minutes.
`Other attempted solutions have been described in U.S. Pat.
`No. 6,703,004 which describes hair bleaching compositions
`comprising an aqueous oxidising agent, persulphate, and a
`hydrophilic oil, in amounts sufficient to provide a mixture
`10 containing 3-5% active oxygen, and 0.7-1.2 meq/gm alkalin(cid:173)
`ity, wherein the composition is capable of bleaching the hair
`in 10 to 30 minutes. Similarly, U.S. Pat. No. 6,669,933
`describes an aqueous hair colouring composition for oxida(cid:173)
`tively colouring hair in less than 12 minutes comprising a dye
`15 and developer mixture, a free alkalinity concentration of0.2-
`0.75 meq/gram and hydrogen peroxide.
`US2004/0078906 describes a process for rapid dyeing and
`decolouration of keratin wherein a specific direct dye is
`applied to the fibres for a leave in time ofless than 5 minutes.
`Alternative attempts to reduce the application time of hair
`dyes on head involve methods which require short consecu(cid:173)
`tive treatments of hair colourants whereby the colour change
`is achieved gradually after time. For example WOOl/76546
`describes a method of colouring hair comprising the steps of
`25 applying a hair colour altering composition to hair and leav(cid:173)
`ing it on hair for about 0.5 to 15 minutes, wherein this method
`is repeated from once a month to about 3 times a day.
`US2003/0154561 describes a method of applying an oxi(cid:173)
`dative shampoo for a time period of from 5 seconds to 5
`30 minutes whereby the treatment is repeated between 2 to 30
`times and the time interval between treatments is 8 hrs to 30
`days. Similarly, US2004/0098814 describes a method of per(cid:173)
`manently whereby the hair is subjected to a number of con(cid:173)
`secutive short treatments whereby the treatment comprises a
`35 dye intermediate in a shampoo or conditioner base, a water
`soluble carbonate releasing salt and a water soluble ammo(cid:173)
`nium salt. US2004/0098816 also describes a method for the
`gradual permanent colouring of hair which includes subject-
`ing the hair to a number of treatments having a set time
`interval between them, wherein the treatment compositions
`comprise ammonium carbonate in combination with a
`chelant.
`However, none of these documents successfully address
`the problems associated with rapid hair colour delivery. In
`45 particular, the problem of hair damage resulting from the use
`ofhigh concentrations ofhydrogen peroxide and ammonia to
`provide the required lift and colour and similarly the problem
`of scalp irritation again typically due to the presence of a high
`concentration of hydrogen peroxide and ammonia and also
`50 the high pH value are not satisfactorily resolved with current
`technologies and marketed products.
`Another critical problem with the rapid colour composi(cid:173)
`tions of the prior art is the delivery of the required resultant
`colour and also the effective coverage of grey hair; the amount
`55 and distribution of which varies considerably from consumer
`to consumer. The prior art not only does not deliver the
`required shade and depth of colour, but, in particular, also
`fails to meet the needs of consumers wishing to lighten their
`hair colour by a number oflevels oflift. The delivery of such
`60 lightening requires significant bleaching which is currently
`only provided by compositions comprising high levels of
`hydrogen peroxide and which are utilised over an extended
`period of time on the hair in order to provide the consumer
`with the desired colour outcome. Likewise, the prior art com-
`65 positions also do not deliver uniform and even colour on the
`hair or maintain the initial colour coverage achieved during
`the post dyeing washing and drying cycle.
`
`2
`
`

`

`3
`Hence, it would be further desirable to provide the con(cid:173)
`sumer with a hair colourant, providing desired levels of lift
`and lightening, as well as improved colour delivery and
`reduced damage, reduced skin and scalp irritation and low
`odour which is effective over shorter time periods of applica(cid:173)
`tion than currently available products and which can be used
`as part of the consumer's regular beauty care routine. More(cid:173)
`over, it would also be desirable to provide a rapid colour
`delivery system whereby the difficulty in applying the com(cid:173)
`position onto the hair in a quick but thorough manner is 10
`addressed.
`It has now been surprisingly found that oxidative hair
`colouring compositions comprising an oxidising agent, a
`source of carbonate ions and an alkali sing agent utilised at pH
`9.5 and below provide a rapidly acting hair bleach or colou- 15
`rant that delivers the required colour requiring less than 20
`minutes development time on the hair of the consumer, whilst
`still delivering the required colour as currently utilised
`ammonia/peroxide systems requiring 45 minutes waiting
`time. Moreover, the method of the present invention reduces 20
`damage to the hair, reduces skin and scalp irritation, has low
`odour and is compatible with current dye and dye precursor
`systems, resulting in improved lift and lightening for blonde
`shades, excellent dye deposition, uniformity and colour, par(cid:173)
`ticularly grey coverage, which is maintained over consumers 25
`wash and styling cycle until the next colouring treatment. The
`method also allows for quick actual application of the com(cid:173)
`positions to the hair and minimises staining of the consumers
`skin, particularly along the hair line, whilst delivering the
`desired colour.
`
`SUMMARY OF THE INVENTION
`
`The present invention relates to a method of oxidative hair
`colouring and hair bleaching comprising the steps of provid(cid:173)
`ing a composition comprising i) at least one source of per(cid:173)
`oxymonocarbonate ions and ii) at least one source of alkaliz(cid:173)
`ing agent, preferably ammonium
`ions wherein said
`composition has a pH of up to and including 9.5 and then
`applying said composition to the hair and retaining said com(cid:173)
`position on the hair for a time period ofless than 20 minutes
`and subsequently rinsing said composition from the hair.
`In a further aspect the present invention relates to the use of
`a composition comprising i) at least one source of peroxy(cid:173)
`monocarbonate ions and ii) at least one source of alkalizing
`agent, preferably monium ions wherein said composition
`has a pH of up to and including 9.5 to oxidatively colour or
`bleach hair in less than 20 minutes.
`Another aspect of the present invention relates to a method
`of sequential oxidative hair colouring or hair bleaching com(cid:173)
`prising the steps of at least two sequential oxidative hair
`colour or hair bleaching treatments wherein the time period
`between each treatment is from 1 day to 60 days, and wherein
`each treatment comprises the steps of providing a composi- 55
`tion comprising i) at least one source of peroxymonocarbon(cid:173)
`ate ions and ii) at least one source of alkalizing agent, pref(cid:173)
`erably monium ions wherein said composition has a pH of
`less than 9.5 and then applying said composition to the hair
`and retaining said composition on the hair for a time period of
`less than 20 minutes and subsequently rinsing said composi(cid:173)
`tion from the hair.
`Another aspect of the present invention relates to a method
`of pre-treatment of the hair whereby the hair is first applied
`with a pre-treatment composition comprising at least one
`conditioning agent which is retained on the hair prior to the
`application of the hair colouring or bleaching composition.
`
`US 7,481,846 B2
`
`4
`DETAILED DESCRIPTION OF THE INVENTION
`
`While the specification concludes with claims, which par(cid:173)
`ticularly point out and distinctly claim the invention, it is
`believed the present invention will be better understood from
`the following description.
`As used herein the term "hair" to be treated may be "living"
`i.e. on a living body or may be "non-living" i.e. in a wig,
`hairpiece or other aggregation of non -living keratinous fibers.
`Mammalian, preferably human hair is preferred. However
`wool, fur and other keratin containing fibers are suitable
`substrates for the compositions according to the present
`invention.
`All percentages are by weight of the total composition
`unless specifically stated otherwise. When more than one
`composition are used during a treatment, the total weight to
`be considered is the total weight of all the compositions
`applied on the hair simultaneously (i.e. the weight found "on
`head") unless otherwise specified. All ratios are weight ratios
`unless specifically stated otherwise.
`Currently marketed hair permanent colourant products
`typically utilize a combination of an alkaliser system, dye
`precursors and an oxidant to deliver the desired hair colour to
`the consumer. The alkaliser is typically ammonia or an
`alkanolamine, such as monoethanolamine and the oxidant is
`typically hydrogen peroxide or a solid form of hydrogen
`peroxide. The final hair colour which is delivered to the
`consumer is a combination of the result of the underlying
`bleaching of the melanin pigment in the hair fibre and the
`30 delivery of the coloured dye chromophore moieties which are
`either preformed, that is direct dyes or are formed by oxida(cid:173)
`tization of the dye precursors within the hair fibre.
`The optimal pH for such systems is typically about pH
`1 0.0. This high pH is necessary in order to produce a sufficient
`35 concentration of the perhydroxy anion (HOO-) to give the
`desired bleaching of the melanin. It has been found that below
`pH 9.5 the concentration of this species is less than 0.01% of
`the added hydrogen peroxide concentration (pKa= 11.6) and
`the amount of melanin bleaching drops dramatically and is
`40 hence insufficient to give the desired final colour.
`However, as discussed herein above, compositions having
`a high pH cause many of the disadvantages noted by consum(cid:173)
`ers for these colourant systems. In particular, the level of the
`volatile ammonia increases at high pH (above pH 9 .5) giving
`45 increased unpleasant odour. Also, some consumers suffer
`from skin and scalp irritation. Furthermore, reactive species
`including the perhydroxy anions react with the hair fibre
`resulting in significant fibre damage. One consequence of this
`reactivity is that the hydrophilicity of the hair fibres is signifi-
`50 cantly increased and this causes an increase in the force
`required to comb the hair compared with hair that has not
`been coloured. Moreover, the higher forces that are exerted
`during combing and styling further result in increased fibre
`damage to the hair fibres.
`It has now been surprisingly found that a method of colour-
`ing and bleaching hair whereby a composition comprising the
`combination of at least one source of peroxymonocarbonate
`ions, preferably formed insitu from a source of hydrogen
`peroxide and a carbonate ion source and at least one source of
`60 alkalizing agents, and preferably at least one source of radical
`scavenger, (as defined hereinafter), and preferably dyes and/
`or dye precursors, at a pH of up to and including 9.5, prefer(cid:173)
`ably7.5 to 9.5, is applied to thehairofthe consumer for a time
`period of less than 20 minutes can deliver improvements to
`65 the desired hair colour results, whilst considerably reducing
`the odour, skin and scalp irritation and damage to the hair
`fibres.
`
`3
`
`

`

`US 7,481,846 B2
`
`5
`6
`Whilst not wishing to be bound by theory, it is believed that
`carbonate, carbamate and hydrocarbonate ions and mixtures
`in the present invention the key species responsible for the
`thereof such as sodium carbonate, sodium hydrogen carbon(cid:173)
`bleaching of the melanin, namely the peroxymonocarbonate
`ate, potassium carbonate, potassium hydrogen carbonate,
`ion (-OC(O)OOH), decomposes at pH values above 9.5 to
`guanidine carbonate, guanidine hydrogen carbonate, lithium
`form oxygen and the hydrogen carbonate ion. At pH values
`carbonate, calcium carbonate, magnesium carbonate, barium
`below 7.5 the hydrogen carbonate ion decomposes to form
`carbonate, armnonium carbonate, ammonium hydrogen car(cid:173)
`carbon dioxide and water. At pH values of9 .0 the bleaching of
`bonate and mixtures thereof. Percarbonate salts may also be
`the melanin and the final colour observed is at an optimal
`utilized to provide both the source of carbonate ions and
`oxidizing agent. Preferred sources of carbonate ions, carbam-
`level. Thus surprisingly the present invention allows for the
`delivery of improved lift, in other words hair lightening which 10 ate and hydrocarbonate ions are sodium hydrogen carbonate,
`is a highly desirable consumer need. Furthermore, composi(cid:173)
`potassium hydrogen carbonate, ammonium carbamate and
`tions having a pH lower than 9.5 have the benefit that not only
`mixtures thereof.
`The compositions of the present invention may comprise
`the unpleasant armnonia odour is significantly reduced but
`from about 0.1% to about 15%, preferably from about 0.1% to
`also the hair fibre damage is reduced. Moreover, due to the
`kinetics of the carbonate system the compositions require 15
`about 10% by weight, more preferably from about 1% to
`about 8% by weight of the carbonate ion. Preferably, if
`only a short development time on the hair of the consumers
`head of up to about 20 minutes in order to deliver improved
`present, the ammonium ions and carbonate ions are present in
`the composition at a weight ratio of from 3:1 to 1: 10, prefer(cid:173)
`uniform colour which is retained during the wash and styling
`ably 2:1 to 1:5. In a particularly preferred embodiment of the
`cycle.
`20 present invention the armnonium ions and carbonate ion
`The compositions according to the present invention thus
`sources are provided by a single source such as armnonium
`comprise a source of peroxymonocarbonate ions. These ions
`carbonate, ammonium hydrogen carbonate, armnomum
`are typically formed insitu from the reaction between a source
`hydrocarbonate or mixtures thereof.
`of hydrogen peroxide and carbonate ion. Consequently, the
`compositions according to the present invention comprise or
`are used in combination with a composition that comprises at 25
`least one source of an oxidizing agent. Preferred oxidizing
`agents for use herein are water-soluble peroxygen oxidizing
`agents. "Water-soluble" as defined herein means that in stan(cid:173)
`dard condition at least 0.1 g, preferably 1 g, more preferably
`10 g of said oxidizing agent can be dissolved in 1 liter of 30
`deionized water. The oxidizing agents are valuable for the
`initial solubilisation and decolorisation of the melanin
`(bleaching) and accelerate the oxidation of the oxidative dye
`precursors (oxidative dyeing) in the hair shaft.
`Any oxidizing agent known in the art may be utilized in the 35
`present invention. Preferred water-soluble oxidizing agents
`are inorganic peroxygen materials capable of yielding hydro(cid:173)
`gen peroxide in an aqueous solution. Water-soluble peroxy(cid:173)
`gen oxidizing agents are well known in the art and include
`hydrogen peroxide, inorganic alkali metal peroxides such as 40
`sodium periodate and sodium peroxide and organic peroxides
`such as urea peroxide, melamine peroxide, and inorganic
`perhydrate salt bleaching compounds, such as the alkali metal
`salts of perborates, percarbonates, perphosphates, persili(cid:173)
`cates, persulphates and the like. These inorganic perhydrate 45
`salts may be incorporated as monohydrates, tetrahydrates etc.
`Alkyl and aryl peroxides and or peroxidases may also be
`used. Mixtures of two or more such oxidizing agents can be
`used if desired. The oxidizing agents may be provided in
`aqueous solution or as a powder which is dissolved prior to 50
`use. Preferred for use in the compositions according to the
`present invention are hydrogen peroxide, percarbonate
`(which may be used to provide a source of both oxidizing
`agent and carbonate ions), persulphates and combinations
`thereof.
`According to the present invention the compositions com(cid:173)
`prise from about 0.1% to about 10% by weight, preferably
`from about 1% to about 7% by weight, and most preferably
`from about 2% to about 5% by weight of an oxidizing agent.
`
`Source of Alkalizing Agent
`According to the present invention the composition also
`comprises at least one source of alkalizing agent, preferably a
`source of ammonium ions and or ammonia. Any agent known
`in the art may be used such as alkanolamides for example
`monoethanolamine, diethanolamine, triethanolamine, mono-
`propanolamine,
`dipropanolamine,
`tripropanolamine,
`2-amino-2-methyl-1 ,3-propanediol,
`2-amino-2-methyl-1-
`propanol, and 2-amino-2-hydroxymethyl-1 ,3-propanediol
`and guanidium salts. Particularly, preferred alkalizing agents
`are those which provide a source of armnonium ions. Any
`source of ammonium ions is suitable for use herein. Preferred
`sources include ammonium chloride, ammonium sulphate,
`ammonium nitrate, armnonium phosphate, armnonium
`acetate, ammonium carbonate, armnonium hydrogen carbon(cid:173)
`ate, ammonium carbamate, armnonium hydroxide, percar(cid:173)
`bonate salts, armnonia and mixtures thereof. Particularly pre(cid:173)
`ferred are armnonium carbonate, armnonium carbamate,
`ammonia and mixtures thereof
`The compositions of the present invention may comprise
`from about 0.1% to about 10% by weight, preferably from
`about 0.5% to about 6%, most preferably from about 1% to
`about 3% of an alkalizing agent, preferably ammonium ions.
`
`55
`
`pH
`According to the method of the present invention the com(cid:173)
`positions of the present invention have a pH up to and includ(cid:173)
`ing pH 9.5. Preferably, the compositions of the present inven(cid:173)
`tion have a pH offrom about 9.5 to about 7 .5, more preferably
`from about 9.5 to about 8.4 and most preferably from about
`9.4 to about 8.5 and even more preferably about pH 9.0.
`Preferably the compositions of the present invention are
`prepared such that prior to application to the hair fibres the pH
`of the composition is no greater than about pH 9 .5. However,
`in another embodiment of the present invention the compo(cid:173)
`sitions may be formulated such that the pH is up to 9.5 during
`60 the time period of application of the composition to the hair
`fibres prior to removal therefrom. Preferably, the pH is up to
`about 9.5 for at least 50% of the time period, preferably at
`least 70%, more preferably at least 80%, most preferably at
`least 90% of the time period of application of the composition
`65 to the hair.
`The pH of the compositions can be determined by using
`either a Mettler Toledo MP220 or a MP225 pH equipment,
`
`Carbonate Ion Source
`According to the present invention the compositions thus
`also comprise at least a source of carbonate ions or carbamate
`ions or hydrocarbonate ions or any mixture thereof. Any
`source of these ions may be utilized. Suitable sources for use
`herein include sodium, potassium, guanidine, arginine,
`lithium, calcium, magnesium, barium, ammonium salts of
`
`4
`
`

`

`US 7,481,846 B2
`
`7
`fitted with a standard laboratory pH electrode. The equipment
`is calibrated before each use using standard calibration buff(cid:173)
`ers and using standard calibration procedure.
`It is known that for good lightening and good colour for(cid:173)
`mation that the final formulation should have a good buffering 5
`capacity or reserve alkalinity (the ability of the system to
`resist the pH shift that would otherwise be caused by addition
`of acid). The reserve alkalinity is measured using a Mettler
`DL70 auto-titrator with O.lN methanolic hydrochloric acid
`being added to 0. 7 mL of thoroughly mixed colourant product 10
`in 50 mL of methanol. The electrode is calibrated and then
`used to measure the amount of acid required to reach the
`sharpest end point triggered by a rapid change in pH. Using
`this method it has been determined that a reserve alkalinity of
`at least 0.2 ml of O.lN of ethanolic hydrochloric acid and
`preferably above 0.4 is required for good lightening and
`colouring. Suitable buffering systems include ammonia/am(cid:173)
`monium acetate mixtures, monoethanolamine tetrasodium
`pyrophosphate, isopropanolamine, benzoic acid
`
`8
`2-(2,5-diamino(cid:173)
`Hydroxyethyl)-2,5-diaminobenzene,
`phenyl)-ethanol, N-( 4-aminophenyl)benzene-1 ,4-diamine,
`2,6-dimethyl-benzene-1 ,4-diamine, 2-isopropyl-benzene-1,
`4-diamine, 1-[( 4-aminophenyl)amino ]-propan-2-ol, 2-pro(cid:173)
`pyl-benzene-1 ,4-diamine,
`1 ,3-bis[ ( 4-aminophenyl)(2-hy(cid:173)
`droxyethyl)amino ]propan-2-ol, N4 ,N4 ,2-trimethylbenzene-
`1 ,4-diamine,
`2-methoxy-benzene-1 ,4-diamine,
`1-(2,5-
`diaminophenyl)ethane-1 ,2-diol, 2,3-dimethyl-benzene-1 ,4-
`diamine, N-( 4-amino-3-hydroxy-phenyl)-acetamide, 2,6-
`diethylbenzene-1 ,4-diamine,
`2,5-dimethylbenzene-1 ,4-
`diamine,
`2-thien-2-y !benzene-! ,4-diamine,
`2-thien-3-
`ylbenzene-1 ,4-diamine, 2-pyridin-3-ylbenzene-1 ,4-diamine,
`1, 1 '-bipheny 1-2,5 -diamine, 2-( methoxymethy I) benzene-! ,4-
`diamine, 2-( aminomethyl)benzene-1 ,4-diamine, 2-(2,5-di-
`15 aminophenoxy)ethanol, N-[2-(2,5-diaminophenoxy)ethyl](cid:173)
`acetamide,
`N,N-dimethylbenzene-1,4-diamine,
`N,N(cid:173)
`diethylbenzene-1 ,4-diamine,
`N,N -dipropylbenzene-1 ,4-
`diamine, 2-[( 4-aminophenyl)( ethyl)amino ]ethanol, 2-[( 4-
`amino-3 -methyl-phenyl )-(2-hydroxy -ethyl )-amino ]-ethanol,
`20 N -(2-methoxyethyl)-benzene-1 ,4-diamine, 3-[ ( 4-aminophe-
`nyl)amino ]propan-1-ol,
`3-[( 4-aminophenyl)-amino ]pro-
`pane-l ,2-diol,
`N-{ 4-[( 4-aminophenyl)amino]
`butyl}benzene-1 ,4-diamine,
`and
`2-[2-(2-{ 2-[(2,5-
`diaminophenyl)-oxy ]ethoxy }ethoxy )ethoxy ]benzene-! ,4-
`25 diamine; 1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)
`amino )-2-propanol;
`2,2'-[1 ,2-Ethanediyl-bis-( oxy-2, 1-
`ethanediyloxy )]-bis-benzene-1 ,4-diamine;
`N,N-Bis(2-
`hydroxyethyl)-p-phenylinediamine;
`p-aminophenol
`derivatives such as: 4-amino-phenol (commonly known as
`30 p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl(cid:173)
`phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-me(cid:173)
`thyl-phenol,
`4-amino-1-hydroxy-2-(2'-hydroxyethylami(cid:173)
`nomethyl)benzene,
`4-amino-2-methoxymethyl-phenol,
`5-amino-2-hydroxy-benzoic acid, 1-(5-amino-2-hydroxy-
`35 phenyl)-ethane-1 ,2-diol, 4-amino-2-(2-hydroxy-ethyl)-phe(cid:173)
`nol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-3-fluoro(cid:173)
`phenol,
`4-amino-2-(aminomethyl)-phenol,
`4-amino-2-
`fluoro-phenol;
`1-Hydroxy-2,4-diaminobenzene;
`1-(2'(cid:173)
`Hydroxyethyloxy)-2,4-diaminobenzene;
`2,4-Diamino-5-
`40 methylphenetol; a-phenylenediamine derivatives such as:
`3,4-Diaminobenzoic acid and salts thereof; o-aminophenol
`derivatives such as: 2-amino-phenol (commonly known as
`o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl(cid:173)
`phenol, 2-amino-6-methyl-phenol, N-( 4-amino-3-hydroxy-
`45 phenyl)-acetamide, and 2-amino-4-methyl-phenol; and het(cid:173)
`erocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine
`(commonly known as 2,4,5,6-tetraaminopyridine ), 1-methyl(cid:173)
`lH-pyrazole-4,5-diamine, 2-( 4,5-diamino-lH-pyrazol-1-yl)
`ethanol, N2,N2-dimethyl-pyridine-2,5-diamine,
`2-[(3-
`50 amino-6-methoxypyridin-2-yl)amino ]ethanol, 6-methoxy(cid:173)
`N2-methyl-pyridine-2,3-diamine, 2,5,6-triaminopyrimidin-4
`(1 H)-one, pyridine-2,5-diamine, 1-isopropyl-1 H -pyrazole-4,
`5-diamine,
`1-(4-methylbenzyl)-lH-pyrazole-4,5-diamine,
`1-(benzyl)-lH-pyrazole-4,5-diamine,
`1-( 4-chlorobenzyl)-
`lH-pyrazole-4,5-diamine, pyrazolo[l ,5-a ]-pyrimidine-3,7-
`diamine,
`5,6, 7 -trimethylpyrazolo[l ,5-a ]pyrimidin-3-
`ylamine hydrochloride, 7 -methylpyrazolo[l ,5-a ]pyrimidin-
`3-ylamine hydrochloride, 2,5,6, 7 -teramethyl-pyrazolo[l ,5-
`a ]pyrimidin-3-ylamine
`hydrochloride,
`5,7 -di-tert-
`60 buty lpyrazolo [ 1 ,5 -a ]pyrimidin-3 -y !amine
`hydrochloride,
`5,7-di-trifluoromethyl-pyrazolo[l,5-a]pyrimidin-3-ylamine
`hydrochloride,
`2-methylpyrazolo[1,5-a]pyrimidin-3,7-di(cid:173)
`amine hydrochloride; 4-Hydroxy-2,5,6-triaminopyrimidine;
`l-(2'hydroxyethyl)-amino-3,4-methylene dioxybenzene; and
`65 1-Hydroxyethyl-4,5-diaminopyrazole sulphate.
`Additional developers include N-(3-furylmethyl)benzene-
`1,4-diamine; N-Thiophen-3-ylmethyl-benzene-1,4-diamine;
`
`55
`
`Additional Components
`The compositions of the present invention may further
`comprise additional ingredients which include, but are not
`limited to, hair dyeing agents such as oxidative dye precur(cid:173)
`sors, non-oxidative dyes, thickeners, solvents, enzymes, sur(cid:173)
`factants, conditioning agents, carriers, antioxidants, stabiliz(cid:173)
`ers, chelants, perming actives, perfume, reducing agents
`(thiolactic acid), hair swelling agents, hydrophobic oils such
`as coconut oil, mineral oil, isopropyl myristrate, linseed oil
`and octyl palmitate and/or polymers. Some of these addi(cid:173)
`tional components are detailed hereafter.
`
`Hair Dyes
`The hair colouring compositions of the present invention
`are preferably hair colouring compositions which comprise
`oxidative dyeing compositions. Such compositions comprise
`oxidative hair dye precursors (also known as primary inter(cid:173)
`mediates) that will deliver a variety of hair colors to the hair.
`These small molecules are activated by the oxidizing agent
`and react with further molecules to form a larger colored
`complex in the hair shaft.
`The precursors can be used alone or in combination with
`other precursors, and one or more can be used in combination
`with one or more couplers. Couplers (also known as color
`modifiers or secondary intermediates) are generally colorless
`molecules that can form colors in the presence of activated
`precursors, and are used with other precursors or couplers to
`generate specific color effects or to stabilize the color.
`The choice of precursors and couplers will be determined
`by the color, shade and intensity of coloration that is desired.
`The precursors and couplers can be used herein, singly or in
`combin