U.S. patent application number 09/331684 was filed with the patent office on 2002-03-21 for hair coloring compositions.
Invention is credited to DIAS, LOUIS CARLOS, DUNBAR, JAMES CHARLES, PRATT, DOMINIC.
Application Number | 20020032933 09/331684 |
Document ID | / |
Family ID | 26310713 |
Filed Date | 2002-03-21 |
United States Patent
Application |
20020032933 |
Kind Code |
A1 |
DIAS, LOUIS CARLOS ; et
al. |
March 21, 2002 |
HAIR COLORING COMPOSITIONS
Abstract
A hair coloring composition comprising: (a) from about 0.0003
moles (per 100 g of composition) to less than about 0.09 moles (per
100 g of composition) of an inorganic peroxygen oxidizing agent;
and (b) an oxidative hair coloring agent; wherein the pH of each of
(a) and (b) is in the range of from about 1 to about 6 and wherein
the combined mixture of (a) and (b) has a pH in the range of from
about 1 to about 6. The products can provide excellent hair
coloring and in-use efficacy benefits including excellent initial
color and good wash fastness in combination with reduced hair
damage at low pH.
Inventors: |
DIAS, LOUIS CARLOS;
(WEYBRIDGE, GB) ; DUNBAR, JAMES CHARLES;
(WEYBRIDGE, GB) ; PRATT, DOMINIC; (KINGSON UPON
THAMES, GB) |
Correspondence
Address: |
S T MURPHY
THE PROCTER & GAMBLE COMPANY
11510 REED HARTMAN HIGHWAY
SHARON WOODS TECHNICAL CENTER PATENT DIV
CINCINNATI
OH
45241
|
Family ID: |
26310713 |
Appl. No.: |
09/331684 |
Filed: |
June 23, 1999 |
PCT Filed: |
December 9, 1997 |
PCT NO: |
PCT/US97/22719 |
Current U.S.
Class: |
8/405 ; 8/406;
8/408 |
Current CPC
Class: |
A61K 8/4926 20130101;
A61Q 5/10 20130101; A61K 8/411 20130101; A61K 8/415 20130101; A61K
8/22 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/408 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 23, 1996 |
GB |
9626713.3 |
Claims
What is claimed is:
1. A hair coloring composition comprising: (a) from about 0.0003
moles (per 100 g of composition) to less than about 0.09 moles (per
100 g of composition) of an inorganic peroxygen oxidising agent;
and (b) an oxidative hair coloring agent; wherein the pH of each of
(a) and (b) is in the range of from about pH 1 to 6 and wherein the
pH of the composition is in the range of from about 1 to about
6.
2. A composition according to claim 1 wherein the pH of the
composition is in the range of from about 1.5 to about 5.8,
preferably from about 1.8 to about 5.5, more preferably from about
2 to about 5, most preferably from about 3.5 to about 4.5.
3. A composition according to claim 1 or 2 wherein the inorganic
peroxygen oxidising agent is present at a molar level of from about
0.0003 moles (per 100 g of composition) to about 0.08 moles (per
100 g of composition), preferably from about 0.0003 moles to about
0.06 moles, more preferably from about 0.0003 moles to about 0.04
moles, most preferably from about 0.0003 moles to about 0.03 moles,
especially from about 0.0003 moles to about 0.02 moles and most
especially from about 0.0003 moles to about 0.015 moles (per 100 g
of composition).
4. A composition according to any of claims 1 to 3 wherein the
inorganic peroxygen oxidising agent is present at a level of from
about 0.01% to less than about 3%, preferably from about 0.01% to
about 2.5%, more preferably from about 0.01% to about 2%, even more
preferably from about 0.01% to about 1%, most preferably from about
0.01% to about 0.8%, especially from about 0.01% to about 0.55% and
especially from about 0.01% to about 0.5% by weight of the total
composition.
5. A composition according to any of claims 1 to 4 wherein the
inorganic peroxygen oxidising agent is hydrogen peroxide.
6. A composition according to any of claims 1 to 5 wherein the
total combined level of oxidative hair coloring agent is from about
0.001% to about 5%, preferably from about 0.01% to about 4%, more
preferably from about 0.1% to about 3%, most preferably from about
0.1% to about 1% by weight.
7. A composition according to any of claims 1 to 6 wherein each
oxidative hair coloring agent is present at a level of from about
0.001% to about 3%, preferably from about 0.01% to about 2% by
weight.
8. A composition according to any of claims 1 to 7 additionally
comprising a preformed organic peroxy acid oxidising agent.
9. A composition according to claim 8 wherein the preformed organic
peroxy acid is present at a molar level of from about 0.0001 moles
to about 0.1 moles (per 100 g of composition), more preferably from
about 0.001 moles to about 0.05 moles, most preferably from about
0.003 moles to about 0.04 moles and especially from about 0.004
moles to about 0.03 moles per 100 g of the hair coloring
composition.
10. A composition according to claim 9 wherein the preformed
organic peroxy acid is present at a level of from about 0.01% to
about 8%, preferably from about 0.1% to about 6%, more preferably
from about 0.2% to about 4% and most preferably from about 0.3% to
about 3% by weight and wherein the weight ratio of the inorganic
oxidising agent:the organic oxidising agent is in the range of from
about 0.00125:1 to about 500:1, preferably from about 0.0125:1 to
about 50:1.
11. A composition according to any of claims 1 to 10 additionally
comprising one or more buffering agents, preferably an organic
and/or organic acid having a first pKa below pH 6, selected from:
aspartic, maleic, tartaric, glutamic, glycolic, acetic, succinic,
salycilic, formic, benzoic, malic, lactic, malonic, oxalic, citric,
phosphoric acid and mixtures thereof, more preferably selected from
acetic, succinic, salycilic and phosphoric acids and mixtures
thereof.
12. A composition according to any of claims 1 to 11 additionally
comprising one or more surfactants selected from anionic, nonionic,
cationic, zwitterionic, amphoteric surfactants and mixtures
thereof.
13. A composition according to any of claims 1 to 12 additionally
comprising thickening agents, stabilisers, antioxidants and/or any
other cosmetically acceptable material.
14. Use of a composition according to any of claims 1 to 13 for
coloring human or animal hair.
15. A process for coloring human or animal hair wherein the hair
coloring composition comprises: (a) from about 0.0003 moles (per
100 g of composition) to less than about 0.09 moles (per 100 g of
composition) of an inorganic peroxygen oxidising agent; (b) an
oxidative hair coloring agent; and (c) a diluent suitable for
application to the hair. wherein the coloring composition has a pH
of from about 1 to about 6.
16. A hair coloring kit comprising an individually packaged
oxidising component and an individually packaged coloring
component, wherein the oxidising component comprises an aqueous
solution of an inorganic peroxygen oxidising agent at a molar level
of from about 0.0003 moles (per 100 g of composition) to less than
about 0.09 moles (per 100 g of composition) having a pH in the
range of from about 1 to about 6, and the coloring component
comprises an oxidative hair coloring agent, capable of delivering a
solution pH in the range of from about 1 to about 6, and wherein
the pH of the combined oxidising agent and coloring components is
in the range of from about 1 to about 6.
17. Use of a hair coloring kit according to claim 16 for the
oxidising and coloring of hair wherein the inorganic oxidising
agent, oxidative hair coloring agents and additional agents are
admixed prior to application to the hair.
18. A method for coloring hair wherein a hair coloring mixture is
applied directly to the hair and wherein the hair coloring mixture
comprises: (a) an inorganic peroxygen oxidising agent at a molar
level of from about 0.0003 moles (per 100 g of composition) to less
than about 0.09 moles (per 100 g of composition) having a pH in the
range of from about 1 to about 6; and (b) an oxidative hair
coloring agent at a pH of from about 1 to 6; wherein the combined
mixture of (a) and (b) has a pH in the range of from about 1 to
about 6, preferably from about 1.5 to 5.8, more preferably from
about 2 to about 5 and especially from about 3.5 to about 4.5.
19. A hair coloring composition suitable for the delivery of a red
shade comprising: (a) an inorganic peroxygen oxidising agent at a
molar level of from about 0.0003 moles (per 100 g of composition)
to less than about 0.09 moles (per 100 g of composition) having a
pH in the range of from about 1 to about 6; and (b) an oxidative
hair coloring agent at a pH of from about 1 to 6; wherein the
change in hair color, delta E, is less than about 5 after 20
washes.
20. A hair coloring composition suitable for the delivery of a
light brown shade comprising: (a) an inorganic peroxygen oxidising
agent at a molar level of from about 0.0003 moles (per 100 g of
composition) to less than about 0.09 moles (per 100 g of
composition) having a pH in the range of from about 1 to about 6;
and (b) an oxidative hair coloring agent at a pH of from about 1 to
6; wherein the change in hair color, delta E, is less than about
2.6 after 20 washes.
21. A hair coloring composition suitable for the delivery of a
brown or black shade comprising: (a) an inorganic peroxygen
oxidising agent at a molar level of from about 0.0003 moles (per
100 g of composition) to less than about 0.09 moles (per 100 g of
composition) having a pH in the range of from about 1 to about 6;
and (b) an oxidative hair coloring agent at a pH of from about 1 to
6; wherein the change in hair color, delta E, is less than about
2.3 after 20 washes.
22. A hair coloring composition, comprising an inorganic peroxygen
oxidising agent and an oxidative hair coloring agent wherein the
change in hair color, Delta E, is greater than about 8, preferably
greater than about 10, more preferably greater than about 12,
especially greater than about 15 and most especially greater than
about 20, and wherein the change in hair color over time (of the
colored hair), % Delta E (fade) is less than about 15%, preferably
less than about 12%, more preferably less than about 10%,-and
especially less than about 8% after 20 washes.
23. A process capable of delivering a red shade to hair comprising:
application to the hair of a composition according to claim 1
comprising: (i) an inorganic peroxygen oxidising agent at a molar
level of from about 0.0003 moles (per 100 g of composition) to less
than about 0.09 moles (per 100 g of composition) having a pH in the
range of from about 1 to about 6; and (ii) an oxidative hair
coloring agent at a pH of from about 1 to 6; wherein the untreated
hair is prepermed, prebleached light brown hair having L, a, b
values of approximately 60, 9 and 32 and wherein the initial shade
of the colored hair has a hue value (arc tangent of (b/a)) in the
range of from about 25 to about 70, preferably from about 30 to
about 65, more preferably from about 35 to about 60 and wherein the
initial color 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 and
wherein the delta E fade is less than about 5.0, preferably less
tha n about 4.5, more preferably less than about 4.0 and wherein
the change in hair color, % delta E, after up to 20 washes, is less
than about 20%, and preferably less than about 15%, more preferably
less than about 10%.
24. A process capable of delivering a brown or black shade to hair
comprising: application to the hair of a composition according to
claim 1 comprising: (i) an inorganic peroxygen oxidising agent at a
molar level of from about 0.0003 moles (per 100 g of composition)
to less than about 0.09 moles (per 100 g of composition) having a
pH in the range of from about 1 to about 6; and (ii) an oxidative
hair coloring agent at a pH of from about 1 to 6; wherein the
untreated hair is prepermed, prebleached light brown hair having L,
a, b values of approximately 60, 9 and 32 and wherein the initial
shade of the colored hair has a hue value (arc tangent of (b/a)) of
less than about 25, preferably less than about 20 and wherein the
initial color intensity (L) is greater than about 1 and less than
about 50, preferably greater than about 5 and less than about 45
and wherein the delta E fade is less than about 2.3, preferably
less than about 2.0, more preferably less than about 1.7 and
wherein the change in hair color, % delta E, after up to 20 washes,
is less than about 5%, preferably less than about 4.5%, more
preferably less than about 4%, most preferably less than about
3.5%.
25. A process capable of delivering a light brown shade to hair
comprising: application to the hair of a composition according to
claim 1 comprising: (i) an inorganic peroxygen oxidising agent at a
molar level of from about 0.0003 moles (per 100 g of composition)
to less than about 0.09 moles (per 100 g of composition) having a
pH in the range of from about 1 to about 6; and (ii) an oxidative
hair coloring agent at a pH of from about 1 to 6; wherein the
untreated hair is prepermed, prebleached light brown hair having L,
a, b values of approximately 60, 9 and 32 and wherein the initial
shade of the colored hair has a hue value (arc tangent of (b/a)) in
the range of from about 70 up to about 110 and wherein the initial
color intensity (L) is greater than about 20 and less than about
95, preferably greater than about 25 and less than about 90 and
wherein the delta E fade is less than about 2.6, preferably less
than about 2.3 and wherein the change in hair color, % delta E,
after up to 20 washes, is less than about 15%, preferably less than
about 12%, more preferably less than about 10%, most preferably
less than about 8%.
26. A method for coloring hair at a pH in the range of from about 1
to about 6 comprising application to the hair of a composition
according to claim 1 comprising: (a) an inorganic peroxygen
oxidising agent at a molar level of from about 0.0003 moles (per
100 g of composition) to less than about 0.09 moles (per 100 g of
composition) having a pH in the range of from about 1 to about 6;
and (b) an oxidative hair coloring agent at a pH of from about 1 to
6; (c) a diluent suitable for application to the hair; and wherein
the combined pH of (a) and (b) is in the range of from about pH 1
to about pH 6.
27. A method for coloring hair at a pH in the range of from about 1
to about 6 comprising application to the hair of a composition
according to claim 1 comprising: (a) an inorganic peroxygen
oxidising agent at a molar level of from about 0.0003 moles (per
100 g of composition) to less than about 0.09 moles (per 100 g of
composition) having a pH in the range of from about 1 to about 6;
and (b) an oxidative hair coloring agent at a pH of from about 1 to
6; (c) a diluent suitable for application to the hair; and wherein
component (b) is applied to the hair, with or without a portion of
component (c), prior to application of components (a) and (c), and
wherein the combined pH of (a), (b) and (c) is in the range of from
about pH 1 to about pH 6.
28. A method for coloring hair at a pH in the range of from about 1
to about 6 comprising application to the hair of a composition
according to claim 1 comprising: (a) an inorganic peroxygen
oxidising agent at a molar level of from about 0.0003 moles (per
100 g of composition) to less than about 0.09 moles (per 100 g of
composition) having a pH in the range of from about 1 to about 6;
and (b) an oxidative hair coloring agent at a pH of from about 1 to
6; (c) a diluent suitable for application to the hair; and wherein
component (a) is applied to the hair, with or without a portion of
component (c), prior to application of components (b) and (c), and
wherein the combined pH of (a), (b) and (c) is in the range of from
about pH 1 to about pH 6.
29. A method for coloring hair wherein a hair coloring mixture
according to claim 1 is present in a single package and applied
directly to the hair.
30. A method for coloring hair wherein a hair coloring composition
acording to claim 1 is present as separately packaged components
(a) and (b) wherein (a) and (b) comprise: (a) an inorganic
peroxygen oxidising agent at a molar level of from about 0.0003
moles (per 100 g of composition) to less than about 0.09 moles (per
100 g of composition) having a pH in the range of from about 1 to
about 6; and (b) an oxidative hair coloring agent at a pH of from
about 1 to 6; wherein each of (a) and (b) are stable at pHs in the
range of from about 1 to about 6 and wherein the combined mixture
of (a) and (b) is stable over time and has a pH in the range of
from about 1 to about 6.
31. A hair coloring composition comprising: (a) an inorganic
peroxygen oxidising agent; and (b) an oxidative hair coloring
agent; wherein the pH of each of (a) and (b) is in the range of
from about 1 to about 6, wherein the combined mixture of (a) and
(b) has a pH in the range of from about 1 to about 6, wherein (a)
and (b) are in the form of intended use, and wherein the molar
level of (a) is from about 0.0003 moles (per 100 g of composition)
to less than about 0.09 moles (per 100 g of composition).
32. Use of a composition according to any of claims 1 to 13 for
coloring textiles and/or fibres.
Description
TECHNICAL FIELD
[0001] This invention relates to hair coloring compositions and
processes for coloring hair, and more especially to hair coloring
compositions comprising an inorganic peroxygen oxidising agent in
combination with an oxidative hair coloring agent at an acidic pH
of between about 1 and about 6.
BACKGROUND OF THE INVENTION
[0002] The desire to alter the color of human hair is not a facet
of modern times. Since the days of the Roman Empire the color of
human hair has been routinely altered to accommodate the changes of
fashion and style. However the attainment of precise initial colors
which are retained by the hair for a desirable period has remained
a more elusive goal. The difficulties in the development of hair
coloring compositions which can deliver precise long-lasting colors
are in part due to the inherent structure of the hair itself and in
part due to the necessary conditions of effective hair coloration
processes.
[0003] In general, the condition and structure of human hair is not
regular along the length of the hair shaft. Human hair is subject
to various chemical and mechanical treatments such as combing,
brushing, shampooing, heating, perming as well as exposure to the
sun. As such, the hair at the ends of the hair shaft will generally
exhibit greater signs of damage relative to the new growth close to
the scalp. This damage can lead to inconsistent coloration when the
hair is dyed due to irregular uptake of the hair coloring agents
along the length of the hair shaft.
[0004] Once the hair has been colored there is a desire for the
color to be resistant to fading, as occasioned by the actions of
washing (also known as wash fastness), perspiration, hair spray and
other exterior factors such as the action of the sun, and further
that the color be retained in a consistent manner for a predictable
period of time. Additionally damage to the hair that can lead to
irregular dye uptake as discussed above, can lead to increased
fading of the damaged portions of the hair and consequently,
irregular levels of color fade over time. An additional difficulty
commonly associated with the dyeing of human hair is the need for
dye systems which avoid any adverse effect on the hair and skin of
the user, such as brittle hair, or, irritation of the skin, or,
staining (coloring) of the skin.
[0005] Thus, it would be desirable to develop a hair coloring
composition which exhibits reduced fade, provides improved
resistance to wash out during a regular cleansing regimen, can
deliver substantially consistent hair color results throughout the
hair, which has reduced irritant effect on the skin, which has
reduced staining on the skin, which has reduced adverse effects on
the hair of the user and also to develop a convenient and
easy-to-use method for the delivery of such a hair coloring
composition to the hair.
[0006] Over the years significant effort has been directed towards
the elimination of many of the problems associated with the dyeing
of human hair. Various approaches to hair dyeing have been
developed, these include, direct action dyes, natural dyes,
metallic dyes and oxidative dyes.
[0007] To color human or animal hair using oxidative dye technology
the hair is generally treated with a mixture of oxidative hair
coloring agents and an oxidising agent. Hydrogen peroxide is the
most commonly used oxidising agent. However, in addition to
oxidising the oxidative coloring agents, hydrogen peroxide
treatment of the hair can also solubilise and decolorise the
colored melanin component in the hair which can lead to undesirable
hair qualities, such as brittleness and hair damage. This is in
part due to the conditions of conventional peroxide treatment, as
part of the hair coloring process, when conducted at high pH
(>pH 9), extended exposure (from 10 to 60 minutes) and a
relatively high concentration of oxidising solution (between about
20% to about 40% volume of oxygen i.e. about 6 -12% wt.) in order
to deliver effective dye oxidisation.
[0008] Oxidative hair coloring agents and peroxygen oxidising
agents can be used to deliver a variety of hair colors to the hair.
However substantial improvement is needed in the areas of color
saturation, color development, precise initial color consistency,
improved wash fastness, improved hair condition and levels of hair
damage.
[0009] Thus there is a need for oxidative hair coloring
compositions which effectively dye the hair but avoid or reduce
damage to the hair, which can color the hair effectively and avoid
or reduce irritation and/or staining to the skin of the user.
[0010] Typically, hair coloring compositions containing oxidative
hair coloring agents are formulated at high pH (from about pH 9 to
about pH 12) and commonly contain, in addition to the oxidative
hair coloring agents and an inorganic peroxygen oxidising agent,
peroxide activating agents and a variety of additional cosmetic,
coloring agent and peroxygen oxidising agent stabilising agents. It
is also known that enhanced oxidative hair coloring agent oxidation
can be achieved via the use of a hair swelling agent (HSA). Such
HSA's enhance the oxidising and coloring process by swelling the
hair fibres to aid both the diffusion of the peroxygen oxidising
agent and the oxidative hair coloring agents into the hair and
enabling faster, more thorough dye oxidisation and hair coloring. A
common HSA is an aqueous (alkaline) solution containing a source of
ammonia, such as ammonium hydroxide. However ammonia can cause skin
irritation and in addition has an undesirable odour and can cause
lacrimatory effects.
[0011] Thus, it would be desirable to develop a hair coloring
composition having desirable odour characteristics comprising
oxidative hair coloring agents which delivers improved hair
coloring benefits and/or delivers faster hair coloring without the
need for an HSA.
[0012] It has now been found that the combination of inorganic
peroxygen oxidising agents with one or more oxidative hair coloring
agents at a pH below the internal pH of hair, between about pH 1 to
about pH 6, and optionally, certain, additional oxidising agents,
in hair coloring compositions can deliver excellent initial hair
color in combination with improved color and wash fastness of the
hair color over time, desirable color saturation and vividness
attributes, reduced hair damage, reduced skin irritation, reduced
skin staining and more efficient dyeing. Furthermore, it has been
found that the efficiency of color development (color change) from
the inorganic peroxygen oxidising agents and particular oxidative
hair coloring agents of the present invention is improved under the
low pH conditions according to the present invention. In addition,
it has been found that the hair coloring compositions according to
the present invention can deliver these excellent hair coloring
attributes results with minimal hair damage, at low pH (about 1 to
about 6 ).
[0013] It is an object of the present invention to provide low pH
hair coloring compositions which deliver the combination of
improved hair coloring attributes, such as, longer lasting color
(reduced fade), initial color generation, increased color uptake
and color consistency across hair types. Hair types as defined
herein means hair of varying age and condition i.e. virgin
untreated, grey, permed, bleached etc.
[0014] It is an additional object of the present invention to
provide low pH hair coloring compositions which have reduced levels
of skin irritation and/or skin staining versus conventional high pH
systems and which impart minimal damage to the hair fibres and
reduced staining of skin in combination with an acceptable
odor.
[0015] It is a still further object of the present invention to
provide low pH hair coloring compositions which exhibit increased
efficacy (improved color development). Color development as defined
herein, means, the change in the hair color, expressed in terms of
Delta E, as defined in the Experimental section herein after). It
is a yet further object of the present invention to provide
coloring compositions with reduced damage to the skin and/or hair
which can deliver equivalent color development (versus conventional
high pH systems) in combination with improved washfastness and
color consistency while using less dye and/or less of the oxidising
agent.
[0016] It has been found that the above objects can be met by the
low pH hair coloring compositions according to the present
invention.
[0017] In addition, conventional, high pH, hair coloring
compositions typically comprise at least two separately packaged
components, which are generally, oxidising agent (at low pH) and
oxidative hair coloring agents (at high pH). These separately
packaged components are admixed at high pH just prior to
application to the hair. Such an admixing step can be messy and
inconvenient to the user. Typically, conventional coloring
compositions, comprising oxidising agent and oxidative hair
coloring agent, need to be used soon after admixing due to
degradation of the resulting coloring composition. As such, excess
admixed coloring composition is disposed of after application of
the required amount to the hair. It has been found that the
oxidant(s) and dyes of the present invention can be admixed in a
singly packaged low pH mixture with improved stability versus
conventional, high pH, oxidative dye systems. The singly packaged
low pH coloring compositions of the present invention are suitable
for use in a multi-application format (i.e. the consumer can use a
single package for several color applications over a period of
time). It has also been found that, at low pH, both the oxidising
agent and oxidative hair coloring agents are stable over time, and
can be stored as such.
[0018] Thus it is another object of the present invention to
provide singly packaged hair coloring compositions which are fast
acting, simple to use and re-usable.
[0019] It is a further object of the present invention to provide
hair coloring compositions comprising stable, separately packaged
oxidant(s) and oxidative hair coloring agent(s) which remain stable
at low pH both when stored individually or when mixed.
[0020] All percentages are by weight of the final compositions in
the form intended to be used unless specified otherwise.
SUMMARY OF THE INVENTION
[0021] The subject of the present invention is a hair coloring
composition suitable for the treatment of human or animal hair.
[0022] According to one aspect of the present invention, there is
provided a hair coloring composition comprising:
[0023] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent; and
[0024] (b) an oxidative hair coloring agent;
[0025] wherein the pH of each of (a) and (b) is in the range of
from about 1 to about 6 and wherein the combined mixture of (a) and
(b) has a pH in the range of from about 1 to about 6 .
[0026] It is to be understood that the percentage weights of the
composition components herein are expressed in terms of the total
composition, and includes the composition in the form of intended
use
[0027] According to a further aspect of the present invention,
there is provided:
[0028] A method for coloring hair wherein a hair coloring mixture
is present in a single package and applied directly to the hair and
wherein the hair coloring mixture comprises:
[0029] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent; and
[0030] (b) an oxidative hair coloring agent;
[0031] wherein the pH of each of (a) and (b), is in the range of
from about 1 to about 6 and wherein the combined mixture of (a) and
(b), has a pH in the range of from about 1 to about 6.
[0032] According to a still further aspect of the present
invention, there is provided:
[0033] A method for coloring hair wherein a hair coloring
composition is present as separately packaged components (a) and
(b) and wherein the hair coloring composition comprises:
[0034] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent wherein the pH of (a), is in
the range of from about 1 to about 6; and
[0035] (b) an oxidative hair coloring agent wherein the pH of (b),
is in the range of from about 1 to about 6;
[0036] wherein each of (a) and (b) are stable at pHs in the range
of from about 1 to about 6 and wherein the combined mixture of (a)
and (b) is stable over time and has a pH in the range of from about
1 to about 6.
[0037] According to an additional object of the present invention
there is provided a hair coloring composition comprising:
[0038] (a) an inorganic peroxygen oxidising agent; and
[0039] (b) an oxidative hair coloring agent;
[0040] wherein the pH of each of (a) and (b) is in the range of
from about 1 to about 6, wherein the combined mixture of (a) and
(b) has a pH in the range of from about 1 to about 6, wherein (a)
and (b) are in the form of intended use, and wherein the molar
level of (a) is from about from about 0.0003 moles (per 1 g of
composition) to less than about 0.09 moles (per 100 g of
composition).
DETAILED DESCRIPTION OF THE INVENTION
[0041] 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 fibres, such as though
used in textiles and fabrics. Mammalian, preferably human hair is
preferred. However wool, fur and other melanin containing fibres
are suitable substrates for the compositions according to the
present invention.
[0042] As used herein the term `hair coloring composition` is used
in the broad sense in that it is intended to encompass compositions
containing the combinations herein of a low pH (from about 1 to
about 6 ) mixture of inorganic peroxygen based dye oxidising agent
and an oxidative coloring agent. Moreover, it is also intended to
include complex compositions which contain other components which
may or may not be active ingredients. Thus, the term `hair coloring
composition` is intended to apply to compositions which contain, in
addition to a mixture of active oxidising agents and oxidative
coloring agents, such things as, by way of example, oxidising aids,
sequestrants, stabilisers, thickeners, buffers, carriers,
surfactants, solvents, antioxidants, polymers, non-oxidative dyes
and conditioners.
[0043] As discussed above, the hair coloring compositions according
to the present invention comprise from about 0.0003 moles (per 100
g of composition) to less than about 0.09 moles (per 100 g of
composition) of an inorganic peroxygen based oxidising agent (a),
in combination with an oxidative hair coloring agent (b) wherein
the pH of each of (a) and (b) is in the range of from about 1 to
about 6 and wherein the pH of the combined mixture of (a) and (b)
is in the range of from about 1 to about 6. Preferably, the pH of
either (a) and/or (b) is in the range of from about 1.5 to about
5.8, more preferably from about 1.8 to about 5.5, most preferably
from about 2 to about 5 and especially from about 3.5 to about 4.5
and wherein the preferred pH of the combined mixture of (a) and (b)
is in the range of from about 1.5 to about 5.8, more preferably
from about 1.8 to about 5.5, most preferably from about 2 to about
5 and especially from about 3.5 to about 4.5. In addition to the
inorganic peroxygen oxidising agent, the compositions may
optionally comprise (among other ingredients) a preformed organic
peroxyacid oxidising agent. Organic peroxyacid as used herein is
intended to cover any organic peroxy acid material which can act
either alone or in combination with a peroxygen oxidising agent to
oxidise dye precursors.
The Dye Oxidisation and Hair Coloring Processes
[0044] It is understood by those familiar in the art that to
successfully color human or animal hair with oxidative dyes it is
generally necessary to treat the hair with a mixture of oxidising
agent and oxidative hair coloring agent. As herein before discussed
the most common oxidising agent is hydrogen peroxide.
[0045] Hydrogen peroxide has a pKa in the range of from about 11.2
to about 11.6, and, as such is generally used as a dye oxidising
agent at pHs in the range of from about 9 to about 12.
Surprisingly, it has now been found that improved color development
is observed in combination with improved color washfastness, in the
low pH oxidative systems according to the present invention, at pHs
in the range of from about pH 1 to about pH 6, preferably from
about pH 1.5 to about pH 5.8, more preferably from pH 1.8 to about
pH 5.5, most preferably from about pH 2 to about pH 5, and
especially from about pH 3.5 to about pH 4.5.
Inorganic Oxidizing Agents
[0046] The compositions of the invention comprise as an essential
feature at least one inorganic oxidising agent (hereinafter called
`inorganic peroxygen oxidising agent`). The inorganic peroxygen
oxidising agent should be safe and effective for use in the
compositions herein. Preferably, the inorganic peroxygen oxidising
agents suitable for use herein will be soluble in the compositions
according to the present invention when in liquid form or in the
form intended to be used. Preferably, inorganic peroxygen oxidising
agents suitable for use herein will be water-soluble. Water soluble
oxidising agents as defined herein means agents which have a
solubility to the extent of about 10 g in 1000 ml of deionised
water at 25.degree. C. ("Chemistry" C. E. Mortimer. 5th Edn.
p277).
[0047] The inorganic peroxygen oxidising agents useful herein are
generally inorganic peroxygen materials capable of yielding
peroxide in an aqueous solution. Inorganic peroxygen oxidising
agents are well known in the art and include hydrogen peroxide,
inorganic alkali metal peroxides such as sodium periodate, sodium
perbromate and sodium peroxide, and inorganic perhydrate salt
oxidising compounds, such as the alkali metal salts of perborates,
percarbonates, perphosphates, persilicates, persulphates and the
like. These inorganic perhydrate salts may be incorporated as
monohydrates, tetrahydrates etc. Mixtures of two or more of such
inorganic peroxygen oxidising agents can be used if desired. While
alkali metal bromates and iodates are suitable for use herein the
bromates are preferred. Highly preferred for use in the
compositions according to the present invention is hydrogen
peroxide.
[0048] It has been found that, under the low pH conditions
according to the present invention, it is possible to deliver both
improved initial color development, color consistency, washfastness
and color intensity versus conventional, high pH, systems (using
equivalent levels of peroxide and dyes) and also equivalent color
development (detailed hereinafter in the Experimental Data section
in terms of Delta E) versus conventional systems at high pH, while
using substantially less of the inorganic peroxygen oxidising agent
(up to 75% less) as well as delivering equivalent color development
versus conventional, high pH, systems while using substantially
less oxidative hair coloring agent (up to 50% less). Thus, the low
pH hair coloring compositions according to the present invention
can be formulated to reduce the level of damage to the hair and
levels of skin irritation and staining. Furthermore, as the low pH
hair coloring compositions according to the present invention can
be formulated without ammonia there are no ammonia related odor or
skin irritation negatives associated with these compositions.
[0049] The inorganic peroxygen oxidising agent is present in the
compositions according to the present invention at a molar level of
from about 0.000294 moles (per 100 g of composition) to less than
about 0.0882 moles (per 100 g of composition), preferably, the
inorganic peroxygen oxidising agent is present at a molar level of
from about 0.0003 moles to about 0.08 moles, more preferably from
about 0.0003 moles to about 0.06 moles, even more preferably from
about 0.0003 moles to about 0.04 moles, most preferably from about
0.0003 mole to about 0.03 moles, especially from about 0.0003 moles
to about 0.02 moles and most especially from about 0.0003 moles to
about 0.015 moles (per 100 g of composition).
[0050] In preferred compositions according to the present invention
the inorganic peroxygen oxidising agent is present at a level of
from about 0.01% to less than about 3%, preferably from about 0.01%
to about 2.5%, more preferably from about 0.01% to about 2%, even
more preferably from about 0.01% to about 1%, most preferably from
about 0.01% to about 0.8%, especially from about 0.01% to about
0.55% and especially from about 0.01% to about 0.5% by weight of
composition.
Preformed Organic Peroxyacid
[0051] The compositions according to the present invention may,
optionally, contain, in addition to the inorganic peroxygen
oxidising agent(s), one or more preformed organic peroxyacid
oxidising agents.
[0052] Suitable, additional, optional, organic peroxyacid oxidising
agents for use in the coloring compositions according to the
present invention have the general formula:
R--C(O)OOH
[0053] wherein R is selected from saturated or unsaturated,
substituted or unsubstituted, straight or branched chain, alkyl,
aryl or alkaryl groups with from 1 to 14 carbon atoms.
[0054] A class of organic peroxyacid compounds suitable for use
herein are the amide substituted compounds of the following general
formulae:
R.sup.1--C--N--R.sup.2--C--OOH R.sup.1--N--C--R.sup.2--C--OOH O
R.sup.5O or R.sup.5O O
[0055] wherein R.sup.1 is, a saturated or unsaturated alkyl or
alkaryl group, or an aryl group, having from 1 to 14 carbon atoms,
R.sup.2 is, a saturated or unsaturated alkyl or alkaryl group, or
an aryl group, having from 1 to 14 carbon atoms, and R.sup.5 is H
or, a saturated or unsaturated alkyl or alkaryl group, or an aryl
group, having from 1 to 10 carbon atoms. Amide substituted organic
peroxyacid compounds of this type are described in
EP-A-0,170,386.
[0056] Other suitable 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, dodecanedioylmonoperoxybenzoic, 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 and derivatives thereof are also
suitable for use herein.
[0057] The preformed organic peroxyacid oxidising agents should be
safe and effective for use in the compositions herein. Preferably,
the preformed organic peroxyacid oxidising agents suitable for use
herein will be soluble in the compositions according to the present
invention when in liquid form and in the form intended to be used.
Preferably, organic peroxyacid oxidising agents suitable for use
herein will be water-soluble. Water-soluble preformed organic
peroxyacid oxidising agents as defined herein means agents which
have a solubility to the extent of about 10 g in 1000 ml of
deionised water at 25.degree. C. ("Chemistry" C. E. Mortimer. 5th
Edn. p277).
[0058] The preferred peroxyacid materials suitable for use herein
are selected from peracetic and pernanoic acids and mixtures
thereof.
[0059] The preformed organic peroxyacid oxidising agent, where
present, is present at a molar level of from about 0.0001 moles to
about 0.1 moles (per 100 g of composition), more preferably from
about 0.001 moles to about 0.05 moles, most preferably from about
0.003 moles to about 0.04 moles and especially from about 0.004
moles to about 0.03 moles per 100 g of the hair coloring
composition.
[0060] The preformed organic peroxyacid oxidising agent, where
present, is preferably present at a level of from about 0.01% to
about 8%, more preferably from about 0.1% to about 6%, most
preferably from about 0.2% to about 4%, and especially from about
0.3% to about 3% by weight of the hair coloring composition. The
weight ratio of the inorganic peroxygen oxidising agent to the
preformed organic peroxy acid is preferably in the range of from
about 0.0125:1 to about 500:1, more preferably from about 0.0125:1
to about 50:1.
[0061] In addition to the inorganic peroxygen oxidising agents and
the additional, optional, preformed organic peroxyacid oxidising
agents suitable for use herein, the compositions according to the
present invention may optionally comprise additional organic
peroxides such as urea peroxide, melamine peroxide and mixtures
thereof. The level of organic peroxide, where present, is from
about 0.01% to about 3%, preferably from about 0.01% to about 2%,
more preferably from about 0.1% to about 1.5% and most preferably
from about 0.2% to about 1% by weight of composition.
Hair Coloring Agents
[0062] The low pH hair coloring compositions of the present
invention include as an essential feature an oxidative hair
coloring agent. Such oxidative hair coloring agents are used in
combination with the peroxide based oxidising systems of the
present invention to formulate permanent, demi-permanent,
semi-permanent or temporary hair dye compositions at low pH.
[0063] Permanent hair dye compositions as defined herein are
compositions which once applied to the hair are substantially
resistant to wash-out. Demi-permanent hair dye compositions as
defined herein are compositions which are substantially removed
from the hair after up to 24 washes. Semi-permanent hair dye
compositions as defined herein are compositions which once applied
to the hair are substantially removed from the hair after up to 10
washes. Temporary hair dye compositions as defined herein are
compositions which once applied to the hair are substantially
removed from the hair after up to 2 washes. These different types
of hair coloring compositions can be formulated via the specific
combination of oxidant and/or dyes at different levels and ratios.
Wash out as defined herein is the process by which hair color is
removed from the hair over time during normal hair cleansing
regimen. Washfastness as defined herein, means, the resistance of
the dyed hair to wash out. Washfastness, as defined herein, can be
measured in terms of the relative color change in the dyed hair
(Delta E) over several washes (shampoos). Substantial removal of
dye from the hair as defined herein means the color change in the
dyed hair (Delta E) is greater than about 2 after up to 10
washes.
[0064] The concentration of each oxidative hair coloring agent in
the low pH coloring compositions according to the present invention
is from about 0.001% to about 3% by weight and is preferably from
about 0.01% to about 2% by weight.
[0065] The total combined level of oxidative hair coloring agents
in the compositions according to the present invention is from
about 0.001% to about 5%, preferably from about 0.01 % to about 4%,
more preferably from about 0.1% to about 3%, most preferably from
about 0.1% to about 1% by weight.
[0066] Typically, in conventional hair coloring compositions the
total level of oxidative hair coloring agents present in the
composition is in the range of from about 0.2% to about 3.5% by
weight. Accordingly, the compositions according to the present
invention can display improved hair coloring attributes, such as
initial color development and initial color consistency in
combination with improved washfastness over time, when compared to
conventional, high pH, systems having similar levels of dye. Color
consistency, as used herein, means, both the relative
predictability of the initial color development and improved color
retention over time across different hair types.
[0067] The efficacy of the oxidative dyes is improved at low pH
such that the compositions of the present invention are valuable
for the delivery of good high intensity colors (dark colors) with
reduced levels of dye. In particular, good hair coloring results in
combination with equivalent color development (versus high pH
systems) can be achieved using the inorganic peroxygen oxidising
agents of the present invention and substantially less dye versus
conventional, high pH, hair coloring compositions.
[0068] Thus according to a further aspect of the present invention
there is provided a hair coloring composition comprising:
[0069] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent; and
[0070] (b) an oxidative hair coloring agent; and
[0071] (c) a diluent suitable for application to the hair;
[0072] wherein the pH of each of (a) and (b) is in the range of
from about 1 to about 6 and wherein the pH of the composition is in
the range of from about 1 to about 6 .
[0073] As herein before described, it has also been found that the
combination of inorganic peroxygen oxidising agents with oxidative
hair coloring agent at low pH is valuable for the delivery of
excellent hair coloring attributes in combination with reduced
levels of hair damage, skin irritation and skin staining in
combination with an improved odor profile (versus conventional high
pH compositions). A further benefit of the low pH coloring
compositions according to the present invention is that reduced
levels of skin staining can be observed from such compositions,
versus conventional, high pH, compositions.
[0074] Thus according to a still further aspect of the present
invention there is provided a hair coloring composition capable of
delivering a light auburn colour to light brown hair having 40%
grey comprising:
[0075] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent; and
[0076] (b) an oxidative hair coloring agent; and
[0077] (c) a diluent suitable for application to the hair;
[0078] wherein the pH of components (a) and (b) are each in the
range of from about 1 to about 6 and wherein the pH of the
composition is in the range of from about 1 to about 6 and wherein
the change in level of skin staining after product application
(Delta E) is less than about 4, preferably less than about 3, more
preferably less than about 2.7. Light brown hair having 40% grey
coverage is defined in terms of L, a, b values as having an `L`
value in the range of from about 35 to about 37, an `a` value in
the range of from about 4.5 to about 5.5 and a `b` value in the
range of from about 11.5 to about 12.7.
[0079] Without being limited by any particular theory, it is
believed that, these improvements (in respect of reduced skin
irritation and/ or staining) result from the combination of (a)
reduced levels of dyes and low pH; (b) the reduction of
paraphenylene diamine (PPD) contact sensitisation at low pH (high
levels of PPD have been shown to display contact sensitisation at
high pH, but not at low pH); (c) the elimination of the formation
of nitrobenzene contact sensitisers (which can occur in high pH
compositions); (d) reduced levels of skin staining at low pH versus
high pH, and; (e) the reduction in skin irritation and odor
negatives as a result of the elimination of ammonia and the use of
alternative oxidising agents in the low pH dyeing compositions
according to the present invention.
Oxidative Hair Coloring Processes
[0080] Any oxidative hair coloring agent can be used in the
compositions according to the present invention. Typically, but
without intending to be limited thereby, oxidative hair coloring
agents, consist essentially of at least two components, which are
collectively referred to as dye forming intermediates (or
precursors). Dye forming intermediates can react in the presence of
a suitable oxidant to form a colored molecule.
[0081] The dye forming intermediates used in oxidative hair
colorants include: aromatic diamines, aminophenols, various
heterocycles, phenols, napthols and their various derivatives.
These dye forming intermediates can be broadly classified as;
primary intermediates and secondary intermediates. Primary
intermediates, which are also known as oxidative dye precursors,
are chemical compounds which become activated upon oxidation and
can then react with each other and/or with couplers to form colored
dye complexes. The secondary intermediates, also known as color
modifiers or couplers, are generally colorless molecules which can
form colors in the presence of activated precursors/primary
intermediates, and are used with other intermediates to generate
specific color effects or to stabilise the color.
[0082] Primary intermediates suitable for use in the compositions
and processes herein include: aromatic diamines, polyhydric
phenols, amino phenols and derivatives of these aromatic compounds
(e.g., N-substituted derivatives of the amines, and ethers of the
phenols). Such primary intermediates are generally colorless
molecules prior to oxidation.
[0083] While not wishing to be bound by any particular theory it is
proposed herein that the process by which color is generated from
these primary intermediates and secondary coupler compounds
generally includes a stepwise sequence whereby the primary
intermediate can become activated (by oxidation), and then enjoins
with a coupler to give a dimeric, conjugated colored species, which
in turn can enjoin with another `activated` primary intermediate to
produce a trimeric conjugated colored molecule.
Chemistry of Oxidative Hair Coloration Across pH
[0084] While not wishing to be bound by any particular theory, it
is generally understood that conventional oxidative dyeing
typically occurs between oxidative precursor molecules, oxidative
coupler molecules and a peroxygen oxidising agent at high pH (8
-10). Typical precursors include 1,4-disubstituted benzene
derivatives and typical couplers include 1,2- or 1,3-disubstituted
benzene derivatives.
[0085] It is generally accepted that the pH within the hair shaft,
of human hair, is around pH 5.5 to pH 6 (C. R. Robbins, Chemical
and Physical Behaviour of Human Hair, 2nd Ed. p157), and that the
hair has an inherent buffering capacity in this pH range.
[0086] Surpisingly it has now been found that, oxidative hair
coloration at pH 6 or less with oxidising agents, at a molar level
of from about 0.000294 moles (per 100 g of composition) to less
than about 0.0883 moles 9per 100 g of composition), and an
oxidative hair coloring agent, is valuable for the delivery of
excellent initial hair color in combination with improved color and
wash fastness of the hair color over time, desirable color
saturation and vividness attributes, reduced hair damage, reduced
skin irritation, reduced skin staining and more efficient dyeing.
Furthermore, it has been found that the efficiency of color
development (i.e., increased color change) from the inorganic
peroxygen oxidising agents and the oxidative hair coloring agents
of the present invention is improved under the low pH conditions
according to the present invention. In addition, it has been found
that the low pH hair coloring compositions according to the present
invention can deliver these excellent hair coloring attributes
results with minimal hair damage.
[0087] It has also been found that at pH levels of less than pH 6,
preferably from abour pH 1.5 to 5.8, more preferably from pH 1.8 to
5.5, and most preferably from about pH 2 to pH 5 and especially
from about pH 3.5 to about pH 4.5 further improvements in color
development are acheived.
Oxidative Dye Precursors
[0088] In general terms, oxidative dye primary intermediates
include those monomeric materials which, on oxidation, form
oligomers or polymers having extended conjugated systems of
electrons in their molecular structure. Because of the new
electronic structure, the resultant oligomers and polymers exhibit
a shift in their electronic spectra to the visible range and appear
colored. For example, oxidative primary intermediates capable of
forming colored polymers include materials such as aniline, which
has a single functional group and which, on oxidation, forms a
series of conjugated imines and quinoid dimers, trimers, etc.
ranging in color from green to black. Compounds such as
p-phenylenediamine, which has two functional groups, are capable of
oxidative polymerization to yield higher molecular weight colored
materials having extended conjugated electron systems. Oxidative
dyes known in the art can be used in the low pH compositions
according to the present invention. A representative list of
primary intermediates and secondary couplers suitable for use
herein is found in Sagarin, "Cosmetic Science and Technology","
Interscience, Special Ed. Vol. 2 pages 308 to 310. It is to be
understood that the primary intermediates detailed below are only
by way of example and are not intended to limit the compositions
and processes herein.
[0089] The typical aromatic diamines, polyhydric phenols, amino
phenols, and derivatives thereof, described above as primary
intermediates can also have additional substituents on the aromatic
ring, e.g. halogen, aldehyde, carboxylic acid, nitro, sulfonic acid
and substituted and unsubstituted hydrocarbon groups, as well as
additional substituents on the amino nitrogen and on the phenolic
oxygen, e.g. substituted and unsubstituted alkyl and aryl
groups.
[0090] Examples of suitable aromatic diamines, amino phenols,
polyhydric phenols and derivatives thereof, respectively, are
compounds having the general formulas (I), (II) and (III) below:
1
[0091] OR 2
[0092] wherein Y is hydrogen, halogen, (e.g. fluorine, chlorine,
bromine or iodine), nitro, amino, hydroxyl, 3
[0093] --COOM or --SO.sub.3M (where M is hydrogen or an alkali or
alkaline earth metal, ammonium, or substituted ammonium wherein one
or more hydrogens on the ammonium ion is replaced with a 1 to 3
carbon atom alkyl or hydroxyalkyl radical), wherein R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are the same or different from each
other and are selected from the group consisting of hydrogen,
C.sub.1 to C.sub.4 alkyl or alkenyl and C.sub.6 to C.sub.9 aryl,
alkaryl or aralkyl, and R.sub.5 is hydrogen, C.sub.1 to C.sub.4
unsubstituted or substituted alkyl or alkenyl wherein the
substituents are selected from those designated as Y, above, or
C.sub.6 to C.sub.9 unsubstituted or substituted aryl, alkaryl or
aralkyl wherein the substituents are selected from those defined as
Y, above. Since the precursors of formula (I) are amines, they can
be used herein in the form of peroxide-compatible salts, as noted,
wherein X represents peroxide-compatible anions of the type herein
before detailed. The general formula of the salt indicated is to be
understood to encompass those salts having mono-, di-, and
tri-negative anions.
[0094] Specific examples of formula (I) compounds are:
o-phenylenediamine, m-phenylenediamine, p-phenylenediamine,
2-chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine,
4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine,
1,3,5-triaminobenzene, 2-hydroxy-p-phenylenediamine,
2,4-diaminobenzoic acid, sodium 2,4-diaminobenzoate, calcium
di-2,4-diaminobenzoate, ammonium 2,4-diaminobenzoate,
trimethylammonium 2,4-, diaminobenzoate,
tri-(2-hydroxyethyl)ammonium 2,4-diaminobenzoate,
2,4-diaminobenzaldehyde carbonate, 2,4-diaminobenzensulfonic acid,
potassium 2,4-diaminobenzenesulfonate, N,N-diisopropyl-p-,
phenylenediamine bicarbonate, N,N-dimethyl-p-phenylenediamine,
N-ethyl-N'-(2-propenyl)-p-p- henylenediamine,
N-phenyl-p-phenylenediamine, N-phenyl-N-benzyl-p-phenylen-
ediamine, N-ethyl-N'-(3-ethylphenyl)-p-phenylenediamine,
2,4-toluenediamine, 2-ethyl-p-phenylenediamine,
2-(2-bromoethyl)-p-phenyl- enediamine, 2-phenyl-p-phenylenediamine
laurate, 4-(2,5-diaminophenyl)benz- aldehyde,
2-benzyl-p-phenylenediamine acetate, 2-(4-nitrobenzyl)-p-phenyle-
nediamine, 2-(4-methylphenyl)-p-phenylenediamine,
2-(2,5-diaminophenyl)-5-- methylbenzoic acid,
methoxyparaphenylenediamine, dimethyl-p-phenylenediami- ne,
2,5-dimethylpara-phenylenediamine,
2-methyl-5-methoxy-para-phenylenedi- amine,
2,6-methyl-5-methoxy-para-phenylenediamine,
3-methyl-4-amino-N,N-di- ethylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
3-methyl-4-amino-N,N-bis(.beta.-hydroxyethyl)aniline,
3-chloro-4-amino-N,N-bis(.beta.-hydroxyethyl)aniline,
4-amino-N-ethyl-N-(carbamethyl)aniline,
3-methyl-4-amino-N-ethyl-N-(carba- methyl )aniline,
4-amino-N-ethyl-(.beta.-piperidonoethyl)aniline,
3-methyl-4-amino-N-ethyl-(.beta.-piperidonoethyl)aniline,
4-amino-N-ethyl-N-(.beta.-morpholinoethyl)aniline,
3-methyl-4-amino-N-ethyl-N-(.beta.-morpholinoethyl)aniline,
4-amino-N-ethyl-N-(.beta.-acetylaminoethyl)aniline,
4-amino-N-(.beta.-methoxyethyl) aniline,
3-methyl-4-amino-N-ethyl-N-(.bet- a.-acetylaminoethyl) aniline,
4-amino-N-ethyl-N-(.beta.-mesylaminoethyl) aniline,
3-methyl-4-amino-N-ethyl-N-(.beta.-mesylaminoethyl) aniline,
4-amino-N-ethyl-N-(.beta.-sulphoethyl) aniline,
3-methyl-4-amino-N-ethyl-- N-(.beta.-sulphoethyl) aniline,
N-(4-aminophenyl)morpholine, N-(4-aminophenyl)piperidine,
2,3-dimethyl-p-phenylenediamine, isopropyl-p-phenylenediamine,
N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulphate.
[0095] In highly preferred compositions according to the present
invention the materials having general formulae (Ia) and (Ib) are
preferred. 4
[0096] except where R.sub.1.dbd.R.sub.2.dbd.Me, Et 5
[0097] and salt
[0098] except where R.sub.1.dbd.R.sub.2.dbd.Me
[0099] wherein Y is hydrogen, halogen, (e.g. fluorine, chlorine,
bromine or iodine), nitro, amino, hydroxyl, 6
[0100] --COOM or --SO.sub.3M (where M is hydrogen or an alkali or
alkaline earth metal, ammonium, or substituted ammonium wherein one
or more hydrogens on the ammonium ion is replaced with a 1 to 3
carbon atom alkyl or hydroxyalkyl radical), wherein RI, R.sub.2,
R.sub.3 and R.sub.4 are the same or different from each other and
are selected from the group consisting of hydrogen, C.sub.1 to
C.sub.4 alkyl or alkenyl and C.sub.6 to C.sub.9 aryl, alkaryl or
aralkyl, and R.sub.5 is hydrogen, C .sub.1 to C.sub.4 unsubstituted
or substituted alkyl or alkenyl wherein the substituents are
selected from those designated as Y, above, or C.sub.6 to C.sub.9
unsubstituted or substituted aryl, alkaryl or aralkyl wherein the
substituents are selected from those defined as Y, above. Since the
precursors of formula (I) are amines, they can be used herein in
the form of peroxide-compatible salts, as noted, wherein X
represents peroxide-compatible anions of the type herein before
detailed. The general formula of the salt indicated is to be
understood to encompass those salts having mono-, di-, and
tri-negative anions. 7
[0101] OR 8
[0102] where X and Y are the same as in formula (I), R.sub.1 and
R.sub.2) can be the same or different from each other and are the
same as in formula (I), R.sub.5 is the same as in formula (I) and
R.sub.6 is hydrogen or C.sub.1 to C.sub.4 substituted or
unsubstituted alkyl or alkenyl wherein the substituents are
selected from those defined as Y in formula (I).
[0103] Specific examples of formula (II) compounds are:
[0104] o-aminophenol, m-aminophenol, p-aminophenol,
2-iodo-p-aminophenol, 2-nitro-p-aminophenol, 3 ,4-dihydroxyaniline,
3,4-diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic acid,
2-hydroxy-4-aminobenzaldehy- de, 3-amino-4-hydroxybenzenesulfonic
acid, N,N-diisopropyl-p-aminophenol,
N-methyl-N-(1-propenyl)-p-aminophenol,
N-phenyl-N-benzyl-p-aminophenol sulphate,
N-methyl-N-(3-ethylphenyl)-p-aminophenol,
2-nitro-5-ethyl-p-aminophenol,
2-nitro-5-(2-bromoethyl)-p-aminophenol,
(2-hydroxy-5-aminophenyl)acetaldehyde, 2-methyl-p-aminophenol,
(2-hydroxy-5-aminophenyl)acetic acid,
3-(2-hydroxy-5-aminophenyl)-1-prope- ne,
3-(2-hydroxy-5-aminophenyl)-2-chloro-1-propene,
2-phenyl-p-aminophenol palmitate, 2-(4-nitrophenyl)-p-aminophenol,
2-benzyl-p-aminophenol, 2-(4-chlorobenzyl-p-aminophenol
perchlorate, 2-(4-methylphenyl)-p-aminoph- enol,
2-(2-amino-4-methylphenyl)-p-aminophenol, p-methoxyaniline,
2-bromoethyl-4-aminophenyl ether phosphate,
2-nitroethyl-4-aminophenyl ether bromide,
2-aminoethyl-4-aminophenyl ether, 2-hydroxyethyl-4-aminoph- enyl
ether, (4-aminophenoxy)acetaldehyde, (4-aminophenoxy)acetic acid,
(4-aminophenoxy)methanesulfonic acid, 1-propenyl-4-aminophenyl
ether isobutyrate, (2-chloro)-1 -propenyl-4-aminophenyl ether,
(2-nitro)-1-propenyl-4-aminophenyl ether,
(2-amino)-propenyl-4-aminopheny- l ether,
(2-hydroxy)-1-propenyl-4-aminophenyl ether, N-methyl-p-aminophenol,
3-methyl-4-aminophenol, 2-chloro-4-aminophenol,
3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol,
3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol,
2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol,
3-hydroxymethyl-4-aminophenol.
[0105] According to the present invention compounds having the
formula IIa are not preferred: 9
[0106] wherein: R.sub.1 is alkyl, hydroxy alkyl, carboxyalkyl or
aminoalkyl; R.sub.2 is hydrogen, alkyl or hydroxyalkyl groups;
R.sub.3 and R.sub.5 are H or --OR where R is an alkyl or
hydroxyalkyl substituents; R.sub.4 is H, alkyl or NHR'; R.sub.6 is
H, alkyl, --OR or NHR'; R' is H, alkyl, hydroxyalkyl: with the
proviso that a) only one of R.sub.4 and R.sub.6 are NHR': b)
R.sub.3 and --OR.sub.1 are not both methoxy when when R.sub.2,
R.sub.5 and R.sub.6 are H and R.sub.4 is NH.sub.2; c) either
R.sub.3, or R.sub.4, or R.sub.5, or R.sub.6 is H; d) R.sub.3,
R.sub.4 and R.sub.5 are not all H when R.sub.6 is NH.sub.2, R.sub.2
is H and R.sub.1 is methyl; e) if R1 is ethyl and R2, R3, R4 and R6
are H, R.sub.4 is not NH.sub.2; f) if R.sub.1 is carboxyalkyl or
aminoalkyl, R.sub.4 is NHR'. 10
[0107] Specific examples of formula (III) compounds are:
[0108] o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol),
p-hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-methoxyphenol,
4-(2-chloroethoxy) phenol, 4-(2-propenoxy) phenol,
4-(3-chloro-2-propenoxy) phenol, 2-chloro-4-hydroxyphenol
(2-chlorohydroquinone),
2-nitro-4-hydroxyphenol(2-nitrohydroquinone),
2-amino-4-hydroxyphenol, 1,2,3-trihydroxybenzene (pyrogallol),
2,4-dihydroxybenzaldehyde, 3,4-dihydoxybenzoic acid,
2,4-dihydroxybenzenesulfonic acid, 3-ethyl-4-hydroxyphenol,
3-(2-nitroethyl)-4-hydroxyphenol, 3-(2-propenyl)-4-hydroxyphenol,
3-(3-chloro-2-propenyl)-4-hydroxyphenol, 2-phenyl-4-hydroxyphenol,
2-(4-chlorophenyl)-4-hydroxyphenol, 2-benzyl-4-hydroxyphenol,
2-(2-nitrophenyl)-4-hydroxyphenol,
2-(2-methylphenyl)-4-hydroxyphenol,
2-(2-methyl-4-chlorophenyl)-4-hydroxyphenol,
3-methoxy-4-hydroxy-benzalde- hyde, 2-methoxy-4-( 1
-propenyl)phenol, 4-hydroxy-3-methoxycinnamic acid,
2,5-dimethoxyaniline, 2-methylresorcinol, alpha napthol and salts
thereof.
[0109] In preferred compositions herein the following compound,
having general formula (III) is not included: 11
[0110] Secondary coupling compounds (color modifiers), such as
those detailed hereinafter, are preferably used in conjunction with
the primary intermediates herein and are thought to interpose
themselves in the colored polymers during their formation and to
cause shifts in the electronic spectra thereof, thereby resulting
in slight color changes.
[0111] Secondary coupling compounds which are suitable for
inclusion in the coloring compositions and processes herein before
described include certain aromatic amines and phenols and
derivatives thereof which do not produce color singly, but which
modify the color, shade or intensity of the colors developed by the
primary oxidized dye intermediates. Certain aromatic amines and
phenolic compounds, and derivatives thereof, including some
aromatic diamines and polyhydric phenols of the types described by
formulas (I), (Ia), (Ib), (II) and (III) above, but which are well
known in the art not to be suitable primary intermediates, are
suitable as couplers herein. Polyhydric alcohols are also suitable
for use as couplers herein.
[0112] The aromatic amines and phenols and derivatives described
above as couplers can also have additional substituents on the
aromatic ring, e.g., halogen, aldehyde, carboxylic acid, nitro,
sulfonyl and substituted and unsubstituted by hydrocarbon groups,
as well as additional substituents on the amino nitrogen, or
phenolic oxygen, e.g. substituted and unsubstituted alkyl and aryl
groups. Again, peroxide-compatible salts thereof are suitable for
use herein.
[0113] Examples of aromatic amines, phenols and derivatives thereof
are compounds of the general formulas (IV) and (V) below: 12
[0114] OR 13
[0115] wherein Z is hydrogen, C.sub.1 and C.sub.3 alkyl, halogen
(e.g. fluorine, chlorine, bromine or iodine) nitro, 14
[0116] --COOM or SO.sub.3M, (where M is hydrogen or an alkali or
alkaline earth metal, ammonium or substituted ammonium wherein one
or more hydrogens on the ammonium ion is replaced with a 1 to 3
carbon atom alkyl or hydroxyalkyl radical), wherein R.sub.1 and
R.sub.2 are the same or different and are selected from the group
consisting of hydrogen, C.sub.1 to C.sub.4 alkyl or alkenyl and
C.sub.6 to C.sub.9 aryl, alkaryl or aralkyl and R.sub.7 is
hydrogen, C.sub.1 to C.sub.4 unsubstituted or substituted alkyl or
alkenyl wherein the substituents are selected from those designated
as Z above or C.sub.6 to C.sub.9 unsubstituted or substituted aryl,
alkaryl or aralkyl wherein the substituents are selected from those
defined as Z above and wherein X is as defined in formula (I).
[0117] Specific examples of formula (IV) compounds are:
[0118] aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline,
p-aminobenzaldehyde, p-aminobenzoic acid, sodium-p-aminobenzoate,
lithium-p-aminobenzoate, calcium di-p-aminobenzoate,
ammonium-p-aminobenzoate, trimethylammonium-p-aminobenzoate,
tri(2-hydroxyethyl)-p-aminobenzoate, p-aminobenzenesulfonic acid,
potassium p-aminobenzenesulfonate, N-methylaniline,
N-propyl-N-phenylaniline, N-methyl-N-2-propenylaniline,
N-benzylaniline, N-(2-ethylphenyl)aniline, 4-methylaniline,
4-(2-bromoethyl)aniline, 2-(2-nitroethyl)aniline,
(4-aminophenyl)acetaldehyde, (4-aminophenyl)acetic acid,
4-(2-propenyl)aniline acetate, 4-(3-bromo-2-propenyl)aniline,
4-phenylaniline chloroacetate, 4-(3-chlorophenyl)aniline,
4-benzylaniline, 4-(4-iodobenzyl)aniline, 4-(3-ethylphenyl)aniline,
4-(2-chloro-4-ethylphenyl)aniline. 15
[0119] wherein Z and R.sub.7 are defined as in formula (IV) and
R.sub.8 is hydrogen or C.sub.1 to C.sub.4 substituted or
unsubstituted alkyl or alkenyl wherein the substituents are
selected from those defined as Z in formula (IV).
[0120] Specific examples of formula (V) compounds are:
[0121] phenol, p-chlorophenol, p-nitrophenol,
p-hydroxybenzaldehyde, p-hydroxybenzoic acid,
p-hydroxybenzenesulfonic acid, ethylphenyl ether,
2-chloroethylphenyl ether, 2-nitroethylphenyl ether,
phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-1-propene,
3-phenoxy-2-nitro-1-propene, 3-phenoxy-2-bromo-1-propene,
4-propylphenol, 4-(3-bromopropvl)phenol, 2-(2-nitroethyl)phenol,
(4-hydroxyphenyl)acetaldehyde, (4-hydroxyphenyl)acetic acid,
4-(2-propenyl)phenol, 4-phenylphenol, 4-benzylphenol,
4-(3-fluoro-2-propenyl)phenol, 4-(4-chlorobenzyl)phenol,
4-(3-ethylphenyl)phenol, 4-(2-chloro-3-ethylphenyl)phenol,
2,5-xylenol, 2,5-diaminopyridine, 2-hydroxy-5-aminopyridine,
2-amino-3-hydroxy pyridine, tetraaminopyrimindine,
1,2,4-trihydroxybenzene,
1,2,4-trihydroxy-5-(C.sub.1-C.sub.6-alkyl)benzene,
1,2,3-trihydroxybenzene, 4-aminoresorcinol, 1,2-dihydroxybenzene,
2-amino-1,4-dihydroxybenzene, 2-amino-4-methoxy-phenol,
2,4-diaminophenol, 3-methoxy-1,2-dihydroxy-benzene,
1,4-dihydroxy-2-(N,N-diethylamino)benzene,
2,5-diamino-4-methoxy-1-hydrox- ybenzene,
4,6-dimethoxy-3-amino-1-hydroxybenzene, 2,6-dimethyl-4-[N-(p-hyd-
roxyphenyl)amino]-1-hydroxybenzene,
1,5-diamino-2-methyl-4-[N-(p-hydroxyph- enyl)amino]benzene and
salts thereof.
[0122] In preferred compositions suitable for use herein the
following combination of primary intermediates and couplers are
excluded: 16
[0123] Where R.sub.1 and R.sub.2 are not H
[0124] in combination with m-aminophenol, resorcinol,
2-methyl-5-aminophenol, 2-metylresorcinol and mixtures thereof.
[0125] Additional primary intermediates suitable for use herein
include catechol species and in particular catechol "dopa" species
which includes dopa itself as well as homologs, analogs and
derivatives of DOPA. Examples of suitable cachetol species include
cysteinyl dopa, alpha alkyl dopa having 1 to 4, preferably 1 to 2
carbon atoms in the alkyl group, epinephrine and dopa alkyl esters
having 1 to 6 , preferably 1 to 2 carbon atoms in the alkyl
group.
[0126] In general suitable catechols are represented by formula
(VI) below: 17
[0127] wherein R.sub.1, R.sub.2 and R.sub.3, which may be the same
or different, are electron donor or acceptor substutuents selected
from H, lower (C.sub.1-C.sub.6) alkyl, OH, OR, COOR, NHCOR, CN,
COOH, Halogen, NO.sub.2, CF.sub.3, SO.sub.3H or NR.sub.4R.sub.5,
with the proviso that only one of the R.sub.1, R.sub.2 or R.sub.3
can be CN, COOH, halogen, NO.sub.2, CF.sub.3 or SO.sub.3H: R.sub.4
and R.sub.5, which may be the same or different, are H, lower
(C.sub.1-C.sub.6) alkyl or substituted lower (C.sub.1-C.sub.6)
alkyl in which the substituent may be OH, OR, NHCOR.sub.6,
NHCONH.sub.2, NHCO.sub.2R.sub.6, NHCSNH.sub.2, CN, COOH, SO.sub.3H,
SO.sub.2NR.sub.6, SO.sub.2R.sub.6 or CO.sub.2R.sub.6; R.sub.6 is
lower (C.sub.1-C.sub.6) alkyl, lower (C.sub.1-C.sub.6) hydroxyalkyl
phenyl linked to the nitrogen by an alkylene chain, phenyl or
substituted phenyl with the substituent defined as R.sub.1, and R
is C.sub.1-C.sub.6 alkyl or C.sub.1-C.sub.6 hydroxyalkyl.
[0128] Also included herein are oxidative hair coloring agents of
the formula: 18
[0129] wherein: R.sub.1=substituted or unsubstituted benzene ring,
tertiary-butyl, etc.; R=substituted or unsubstituted benzene ring
and the formula: 19
[0130] wherein R=aminoalkyl, amidoalkyl, aminobenzene (substituted
or unsubstituted), amidobenzene (substituted or unsubstituted),
alkyl, substituted or unsubstituted benzene ring;
R.sub.1=substituted or unsubstituted benzene ring.
[0131] The primary intermediates can be used herein alone or in
combination with other primary intermediates, and one or more can
be used in combination with one or more couplers. The choice of
primary intermediates and couplers will be determined by the color,
shade and intensity of coloration which is desired. There are
nineteen preferred primary intermediates and couplers which can be
used herein, singly or in combination, to provide dyes having a
variety of shades ranging from ash blonde to black; these are:
pyrogallol, resorcinol, p-toluenediamine, p-phenylenediamine,
o-phenylenediamine, m-phenylenediamine, o-aminophenol,
p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine,
N-phenyl-p-phenylenediamine, m-aminophenol,
2-amino-3-hydroxypyridine, 1-napthol, N,N bis
(2-hydroxyethyl)p-phenylene- diamine, 4-amino-2-hydroxytoluene,
1,5-dihydroxynapthalene, 2-methyl resorcinol and
2,4-diaminoanisole. These can be used in the molecular form or in
the form of peroxide-compatible salts, as detailed above.
[0132] The primary intermediates and coupling compounds as
aforementioned herein may be combined to deliver a wide variety of
colors to the hair. The hair colors can vary by both depth of color
and intensity of color. As hereinbefore described the compositions
according to the present invention are valuable for the provision
of high intensity colors. Intensity of color as defined herein
means the quantity of color compound formed on and retained in the
hair. In general, high intensity as defined herein means dark or
deep colors such as dark red, dark brown or black etc. In
accordance, with the above it is possible to formulate hair colors
of varying color intensity by adjusting the initial levels of each
of the oxidative dyeing materials.
[0133] For example low intensity colors such as natural blond to
light brown hair shades generally comprise from about 0.001% to
about 5%, preferably from about 0.1% to about 2%, more preferably
from about 0.2% to about 1% by weight of coloring composition of
total oxidative dyeing agents and may be achieved by the
combination of primary intermediates such as 1,4-diamino-benzene,
2,5-diamino toluene, 2,5-diamino-anisole, 4-aminophenol,
2,5-diamino-benzyl alcohol and 2-(2',5'-diamino)phenyl-eth- anol
with couplers such as resorcinol, 2-methyl resorcinol or 4-chloro
resorcinol.
[0134] Similarly combination of the above primary intermediates
with couplers, such as, 5-amino-2-methyl phenol and
1,3-diamino-benzene derivatives such as 2,4-diamino-anisole at
levels of from about 0.5% to about 1% of total dyeing agents can
lead to medium intensity red colors. High intensity colors such as
blue to blue-violet hair shades can be produced by the combination
of the above primary intermediates with couplers such as
1,3-diamino-benzene or its derivatives such as 2,5-diamino-toluene
at levels of from about 1% to about 6% by weight of composition of
total dyeing agents. Black hair colors can be obtained by combining
the aforementioned primary intermediates with couplers such as
1,3-diaminobenzene or its derivatives
[0135] However considerations have been raised against the
physiological compatibility of para-amino phenol which is commonly
used to impart red colors to the hair. Similarly, the physiological
compatibility of some of the agents favoured for the production of
black color such as paraphenylene diamine (PPD) has been called
into question. Thus a need exists for oxidative hair coloring
compositions which have an improved safety profile and in
particular oxidative hair compositions for the delivery of dark
colors i.e. high color intensity dyes, which have an improved
safety profile. As discussed herein before, the low pH compositions
of the present invention provide excellent hair coloring attributes
in combination with reduced levels of hair damage and skin staining
and/or irritation.
[0136] As such the compositions according to the present invention
are valuable for the delivery of improved hair condition attributes
in combination with good initial color development and consistency
and improved wash fastness over time in addition to having reduced
levels of hair damage and skin irritation and/or staining.
Non-oxidative and Other Dyes
[0137] The hair coloring compositions of the present invention may,
in addition to the essential oxidative hair coloring agents,
optionally include non-oxidative and other dye materials. Optional
non-oxidative and other dyes suitable for use in the hair coloring
compositions and processes according to the present invention
include both semi-permanent, temporary and other dyes.
Non-oxidative dyes as defined herein include the so-called `direct
action dyes`, metallic dyes, metal chelate dyes, fibre reactive
dyes and other synthetic and natural dyes. Various types of
non-oxidative dyes are detailed in: `Chemical and Physical
Behaviour of Human Hair` 3rd Ed. by Clarence Robbins (pp250-259);
`The Chemistry and Manufacture of Cosmetics`. Volume IV. 2nd Ed.
Maison G. De Navarre at chapter 45 by G. S. Kass (pp841-920);
`cosmetics: Science and Technology` 2nd Ed., Vol. II Balsam
Sagarin, Chapter 23 by F. E. Wall (pp 279-343); `The Science of
Hair Care` edited by C. Zviak, Chapter 7 (pp 235-261) and .`Hair
Dyes`, J. C. Johnson, Noyes Data Corp., Park Ridge, U.S.A. (1973),
(pp 3-91 and 113-139).
[0138] 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.
[0139] Nitrodyes are added to dyeing compositions to enhance colour
of colorant and to add suitable aesthetic colour to the dye mixture
prior to application.
[0140] Further examples of 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.--10,345; basic violet 1, C.I.--42,535,
basic violet 3, C.I.--42,555; greenish blue, C.I.--42090 (FD&C
Blue no.1); yellowish red, C.I.--14700 (FD&C red no.4); yellow,
C.I.19140 (FD&C yellow no5); yellowish orange, C.I.15985
(FD&C yellow no.6); bluish green, C.I.42053 (FD&C green
no.3); yellowish red, C.I.16035 (FD&C red no.40); bluish green,
C.I.61570 (D&C green no.3); orange, C.I.45370 (D&C orange
no.5); red, C.I.15850 (D&C red no.6); bluish red,
C.I.15850(D&C red no.7); slight bluish red, C.1.45380(D&C
red no.22); bluish red, C.I.45410(D&C red no.28); bluish red,
C.I.73360(D&C red no.30); reddish purple, C.I.17200(D&C red
no.33); dirty blue red, C.I.15880(D&C red no.34); bright yellow
red, C.I.12085(D&C red no.36); bright orange, C.I.15510(D&C
orange no.4); greenish yellow, C.1.47005(D&C yellow no.10);
bluish green, C.I.59040(D&C green no.8); bluish violet,
C.I.60730(Ext. D&C violet no.2); greenish yellow,
C.I.10316(Ext. D&C yellow no.7);
[0141] Fibre reactive dyes include the Procion (RTM), Drimarene
(RTM), Cibacron (RTM), Levafix (RTM) and Remazol (RTM) dyes
available from ICI, Sandoz, Ciba-Geigy, Bayer and Hoechst
respectively.
[0142] Natural dyes and vegetable dyes as defined herein include
henna (Lawsonia alba+L), camomile (Matricaria chamomila or Anthemis
nobilis), indigo, logwood and walnut hull extract.
[0143] Temporary hair dyes, or hair coloring rinses, are generally
comprised of dye molecules which are too large to diffuse into the
hair shaft and which act on the exterior of the hair. They are
usually applied via a leave-in procedure in which the dye solution
is allowed to dry on the hair surface. As such these dyes are
typically less resistant to the effects of washing and cleaning the
hair with surface active agents and are washed off of the hair with
relative ease. Any temporary hair dye may suitably be used in the
compositions of the invention and examples of preferred temporary
hair dyes are illustrated below. 20
[0144] 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. Typically,
semi-permanent dyes act in a similar manner to oxidative dyes in
that they have the potential to diffuse into the hair shaft.
However, semi-permanent dyes are generally smaller in size than the
aforementioned conjugated oxidative dye molecules and as such are
pre-disposed to gradual diffusion out of the hair again. Simple
hair washing and cleaning action will encourage this process and in
general semi-permanent dyes are largely washed out of the hair
after about 5 to 8 washes. Any semi-permanent dye system may be
suitably used in the compositions of the present invention.
Suitable semi-permanent dyes for use in the compositions of the
present invention are HC Blue 2, HC Yellow 4, HC Red 3, Disperse
Violet 4, Disperse Black 9, HC Blue 7, HC Yellow 2, Disperse Blue
3, Disperse violet 1 and mixtures thereof. Examples of
semi-permanent dyes are illustrated below: 21
[0145] Typical semi-permanent dye systems incorporate mixtures of
both large and small color molecules. As the size of the hair is
not uniform from root to tip the small molecules will diffuse both
at the root and tip, but will not be retained within the tip, while
the larger molecules will be generally only be able to diffuse into
the ends of the hair. This combination of dye molecule size is used
to help give consistent color results from the root to the tip of
the hair both during the initial dyeing process and during
subsequent washing.
Buffering Agents
[0146] The coloring compositions of the present invention have a pH
in the range of from about 1 to about 6 , preferably from about 1.5
to about 5.8, more preferably from about 1.8 to about 5.5, most
preferably from about 2 to about 5 and especially from about 3.5 to
about 4.5.
[0147] As herein before described the pH of the preferred coloring
compositions of the present invention are maintained within the
desired pH range via the action of the inorganic peroxygen
oxidising agent. However, if so desired, the compositions may
contain one or more optional buffering agents and/or hair swelling
agents (HSAs). Several different pH modifiers can be used to adjust
the pH of the final composition or any constituent part
thereof.
[0148] 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/phosphori- c 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, succinic acid and
mixtures thereof.
[0149] Examples of alkaline buffering agents are ammonium
hydroxide, ethylamine, dipropylamine, triethylamine and
alkanediamines such as 1,3-diaminopropane, anhydrous alkaline
alkanolamines such as, mono or di-ethanolamine, preferably those
which are completely substituted on the amine group such as
dimethylaminoethanol, polyalkylene polyamines such as
diethylenetriamine or a heterocyclic amine such as morpholine as
well as the hydroxides of alkali metals, such as sodium and
potassium hydroxide, hydroxides of alkali earth metals, such as
magnesium and calcium hydroxide, basic amino acids such as
L-argenine, lysine, alanine, leucine, iso-leucine, oxylysine and
histidine and alkanolamines such as dimethylaminoethanol and
aminoalkylpropanediol and mixtures thereof. Also suitable for use
herein are compounds that form HCO.sub.3-- by dissociation in water
(hereinafter referred to as `ion forming compounds`). Examples of
suitable ion forming compounds are Na.sub.2CO.sub.3, NaHCO.sub.3,
K.sub.2CO.sub.3, (NH4).sub.2CO.sub.3, NH.sub.4HCO.sub.3, CaCO.sub.3
and Ca(HCO.sub.3) and mixtures thereof.
[0150] Preferred for use herein as buffering agents are organic and
inorganic acids having a first pKa below pH 6, and their conjugate
bases. As defined herein, 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, salycilic, formic, benzoic, malic, lactic,
malonic, oxalic, citric, phosphoric acid and mixtures thereof.
Particularly preferred are acetic, succinic, salycilic and
phosphoric acids and mixtures thereof.
[0151] The low pH coloring compositions according to the present
invention, may, as will be described later herein, be comprised of
a final solution containing both peroxide and a oxidative hair
coloring agents which have been admixed prior to application to the
hair or a single component system. As such, the compositions
according to the present invention may comprise coloring kits of a
number of separate components.
[0152] In oxidising and coloring kits comprising a portion of
inorganic peroxygen oxidising agent, such as hydrogen peroxide,
which may be present in either solid or liquid form, a buffering
agent solution can be used to stabilise hydrogen peroxide. Since
hydrogen peroxide is stable in the pH range from 2 to 4, it is
necessary to use a buffering agent having a pH within this range.
Dilute acids are suitable hydrogen peroxide buffering agents.
[0153] In oxidising and coloring kits comprising an oxidising agent
(which may be in solid or liquid form) in combination with one or
more coloring agents, a buffering agent capable of maintaining a
solution pH in the range of from about 1 to about 6 , preferably
from about 1.5 to about 5.8, more preferably from about 1.8 to
about 5.5, most preferably from about 2 to about 5 and especially
from about 3.5 to about 4.5. As such it is necessary to use a
buffering agent having a pH within this range.
Catalyst
[0154] The coloring compositions herein may optionally contain a
transition metal containing catalyst for the inorganic peroxygen
oxidising agents and the, optional, preformed peroxy acid oxidising
agent(s). One suitable type of catalyst is a catalyst system
comprising a heavy metal cation of defined bleach catalytic
activity, such as copper, iron or manganese cations, an auxiliary
metal cation having little or no bleach catalytic activity, such as
zinc or aluminium cations, and a sequestrant having defined
stability constants for the catalytic and auxiliary metal cations,
particularly ethylenediaminetetraacetic acid, ethylenediaminetetra
(methylenephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. No. 4,430,243.
[0155] Other types of suitable catalysts include the
manganese-based complexes disclosed in U.S. Pat. No. 5,246,621 and
U.S. Pat. No. 5,244,594. Preferred examples of these catalysts
include
Mn.sup.IV.sub.2(u-O).sub.3(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-
-(PF.sub.6).sub.2, Mn.sup.III.sub.2(u-O) 1
(u-OAc).sub.2(1,4,7-trimethyl-1-
,4,7-triazacyclononane).sub.2-(ClO.sub.4).sub.2,
Mn.sup.IV.sub.4(u-O).sub.-
6(1,4,7-triazacyclononane).sub.4-(ClO.sub.4).sub.2,
Mn.sup.IIIMn.sup.IV.sub.4(u-O).sub.1(u-OAc).sub.2-(1,4,7-trimethyl-1,4,7--
triazacyclononane).sub.2-(ClO.sub.4).sub.3, and mixtures thereof.
Others are described in EP-A-0,549,272. Other ligands suitable for
use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane,
2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane,
1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures
thereof.
[0156] For examples of suitable catalysts see U.S. Pat. No.
4,246,612 and U.S. Pat. No. 5,227,084. See also U.S. Pat. No.
5,194,416 which teaches mononuclear manganese (IV) complexes such
as Mn(1,4,7-trimethyl-1,4,7-tri-
azacyclononane)(OCH.sub.3).sub.3-(PF.sub.6). Still another type of
suitably catalyst, as disclosed in U.S. Pat. No. 5,114,606, is a
water-soluble complex of manganese (III), and/or (IV) with a ligand
which is a non-carboxylate polyhydroxy compound having at least
three consecutive C--OH groups. Other examples include binuclear Mn
complexed with tetra-N-dentate and bi-N-dentate ligands, including
N.sub.4Mn.sup.III(u-O).sub.2Mn.sup.IVN.sub.4).sup.+ and
[Bipy.sub.2Mn.sup.III(u-O).sub.2Mn.sup.IVbipy.sub.2]-(ClO.sub.4).sub.3.
[0157] Further suitable catalysts are described, for example, in
EP-A-0,408,131 (cobalt complex catalysts), EP-A-0,384,503, and
EP-A-0,306,089 (metallo-porphyrin catalysts), U.S. Pat. No.
4,728,455 (manganese/multidentate ligand catalyst), U.S. Pat. No.
4,711,748 and EP-A-0.224,952, (absorbed manganese on
aluminosilicate catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate
support with manganese and zinc or magnesium salt), U.S. Pat. No.
4,626,373 (manganese/ligand catalyst), U.S. Pat. No. 4,119,557
(ferric complex catalyst), DE-A-2,054,019 (cobalt chelant catalyst)
CA-A-866,191 (transition metal-containing salts), U.S. Pat. No.
4,430,243 (chelants with manganese cations and non-catalytic metal
cations), and U.S. Pat. No. 4,728,455 (manganese gluconate
catalysts).
Heavy Metal Ion Sequestrant
[0158] The coloring compositions of the invention may contain as an
optional component a heavy metal ion sequestrant. By heavy metal
ion sequestrant it is meant herein components which act to
sequester (chelate or scavenge) heavy metal ions. These components
may also have calcium and magnesium chelation capacity, but
preferentially they show selectivity to binding heavy metal ions
such as iron, manganese and copper. Such sequestering agents are
valuable in hair coloring compositions as herein described for the
delivery of controlled oxidising action as well as for the
provision of good storage stability of the hair coloring
products.
[0159] Heavy metal ion sequestrants are generally present at a
level of from about 0.005% to about 20%, preferably from about
0.01% to about 10%, more preferably from about 0.05 % to about 2 %
by weight of the compositions.
[0160] Various sequestering agents, including the amino
phosphonates, available as Dequest (RTM) from Monsanto, the
nitriloacetates, the hydroxyethyl-ethylene triamines and the like
are known for such use. Suitable heavy metal ion sequestrants for
use herein include organic phosphonates, such as the amino alkylene
poly (alkylene phosphonates), alkali metal ethane 1-hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
[0161] Preferred among the above species are diethylene triamine
penta (methylene phosphonate), ethylene diamine tri (methylene
phosphonate) hexamethylene diamine tetra (methylene phosphonate)
and hydroxy-ethylene 1,1 diphosphonate.
[0162] Preferred biodegradable non-phosphorous heavy metal ion
sequestrants suitable for use herein include nitrilotriacetic acid
and polyaminocarboxylic acids such as ethylenediaminotetracetic
acid, ethylenetriamine pentaacetic acid, ethylenediamine disuccinic
acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic acid or any salts thereof. Especially preferred is
ethylenediamine-N,N'-disuccinic acid (EDDS). see U.S. Pat. No.
4,704,233, or the alkali metal, alkaline earth metal, ammonium, or
substituted ammonium salts thereof, or mixtures thereof.
[0163] Other suitable heavy metal ion sequestrants for use herein
are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic
acid or glyceryl imino diacetic acid, described in EP-A-317,542 and
EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic
acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic
acid sequestrants described in EP-A-516,102 are also suitable
herein. The .beta.-alanine-N,N'-diaceti- c acid, aspartic
acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and
iminodisuccinic acid sequestrants described in EP-A-509,382 are
also suitable.
[0164] EP-A-476,257 describes suitable amino based sequestrants.
EP-A-510,331 describes suitable sequestrants derived from collagen,
keratin or casein. EP-A-528,859 describes a suitable alkyl
iminodiacetic acid sequestrant. Dipicolinic acid and
2-phosphonobutane-1,2,4-tricarboxy- lic acid are also suitable.
Glycinamide-N,N'-disuccinic acid (GADS),
ethylenediamine-N-N'-diglutaric acid (EDDG) and
2-hydroxypropylenediamine- -N-N'-disuccinic acid (HPDDS) are also
suitable.
[0165] The heavy metal ion sequestering agents of the present
invention may be used in their alkali or alkaline earth metal
salts.
Thickeners
[0166] The coloring compositions of the present invention may
additionally include a thickener at a level of from about 0.05% to
about 20%, preferably from about 0.1% to about 10%, more preferably
from about 0.5% to about 5% by weight. Thickening agents suitable
for use in the compositions herein are selected from oleic acid,
cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol,
stearyl alcohol, synthetic thickeners such as Carbopol, Aculyn and
Acrosyl and mixtures thereof. Preferred thickeners for use herein
are Aculyn 22 (RTM), steareth-20 methacrylate copolymer; Aculyn 44
(RTM) polyurethane resin and Acusol 830 (RTM), acrylates copolymer
which are available from Rohm and Haas, Philadelphia, Pa., USA.
Additional thickening agents suitable for use herein include sodium
alginate or gum arabic, or cellulose derivatives, such as methyl
cellulose or the sodium salt of carboxymethylcellulose or acrylic
polymers.
Diluent
[0167] Water is the preferred diluent for the compositions
according to the present invention. However, the compositions
according to the present invention may include one or more solvents
as additional diluent materials. Generally, solvents 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.sub.1-C.sub.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. Thus, a preferred group includes
ethanol, isopropanol, n-propanol, butanol, propylene glycol,
ethylene glycol monoethyl ether, and mixtures thereof. Water is the
preferred principal diluent in the compositions according to the
present invention. Principal diluent, as defined herein, means,
that the level of water present is higher than the total level of
any other diluents.
[0168] 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.
Enzyme
[0169] A further additional material useful in the hair coloring
compositions according to the present invention is one or more
enzymes.
[0170] Suitable enzymatic materials include the commercially
available lipases, cutinases, amylases, neutral and alkaline
proteases, esterases, cellulases, pectinases, lactases and
peroxidases conventionally incorporated into detergent
compositions. Suitable enzymes are discussed in U.S. Pat. Nos.
3,519,570 and 3,533,139.
[0171] 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.sub.2O.sub.2. The decomposition
of H.sub.2O.sub.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.sub.2O.sub.2
among other acceptors, and the coenzyme peroxidases resemble these
rather than the classical peroxidases in not being specific for
H.sub.2O.sub.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.
[0172] Enzymes are optionally incorporated at levels sufficient to
provide up to about 50 mg by weight, more typically about 0.1 mg to
about 10 mg of active enzyme per gramm of the hair treatment
composition of the invention. Stated otherwise the peroxidase
enzyme may be incorporated into the compositions in accordance with
the invention at a level of from about 0.0001% to about 5%,
preferably from about 0.001% to about 1%, more preferably from
about 0.01% to about 1% active enzyme by weight of the
composition.
[0173] Commercially available 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.
[0174] Amylases include, for example, .alpha.-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
0.000 1% to 2% active enzyme by weight of the composition.
[0175] 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 Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are
also useful herein. A preferred lipase is derived from Pseudomonas
pseudoalcalipenes, which is described in Granted European Patent,
EP-B-0218272.
[0176] 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. Pat. No. 4,810,414,
Huge-Jensen et al, issued Mar. 7, 1989.
Surfactant Materials
[0177] The compositions of the present invention can additionally
contain a surfactant system. Suitable surfactants for inclusion in
the compositions of the invention generally have a lipophilic chain
length of from about 8 to about 22 carbon atoms and can be selected
from anionic, cationic, nonionic, amphoteric, zwitterionic
surfactants and mixtures thereof.
[0178] (i) Anionic Surfactants
[0179] Anionic surfactants suitable for inclusion in the
compositions of the invention include alkyl sulphates, ethoxylated
alkyl sulphates, alkyl glyceryl ether sulfonates, methyl acyl
taurates, fatty acyl glycinates, N-acyl glutamates, acyl
isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosuccinates,
alpha-sulfonated fatty acids, their salts and/or their esters,
alkyl ethoxy carboxylates, alkyl phosphate esters, ethoxylated
alkyl phosphate esters, alkyl sulphates, acyl sarcosinates and
fatty acid/protein condensates, and mixtures thereof. Alkyl and/or
acyl chain lengths for these surfactants are C.sub.12-C.sub.22,
preferably C.sub.12-C.sub.18 more preferably C.sub.12-C.sub.14.
[0180] (ii) Nonionic Surfactants
[0181] The compositions of the invention can also comprise
water-soluble nonionic surfactant(s). Surfactants of this class
include C.sub.12-C.sub.14 fatty acid mono-and diethanolamides,
sucrose polyester surfactants and polyhydroxy fatty acid amide
surfactants having the general formula below. 22
[0182] The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy
fatty acid amide surfactants according to the above formula are
those in which R.sub.8 is C.sub.5-C.sub.31 hydrocarbyl, preferably
C.sub.6-C.sub.19 hydrocarbyl, including straight-chain and branched
chain alkyl and alkenyl, or mixtures thereof and R.sub.9 is
typically hydrogen, C.sub.1-C.sub.8 alkyl or hydroxyalkyl,
preferably methyl, or a group of formula --R.sup.1--O--R.sup.2
wherein R.sup.1 is C.sub.2-C.sub.8 hydrocarbyl including
straight-chain, branched-chain and cyclic (including aryl), and is
preferably C.sub.2-C.sub.4 alkylene, R.sup.2 is C.sub.1-C.sub.8
straight-chain, branched-chain and cyclic hydrocarbyl including
aryl and oxyhydrocarbyl, and is preferably C.sub.1-C.sub.4 alkyl,
especially methyl, or phenyl. Z.sub.2 is a polyhydroxyhydrocarbyl
moiety having a linear hydrocarbyl chain with at least 2 (in the
case of glyceraldehyde) or at least 3 hydroxyls (in the case of
other reducing sugars) directly connected to the chain, or an
alkoxylated derivative (preferably ethoxylated or propoxylated)
thereof. Z.sub.2 preferably will be derived from a reducing sugar
in a reductive amination reaction, most preferably Z.sub.2 is a
glycityl moiety. Suitable reducing sugars include glucose,
fructose, maltose, lactose, galactose, mannose, and xylose, as well
as glyceraldehyde. As raw materials, high dextrose corn syrup, high
fructose corn syrup, and high maltose corn syrup can be utilised as
well as the individual sugars listed above. These corn syrups may
yield a mix of sugar components for Z.sub.2. It should be
understood that it is by no means intended to exclude other
suitable raw materials. Z.sub.2 preferably will be selected from
the group consisting of --CH.sub.2--(CHOH).sub.n--CH.sub.2OH,
--CH(CH.sub.2OH)--(CHOH).sub.n-1--C- H.sub.2H,
CH.sub.2(CHOH).sub.2(CHOR')CHOH)--CH.sub.2OH, where n is an integer
from 1 to 5, inclusive, and R' is H or a cyclic mono- or
polysaccharide, and alkoxylated derivatives thereof. As noted, most
preferred are glycityls wherein n is 4, particularly
--CH.sub.2--(CHOH).sub.4--CH.sub.2OH.
[0183] The most preferred polyhydroxy fatty acid amide has the
formula R.sub.8(CO)N(CH.sub.3)CH.sub.2(CHOH).sub.4CH.sub.2OH
wherein R.sub.8 is a C6-C19 straight chain alkyl or alkenyl group.
In compounds of the above formula, R.sub.8--CO--N< can be, for
example, cocoamide, stearamide, oleamide, lauramide, myristamide,
capricamide, palmiamide, tallowamide, etc.
[0184] Suitable oil derived nonionic surfactants for use herein
include water soluble vegetable and animal-derived emollients such
as triglycerides with a polyethyleneglycol chain inserted;
ethoxylated mono and di-glycerides, polyethoxylated lanolins and
ethoxylated butter derivatives. One preferred class of oil-derived
nonionic surfactants for use herein have the general formula
below:
O
RCOCH.sub.2CH(OH)CH.sub.2(OCH.sub.2CH.sub.2).sub.nOH
[0185] wherein n is from about 5 to about 200, preferably from
about 20 to about 100, more preferably from about 30 to about 85,
and wherein R comprises an aliphatic radical having on average from
about 5 to 20 carbon atoms, preferably from about 7 to 18 carbon
atoms.
[0186] Suitable ethoxylated oils and fats of this class include
polyethyleneglycol derivatives of glyceryl cocoate, glyceryl
caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate,
glyceryl stearate, glycervl 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.
[0187] Preferred for use herein are polyethyleneglycol based
polyethoxylated C.sub.9-C.sub.15 fatty alcohol nonionic surfactants
containing an average of from about 5 to about 50 ethyleneoxy
moieties per mole of surfactant.
[0188] Suitable polyethylene glycol based polyethoxylated
C.sub.9-C.sub.15 fatty alcohols suitable for use herein include
C.sub.9-C.sub.11 Pareth-3, C.sub.9-C.sub.11 Pareth4,
C.sub.9-C.sub.11 Pareth-5, C.sub.9-C.sub.11 Pareth-6,
C.sub.9-C.sub.11 Pareth-7, C.sub.9-C.sub.11 Pareth-8,
C.sub.11-C.sub.15 Pareth-3, C.sub.11-C.sub.15 Pareth-4,
C.sub.11-C.sub.15 Pareth-5, C .sub.11-C.sub.15 Pareth-6,
C.sub.11-C.sub.15 Pareth-7, C.sub.11-C.sub.15 Pareth-8,
C.sub.11-C.sub.15 Pareth-9, C.sub.11-C.sub.15 Pareth-10,
C.sub.11-C.sub.15 Pareth-11, C.sub.11-C.sub.15 Pareth-12,
C.sub.11-C.sub.15 Pareth-13 and C.sub.11-C.sub.15 Pareth-14. PEG 40
hydrogenated castor oil is commercially available under the
tradename Cremophor (RTM) from BASF. PEG 7 glyceryl cocoate and PEG
20 glyceryl laurate are commercially available from Henkel under
the tradenames Cetiol (RTM) HE and Lamacit (RTM) GML 20
respectively. C.sub.9-C.sub.11 Pareth-8 is commercially available
from Shell Ltd under the tradename Dobanol (RTM) 91-8. Particulary
preferred for use herein are polyethylene glycol ethers of ceteryl
alcohol such as Ceteareth 25 which is available from BASF under the
trade name Cremaphor A25.
[0189] 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.
[0190] Other suitable oil-derived nonionic surfactants include
ethoxylated derivatives of almond oil, peanut oil, rice bran oil,
wheat germ oil, linseed oil, jojoba oil, oil of apricot pits,
walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade
oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil,
soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil,
olive oil, grapeseed oil, and sunflower seed oil.
[0191] (iii) Amphoteric Surfactants
[0192] Amphoteric surfactants suitable for use in the compositions
of the invention include:
[0193] (a) imidazolinium surfactants of formula (VII) 23
[0194] wherein R.sub.1 is C.sub.7-C.sub.22 alkyl or alkenyl,
R.sub.2 is hydrogen or CH.sub.2Z, each Z is independently CO.sub.2M
or CH.sub.2CO.sub.2M, and M is H, alkali metal, alkaline earth
metal, ammonium or alkanolammonium; and/or ammonium derivatives of
formula (VIII) 24
[0195] wherein R.sub.1, R.sub.2 and Z are as defined above;
[0196] (b) aminoalkanoates of formula (IX)
R.sub.1NH(CH.sub.2).sub.nCO.sub.2M
[0197] iminodialkanoates of formula (X)
R.sub.1N[(CH.sub.2).sub.mCO.sub.2M].sub.2
[0198] and iminopolyalkanoates of formula (XI) 25
[0199] wherein n, m, p, and q are numbers from 1 to 4, and R.sub.1
and M are independently selected from the groups specified above;
and
[0200] (c) mixtures thereof.
[0201] Suitable amphoteric surfactants of type (a) are marketed
under the trade name Miranol and Empigen and are understood to
comprise a complex mixture of species. Traditionally, the Miranols
have been described as having the general formula (VII), although
the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the
non-cyclic structure (VIII) while the 4th Edition indicates yet
another structural isomer in which R.sub.2 is O-linked rather than
N-linked. In practice, a complex mixture of cyclic and non-cyclic
species is likely to exist and both definitions are given here for
sake of completeness. Preferred for use herein, however, are the
non-cyclic species.
[0202] Examples of suitable amphoteric surfactants of type (a)
include compounds of formula XII and/or XIII in which R.sub.1 is
C.sub.8H.sub.17 (especially iso-capryl), C.sub.9H.sub.19 and
C.sub.11H.sub.23 alkyl. Especially preferred are the compounds in
which R.sub.1 is C.sub.9H.sub.19, Z is CO.sub.2M and R.sub.2 is H;
the compounds in which R.sub.1 is C.sub.11H.sub.23, Z is CO.sub.2M
and R.sub.2 is CH.sub.2CO.sub.2M; and the compounds in which
R.sub.1 is C.sub.11H.sub.23, Z is CO.sub.2M and R.sub.2 is H.
[0203] In CTFA nomenclature, materials suitable for use in the
present invention include cocoamphocarboxypropionate,
cocoamphocarboxy propionic acid, and especially cocoamphoacetate
and cocoamphodiacetate (otherwise referred to as
cocoamphocarboxyglycinate). Specific commercial products include
those sold under the trade names of Ampholak 7TX (sodium carboxy
methyl tallow polypropyl amine), Empigen CDL60 and CDR 60 (Albright
& Wilson), Miranol H2M Conc. Miranol C2M Conc. N. P., Miranol
C2M Conc. O. P., Miranol C2M SF, Miranol CM Special (Rhne-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).
Further examples of amphoteric surfactants suitable for use herein
include Octoxynol-1 (RTM), polyoxethylene (1) octylphenyl ether;
Nonoxynol-4 (RTM), polyoxyethylene (4) nonylphenyl ether and
Nonoxynol-9, polyoxyethylene (9) nonylphenyl ether.
[0204] It will be understood that a number of
commerciallv-available amphoteric surfactants of this type are
manufactured and sold in the form of electroneutral complexes with,
for example, hydroxide counterions or with anionic sulfate or
sulfonate surfactants, especially those of the sulfated
C.sub.8-C.sub.18 alcohol, C.sub.8-C.sub.18 ethoxylated alcohol or
C.sub.8-C.sub.18 acyl glyceride types. Note also that the
concentrations and weight ratios of the amphoteric surfactants are
based herein on the uncomplexed forms of the surfactants, any
anionic surfactant counterions being considered as part of the
overall anionic surfactant component content.
[0205] Examples of preferred amphoteric surfactants of type (b)
include N-alkyl polytrimethylene poly-, carboxymethylamines sold
under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel
and also salts, especially the triethanolammonium salts and salts
of N-lauryl-beta-amino propionic acid and
N-lauryl-imino-dipropionic acid. Such materials are sold under the
trade name Deriphat by Henkel and Mirataine by Rhne-Poulenc.
[0206] (iv) Zwitterionic Surfactants
[0207] Water-soluble auxiliary zwitterionic surfactants suitable
for inclusion in the compositions of the present invention include
alkyl betaines of the formula R.sub.5R.sub.6R.sub.7N.sup.+
(CH.sub.2).sub.nCO.sub.2M and amido betaines of the formula (XII)
below: 26
[0208] wherein R.sub.5 is C.sub.11-C.sub.22 alkyl or alkenyl,
R.sub.6 and R.sub.7 are independently C.sub.1-C.sub.3 alkyl, M is
H, alkali metal, alkaline earth metal, ammonium or alkanolammonium,
and n, m are each numbers from 1 to 4. Preferred betaines include
cocoamidopropyldimethylca- rboxymethyl betaine,
laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine
(RTM).
[0209] Water-soluble auxiliary sultaine surfactants suitable for
inclusion in the compositions of the present invention include
alkyl sultaines of the formula (XIII) below: 27
[0210] wherein R.sub.1 is C.sub.7 to C.sub.22 alkyl or alkenyl,
R.sub.2 and R.sub.3 are independently C.sub.1 to C.sub.3 alkyl, M
is H, alkali metal, alkaline earth metal, ammonium or
alkanolammonium and m and n are numbers from I to 4. Preferred for
use herein is coco amido propylhydroxy sultaine.
[0211] Water-soluble auxiliary amine oxide surfactants suitable for
inclusion in the compositions of the present invention include
alkyl amine oxide R.sub.5R.sub.6R.sub.7NO and amido amine oxides of
the formula (XIV) below: 28
[0212] wherein R.sub.5 is C.sub.11 to C.sub.22 alkyl or alkenyl,
R.sub.6 and R.sub.7 are independently C.sub.1 to C.sub.3 alkyl, M
is H, alkali metal, alkaline earth metal, ammonium or
alkanolammonium and m is a number from 1 to 4. Preferred amine
oxides include cocoamidopropylamine oxide, lauryl dimethyl amine
oxide and myristyl dimethyl amine oxide.
Optional Materials
[0213] A number of additional optional materials can be added to
the coloring compositions herein described each at a level of from
about 0.001% to about 5%, preferably from about 0.01% to about 3%,
more preferably from about 0.05% to about 2% by weight of
composition. Such materials include proteins and polypeptides and
derivatives thereof; water-soluble or solubilizable preservatives
such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and
butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400,
natural preservatives such as benzyl alcohol, potassium sorbate and
bisabalol, benzoic acid, sodium benzoate and 2-phenoxyethanol;
antioxidants such as sodium sulphite, hydroquinone, sodium
bisulphite, sodium metabisulphite and thyoglycolic acid, sodium
dithionite, erythrobic acid and other mercaptans; dye removers such
as oxalic acid, sulphated castor oil, salicylic acid and sodium
thiosulphate; H.sub.2O.sub.2 stabilisers such as tin compounds such
as sodium stannate, stannic hydroxide and stannous octoate,
acetanilide, phenacetin colloidal silica such as magnesium
silicate, oxyquinoline sulphate, sodium phosphate, and tetrasodium
pyrophosphate; and p-hydroxybenzoates; moisturising agents such as
hyaluronic acid, chitin , and starch-grafted sodium polyacrylates
such as Sanwet (RTM) IM-1000, IM-1500 and IM-2500 available from
Celanese Superabsorbent Materials, Portsmith, Va., USA and
described in U.S. Pat. No. 4,076,663 as well as methyl cellulose,
starch, higher fatty alcohols, paraffin oils, fatty acids and the
like; solvents ; anti-bacterial agents such as Oxeco (phenoxy
isopropanol); low temperature phase modifiers such as ammonium ion
sources (e.g. NH.sub.4 Cl); viscosity control agents such as
magnesium sulfate and other electrolytes; quaternary amine
compounds such as distearyl-, dilauryl-, di-hydrogenated beef
tallow-, dimethyl ammonium chloride, dicetyldiethyl
ammoniumethylsulphate, ditallowdimethyl ammonium methylsulphate,
disoya dimethyl ammonium chloride and dicoco dimethyl ammonium
chloride; hair conditioning agents such as silicones, higher
alcohols, cationic polymers and the like; enzyme stabilisers such
as water soluble sources of calcium or borate species; colouring
agents; TiO.sub.2 and TiO.sub.2-coated mica; perfumes and perfume
solubilizers; and zeolites such as Valfour BV400 and derivatives
thereof and Ca.sup.2+/Mg.sup.2+ sequestrants such as
polycarboxylates, amino polycarboxylates, polyphosphonates, amino
polyphosphonates etc. and water softening agents such as sodium
citrate.
[0214] The present invention is represented by the following
non-limiting examples. In the examples, all concentrations are on a
100% active basis and all percentages are by weight unless
otherwise stated and the abbreviations have the following
designations:
1 Oxidising agent hydrogen peroxide Oxidative Dye 1 para-phenylene
diamine Oxidative Dye 2 para-aminophenol Oxidative Dye 3
meta-aminophenol Oxidative Dye 4 2-amino-3-hydroxy pyridine
Oxidative Dye 5 4-amino-2-hydroxy toluene Non-oxidative Dye Basic
red 76 Chelating agent Ethylenediamine tetraaceticacid Surfactant 1
Ceteareth-25 Surfactant 2 Cocoamidopropyl betaine Thickener 1 Cetyl
alcohol Thickener 2 Stearyl alcohol Antioxidant Sodium sulphite
Buffering Agent 1 Acetic acid
EXAMPLES I-VII
[0215] The following are hair treatment compositions in the form of
hair coloring compositions which are representative of the present
invention.
2 Ingredient I II III IV V VI VII Oxidising Agent 0.7 0.7 0.7 0.7
0.7 2.5 1.5 Oxidative Dye 1 0.24 0.14 0.24 0.15 0.24 0.4 0.4
Oxidative Dye 2 0.09 0.05 0.009 0.5 0.09 0.1 0.1 Oxidative Dye 3
0.006 0.004 0.006 -- 0.006 -- -- Oxidative Dye 4 0.06 0.03 0.06 0.1
0.06 0.06 0.06 Oxidative Dye 5 -- -- -- 0.5 -- -- -- Non-Oxidative
Dye -- -- -- -- -- 0.1 -- Surfactant 1 1.5 1.7 1.5 1.5 1.5 1.5 --
Surfactant 2 -- -- -- -- -- -- 1.5 Chelating agent 0.1 0.06 0.09
0.2 0.1 0.1 0.1 Thickener 1 2.3 2.6 2.3 2.3 2.3 4.0 4.0 Thickener 2
2.3 2.6 2.3 2.3 2.3 2.0 2.0 Antioxidant 0.1 0.06 0.1 0.2 0.1 0.1
0.1 Buffer 1 -- -- -- 0.5 0.5 0.2 0.2 Water to balance pH 4.0 3.8
3.9 4.6 2.7 -- --
[0216] In the examples, water is used as the diluent. However in
variations hereof water can be replaced, in part, by from about
0.5% to about 50% by weight of the total water content of the
examples by diluents such as lower alcohols, e.g., ethylene glycol,
ethylene glycol monoethyl ether, diethylene glycol, diethylene
glycol monoethyl ether, propylene glycol, 1,3-propane diol,
ethanol, isopropyl alcohol, glycerine, butoxyethanol,
ethoxydiglycol, hexylene glycol, polyglyceryl-2-oleyl ether and
mixtures thereof.
Experimental Methods
[0217] I Assessment of Initial Color and Color Change
[0218] The equipment used to measure both the initial color and
color change on substrates (hair/skin) dyed with the low pH
coloring compositions of the present invention is a Hunter
Colorquest spectrophotometer. The value used to express the degree
of color change on any particular substrate is Delta E
(.sup..DELTA.E). Delta E, as defined herein, is represented by a
factual sum of L, a, and b values such that:
.sup..DELTA.E=(.sup..DELTA.L.sup.2+.sup..DELTA.a2+.sup..DELTA..sub.b2)1/2
[0219] and L is a measure of lightness and darkness (color
intensity), wherein L=100 is equivalent to white, and L=0 is
equivalent to black. Further, `a` is a measure of the red and green
quotients (color hues) such that positive equates to red and
negative equates to green, and `b` is a measure of the yellow and
blue quotients (color hues) such that positive equates to yellow
and negative equates to blue.
[0220] Hunter Colorquest measurements can be carried out on the
Hunter Labscan Colorimeter which is full scanning
spectrocolorimeter with a wavelength of from 400-700 nanometers
which records the color of test hair switches (tresses) in terms of
`L`, `a` and `b` values. The machine is set to: mode--0/45; port
size--1 inch; view size--1 inch; light--D65; field of
view--10.degree.; UV lamp/filter--none. The hair is placed in a
sample holder designed to hold the hair in a uniform orientation
during measurement. Equivalent calorimeters can be used, but it
must be ensured that the hair does not move during measurement. The
hair must be spread to cover the 1 inch port during color
measurement. Dots are placed on the switch holder to guide the
positioning of the holder at the port. The dots are lined up with a
mark on the port and readings are taken at each spot.
[0221] Eight measurements are run per switch, 4 on each side, and
three switches are run per treatment.
[0222] II. Standard Hair Switch
[0223] The compositions according to the present invention can be
used to color hair of all colors, types and condition. For the
purposes of illustration two test hair switch types; light brown
and light brown with 40% grey coverage have been tested herein.
These standard hair switches can be measured in terms of their
approximate L, a, b values.
3 L a b Light brown 60 9 32 40% grey light brown 35-37 4.5-5.5
11.5-12.7
[0224] III Hair Switch Coloring Method
[0225] To color hair, a 4 gramme switch of about 8 inch long hair
is hung over a suitable container. The test coloring product is
then prepared (i.e., where applicable the separate bottle
components are mixed together) and about 8 grammes of product is
applied directly to the test hair switch. The colorant is massaged
through the hair switch for up to about 1 minute and then left on
the hair switch for up to about 30 minutes. After rinsing with
running water for about 1 or 2 minutes the colored hair switch is
then cleansed (according to the shampoo protocol) and dried. Drying
can be effected either naturally (without heat assistance) or using
a drier. The color development (initial color) of the colored,
cleansed, dried test hair switch can then be assessed using the
Hunter Colorquest spectrophotometer.
[0226] For the delivery of a red shade (hue) to prepermed,
prebleached light brown hair (having L, a, b values of
approximately 60, 9 and 32) the preferred initial shade of the
colored 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 color 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.
[0227] For the delivery of a brown or black shade (hue) to
preperned, prebleached light brown hair (having L, a, b values of
approximately 60, 9 and 32) the preferred initial shade of the
colored hair will have a hue value (arc tangent of (b/a)) of less
than about 25, preferably less than about 20 and the initial color
intensity (L) will be greater than about 1 and less than about 50,
preferably greater than about 5 and less than about 45.
[0228] For the delivery of a light brown shade (hue) to prepermed,
prebleached light brown hair (having L, a, b values of
approximately 60, 9 and 32) the preferred initial shade of the
colored 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
color intensity (L) will be greater than about 20 and less than
about 95, preferably greater than about 25 and less than about
90.
[0229] A significant color change, as delivered via the coloring
compositions according to the present invention, means a color
change in terms of Delta E which is greater than about 8,
preferably greater than about 10, more preferably greater than
about 12, most preferably greater than about 15 and especially
greater than about 20.
[0230] Hair Switch Cleansing Method
[0231] Switches of colored hair are subjected to a repeated
cleansing cycle wherein the following process is repeated up to 10
times.
[0232] A 4 gramme, 8 inch test switch of colored hair is clamped
over a suitable container and rinsed thoroughly for about 10
seconds using warm water (at about 100.degree. F. at about 1.5
gallons/minute pressure). Shampoo (about 0.4 ml non-conditioning
shampoo) can then be applied directly to the wet test switch using
a syringe. After lathering the hair for about 30 seconds the hair
is rinsed in running warm water for about 30 seconds. 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. The test switch is then dried either natrually,
or using a pre-heated dryer box at about 140.degree. F. (for about
30 minutes). The colored, cleansed, dried test hair switch can then
be color assessed (Delta E fade).
[0233] During any single test cycle each different switch to be
assessed should be tested in water of equivalent temperature,
pressure level and hardness level.
[0234] Delta E fade results for prepermed, prebleached light brown
hair (having L, a, b values of approximately 60, 9 and 32) which
has been colored a red shade (of hue value in the range of from
about 25 to about 70) are generally less than about 5.0, preferably
less than about 4.5, more preferably less than about 4.0 and
wherein the change in hair color, % delta E, after up to 20 washes,
is less than about 20%, and preferably less than about 15%, more
preferably less than about 10%.
[0235] Delta E fade results for prepermed, prebleached light brown
hair (having L, a, b values of approximately 60, 9 and 32) which
has been colored a brown or black shade (of hue value of less than
about 25) are generally less than about 2.3, preferably less than
about 2.0, more preferably less than about 1.7 and wherein the
change in hair color, % delta E, after up to 20 washes, is less
than about 5%, preferably less than about 4.5%, more preferably
less than about 4%, most preferably less than about 3.5%.
[0236] Delta E fade results for preperned, prebleached light brown
hair (having L, a, b values of approximately 60, 9 and 32) which
has been colored a light brown shade (of hue value in the range of
from about 70 to about 110) are generally less than about 2.6,
preferably less than about 2.3 and wherein the change in hair
color, % delta E, after up to 20 washes, is less than about 15%,
preferably less than about 12%, more preferably less than about
10%, most preferably less than about 8%.
[0237] In preferred compositions herein, the change in the color of
the dyed hair over time (Delta E fade) is less than about 15%,
preferably less than about 12%, more preferably less than about 10%
and most preferably less than about 8%.
[0238] V Skin Staining Test Method
[0239] For the purposes of the present invention skin staining
results are based on pig skin data.
[0240] Skin staining measurements can be made on pigs ears,
preferably the ears of recently deceased pigs. The ears should not
have been subject to undue heating (scalding). Hair is shaved from
the most flat section of the ear to be stained. An area of at least
1 cm.times.5cm is pre-marked on the ear (using a pernenant marker)
and the ear is then cleansed with non-conditioning shampoo (0.1
g/cm.sup.2 at 10% dilution). After massaging in the shampoo for
about 1 minute the ear is rinsed for about 30 seconds then gently
patted dry by hand with a paper towel. Baseline color assessment
readings (L, a, b) are then taken for the pre-marked area. The test
dye is then applied to the pre-marked test area (about 0.25
g/cm.sup.2) and massaged in for about 1 minute and allowed to
remain on the ear for about 30 minutes. The colored ear is then
rinsed with about 2 liters of tap water at about 37.degree. C. and
hand dried as above. Color assessment readings (L, a, b) are then
taken for the pre-marked area of the dyed ear. Total color change
(Delta E) can then be calculted from the L, a, b values and
expressed as relative levels of skin staining (versus the baseline
color).
[0241] VI Measurement of pH
[0242] For the purposes of the present invention, as described
herein, all pH measurements were carried out on a Mettler Toledo
320 pH meter. All pH measurements of dyes, oxidising agents and
mixtures thereof, either singly or in combination with a suitable
delivery medium, such as water and surfactant and /or thickeners,
were carried out at room temperature (about 25.degree. C.). The pH
of dye mixtures were measured in the form of intended use and prior
to application.. A preferred delivery medium for use herein
comprises an emulsion of ceteareth-25 at a level of from about 1%
to about 3% by weight, cetyl alohol at a level of from about 2% to
about 5% by weight and stearyl alcohol at a level of from about 2%
to about 5% of solution or composition.
Experimental Data
[0243] I Initial Color and Wash Fastness
[0244] Example formula I provides improved initial color and fade
resistance versus a similar composition having pH outside the scope
of the present invention.
[0245] Example formula II provides improved intial color
development and washfastness versus a similar high pH formula
containing the same level of oxidant and up to 60% more dye.
[0246] Example formula III provides improved initial color
development versus a high pH formula containing the same level of
dye but more inorganic peroxygen oxidising agent.
[0247] II Relative Skin Staining
[0248] Example formula IV provides reduced levels of skin staining
on a pigs ear versus an equivalent composition at high pH.
[0249] Method of Manufacture
[0250] It is important that dyeing compositions be in a form which
is easy and convenient to prepare and use by the consumer, since
the oxidising agent must remain in contact with the hair for a
certain period of time and not run or drip off of the hair,
possibly causing eye or skin irritation.
[0251] To address the above, the coloring compositions of the
present invention can be provided in both a single pack or in kit
form as separately packaged components to maintain stability, and,
if so desired, either mixed by the user immediately prior to
application to the hair, or mixed and stored for future use, or
mixed and partly used and the remainder stored for future use.
[0252] As hereinbefore described, the compositions according to the
present invention may be used by the consumer as a single component
package. Such a single pack would comprise a single solution at pH
1 to 6 containing both the inorganic peroxygen oxidising agent and
the oxidative dye precursors. The solution would be applied
directly to the hair by the consumer without the need for any
pretreatments or mixing thereby providing a simple, fast, easy to
use, `no-mess` hair coloring system. A further advantage of such a
single component system is that it could be stored and re-used
i.e., a single package could contain enough coloring composition
for several applications over time.
[0253] Thus, according to a further aspect of the present
invention, there is provided:
[0254] A method for coloring hair wherein a hair coloring mixture
is present in a single package and applied directly to the hair and
wherein the hair coloring mixture comprises:
[0255] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent; and
[0256] (b) an oxidative hair coloring agent; and
[0257] wherein the pH of each of (a) and (b), when in solution, is
in the range of from about 1 to about 6 and wherein the combined
mixture of (a) and (b), when in solution, has a pH in the range of
from about 1 to about 6.
[0258] According to a still further aspect of the present
invention, there is provided:
[0259] A method for coloring hair wherein a hair coloring
composition is present as separately packaged components (a) and
(b) and wherein the hair coloring composition comprises:
[0260] (a) from about 0.0003 moles (per 100 g of composition) to
less than about 0.09 moles (per 100 g of composition) of an
inorganic peroxygen oxidising agent wherein the pH of (a), is in
the range of from about 1 to about 6; and
[0261] (b) an oxidative hair coloring agent wherein the pH of (b),
is in the range of from about 1 to about 6;
[0262] wherein each of (a) and (b) are stable at pHs in the range
of from about 1 to about 6 and wherein the combined mixture of (a)
and (b) is stable over time and has a pH in the range of from about
1 to about 6.
[0263] Alternatively the compositions according to the present
invention can be packaged as follows: one component of the kit
comprises an individually packaged oxidising component while
further kit components could comprise coloring agent mixture and,
optionally, individually packaged additional, optional, oxidising
agent(s), or two separate individual packages of oxidising agent(s)
and coloring agents. In one embodiment of the present invention the
oxidising component comprises a stabilised aqueous solution of an
inorganic peroxygen oxidising agent, most generally hydrogen
peroxide in an amount such that the final concentration of the
coloring composition for use on the hair is from about 0.05% to
about 6% by weight and additional agents as herein before
described. The compositions can either be mixed by the user
immediately prior to application to the hair or can be applied
separately. Examples of such kits are as follows:
[0264] I. A hair coloring kit is assembled comprising a single
package including therein: (1) a 50 ml bottle of hydrogen peroxide
(1.4% by weight of H.sub.2O.sub.2), and optionally buffering agents
and/or stabilisers; and (2) a 50 ml bottle containing one or more
oxidative hair coloring agents and, optionally, additional agents
such as surfactants, stabilisers, buffering agents, antioxidants,
thickeners etc. The oxidative hair coloring agents can either be
admixed with the hydrogen peroxide to form the low pH dyeing system
of the present invention and the resulting solution can be either
applied to the hair to color it or stored for future use, or the
separately packaged stable components can be stored and mixed when
required.
[0265] II. A hair coloring kit as described above wherein the
hydrogen peroxide containing component is applied to the hair prior
to application of the oxidative hair coloring agents and additional
materials to the hair.
[0266] III. Further examples of kit components for the hair
coloring compositions according to the present invention include
separately packaged oxidant and oxidative hair coloring agents
wherein either one or both components are present in particulate
form.
[0267] Method of Use
[0268] The compositions herein described are used to color hair.
The coloring compositions herein are applied to the hair for
periods of from 1 minute to 60 minutes depending upon the degree of
coloring required. A preferred time is between 5 minutes and 30
minutes. The coloring compositions according to the present
invention can be applied to both wet and dry hair.
[0269] As hereinbefore described the coloring composition can be
present as a single package, at low pH, suitable for direct
application to the hair. Alternatively, the coloring composition
can be present in kit form wherein one component comprises an
oxidising agent and a further component comprises oxidative hair
coloring agents. Hair coloring kits according to the present
invention can be used to color the hair in several ways
including:
[0270] (i) the kit components are admixed to form a low pH coloring
composition prior to application to the hair.
[0271] (ii) the hair oxidising agent is applied to the hair prior
to application of the oxidative hair coloring agents.
[0272] (iii) the oxidative hair coloring agents are applied to the
hair prior to application of the oxidising agent.
[0273] The products provide excellent initial hair coloring and
in-use efficacy benefits including improved washfastness, color
saturation and reduced hair damage at lower pH.
* * * * *