Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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ThiS invention x.elates to co~positions o~ pre~ar~t~on~
~or coloring or darkening ha~r, and moxe pa~ticul~rl~ to such
preparations containing a mixtu~e of two certain types of com-
pounds, and a method for their use.
It has long been known in the prior art that p-phenylene
diamine and p-toluylene diamine a~e capable of coloring hair,
but the coloring process is very slow unless applied in combina-
tion with an oxidizing agent suc~ as hydrogen peroxtde which
must be kept apart from these diamines until immediately prior
to use and which often damages the hair. It has also long
been known in the prior art that benzenetriols such as 1,2,4-
benzenetriol ~4-hydroxy catechol, hydroxy quinol) and 2,4,5- ;
trihydroxytoluene are l~kewise capable o coloring hair, but
: although the coloring process under atmospheric conditions
is relatively rapid, it yields only relatively light shades.
Several references in ~he prior art refer to the use
of the above compounds for coloring hair. In this connection, ~-
attention is in~ited to U S. Patents 2,162,458, 2,733,186,
2,975,101, 3,214,472, 3,236,734, and 3,920,384, and British
Patents 710,134, 745,532, 754,948, 754,949, 824,519, and
827,439. However, although some o these references, for
example U.S. 2,162,458, British 710,134 and British 827,439,
state that mixtures of certain p-phenylene d~amine compounds
and benzenetriol compounds were theretofore suggested for
coloring hair, they fail to specifically disclose any such
mixtures, implying that such mixtures were found to be
unsatisfactory, perhaps wîth respect to coloring rate, depth
of color, safety, drabness, permanence and/or facility in
production or use or the like,
It is an object of this in~ention to provide hair
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coloring (including darkening2 ~reparations which will not be
subject to one or more of the above: disadvanta~es,
Other objects and advantages will appear as thé
descrip~ion proceeds.
The attainment o~ the above okjects is ~ade possible
by this invention which includes the provision of an
autoxidizable hair preparation capab.le of coloring (includ~ng
darkening~ hair when appl.ied t~ereto and exposed to t~e at-
mosphere comprising a mixture of (I~ at least one p-phenylene
diamine c~mpound or an acid addition salt thereof, and (II~
at least one 1,2,4- benzenetriol compound, each compound
optionally containing nuclearly s~bstituted halogen or Cl_4
alkyl, alkoxy or hydroxyalkyl, T~e op~ional nuclear substi-
tuen~ is preferably methyl, and preferably in the 5-position ln
the benzenetriol compound.
The above-defined preparations of this invention7 when
applied to the hair, e~g. gray hair~) at leas~ onse and
preferably up to four or more times, with exposure to the
atmosphere at ambient te~peratures arter each app.lication, for
example twice a day for two days, have been found to yield
natural-looking, drab medium to dark brown colorations which
are relatively durable and resistant to further color change
when subsequently shampooed.
As iIlustrative of suitable compound (I) type compounds,
there may be mentioned the 1,4-diamino-5-ethyl,-~8sbutyl?.
-methoxy,-butoxy,-hydroxyethyl,~chloro, and -bromo benzenes,
and preferably p-phenylene diamine (PPD,1,4-diamino benzene,
p-amino aniline)~ and p-toluylene diamine (PTD,1,4-diamino 5-
methyI benzene), and their ac.id addition salts (e,g, sulfate,
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chloride, bromide, etc.~,and mi~tures the~eof,.
As illustrative of suitabl~ compou~d (II~ type
compounds, there may be me~ione~ ~he 1,2?4-trih~droxy-3-?-6,
-7- and preferably -5-ethyl,-isobutyl,-methoxy,-butoxy,
-hydroxyethyl,-chloro,-br~mo, and pre~erab~y-methyl benzenes,
and especially 1,2,4 benzenetriol CBenz T, 4-hydroxy catec~ol,
hydrox~ hydroquinone), and 2,4,5-trihydroxy toluene
(THTJ 1,2,~-trihydroxy~5- me~h~l benzene, 4-hydroxy-5-
methyl catechol), and mixtures thereof,
The molar ratio of compound (I? (or mixtures thereof~
to compound (II) (or mixtures thereo~ in the mixtures of this
invention may range from about 1: 8 to about 4 :1, preferably
about 1:2 to about 2:1, and the preparations o~ this inven~ion
may contain about 0. 04 to about 8%, preferably about 0.1 to ~ ~:
about 6%, by weight o~ suc~ mix~ures. Such preparations will
usually contain about 0.02 to about 1.0% b~ weight o~ each of
said compounds ~I) and (II~
In view of the sensiti~ity o these mixtures and
preparations to oxidation, the compound (II) type triols es-
pecially tending to oxidize rapidly, such mixtures and prepara-
tlons should preferably be prepared, packaged and stored under
anaerobic conditions. When packaged as an aerosol under pressure~
the usual hydrocarbon or halohydrocarbon propellan~s therein
effectively provide such anaerobic conditions. Free space in
other containers for these mixtures and preparations may be
eliminated, minimized or filled with nitrogen or other inert
gas. Premature oxidation may be further reduced or elimina~ed
by including in such prepara~ions small amounts, such as about
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0.03% to 5% by weight, o~ on~ or moXe an~io~id~nt$ or reducing
agents, for example sodium sulfi.te! sodium bisulf~te, ~scorbic
acid, aliphatic mercaptans suc~ as thiogIycollic acid, t~iolac-
tic acid and thioglycerol and the like. Alternatively, the
compound ~II) type triol compounds may be protected from pre
mature oxidation by acylation, e. e . as the tria~etate, and the
acylated compound saponified to the triol in known manner
immedia~ely prior to or co~currently ~ith application of ~he
preparation to the hair. In any case, it will be understood
that the fluid vehicle in which the mixture is generally
suspended, dispersed or dissolved usually provides an
additional substan~ially anaerobic environment further tending
to reduce premature cxidation of the dye mixtures of this in-
vention until it is e~posed to atmospheric oxygen in situ on
the hair,
The preparations of this in~ention are generally fluid
or liquid, in the form of a solution, dispersion, suspension,
cream, lotion, gel or aerosol or the like, and optionally in com~
binati.on with hair grooming or hair condi~ioning agents whereby
the hair, whether it be live as on the head, or dead as in a
swatch7 wig or hairpiece, is simultaneously colored and groomed
or conditioned. W~X is ordinarily ~he maior cons~i~uent
or vehicle in ~he instant preparations, and may for example
constitute from about 30 to about 95% by weight thereof.
Alcohols such as ethanol, isopropyl alcohol, glycols, and de-
rivatives thereof, ranging from about 0 to about 30% by weight in
the preparations, may be încluded as mutual solvents or solubiliz-
ing a~ents. The p~ of these preparations ~s ordinarily adjusted
~o about ~ to 11/ preferably a~out 6 to 10~ more preferably about
~;~Q~;~3S
7 to 9, wit~L acidic mater~a,ls, bu:~:fers or alkali~zing agents such
as m,ono- ,di- alld tri-et~sanc)lamine, sodiu~ carb~nate and bi::ar-
bonate, disodium hydrogen phosphate, sodium dihydrogen phosphate,
and the like.
These preparatlons may al~o contain up to about 6%
by weight of known couplers, which are ar~ma~ic compounds common-
ly employed to co~trol or ~ary the hair color or shade, such as
2 4-dlamino-phenol,-a~isole and -toluene, m-metho~yoa~d-amino-
phenol, 2~5- and 2,6-xyl nol, cat~chol, resorcinol, m-phenylene
L0 diamine, 3~amino-4-meth~L and-6-meth~l phenolj alpha-naph~hol, :
l-phenyl-3-methyl-5-pyrazolone and the like,
The preparations of this invention may also con~ain known
additives or assistants such as hair grooming agents, for e~ample
quaterni~ed vinyL pyrrolidQ~e copolymers, carbox~vinyl polymers
and the like, plasticizers, condi~ioners, thickeners~slip and
wettlng agents such as polyoxyethylenated fatty {e.g. lauryl) ~ -
alcohols, stearyldimethylammo~ium chloride, silicone copolymer,
; - foam boosters, preservati~e~, per~ s and the like. For
packaging and dispensing as an aerosol, from about 5 to 50% or
more by weight of:a known propellant or mixture thereof may
be included such as the hydrocarbons, e.g. propane and but~ne, : :
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and halohydrocarbons, e.g. Freons 12,114,152A, etc.
The hair is preferably first washed or sha~pooed before
applyir~g the present prepara~ions. The application may be dis-
~ontinuous, as for example when a streaking or other decorative ?
effeet is deslred, or uniformly in which case a sufficient amoun~ :
: of the preparation is employed to thoroughly we~ the hair. For
a normal head of hair ~hiS for example would generally ~all for
application of about 15 ~o 20 ~1. o the prepara~ion~ The
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i;n~1 color and/or depth Qf sh~de in ~ny pa~ticul~ nstance
~zill for t~e mos~t pa~t de~end upon the concentrations of the
(I~ and CII2 type compounds in the preparat~on, t~e temperature
a~d duration of exposure of the we~ted ha~r ~o atmosp~eric o~ygen,
and the number of repeated applications,increase~ in all o~
w~ich will gen rally yield an increased dept~ or intensity of
color or sha~e. No shampooing or rinsing is required afte~
application as in the case with the usual halr coloring products.
The follo~ng ex~mple~ are only further illustrative
of preferred embod~m~nts of this invention~ All ~mounts a~d
proportion~ referred to herein and in the appe~ded claims are D'J .~`
weight unles~ o~herwi.se indicated. As employed herein, the
~ollowing terms have the indicated meanings:
*
Gafquat 7S5: quate~nized vinyl pyrrolidane copolymer,
average M.W. over 1,000,000, relative viscosity (Ostwald-Fenske)
l.5-2.0 as an 0.1% solutlon i~ a~hydrous SD40 ethanol, mi~imum
-~ 19% solids in a water vehicle; GAF Corporation.
*:
Emulphor AM650: 1 mole isostearyl alcohol reacted with
10 moles ethylene oxide (E.O.), GAE Corporation.
Brij 35: 1 mole laur~l alcohol reacted wi~h 23 moles
E.O.; ICI America
Silicone SF-1066: dimethyl poly~iloxane/polyethylene oxide/
polypropylene oxide copolymer, visc. 1200 1500 centistokes at
25C ., ~p . gr. 1 . 04 at 20C ., General Electric Co .
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Propellan~ 152a~ di1uoroethane
ProDellant 114:. 1,2-dichloro-l,L,2?2-tet~a~.~oroethane
Propellant 12: dichlorodifluoromethane
Carbopol 941: water soluble salt of a polymer o~
acrylic acid cross~ ked wi~h a~out lV/o o~ a polyalkyl e~her
o~ ucrose having anaverage of 5. 8 allyl g;roups per ~uGrose mole-
cule, ~ . of the order of 1)000,000, descri~ed in U.S. 2~798,053,
B.F. Goodrich ~o.
PPD tp-phenylene diami~e) 0.147%
Benz T ~1,2,4-benzenetriol) 0.171
sodiu~ sulfi~e 0.030
sodium ery~horbate 0.030
triethanolamine 3.000
- 15 deionized water q.s. to 100,000
.
pH adjusted to 8.0 wlt~ sulfuric acid.
The above preparation, preferably blended and mai~
: tained undPr anaerobic co~ditions, is applied ~our times
(twiee a d~y for 2 days) to gray hair, each time ollowed with
color development by aix oxidation, to yield a natural looking
:~ medium to dark drab brown shade.
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EXA~PLE 2
The procedure of Example 1 is repeated, e~cept for
substitution of the Benz T by an equivalent amount of THT
~25 (2,4,5-trihydroxy~oluene), with similar resul~s.
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PTD (p-t~lu~lene~:amine~ 0,300.
Benz T 0.171
sodium ~ulfite 0.030
sodium erythorhate 0,03Q
triethanol2mine 3.00Q
deionized water q.s. to100.000 ~:
pH adjusted ~o 8;0 with sulfuric acid.
This.preparation applied as described~lln Example 1
l~ ylelds similar results.
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The procedure o~ E~ample 3 is repea~ed, except ~or
~ subs~itution of the Be~z T by an equivalent amount o
:. THT, with s~milar results.
~ :~XA~L~ 5 _ A3~905 ~AY
~: A clear near colorless solutio~ is produced by blending
. with the ormulation o~;Example l~(disregarding the waterj:
ethyl alcohol (95%) 23.000
&afquat 755 2.000
Emulphor ~M650 0.053
perfume ~ O.013
stearyld~methylbenzylammonium chlorid; 0.067
Silicone SF-1066 0.053
Brij 35 0-Q40
. 25 Water ~ q.s. to 100.000
: To 94 8. of the above preparation, 6 g. of a
: 30/35/35 pro~eilant ~l~nd of 152aill4/12 ls added to obtain
9 quick breaking aerosol foam. Application ~o hair as i~
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Example 1 yields simil~F re~ults, Likewi~e, simi~a~ ~ddit~on
o~ the above materTals tq t~e ~ormul~tio~s of Exa~ples 2-4
and combining with the pr~pellant mixtu~e y~eld~ qu~c~
breaking aerosol foams wh~çh are a~pl~ed to h~ir with like
results. ::~
EXAMPLE 6-GEL
10 g. of Carbopol 941 are dispersed in 750 g. of
cold water while vigorously agit.ating and raising the ~empera~
ture to abou~ 40-50G and cooling to ro~m temperature. To the
smooth dispersion are added with stirring ~.47 g. o PPD and
1.2 g. o~ sodium sulfite, then a solu~ion of 0~13 g. o per~ume
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in 0.4 g. of Brij 35, then 1.71 g. Benæ T, and then 43 g. of
trietha~olamine. The pH of the resulting solution i~ adjusted
to about 7.9-8.~ with triethanolamine and!suLfuric acid, :
and water added to make 1,000 g. of a s~t gel.
~air is treated with the resulting gel as described
in Example 1, with slmilar results. Substitution of the PPD
by an e~uivalen~ amount of PTD, and/or o the Benz T by an
equivalent amount of THT, yields similar results.
This in~ention has been disclosed with respect
to certain preferred embodiments, and it will be understood
tha~ modifications and variations ~hereof obvious ~o those
skilled in the art are to be included within the spiri~ and purview
of this application and the scope of the appended claims.
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