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Patent 1101335 Summary

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Claims and Abstract availability

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(12) Patent: (11) CA 1101335
(21) Application Number: 269210
(54) English Title: P-PHENYLENE DIAMINES AND 1,2,4-BENZENETRIOLS AS HAIR DYE PREPARATION
(54) French Title: TRADUCTION NON-DISPONIBLE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 167/302
(51) International Patent Classification (IPC):
  • A61K 8/41 (2006.01)
  • A61K 8/34 (2006.01)
  • A61Q 5/06 (2006.01)
(72) Inventors :
  • FEINLAND, RAYMOND (United States of America)
  • ISCOWITZ, SIGMUND (United States of America)
(73) Owners :
  • BRISTOL-MYERS SQUIBB COMPANY (United States of America)
(71) Applicants :
(74) Agent: GOWLING LAFLEUR HENDERSON LLP
(74) Associate agent:
(45) Issued: 1981-05-19
(22) Filed Date: 1977-01-06
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
701,440 United States of America 1976-06-30

Abstracts

English Abstract



ABSTRACT OF THE DISCLOSURE

An autoxidizable hair dye preparation is disclosed
capable of coloring or darkening hair when applied thereto
and exposed to the atmosphere comprising a mixture of (I)
at least one p-phenylene diamine compound, or an acid addition
salt thereof, and (II) at least one 1,2,4- benzenetriol compound,
each compound optionally containing nuclearly substituted C1-4
alkyl, alkoxy, hydroxyalkyl or halogen. The preparation is pre-
ferably applied and exposed to the atmosphere repeatedly until
the desired degree of darkening or color build-up is attained.

- 1 -


Claims

Note: Claims are shown in the official language in which they were submitted.



The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:

1. A preparation capable of coloring hair when exposed
to oxygen, comprising a mixture of
(I) at least one aryldiamine compound of the formula

Image

or an acid addition salt thereof, and
(II) at least one 4-hydroxy catechol compound of the
formula


Image

wherein R1 and R are individually hydrogen, or methyl, said
preparation being maintained under substantially anaerobic
conditions.


2. A preparation according to Claim 1 wherein R1 and
R are each hydrogen.

3. A preparation according to Claim 1 wherein R1 is
hydrogen and R is methyl.


11

4. A preparation according to Claim 1 wherein R1 is
methyl and R is hydrogen.

5. A preparation according to Claim 1 wherein R1 is
methyl and R is methyl.

6. A preparation according to Claim 1, 2 or 3 wherein
said mixture of (I) and (II) compounds comprises about 0.1 to
about 6% by weight of the preparation.

7. A preparation according to Claim 1, 2 or 3 containing
about 0.02 to about 1.0% by weight of each of said compounds (I)
and (II).

8. A preparation according to Claim 1, 2 or 3 wherein
the molar ratio of compound (I) to compound (II) ranges from
about 1:8 to 4:1.
9. A preparation according to Claim 1, 2 or 3 in the
form of an aqueous solution.

10. A preparation according to Claim 1, 2 or 3 in the
form of an aerosol composition also containing a propellant
system.

11. A preparation according to Claim 1, 2 or 3 also
including a hair grooming agent.

12. A method of coloring hair comprising applying to the
hair an effective amount of a preparation according to
Claim 1, 2 or 3.

12


13. A method of coloring hair comprising applying to
the hair an effective amount of a preparation according to
Claim 1, 2 or 3, and wherein the preparation is applied to the
hair at multiple spaced intervals of time and permitted to be
exposed to the atmosphere after each application whereby a
gradual build-up of color is developed in said hair.


13

Description

Note: Descriptions are shown in the official language in which they were submitted.


~ 3 3 ~ :

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


- 2 -



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,



-- 3 --

335


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



-- 4 --

~ 3 3 5


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, : :
*
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

*Trade Mark

` ~ 6 -
,.,.,. : :

33~i

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 .
'
*Trade Mark



-- 7
i. ,~

3 3 ~

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.
'.
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.
*TradP Mark



'


, ~ .
: - ,

~ 3


E ~ LE 3
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.
.~ ... . :
" E~A~
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~



. . .

E~ - g

33~


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
*




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.


*Trade Mark




1 0 - ~
, ~ -:

Representative Drawing

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Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date 1981-05-19
(22) Filed 1977-01-06
(45) Issued 1981-05-19
Expired 1998-05-19

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1977-01-06
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
BRISTOL-MYERS SQUIBB COMPANY
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-03-14 1 23
Claims 1994-03-14 3 78
Abstract 1994-03-14 1 22
Cover Page 1994-03-14 1 29
Description 1994-03-14 9 459