Note: Descriptions are shown in the official language in which they were submitted.
11~3167
This lnvention relates to a hair conditionlng compo-
sit;ion and process for making and using the sameO More par
ticularly, thls invention relates to a hair conditioning com-
position, a creme rinse composition, a process for producing a
hair conditioning or creme rinse compositlon which includes
homogenizing the composition, and a process for treating the
ha~r.
Although hair conditioners and creme rinses utilize
similar ingredients at different concentrations, their uses
are substantially different. A hair conditioner is generally
utilized as a periodic treatment to restore the condition to
hair which has been damaged due to regular use or misuse of
hair waving compo~itions or hair colorant compositionsO A
creme rinse, however~ is generally utilized as an after-shampoo
treatment which improves the mangeability and combabllity of
the hair. Creme rinses have become particularly attractive to
individuals having long hair which subsequent to shampooing
becomes difficult to control and comb.
~oth hair conditioners and creme rinses generally
utilize cationic compounds which are substantive to the hair.
These compositions also may include small percentages of wa~y
materials such as higher alcohols which also appear to effect
the condition of the hair. These higher alcohols, although
they are recognized as improving conditioning, have had a
detrimental effect on the stability of prior art creme ri.nse
products.
Generally prior art creme rinse formulations use
about 2.5% to 7% quaternary compound such as stearyl dimethyl
benzyl ammonium chloride and may include up to 1~ by ~eight of
an oil-soluble waxy material, such as a higher alcohol such as
isostearyl alcohol, cetyl alcohol, stearyl alcohol, liquid
--1
~;~
3~67
hexadecanol, or octaphenoxy ethanol, waxy esters such as gly~
cerol mono~, di~ and tri~stearate, ethylene gly-col mono- and
distearate9 propylene glycol stearates, sorbltan stearates 9
etc. These materials are substantially water insoluble and
are not self-dispersing, and for this reason only small quan-
tities are used. Water-diæpersible or water-soluble materials
are often incorporated in prior art compositions in relatively
large amount~ in attempts to solubilize water-insoluble ma-
terials or stabilize the formulation. These materials include
various water-soluble or dispersible surfactants or salts.
Other conventional creme rinse formulations are disclosed on
pages 1102-1105 of THE CHEMISTRY AND MANUFACTURE QF COSMETICS,
Vol. 4, 2nd edition, by Maison G. deNavarre O
Prior art hair conditioning compounds, as exempli~
!
fied by pages 1097-1101 of the above book, also include quat~
ernary compounds mixed with higher alcoholsO In particular, a
B formulation described on page 1100 described Adogen 432 CG, a
quaternary ammonium compound, mixed with cetyl alcohol, sodium
chloride, and water. This composition contain~ a relatively
20 high percentage of cetyl alcohol and would appear to show that
the same is desirable in providing some conditioning properties
to the hair.
Prior art compounds used higher levels of quaternary
to provide ~mproved performance, as has been noted previously
only relatlve small percentages of cetyl alcohol could be in~
corporated into the composition without impairing the stabil
ity of the compound. Further, prior art compositions generally
have what can be best described as a stringy or lumpy appear-
ance or consistency. This is due in part to the natural ag~
30 glomeratlve effects of the quaternary compounds themselves.
The prior art compositions commonly have particle sizes in the
nOfe5 tr6~e ma~K -2
11~3:167
range of 40 to 60 mi.crons or higher.
lt has been, therefore9 most surpris~ngly found that
a highly acceptable stable creme rinse formulation and hair -~
conditioning compositi.on can be prepared uslng a lower level
of active ingredients than heretofore thought possible by pre~
paring a composition of from 0. 5-2~o by weight quaternary con
ditioning compound, 0. 5-2~ by weight cetyl alcohol, up to
about 10.0~ by weight of a protective colloid, and the balance
containing water to 100~, this composition having a viscosity
of less than 10,000 centipoise when used as a conditioning
treatment, and less than 4,000 centipoise when used as a creme
: rinse.
It is most surprising that the composition of the
present invention is quite stable and is readily dispersible
in water and provides outstanding performance and properties
even at dilute concentrations which were not recognized pre-
viously.
The process of preparing the above composition com-
prises mixing the quaternary compound and water and heating
the same~ followed by melting the cetyl alcohol and blending
these two materials together and cooling the same. This cool
mixture is then homogenized at a pressure of from 500-8,000
psi, followed by blending with a dispersion of the thlckener
in water.
The attached drawing is a schematic plot of the
quaterrlàry contribution to monolayer area versus concentra~
tion described in Example 8.
The present invention provides a hair conditioning
composition consisting essentially of from about 0.5-2~ by
weight of a quaternary conditioning compoundg from about 0.5-
2% by weight of cetyl alcohol3 up to about 10.0~ by weight of
-3
3~
a protective colloid, and from about 99.o-86.o% by weight
water; the quaternary conditioning compound and cetyl alcohol
belng present in a ratio of from 1.5:1 to 0.4201, said compo~
sition having a viscosity of less than 10,000 centipoise.
The creme rinse composition of the present invention
consists essentially of from about 0.5-1.5% by weight of a
quaternary conditioning ~cmmpound, from about 0.5-1.5% by
weight of cetyl alcohol, up to about 5.0% by weight of a pro~
tective colloid, and from about 99.0-92~ by weight waterg the
. 10 quaternary conditioning compound and cetyl alcohol being pres~
ent in a ratio of from 1.5:1 to 0.6601, said composition hav~
ing a viscosity of less than 4,000 centipoiseO
The process of the present invention comprises pre-
paring a hair conditioning composition consisting essentially
of from about 0.5-2~ by weight of a quaternary conditioning
compound, from about 0.5-2~ by weight cetyl alcohol, up to
about 10.0% by weight of a protective colloid, and from about
990 o-86. o~ by weight water, the quaternary conditioning com-
pound and cetyl alcohol being present in a ratio of from 1.5:1
to 0.42-1 comprising 1) combining the quaternary conditioning
compound, a portion of the water, and the cetyl alcohol at a
~ J~70/~
L~ temperature above ~P~. to form.an intermediate~ 2) cooling
the intermediate to a temperature within the range of from
80-120F., 3) homogenizing the intermediate at a pressure of
from 500-8,000 psi, 4) dispersing the protective colloid in
water, and 5) blending the intermediate and dispersed protec~
tive colloid.
The process of conditioning hair of the present ln-
vention comprises 1) cleaning the hair and 2~ applying from 1
to 5 grams of a composition consisting essentially of from
about 0.5-2% by weight of a quaternary conditioning compound~
~4
~3~7
from about 0.5-2~ by weight cetyl alcohol3 up to about 10.0%
by weight of a protective colloid, and from about ggOo~86.o~ ;
by weight water, the quaternary conditioning compound and
cetyl alcohol being present in a ratio of from 1.5~1 to 0.42:1.
The quaternary conditioning compounds suitable for
use in the compositions and processes of the present invention
include stearyl dimethyl benzyl ammonium chloride, dihydro-
genated tallow di~,ethyl ammonium chloride, mi~ed higher alkyl
C12-C18 trimethyl ammonium chloride, cetyl dimethyl amine oxide3
stear~l dimethyl amine oxide, and mixtures thereof. The pre-
~erred quaternary conditioning compound is stearyl dimethyl
benzyl ammonium chloride. The quaternary conditioning com-
pound is present in the composition o~ the present invention
in an amount ranging from about 0.5-2~ by weight when the com-
position is designed for use as a hair condltioner and from
about 0.5 1.5% by weight when the composition is designed for
use as a creme rinse. The preferred composition includes from
about 0075-1.25% by weight quaternary conditioning compound.
The second ingredient used in the composition of the
present invention is cetyl alcohol. The cetyl alcohol aids in
conditioning the hair~ Howe~er, unless the composition is
homogenized, the cetyl alcohol causes the compositio~ to be-
come unstable~ The viscosity of unhomogenized samples rises
quite quickly~ forming an unusable composition. The cetyl al-
cohol is present in an amount from about 0.5-2~ by weight when
the composition is to be used as a conditioner and from about
0.5 1.5% by weight when this composition is to be used as a
creme rinse. More particularly, the cetyl alcohol is present
in an amount of from about 0.75-1.25% by weight.
The relative ratio of quaternary conditioning com-
pound to cetyl alcohol is from 105:1 to 0.4201 and for a creme
--5--
3~
rinse preferably from about 105-l to 0 66~10 It is within the
above ranges that the conditioni.ng propertie 9 0 f the composi-
tion of the present invention and the remarkable stabillty of
this composition is most evident. At ratios above or below
the above ratio, the compositlons become unstable in that the
composition separates unduly on standing or that the composi~
tion becomes so thick upon standing as to become unpourableO
Furth0rmore, it is the extremely small particle size dispersi.on
of the creme rln~e composition which aids in the desirable per-
formance properties thereof. It is most difficult to maintainthis small particle size at ratios outside the above~noted
ratios. In this regardJ when a quaternary compound such as
stearyl dimethyl benzyl ammonium chloride is processed utiliz-
lng the process o~ the present invention without incorporating
any cetyl alcohol in the composition, the viscosity is initial~
ly low, however, the particles tend to agglomerate and the com~
position becomes less easily dispersible and in turn as an ef-
fective conditioning compound. Also, when cetyl alcohol is
added without homogenization, the viscosity of the resultant
~0 composltions rises dramatically. Further, even when homogen-
ized, compositions outside the above range exhibit higher vis-
cosities and become more unstable.
When the term viscosity i5 used ln this specifica~
tion and in the attached clalms, it .refers to Brookfield Vis~
-~' cosity measured using Brookfield LV Viscometer with either #2
or #3 spindle~ and from 6 to 60 rpm.
Also, as an aid to stabilize the vlscosity of this
composition and to impart asthetic qualities9 a small amount
of a protective colloid may be utilized in an amount of up to
about lO~ and preferably from 0.1-10% and most prefer~bly 0~
5~. Suitable protec~i~e colloids include various cellulosic
~e~ e m~
~ 3~7
deri~atives such as methyl cellulose, h~droxyeth~l celluloseg
ethyl cellulose, guar gums, and various other nonionic or
cationic protective colloids, etc., which are known to be cos-
metically acceptable. Examples of these materials include
thickeners and other compositlons sold under the trade names
such as Natrosol~ Other similar protective colloids can be
; ùtilized in the composltlons of the present invention as the
exact composition of the protective colloid is unlmpo~1ant so
long as the same is cosmetically acceptable and chemically
10 compatibleO
The bulk of the composition of the present invention
comprises water, i.e., in the range of from 99~ o-86. o~ by
weight. Although tap water can sometimes be used if the same
contains a relatively low level of ions, it is preferred to
use deionized water.
Also, other conventional additives can be incorpor-
ated into the composition of the present invention such as
various dyes and perfumes which are cosmetically acceptable.
These materials are added in the composition in relatively
small amounts and do not affect the overall performance and/or
stability thereof~ However, salts as are commonly found in
prior art compositions should not be incorporated into the
compositions as they tend to make the compositions more un~
stableO
The compositions of the present inventi.on are pre-
pared by means of the process of the present invention which
process includes the steps of mixing the quaternary compound
and the cetyl alcohol under conditions of agitation and heat
prior to homogenizing the sameO This mixed composition is
then cooled to a temperature in the range of from 80 -120Fo g
preferably from 100-110F. This cooled mixture is then hom-
D 7_
~1~3~67
- o~enized at 500~89000 psio Subsequent to the homogenization
step, it 1~ preferred to force cool, i.e., cool rapi.dly9 the
intermediate to a temperature in the range of 80-9oF. This
aids in maintaining the desirable small particle size. ~t
this time, a dispersion of the protective colloid is added as
well as any perfumes and dyes which may be required. ~he pro--
tective colloid should be well dispersed in water before it is
added to the intermediate. Depending on the particlllar mater-
ial used, it may be necessary to heat the water-protective
colloid mixture to temperatures of up to 200F. If heat is
necessary to completely disperse the protective colloid, this
material should be cooled before the blending step. The pro~
cess of the preesent invention has the effect of provlding a
composition with relatively small particle size. Relatively
small particle size ls known to produce quaternary composi
tions which are considerably more active than similar composi-
tions with a larger particle sizeO In this regard, it is
found that the compositions of the present invention effective-
ly form a very thin film having a degree of integrity approach-
ing mono-layer type properties and have the combined proper-
ties of the ~uaternary compound and the cetyl alcohol.
The primary purpose or object of the process of the
present invention is to provide a final product with as small
a particle size as possible and to insure that the parti.cle
size remains small over standing. As has been disclosed in
U.S. Patent 3,954,634 which discloses the concept of homogen~
izing quaternary compounds to improve the particle size of the
resultant dispersion and stability thereofS smaller particle
size enables the quaternary compound to act more efficiently.
The compositions of the present invention are ready~
to use ha~r conditioners or creme rinses which are applied
~8~
31~7
directly to the hair of the user subsequent to shampooing.
These compositions are easily and re,adily dispersible across
the hair fibers and forms substantially thin films on the hair
fibers to replace the oils which are stripped from the hair
during shampooing. Also, the compositions can be readily dis~
persed in small quantities of water, io e., from 10-200 ml. of
water per 20 5 grams of product.
The composition of the present lnvention will now be
illustrated by way o~ the following examples~
EXAMPLE 1
A creme rinse composition having the following com~
position was preparedO
Stearyl dimethyl benz~l ammonium
chloride (25% solids) 3.6
Cetyl alcohol 1.1
Hydroxyethyl cellulose 0O75
Per~ume 0.25
Water Q.S. to 100
A portion of the water is mixed with the stearyl di~
methyl benzyl ammonium chloride and the mixture is heated to
180F. The cetyl alcohol is heated to above its melt point,
i.e., 150F., and the melted cetyl alcohol i9 added to the
water-quaternary mixture. This mixture is cooled to between
85 and 100F. and homogenized at a pressure of 5000 psi. The
remaining water is mixed with the hydroxyethyl cellulose and
heated to 120CF. with agitation. This dispersion is cooled to
75F.j and the hydroxyethyl cellulose dispersion is blended
with the cetyl alcohol~quaternary mixture.
The above composition was tested against a leading
commerciall~ available creme rinse and was found to provide
excellent conditioning and a cleaner less oily feeling than
3~67
the leading creme rinse.
EXAM_LE 2
A number of compositions were prepared without the
thickener to observe the stability of the compo~ition and the
viscosity with and without homogenization.
-10-
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'~J ~D0~00O~D0~0~U~O~C~0~00~000 S~
V ~ J~ ~ ~ ~ N ~7 ~) 0 (~ ='r ~r ~ N O O
o~ o ~ ~ ~D ~ ~O
)N ~1 ~U
~J C~
.,1
o-~ ~a~oo~ o~,~(~~ D ('-)~
C~ D O ~ 0 t~(~) C-oo
~I N 1~1 t~ N ~) (r~ r-l N (r)
S ~og ~ ~)I--CO $ ~_~ N ~O~ N
N ~1 1--I C~~ 1~0 ~ N I
r~l H N N N (r~ ~~ N (~)
\ >~ .
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O ¢ ~ N~ (~) oNo ~ ~Y~ oN~ ~ ~Y) ~ ~ oNo ~ (r)N
~) ~ N ~ rl N ~) H N ~I N ~f) ~I N ~ l N N N N N N N
V
~ .
H ~ IS~
~ g~ 0~ ~D C\J O 0 ) C~ ~0 0 0 l~ N 0 15~ N O 1~\~ CO Lr~O 00
~ ~D ooo~oooo~o~ oooooo
~o
td L~
~O ~0~0 0~0 L--C~O N O NL~O N lS~O ~D O t~)~0 ~,
, O O O O ri O O O O ~i ~i ~i ~i~i~i ~i ~i ~i ~ ,~ ~i ~i ~i Lq ~3
$ ~g
~d
bD C~
~ , ~e
C) co tq tq tq tq M O O O O O Cq tO Lq O O O ~q Cq ~q O O o ~ Q
~ ~ ~ ¢
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~ ~ m c~ ~ H ~ ~ ~ æ o P~ x
o o
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As is apparent from the above table, the viscosity
increases as concentration increases or cetyl alcohol ln~
creases. Also, the homogenized samples generally have a lower
viscosity than non-homogenized samples. On performance, the
homogenized samples performed better than the non~homogenized
samples.
EXAMPLE 3
The combing ease of a number of samples having dif~
ferent ratios of quaternary to cetyl alcohol by measuring the
work required to pass a comb through a hair swatch. The hair
was first washed with a commercially available shampoo.
Run _ Ratio of Cetyl Alc~Quat _ ~alue
A 0.25~1 100
B lol 84
C 2.301 64
D 1.5:1 80
E 1.22 1 82
The lower the value, the easier the combing. As is
apparent~ Run C (2.3:1) was the eas~estO Howeverg at this
ratio, the product was extremely viscous even after homgen-
ization. This indicates that higher levels of cetyl alcohol
produce more conditioning.
EXAMPLE 4 and COMPARATIVE EXAMPLE 1
Two formulations having an identical composition
; were prepared:
Ammonyx 4 (25% solids) 702
-~ (stearyl dimethyl benzyl
ammonium chloride)
Cetyl alcohol 2.2
Perfume 0.5
Water Q.S. to 100
The only difference in the compositions is that Ex~
ample 4 was homogenized at 5,000 psi and had a viscosity of
15 cps, while ComparatiYe Example 1 was not homogenized and
olenote~ 4~ e ~ K -12-
~1~i3167
had a viscosity of 69 660 cps
These compo~itions were applied to 33 models using
a half-head technlque by professional operators. The models
pe:rceived signiflcantly more conditioning in the Example 4
sample at the 95~ confidence level. Although other prefer~
ences were not statistically confident at 95%, the Example 4
composition was generally preferred in almost all attributes
of a creme rinse by both models and operatorsO
The following composition was prepared using the
procedure of Example 1:
Am~onyx 4 (25% solids) 3.0
Cetyl alcohol 0.75
Perfume 0.3
Hydroxyethyl cellulose 0.75
Water ~ 20
'100. 00
The composition was applied at various dilution
levels, i.e., 1 0, 2.5, and 4.0 grams in 200 ml. water and
compared to Tame, a commercially available creme rinse, at
2.5 grams in 200 ml. water. Tame has an approproximate com-
position,by analysis of 206~ dimethyl stearyl benæyl ammonium
chloride and 1.~% polyethoxylated long-chain fatty alcohol.
The models statistically preferred the composition
of Example 5 at all three use levels in areas of residue on
comb, lubricity, clean ~eel, wet preferenceg and dry prefer
enceO Although the 1.0 gram dilution did not provide as good
comb~ng as the 2~5 and 4.0 samples, it did condition at a
level equal to or better than Tame at much lower solids level.
EXAMPLE 6
The composition of Example 1 was compared to a com-
~enDt~) ~rJc ~ark ~13-
'3~7
mercially available creme rinse having a composition by anal~
ysi.s of 1.9% dimethyl stearyl benzyl ammonium chloride, 005
polyethoxylated ester, 6.8~ a mix of fatty esters, fatty al~
cohols and hydrocarbon oily and 0.9% protein derivative at
equal use levels on 34 modelsO The composition of Example 1
was found significantly more conditioned~ both wet and dry,
and had less residue on the comb, le~t the hair feeling
cleaner and with less flyawayO
EXAM_LE 7
A composition was prepared using the procedure of
Example 1 having the formulaO
! Ammonyx 4 (25% solids) 3.33
Cetyl alcohol lo 02
Perfume 0.24
Hydroxyethyl cellulose 0.75
Water Q.S.to 100%
The ratio of quat to cetyl alcohol is 45/55 at 1.8~
solids. This formula was signi.ficantly preferred by 31 models
and the professional operat~rs over Tame, a cornmercially
available creme rinse, in areas of oily feel, clean feel,
easier rinsing9 less residue, less coated, overall preferences,
and body ~nd manageability.
EXAMPLE 8
In order to determine if there is any molecular
interaction between the cetyl alcohol and quaternary compounds
at the ratios of the compositions of the present invention, a
mono-layer study on a 5~ NaCl aqueous solution using the
Wilhelmy method was performed on a series of mixtures of cetyl
alcohol (Aldo 52) and stearyl dimethyl benzyl an~nonium chlo~
ride. The mixtures were prepared in a hexane~ethanol sol~ent
spreading medium. The surface tension, ~ , of the 5~ ~aCl
~3e~7~ fl~4e n~rK -14-
1~3~67
solution is measured as the spread mono-layer is slowly com-
pressedO The film pressure~ ~ , is equal to the difference
between ~O, the surface tension o~ the clean substrate, and
'r the measured surface tension of the ~ilm covered substrate~
The limiting area Ao is the film area at the film collapse
point and represents the area of closest packing.
The schematic graph in the attached drawing is de-
veloped using the following analysis technique. Y, the assumed
contribution of the quaternary, equals the observed A.o minus
contribution of cetyl alcohol, assuming the cetyl alcohol acts
as if nothing else was present in the systemO The observed Ao
was taken for a number of mixtures and Y values were calculated
and plotted versus weight fraction. The observed Ao was mea~
sured using the apparatus described in ACS Symposium Series #8,
Adsorption at Interfaces, Monolayer Studies V~ pages 157-169
(1975) and ~. Colloidal & Interface Science9 V28, page 481
(1968).
As shown by the schematic plot within the ratios of
the compositions of the present invention, there is a shoulder
indicating some interaction between the cetyl alcohol and
; quaternary compound.
~15
,
