Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1~3~Q~
~AIR CONDITIONING CO~OSI~ION CONTAI~ING
CATIONIC POLYMæR, AMPHOTERIC SURFACTANT AND A
BETAINE AND METHOD FOR USE
This invention relates to compositions that are
useful in conditioning hair and to processes for condi-
tioning hair that employ such compositions.
It is known in the prior art to treat hair with
certain quaternary amine compounds for the purpose of
conditioning it i.e. to improve its combability, manage-
ability, softness, etc. Although such prior art composi-
tions have proven to be effective in varying degrees, one
of the chief drawbacks has been the fact that the effect
has not been long-lasting i.e. it does not survive repeated
shampooings.
It has also been suggested that hair conditioning
compositions may be provided which are relatively stable
to repeated shampooings by formulating such compositions
so that they consist essentially of an aqueous solution
containing a cationic polymer, an amphoteric detergent
and sufficient acid to give the aqueous solution a pH
in the range of about 1 to 6.
It has now been found that a still further increase
in efficacy as a hair conditioning agent can be obtained
if there is added to the aqueous acid composition contain-
ing a cationic polymer and an amphoteric detergent, an
effective amount of a betaine. Thus, whereas the betaines
in and of themselves in solution do not effect any hair
conditioning; in combination with the cationic polymer
and amphoteric surfactant, the efficacy of the latter
` combination as a hair conditioning agent is significantly
enhanced.
,
. . .
. .
113~0~
--2--
It is accordingly an object of the present invention
to provide a hair conditioning composition that is
stable to repeated hair shampooings.
It is also an object of the present invention to
provide a process for treating hair using the aforesaid
composition which has a conditioning effect on the hair
that is relatively stable to repeated shampooings.
It is a further object of this invention to provide
a composition of the aforesaid type which consists essen-
tially of an aqueous acidic solution containing a cationic
polymer, an amphoteric detergent and a betaine and to
provide a process for treating hair with such a composi-
tion.
Other and more detailed objects of this invention
will be apparent from the following description and claims.
The betaines that are useful for the purposes of
the present invention may be described by the formula:
CH3
(I) R - X - CH2COO
CH3
in which R is a long chain aliphatic radical containing
10 to 24 atoms. As used herein, the term long chain
aliphatic radical includes saturated and unsaturated
straight chain and branched chain radicals, hydrocarbon
radicals as well as chain radicals that include other
atoms in addition to carbon atoms in the chain (e.g.
oxygen, nitrogen, etc.).
By way of illustrating typical betaines that ~ay
be used in this invention, mention may be made of
cocamidopropyl betaine, oleyl betaine, cetyl betaine,
coco betaine, etc. Cocamidopr~pyl betaine is described
by the formula:
0~0
--3--
O CH3
Il l+
(II) R C NH (C~2)3 ~ CH2 O
CH3
wherein RC- is the cocs fatty acid acyl radical. Coco
fatty acid is a mixture of fatty acids obtained from
Coconut Oil which are predominantly C12 acids. Oleyl
betaine, on the other hand, may be described by the
formula:
~H3
(III) CH3(CH2)7CH = CH(C~2)7 CH2 ~ 2
CH3
Structu~ally the coco betaine and cetyl betaine res~mble
the oleyl betaine shown in formula III above excepting that
the oleyl radical is replaced with coco fatty radicals or
the cetyl radical respectively. A number of betaines that
are useful for the purposes of the present invention are avail-
able commercially. Among these mention may be made of
* * * *
CHEMADENE NA 30, LONZAINE 12C, LO~Z~INE 14C, ~ONZAII7E 16S, etc.
The quantity of the betaine that may be incorporated in
the composition of the present invention may vary~ Usually,
it will comprise between about 0.1% to about 5~ by weig~t
-and preferably between about 0.3~ to about 3~ by weight based
on the total weight of the composition.
The cationic polymers ~hat are useful for the purposes of
the present invention can vary somewhat. Two classes of
polymers that have been found to be particularly useful are
those s*old under the trade names MERQUAT (e.g. MERQUAT 100,
MERQUAT 550) and ONAMER (e.g. ONAMER M). MERQUAT 100 is a
polymer of dimethyldiallyl ammonium chloride and is probably
a mixture of compounds having the formula A or B given
below:
*Trade Marks
'
1136050
-4-
(A) (B)
~ ~CH2~ ~CH2~ CH2 ~ ,
CH - CH _ ~H CH CH -- _
(IV) l l 21 1
S ~
H3C CH3 n CH3 CH3 n
MERQUA~ 550 is a polymeric quaternary ammonium salt made of
acrylamide and dimethyl diallyl ammonium chloride monomers.
These vary in molecular weight. Ordinarily, however, the
polymers of this class.that will be employed have a molecular
weight in the range of from 4,000 to 550,000 and preferably
in the range of from 20,000 to 100,000.
The ONAMER type polymers that are useful for the present
purposes are poly(dimethyl butenyl ammonium chloride)-
a,~-bis(triethanol ammonium chlorides) that may be
described by the general formula-:
C 2C 2 ~ -~CH3 ~ CH2CH2OH
(~) OH-CH2CH2 - N~- -N+-CH2-CH = CH-CH2 - ~ 2 2
OH-CH2CH2 _CH3 n 2 2
.
The molecular weights of these polymers that may be employed
herein can also vary somewhat. For the most part, however,
this will be in the range of from about 800 to 5000 and
preferably, in the range of from about 1000 to 3000
The quantity of cationic polymer contained in the
present aqueous solutions will depend on the particular
results that are desired. Ordinarily, this will constitute
113~0~0
--5--
between about 0.4% to about 10% by weight based on the
total weight of the aqueous composition with the optimal
range being between about 1% to about 5~ on the same
weight basis.
Another essential component of the compositions of
this invention are the amphoteric detergents. A character-
istic of these materials is that many assume the character
of an anionic or a cationic surfactant compound depending
upon the pH of the solution in which it may be contained.
There are a number of amphoteric detergents that are
suitable for use in the present invention. However, two
classes of detergents have been ~ound to be especially
effective. The first class can be defined by the formula:
7H2COONa
(VI) R - C 2 2 2
N CH2
CH2
in which R is a long chain fatty radical containing ~rom
10 to 18 carbon atoms. A typical example of such a com-
pound or compounds is the case in which R represents coconut
fatty radicals. A material of this character is sold under
the trade name MIRANOL C2MSF and is described in the CTFA
Cosmetic Ingredient Dictionary (1973) under the name
AMPHOTERIC-2.
A second class of amphoteric detergents that is
particularly effective for the purposes of the present
invention can be defined by the formula:
(VII) R- NH- CH - CH - COOH
wherein R is a long chain fatty alkyl group having from 10
*Trade Marks
.1 ' '~
113~;0~;0
--6--
to 18 carbon atoms. An example of such a detergent is
marketed under the trade name DERIP~AT 170C in which the
R in formula VII is a mixture of lauryl and myristyl fatty
alkyl groups. This material is described in the CTFA
Cosmetic Ingredient Dictionary (1973) as Lauraminopro~ionic
Acid.
The quantity of amphoteric detergent which will be
contained in the composition of th$s invention will vary
somewhat again depending on the economics and the results
sought. ~owever, usually this will be in the range of
from about 0.2 to about 20% by weight and ideally in the
range of from about 1% to about 5% by weight based on the
total weicht of the composition.
Another feature of the present compositions is that
they have an acid pH that is a pH that falls in the range
of from about 1 to 6. Any of a variety of acids may be
used in adjusting the pH of these compositions to the
proper level thydrochloric, citric, lactic and phosphoric
ae~ds ~ere found to be particularly useful and suitable.
Although the betaines, cationic polymers, the ampho-
teric detergents and the acid pH above are the essential
features in the present compositions, the compositions
contemplated by the present invention may also contain
other ingredients which may serve to improve the
organoleptic character of the product or its ease of
application. Thus, it is within the purview of this
invention to incorporate in the present compositions such
materials as solvents, fragrances, thickenin~ agents,
fragrance solubilizers, bactericides, etc.
A variety of sol~ents can be.e~loyed in the composi-
tions of this invention. These will usually take the form
of an aliphatic alcohol, either-a monoh~dric or olyhydric,
*Trade Mark
. ~
,
V
-7-
preferably having from 1 to 6 carbon atoms. As employed
herein, the term "aliphatic alcohol" is used in its
generic sense and includes such alcohols as straight
chain and branched chain alkyl alcohols that can be
monohydric or polyhydric (e.g. dihydroxy)ether alcohols,
ester alcohols, etc. By way of illustrating the sol~ents
that may be useful for the present composition, mention
may be made of ethanol, carbitol, hexylene glycol,
propylene glycol. The solvents may be used at levels from
0% to about 50% and preferably in the range of from 0%
to 5~ by weight based on the total weight of the composi-
tion.
Optionally, a neutral surfactant may also be incor-
porated in the compositions of this invention. These will
constitute between 0~ to 10% by weight based on the total
wei~ht of the composition but more often, a range of o%
to 2% is preferred. Suitable examples of such neutral sur-
factants are Igepal C0-630 (CTFA name nonoxynol-9);
Arlasolve 200 (polyoxyethylene(20)isohexadecyl ether);
Tween 20 (CTFA name polysorbate 20).
To facilitate the application of the present compositions
to the hair it is often useful to increase its viscosity
somewhat. Many thickening agents can be used for this purpose.
Amon~ these mention may be made of hydroxethyl cellulose,
carboxymethyl cellulosel the Carbopols e.g. Carbopol 940.
However, hydroxethyl cellulose has been found to be particu-
larly suitable. The concentration of the thickening agent may
vary ~omewhat depending on the results desired. Usually, this
will be present in the range of from 0% to about 10~ by
weight based on the total weight of the composition.
*Trade Marks
3~iiQ~(~
--8--
It is often useful to incorporate a bactericide
in the compositions of this invention. A variety of
materials are known in the prior art that will ser~e
this purpose. By way of illustration, mention may
be made of a material sold under the trade name
DOWICIL 200. This is identified in the CTFA Cosmetic
Ingredient Dictionary, second edition, as quaternium-15
and chemically as 1-(3-chloroallyl)-3,5,7-triaza-1-
azoniaadamantane chloride. The quantity of bactericide
that will be contained in the present compositions
will vary somewhat depending on the nature of the
particular composition. Usually, however, it will
comprise between 0% to about lQ% by weight based on the
total weight of the composition.
Aside from the absolute quantities of the cationic
polymer and amphoteric detergent contained in the present
compositions, it has been found that their conditioning
effectiveness is highly dependent upon the ~molar ratio~
of polymer to detergent. The term "molar ratio"
as used herein is designated by the latter ~ and
is defined as:
, . ~
1136Q~iO
[ Polymer ~mer) ]
c~ =
[ Detergent (mol) ]
In the above expression and elsewhere in the specification
S and claims, the term lPolymer (mer)] refers to the number
of mols of the repeating units of the polymer bearing a
single positive charge contained in the composition.
The term [Detergent (mol)] in the aforesaid expression
and elsewhere is defined as the number of mols of detergent
contained in the composition. The ratio ~ may vary
somewhat. Ordinarily, this will be in the range of from
about .2 to about 5 and preferably in the range of from
about 1 to a~out 2.
The compositions of this invention may be applied
to hair in any suitable manner. One typical procedure
involves applying the conditioning composition, such as
described in Example 1 below to freshly dyed or bleached
hair, working it gently into the hair mass, leaving the
said composition on hair for one to three minutes and rinsing
the hair thoroughly with water prior to combing and drying.
Amount of the conditioning composition applied to hair
may vary but, in general, should not be less than 1~ of the
hair weight and does not need to exceed 20~ of the hair
weight.
It is generally visualized that the compositions of
this invention will be applied to hair that has previously
been given a treatment that leaves the hair somewhat
alkaline. Typical of such treatment are treatments with
oxidation hair dye systems or bleaching systems. One such
treatment involves mixing a dye base containing among
other things the oxidation dye intermediates with an
aqueous vehicle containing an oxidizing agent such as
,,,~
~3~ 0
--10--
hydrogen peroxide and then shampooing this mixture into
the hair. These mixturesbefore being applied to the hair
usually have an alkaline pH e.g. in the range of from
7 to 12 and preferably 8 to 11. Another such treatment
involves for example treating the hair with an alkaline
bleaching solution which contains the usual oxidizing
agent (e.g. aqueous hydrogen peroxide), boosters (e.g.
potassium persulfate and ammonium persulfate), alkalizing
agents, etc.
When the compositions of this invention are applied
to hair that has been previously treated as indicated
above, the combination of amphoteric deteryent and cationic
polymer precipitates out on the hair forming a condition-
ing complex that is highly resistant to repeated shampoo-
ings.
The pH of the hair conditioning compositions that
are employed in the present invention will be selected
to some extent on the basis of the alkalinity of the
hair to be treated and the relative amounts of cationic
polymers and amphoteric detergent. In general, the pH is
selected so that after the composition is applied to the
hair and comes under the influence of the alkalinity of
the hair that the pH of the composition is increased by
approximately 1 pH unit above which the precipitation of
the complex takes place. Generally, under these conditions
the optimum precipitation of the conditoning complex
appears to take place.
The following Examples are given to further illus-
trate the present invention. It is to be understood, however,
that the invention is not limited thereto.
~13~V5;0
--11--
Where the CTFA name i9 given herein, reference is
made to the name given to the material in the CTFA
Cosmetic Ing~edient Dictionary of 1973 or the 2nd
Edition of 1977.
EXAMPLE_l
Ingredient ~ by Wt.
Merquat lO0 1 3.50
Miranol C2MSF 1.75
Hydroxyethyl cellulose2.00
Sodium hydroxide 0.01
Phosphoric acid 0.07
Ethanol 4.00
Cocamidopropyl betaine 32.00
Water QS to 100.00
pH 4.5
1 CTFA name Quaternium-40
2 CTFA name ~mphoteric-2
3 CTFA name
EXAMPLE 2
Same as Example l except that 2.00% oleyl betaine
is used in place of the cocamidopropyl betaine used
in Example l. This composition had a pH of 4.5.
*Trade Marks
~r ~
~ ~ )
~ ~3~0~0
: Ingredient % by Wt.
Ex. 3Ex. 4 Ex. 5
Merquat 100 5.0
Hydroxethyl cellulose 2.250
Phosphoric Acid 0.450
Sodium hydroxide 0.015
Miranol C2MSF 2.560 >
Sorbic*acid 0.100
; Dowicil 200 4 0.100
Carbitol 3-000
; Cocamidopropyl betaine 0.600
Fxagrance 0.400_ ~ :
Tween 20 5 --- .001 ---
Arlasolve 200 6 --- --- .001
Water to 100%
pH 4.84.5 4.5
4 CTFA name Quaternium-15
5 CTFA name Polysorbate-20
6 Polyoxyethylene(20)isohexadecyl ether
i
*Trade Marks
,,
5;
t
- 12 -
:''
.
,
3~i;0~iO
-13-
% by Wt.
Ex. Ex. Ex. Ex. Ex. Ex.
Ingredients 6 7 8 9 10 11
Merquat 100 5.0 -- -- 5.0 5.0 5.0
Hydroxyethyl cellulose 2.25
Sodium hydroxide 0.15 _ .
PhosphorLc acid .2 0.46
Deriphat 170C 2.0 -- -- -- -- --
Miranol C2MSF -- 2.56
Sorbic*acid 0.1 0.10 >
Dowicil*200 .10 0.10 >
Carbitol . 3.0
Fragrance .40 _
Chemadene NA30 2 . 0 2 . 0 2 . O -~
Merquat 550 9 -- -- 12.5 -- -- --
*M 10 __ 5.0 -- ~~
Lonzaine 12C 11 __ __ __ 2 . 0 -- __
Lonzaine 14 12 2.0 __
Lonzaine 16S 13 -- __ __ __ __ 2.0
Water to 100% >
pH 4.5
7 CTFA name Lauramopropionic acid
8 CTFA name Cocamidopropyl betaine
9 CTFA name Quaternium-41
10 Poly(dimethyl butenyl ammonium chloride)~,~-bis(triethanol
ammonium chloride)
11 CTFA name Coco betaine
12 CTFA name Lauryl betaine
13 CTFA name Cetyl betaine
To compare the relative effectiveness of compositions
of this invention containing a betaine and one which contains
the cationic polymer and amphoteric surfactant but no betaine,
the following compositions were prepared:
*Trade Marks
-- 13 --
-
'
1~3~
-14-
COMPOSITION A
Ingredient % by Wt.
Nerquat 100 3.50
Miranol C2MSF 1.75
Hydroxyethyl cellulose 2.00
Sodium hydroxide 0.01
Phosphoric acid 0.07
Ethanol 4.00
Cocamidopropyl betaine --
Water QS to 100.00
pH 4.5
COMPOSITION A-l
Ingredient % by Wt.
~lerquat*100 5.000
Hydroxyethyl cellulose 2.250
Phosphoric acid 0~450
Sodium hydroxide 0.015
Miranol C2MSF 2.560
Sorbic a*cid 0.100
Dowicil 200 0.100
Carbitol 3.000
Cocamidopropyl betaine --
Fragrance 0.400
Water QS to 100.000
pH 4.5
In addition, the following hair dye preparation was formulated
to be applied before the hair conditioning treatment.
COMPOSITION B
Ingredient % by Wt.
p-Phenylenediamine 0.35
N,N-bis(2-hydroxethyl)-p-
phenylenediamine sulfate 0.18
Resorcinol 0.31
l-Naphthol 0.08
Oleic acid 7.50
Propylene glycol 4.40
Isopropanol 4.35
Hydrogen peroxide 3.00
*Octoxynol-l 3.50
**Trade Marks
- 14 -
,, ~
.~
~ 3~iQ~
-15-
COMPCSITION B (Cont'd)
Sulfated Castor Oil1.50
Ammonium hydroxide1.15
*Cocamide DEA 0.75
Fragrance 0.15
Sodi~m sulfite 0.05
ED~A 0.01
Water QS to 100.00
pH 9.8
10 *CTFA name tSee CTFA Cosmetic Ingredient Dictionary, 2nd
Edition, 1977)
Swa~ches of intact Caucasian hair were colored with
Composition B above. This was applied to dry hair working the
composition into a lather. The composition was permitted to
remain ~n contact with the hair for 20 min. at ambient temp-
eratures. A little warm water was then added to the hair and
worked into a lather. The hair was the~ rinsed with water
until the water ran clear. The ratio of the amount of solu-
tion to weight of hair, temperature and qua~tity of water
used for rinsing after treatment, were all maintained so as
to simulate conditions on the head. After rinsing, the
conditioning materials of Example 1 and ~omposition A above
were applied to hair (0.1 g of each pxoduct per 1 g of hair),
they were worked in for 30 seconds and left on the hair for
additional 1 minute after which time the hair was rinsPd
and combed. The combing measurements were performed by the
procedure described in the paper by Garcia and Diaz (J. Soc.
Cosmet. Chem. 27, 379-398, 1976). The test essentially involves
passing of a hair tress through a comb attached to ~ strain
gauge which in turn is connected to a recording device. Work
is expended to accomplish the passage of the hair tress
through the comb, and this work, reaa off the integrator, is
the objective measure of combing ease/difficulty.
**Trade Mark
~L~3~0~iO
-16-
Having determined the combing properties of hair
after coloring and conditioning treatments, the swatches
were shampooed with Herbal Essence Shampoo the number
of times indicated in Table I and again tested for
combing. The shampooing procedure involved application
of the shampoo ~0.1 g per 1 g of hair~, working it into
the hair over the period of 60 seconds to produce a
copious lather and rinsing the shampooed hair for at
least 1 minute. Each shampoo step consisted of two
lathering/rinsing sequences.
The results of combability tests are summarized in
Table I below. In the Table, the "Work of Combing" is
expressed in units of work (gcm). The higher the values,
the harder was it to comb the hair.
TABLE I
Treatment Average Combing Work (gcm)
With on wet Hair
BeforeAfter
Treat-Treat- +4 +5 +6
~ent ment Shampoos Shampoos Shampoos
Composition of
Example 1 on 4100 228 349 438 531
hair dyed with
Composition B
Composition A on
hair dyed with 4100 323 520 530 689
Composltlon B
-
As will be noted, the hair treated with the Composition
of Example 1 of this invention containing the betaine is
easier to comb both i~mediately after treatment as
well as after several shampoos when compared with hair
treated with Composition A that does not contain the betaine.
This result has been further confirmed in experiments on
live heads. It should be noted that betaines by themselves
`` 1~3i0~0
-17-
do not ef~ect any conditioning when applied in a formula-
tion in combination with the cationic polymer e.g.
MERQUAT 100 or ONAMER M. It is only when other ampho-
terics, such as the ones described above, are also
present in the formula that additional conditioning is
obtained from use of the betaine.
A similar test was run comparing the results obtained
with Composition B embodied in this invention with a
comparable composition i.e. Composition A-l above that
does not contain the betaine. Similarly, results were
obtained which are summarized in Table ~I below.
TABLE II
Before After + 4 + S + 6
Treat- Treat- Shampoos Shampoos Shampoos
ment ment
Composition of
Example 3 on 5233 300 486 533 617
Hair Dyed with
Composition B
Composition A-l 5233 580 641 809 916
on Hair Dyed with
Composition B
;
*Trade Marks
- 17 -
,
;