QUATERNARY AMMONIUM COMPOUNDS IN PRETREATMENT OF HAIR BEFORE SHAMPOOING WITH AN ANIONIC SHAMPOO

COMPOSES D'AMMONIUM QUATERNAIRE POUR LE PRETRAITEMENT DES CHEVEUX AVANT L'APPLICATION D'UN SHAMPOOING ANIONIQUE

English Abstract

Abstract of the Disclosure
This invention is concerned with the pretreatment of
hair on the human head, preceding shampooing the hair with anionic
type hair shampoos, and with compositions for effecting such
pretreatment, to obtain highly improved manageability of the hair
after shampooing and with improved fullness, combability and
other desired properties of the hair. The pretreatment composi-
tions utilize readily water-soluble quaternary ammonium compounds,
particularly in combination with certain agents, notably poly-
ethylenimines and N-ethanolacetamide, and desirably together with
various supplemental ingredients.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of treating hair to improve the manage-
ability thereof, which comprises initially contacting the hair
with a dilute aqueous composition containing from about 0.5
to about 4% by weight of a water-soluble quaternary ammonium
compound containing at least one long chain alkyl radical
attached to the central nitrogen atom thereof, and then
shampooing the hair with an anionic shampoo.
2. The method of claim 1, in which the quaternary
ammonium compound has the formula
<IMG>
wherein R1 is C8-C18 alkyl; each of R2, R3 and R4 is C1-C3 alkyl,
the total number of carbon atoms in R2, R3 and R4 not exceeding
6; and A is an innocuous anion.
3. The method of claim 1, in which the dilute aqueous
composition containing the quaternary ammonium compound also
contains at least one member of the group of N-ethanolacetamide
and a fatty acid ethanolamide in which the fatty acid comprises
predominately lauric acid.
4. The method of claim 1, in which the dilute aqueous
composition containing the quaternary ammonium compound also
contains polyethlenimine having a molecular weight between
about 10,000 and about 70,000.
5. The method of claim 3, in which the dilute aqueous
composition also contains polyethylenimine having a molecular
weight between about 10,000 and about 70,000.

6. A method of treating hair to improve the manage-
ability thereof, which comprises initially contacting the hair
with a dilute aqueous solution, clear to the naked eye, con-
taining from about 0.5 to about 4% by weight of a water-soluble
quaternary ammonium compound containing at least one long chain
alkyl radical attached to the central nitrogen atom thereof,
N-ethanolacetamide, polyethylenimine having a molecular weight
between about 10,000 and about 70,000, and at least one acid
selected from the group consisting of formic acid and acetic
acid in an amount to impart to said solution a pH in the range
of about 3 to below 7, and subsequently shampooing the hair with
an anionic shampoo.
7. The method of claim 6, in which the dilute
aqueous solution contains the stated ingredients in approximately
the following proportions by weight of said solution:
Water..................................70 to 90%
Quaternary ammonium compound..........Ø5 to 4%
N-ethanolacetamide.....................3 to 18%
Polyethylenimine......................Ø5 to 5%
8. A composition for pretreatment of hair prior to
shampooing said pretreated hair with an anionic shampoo, said
composition comprising a major proportion of water, and from
about 0.5 to about 4% by weight of a readily water-soluble
quaternary ammonium compound containing at least one long chain
alkyl radical attached to the central nitrogen atom thereof,
and polyethylenimine having a molecular weight in the range of
about 10,000 to about 70,000, said composition also including
at least one water-soluble acid and having a pH in the range of
about 3 to below 7.
9. The composition according to claim 8, which
also includes a minor proportion of at least one member of the
group of N-ethanolacetamide and a fatty acid ethanolamide in
which the fatty acid comprises predominately lauric acid.
26

10. A composition according to claim 8, in which
the quaternary ammonium compound has the formula
<IMG>
wherein R1 is C8-C18 alkyl, each of R2, R3 and R4 is C1-C3
alkyl, the total number of carbon atoms in R2, R3 and R4
not exceeding 6; and A is an innocuous anion.
11. The composition according to claim 10, wherein
R1 is predominately dodecyl; each of R2, R3 and R4 is methyl;
and A is chlorine or bromine.
12. The composition of claim 8, in which said
water-soluble acids are formic or acetic acid.
13. A composition for pretreatment of hair prior
to shampooing said pretreated hair with an anionic shampoo, said
composition comprising a clear aqueous solution containing from
about 70 to about 85% of water, from about 1.5 to about 2% of
a readily water-soluble quaternary ammonium compound having
the formula
<IMG>
where R1 is alkyl containing predominately from 10 to 14 carbon
atoms; R2, R3 and R4 are each methyl; and A is chlorine or
bromine; from about 12 to 15% of N-ethanolacetamide, and from
about 1 to 2% of polyethylenimine having a molecular weight
between about 40,000 to about 60,000, said percentages being
by weight of the composition, said composition also including at
least one water-soluble acid and having a pH in the range of about
3 to below 7.
14. The composition of claim 13, in which the
water-soluble acid is formic acid or acetic acid.
15. A composition for pretreatment of hair prior
27

to shampooing said pretreated hair with an anionic shampoo,
said composition comprising a major proportion of water, from
about 0.5 to about 4% by weight of a readily water-soluble
quaternary ammonium compound containing at least one long chain
aliphatic hydrocarbon radical directly or indirectly linked to
a quaternary nitrogen atom in said quaternary ammonium compound,
and a minor proportion of a polyethylenimine having a molecular
weight in the range of about 10,000 to about 70,000, said com-
position also including at least one water-soluble acid and ha-
ving a pH in the range of about 3 to below 7.
16. The composition according to claim 15, which
also includes a minor proportion of at least one member of the
group of N-ethanolacetamide and a fatty acid ethanolamide in
which the fatty acid comprises predominately lauric acid.
17. A composition for pretreatment of hair prior
to shampooing said pretreated hair with an anionic shampoo,
said composition containing from about 70 to about 90% of water,
from about 0.5 to about 4% of a readily water-soluble quaternary
ammonium compound containing at least one long chain aliphatic
hydrocarbon radical directly or indirectly linked to a quater-
nary ammonium nitrogen atom in said quaternary ammonium compound,
from about 3 to 18% of N-ethanolacetamide, and from about 0.2
to 5% of polyethylenimine having a molecular weight in the range
of about 10,000 to about 70,000, said percentages being by
weight of the composition, said composition also including at
least one water-soluble acid and having a pH in the range of
about 3 to below 7.
18. The composition of claim 17, in which the acid
is formic acid or acetic acid.
19. The composition of claim 17, in which the acid
is hydrochloric acid.
20. A composition for pretreatment of hair prior
to shampooing said pretrea ted hair with an anionic shampoo,
said composition comprising a clear aqueous solution containing
28

from about 70 to about 85% of water, from about 1.5 to about 2
of a readily water-soluble quaternary ammonium compound having
the formula
<IMG>
where R1 is C8-C18 alkyl; R2 is C1-C3 alkyl; R3 and R4 are C1-C3 alkyl
or benzyl; and A is an innocuous anion; from about 12 to 15%
of N-ethanolacetamide, and from about 1 to 2% of polyethyl-
enimine having a molecular weight between about 40,000 to about
60,000, said percentages being by weight of the composition,
and at least one water-soluble acid, said composition having
a pH in the range of about 3 to below 7.
21. A composition for pretreatment of hair prior
to shampooing said pretreated hair with an anionic shampoo,
said composition being free from heavy metal salts of 2-
pyridinethiol-1-oxide, and consisting essentially of a major
proportion of water, and from about 0.5 to about 4% by weight
of a readily water-soluble quaternary ammonium compound con-
taining at least one long chain aliphatic hydrocarbon radical
directly or indirectly linked to a quaternary nitrogen atom
in said quaternary ammonium compound, and polyethylenimine
having a molecular weight in the range of about 10,000 to about
70,000.
22. The composition according to claim 21, which
also includes a minor proportion of a member selected from the
group consisting of N-ethanolacetamide and a fatty acid ethanol-
amide in which the fatty acid comprises predominately lauric
acid.
23. The composition of claim 22, which also includes
at least one water-soluble acid and has a pH in the range of
about 3 to below 7.
24. The composition of claim 23, in which the acid
29

is formic acid, acetic acid or hydrochloric acid.
25. A composition for pretreatment of hair prior
to shampooing said pretreated hair with an anionic shampoo, said
composition being free from heavy metal salts of 2-pyridinethiol-
1-oxide and consisting essentially of from about 70 to about 90%
of water, from about 0.5 to about 4% of a readily water-soluble
quaternary ammonium compound containing at least one long chain
aliphatic hydrocarbon radical directly or indirectly linked
to a quaternary ammonium nitrogen atom in said quaternary ammonium
compound, from about 3 to about 18% of N-ethanolacetamide, and
from about 0.2 to 5% of polyethylenimine having a molecular weight
in the range of about 10,000 to about 70,000, said percentages
being by weight of the composition.
26. The composition according to claim 25, which
also includes at least one water-soluble acid and has a pH in
the range of about 3 to below 7.
27. The composition of claim 26, in which the acid
is formic acid, acetic acid or hydrochloric acid.
28. A composition for pretreatment of hair prior to
shampooing said pretreated hair with an anionic shampoo, said
composition being free from heavy metal salts of 2-pyridinethiol-
1-oxide, and consisting essentially of a clear aqueous solution
containing from about 70 to about 85% of water, from about 1.5
to about 2% of a readily water-soluble quaternary ammonium com-
pound having the formula
<IMG>
where R1 is alkyl containing predominately from 10 to 14 carbon
atoms; R2, R3 and R4 are each methyl; and A is chlorine or
bromine; from about 12 to 15% of N-ethanolacetamide, and from
about 1 to 2% of polyethylenimine having a molecular weight
between about 40,000 to about 60,000, said percentages being
by weight of the composition.

29. A method of treating hair to improve the manage-
ability thereof, which comprises initially contacting the hair
with a dilute aqueous composition containing from about 0.5 to
about 4% by weight of a water-soluble quaternary ammonium com-
pound containing at least one long chain aliphatic hydrocarbon
radical directly or indirectly linked to a quaternary nitrogen
atom in said quaternary ammonium compound, and then shampooing
the hair with an anionic shampoo.
30. The method of claim 29, in which the quaternary
ammonium compound has the formula
<IMG>
wherein R1 is C8-C18 alkyl, R2 is C1-C3 alkyl; R3 is C1-C3
alkyl or benzyl; R4 is C1-C3 alkyl or benzyl; and A is an
innocuous anion.
31. The method of claim 30, in which the quaternary
ammonium compound is a N-(acylcolaminoformylmethyl)-pyridinium
chloride, where acyl is a C8-C18 aliphatic hydrocarbon acyl
radical.
32. The method of claim 31, in which the acyl radical
is predominately lauroyl.
33. The method of claim 29, in which the quaternary
ammonium compound is a diquaternary ammonium compound.
34. The method of claim 29, in which the dilute
aqueous composition containing the quaternary ammonium compound
also contains at least one member of the group of N-ethanol-
acetamide and a fatty acid ethanolamide in which the fatty acid
comprises predominately lauric acid.
35. The method of claim 29, in which the dilute
aqueous composition containing the quaternary ammonium compound
also contains polyethylenimine having a molecular weight between
about 10,000 and about 70,000.
31

36. The method of claim 34, in which the dilute
aqueous composition also contains polyethylenimine having a
molecular weight between about 10,000 and about 70,000.
37. The method of claim 29, in which the dilute
aqueous solution contains the stated ingredients in approximately
the following proportions by weight of said solution:
Water.................................70 to 90%
Quaternary ammonium compound.........Ø5 to 4%
N-ethanolacetamide....................3 to 18%
Polyethylenimine.....................Ø5 to 5%
38. The method of claim 1 in which, subsequently to
the step of initially contacting the hair with said dilute
aqueous composition containing said quaternary ammonium compound,
the hair is rinsed with water, and then, while wet, is then
shampooed with said anionic shampoo.
39. The method of claim 7, in which, subsequently to
the step of initially contacting the hair with said dilute aqueous
composition containing said quaternary ammonium compound, the
hair is rinsed with water, and, while wet, is then shampooed with
said anionic shampoo.
32

Description

~O~ Z6
~. I
il This invention xelates l:o improvements in the treatment
! I of hair on the human head. As used hereafter, the term "hair"
! is to be understood to mean hair on the human head.
~j . . _.,. . , - .
In connection with the treatment of hair, it has been a
common practice, after washing or shampooin~ the hair, to subject
it to various hair treatment compositions to impart certain
desirable properties thereto. Among such hair treatment composi-
tions, used after the washing or shampooing of the hair, are those
~commonly called, or characterized as, rinses and conditioners,
~which are formulated or designed to impart softness or smoothness
'~ .
ii I

10811Z6
~of feel, luster, body or weight, manageability, combability and
~other properties to the hair. This is, in general achieve~ by
effecting a deposit on the hair of a film of a character such as
serves, to some extent or other, to impart to the hair one or more
of the above-stated properties or characteristics. The aforesaid ¦
lhair treatment compositions may take various forms, such as
aqueous or aqueous-alcoholic solutions, lotions, or dispersions;
icreams, etc.
Among such hair treatment compositions which have
heretofore been known and some of which have been used to a
substantial commercial extent are those of the type which contain
cationic agents, generally of the quaternary ammonium type and
! exemplified by compounds such as cetyldimethylbenzyl ammonium
,Ichloride; cetyldimethylethyl ammonium chloride; stearyldimethyl-
,ibenzyl ammonium chloride; distearyldimethyl ammonium chloride;
i! laurylisoquinolinium bromide; and quaternary ammonium salts of
~homopolymers of dimethyl-or diethyl-aminoethyl methacrylate.
IISuch hair treatment compositions are commonly compounded in the
¦Iform of emulsions or dispersions and, as indicated above, they
are applied to the hair after first washing the hair with a soap
¦or a hair shampoo which commonly contains, as an in~redient
¦¦thereof, soaps or anionic synthetic detergents, followed by
!! thorough rinsing of the hair with water, after ~hich the aforesaid
¦¦hair treatment compositions are applied to the hair. The thorough
rinsing of the hair with water is effected to remove as much of
the soaps or anionic detergents as possible since, otherwise,
,precipitates form in the hair by virtue of the incompatibility
of the cationics with the anionics.
- 2 ~
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,
,~ .

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Cationic agents are known generally to ~e substantive
to the hair and, therefore, in the use of the above-mentioned
¦hair treatment compositions which con-tain cationic agents, a
Il film or deposit is formed on the hair shafts, by adsorption, and
!I due to reaction between the cationic agent and the keratinous
material of the hair. The character and the amount of such film
jas is formed and deposited on the hair influence the properties
¦and characteristics of the hair.
The foregoing known practices serve a distinctly useful
¦Ipurpose and, in general, are reasonably effective in imparting
to the hair, to at least a fairly good extent, properties and
characteristics of the nature described above. They are
~frequently, however, less effective than is desired, particularly
with respect to the matter of control of the weight of the hair
and its manageability.
The present invention is based upon discoveries which
have been made which enable more effective management of the hair
with excellent and improved results in one or more respects with
regard to body or weight control, combability, fluffiness and
spring and, in general, desired configuration control of the hair.
In accordance with the present invention, the hair is
first treated with an aqueous composition which contains certain
types of quaternary ammonium compounds which are substantive to
¦the hair, and which are exemplified hereafter in some substantial
~detail, and thereafter, with or without intermediate rinsing with
¦water, is washed with soap or, more desirably, with a formulatea
~shampoo of the type which contains an anionic cleanser or
detergent such as soaps and/or anionic synthetic detergents, all
as is described in detail below. It may, however, here be
~ - 3 -

. I 10811Z6
l .
observed, and as will be noted further below, that no novelty is
clai~ed broadly in the practice of treating hair first with cm
agent which, broadly speaking, has certain cationic properties and
then iollowed by washing the hair with a shampoo containing an
¦ anionic detergent.
Pursuant to the present invention, the hair pretreatment
composition, which is applied to the hair prior to the washing
step with soap or shampoo containing soap and/or an anionic
synthetic detergent, comprises an aqueous composition which
contains a reaAily water-soluble quaternary ammonium compound
¦ which is s~stantive to the hair and whose solubility is such
that, in water at room temperature, it forms a solution, in use
concentrations of at least 0.5%, by weight of the solution, which
is clear to the naked eye. Since the use concentration of the
¦ quaternary ammonium compound may be as high as about ~%, by
¦weight of the solution, those quaternary ammonium compounds which I
are utilized in such concentrations should have water solubilities,
such thaL, when looked at with the naked eye, they appear to be
clear, even though, in actual fact, micelles or agglo~erates may
be present which would establish that the apparently clear solution
is not a true solution. For the purposes of the present invention,
reference to a clear solution means a solution which is optically
clear to the naked eye unaided by sophisticated optical
instruments. -
While, as stated above, the quaternary ammoniumcompounds which are used in the hair pretreatment compositions of
¦the present invention should have the solubility characteristics
¦to form clear solutions in water at room temperature at the use
!I concentration.s, in the ran~e of 0.5~about ~, and while the ¦
I¦ finishod hair psetreatment compositlons as oommercially market~
Il _ 4 -

. ~ ~ ~081:~Z6
¦ are most desirably in the form of c]ear aqueous solutions, which
may be uncolored, or coloxed using for instance, a desired dye, -
the hair pretreatrnent cornpositions can be made up in other forms,
for instance, as cream products, with the use of acid-stabilized
glyceryl monostearate or other agents. ~owever, since the hair,
after the applica-tion thereto of the prctreatrnent composition,
and with or without intermediate rinsing with water, is to be
washed with soap or with a shampoo containing soaps and/or anionic
synthetic detergents, ingredients should not be included in the
pretreatment composition which would unduly interfere with or
cause undue difficulties in the washing step with the soap or said
hair shampoos.
The quaternary ammonium compounds which can be used in
the practice of our invention, in addition to being substantive to
live human hair and possessing the water-solubility characteristics
discussed above, may generally be characterized as containing a
l long chain, aliphatic hydrocarbon radical directly or indirectly
¦ linked to a quaternary nitrogen atom thereof. The long chain
¦ aliphatic radical or radicals can be alkyl or acyl radicals which,
¦generally, comprise a straight or branched chain hydrocarbon
Iradical having from 8 to 18, more particularly from 12 to 16
¦carbon atoms. There can be one or two quaternary nitrogen atoms
¦in the molecule. Especially useful are those qua.ernary ammonium
compounds wh~h an be represented h the formul-
jN\
I
- s -
... ,.. ,.,, .ll .. ,.. , ... , .... .... ... ., ... ...... , .,, .,,.. ," ~ . ,,, .. , . ,. ,.. ,,., .

10~ 6
said quaternary ammonium compounds containin~ at least one, most
advanta~eously one, long chain aliphatic hydrocarbon radical
attached to a central nitrogen atom of the quaternary ammonium
compound. The long chain alkyl or acyl radical or radicals should
be selected so that there does not result a loss of the stated
water-solubility properties deslred in the quaternary ammonium
compound. Hence, while, in general, the long chain alkyl or acyl
iradical may contain from 8 to 18 carbon atoms, it is particularly
idesirable that it contain from 10 to 14 carbon atoms, and, better
¦¦still, predominately 12 carbon atoms in most cases. The absence
,¦of a long chain radical, or the substantial equivalent thereof as
llnoted below, will result in an inadequately satis~actory coating
,lon the hair sha~t and an unsatisfactory coating or deposit in the
¦ pores or crevices or on the hair shaft after the shampooing step,
as hereafter pointed out. Thus, illustratively, in the aforesaid
¦formula I, Rl is a C8-C18, particularly C10-Cl4 with C12 predomin-
¦ating, alkyl radical; each of R2, R3 and R4 is a Cl-C3 alkyl
llradical particularly a methyl radical or one or two, especially
¦¦one, of the R2, R3 or R4 radicals may be a benzyl radical; and the
~total of the number of carbon atoms in R2, R3 and R4 generally,
,and most desirably, should noi exceed 6, except, for example, when
one of said R2, R3 or R4 radicals is a benzyl raaical; and A is an
innocuous inorganic or organic anion, particularly halogen such as
~¦chlorine or bromine, but which may also be other anions such as
¦¦sulfate, sulfite, phosphate, nitrate, nitrite, acetate, methyl-
!¦ sulfate, and toluenesul~onate. Illustrative examples of such
¦¦quaternary ammonium compounds are octyltrimethyl ammonium chloride
decyltrimethyl ammonium chloride; dodecyldimethylethyl a~imonium
chloride; dodecyltrimethyl a~monium chloride; tetradecyltrimethyl
ammonium chloride; hexadecyltrimethyl ammonium chloride;
octadecyltrimethyl ammonium chloride; dodecyldimethylbenzyl ---~
i'~ ,
1'1 ' . .
~ 6 -

1081~Z6
ammonium chloride; tetradecyldimethylbenzyl ammonium chloride;
octadecyldimethylbenzyl ammonium chloride; octylmethyldibenzyl
ammonium chloride; mixed higher alkyl trimethyl ammonium chlorides¦
containin~ mixtures of predominately C8-C18 alkyl radicals such
as are derived from sources such as coconut oil or special frac-
tlons thereof high in C12, soya bean oil, cottonseed oil, tallow,
babassu oil, palm oil, etc.; and corresponding compounds wherein
the anion is other than halogen, as noted above.
To obtain the desired good solubility in water of the
quaternary ammonium compounds, there should, in general, be only
one C8-C18 alkyl group in the compounds. However, ~uaternary
ammonium compounds with suitable solubility can be used such as
dihexyldimethyl ammonium chloride or bromide; dimethyl dicoco
ammonium chloride; dimethyl didecyl ammonium chloride; methyl-
ethyldioctyl ammonium chloride; or similar compounds with anions
other than chlorine or bromine. Moreover, various ~uaternary
ammonium compounds may contain more than one long chain aliphatic
hydrocarbon radical and still possess adequate water-solubility
for the purposes of the present invention. ~uaternary ammonium
compounds in which all of the alkyl groups are of low molecular
weight, such as tetramethyl - or tetraethyl ammonium chloride or
bromide are unsatisfactory because, while they are very soluble
in water, they do not form a satisfactory film on the hair and do
not adequately "weight" the hair, and, in any event, they do not
impart the desired properties to the hair such as are achieved
¦through the use of compounds such as, for instance, dodecyltri-
methyl ammonium chloride or bromide when used in accordance with
the practice of the present invention.

1081~ 6
. ' '.
Various otiler quaternary ammonium compounds, some of
which do and o~hers of which do no~ fall within the scope of the
foregoing formula I, which formula encompasses the particularly
desirable compounds for use.i.n the practice of the present inven-
tion, can, nevertheless, be used with reasonably good results,
illustrative examples of which are long chain or C8--Cl~ alkyl-
dimethylbenzyl ammonium chloricles such as dodecyldimethylbenzyl.
ammonium chloride; tetradecyldimethylbenzyl ammonium chloride;
hexadecyldimethylbenzyl ammonium chloride; octadecyldimethylbenzyl
ammonium chloride; dodecylpyridinium chloride; hexadecylpyridinium
¦chloride; C8-C18 alkyl isoquinolinium chlorides or bromides as, 1:
¦for example, isoquinolinium dodecyl chloride; n-dodecyl-dimethyl-
. ~p-chlorobenzyl an~monium chloride; N-(acylcolaminoformylmethyl)- .
: pyridinium chlorides and bromides where the acyl radical contains
from 8 to 18 carbon atoms such as octoyl, lauroyl, palMitoyl and
stearoyl, exemplary of such compounds being N~(lauroylcolamino-
¦formylmethyl)-pyridinium chloride and N-(stearoylcolaminoformyl- :
methyl)-pyridinium chloride, said compounds and the class of which
they forM a part being represented by the formula R-CO-O-(C2H~-NH) ~ .
CO-tC~I2)n~ ~ where R-CO- is a C8-C18 fatty acid acyl
A~ ~ :
: radical, m and n are small whole numbers, for instance, 1, and A
: is chlorine or bromine, such compounds being disclosed in U.S.
Patent No. 2,189,66~; diisobutyl-phenoxyethyldimethyl-benzyl
- ammonium chloride; 9-octadecenyldimethylethyl ammonium chloride;
_ . myristyl- ~ -picolinium chloride; diisobutylcresoxyethyldimethyl-
benzyl ammonium chloride; diisobutylphenoxyethoxy ethyl dimethyl-
benzyl ammonium chloride; diisobutylcresoxyethoxy ethyl dimethyl- . .
benzyl ammonium chloride; tetradecyldimethylbenzyl ammonium chlori e;
dimethyl tallow benzyl quaternary ammonium chloride; octyldimethyl
ethylbenzyl ammonium chloride; higher fatty acid amide N,N-dialkyl
¦amine salts; dialkyl aminoalkyl fatty acid amides; acid salts of
- 8 -
,.,.' '
. .

Il !
1, 1081~LZ6
. higher fatty acid amides of N,N-dialkylamines; quaternary ammonium'
compounds as shown in U.S. Patent No. 2,678,716 and exemplified
by the formula
I R ~ CH2-~ ~ R2 ~ exemplified by
¦lcompounds where R is C8-C18 alkyl, R1, RZ and R3 are lower alkyl
I and A is an ion and illustrated by such compounds as
I ~
C12H25 ~ CH2~ (CH3)3 and ! :
Cl~3
il
; and various diquaternary ammonium
¦ C12E125~=,rCH2--~ . .
-Cl~ . .
. .
. . , . ..
compounds, for instance those containing one long chain alkyl ~.
group, such as are shown in U.S. Patent No. 2,617,806. Other
l~quaternary ammonium compounds which are useful in the practice of
i! the present invention~ as pretreatments for the hair prior to
¦ shampooing the hair with soap or an anionic shampoo, are those
~ disclosed in U.S. Patent No. 3,155,591. Still other compounds are
1,i . . I
i'1 _ 9 _ ~

8~ ~Z6
~he amine oxides such as dodecyldimethylamine oxide; dodecyl-
¦¦diethylamine oxide; and 9-octadecenyldimethylamine oxide; which
¦!amine oxides, under certain known acid conditions, are converted
into or function as quaternary ammonium compounds.
It will be understood that any two or more of the fore-
going, or other, quaternary ammonium compounds can be used so
long as they meet the criteria set forth above and are not
mutually incompatible.
It is especially advantageous, in the more important
embodiments of the present invention, to utilize, in conjunction
with the quaternary ammonium compounds in the hair pretreatment
compositions, minor proportions of (a) N-ethanolacetamide or
lauric ethanolamide or coconut oil mixed fatty acid ethanolamides,
and (b) polyethylenimines.
. -:,
The aforesaid (a) ingredient has heretofore been used
in hair treatment compositions and no novelty is claimed broadly
in its use in the treatment of hair. It serves to aid in the
retention by the hair of a certain amount OL water and plays a
role in the control of hair weigllt or the weight of the filmed
hair.
The polyethylenimines, which are made by polymerizing
ethylenimine, may be used in the form of ethylenimine polymers, -
or polyethylenimines, of variable molecular weights,-advantage-
ously of the order of M.W. about 10,000 to about 70,000, with a
good average in the range of about 40,000 to about 60,000. In
conjunction with the quaternary ammonium compounds they cooperate
and function to form a coating or film on the hair shafts of a
character such that exceptional manageabilitv or control and
. . .'
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! . .

lO~liZ~; ~
luster and natural appearance are imparted to the hair after the
step of washing the hair with the soap or anionic shampoo is
effected followed by rinsing out the soap or shampoo with water.
It may also be notea that no novelty is claimed in the
use broadly or per se of polyethylenimines of varying molecular
weights, including molecular weights of the order of 60,000, for
the treatment of hair. Thus, they have been used in hair
shampoos to obtain increased sheen, body and manageability of the
hair and improved combability. They have also been used in
treating hair prior to washing or shampooing the hair with anionic
shampoos. It is known that the polyeth~lenimines are themselves
cationic in character under certain conditions and are substantive
to hair. However, it has been found that the objectives behind
their use, in hair shampoos or for treating hair prior to shampoo-
ing w.ith soap or anionic shampoos, are inadequately achieved.
Tests carried out with the washing or shampooing of hair with
anionic detergent shampoos containing added polyethylenimines, as
well as tests carried out by pretreatment of hair using polyethyl
enimines alone followed by washing with soap or with anionic
shampoos, have given results which have left much to be desired.
Used in conjunction with the quaternary ammonium compounds in a
pretreatment of the hair, followed by washing or shampooing (with
or without intermediate water rinsing between the pretreatment
and shampooing steps) with soap or anionic detergent shampoos,
according to the present invention, the results obtained have bee
markedly superior.
The particularly important though more limited, aspects
f the present invention, therefore, involve the utilization, for
the pretreatment of the hair, of aqueous compositions, and

10811'~6
especially clear solutions, containing water-soluble quaternar~
~ammonium compounds in conjunction with polyethylenimines, and most;
desirably also in conjunction with N-ethanolacetamide or the
aforesaid ethanolamides, and the proportions involved will
. generally fall within the following approximate ranges in terms of¦
¦1% by weight of the pretreatment compositions:
¦Quaternary ammonium compound ~.5 to 4
¦Polyethylenimine 0.2 to 5
N-Ethanolacetamide or ethanolamide 3 to 18
Water 70 to 90 :
::
. . .
A preferred range of proportions is 1.5 to 2.5%, generally about .. .
2%, of the quaternary ammonium compound; 0.2 or 0.~ to 2%, gener-
ally about 0.4 or 0.5 to 1.5~, of the polyethylenimine; 3 to 18%,
¦ generally about 4 to 15%, of the N-ethanolacetamide or ethanol-
amide; and the balance very predominately water, generally from .
about 70 to about 85%, preferably about 75%.
Supplemental agents may and, generally, are desirably
included in the hair pretreatment compositions such as, for
instance, one or more of thickeners or viscosity modifiers,
proteins, silicone hair lubricants, hydroxyethylcelluloses,
preservatives, perfumes, emulsifiers, advantageously nonionic
emulsifiers, solubilizers for said perfumes, coloring agents, etc.
¦I In those instances in which polyethlenimines are
¦~ utilized in the hair pretreatment compositions in conjunction with
the quaternary ammonium compounds, which, as indicated above,
12 -
., . ~1 , . 1
''' ' ', . ' ' ' ' ' ', ' ' . '

lOl~liZ6
represent particularly important embodiments of the presen~
invention, it is highly desirable, for insuring clarity of the
pretreatment compositions, to add particular types of acids to
the compositions. Without the addition of an acid, the pH of
¦ the compositions will commonly be weakly basic. The addition of
low molecular weight monobasic inorganic or organic acids, partic-
ularly hydrochloric acid, hydrobromic acid, formic acid or acetic
acid, in amounts to reduce the pH of the composition to the order
I of about 3.2 to about 3.7, optimally about 3.5, leaves solutions
I which are clear to the naked eye. While other acids can be used,
; l¦such as tartaric acid or citric acid or phosphoric acids, or other
¦¦water-soluble polybasic acids, to produce solutions which have an
¦I acid pH of the general order indicated above, their use is not
preferred because they tend to produce solutions which are not
clear and are of generally turbid character. The pretreatment
compositions will generally be formed so as to have a pH from
about 3 to below or about 7, with a range of about 3.5 to 6.0 or
6.5 being generally most desirable.
The following examples are illustrative of hair pre-
treatment compositions which are useful in the practice of the
present invention. Other compositions can readily be prepared in
light of the disclosures and guiding principles and teachings
¦ provided herein. ~11 numerical values represent percentages by
weight of the compositions, and reference to "Balance" means the
weight of the water to bring the composition to 100%.
I .
I .
Il - 13 -
.j
' ::

Il 10811Z6
~IEX~PLE 1
- * .
~rquad C-50 (50% active)l 4.0
N-ethanolacetamide 15.0 :
Polyethylenimine (60,000 M.W.) (40~ active) 1.25
Volpo* 202 2.0
~ormic acid (90~ active) 1.4
Cellosize QP 100 M113 0.37
Methyl Paraben4 0.1 .
Pexfume Q.v. :
- Water (deionized) Balance
There is nothing critical about the order of mixing of
.the ingredients. They may simply be admixed in the ~7ater, under .
conditions of stirring or agitation, heating slightly, if desired,
to hasten the formation of the solution, which, especially
desirably, is clear to the naked eye. Generally, the p~rfume,
where used, is added after the other ingredients have been
dissolved. :
' ' .
1 Coco trimethyl ammonium chloride
2 Nonionic emulsifier to solubilize perfume
3 Nonionic thickener .
4 Preservative (methyl ester of p-hydro~y benzoic acid)
., .
- I -' , -'
¦ * Trademark
I ' ' . ,.
B

I~ 10811'~6
¦ EXAMPLE 2
! *
' ~r~uad C-50 (50% ac~ive) ~.5 .
,¦ N-ethanolacetamide 15.0 :
Polyethylenimine (60,000 M.W.) (40% active) 1.5
Volpo*20 2.0
~ormic acid (90% active) 1.4
,I Cellosolve QP 100 MH 0.37
Methyl Paraben , 0.1
,I Perfume Q.v.
~ ater (deionized) Balance
~1 '
il EXAMPLE 3
,1 . *
. Arquad C-50 (50% acti.ve) 4.0
N-ethanolacetamide 15.0
¦j Polyethylenimine (60,000 M.W,) (40% active) 1.5
. Volpo*20 2.0
~,¦ Orthophosphoric acid (70%) . 0'5 ¦
¦ Cellosize OP 100 MH 0.37 ¦
I Methyl Paraben 0.1
¦I Per~ume - Q.v :
1~ Water (Deionized) Balance
1~ ' .
Il * Trademark . '
!l
I, , - I .
.~ I,. ......... .... . .. . ................ ,.. ,1

11 10811Z6
1~ ~X~MPLE 4
'!
;, ~rquad C-S0 (50% active) ~.0
N-ethanolacetarnide 5.0
,I Polyethylenimine (60,000 M.W.) (40% active) 1.25 .
il Volpo* 20 2.-0
~ Formic acid (90% active) 1.15 .
I~ Cellosolve QP 100 MEI 0.37
jl Methyl Paraben 0.1
ii Perfur.e Q.v.
! Water (deioni~ed) Balance
,1 . ,, .
! j EX~MPLE 5
!1 Arquad C-50 (50% active) 4.0
jl N-ethanolacetamide 15.0
¦I Polyethylenimine (60,000 M.W.) (40% active) 1.25
Volpo*20 2.0 :
ll Formic acid (90~ active) . 1.15 -
¦I Cellosolve QP 100 MH 0.37 .
Methyl Paraben 0.1 ;
j Perf~e Q.v.
Water (deionized) Balance
I .
!l - ~: ~
I¦ ~ Trademarlc
., , ' . ',
.
,, - 16 - ~'
1. . . :
. 1~
, . . . . . . . ... .... . . .. .. . .. ... ..... ....... ..... ~

~1 10811;~6
EX~PL~ 6
Arquad C-50 ~50% active) 4-0
Polyethylenimine (60,000 M.W.) (40~ active) 1.5
Volpo* 20 0.2
Orthophosphoric acid (75P~) 0.5
. Cellosolve QP 100 MH 0.1
Methyl Paraben 0.1
Do~7-Corning 472 Si.licone Fluid ' 1.0
Perfume Q.v.
Water (deionized) Balance
EXAMPLE 7
Arquad C-50 (50% active) 4.0
N-ethanolacetamide 12.0 .
Cellosize P~ 100 MH 0~35
Methyl Paraben 0.1
¦ Water (deionized) Balance :-
EXAMPLE 8
Dodecyldimethylbenzyl ammonium chloride 2.0
N-ethanolacetamide 10.0
Polyethylenimine (60,000 M.W.) (40~ active) 1.2
Acetic acid 1.0 .
Perfume ~ Q.v. . :
Water . Balance
* Trademark
. ~
I - 17-
I . ' ' 'I
- ~

101911Z~ I
EX~MPL~ 9
Cetylpyridin.ium chloxide 1.8
N-ethanolacetamide ~.5
Polyethylenimine (40,000 M.W.) (~0% active) 1.7
Formic acid (90~ active) 1,1
Water (deionized) Balance
EXAMPLE 10
: Lorol trieth~]. ammonium chloride 2.0
¦ N-ethanolacetamide 12 . o
Polyethylenimine (60,000 M.W.) (40% active) 1.3 .
Formic acid (90% active) 1.4
Cellosize QP 100 MH 0.3
~ater (deionized) Balance
. , . .
EXAMPLE 11
. N-(lauroylcolamino-formylmethyl)- .
. - pyridinium chloride 3.0 :
: N-ethanolacetamide 15 0
. Polyethylenimine (60,000 M.W.) (40~ active) 1.25
Volpo* 202 2.0 .
Formic acid (90% active) 1.4
Cellosize QP 100 MH3 0.37
Methyl Paraben 0.1 ~-
Perfume Q.v.
Water (deionized) Balance .
, '. .
* Trademark
- 18 -
.; -

I! i~811Z6
¦¦ E~MPLl; 12
I Stearyldimetilyl benzyl al~onium chloride 2.5
¦~ N-ethanolace tamide 15 . O
Polyethy]enimin~ (60,000 ~.W.) (~0~ active) l.S
Volpo*20 2.0
Formic acid (90~ active) 1.4
Cellosolve QP 100 M~l 0.37
!! Methyl Paraben 0.1
!I Pexfume Q.v.
¦¦ Water (deionized) Balance
! E ~ iPLE 13
li Dodecylbenzene methyl pyridinium chloride 2.0
I N-ethanolacetamide 15.0
¦I Polyethylenimine (60,000 M.W;) (40% active) 1.5
Volpo*20 2.0
Hydrochloric acid (conc.) 0.5
Cellosize QP 100 MH 0.37
Methyl Paraben 0.1
Perfume Q.v.
Water (Deionized) Balance
. .~.
The hair pretreatment compositions, as notcd above, are
jmost desirably marketed.and used in the form of aqueous solutions
¦land are dispensed from conventional non-pressurizcd containers,
jlincluding~ for example, squeezable plast.ic or metal tubes. If
¦~desired, they can also be packaged in atomizer containers or
¦lin convelltional aerosol pressure packages usin~ volatile liquid
~Ipropellants such as the well known "Freons."
~ ~ .
- 19 -
* ~rademark
I .
: ~ .

10811'~
Il . ,
In the treatrnent of the hair, in accordance with the
¦present invention, as indica-ted above, the pretreatment quaternary
¦ammonium composition, at room tcmperature or warmed or hot as may
¦be desired, is applied to the hair and distributed therethrough
reasonably thoroughly and uniformly, in any suitable or convenient
manner, as, for instance, by rubbing with the fingers. If
desired, the hair may be initially wetted with water prior to the
application of said pretreatment quaternary ammonium composit:ion.
¦Then, promptly, or after waiting, if desired, for a convenient
¦~time but most desirably while the hair is still wet, or, if
¦ desired, after rinsing the pretreated hair with water of ambien-t
¦temperature or warm water, the hair is then washed, in conventional
manner, with a soap or with a shampoo containing a soap and/or a
Isynthetic anionic detergent. Any of numerous known and commer-
¦Icially marketed soaps or shampoos, in liquid, cream or paste form,
¦Ican be employed comprising or containing, for instance, water-
¦Isoluble soaps such as coconut oil fatty acid soaps or water-solubl,
synthetic anionic detergents such as primary long chain alkyl
¦sulfate salts exemplified by sodium lauryl sulfate or triethanol-
lamine lauryl sulfate or other salts of lauryl sulfate; or salts
,of long chain alkylbenzene sulfonic acids such as sodium or
triethanolamine salts of linear or branched chain dodecylbenzcne
sulfonic acids; salts of sulfated monoglyceride such as sodium,
ammonium and alkanolamine salts of coconut oil mixed fatty acid
monoglycerides; salts of sulfated tridecyl alcohol; or other known
¦anionic synthetic detergents conventionally used in anionic
l¦detergent-containing shampoos. The soap or shampoo is then
¦Ithoroughly rinsed away with water in the usual manner The hair
!lis then ready to be combed and set or shaped as may be desired.
Il . . . ' ~':
li . . ~
- 20 -
1 . ~
Ij ' .

1~ 6
Il . ' .
By employing ~uaternary ammonium compounds of the
character describ~a above in the pretreatment step, a substantial
quantity of the quaternary ammonium compound penetrates into the
¦Iscalp area ~nd permeates the hair deeply and guickly and is depos--
¦ited as a film through its substantive action on the hair. Where
¦a polyethylenimine is utilized in the pretreatment composition,
lit contributes its effect, also, in the forrnation of a film on
¦¦the hair. ~t any rate, the film formation occurs quickly through-
l~out the body of the hair around the hair shafts, and also in the
areas, particularly the deeper areas closely adjacent the scalp
I proper, and also where the hair may have been or has previously
¦ been damaged due to other treatments and where, therefore, there
¦ may be internal voids or crevices in the hair shafts. The films
¦which are formed as a result of the pretreatment, or which form
¦and are present as a result of the subsequent reaction with soap
or an;onic synthetic detergent in the subsequent washing or sham
llpooing step, appear to exert a favorable effect in the direction
¦¦of repair or alleviation of damaged hair shafts. Rinsing the
~! hair with water after the application to the hair of the pretreat-
¦ment guaternary ammonium composition and prior to the shampooing
of the hair with the soap and/or synthetic anionic detergent is of
no materiality. The rinsing has no adverse effect on the results
¦ obtained because the substantive action of the quaternary ammonium
¦¦compound in the pretreatment composition forms a strongly bonded
~adherent film on the hair which is essentially undisturbed or
junaffected by the rinsing with water prior to the shampooing with
the soap or other anionic shampoo.
,1 . ',
'i After the washing or shampooing of the pretreated hair
¦! and the subsequent rinsing with water, it appears that appreciable
1 filmed hair shafts remain, particularly in the cracks and crevices -~
. . : ~
- 21 - ~ ~
.~,.: - '

1081126
Il indeed to a greater e~:tent than is the situation with prior known
!I practices in the art, and which are of a character such that,
overall, the improvements ~Jhich result from the practice of the
present invention are achieved or brought about.
By way of further explanation, it may be pointed out
that it is desirable to maintain lony chain-or fatty chain-contain -
ing substances within cracks and crevices of individual hair
¦Istrands. These cracks and crevices generally develop during the
1, process of combing, curling, brushing and application of other ~-
¦ cosmetic treatments to the hair. They are the physical result
which is involved in hair darnage. The presence of these fatty
deposits within the hair strand ma};e it more supple, less brittle,
and thus, helps to prevent further breakage on combing-.
It is important, to the practice of the present invention
for most effective results, to get deep penetration during the
¦¦short time available in treating hair under practical conditions.
¦BY making use of small, water-soluble, rapidly diffusing quaternar~
¦ammonium molecules at the first stage, as distinguished from
polymeric cationic substances or high molecular weight relatively
poorly water-soluble substances such as, for instance, distearyl-
dimethyl ammonium chloride, generally maximal penetration of the
hair shaft is effected. Then, in the subsequent shampooing step,
where anionic shampoos are used, and particularly where they are
water-soluble and have molecular weights of the general order of
¦those of the water-soluble quaternary ammonium compounds used in
the pretreatment step, or somewhat higher or somewhat lower
molecular weights than that of said quaternary ammonium compounds,
deep penetration of said anionic material into the hair shaft also
¦~appears to take place. l~hen the quaternary ammonium compound
!
- 2~ -
.

.. . ~811;~6
,','' " . '
and the anionic detcrgent come into contact, a rcac~ion ta~es
piace resulting in the formation of a double long chain-or fatty-
chain like salt which is esscntially insoluble in the xinse water
and rcmains in place within, and, ~enerally rclatively deeply
within, thc hair shaft.
Polymeric cationic materials and other ca~ionic material
of unduly high molccular weight diffuse, at bcst, very slowly
into hair str~nds. Hence, deposition oE such ca~ionic materials
is not specific to the deep crac~s and creviccs in the hair
strands but, on the contrary, tends to becomc relatively uniformly
distributed over the hair, an effect which is undesirable. Thus,
for instance, coating the surface of the hair with a cationic
polymer tends to weight down individual hair strands. This added
weight tends to ma~e the hair flatter from the scalp and rcse~les
in appearance the effect of dirt on the hair.
In the practice of the present invention, the reaction
product which results between the water-soluble quaternary
ammonium compound and the anionic detergent of the shampoo, under
the particular conditions under and in the environment in which
it is formed, is beneficial to the objectives of the invention.
Thus, when in contact with the large amoun~s of anionic materials
in the shampooing step, the reaction product formed from said
anionic material and the water-soluble quaternary ammonium
compound from the pretreatment step, is solubilized into the
aqueous phase. Deeply imbedded material does not tend to come
in contact with excess anionic during the shampooing process.
~lowever, material deposited in morc available locations such as
the hair shaft surface is solubilized and removed durin~ the
shampoo process. ~s a consoquence, only the d~eply imbeddcd
. - 23 -
. . , ' ' ~ ........................................... ..

10811Z6
¦material remains in the hair after the shampoo process. In
~,¦essence, the "repair" material is deposited efficien-tly where it
¦l is needed without the negative effect of having too much material
¦ left on the hair as is the case when a cationic polymer is used.
i¦In other words, both the water-soluble quaternary ammonium ~-
i! compound and the water-soluble anionic detergent are able to
¦penetrate deeply into the hair shaft. There they form an
insoluble compound which stays in place through many later
shampoos, adding body and suppleness to the hair strand.
For convenience of expression, the term "anionic''
shampoo is used in the claims to mean soaps, as well as shampoos
for washing the hair in which the shampoos contain as an essential
cleanser or detergent one or more soaps and/or anionic synthetic
detergents, with or without various additional or supplemental
ingredients illustrative of which are nonionic surfactants,
alkanolamides, thickeners, etc.
.' ' . ..
.,
. .