Note: Descriptions are shown in the official language in which they were submitted.
~0~15142'7 : `
Field of the Invention
.
m is invention relates to aqueous shampoo ccmpositions
comprising mixtures of specified anionic, nonionic and c~mpholytic
surfactants and having desirably high levels of cleansing and foaming
while at the sclme time exhibiting low levels of eye irritation.
- Background of the Invention
It has long been the goal of those engaged in the
development and formulation of shampoo products for use on human hair
to achieve the best possible balance of the criteria perceived c~d
use~ by the cons~mer as measures of product satisfaction.
One of these criteria is the ability of a shampoo to
cleanse the hair and scalp to the proper degree, neither lea~iny the
hair fibers coated with a perceivable residue of sebum as a result o
insuE~icient detergency, nor leavincJ th~m ccmpletely scour~l an~l
strawlike as a result of ~oo complete a removal of the natural oil8
Another o the criteria which consumers use as a measure of
satisfaction in the evaluation of a shampoo product is its foamincJ
charaateristics. It is desirable that a relatively small quantity of
shampoo, when worked into the wet hair, rapidly generate a large volume
of dense, creamy and lubrous foam, stable through the shampooing
procedure.
~esthetic considerations also are important in the
formulation o shampoo products. Not only should a ormulation retain
its compositional integrity to obviate any need for shaking before
use, but it is also desirable to be able to offer the consumer a
product which is water clear and which may be attractively colored for
packaging in transparent containers.
Another very important requirement in the develoFment of
products such as hair shampoos htended for use near the eyes is that
the potential for stinging or irritation as a result of accidental
installation during use be minimized. ;~
--1-- ...
~ 384~7
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While the various types of surfactants which have been
employed in the formulation of shampoos exhibit satisfactory ;
properties in one or more of the above areas, no single type
has provided a completely satisfactory combination of all
properties. It is for this reason that a good deal of effort
continues to be devoted to the search for mixtures of surface
active agents which will possess all of the attributes desirable ~ -
- in an ideal shampoo.
One class of surfactant of particular interest in the
formulation of shampoo compositions having reduced eye
irritation potential is the ampholytes, from 2-alkyl-substituted
lmidazolines. Much effort has gone into the development of
mixtures of these imidazoline derivatives with a variety of
other surfactants to improve their detergency, foaming properties
and ease of Eormulation without affecting their inherent mildness.
See, for example, U.S. Patents 3,1~6,656; 3,341,460; and ~; ;
3,723,360.
Summary of the Invention ;~
In one particular aspect the present invention provides
an aqueous shampoo composition exhibiting reduced levels of -~
eye irritation which comprises water in combination with n
ampholytic surfactant comprising a 2-alkyl-substituted
imidazoline, a nonionic surfactant comprising a polyoxyethylene- ;
polyoxypropylene block copolymer and an anionic surfactant
comprising an alcohol ether sulfate, the quantity of said
ampholytic surfactant being 6.0 to 15.0% by weight, the
ratio of said nonionic surfactant to said anionic surfactant
being 0.5:1 to 10:1 and the proportion of the total of said
nonionic surfactant and anionic surfactant to said ampholytic
surfactant being l:l to 5:1.
Detailed Description of the Invention 1!~'' .'.. "'".
We have discovered that shampoos having a very :low eye
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.
irritation potential along with excellent foaming and cleansing
characteristics can be prepared by combining in specified
proportions 1) an ampholytic surfactant comprising a 2-alkyl-
substituted imidazoline, 2) a nonionic surfactant comprising
a polyoxyethylene-polyoxypropylene block copolymer, and 3) an
anionic surfactant comprising an alcohol ether sulfate.
. ..: : .
The imidazoline compounds which we have found useful in
achieving the above objectives include those having the ~;
following structures~
. ::
/ CH2 ... ~ :
N CH2
Il I `.' :,' :',
R -C N - Rl - OM ~ -
R4 R2 - COOM .
C~l .
\
N C1l2
Il I :''
R - C - N - R~ -- O R3 - COOM
R4/ R2 - COOM
:. ,: .'
and
CH2 . '
N CH2
R - C N - R~ - OM
. R4 R2 SO3M
ln whlch R ls a hydroearbon group having from 4 to 18 carbon
atoms.
.: . - .
Rl, R2 and R3 are selected from the group consisting of
a) aliphatic hydrocarbon groups of 1 to 4 carbon atoms,
b) hydroxy-substituted aliphatic hydrocarbon groups of
1 to 4 carbon atoms,
e) aliphatic hydrocarbon groups having a single ether
i 30
linkage and of 2 to 4 carbon atoms,
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d) hydroxy-substituted aliphatic hydrocarbon groups .-~:
having single ether linkage and of 2 to 4 carbon .,~
atoms, .
e) aliphatic keto groups containing only a single keto : :
linkage and otherwise being hydrocarbon of 2 to 4 ;
carbon atoms, :~ :
f) aliphatic keto groups containing only a single keto
linkage and otherwise being hydroxy-substituted
hydrocarbon of 2 to 4 carbon atoms . -
R4 is selected from the group consisting of
a) a hydroxyl group and ;
b) the group -OS03 (CH2CH2O)nR5 in which
R~ is a hydrocarbon group containing 8 to 18 carbon :~.
at.oms and n is a whole number from 0 to 4 incluslve,
and
M is an alkal:L metal. .:.
. ;,,
-
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Imidazoline derivatives of this type are well .
known and methods for their preparation are described in :
various U. S. patents issued to Hans S. Mannheimer and are
sold by the Miranol Chemical Company under the registered . ~
trademark MIRANOL. :~:
The nonionic surfactants which we use Ln our
invention to provide enhanced cleansing abilities without
the impartation of eye irritation problems are water soluble
block copolymers of polyethylene and polypropylene selected
from the group consisting of: ..
(a) condensation products of ethylene oxide with
bases formed by condensing propylene oxide with
propylene glycol, and having a molecular weight .
o 1,000 - 15,000,
~b) condensation producks of propylene oxide with
bases ~ormed by condensing ekhylene oxide with
ethylene glycol and having a molecular weight o
1,000 - 10,000, and
(c) condensation products of ethylene oxide with
bases formed by condensing propylene oxide with ,~
ethylenediamine and having a molecular weight of
1,000 - 30,000.
Suractants o this type are described in U.S.
: Patents No. 2,674,619; No. 3,036,118; and No.
2,979,528 and are sold by the BASF Wyandotte : ~
Corp. under the trademarks PLURONIC ~ PLURONIC R ` ; ;
and TETRONIC . .
The anionic surfactants which we use in our .:~
invention to insure the dev~lopment o a rich and copious
lather and to promote clarity when the compositions are . -~
formulated at pE~ levels on the acid side are the sulfates ;;
of ethoxylated fatty alcohols having the formula .. :
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~ 8427
R - (OCH2CH2)nOSO3M
where R equals a hydrocarbon radical of 4 to 18 carbon atoms,
preferably 12 to 14,
n equals a whole number from 5 to 30 inclusive,
preferably 8 to 14,
M equals an alkali metal, ammonium or a lower
: . .
mono,- di, or trialkanolamlne in which the alkyl groups
contain from one to four carbon atoms, preferably sodium
. . .
or ammon}um.
As mentioned hereinabove, the 2-alkyl-substituted
imidazolines of this invention are well known as detergents
for use in the formulation of personal care shampoo products.
While these materials themselves, especially the compound
having the structure.
CH2
\
N CH2
¦¦ I ,S~H2CH20Na
C l l H 2 3 C -N <
¦ CH2COONa
' OS03 (CH2CH2O)3C13H27
possess an unusually good combination of foaming, cleansing
and irritation properties, we have discovered that by
limiting the amount of imidazoline used and ~ombining it
with at least an equal quantity of a mixture of the nonionic
and anionic surfactants described herein, there is produced
a composition showing improvement in all three areas, i.e.
foaming, cleansing, and irritation potential.
We have found that useful aqueous shampoo
compositions can be based upon solutions of 2-alkyl-
30~ substituted imidazoIines containing 6.0 to 15.0% imidazoline
by weight. Compositions containing less than -this will be
. . .
found to provide sufficient foaming while those containing
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81!342~ :
more than 15% may cause eye irritation which cannot be
effectively reduced by the incorporation of the nonionic- .
anionic detergent mixtures described herein. We prefer to
use 8 to 10~ imidazoline.
The nonionic-anionic detergent mixtures, which
not only reduce the eye irritation potential of the .
imidazolines but also improve their foaming and cleansing .
properties comprise one or more each of the specified
nonionic and anionic detergents described herein in which the
weight ratio of the nonionic to anionic components may range . .
from 0.5:1 to 10:1. When it is intended to formulate
compositions of this invention at a pH of less than 7.5, it
is important that the ratio of nonionic to anionic
components not exceed ~:1 to insure that the compositions
remain homogeneous, transparent, and non-irritatin~. One o~
the preferred forms of this invention comprises non-
. alkaline formulations inaving a pH of 2.0 to 6.0 capable of
cle~nsing the ha.ir without signiicantly altering its
natural pH balance.
It is necessary that the proportion o~ the total
nonionic-anionic detergent mixture to 2-substituted-alkyl-
imidazoline be ~t least 1 to 1 to insure signif~cant
improvement in shampoo properties. While proportions as
high as 5 to 1 may be employed, we prefer to use proportions
ranging from 2 to 1 to 3 to 1, to insure low irritation and
good lathering at pH levels below 7.5.
Any of the usual additives such as opacifiers, .
perfumes, coloring agents, stabilizers, preservaties, : :
thickeners such as the polyethylene glycol distearates and
the like may also be included in the compositions if . :
desired. :
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The following specific examples are intended to
illustrate more clearly the nature of the invention, but are
not intended as a limitation upon the scope of the claims.
Example 1
An aqueous solution was preparecl containing 8.0~ -~
.... ~ .
- of the 2-substituted-alkyl imidazoline sold under the name -
~ Miranol~ MHT and having the structure. ~ -
- - .: :
CH2
:,
lo I F ~cH2cH2oNa
Cl~H~3 - N CH2COONa
.. . ;.
OSO9(CH2CH20)9C~3H27
There was added 10~ by weight of a condensate of ethy lene
oxide with a ba~e formed by condensing propylene oxide with
propylene glycol sold as Pluronic F-88 (BASF Wyandotte Co.)
and 8.0~ by welght of a~ ethoxylated (12 mols) so~ium lauryl
.,
sulfate sold as Standapol (Henkel Inc.). The composition
was thickened by the incorporation of 2.0% polyethylene
glycol 6000 distearate.
Evaluation of the shampoo formulation showed it to
have very good cleansing and foaming properties with a level
of eye irritation potential low enough to enable it to be
used on infants.
Example II -
::
An aqueous solution was prepared containing 10.0% -
of the 2-substituted-alkyl imida~oline sold under the name -~
Miranol~ 2MCAS-modO a~d having the structure
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CHz
/ \, ',
N CH2
ll ¦ CH2COONa
CllH23C I <CH2CH20CH2COONa
oso3c,2H2 5
There was added 10% by weight of a condensate of ethylene
oxide with a base formed by condensing propylene oxide with
propylene glycol sold as Pluronic F-88 (BASF Wyandotte Co.)
and 8.0~ by weight of an ethoxylated (12 mols) sodium lauryl
sulfate sold as Standapol (Henkel Inc.). The compositlon
was thickened by the incorporation of 2.0~ polyethylene
glycol 6000 distearate.
Compari~on of the abo~e formulation with thak
: described in Example I indicated that while the composition
had equivalent cleansing and irritation properties, it was
I somewhat less efficien~ in foaming and lathering.
Example,III
.
Ingredient % by Weight
; 20 2-substituted-alkyl-imidazoline
; of Example I (Miranol MHT,
Miranol Chemical Co.) 8.0
Condensate of ethylene oxide
with a base formed by condensing
propylene oxide with propylene
glycol (Pluronic F-87, BASF
Wyandotte Corp.) 10.0
Ethoxylated (12 mols) sodium
lauryl sulfate (Standapol,
Henkel Inc.) 8.0
Polyethylene glycol 6000
distearate
Water To 100.0
-8-
bm:
., . ... :
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1~J88427
Example IV
Ingredient % by Weight
2-substi~uted-alkyl-imidazoline
of Example I (Miranol MHT,
Miranol Chemical Co.) 10.0
Condensate of ethylene oxide
with a base formed by condensing
propylene oxide with propylene glycol
~Pluronic L-64, BASF Wyandotte Corp.~ 14.0
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)4.0
Polyethylene glycol 6000 distearate 2,0
Water To 100.0
Example V
Ingredient % by Weight
2-substituted-alkyl-imidazoline
o~ Example I (Miranol MHT,
Miranol Chemical Co.) 8.0
Condensate of ethylene oxide with
a base formed by condensing propylene
oxide with propylene gylcol (Pluronic
F-127, BASF Wyandotte Corp.) 10.0 --:
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)8.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
Example VI
In~redient ~ by Weight
2-substituted-alkyl-imidazoline
of Example II (Miranol 2MCAS-mod.,
Miranol Chemical Co.) 8.0
Condensate of ethylene oxide with
a base formed by condensing propylene
oxide with propylene glycol (Pluronic :-
F-127, BASF Wyandotte Corp.) 10.0
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)8.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
:'
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bm:
~L0884Z~7 -
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Example VII
Ingredient ~ by Weight ~-
2-substituted-alkyl-imidazoline
of Example I (Miranol MHT, Miranol
Chemical Co.) 8.0
Condensation product of ethylene
oxide with a base formed by condensing
propylene oxide with ethylenediamine
(Tetronic 704, BASF ~yandotte Corp.~ 10.0
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)8.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
Example VIII
Ingredient % by Weight
2-substituted-alkyl-imidazoline
of Example I (Miranol MEIT, Miranol
Chemical Co.) 8. n
: Condensation product of ethylene
oxide with a base formed by condensing
propyLene oxide with ethylenediamine
~Tetronic 707; B~SF ~Iyandotte Corp.) 8.0 -
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)10.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
Example IX
In~redient % by Wei~ht
2-substituted-alkyl-imidazoline
of Example I ~Miranol ME~T, Miranol
Chemical Co.) 8.0
Condensation product of ethylene
oxide with a base formed by condensing
propylene oxide with ethylenediamine
(Tetronic 707; BASF Wyandotte Corp.) 8.0 -
Ethoxylated (12 mols) sodium lauryl i
sulfate (Standapol, Henkel Inc.)10.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
--10--
bm:
108~ 7
Example X
Ingredient % by Weight
:. :
2-substituted-alkyl-imidazoline
of Example I (Miranol MHT, Miranol
Chemical Co.) 8.0
Condensation product of propylene
oxide with a base formed by condensing `~
ethylene oxide with ethylene glycol
(Pluronic 17R~, BASF ~yandotte Corp.) 8.0
Ethoxylated (12 mols) sodium lauryl
sulfate (Standapol, Henkel Inc.)10.0
Polyethylene glycol 6000 distearate 2.0
Water To 100.0
'. .- '.
While the compositions of Examples III through X
exhibit variations in relative cleansing and foaming abilities,
all are satisfactory or use as hair æhampoo compositions
and all exhibit eye irritation properties superior to the
2-substituted-alkyl-imidazolines alone.
Although the present invention has been described
~p; with reference to particular embodiments and examples, it
will be apparent to those skilled in the art that variations ;
and modifications can be substituted therefor without
departing from the principles and the true spirit of the
invention.
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