Note: Descriptions are shown in the official language in which they were submitted.
B~CKGROUND
This invention deals with novel sulfated condensation
products of ethylene oxide with bases formed by condensing propy-
lene oxide with propylene gylcol~ and having a molecular weight
of about 110~ to 4800. T~e sulfated condensation products are
useful as components in hair shampoo systems to provide an after-
shampoo conditioning effect.
The primary function of any hair shampoo product is,
of course, to thoroughIy remove from the hair accumulated deposits
of sebum, airbbrne particulate materials, and residues of hair
treating compositions such as hair sprays or other grooming
aids. At least as important, however, from the standpoint of
consumer satisfaction are the wet and dry combing properties
of the hair a~ter shampooing and the feel and appearance of the
hairO As a general rule, shampoos that thoroughly clean the
hair tend to leave it hard to comb ancl in a dry, flyaway
condition. Conversely, shampoos which avoid "over-drying" the
hair, usually do so at the expense of cleaning effectiveness.
We have discovered a class of materials which when
formulated with certain foam promoting agents as will be
hereinafter detailed, yield compositions comparable to the better
commercially available shampoo compositions in foaming and
detergent activity. The compositions of the invention not only
impart a smooth, scft feel to the hair, but combing, both wet
and dry, is markedly improved~
The prior art describes in, for example, U.S. Patent
2,674,619, methods of ma~ing condensation products of ethylene
oxide with bases formed by condensing propylene oxide with
propylene gylcol. We s~lfate these condensation products to
Tn c ~
,.
Z87
yield the no~el detergents of this i~vention. The 'prior art
also discloses a family of polyoxypropylene glycol disulfate
detergents described as superior heavy-duty fabric detergents
having low foaming properties. These' materials are shown in
.S. Patent 2,802,7890 Also shown in U.S. Patent 3,243,455
is a class of polyether hydroxy sulfonate surface active agents
said to be useful in emulsi~ication and demulsification and
as components in laundering compositions having good soil
anti-redeposition properties. Nowhere'in the art, however, is
there'disclosed the class of sulfated condensation products
described herein or the use of such'products as components
in hair shampoo compositions.
According to an aspect o~ the invention there is
' provided an aqueous hair shampoo composition containing about
10 to 20~ by weight of (1) an anionic surface active agent
comprising a sulated condensation product of ethylene oxide
with a base formed by condensing propylene oxide with'propylene
glycol and having a molecular weight of about 1100 ta 48~0,
the'condensation product having the structure:
20, Ho-(c2H~o)x(c3H6o)y(c2Hl~o)z-H
where y is an integer from about 30 to 70, and
(C2H40)x+z equals about 5 to 20~ of the total weight
o~ the compound,
in combination with (2) about 5 to 15~ by weight of a foam
promoter comprising an amine oxide of the general formula:
RlR2R3N ) O
wherein Rl is an alkyl group containing`from about 10 to 16
carbon atoms and R2 and R3 are each selected from the group
consisting oi methyl and e-thyl groups.
-- 2 --
ms/~-,~
.f~ g~
DETAILED DESC'RIPTIQN OF THE INVENTI'QN
The'class of condensation ~roduct precursors which
are'sulfated in the practice of our invention is a we'll known
class of nonionic sùrfactant polyols c~aracterized by high
molecular we'ight predictability of behaviour and an extremely
low order of toxicity~ the'molecule having hydrophilic groups
at both ends of a variable hydrophobic base. Varying the'
size of both the hydrophiles and the hydrophobe'permits the
produetion of eompounds having a mix of properties tailored
0 to the needs of the formulating chemist.
Normally it would be'expected that the sulfation of
such nonionic speeies to produce the corresponding anionic
materials would result in an inerease'in skin and/o,r eye
irritation levels when sueh'materials were employed as
eomponents in aqueous hàir shampoo eompositions. We ha~e
diseovered, however, that the partial or eomplete sulfation
of eertain of such eondensation produets produees eosmetieally
useful detergent materials retaining the advantageous irritation
properties of the nonionic precursor.
The condensation products which we sulfate in the
praetiee of our invention are those having the formula,
HO-(C2H,IjO)x(c3H6o~y~c2Hl~o)z-H
where ry is an integer from about 30 to 70, ~referably
about 40 to 6~, and
(C~H40) X+2 equals about 5 to 20% of the total weight
of the compound, preferably about 7 to 13%.
These materials are eommercially available in low
HLB values of 1 to 4 and when sulfated and neutralized yield
water soluble copolymers having an HLB range equivalent to
- 3 -
sodium lauryl sulfateO ~92~7
The preparation of the nonionic surface active polyols
which serve as the precursors for the.sulfated anionic surface
active agents of this invention is well known in the prior
art and is described, inter alia, in UOS. Patent 2,674,619~
The first step comprises the condensation of propylene oxide
with propylene glycol to prepare a polyoxypropylene polymer
of at least about 950 molecular weight. This polymer is
~hen condensed with ethylene oxide.
In the first step propylene oxide is condensed with
propylene glycol to prepare the polyoxypropylene polymer as
follows: ~
HO-eHCH2OH + CH ~ H-CII3 >HO(fHCH2OjyH
H.3 CH3
In the second step o the preparation, the polyoxy-
ethylene chain is introduced into the molecule by condensation
with ethylene oxide as follows:
~0~
HO(~HCH.. 2O)yH + C~ CH2- ~ HO-(C2H~O)x(C3H6O)y(C2HI!O)zH
H3
In preparing the p~lyoxyethylene polymer the
condensation of propylene oxide with propylene glycol is
normally carried out at elevated temperatures and pressures
in the presence of an alkaline catalyst such as sodium
alkoxide, a quaternary ammonium base, or preferably sodium
hydroxide.
Although the reaction may be carried out by simply
heating the mixture of the reactants under pressure at a
sufficiently high temperature, this procedure is not
.~ - 4 -
ms~
3'~37
ordinarily used as the temperature and pressures required
are excessive and control of the reaction is difficult.
The preferred method of carrying out the reaction is
to add the propylene oxide'to a stir,red heated mixture of
the propylene glycol and alkaline catalyst in a sealed reaction
vessel. By adding the propylene'oxide to the reaction
yessel at such'a rate that it reacts as rapialy as added, an
excess of propylene oxide'is avoided and control of the'-
reaction~is simplified.
The condensation of ethylelie oxide'with the polyoxy-
propylene polymer is carried out in an analogaus manner.
Partial or complete sulfation of the hydroxyl groups
present in the'condensation products produced as described
above 'is accomplished through'the use'of conventional sulfating
agents such'as those used in the sulfation of fatty alcohol
sulfates and their alkoxylated derivatives. These include
the various known complexes of sulfur trioxide such as the
complexes with dioxane,' trieth~lamine~ ammonia, and hydro-
chloric acid. '~e prefer to sulfate by the slow addition of
2Q a hydroxy equivalent of chlorosulfonic acid to a methylene
chloride solution of the condensed material. Water dispersible,
surface active condensation products are obtained over the
range of ~.5 to 2.~ moles of sulfating agent per mole of
condensation product. ~here hydrophilic condensation products
relatively high in ethylene oxide are to be sulfated,
concentrations of sulfating agent at the lower end of the
range should be employed to retain surface active properties.
The stirred reaction solution is cooled to prevent
the temperature from exceeding 25C. Upon completion of the
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ms ~
Z8~7
addition~ the solution is sparged ~i~th nitrogen to remove any
HCl which'is present. The'sulfuric acid ester is then conyerted
to a salt by pouring the reaction mixture into an e~uivalent
amount of stirred aqueous ammonia, amine or alkali or alkaline
earth metal hydroxide. The pH'of the resulting emulsion is
ad~usted to 8 to 9 with additional aqueous sodium hydroxide.
The organic solvents are then removed by distillation to yield
a concentrated a~ueous solution of the sodium salt of the
sulfated condensation ,roduct. The'ionic group of the surface
active condensation product prepared as described above is the
sulfate ion, the'most hydrophilic of the anionic functional
groups. It is especialiy useful in the formulation of
compositions for the treatment oE hair and skin because of its
minimal tendencies to complex with metal ions and its
minimal sensitivity to hard water.
' While the soil removal efficiency of the 'sulfated
compounds oE this invention makes them suitable'for use in
the formulation of aqueous hair shampoo compositions, it is
necessary to enhance their foaming properties by the inclusion
of low-irritating foam promoters taken from the group
consisting of amine oxides of the general formula:
1 2 3 ~
The arrow is a conventional reDresentation of a semi-polar
bond. These compounds are generall~ prepared by the direct
oxidation o~ the approDriate tertiary amine. When Rl is a
much longer chain the R2 and R3, the amine oxides have surEace
activi-ty. For the purpose of this invention Rl is an alkyl
group having from 1~ to 16 carbon atoms. Desirable surface
active properties are lost if Rl is substantially less than 1
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ms/~,~(
s3~37
carbon atoms, and the compounds are insufficiently soluble
if Rl is greater than 16 carbon atoms. R2 and ~3 are each
selected from the group consisting of methyl and eth~l groups~
PreferabIy Rl is a dodecyl group or a mixture of dodecyl with
decyl, tet'radecyl and hexadecyl, such that at least 50% of
the groups are dodecyl groups. R2 and R3 are preferably
methyl groups. A preferred amine oxide'for the purpose'of
this invention is dodecyldimethylamine`oxide~
We have'found that in general from about 10 to 20%
of the sulfated condensation product should be employed along
with'about 5 to 15% of the foam promoter. Conventional
shampoo adjuvants may, of course, be employed in the formulation
of shampoo compositions of this invention including other
anionic, nonionic, or ampholytic surface active agents useful
in modifying cleansing and foaming pro~erties as well as
thickeners, perfumes, dyes and the li};e.
.... .. . ....
EXAMPLE I
__ .
To a three-neck flask equipped with stirrer~
thermometer, dropp~ing funnel and nitrogen inlet tube was added
100 grams (~ equivalent of OH) of PLURONIC~ L-61 (BASF
Wyando-tte Corp.) a polyoxypropylene-polyoxyethylene copolymer
having a molecular weight of approximately 2000 and containing
about 10% oxyethylene units on a molar basis. This was
followed ~y the addition of 50~ grams of dioxane and 200 mL
of methylene chloride. To the dropping funnel was charged
11.6 grams (0.10 mole) of chlorosulfonic acid. The acid
was slowly added to stirred solution and cooling applied to
maintain a solution temperature of less than 25C. Upon
completion of the addition of the acid, an additional 50 mL
j ~,
- 7
ms/ ~
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of methylene chloride was ~dded to the flask~ Then, and
additional 1.2 grams of chIorosulfonic aci~ was added slo~ly
through the'dropping funnel. The reaction flask contents were
allowed to come ~o room temperature while being sparged with
nitrogen to remove dissolved HCl.- The solution of the mono-
sulfuric acid ester of the PLURONIC~ L-61 was then added to
4 grams of sodium hydroxide dissolved in one L of distilled
water. Additional 10% aqueous sodium hydroxide was added to
stabilize the pH at 8-9. The methylene chIoride and dioxane
reaction solvents were'removed by distillation to yield an
aqueous solution of PLURONIC~ L-61 monosulfuric!~sodium salt.
. .
EXAMPLE II
The disulfate, sodium salt of PLURONIC~ L-61 was
prePared following the procedure employed in Example 1.
Using 100 grams of PLURONIC~ L-61, the polymer was disulfated
with' 22.7 grams (0.2~ moles) of chlorosulfonic acid. After
addition of the acid was complete, an additional charge of
methylene chloride was made to the reaction vessel as
previously described. Then 2.3 gra~s additional chIorosulfonic
acid-was added. After warming to room temperature with'a
nitrogen sparge, the reaction solution was poured slowly into
a solution of 8 grams of sodium hydroxide dissolved in one L
of distilled water. Additional 10% aqueous sodium hydroxide
was added to stabilize the pH at 8-9. The organic solvents
were removed by distillation to give an a~ueous solution of
PLURONIC~ L-61 disulfate, sodium salt.
EXAMPLE I'II
The following hair shampoo composition was prepared.
8 -
ms/ ~t~
Ingredient ' % by Weight
Disulfated PI.URONIC~ L~61, sodium salt 1~.0
Aromox~DIlC (Akzona Inc.~'~a dimethyl-
cocoamine 'oxide)' 10.0
Perfume, Perservative, color and Water qOs. to 100
- The''a~ove'shampoo was tested for soil removal
efficiency (a measure of the cleansing power of the shampoo)
and compared with'the efficacy of its individual com~onents
as well as a commercial baby-shampoo. The' results are'shown
below~
% Soil Removal
- Ef~iciency at
Shampoo Sy'stem -2 0 Concentration
Disulfated PLURONIC~ L-61 24
Aromox~DMC 28
Shampoo of Example IV ' 33
Commercial Baby Shampoo 3~
The soil removal efficiencies exhibit a synergistic
effect in the use of the mixture containing both the sulfated
PLURONIC~ and the dimethylcocoamine foam promoter. Evaluation
of the shampoo composition by panelists in a blind comparison -
test showed thè shampoo to be effective in cleaning, lather,
rinsing, appearance and feel. A persistant talc-likb'effect
was noted on the skin and hair. Rabbit eye'irritancy tests
showed the sulfated PLURONIC~ shampoo system to be of low
irritation potential comparable to commeroial baby shampoos.
EXAMPLE V
Ingredient % by Weight
Disulfated PLURONIC~ L~101, sodium salt 10.
3~ Ammonyx~CDO (Akzona Inc.) (a cocoamido '
propyl di~ethylamine oxide) 1~.0
Perfume preservative, color and water q.s. to 1
.
~r
g _.
ms/
.)~.. ~..'~92~7
EX~PLE VI
Ingredient % by Weight
Monosulfated PLURONIC~ L-31, sodium salt 10.0
Aromox~DMC 10.0
Perfume, preservative, color and water q.s. to 100
Each oE the above two examples when employed as
a hair shampoo provides the hair with adequate cleansing,
manageability and cosmetic appearance with the benefit of
a low level of skin and eye irritation.
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