U.S. patent number 3,718,609 [Application Number 05/131,461] was granted by the patent office on 1973-02-27 for liquid detergent compositions.
This patent grant is currently assigned to Continental Oil Company. Invention is credited to Dean R. Weimer.
United States Patent |
3,718,609 |
Weimer |
February 27, 1973 |
LIQUID DETERGENT COMPOSITIONS
Abstract
A liquid detergent composition is provided having an aqueous
layer and a layer of a liquid water-immiscible oily material, which
composition when shaken, forms a temporary oil-in-water emulsion.
The aqueous layer contains a foam-producing water-soluble organic
detergent, a non-emulsifying foam stabilizer, and water.
Inventors: |
Weimer; Dean R. (Ponca City,
OK) |
Assignee: |
Continental Oil Company (Ponca
City, OK)
|
Family
ID: |
22449568 |
Appl.
No.: |
05/131,461 |
Filed: |
April 5, 1971 |
Current U.S.
Class: |
510/417; 510/476;
516/14; 516/19; 516/59; 510/127; 510/505; 510/135; 510/426;
510/461; 510/432 |
Current CPC
Class: |
A61K
8/03 (20130101); C11D 3/3765 (20130101); C11D
17/0017 (20130101); A61Q 5/02 (20130101) |
Current International
Class: |
C11D
3/37 (20060101); C11D 17/00 (20060101) |
Field of
Search: |
;252/307,312,545,158,153,155,160 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
chemical Abstracts, Vol. 47, Col. 3553, Vol. 49, Col. 1407i, Vol.
55, Col. 1038b..
|
Primary Examiner: Welsh; John D.
Claims
Having thus described the invention, I claim:
1. A liquid detergent composition having an aqueous phase and a
liquid water-immiscible oily material phase which composition, when
shaken, forms a temporary oil-in-water emulsion, said aqueous phase
consisting essentially of a foam producing water-soluble,
non-cationic organic detergent, a water-soluble neutralized salt of
a polyacrylate having a molecular weight in the range of from about
50,000 to about 150,000 and water.
2. The composition of claim 1 wherein the poly portion of said
water-soluble neutralized salt of a polyacrylate is represented by
the formula
wherein x is an integer of from about 550 to about 2,250 and the
cation constituent of said neutralized salt is selected from the
group consisting of sodium, magnesium, ammonium, and mono-, di-,
and triethanolamine.
3. The composition of claim 2 wherein said cation constituent is
selected from sodium and triethanolamine.
4. The composition of claim 2 wherein said composition contains
from about 5 to about 50 percent by weight of said water-immiscible
oily material and from about 95 to 50 percent by weight said
aqueous phase, said aqueous phase containing from about 5 to about
40 percent by weight of said foam-producing water-soluble organic
detergent and from about 2 to about 10 percent by weight said
water-soluble neutralized salt of said polyacrylate.
5. The composition of claim 4 wherein said water-immiscible oily
material is present in an amount of at least 20 percent, said oily
material being selected from the group consisting of mineral oils,
and blends of mineral oils and vegetable oils, and said aqueous
phase contains from about 5 to 25 percent of said foam-producing,
water-soluble detergent and from about 3 to 5 percent of said
water-soluble neutralized salt of said polyacrylate.
6. The composition in claim 4 wherein said water-immiscible oily
material is present in an amount of about 5 to 20 percent, said
oily material being selected from the group consisting of mineral
oils, and blends of mineral oils and vegetable oils, and said
aqueous phase contains from about 10 to 30 percent of said
foam-producing, water-soluble detergent and from about 3 to 5
percent by weight of said water-soluble neutralized salts of said
polyacrylate.
7. The composition of claim 6 wherein said oily material is present
in an amount of about 13 percent, said aqueous phase is present in
an amount of about 87 percent and the detergent constituent is
triethanolamine lauryl sulfate and is present in an amount of about
21 percent.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to liquid detergent compositions. In
one aspect the invention relates to a multi-phase liquid detergent
composition having an aqueous phase and a liquid, water-immiscible,
oil material phase, which composition when shaken forms a temporary
oil-in-water emulsion.
2. Brief Description of the Prior Art
In the liquid detergent field, such as shampoos, the present trend
is to produce a multi-phase product which, when shaken, forms a
temporary emulsion. In such formulations, the lower phase is an
aqueous phase which contains the necessary cleaning ingredients,
and the upper phase is an oil material which conditions the hair.
Further, similar compositions are employed as bubble bath/bath oil
compositions, the basic distinction between the shampoo
formulations and the bubble bath/bath oil compositions being in the
proportion of oil in the upper phase.
The multi-layer physical state of the composition referred to above
is essential so that the compositions will produce foam in a
product designed to have good skin and hair cleansing properties,
and yet, in the case of the bubble bath/bath oil compositions leave
an oily film upon the skin of the bather and, in the case of the
shampoo formulation, leave a suitable amount of oil on the hair so
that the hair will be manageable for grooming. A problem
encountered in manufacturing such a product has been that the
conventional active-foam booster ingredients normally used in
shampoos and the like emulsify the oil so that a clean phase split
does not occur between the aqueous phase and the oily material
phase. In an effort to overcome these problems, de-emulsifiers have
been used to prevent emulsification of the aqueous phase and oily
material phase. However, such de-emulsifiers are not always
effective and often inhibit the desirable properties of the
product. For example, many of the de-emulsifiers employed in prior
art liquid detergent compositions having a multi-phase product have
inhibited the effectiveness of the foam booster incorporated in the
composition resulting in a product not possessing desired foam
properties. Thus, new formulations are constantly being sought
wherein a liquid detergent formulation can be employed to produce a
two-phase product, and yet at the same time, remove the need for
the incorporation of ingredients such as de-emulsifiers which
inhibit the effectiveness of the resulting products.
OBJECTS OF THE INVENTION
An object of the present invention is to provide an improved liquid
detergent composition. Another object of the present invention is
to provide an improved multi-phase liquid detergent composition
which possesses effective cleaning properties as well as
conditioning properties without suffering from the deficiencies of
the prior art multi-phase liquid detergent compositions. Another
object of the present invention is to provide a novel multi-phase
liquid detergent composition which possesses a clean phase split
between the aqueous and oily material phase without inhibiting the
desired cleaning and conditioning properties of the liquid
detergent composition. These and other objects, advantages and
features of the present invention will become apparent to those
skilled in the art from a reading of the following detailed
description.
SUMMARY OF THE INVENTION
According to the present invention there is provided a liquid
detergent composition having an aqueous phase and a liquid,
water-immiscible oily material phase, which composition, when
shaken, forms a temporary oil-in-water emulsion. The aqueous phase
consists of a foam-producing water-soluble organic detergent, a
non-emulsifying foam stabilizer, and water.
Further, according to the invention, there is provided a liquid
detergent composition having an aqueous phase and a liquid,
water-immiscible oily material phase wherein the non-emulsifying
foam stabilizer incorporated into the aqueous phase in a
water-soluble salt of an acrylic acid polymer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The liquid detergent compositions of the present invention include
compositions which provide detergency and simultaneously provide
for the deposition of a certain amount of oily material on the
subject being cleaned. As previously stated, typical examples of
such liquid detergent compositions are bubble bath/bath oil
compositions and shampoo compositions. The duality of properties
possessed by such a multi-phase liquid detergent composition is due
to the fact that the compositions contain an oily phase and an
aqueous phase which form temporary oil-in-water emulsions when
shaken. The aqueous phase contains a foam-producing water-soluble
liquid detergent, a non-emulsifying foam stabilizer and water. The
oily phase, as the name implies, furnishes oily material which
serves as a hair conditioning aid, in the case of shampoo
formulations, and as a skin softener, in the case of the bubble
bath/bath oil composition.
Although the liquid detergent compositions of the invention exist
in the form of separate phases or layers that are shaken prior to
use whereupon they form oil-in-water emulsions which are only
temporary. However, this emulsion state enables the user to measure
out the required amount of the composite compositions each time the
liquid detergent compositions are used. The actual time required
for the detergent composition to return to the layered or
multi-phase state will be dependent on the actual formulation, but
generally such phase splitting will occur within about 12
hours.
In order that the multi-phase liquid detergent compositions have
the desired properties described above, it is essential that they
contain four ingredients, namely, a water-immiscible oily material,
a foam-producing water-soluble organic detergent, a non-emulsifying
foam stabilizer, and water. As is evident, the foam-producing
water-soluble organic detergent, the non-emulsifying foam
stabilizer and the water constituents form the aqueous phase and
the water-immiscible oily material forms the oily phase. The
amounts of the various ingredients can vary widely and will be
dependent upon the nature of the particular ingredients present, as
well as upon the nature or use of the composition.
The multi-phase liquid detergent compositions preferably contain at
least 5 percent by weight of one or more water-immiscible oily
materials. Although in certain cases amounts up to 50 percent may
be used, the amount of oily material usually will not be more than
50 percent. In the composite shampoo/hair conditioning compositions
the amount of oily material is desirably from 5 to 20 percent by
weight, while in the composite bubble bath/bath oil compositions
the amount of oily material will usually be at least about 20
percent by weight. The oily material serves as a skin softener or
emollient and as a hair conditioner or hair grooming aid.
Typical suitable oily materials which can be employed to form the
oily phase of the compositions of the present invention include
light to heavy mineral or hydrocarbon oils, such as the light
mineral oils having a Saybolt viscosity of 65-75 cps. 38.degree. C
and a specific gravity of 0.835 to 0.845 at 15.5.degree. C animal
and vegetable oils, such as linseed oil, castor oil, olive oil,
cotton seed oil, safflower oil, almond oil, peanut oil, coconut
oil, coconut oil fractions, cornoil, sesame oil, and brominated
vegetable oils; synthetic oils which are fatty acid alkyl esters
containing a total of from 16 to 22 carbon atoms, such as isopropyl
myristate, isopropyl palmitate and isopropyl stearate; and lanolin
compounds, such as the well-known lanolin esters and lanolin
alcohols. Desirable results are obtained wherein the oily material
is mineral or hydrocarbon oil, because of the sharpness of the
interface which occurs between the oil phase and the aqueous phase.
In addition, the oily phase should be liquid at room temperature,
and preferably also at 0.degree. C.
As previously mentioned, the aqueous phase of the multi-phase
liquid detergent composition contains a foam-producing
water-soluble organic detergent, a non-emulsifying foam stabilizer,
and water. The amount of foam-producing water-soluble organic
detergent employed can vary widely depending upon the particular
formulation desired and its use. Generally, however, the
foam-producing water-soluble organic detergent will be present in
an amount within the range of from about 5 to 40 percent by weight,
based on the total weight of the aqueous phase.
In the composite bubble bath/bath oil compositions the amount of
the foaming organic detergent is preferably from 5 to 25 percent by
weight, while in the composite shampoo/hair conditioning
compositions the amount of the foaming organic detergent is
preferably from 10 to 30 percent by weight.
The foam-producing organic detergent compositions which can be
employed comprises one or more water-soluble non-cationic
surface-active agents, i.e. an anionic, or amphoteric surfactant,
or a mixture thereof, which produces acceptable foam. Preferred
anionic detergents are sulfonated and sulfated anionic detergents
and in particular the sodium, magnesium, ammonium, mono, di- and
triethanolamine salts of sulfated fatty alcohols as well as these
salts of the sulfonated alkylaryl compounds, all of which have a
total of from 12 to 21 carbon atoms. Typical anionic detergents
include sodium lauryl sulfate, sodium oleyl succinate, ammonium
lauryl sulfosuccinate, sodium lauryl ether sulfate, ammonium lauryl
sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl
sulfate, sodium dodecylbenzene sulfonate, triethanolamine
dodecylbenzene sulfonate and sodium N-lauroyl sarcosinate. Other
anionic detergents include triethanolamine alurate-myristate and
triethanolamine oleate.
Amphoteric or ampholytic detergents include
N-lauryl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine,
coco-beta-alanine, and the Miranol compounds described in U.S. Pat.
Nos. 2,528,378 and 2,781,354.
The second essential ingredient of the composition which is present
in the aqueous layer is the non-emulsifying foam stabilizer. The
amount of the non-emulsifying foam stabilizer can vary widely but
is generally present in an amount of from about 2 to about 10
percent by weight based upon the total weight of the aqueous phase
of the composition. Desirable results have been obtained wherein
the non-emulsifying foam stabilizer is present in the amount of
about 3 to 5 weight percent. The non-emulsifying foam stabilizers
which can be employed in the composition of the present invention
are the water-soluble salts of acrylic acid polymers. This acrylic
acid polymers can be represented by the structural formula
wherein x is an integer from about 550 to about 2,250. The polymers
are neutralized to form a salt and the cation constituent of the
salt is selected from the group consisting of sodium, magnesium,
ammonium, mono-, di-, and triethanolamine. Especially desirable
results have been obtained wherein the salt is the sodium salt or
the triethanolamine salt and the molecular weight of the resulting
acrylate is from about 50,000 to about 150,000 with the lower
molecular weight polymer being the most desired.
The third essential ingredient in the aqueous phase is water and
the amount will vary depending upon the amount of the foam
producing organic detergent and non-emulsifying foam stabilizer
employed. In addition, the amount of water in the total composition
will vary depending upon the amount of oily material present in the
total composition.
While the compositions of the invention contained the
above-mentioned ingredients, other compatible adjuvants can also be
included therein. Thus the composition may, for example, contain
one or more of the following: a perfume or essential oil, an
oil-soluble or water-soluble dye, a germicide, a protein
hydrolysate, and the like.
The compositions of the invention can be prepared merely by
blending together the various ingredients. Usually the ingredients
required to form the aqueous phase component of the composition
will be blended together separately, and then admixed with the
ingredients employed to produce the oily phase of the
composition.
In order to more fully describe the invention the following
examples are presented. However, it is to be understood that the
examples are for illustrative purposes only and any enumeration or
details contained therein are not to be interpreted as a limitation
on the invention except as indicated in the appended claims. All
parts and percentages of constituents referred to in the following
examples are by weight unless otherwise indicated.
EXAMPLE
A series of experiments were conducted on the novel multi-phase
liquid detergent composition to determine its foam producing
properties, the stability of the foam generated, and the
compositions ability to form a clean phase split between the oily
material phase and the aqueous phase. In each experiment
triethanolamine lauryl sulfate was used as the foam-producing
water-soluble organic detergent constituent, sodium polyacrylate,
having a molecular weight ranging from 50,000 to about 150,000, was
employed as the non-emulsifying foam stabilizer and the oily
material constituent was light mineral oil or a blend of about
one-third olive oil and two-thirds light mineral oil. The materials
were then admixed to form a liquid detergent formulation having an
87 percent aqueous phase and a 13 percent oily material phase. The
aqueous phase of the liquid detergent contained about 21 percent
triethanolamine-lauryl sulfate. The amount of sodium polyacrylate
was varied, as shown in the following table to determine
concentration variables for same. Tests were then run by the
standard shampoo test which measures the foam generation ability by
the milliliters of foam and the stability of the foam as the time
required for 75 milliliters of the liquid to draw from the foam.
Therefore, the higher values of the foam generated and the longer
the time required for the drainage are desirable and indicate a
product having the desired foam and foam stability properties.
The standard shampoo test referred to above and utilized to test
the novel liquid detergent formulation is as set forth hereinbelow.
The amount of the ingredients was varied as shown in Table I.
TEST PROCEDURE
1. Weight 10.0 and 25.0 grams of test shampoo into separate 150 ml
Griffin low form glass beakers.
2. Mix synthetic sebum which has been allowed to return to room
temperature with a metal spatula. The sebum is a synthetic soil to
simulate actual conditions.
3. Distribute 3.0 grams of sebum around the sides of the 150 ml
beaker taking care not to allow it to come into contact with the
shampoo nor to come up so high in the beaker to be above the water
level when it is introduced.
4. Premeasure 90, 85, 80 and 75 ml of water of the desired hardness
(50 and/or 250 ppm) in four separate 100 ml cylinders.
5. Add the hard water to the following manner to result in the
following concentrations of shampoo:
Conc. Hard Water (Ml) Shampoo (Grams in Beaker)
__________________________________________________________________________
10% 90 10.0 25% 75 25.0
6. After adding the required amount of hard water, add a magnetic
stirring bar and place sample on the Thermolyne Stir Plate. Set
glass thermometer into sample. Stir at full speed with heater on
thereby allowing the temperature to reach 100.degree. F in 4 to 5
minutes.
7. While the sample is warming, rinse out a 500 ml glass cylinder
and prewarm with 100.degree. F tap water. Cylinder should contain
the capped plastic tube filled with water.
8. Drain the 500 ml glass cylinder when sample temperature reaches
98.degree. F.
9. Pour sample into 500 ml cylinder when temperature reaches 100
degrees F being careful not to allow the magnetic stirring bar to
drop into the cylinder.
10. Attach the 500 milliliter cylinder to the rotator assembly to
keep the cylinder in the perpendicular plane when rotating.
11. Rotate the cylinder a total of 20 complete circles (40 half
circles) to generate foam. The rate at which the cylinder is
rotated is critical. Consistent results are obtained if the
rotations are completed within 35-45 seconds. It is also important
to rotate at a constant speed. If difficulties are encountered, a
Metronome should be used.
12. Start the stopwatch immediately upon completion of the
rotations.
13. Remove the stopper and read the total foam volume (including
liquid). Record this as the volume of foam generated.
14. Remove the 500 ml graduated cylinder from the rotator assembly
gently and set it on the table top.
15. Stop the stopwatch when the liquid level reaches the 100 ml
mark. (Actually, 75 ml have drained since the plastic cylinder
displaces 25 ml of liquid). Record the time interval from the
completion of the rotations to the point at which 100 ml of
apparent liquid has drained as the drainage time.
16. The test results are recorded as ml of foam/drainage time in
seconds.
Results of the test on the novel liquid detergent composition of
the present invention are tabulated in Table I. The date clearly
illustrate the utility of the novel detergent composition as a
two-phase shampoo wherein sodium polyacrylate is employed as a
non-emulsifying foam stabilizer. Further, the data illustrate the
effectiveness of the sodium polyacrylate in giving a clean phase
split between the oily material phase and the aqueous phase.
##SPC1##
In addition to the above, experiments were conducted in which other
types of water-soluble polymers were employed as the
non-emulsifying foam stabilizer. These other types of water-soluble
polymers were guar gum and ethylene maleic anhydride polymers. The
formulation containing the guar gum was a thick gummy mixture
showed no signs of splitting into two phases. The formulations
containing the ethylene maleic anhydride copolymers produced three
phase products at concentrations of both 2 and 5 weight
percent.
Therefore, the above data clearly indicate that a multi-phase
liquid detergent composition in which the aqueous phase contains a
foam-producing, water-soluble organic detergent and a water-soluble
salt of a polyacrylate possesses the desired foam and foam
stability properties, as well as the desired phase splitting
properties.
* * * * *