U.S. patent number 3,755,206 [Application Number 05/118,939] was granted by the patent office on 1973-08-28 for detergent compositions.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Denise Verdier.
United States Patent |
3,755,206 |
Verdier |
August 28, 1973 |
DETERGENT COMPOSITIONS
Abstract
A liquid detergent system having a controllable viscosity and
clarity, including a water-soluble paraffin sulfonate and a
water-soluble, higher alkane, ether sulfate. Control of the
viscosity and clarity is accomplished by using a control system
comprising a lower aliphatic alcohol and urea.
Inventors: |
Verdier; Denise (Le Bourget,
FR) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
Family
ID: |
26215603 |
Appl.
No.: |
05/118,939 |
Filed: |
February 25, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Mar 9, 1970 [FR] |
|
|
7008310 |
Nov 9, 1970 [FR] |
|
|
7040196 |
|
Current U.S.
Class: |
510/429; 510/235;
510/237; 510/425; 510/433 |
Current CPC
Class: |
C11D
1/37 (20130101); C11D 1/86 (20130101); C11D
3/323 (20130101); C11D 1/29 (20130101); C11D
1/655 (20130101); C11D 3/3418 (20130101); C11D
1/143 (20130101); C11D 1/523 (20130101); C11D
1/72 (20130101) |
Current International
Class: |
C11D
3/32 (20060101); C11D 1/02 (20060101); C11D
1/37 (20060101); C11D 3/26 (20060101); C11D
1/29 (20060101); C11D 17/00 (20060101); C11D
1/14 (20060101); C11D 1/72 (20060101); C11D
1/38 (20060101); C11D 1/52 (20060101); C11d
001/14 (); C11d 001/37 (); C11d 001/655 (); C11d
001/831 () |
Field of
Search: |
;252/532,551,531,550,554,535,153,525,544,545,548 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
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|
|
1,104,692 |
|
Feb 1968 |
|
GB |
|
279,352 |
|
Jan 1965 |
|
AU |
|
513,726 |
|
Sep 1952 |
|
BE |
|
214,861 |
|
May 1958 |
|
AU |
|
808,805 |
|
Feb 1959 |
|
GB |
|
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Willis; P. E.
Claims
What is claimed is:
1. A clear, stable liquid detergent consisting essentially of a
water-soluble paraffin sulfonate salt having from 10 to 20 carbon
atoms in the molecule, a compatible water-soluble higher alkyl
ether sulfate salt in a ratio of paraffin sulfonate to ether
sulfate of about 10:1 to 1:1; and means for controlling the
viscosity and clarity of said liquid detergent; wherein the total
content of said paraffin sulfonate and alkyl ether sulfate salts is
about 10 percent to about 60 percent by weight in an aqueous
medium, the means for controlling the viscosity and clarity
constitutes from about 6 to 13 percent by weight of the liquid
detergent composition and comprises a mixture of urea and a lower
alkanol in a ratio of 1:1.5 to 1:3; said alkyl ether sulfate being
represented by the formula:
RO(C.sub.2 H.sub.4 O).sub.n SO.sub.3 X
in which R is an alkyl group having 10 to 18 carbon atoms per
molecule, n is a number from 1 to 10, and X is a cation; and the
cation of the sulfonate and said sulfate being selected from the
group consisting of alkali metals, alkaline earth metals, ammonium,
and lower amines.
2. A detergent as set forth in claim 1 in which said paraffin
sulfonate is a mixture of compounds having about 13 to 18 carbon
atoms per molecule.
3. A detergent as set forth in claim 1 in which R is an alkyl group
having between 12 and 14 carbon atoms per molecule and n is a
number from 3 to 6.
4. A detergent as set forth in claim 1 which also contains a
nonionic foam builder selected from the group consisting of
compounds represented by the formula:
RO(C.sub.2 H.sub.4 O).sub.n H
in which R is an alkyl group having 10 to 18 carbon atoms and n is
a number from 0 to 10, and mono- and diethanolamides and
isopropanolamides of a C.sub.10 -C.sub.14 fatty acid, said foam
builder being present in amounts up to about 10 percent by weight
of the liquid detergent.
5. A detergent as set forth in claim 4 in which R is an alkyl group
having 10 to 18 carbon atoms, n in the formula for said nonionic
foam builder is a number from 3 to 6.
6. A detergent as set forth in claim 4 in which said nonionic foam
builder is lauric-myristic monoethanol-amide.
7. A detergent as set forth in claim 1 which contains 20 to 35
percent by weight of sodium C.sub.13 -C.sub.18 paraffin sulfonate;
6 to 15 percent by weight of ammonium C.sub.12 -C.sub.15 alkyl
triethenoxy ether sulfate; 0 to 6 percent by weight of lauric
myristic monoethanolamide; a viscosity and clarity control agent
comprising 0.5 to 5 percent by weight of urea and 2 to 10 percent
by weight of lower alkanol; and water.
8. A detergent as set forth in claim 7 in which said alkanol is
ethyl alcohol.
9. A detergent as set forth in claim 7 in which said means for
controlling the viscosity and clarity further includes a lower
alkyl benzene sulfonate hydrotrope.
Description
The present invention relates to clear, stable, liquid detergent
compositions containing:
A. Water soluble salts of paraffin sulfonates,
B. Compatible water soluble salts of higher alkyl ether sulfates in
a ratio of A:B of about 10:1 to 1:1, and
C. a viscosity and clarity control system.
Preferably, the compositions are prepared in the form of a clear,
stable liquid detergent composition containing A and B in a total
content of about 10 to about 60 percent by weight in an aqueous
medium.
Liquid detergent compositions are known which comprise sodium
dodecyl benzene sulfonate and ammonium alkyl ether sulfate. In
order to formulate liquid detergents comprising these two
ingredients in sufficient concentration to be practical, it has
been necessary to include in the composition relatively high
proportions of solubilizing agents or hydrotropes such as the lower
aliphatic alcohols (e.g., ethyl alcohol), urea, low molecular
weight alkylbenzene sulfonates (e.g., sodium xylene sulfonate), and
the like.
It has now been discovered that commercially acceptable liquid
detergent compositions can be formulated based on:
A. water soluble salts of paraffin sulfonates,
B. compatible water soluble salts of alkyl ether sulfates, as
hereinafter defined, with as high as 60 percent active ingredients
in an aqueous liquid provided the ratio of A:B is from 10:1 to 1:1,
and
C. a viscosity and clarity control system, as hereafter
defined.
The liquid detergent compositions of the present invention have
significant advantages over the previously known liquid detergents
based on alkyl aryl sulfonates and alkyl ether sulfates.
Among the advantages of the present invention over the previously
known liquid detergents are the following:
1. Liquid detergent compositions of substantially equal percentage
of active ingredients and comparable clarity can be produced in
accordance with the present invention with significantly lower
percentages of hydrotropes than were necessarily used in the
previously known compositions.
2. The compositions of the present invention produce better foam
than the prior art compositions both in quantity and
durability.
3. Compositions of the present invention, when diluted to the same
concentration for use as the prior art compositions give
substantially higher performance, particularly in dish washing.
4. Washing compositions made with the product of the present
invention also have significantly lower surface tension than
compositions of the same concentration using prior art
compositions.
Among the advantages of the present invention are improved and
controlled performance such as foaming and dish washing ability,
viscosity and clarity which are important features in consumer
acceptability.
The paraffin sulfonates used in the present invention are usually
mixed secondary alkyl sulfonates having from ten to twenty carbon
atoms per molecule, preferably they will have at least 80 percent,
usually at least 90 percent, of from 10-17 carbon atoms per
molecule. Where the major proportion has 14-15 carbon atoms per
molecule, optimum foaming performance appears to be obtained at
varying concentrations and water hardnesses. These sulfonates are
preferably prepared by subjecting a cut of paraffin, corresponding
to the chain lengths specified above, to the action of sulfur
dioxide and oxygen in accordance with the well known sulfoxidation
process. The product of this reaction is a secondary sulfonic acid
which is then neutralized with a suitable base to provide the water
soluble secondary alkyl sulfonate for use in the present invention.
Similar useful secondary alkyl sulfonates may be obtained by other
methods, e.g., by the sulfochlorination method in which chlorine
and sulfur dioxide are reacted with paraffins in the presence of
actinic light, the resulting sulforyl chlorides being hydrolyzed
and neutralized to form the secondary alkyl sulfonates.
The higher alkyl ether sulfates used in the present invention are
represented by the formula:
RO(C.sub.2 H.sub.4 O).sub.n SO.sub.3 X
in which R is a primary or secondary alkyl group that may be
straight or branched having from 10 to 18 carbon atoms, preferably
12 to 14, X is a suitable cation, as hereinafter defined, and n is
a number from 1 to 10, preferably 3 to 6. These detergents are
produced by sulfating the corresponding ether alcohol and then
neutralizing the resulting sulfuric acid ester thereof.
The cation of the paraffin sulfonate and alkyl ether sulfate may be
an alkali metal, an alkaline earth metal (e.g., magnesium),
ammonium or lower amine (including alkylolamines). It is preferred
to use the sodium salt of the paraffin sulfonic acid and an
ammonium salt of the alkyl ether sulfuric acid ester.
It is advantageous to include non-ionic surface active agents in
the composition to improve the quantity and the lasting quality of
the foam. Among the non-ionic surface active agents which may be
used satisfactorily are higher alcohols, ether alcohols,
ethoxylated phenols, and higher fatty acid amides.
It is preferred that the liquid detergent composition contain a
higher fatty acid alkylolamide material in sufficient amount to act
as a suds builder. Its presence results in a product which exhibits
high foaming power in use, particularly in the stability of the
foam generated during dish washing or laundering operations. It
should not be employed in an amount sufficient to destroy the
desired physical properties. The acyl radical of the alkylolamide
is selected from the class of fatty acids having 8 to 18 carbon
atoms and each alkylol group usually has up to 3 carbon atoms. It
is preferred to use the monoethanolamides of lauric and myristic
acids but diethanolamides and isopropanolamides as well as
monoethanolamides of fatty acids having about 10 to 14 carbon atoms
in the acyl radical are satisfactory. Examples are capric,lauric,
myristic and coconut monoethanolamides, diethanolamides and
isopropanolamides and mixtures thereof. There may be employed also
the alkylolamides which are substituted by additional alkylol
groups, suitable examples may be the above amides condensed with 1
or 2 moles of ethylene oxide.
While any suitable ratio of paraffin sulfonates to alkyl ether
sulfates may be used as described, it has been found that the ratio
should be at least about 60 - 40 for an optimum combination of
properties, particularly in the presence of amide or the like.
Suitable ratios are 60:40, 70:30, 80:20 and 85:15 by weight with
0-8 percent alkylolamide, preferably 1-6 percent and usually 4-6
percent, such as coconut monoethanolamide, diethanolamide, or
ethanolamide condensed with about 1-4 moles of ethylene oxide. It
is understood that the sulfonate and sulfate salts may be in any
suitable water-soluble salt form such as the sodium, potassium,
ammonium, and mono-, di- and tri-ethanolamine salts, or mixtures
thereof.
The higher alcohols and ether alcohols which may be used as foam
builders in the present invention are represented by the
formula:
RO(C.sub.2 H.sub.4 O).sub.n H
exemplifications of which include decoxytriethoxyethanol,
lauroxytetraethoxyethanol, tetradecoxypentaethoxyethanol,
hexadecoxynonaethoxyethanol and octadecoxyheptaethoxyethanol among
the general class illustrated, and referring to the formula in
which R represents an alkyl group that may be straight or branched
having from 10 to 18 carbon atoms and n is a number from 0 to 10,
preferably 3 to 6. In the case of higher ether alcohols, the
preferred chain length for the alkyl group is from C.sub.10 -
C.sub.14 when n has a value from 3-6 as preferred.
When used, the non-ionics may be present in the formula up to about
10 percent by weight of the product, preferably up to about 4
percent of the alcohol ether and up to about 8 percent of the fatty
acid alkylolamide.
The viscosity and clarity control system used in the liquid
detergent composition of the invention comprises urea, a lower
aliphatic alcohol, and optionally a water-soluble hydrotropic
substance which is effective in promoting the compatibility of the
ingredients in the liquid product and can be substituted for part
of the urea or alcohol.
Suitable hydrotropic substances are the alkali metal organic
sulfonated (including sulfated) salts having a lower alkyl group up
to about 6 carbon atoms. The preferred sulfonated hydrotropes are
alkyl aryl sulfonates having up to 3 carbon atoms in the lower
alkyl group, e.g., the sodium and potassium xylene, toluene,
ethylbenzene and isopropyl benzene (cumene) sulfonates. Sulfonates
made from xylene include orthoxylene sulfonate, metaxylene
sulfonate, paraxylene sulfonate and ethylbenzene sulfonate.
Commercial xylene sulfonates usually contain metaxylene sulfonate
as the main ingredient. Analysis of typical commercial xylene
sulfonate products shows about 40- 50 percent metaxylene sulfonate,
10-35 percent orthoxylene sulfonate and 15-30 percent paraxylene
sulfonate with 0-20 percent ethylbenzene sulfonate. Any suitable
isomeric mixture, however, may be employed. Sodium cumene sulfonate
and sodium xylene sulfonate are preferred lower alkyl aryl
sulfonates to use in the compositions of the present invention. It
is also permissible to use suitably lower alkyl sulfate salts
having about 5 to 6 carbon atoms in the alkyl group such as alkali
metal n-amyl and n-hexyl sulfates.
The use of the viscosity and clarity control system imparts
superior low temperature clarity of the liquid detergent
composition and provides control of the viscosity of the product
over a wider range for any particular concentration of active
ingredients, as will be set forth in greater detail
hereinafter.
The lower aliphatic alcohols preferably have two or three carbon
atoms. Thus, ethyl alcohol, propyl alcohol, isopropyl alcohol or
propylene glycol can be used, preferably, ethyl alcohol will be
used.
The exact proportions of urea, lower alcohol, and hydrotropic
substance best suited for any particular composition may be
determined by the formulator by conventional tests. The weight
content of this viscosity and control system based upon the total
composition will vary from 2.5-15 percent and preferably from 6 to
13 percent. Within that range, the urea and the alcohol will vary
within the ranges of 0.5 to 5.0 percent, preferably 1 to 4 percent
and 2 to 10 percent, preferably 5 to 8 percent, respectively. It is
desirable to maintain the ratio of urea to alcohol within the range
of 1:1.5 to 1:3 parts by weight, most preferably, at about 1:2.5
when using an active ingredient content above about 30 percent by
weight, preferably 35- 45 percent including alkylolamide or the
like. Varying amounts of hydrotrope such as xylene sulfonate or the
like may be added or substituted in part for the alcohol or urea so
as to form a ternary system with special properties such as to
markedly increase the viscosity to greater levels. The amount
should be selected by formulation so as to maintain a satisfactory
viscosity and cloud point and maintain other desirable properties.
Generally, the hydrotrope may constitute up to about 50 percent by
weight of the total viscosity and control system.
The liquid detergents of the present invention may also contain any
of the additives heretofore used in other liquid detergent
compositions such as sequestrants, e.g., salts of ethylenediamine
tetraacetic acid, such as the sodium and potassium salts, and salts
of hydroxy ethyl ethylene diamine triacetate. It is desirable in
some cases to tint or color the liquid detergent composition and
any suitable dyes may be used for this purpose. Perfume may also be
added to these compositions to give them a pleasant odor.
Water is used as the liquid vehicle for the liquid detergent
compositions of the present invention. It will vary in proportion
from about 50 to 90 percent, depending upon the content of the
other ingredients of the composition.
In order to illustrate some of the benefits of the present
invention, two compositions containing sulfonated hydrotropes and
alcohol are compared with two conventional type liquid detergent
compositions based on sodium dodecyl benzene sulfonate. Table 1
sets forth the four compositions. Sodium paraffin sulfonate is used
in Examples 1 and 2 at the same level of concentration as the
sodium dodecyl benzene sulfonate is used in Examples 1A and 2A
respectively. Ammonium alkyl ether sulfate is also present at the
same levels in each Example of pair 1 and 1A and of pair 2 and 2A.
The non-ionic detergent (alcohol ether in Examples 1 and 1A and
lauric myristic monoethanol amide in Examples 2 and 2A) is also at
the same level in the two Examples of each pair. The sodium xylene
sulfonate and alcohol content is adjusted to give the same physical
properties to each Example of pair 1 and 1A and of pair 2 and 2A,
respectively. The import of Table 1 is that satisfactory formulas
having properties quite comparable from the physical standpoint
with prior art formulas are obtainable in accordance with the
present invention with a significantly reduced percentage of
alcohol and sodium xylene sulfonate. ##SPC1##
Referring to Table I, it will be noted in Example 1 that the same
physical properties were obtained with 6 percent ethyl alcohol that
required 8.5 percent for Example 1A. Example 2 had the same
physical properties with 4 percent sodium xylene sulfonate and 5.5
percent alcohol that Example 2A possessed at 6 percent sodium
xylene sulfon-ate and 7 percent alcohol.
Table II compares the results of two different performance tests on
washing solutions made from Examples 1 and 2 and rom Examples 1A
and 2A. One of the performance tests is a dishwashing test which
was carried out at two different levels of water hardness, viz., at
50 and 300 parts per million (PPM) of hardness, and at two
concentrations of detergent, viz., 0.075 percent and 0.15 percent
for each level of water hardness. The other test is a test of foam
height at 300 parts per million water hardness at 0.05 percent
level of concentration of detergent.
The dishwashing tests mentioned above and hereinafter were carried
out by uniformly soiling standard plates with a soil which consists
of a commercial hydrogenated fatty (cottonseed) oil by spreading a
small amount, equally, on each plate.
The plates are washed in dishpans which contain 6 liters of wash
water at 43.degree.C. Each of the compositions to be tested (at the
two different concentrations of the liquid detergent, and at the
two different water hardnesses) is prepared and placed, separately,
in different dishpans. The plates are then washed in the dishpans
to an endpoint of a permanent break in the foam covering the
dishpan; the number of plates which can be washed to that end point
is noted and recorded. A difference of 2 plates in the results
obtained is generally considered necessary in order to be
significant at a 95 percent confidence level.
The second test also mentioned above and which is employed to
ascertain the foam characteristics of the compositions is the foam
height test, and specifically, the well known Ross & Miles Test
(Pour Foam Test). This test consists essentially of measuring foam
in a measuring cylinder. A jacketed measuring cylinder is employed
into which a portion of the solution (at 0.05 percent in 300 ppm
water) to be tested is placed. The foam is formed by allowing a
second portion of the solution to stream in from a fixed height
through a standard orifice. The foam is recorded as the maximum
reached in the measuring cylinder. ##SPC2##
It will be noted that Examples 1 and 2 are significantly better
under all test conditions than Examples 1A and 2A.
The foregoing results are typical of the improved performance which
can be obtained in accordance with the present invention as
compared with compositions of the prior art.
Table III shows the improvement in surface tension of compositions
of the present invention compared with the prior art. ##SPC3##
The number of drops is that delivered by a stactometer (or
stalagmometer) from a given volume of the detergent solution at the
considered concentration and water hardness. The surface tension is
inversely proportional to this number of drops. Thus, the higher is
the number of drops, the lower is the surface tension, and the
better the detergent.
Table IV gives the general ranges of the principal ingredients
within which the preferred compositions of the invention are
formulated.
TABLE IV
The preferred ranges are as follows:
% Paraffin sulfonates 15-40 Alcohol ether sulfates 4-15
Alkylolamide or alkylolamide - Eto condensate 0- 8 Urea 1- 4
Ethanol 5- 8 Water QS
the following examples further describe the invention, with all
amounts being by weight:
EXAMPLE 3
% Sodium paraffin sulfonate 30 C.sub.12 -C.sub.15 Fatty alcohol EO
: 1 NH.sub.4 sulfate 8 Coconut fatty acid monoethanolamide 2 Urea 2
Ethyl alcohol 5.4 Sodium ethylene diamine tetraacetate 0.075 Water
(with small amounts of color, preservative and perfume) QS Total
100
The above product exhibits satisfactory foaming and dishwashing
properties combined with preferred physical properties such as a
cloud point of about 5.degree.C. and a viscosity of about 170 cps.
at 25.degree.C. using a Brookfield Viscosimeter Model LVF Spindle 1
at 30 RPM. The paraffin sulfonate employed has the following
approximate composition : 5% C.sub.13, 16% C.sub.14, 30% C.sub.15,
30% C.sub.16, 15% C.sub.17 and 4% C.sub.18, with an average
molecular weight of about 328. Various impurities may be present in
commercial products such as small amounts of free paraffin or
disulfonates.
EXAMPLE 4
A liquid detergent having similar properties as that of Example 3
is prepared by substituting an equivalent amount of coconut
monoethanolamide condensed with about 2 moles of ethylene oxide for
the monoethanolamide.
EXAMPLE 5
A satisfactory liquid detergent is prepared using the same
materials as Example 3 in the following proportions : 22 percent
paraffin sulfonate, 13 percent alkyl ether sulfate, 5 percent
lauric myristic monoethanolamide, 5 percent urea and 6 percent
ethanol with the balance being essentially water.
EXAMPLE 6
A satisfactory liquid detergent is prepared with the same formula
as Example 3 except that it contains 5.6 percent ethanol, 0.6
percent sodium xylene sulfonate and 1.8 percent urea.
One of the advantages of the urea-lower alcohol control system is
that a change in the physical characteristics of the composition is
possible by varying the ratio of alcohol to urea. In the specific
composition of Example 3, the ratio of alcohol to urea is 5.4 to 2
(2.7:1) which resulted in the clear point below 7.degree.C. and the
viscosity of 170. By changing the alcohol: urea ratio by increasing
the alcohol content, it is possible to decrease the viscosity and
raise the clear point whereas by decreasing the alcohol content the
clear point can be lowered and the viscosity increased. Hydrotropes
such as sodium xylene sulfonate tend to have an effect similar to
that of the alcohol, ie., increases thereof will raise the clear
point but lower the viscosity. It is important to balance these
constituents of the control system within the cited ranges to
obtain the desired results. For optimum balance of clear point and
viscosity, the total content of the control system will vary with
the content of the active ingredients (paraffin sulfonate, alcohol
ether sulfate and non-ionic detergents).
The clear point is also influenced by the amount of esters in the
amide and sodium sulfate in the paraffin sulfonate and alkyl ether
sulfate used as raw materials in preparing the compositions and,
for compositions having a low clear point, raw materials with low
content of these impurities should be used. The characteristics
given above for the specific composition of Example 3 can best be
obtained if the amide does not contain over 2 percent esters and
the paraffin sulfonate does not contain over 4 percent sodium
sulfate.
Although the present invention has been described and illustrated
with reference to certain specific compositions, these are to be
considered as illustrative of and not as limitations on the present
invention. All proportions are given hereinabove in percentages by
weight of the entire composition unless otherwise indicated.
* * * * *