U.S. patent number 3,623,990 [Application Number 04/649,019] was granted by the patent office on 1971-11-30 for liquid detergent composition.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Cushman Merlin Cambre.
United States Patent |
3,623,990 |
Cambre |
November 30, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
LIQUID DETERGENT COMPOSITION
Abstract
Stable, liquid detergent compositions for cleaning hard surfaces
containing particulate materials (e.g., abrasives), water,
alkylbenzenesulfonate detergent, zwitterionic synthetic detergent
and electrolyte, which preferably comprises a detergency
builder.
Inventors: |
Cambre; Cushman Merlin
(Cincinnati, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
27560789 |
Appl.
No.: |
04/649,019 |
Filed: |
June 26, 1967 |
Current U.S.
Class: |
510/397; 510/428;
510/494; 510/469 |
Current CPC
Class: |
C11D
1/94 (20130101); B21D 39/06 (20130101); C11D
17/0013 (20130101); D06B 23/042 (20130101); C11D
3/0047 (20130101); C11D 3/2075 (20130101); H05K
13/04 (20130101); C11D 1/22 (20130101); C11D
1/92 (20130101) |
Current International
Class: |
C11D
3/12 (20060101); C11D 3/395 (20060101); C11D
9/04 (20060101); C11D 9/22 (20060101); C11D
9/00 (20060101); C11D 1/02 (20060101); C11D
9/18 (20060101); C11D 7/02 (20060101); C11D
1/00 (20060101); D06B 23/04 (20060101); D06B
23/00 (20060101); B21D 39/06 (20060101); B21D
39/00 (20060101); C11D 1/88 (20060101); C11D
1/94 (20060101); C11D 10/04 (20060101); C11D
1/22 (20060101); C11D 10/00 (20060101); C11D
3/37 (20060101); C11D 17/00 (20060101); C11D
1/92 (20060101); C11D 3/00 (20060101); C11D
9/14 (20060101); C11D 9/16 (20060101); C11D
7/20 (20060101); H05K 13/04 (20060101); C11d
003/06 (); C11d 003/08 (); C11d 001/84 () |
Field of
Search: |
;252/137,138,140,152,155,160,161,156,DIG.14 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1,447,747 |
|
Jun 1966 |
|
FR |
|
1,484,489 |
|
May 1967 |
|
FR |
|
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Halpern; M.
Claims
What is claimed is:
1. A stable, liquid detergent composition which is free of soaps,
amides and hydrotropes and which has a yield value of from about 5
to about 600 dynes per square centimeter and an apparent viscosity
below about 12,000 centipoises consisting essentially of
1. an anionic alkylbenzenesulfonate synthetic detergent having the
general formula:
R-C.sub.6 H.sub.4 -SO.sub.3 M
wherein R is an alkyl chain containing from about nine to about 15
carbon atoms, and M is a cation selected from the group consisting
of potassium, sodium, ammonium, monoethanolammonium,
diethanolammonium, and triethanolammonium cations;
2. a zwitterionic quaternary ammonio synthetic detergent having the
general formula:
wherein R' is an alkyl chain containing from about 10 to about 18
carbon atoms; R" is selected from the group consisting of hydrogen
and hydroxyl; the ratio of alkylbenzenesulfonate detergent to the
zwitterionic synthetic detergent ranges from about 0.4:1 to about
4:1 and the combined weight of the alkylbenzenesulfonate detergent
and the zwitterionic synthetic detergent ranges from about 5
percent to about 20 percent by weight of the finished composition;
3. from about 1 percent to about 60 percent, by weight of the
finished composition, of insoluble, particulate material having
particle diameters ranging from about 1 micron to about 200
microns, and a density of from about 0.5 to about 5.0 (g./cc.)
wherein the particulate material is an abrasive selected from the
group consisting of quartz, pumice, pumicite, talc, silica sand,
calcium carbonate, china clay, zirconium silicate, bentonite,
diatomaceous earth, whiting feldspar and aluminum oxide; 4. from
about 1 percent to about 10 percent by weight of the finished
composition, of a polyvalent electrolyte effective to lower the
solubility and thereby salt out said anionic alkylbenzenesulfonate
synthetic detergent and said zwitterionic quaternary ammonio
synthetic detergent from a continuous phase wherein said
electrolyte is selected from the group consisting of sodium
sulfate, tetrapotassium pyrophosphate, trisodium ethane
hydroxydiphosphonate, sodium tripolyphosphate, trisodium
orthophosphate, sodium tetraborates, and mixtures thereof;
5. from about 25 percent to about 85 percent, by weight of the
finished composition, water; and
6. sufficient strong base to adjust the pH of the composition to
from about 7.5 to about 13.0;
said yield value being sufficient to support said insoluble,
particulate material; said pH being adjusted to a pH of up to about
11 when said insoluble, particulate material is aluminum oxide.
2. The composition of claim 1 wherein the alkylbenzenesulfonate
detergent is sodium n-dodecylbenzenesulfonate, and in the formula
given for the zwitterionic detergent, R" is hydroxyl.
3. The composition of claim 1 wherein the alkylbenzenesulfonate
detergent comprises from about 2 percent to about 12 percent by
weight of the finished detergent compositions, the zwitterionic
synthetic detergent comprises from about 2 percent to about 14
percent by weight of the finished detergent composition, and the
ratio of alkylbenzenesulfonate detergent to zwitterionic detergent
is from about 0.4:1 to about 2.0:1.
4. The composition of claim 1 wherein the alkylbenzenesulfonate
detergent comprises from about 2 percent to about 6 percent by
weight of the finished detergent composition, the zwitterionic
synthetic detergent comprises from about 2 percent to about 7
percent by weight of the finished detergent composition, the ratio
of alkylbenzenesulfonate detergent to zwitterionic detergent is
from about 0.4:1 to about 2.0:1, and the total amount of
alkylbenzenesulfonate and zwitterionic detergents is from about 5
percent to about 12 percent of the finished detergent
composition.
5. The composition of claim 1 wherein the ratio of
alkylbenzenesulfonate detergent to zwitterionic detergent is about
0.086:1, and the total amount of alkylbenzenesulfonate and
zwitterionic detergents is from about 6 percent to about 7 percent
by weight of the finished detergent composition.
6. The composition of claim 1 wherein the insoluble, particulate
material comprises from about 40 percent to about 50 percent by
weight of the finished detergent composition and wherein the
insoluble, particulate material has particle diameters ranging from
about 2 microns to about 60 microns and has a specific gravity of
from 1 to about 2.8.
7. The composition of claim 1 wherein the electrolyte comprises a
builder salt selected from the group consisting of from 0 percent
to about 6 percent of potassium pyrophosphate; from 0 percent to
about 2 percent of sodium tetraborate decahydrate; from 0 percent
to about 5 percent of trisodium ethanehydroxydiphosphonate; from 0
percent to about 3 percent of sodium tripolyphosphate; from 0
percent to about 7 percent of trisodium orthophosphate; and
mixtures of the above.
8. The composition of claim 7 wherein the electrolyte comprises
from about 3 percent to about 4 percent potassium
pyrophosphate.
9. The detergent composition of claim 1 wherein the pH is adjusted
to from about 8 to about 11 by adding a strong base selected from
the group consisting of sodium hydroxide and potassium hydroxide.
Description
CROSS-REFERENCE TO RELATED APPLICATION
Other stable liquid detergent compositions for cleaning hard
surfaces are disclosed in applicant's copending application Ser.
No. 603,098, filed Dec. 20, 1966, now U.S. Pat. No. 3,520,818.
BACKGROUND OF THE INVENTION
This invention relates to liquid detergent compositions adapted for
cleaning hard surfaces. More particularly, this invention relates
to a liquid detergent composition having a yield value of from
about 5 to about 600 dynes per square centimeter.
There has been an increasing demand for liquid detergent
compositions adapted for cleaning hard surfaces. These liquid
detergent compositions are provided in convenient form and are
especially formulated for this particular cleaning application. To
obtain optimum cleaning and consumer acceptance, these detergent
compositions must be homogeneous and easily pourable. These
compositions, when intended for the retail consumer market, should
maintain their homogeneity during ordinary periods of storage and
use, and should have acceptable freeze-thaw characteristics. It is
highly desirable that liquid detergent compositions for cleaning
hard surfaces should exhibit Bingham plastic characteristics; that
is, they should exhibit a substantial yield value in order to keep
particulate material from settling to the bottom of the
container.
When these liquid detergent compositions are intended for
industrial applications, extended product stability, as described
above, is not as important as it is in the retail consumer market.
In industrial applications, the compositions can be reintegrated
and the particulate material redistributed before use, for example,
by mixing or shaking the compositions. However, even these products
should be stable for at least a 24-hour period.
A. Yield Value
The consistency of simple (or Newtonian) liquids is a function of
the nature of the material, temperature, and pressure only. This
consistency is known as the "fluid viscosity coefficient,"
"absolute viscosity," or merely "viscosity," and is usually
measured in centipoises (1 centipoise =0.01
gram/centimeter-second). With a Newtonian liquid, any force applied
to the system produces some deformation, according to the formula
du/dr=F/.mu. where du/dr = the rate of shear; F = the shear stress,
or shearing force per unit area; and .mu.= the viscosity
coefficient.
In the case of non-Newtonian liquids, on the other hand, the
consistency is a function of the material, pressure, temperature,
and also the shear stress applied to the system. Those
non-Newtonian liquids which are classified as Bingham plastics, or
real plastics, are not always deformed when a force is applied to
the system. Deformation, if any, takes place according to the
formula du/dr=(F-f)/.mu..sub.a where .mu..sub.a = the apparent
viscosity, or plastic viscosity, at the shear stress F; f= a
characteristic of the liquid called the yield stress, or yield
value, measured in units of pressure; and du/dr and F are as
defined above.
If the shear stress applied to the system is less than the yield
value, the system will not be deformed at all. Hence, a Bingham
plastic system is capable of supporting indefinitely insoluble
particulate material which has a density greater than that of the
supporting medium, so long as the material has such a particle size
and density that the shear stress which each particle places on the
supporting medium does not exceed the yield value.
This is to be contrasted with suspension of heavy insoluble
particulate material in Newtonian liquids with high viscosities. In
highly viscous Newtonian liquids, insoluble particulate material is
suspended only because the rate of flow is slow. In Bingham
plastics, insoluble particulate material is suspended because the
stress imposed by the particles does not exceed the yield value of
the liquid, and therefore, there is no flow at all. Of course, if
the yield value of the supporting medium should sufficiently
decrease for any reason, the particles would no longer be
suspended. This could be caused, for example, by a physical or
chemical change in the supporting medium. If one of the components
of the supporting medium is an emulsion which settles into layers
upon standing, the yield value can be lost temporarily; but in such
a case, the original composition can be reconstituted by mixing. If
a chemical reaction either consumes a vital component or produces a
damaging one, the loss of yield value can be permanent.
B. Previous Compositions
Liquid detergent compositions containing a combination of alkali
metal soaps, ethanol amides and potassium pyrophosphates are known
(see U.S. Pat. No. 3,234,138). Although liquid detergent
compositions containing alkali metal soaps, amides and phosphates
exhibit useful properties, these compositions also have some
disadvantageous features. For example, when particulate materials
are added to these compositions and the compositions are then
subjected to ordinary storage conditions, they may separate into
two layers. As these liquid detergent compositions separate, they
lose their ability to support particulate material and,
accordingly, the particulate material settles. As another example,
a portion of the amides in these compositions is hydrolyzed to soap
if the compositions are subjected to high storage temperatures,
e.g., 110.degree. F. As the amide hydrolyzes, the liquid detergent
compositions separate and lose their Bingham plastic
characteristics. Again, the particulate material in these
compositions is deposited on the bottom of the respective
containers.
A variety of detergent compositions containing synthetic anionic
detergents, soaps, or both, as well as detergency builders and
abrasives, are known. See, for example, U.S. Pat. Nos. 3,149,078;
3,210,285; 3,281,367; Canadian Pats. Nos. 635,321 and 685,394.
These compositions usually require the presence of amides, and
frequently contain soaps.
Soaps and amides are undesirable in many situations, however. Soaps
react with calcium, magnesium, and other ions present in hard
water, forming undesirable scum. Soaps containing about eight or
fewer carbon atoms in their molecular structure act as solubilizing
agents, and cause multiple phase systems to lose their Bingham
plastic characteristics. Soaps in which the alkyl group is derived
from coconut are relatively expensive, as compared to
alkylbenzenesulfonate synthetic anionic detergents.
Amides are subject to hydrolysis, especially when compositions are
stored at high temperatures, e.g., 110.degree. F. Upon hydrolysis,
amides yield ammonium soaps, which are subject to the disadvantages
outlined above. For these and other reasons, the use of soaps and
amides is to be avoided in practicing the present invention.
Other stable liquid detergent compositions for cleaning hard
surfaces are disclosed in applicant's U.S. Pat. No. 3,520,818. The
detergent compositions of U.S. Pat. No. 3,520,818 are free of
amides, but are required to contain soap. The compositions of U.S.
Pat. No. 3,520,818 also differ in the kind and relative proportions
of components which can be employed.
Accordingly, it is an object of this invention to provide liquid
detergent compositions which exhibit Bingham plastic
characteristics and which are stable for protracted periods of
time. It is a further object of this invention to provide liquid
detergent compositions which remain stable when subjected to both
depressed and elevated storage temperatures. A still further object
of this invention is to provide Bingham plastic, liquid detergent
compositions in which particulate material will not settle to the
bottom of the containers when the compositions are stored for
protracted periods of time. Another object of this invention is to
provide liquid detergent compositions which exhibit Bingham plastic
characteristics and which do not contain soaps or amides. It is
another object of this invention to provide a detergent composition
in convenient pourable form.
Still further objects and the entire scope of applicability of the
present invention will become apparent from the detailed
description given hereinafter. It should be understood, however,
that the detailed description and specific examples, while
indicating preferred embodiments of the invention, are given by way
of illustration only since various changes and modifications within
the spirit and scope of this invention will become apparent to
those skilled in the art. All parts, percentages and ratios set
forth herein are by weight.
SUMMARY OF THE INVENTION
It has surprisingly been discovered, according to the present
invention, that the foregoing objects are obtained with an opaque,
liquid detergent composition which is substantially free of soaps,
amides and hydrotropes and which has a yield value of from about 5
to about 600 dynes per square centimeter and an apparent viscosity
below about 12,000 centipoises consisting essentially of, by weight
of the finished composition,
1. an anionic alkylbenzenesulfonate synthetic detergent having the
general formula:
R=1/M C.sub.6 H.sub.4 =(1/M= SO.sub.3 M
wherein R is an alkyl chain containing from about nine to about 15
carbon atoms, and M is a cation selected from the group consisting
of potassium, sodium, ammonium, monoethanolammonium,
diethanolammonium, and triethanolammonium cations;
2. A zwitterionic quaternary ammonio synthetic detergent having the
general formula:
wherein R' is an alkyl chain containing from about 10 to about 18
carbon atoms, and R" is selected from the group consisting of a
hydrogen atom and a hydroxyl group; the ratio of
alkylbenzenesulfonate detergent to the zwitterionic synthetic
detergent ranges from about 0.4:1 to about 4:1; and the combined
weight of the alkylbenzenesulfonate and zwitterionic synthetic
detergents ranges from about 5 percent to about 20 percent by
weight of the finished composition;
3. from 1 percent to about 60 percent of an insoluble, particulate
material having particle diameters ranging from about 1 micron to
about 200 microns, and a density of from about 0.5 to about 5.0;
(The term "density" as used herein has the units of g./cc.)
4. from about 1 percent to about 10 percent of polyvalent
electrolyte;
5. from about 25 percent to about 85 percent water; and
6. sufficient strong base to adjust the pH of the composition to
from about 7.5 to about 13.0; wherein said yield value is
sufficient to support said insoluble, particulate material.
DETAILED DESCRIPTION
At this juncture, the liquid detergent composition of this
invention will be characterized, in its entirety, in order to
facilitate a better understanding of the individual components and
their functions in these liquid detergent compositions.
A. Yield Value
It is believed that the supporting medium of the liquid detergent
composition of this invention (that is, the total composition less
the insoluble particulate material) is a suspension which comprises
two phases. One phase is isotropic and continuous, and consists
mainly of inorganic materials such as water, base, and electrolyte.
The other phase is present as discrete particles, and consists
mainly of organic materials such as detergent. These discrete
particles are mesomorphic and have a highly oriented physical
structure. It is apparently this high degree of orientation which
imparts the yield value to the system. The presence of two liquid
phases is possible only in the absence of hydrotropes and other
solubilizing agents. Furthermore, electrolyte is required in the
system to "salt out" the organic materials from the continuous
phase; i.e., to lower the solubility of the discrete (mainly
organic) phase in the continuous (mainly inorganic) phase.
Because it is usually not known whether a system behaves in a truly
plastic manner at low shear rates, the measurement of exact yield
values is quite difficult. A close approximation can be obtained by
using a Brookfield viscometer. The yield value is estimated, in
dynes per square centimeter, by the following relationship:
This relationship represents an extrapolation of the shear curve to
0 r.p.m. since an absolute shear stress cannot be measured at 0
r.p.m.
The yield value of the liquid detergent compositions of this
invention ranges from about 5 to about 600 dynes per square
centimeter. If the yield value is too low, the insoluble,
particulate material will not be suspended, because the weight of
the individual particles, distributed over the area which supports
the particles, will exceed the yield value. However, if the yield
value is too great, the composition will become thick and
unmanageable because as the yield value increases, so will the
apparent viscosity.
A preferred range of yield values to support the insoluble
particulate material used in the liquid detergent compositions of
this invention is from about 100 to about 400 dynes per square
centimeter.
B. Individual Components
The essential individual components of the liquid detergent
composition of this invention are alkylbenzenesulfonate detergent,
zwitterionic synthetic detergent, insoluble particulate materials,
electrolyte, and water. Optional components include detergency
builders, strong base to adjust pH level, and minor ingredients
which have aesthetic value or which improve the effectiveness of
the composition. Strong base is not optional, however, if the pH of
the detergent composition without it is below about 7.5. The pH of
a composition of course varies with the identity and relative
amounts of the components used in it; usually no base is necessary.
The alkylbenzenesulfonate detergent, zwitterionic synthetic
detergent, and, if employed, the detergency builders, are the
primary cleaning or detergent components of this composition.
In preferred embodiments of this invention, abrasives and
detergency builders, as hereinafter defined, are added to the
liquid detergent composition of this invention. All of these
compositions are capable of suspending insoluble particulate
materials of the hereinafter specified density and particle size
and, accordingly, these particulate materials can be included as
components of these liquid detergent compositions.
1. Alkylbenzenesulfonate Detergent
The alkylbenzenesulfonate detergent used in the liquid detergent
compositions has the general formula:
R-C.sub.6 H.sub.4 -SO.sub.3 M
wherein R is an alkyl chain containing from about nine to about 15
carbon atoms, and M is a cation selected from the group consisting
of potassium, sodium, ammonium, monoethanolammonium,
diethanolammonium, and triethanolammonium cations; it is preferred
that R average from 12 carbon atoms and be a normal (straight
chain) alkyl group.
From about 2 percent to about 12 percent of the above-described
alkylbenzenesulfonate detergent, by weight of the finished
detergent composition, is utilized in the detergent compositions of
this invention. It is preferred that the finished composition
contain from about 2 percent to about 6 percent
alkylbenzenesulfonate. More important than the amount of
alkylbenzenesulfonate or zwitterionic detergent present
individually, however, is the total amount of these two detergents,
and the relative amounts in which they are present, as described
below.
2. Zwitterionic Synthetic Detergent
The zwitterionic quaternary ammonio synthetic detergent of this
invention has the following structural formula:
wherein R' is an alkyl radical containing from about 10 to about 18
carbon atoms, and R" is selected from the group consisting of a
hydrogen atom and a hydroxyl group. It is preferred that R' be
dodecyl or the alkyls derived from coconut fatty alcohol, and that
R" be a hydroxyl group.
The zwitterionic synthetic detergent described above is utilized in
this invention in amounts of from about 2 percent to about 14
percent by weight of the finished detergent composition. It is
preferred that the zwitterionic synthetic detergent be utilized in
amounts of from about 2 percent to about 7 percent by weight of the
finished composition.
The total amount of alkylbenzenesulfonate and zwitterionic
detergents, and the relative amounts in which they are present, are
more important than the absolute amount of either. While the
absolute amount of each detergent is of little independent
significance, the total amount of both detergents determines yield
value and ability to dissolve grease and dirt, and if excessive,
makes the detergent composition too thick and unmanageable. The
relative amounts of alkybenzenesulfonate and zwitterionic
detergents sharply affect the ability of the system to support
abrasive. Neither alkylbenzenesulfonate nor zwitterionic synthetic
detergent, alone, will provide a stable support for insoluble
particulate material; however, when they are used together as
herein described, they cooperate synergistically in a surprising
and unexpected way to provide a stable medium with a yield value
that will support insoluble particulate material.
The combined weight of alkylbenzenesulfonate and zwitterionic
detergents in the detergent compositions of this invention is from
about 5 percent to about 20 percent of the total weight of the
finished composition. A preferred embodiment contains from about 5
percent to about 12 percent of these detergents. About 6 percent to
about 7 percent was found to be a level which produces a
sufficiently high yield value, but not an unduly thick
composition.
Within the preferred range of insoluble particulate material (about
40 percent to about 50 percent, see below), it can be further said
that between about 10 percent and about 18 percent of the
supporting medium (that is, the entire composition less suspended
insoluble particulate material) should be detergent, and about 10
percent to about 16 percent is preferable. About 12 percent to
about 14 percent gives the best results. At the higher detergent
concentrations, the combined detergent and abrasive make the
compositions too thick to be manageable; at the lower detergent
concentrations there is not enough detergent to provide sufficient
yield value to support the abrasive. The upper limit on combined
detergent and abrasive is a functional one, and is best expressed
in terms of apparent viscosity. The detergent compositions of this
invention have an apparent viscosity below about 12,000
centipoises; it is preferred that the apparent viscosity be below
about 10,000. As used here and elsewhere in this specification,
"apparent viscosity" means the value obtained with a Brookfield
viscometer, Model LVF, using spindle number 3 at 12 r.p.m. At lower
(below 40 percent) abrasive concentrations, the concentration of
total detergent in the supporting medium becomes less important,
and up to about 20 percent of the total composition can be
detergent.
It is important in the practice of this invention to maintain the
weight ratio of alkylbenzenesulfonate to zwitterionic synthetic
detergent in the range between from about 0.4:1 to about 4:1. When
the alkylbenzenesulfonate to zwitterionic ratios do not fall within
these limits, the detergent compositions of this invention may have
unacceptably low yield values, or they may separate into two layers
at room temperature, or both. It is preferred that the
alkylbenzenesulfonate to zwitterionic synthetic detergent ratio be
in the range of about 0.4:1 to about 2.0:1. The exact value of this
ratio depends on other materials present in the system. For
example, a ratio of about 0.86:1 was found particularly effective
for a system containing alkylbenzenesulfonate and zwitterionic
detergents, sodium sulfate and sodium chloride.
3. Insoluble Particulate Material
The insoluble, particulate material which is utilized in this
invention can comprise abrasives, bactericides, or other insoluble,
particulate material having a particle size diameter ranging from
about 1 to about 200 microns and a density of from about 0.5 to
about 5.0. It is preferred that the diameter of the particles range
from about 2 microns to about 60 microns and that the density range
from about 1.0 to about 2.8. The abrasives which can be utilized in
this invention include, but are not limited to, quartz, pumice,
pumicite, talc, silica sand, calcium carbonate, china clay,
zirconium silicate, bentonite, diatomaceous earth, whiting,
feldspar, and aluminum oxide. Silica is the preferred abrasive for
use herein. If aluminum oxide is used, the pH of the composition
should not be above about 11, or the aluminum oxide will dissolve.
Furthermore, if a high density abrasive (such as aluminum oxide,
pumice containing aluminum oxide, or zirconium silicate) is used,
particular care must be taken that the yield value is sufficiently
high to support particles of the size and density used. For any
particular system, the yield value required can be calculated from
the density and particle size of the suspended particles, and from
the density of the supporting medium. The yield value required is
equal to the pressure per unit area which the weight of the
particle exerts on the supporting medium, taking into account the
buoyant force of the supporting medium. For a spherical particle of
greater density than the supporting medium, this yield value is
given by the formula
f = [2Dg(d-d')] /3 ,
where f is the yield value in dynes per square centimeter, D is the
particle diameter in centimeters; g is the gravitational constant,
980.665 centimeters per second per second; d is the density of the
particle to be supported; and d' is the density of the supporting
medium (both densities in grams per cubic centimeter). This
theoretical yield value should be multiplied by a "safety factor"
of about 1.5 or 2.0, to take into account such factors as
nonspherical particles, inaccuracy in estimating yield value, and
occasional agglomeration of two or more particles, in order to
calculate the yield value (as observed) which is necessary to
support the particular material which is to be suspended.
In the practice of this invention, from 1 percent to about 60
percent of the composition of this invention is insoluble
particulate material. It is preferred, however, that from 40
percent to about 50 percent by weight of the finished composition
be insoluble, particulate material.
4. Polyvalent Electrolyte
From about 1 percent to about 10 percent of the finished
composition is required to be polyvalent electrolyte. For example,
from about 1 percent to about 10 percent sodium sulfate can be
employed, but from about 2 percent to about 3 percent is preferred,
as this allows higher amounts of detergency builders to be used.
One or more detergency builders can be included in this electrolyte
to serve as a cleaning aid and as a pH buffer. The amount of
detergency builder to be included depends on the particular builder
used, but in any case should be between 0 percent and about 10
percent by weight of the finished composition. It is preferred that
the total amount of builders be from about 1 percent to about 7
percent. Many builders, if present in too great a quantity, will
cause the system to lose its yield value and suspending
capability.
Tetrapotassium pyrophosphate is preferred to other detergency
builders because of its good cleaning characteristics and excellent
solubility characteristics. The liquid detergent compositions built
with tetrapotassium pyrophosphate also exhibit excellent stability
characteristics over a wide range of temperatures.
From 0 percent to about 6 percent of tetrapotassium pyrophosphate
by weight of the finished detergent composition can be utilized in
this invention. To maximize stability and optimize the cleaning
characteristics of the liquid detergent compositions, about 3
percent to about 4 percent tetrapotassium pyrophosphate should be
utilized herein.
Tetraborate can be added to these detergent compositions to improve
cleaning (as a detergency builder), to improve low temperature
stability properties, and to raise the yield value. The tetraborate
can be introduced into the detergent composition in several forms,
e.g., anhydrous sodium tetraborate, sodium tetraborate
pentahydrate, and sodium tetraborate decahydrate. Sodium
tetraborate decahydrate is preferred for use herein as it is
readily available to the detergent industry. When the anhydrous or
hydrated tetraborate compounds are utilized, they ionize and
tetraborate ions are then present in these liquid detergent
compositions. It has been found that from 0 percent to about 0.8
percent tetraborate, by weight of the finished detergent
composition, can be utilized in this invention. This range
corresponds to 0 percent to about 2 percent sodium tetraborate
decahydrate by weight of the finished composition.
Other detergency builders which can be employed without destroying
the particle suspending ability of the composition include
trisodium ethanehydroxydiphosphonate, CH.sub. 3 COH(PO.sub. 3).sub.
2 HNa.sub. 3, in an amount ranging from 0 percent to about 5
percent; sodium tripolyphosphate, Na.sub. 5 P.sub. 3 0.sub. 10, in
an amount ranging from 0 percent to about 3 percent, and trisodium
orthophosphate, Na.sub. 3 PO.sub. 4, in an amount ranging from 0
percent to about 7 percent. Mixtures of these builders can also be
employed.
5. Water
From about 25 percent to about 85 percent of this composition is
water. It is preferred that from about 30 percent to about 50
percent by weight of the finished composition be water to optimize
yield values and cleaning characteristics of the finished product.
It is also preferred that soft water be utilized in this
invention.
6. Strong Base
The pH of the composition is from about 7.5 to about 13, preferably
from about 8 to about 11. If necessary, the pH is adjusted to this
level by adding a strong base. The most desirable strong bases for
use herein are sodium hydroxide and potassium hydroxide. In the
preferred pH range (about 8 to about 11), the liquid detergent
compositions of this invention have higher yield values and greater
stability, as well as better cleaning capability. Frequently no pH
adjustment is required, however, because the builder salts included
raise the pH of the composition to within the desired range.
7. Minor Ingredients
Minor amounts of materials which make the composition of this
invention more attractive or more effective can be added if they do
not significantly alter the excellent physical properties of this
composition. The following materials are mentioned merely by way of
example: soluble sodium carboxymethyl cellulose, tarnish inhibitors
such as benzotriazole or ethylenethiourea, brighteners, bleaches,
fluorescers, dyes, bluing agents, perfumes, bactericides and
corrosion inhibitors.
Hydrotropes such as sodium or potassium xylenesulfonate,
toluenesulfonate, or benzenesulfonate, should not be present in
these compositions. Even very small amounts of these hydrotropes
solubilize the discrete phase into the continuous phase. The
detergent composition, thus, becomes a one-phase solution and loses
its Bingham plastic characteristics with concomitant settling of
insoluble, particulate material, e.g., abrasive. The composition,
in this condition, is aesthetically undesirable and not salable on
the retail consumer market or the industrial market.
Also to be avoided are soaps, amides, and other materials which are
presently or potentially solubilizing agents, or which combine with
water hardness ions.
The following example illustrates the present invention.
EXAMPLE
Twenty detergent compositions were prepared from water, abrasive,
zwitterionic synthetic detergent, sodium dodecylbenzenesulfonate
detergent, sodium chloride (present as an impurity in the detergent
ingredients), sodium sulfate, and builder salts. Each of these
twenty compositions is designated as a "Run;" of these, Runs 1, 2,
7, 8, and 13 are not examples of the invention, but are included
for comparative purposes.
The abrasive, except in Runs 17 and 18, was silica (quartz,
specific gravity about 2.65) of the following particle size
distribution:
1--3 microns 0.4% 3--6 microns 4.1% 6--10 microns 11.5% 10--15
microns 16.0% 15--20 microns 16.0% 20--30 microns 24.0% 30--40
microns 17.0% 40--60 microns 11.0% 100.0%
Run 17 contained feldspar, specific gravity about 2.65, of the
following particle size distribution:
On 65 mesh (208 microns and larger) 0.022% On 100 mesh (147 microns
to 208 microns) 0.082% On 200 mesh (74 microns to 147 microns) 2.94
% On 325 mesh (43 microns to 74 microns) 18.15 % Through 325 mesh
(smaller than 43 microns) Balance
Run 18 contained calcium carbonate (calcite), specific gravity
about 2.8, and particle diameter about 25 microns.
The zwitterionic synthetic detergent had the formula
wherein R' represents alkyls derived from coconut fatty alcohol, by
distillation in which the low-boiling and high-boiling fractions
were excluded. The alkyl groups (so-called "middle-cut coconut")
had approximately the following distribution:
C.sub. 10 0.5% C.sub. 12 67.5% C.sub. 14 24.5% C.sub. 16 7.0%
C.sub. 18 0.5% 100.0%
these 20 runs had the composition given in the following table. In
each case, except as noted, the run contained 50 percent abrasive
and no builder; the balance necessary to give a total of 100
percent was water; and the "other" ingredients were impurities in
the starting materials, unreacted starting materials, and
by-products of the reactions to produce the alkylbenzenesulfonate
and zwitterionic detergents, comprising alkylbenzene, alkyl
sulfate, benzenesulfonate, methanol, organic chlorides (e.g.,
sodium 1-chloro-2-hydroxypropane-3-sulfonate), alkyl dimethyl
tertiary amines, quaternary-substituted ammonium compounds (e.g.,
dimethylalkylamine quaternarized with 3-chloro-1,2-propanediol or
1,3-dichloro-2-propanol), aliphatic alcohols, olefins,
epichlorohydrin polymers, paraffins, disodium
2-propanol-1,3-disulfonate, and sodium
1,3-dihydroxypropane-1-sulfonate. ##SPC1## ##SPC2##
Runs 1 and 2 show the effect of too small a relative amount of
alkylbenzenesulfonate detergent; Run 7 shows the effect of too
great a relative amount of alkylbenzenesulfonate detergent. Runs 8
and 13 illustrate the use of too little or too much total
detergent, respectively: Run 8 does not contain enough total
detergent to support the abrasive, even though the ratio of
alkylbenzenesulfonate to zwitterionic detergents is optimum; Run
13, containing 20 percent detergent in the supporting medium and 50
percent abrasive, was too thick to form a workable composition, and
was discarded. All runs except 13 were divided into three portions
each, stored respectively for one week at 50.degree. F., room
temperature (about 74.degree. F.), and 100.degree. F. After this
time, the samples were examined, and the pH, percent separation,
yield value (dynes per square centimeter) and apparent viscosity
(centipoises) were measured. Since the maximum separation resulted
in about the bottom 40 percent of the sample bottle containing the
bulk of the abrasive, this was defined as 100 percent separation.
The percent separation was then calculated by measuring the height
of liquid relatively free from abrasive at the top of the bottle,
dividing by the total height of the sample and multiplying by 166.7
percent (0.6 of sample free from abrasive .times. 166.7% = 100%).
Thus, although the total height of the samples was not constant, a
sample with a total height of 10 inches, and having the following
height of liquid relatively free from abrasive, would have the
following percent separation:
Inches Relatively Percent Free of Abrasive Separation
__________________________________________________________________________
0.0 0.0 0.6 10.0 1.2 20.0 1.8 30.0 2.4 40.0 3.0 50.0 3.6 60.0 4.2
70.0 4.8 80.0 5.4 90.0 6.0 100.0
The following results were obtained. ##SPC3## ##SPC4##
In each case, viscosity and yield value data were measured at room
temperature (about 74.degree. F.), even though the samples may have
been stored at higher or lower temperatures. The apparent
viscosities were read with a Brookfield viscometer, Model LVF,
using spindle number 3 at 12 r.p.m. viscosity measurements for
yield values were made with a Brookfield viscometer, Model RVT,
using spindle number C2 at one-half and 1 r.p.m.
The above runs can be considered to be five series, each of which
illustrates a different point. A horizontal line separates each
series. The first series contains Runs 1--7, showing the effect of
varying the ratio of sodium dodecylbenzenesulfonate to zwitterionic
detergent. The second series contains Runs 8, 9, 10, 4, 11, 12, and
13, showing the effect of varying the total amount of detergent. In
the above tables, Run 4 is repeated in several locations for ease
of comparison. In each of the series, the other variables were held
as near constant as practicable, in order to clearly show the
effect of varying the ratio or total detergent, respectively. All
of the compositions were effective cleaning compositions; however,
Runs 1, 2 and 7 (outside the ratio of detergents to be used in
compositions of this invention) were poor in suspending abrasive,
as was Run 8 (below the range of total detergent amount); Run 12
(at high end of total detergent amount) was very thick, and not
easily manageable.
In the runs of the first two series (Runs 1--13), the amount of
sodium sulfate was held constant at about 6 percent; since some
sodium sulfate is present as a byproduct of sulfating
dodecylbenzene, it was necessary to add up to almost 6 percent to
some runs to reach this level. The more effective cleaning
compositions contain less sodium sulfate (about 2 percent to about
3 percent), however, as this allows a greater proportion of
detergency builders to be present without destroying the yield
value and ability of the system to suspend insoluble particulate
material. The addition of builders usually raises pH; any
additional increase in pH is best accomplished by the addition of
sodium hydroxide or potassium hydroxide.
Runs 14-16 form a third series, illustrating the use of builders.
The following builders can be used, alone or in combination, in the
amounts indicated, with substantially equivalent or better results
(and in particular, without destroying the yield value and ability
to suspend particles), provided the level of sodium sulfate does
not exceed about 3 percent; tetrapotassium pyrophosphate, from 0
percent to about 6 percent, from about 3 percent to about 4 percent
being preferred, as it increases yield value; sodium tetraborate,
from 0 percent to about 2 percent (as decahydrate); trisodium
ethanehydroxydiphosphonate, from 0 percent to about 5 percent;
sodium tripolyphosphate from 0 percent to about 3 percent; and
trisodium phosphate, from 0 percent to about 7 percent.
Runs 4, 17 and 18 constitute the fourth series which illustrates
the use of various abrasives. The following can be substituted,
with substantially equivalent results, for the silica, feldspar and
calcium carbonate illustrated: quartz, pumice, pumicite, talc,
china clay, zirconium silicate, bentonite, diatomaceous earth,
whiting and aluminum oxide, of the same particle sizes. By
"substantially equivalent" results in this and the previous
paragraph, it is meant that stable suspensions with effective
cleaning properties are obtained.
Runs 19, 4 and 20 constitute the fifth series illustrating
variations in the abrasive level. The supporting medium in each of
these three runs is identical, with only the amount of abrasive
varied. It can be seen that at 33.33 percent and at 60.00 percent
abrasive level, some separation occurs; and although it is not
excessive, except under adverse storage conditions (see, e.g.,
results for run 19 at 50.degree. F.), it is therefore preferred
that the total abrasive be between about 40 percent and about 50
percent.
* * * * *