Note: Descriptions are shown in the official language in which they were submitted.
~69845
~P- IR- 4681X
BINEAR ~ISCOELASTIC AQUEOUS
LIQUID AUTOMATIC DISHWASHER
DETERGENT COMPOSITION
Background of the Invention
' ~iquid automatic dishwasher detergent compositions, both
aqueous and nonaqueous, have recently received much attention,
and the aqueous products have achieved commercial popularity.
The acceptance and popularity of the liquid formulations
as compared to the more con~entional powder products stems
from the convenience and performance of the liquid products.
However, even the best of the currently available liquid
formulations still suffer from two major problems, product
phase instability and bottle residue, and to some extent cup
leakage from the dispenser cup of the automatic dishwashing
machine.
Representative of the relevant patent art in this area,
mention is made of Rek, U.S. Patent 4,556,504; Bush, et al.,
U.S. Patent 4,226,736; Ulrich, U.S. Patent 4,431,559;
Sabatelli, U.S. Patent 4,147,650; Paucot, U.S. Patent
4,079,015; Leikhem, U.S. Patent 4,116,849; Milora, U.S. Patent
4,521,332; Jone~, U.S. Patent 4,597,889; Heile, U.S. Patent
4,512,908; Laitem, U.S. Patent 4,753,748; Sabatelli, U.S.
Patent 3,579,455; Hynam, U.S. Patent 3,684,722: other patents
relatin~ to thickened detergent compositions include U.S.
Patent 3,985,668; U.K. Patent Applications GB 2,116,199A and
GB 240,450A; U.S. Patent 4,511,487; U.S. Patent 4,752,409
(Drapier, et al.); U.S. Patent 4,801,395 (Drapier, et al.);
U.S. Patent 4,801,395 (Drapier, et al.).
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2069845
~rief Descrip~ion of the Drawings
Figures 1-13 are rheograms, plotting elastic modules G'
and viscous modulus G~ as a function of applied strain, for
the compositions of Example 1, Formulations A, C, D, G, J, H,
I and K, Example 2, A and B, Example 3, L and M and
Comparative Example 1, respectively and Figures 14-30 are
rheograms as functions of frequency and applied strain for the
compositions of Example v.
Summary of the Invention
According to the present invention there is provided a
novel aqueous liquid automatic dishwasher detergent
composition. The composition is characterized by its linear
viscoelastic behavior, substantially indefinite stability
again~t phase separation or settling of dissolved or suspended
particles, low levels of bottle residue, relatively high bulk
density, and substantial absence of unbound or free water.
This unique combination of properties i9 achieved by virtue of
the incorporation into the aqueous mixture of dishwashing
detergent surfactant, alkali metal detergent builder salt(s)
and chlorine bleach compound, a small but effective amount of
high molecular weight cross-linked polyacrylic acid type
thickening agent, a physical stabilizing amount of a long
~: : chain fatty acid or salt thereof, and a source of potassium
; ions to provide a potassium/sodium weight ratio in the range
~ 25 of from 1:1 to 45:1, such that substantially all of the
: detergent builder salts and other normally solid detergent
additives present in the composition are present dissolved in
:~ the aqueous phase. The compositions are further characterized
20~4~
by a bulk density of at least 1.32 g/cc, such that the
density of the polymeric phase and the density of the aqueous
(continuous) phase are approximately the same.
~etaiLed Description of the Preferred Embodiments
The compositions of this invention are aqueous liquids
containing various cleansing active ingredients, detergent
adjuvants, structuring and thickening agents and stabilizing
components, although some ingredients may serve more than one
of these functions.
The advantageous characteristics of the compositions of
this invention, including physical stability, low bottle
residue, high cleaning performance, e.g. low spotting and
filming, dirt residue removal, and 90 on, and superior
aesthetics, are believed to be attributed to several
interrelated factors such as low solids, i.e. undissolved
particulate content, product density and linear viscoelastic
rheology. These factors are, in turn, dependent on several
critical compositional components of the formulations, namely,
(1) the inclusion of a thickening effective amount of
polymeric thickening agent having high water absorption
capacity, exemplified by high molecular weight cross-linked
polyacrylic acid, (2) inclusion of a physical stabilizing
amount of a long chain fatty acid or salt thereof, (3)
potassium ion to sodium ion weight ratio K/Na in the range of
from 1:1 to 45:1, especially from 1:1 to 3.1, and (4) a
product bulk density of at least 1.32 g/cc, such that the
bulk density and liquid phase density are the same.
206984~
The polymeric thickening agents contribute to the linear
viscoelastic rheology of the invention composition~. A9 used
herein, ~linear viscoelastic ~or~ linear viscoelasticity~
means that the elastic (storage) moduli (G') and the viscous
i(loss) moduli (G~) are both substantially independent of
strain, at lea~t in an applied strain range of from 0-50%, and
preferably over an applied strain range of from 0-80~. More
specifically, a composition i9 considered to be linear
viscoelastic for purposes of this invention, if over the
strain range of 0-50~ the elastic moduli G~ has a minimum
value of lO0 dynes/sq.cm., preferably at least 250
dynes/sq.cm., and varies less than 500 dynes/sq.cm,
preferably less than 300 dynes/sq.cm., especially preferably
less than 100 dynes/sq.cm. Preferably, the minimum value of
G' and maximum variation of G~ applies over the strain range
of 0 to 80~. Typically, the variation in 1098 moduli G~ will
be less than that of G'. As a further characteristic of the
preferred linear viscoelastic compositions the ratio of G"/G
(tan~ i9 less than 1, preferably less than 0.8, but more than
0.05, preferably more than 0.2, at least over the strain range
of 0 to 50~, and preferably over the strain range of 0 to 80~.
It should be noted in this regard that ~ strain is ~hear
strain xlO0.
3y way of further explanation, the elastic (storage~
modulus G' is a measure of the energy stored and retrieved
when a strain is applied to the composition while viscous
(1099) modulus G~ is a measure to the amount of energy
20698~
dissipated as heat when strain is applied. Therefore, a value
of tand,
0.05~ tan ~ cl,
preferably
' 0.2 c tan Sc 0.8
means that the compositions will retain sufficient energy when
a stress or strain i9 applied, at least over the extent
expected to be encountered for products of this type, for
example, when poured from or shaken in the bottle, or stored
in the dishwasher detergent dispenser cup of an automatic
dishwashing machine, to return to its previous condition when
the stress or strain is removed. The compositions with tan
values in these ranges, therefore, will also have a high
cohesive property, namely, when a shear or strain is applied
to a portion of the composition to cause it to flow, the
surrounding portions will follow. As a result of this
cohesiveness of the subject linear viscoelastic compositions,
the compositions will readily flow uniformly and homogeneously
from a bottle when the bottle i9 tilted, thereby contributing
to the physical (phase) stability of the formulation and the
low bottle residue (low product 109g in the bottle) which
characterizes the invention compositions. The linear
viscoelastic property also contributes to improved physical
stability against phase separation of any undissolved
suspended particles by providing a resistance to movement of
the particles due to the strain exerted by a particle on the
surrounding fluid medium.
2~6984~
The present invention also relates to polymeric
compositions which are thickened aqueous polymeric solutions
formed from water and 0.1 to 20 weight ~, more preferably
0.5 to 14 weight percent of a polymeric complex which
icomprises an alkali metal neutralized anionic polymer having a
molecular weight of 60,000 to 10,000,000 complexed at a pH of
7-10 with a structuring agent such as an amphoteric metal
oxide compound having a particle size of 0.5 to 40 microns,
which improves the formation of the polymeic matrix of the
anionic polymer, wherein a weight ratio of the alkali metal
neutralized anionic polymer to the amphoteric metal oxide
compound is 10:1 to 1:10 and the aqueous thickened polymeric
solution has a pH of 7 to 10 and a complex viscosity at 10
radians/seconds at room temperature as applied for 30 seconds
lS of 2 to 800 dynes seconds/sq.cm
The aqueous thickened polymeric solution has a G/ of at
least 80 dyne~/sq.cm. at 10 radians/second, a G of at least
10 dynes/sq.cm., a ratio of ~/G/ of less than 1 and Gl i9
substantially linear over a range of frequency of 0.1 to 50
radians/second and a Brookfield viscosity at RT at 20 rpms
with a #6 spindle of 700 to aoubt 27,000`cps. When the
aqueous thickened polymeric solution has a minimum yield
stress at least 2, dynes/sq.cm., more preferably 2 to 1200
;~ dynes/sq.cm., it is capable of suspending solid particles ~uch
~25 as alkali metal ~ilicates and alkali metal detergent builder
salts such that they will not settle out of solution.
.
~ 6
20698~
The solid particles to be suspended are not limited to alkali
metal compounds, but can be any metal containing compound,
organic compound, polymeric compound or even glass beads.
The structuring agents such as the amphoteric materials
bf the instant invention are preferably aluminum oxides having
a powdered particle size of 10-20 microns, a particle size
dispersed in water of 10 to 60 nanometers, a powdered
surface area of 1~0-250 m2/g, and a crystalline size of less
than 60 micron~. An especially preferred aluminum oxide is
Dispal T23 sold by ~ista Chemicals. Also suitable structuring
agents are mixtures of aluminum oxide~ and magne~ium oxides,
zeolites, synthetic clays 3uch as laponite, calcium rich clays
such as Promat. Natural clays such as Bentonite, Hectorite
and Attapolgite and polymeric aluminum ~alts sold by Reheis
are al~o useful as a structuring agent.
It is an object of the instant invention to provide
thicken aqueous polymeric solutions which exhibit both
increased viscosity and an improved degree of shear
insensitivity, wherein these polymeric solution~ maintain
their improved viscosity and shear insensitively properties,
when various ingredients are added to the thickened aqueous
polymeric solutions to form a variety of diversified products.
A means for further improving the structuring of the gel
formulations of the instant invention in order to obtain
improved viscosity as well as G/ and G values is to form an
; aqueous polymeric solution of a crosslinked anionic polymer
; such as a crosslinked polyacrylic acid thickening agent at
room temperature with mixing and subsequently with mixing
20698~5
eutrai~zing the anionic groups ~uch as the carboxylic acid
groups by the addition of an excess basic material such as
caustic soda to form an alkali metal neutralized crosslinked
polyacrylic acid polymer. To the aqueous solution of the
~lkali metal neutralized crosslinked polyacrylic acid
containing excess caustic soda is added with mixing an
amphoteric compound. The alkali metal crosslinked neutralized
polyacrylic acid pol~mer in combination with the amphoteric
compound provides improved G/ and G values as well as
improved viscosification of the aqueous polymeric solution
having a pH of 7 to 10 as compared to the use of the alkali
metal neutralized crosslinked polyacrylic acid alone as a
viscosification agent. It is theorized that the improvement
in viscosification results from the association of the
amphoteric material and the alkali metal neutralized
crosslinked polyacrylic acid polymer in the water, wherein the
negative charges of the amphoteric compound and the negatively
charged anionic groups of the polyacrylic acid are repulsive
to each other thereby causing an uncoiling of the polymeric
chain of the alkali metal neutralized crosslinked polyacrylic
acid which provides a further building of the polymeric
structure within the water. To the solution of the alkali
metal neutralized crosslinked polyacrylic acid polymer, water
and amphoteric compound detergent builder sa}ts, silicates,
surfacants, foam depressants and bleachants can be added
without signi icantly damaging the polymeric structure to form
a gel like automatic dishwashing composition. Other
commercial and industrial compositions can be formed for a
2~984~
,ariety of applications such as toothpastes, creams or a
toothpaste gels, cosmetics, fabric cleaners, shampoos, floor
cleaners, cleaning paste, tile cleaners, thickened bleach
compositions, ointments, oven cleaners, pharmaceutical
suspensions, concentrated coal slurries, oil drilling muds,
cleaning prestoppers and aqueous based paints. These
compositions can be formulated by adding the appropriate
chemicals to the aqueous polymeric solution of alkali metal
neutralized polyacrylic acid polymer, caustic soda and the
amphoteric compound to form the desired composition. The
polymeric aqueous solution of water, caustic soda, alkali
metal neutralized polyacrylic acid polymer and the amphoteric
compound has a complex viscosity at room temperature at 10
radians/second of 2 to 800 dynes second/sq.cm., more
15 preferably 3 to 600 dynes second/sq. cmThe polymeric
solution comprises .05 to 4.0 weight %, more preferably 0.1
to 4.0 weight ~ of an amphoteric compound, 0.1 to 4.0 weight
~, more preferably 0.2 to 3.0 weight ~ of an alkali metal
neutralized crosslinked anionic polymer such as a metal
neutralized crosslinked polyacrylic polymer and water, wherein
the aqueous polymeric solution has a G/ value of at least 80
dynes/sq. cm at a frequency of 10 radians/second, a G value of
at least 10 dynes/3q. cm at a frequency of 10 radians/second,
a ratio of G /GI i9 less than 1 and G/ is substantial constant
over a frequency range of 0.01 to 50.0 radians/second.
If the polymeric solution has a G' value of at least 80
dynes/sq. cm. at a frequency of 10 radians/second and the G
valve is at least 10 dynes/sq. cm at a frequency of 10
2~
adians/second, wherein G' is substantially constant over a
frequency range of 0.01 to 50 radians/second and a ratio of
G/GI is less than 1 and a yield stress of at least 2
dynes/sq.cm., more preferably 2 to 1200 dynes/sq. cm., the
~olymeric solution will be a gel which can function as a
suspension medium for a plurality of solid particles,
immiscible liquid droplets or gaseous bubbles. The solid
particles or liquid droplets or gaseous bubbles can be
inorganic, organic or polymeric. The solid material liquid
droplets or gas bubbles which are not soluble in the water
phase, should not decompose in an aqueous solution or react
with the anionic groups of the anionic polymer or the
carboxylate groups. The concentration of the solid particles,
liquid droplets or gaseous bubbles in the suspension medium is
0.1 to 70 weight percent, more preferably 1 to 50 weight ~.
Additionally, by the way of explanation, it is necessary
to clearly emphasize that in order to minimize the rate and
amount of sedimentation of solid particles that are insoluble
in the suspension medium that the suspension medium should
exhibit frequency independent moduli. For materials that
exhibit frequency independence of the viscoelastic moduli (G'),
these materials tend to exhibit a critical property known as
the yield stress which prevents the sedimentation of insoluble
particles from the suspension medium. It is also critical in
the understanding of the data a~ presented in Example V of
this invention that by linear viscoelastic gel it is meant
that G/ is substantially constant over a strain range frequency
of 0 to 50 percent. The minimum yield stress for the gel
2069845
.lecessary to suspend each of the solids, liquid or gaseous
particles in the ~el such that each particles will not settle
from the gel is at least 2 dynes/sq. cm., more preperably 2
to 1200 dynes/sq.cm.
' Illustrative of alkali metal neutralized anionic polymers
contemplated within the scope of the instant invention beside
polyacrylic and polymers such as the Carbopols are: sulfonated
polymers containing a sulfonate functionality as defined in
U.S. Patent Nos. 3,642,728; 4,608,425; 4,619,773; 4,626,285;
4,637,882; 4,640,945; 4,647,603; 4,710,555; 5,730,028;
4,963,032; 4,970,260 and 4,975,482, wherein these
aforementioned patents are all hereby incorporated by `
reference. as well as polymers and monomers containing a
carboxylic acid functionally as defined in U.S. Patent Nos.
lS 4,612,332; 4,673,716; 4,694,046; 4,694,058; 4,709,759;
4,734,205, 4,780,517; 4,960,821 and 5,036,136, as well as
copolymers containing a maleic anhydride functionality such as
Gantrez provided that these is a sufficient association
between the alkali metal neutralized salts of these polymers
in the aforementioned patents and the Aluminum oxide to
create a viscoelastic gel having the G/ and properties as
defined herein.
The thickened aqueous polymeric solutions are made by
neutralizing at room temperature with mixi~g an aqueous
solutLon of the Carbopol resin with caustic soda such that to
the resultant aqueous solution of the alkali metal neutralized
Carbopol is added at room temperature with mixing an aqueous
dispersion of aluminum oxide to form the thickened aqueous
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206984~
~olymeric solution. A further enhancement of thickening can
be achieved by the further addition of 0.02 to 1.0 weight
percent of a fatty acid or a metal salt of a fatty acid.
Also contributing to the physical stability and low
~ottle residue of the invention compositions is the high
potassium to sodium ion ratios in the range of 1:1 to 45:1,
preferably 1:1 to 4:1, especially preferably from 1.05:1 to
3:1, for example 1.1:1, 1.2:1, 1.5:1, 2:1, or 2.5:1. At these
ratios the solubility of the solid salt components, such as
detergent builder salts, bleach, alkali metal silicates, and
the like, is substantially increased since the presence of the
potassium (K+) ions requires less water of hydration than the
sodium (Na+) ions, such that more water is available to
dissolve these salt compounds. Therefore, all or nearly all
of the normally solid components are present dissolved in the
aqueous phase. Since there is none or only a very low
percentage, i.e. less than 5~, preferably less than 3~ by
weight, of suspended solids present in the formulation there
i9 no or only reduced tendency for undissolved particles to
settle out of the compositions causing, for example, formation
of hard masses of particles, which could result in high bottle
residues (i.e. 1099 of product). Furthermore, any undissolved
solids tend to be present in extremely small particle sizes,
usually colloidal or sub-colloidal, such as 1 micron or less,
thereby further reducing the tendency for the undissolved
particles to settle.
A still further attribute of the invention compositions
contributing to the overall product stability and low bottle
12
2~69845
residue is the high water absorption capacity of the cross- -
linked polyacrylic acid type thickening agent. As a result of
this high water absorption capacity virtually all of the
aqueous vehicle component is held tightly bound to the polymer
~atrix. Therefore, there is no or substantially no free water
present in the invention compositions. This absence of free
water (as well as the cohesiveness of the composition) is
manifested by the observation that when the composition is
poured from a bottle onto a piece of water absorbent filter
paper virtually no water is absorbed onto the filter paper
and, furthermore, the mass of the linear viscoelastic material
poured onto the filter paper will retain its shape and
structure until it i9 again subjected to a stress or strain.
As a result of the absence of unbound or free water, there is
virtually no phase separatin between the aqueous phase and the
polymeric matrix or dissolved solid particles. This
characteristic is ~anifested by the fact that when the subject
compositions are subjected to centrifugation, e.g. at 1000 rpm
for 30 minutes, there is no phase separation and the
composition remains homogeneous.
However, it has also been discovered that linear
viscoelasticity and K/Na ratios in the above-mentioned range
do not, by themselves, assure long term physical stability (as
determinèd by phase separation). In order to maximize
;25 physical (phase) stability, the density of the composition
should be controlled such that the bulk density of the liquid
phage i9 approximately the same as the bulk density of the
entire composition, including the polymeric thickening agent.
206984~
lhis control and equalization of the densities is achieved,
according to the invention, by providing the composition with
a bulk density of at least 1.28 g/cc, preferably at least 1.35
g/cc, up to 1.42 g/cc, preferably up to 1.40 g/cc.
~urthermore, to achieve these relatively high bulk densities,
it is important to minimize the amount of air incorporated
into the composition (a density of 1.42 g/cc is essentially
equivalent to zero air content).
It has previously been found in connection with other
types of thickened aqueous liquid, automatic dishwasher
detergent compositions that incorporation of finely divided
air bubbles in amounts up to 8 to 10% by volume can function
effectively to stabilize the composition against phase
separation, but that to prevent agglomeration of or escape of
the air bubbles it was important to incorporate certain
surface active ingredients, ecpecially higher fatty acids and
the salts thereof, 9uch as stearic acid, behenic acid,
palmitic acid, sodium stearate, aluminum stearate, and the
like. These surface active agent~ apparently functioned by
forming an interfacial film at the bubble surface while also
forming hydrogen bonds or contributing to the electrostatic
attraction with the suspended particles, such that the air
bubbles and attracted particles formed agglomerates of
approximately the same density as the density of the
continuous liquid phase.
Therefore, in a preferred embodiment of the present
invention, stabilization of air bubbles which may become
incorporated into the compositions during normal processing,
: ' ''
2Q6~845
such as during various mixing steps, is avoided by post-adding
the surface active ingredients, including fatty acid or fatty
acid salt stabilizer, to the remainder of the composition,
under low shear conditions using mixing devices designed to
~inimize cavitation and vortex formation.
As will be described in greater detail below the surface
active ingredients present in the composition will include the
main detergent ~urface active cleaning agent, and will also
preferably include anti-foaming agent and higher fatty acid or
salt thereof as a physical stabilizer.
Exemplary of the cross-linked polyacrylic acid-type
thickening agents are the products sold by ~.F. Goodrich under
their Carbopol trademark, especially Carbopol 941, which is
the most ion-insensitive of this class of polymers, and
lS Carbopol 940 and Carbopol 934. The Carbopol resins, also
known as "Carbomer", are hydrophilic high molecular weight,
cros~-linked acrylic acid polymers having an average
equivalent weight of 76, and the general structure illustrated
by the following formula:
H H
H l ~
~25 HO O n.
Carbopol 941 has a molecular weight of 1,250,000; Carbopol
940 a molecular weight of approximately 4,000,000 and Carbopol
934 a molecular weight of approximately 3,000,000. The
Carbopol resins are cross-linked with polyalkenyl polyether,
e.g. 1~ of a polyallyl ether of sucrose having an average of
,
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206~8~
5.8 allyl groups for each molecule of sucrose. Further
detailed information on the Carbopol resins is available from
.F. Goodrich, see, for example, the B.F. Goodrich catalog GC-
67, Carbopol~ Water Soluble Resins.
' ~ile most favorable results have been achieved with
Carbopol 941 polyacrylic resin, other lightly cross-linked
polyacrylic acid-type thickening agents can also be used in
the compositions of this invention. As used herein
"polyacrylic acid-type" refers to water-soluble homopolymers
of acrylic acid or methacrylic acid or water-dispersible or
water-soluble salts, esters or amides thereof, or water-
soluble copolymers of these acids of their salts, esters or
ameides with each other or with one or more other etylenically
unsaturated monomers, such as, for example, styrene, maleic
acid, maleic anhydride, 2-hydroxyethylacrylate, acrylonitrile,
vinyl acetate, ethylene, propylene, and the like.
The homopolymers or copolymers are characterized by their
high molecular weight, in the range of from 500,000 to
10,000,000, preferably 500,000 to 5,000,000, especially from
1,000,000 to 4,000,000, and by their water solubility,
generally at least to an extent of up to 5~ by weight, or
more, in water at 25C.
These thickening agents are used in their lightly cross-
linked form wherein the cross-linking may be accomplished by
means known in the polymer arts, as by irradiation, or,
preferably, by the incorporation into the monomer mixture to
be polymerized of known chemical cross-linking monomeric
agents, typically polyunsaturated (e.g. diethylenically
16
2069~4~
unsaturated) monomers, such as, for example, divinylbenzene,
divinylether of diethylene glycol, N, N~-methylene-
bisacrylamide, polyalkenylpolyethers (such as described
above), and the like. Typically, amounts of cross-linking
agent to be incorporated in the final polymer may range from
0.01 to 1.5 percent, preferably from 0.05 to 1.2 percent,
and especially, preferably from 0.1 to 0.9 percent, by
weight of cros~-linking agent to weight of total polymer.
Generally, those skilled in the art will recognize that the
degree of cross-linking should be sufficient to impart some
coiling of the otherwise generally linear polymeric compound
while maintaining the cross-linked polymer at least water
dispersible and highly water-swellable in an ionic aqueous
medium. It i9 also understood that the water-swelling of the
polymer which provides the desired thickening and viscous
properties generally depends on one or two mechanisms, namely,
conversion of the acid group containing polymers to the
corresponding salts, e.g. sodium, generating negative charges
along the polymer backbone, thereby causing the coiled
molecules to expand and thicken the aqueous solution; or by
formation of hydrogen bonds, for example, between the carboxyl
groups of the polymer and hydroxyl donor. The former
~` mechanism is especially important in the present invention,
and therefore, the preferred polyacrylic acid-type thickening
~25 agents will`contain free carboxylic acid (COOH) groups along
the polymer backbone. Also, it will be understood that the
degree of cross-linking should not be so high as to render the
cross-linked polymer completely insoluble or non-dispersible
17
. -.. . .. .. .. .
.
2~698~
in water or inhibit or prevent the uncoiling of the polymer
molecules in the presence of the ionic aqueous system.
The amount of the high molecular weight, cross-linked
polyacrylic acid or other high molecular weight, hydrophilic
~ross-linked polyacrylic acid-type thickening agent to impart
the desired rheological property of linear viscoelasticity
will generally be in the range of from 0.1 to 2%, preferably
from 0.2 to 1.4~, by weight, based on the weight of the
composition, although the amount will depend on the particular
cross-linking agent, ionic strength of the composition,
hydroxyl donors and the like.
The compositions of this invention must include
sufficient amount of potassium ions and sodium ions to provide
a weight ratio of K/Na of at least 1:1, preferably from 1:1 to
45:1, especially from 1:1 to 3:1, more preferably from 1.05:1
to 3:1, such as 1.5:1, or 2:1. When the K/Na ratio is less
than 1 there is insufficient solubility of the normally solid
ingredients whereas when the K/Na ratio is more than 45,
especially when it is greater than 3, the product becomes too
liquid and phase separation begins to occur. When the K/Na
ratio is more than 45, especially when it i9 greater than 3,
the product becomes too liquid and phase separation begins to
occur. When the K/Na ratios become much larger than 45, such
as in all or mostly potassium formulation, the polymer
thickener loses its absorption capacity and begins to salt out
of the aqueous phase.
The potassium and sodium ions can be made present in the
compositions as the alkali metal cation of the detergent
2~69~
builder salt(s), or alkali metal silicate or alkali metal
hydroxide components of the compositions. The alkali metal
cation may also be present in the compositions as a component
of an ionic detergent, bleach or other ionizable salt compound
~dditive, e.g. alkali metal carbonate. In determining the
K/Na weight ratios all of these sources should be taken into
consideration.
Specific examples of detergent builder salts include the
polyphosphates, such as alkali metal pyrophosphate, alkali
metal tripolyphosphate, alkali metal metapho~phate, and the
like, for example, sodium or potassium tripolyphosphate
(hydrated or anhydrou~), tetrasodium or tetrapotassium
pyrophosphate, sodium or potassium hexa-metaphosphate,
trisodium or tripotassium orthophosphate and the like, sodium
or potassium carbonate, sodium or potassium citrate, sodium or
potassium nitrilotriacetate, and the like. The phosphate
~uilders, where not precluded due to local regulations, are
preferred and mixtures of tetrapotassium pyrophosphate (TKPP)
and sodium tripolyphosphate (NaTPP) (especially the
hexahydrate) are especially preferred. Typical ratios of
NaTPP to TKPP are from 2:1 to 1:8, especially from 1:1.1 to
1:6. The total amount of detergent builder salts is
preferably from 5 to 35~ by weight, more preferably from 15
to 35~, especially from 18 to 30~ by weight of the
composition.
Other useful low molecular weight noncrosslinked polymers
are Acusol~640D provided by Rohm ~ Haas; Norasol QR1014 from
Norsohaas having a GPC molecular weight of 10,000.
19
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2069~45
The linear viscoelastic compositions of this invention
may, and preferably will, contain a small, but stabilizing
effective amount of a long chain fatty acid or monovalent or
polyvalent salt thereof. Although the manner by which the
fatty acid or salt contributes to the rheology and stability
of the composition has not been fully elucidated it is
hypothesized that it may function as a hydrogen bonding agent
or cross-linking agent for the polymeric thickener.
The preferred long chain fatty acids are the higher
aliphatic fatty acids having from 8 to 22 carbon atoms, more
preferably from 10 to 20 carbon atoms, and especially
preferably from 12 to 18 carbon atoms, and especially
preferably from 12 to 18 carbon atoms, inclusive of the
carbon atom of the carboxyl group of the fatty acid. The
aliphatic radical may be saturated or unsaturated and may be
straight or branched. Straight chain saturated fatty acids
are preferred. Mixtures of fatty acids may be used, such as
those derived from natural sources, such as tallow fatty acid,
coco fatty acid, soya fatty acid, mixtures of these acids,
~20 etc. Stearic acid and mixed fatty acids, e.g. stearic
acid/palmitic acid, are preferred.
When the free acid form of the fatty acid is used
directly it will generally associate with the potassium and
sodium ions in the aqueous phase to form the corresponding
alkali metal fatty acid soap. However, the fatty acid salts
may be directly added to the composition as sodium salt or
potassium salt, or as a polyvalent metal salt, although the
20698~
alkali metal salts of the fatty acids are preferred fatty acid
salts.
The preferred polyvalent metals are the di- and tri-
valent metals of Groups IIA, IIB and IIIB, such as magnesium,
calcium, aluminum and zinc, although other polyvalent metals,
including those of Groups IIIA, IVA, VA, IB, IVB, VB VIB, VIIB
and VIII of the Periodic Table of the Elements can also be
used. Specific examples of such other polyvalent metals
include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc.
Generally, the metals may be present in the divalent to
pentavalent state. Preferably the metal salts are used in
their higher oxidation states. Naturally, for use in
automatic dishwashers, as well as any other applications where
the invention composition will or may come in contact with
articles used for the handling, storage or serving of food
products or which otherwise may come into contact with or be
consumed by people or animals, the metal salt should be
selected by takiny into consideration the toxicity of the
metal. For this purpose, the alkali metal and calcium and
magnesium salts are especially higher preferred as generally
safe food additives.
The amount of the fatty acid or fatty acid salt
stabilizer to achieve the desired enhancement of physical
stability will depend on such factors as the nature of the
fatty acid or its salt, the nature and amount of the
thickening agent, detergent active compound, inorganic salts,
other ingredients, as well as the anticipated storage and
shipping conditions.
21
2~698~
Generally, however, amounts of the fatty acid or fatty
acid salt stabilizing agents in the range of from 0.02 to 2~,
preferably 0.04 to 1~, more preferably from 0.06 to 0.8%,
especially preferably from 0.08 to 0.4~, provide a long term
~tability and absence of phase separation upon standing or
during transport at both low and elevated temperatures as are
required for a commercially acceptable product.
Depending on the amounts, proportions and types of fatty
acid physical stabilizers and polyacrylic acid-type thickening
agents, the addition of the fatty acid or salt not only
increases physical stability but also provides a simultaneous
increase in apparent viscosity. Amounts of fatty acid or salt
to polymeric thickening agent in the range of from 0.08-0.4
weight percent fatty acid salt and from 0.4-1.5 weight
percent polymeric thickening agent are usually sufficient to
provide these simultaneous benefits and, therefore, the use of
these ingredients in these amounts is most preferred.
In order to achieve the desired benefit from the fatty
acid or fatty acid salt stabilizer, without stabilization of
excess incorporated air bubbles and consequent excessive
lowering of the product bulk density, the fatty acid or salt
should be post-added to the formulation, preferably together
with the other surface active ingredients, including detergent
active compound and anti-foaming agent, when present. These
surface active ingredients are preferably added as an emulsion
in water wherein the emulsified oily or fatty materials are
finely and homogeneously dispersed throughout the aqueous
phase. To achieve the desired fine emulsification of the
2069~4~
fatty acld or fatty acid salt and other surface active
ingredients, it i9 usually neces~ary to heat the emulsion (or
preheat the water) to an elevated temperature near the melting
temperature of the fatty acid or its salt. For example, for
~tearic acid having a melting point of 68C-69C, a temperature
in the range of between 50C and 70C will be used. For lauric
acid (m.p.=47C) an elevated temperature of 35C to 50C can be
used. Apparently, at these elevated temperatures the fatty
acid or salt and other surface active ingredients can be more
readily and uniformly dispersed (emulsified) in the form of
fine dropléts throughout the composition.
In contrast, as will be shown in the examples which
follow, if the fatty acid i9 simply post-added at ambient
temperature, the composition is not linear viscoelastic as
defined above and the stability of the composition i8 clearly
inferior.
Foam inhibition is important to increase dishwasher
machine efficiency and minimize destabilizing effects which
might occur due to the presence of excess foam within the
washer during use. Foam may be reduce by suitable selection
of the type and/or amount of detergent active material, the
main foam-producing component. The degree of foam is also
somewhat dependent on the hardness of the wash water in the
machine whereby suitable adjustment of the proportions of the
builder salts such as NaTPP which has a water softening
effect, may aid in providing a degree of foam inhibition.
However, it is generally preferred to include a chlorine
23
'
.
~ " .
2Q698~5
bleach stable foam depressant or inhibitor. Particularly
effective are the alkyl phosphoric acid esters of the formula
S ~0 I~R
and especially the alkyl acid phosphate e~ters of the formula
ll
HO-P-OR
OR
In the above formulas, one or both R groups in each type of
ester may represent independently a C12-C20 alkyl or ethoxylated
alkyl group. The ethoxylated derivatives of each type of
ester, for example, the condensation products of one mole of
ester with from 1 to 10 moles, preferably 2 to 6 moles, more
preferably 3 or 4 moles, ethylene oxide can also be used.
Some examples of the foregoing are commercially available,
~uch as the products SAP from Hooker and LPKN-158 from
Knapsack. Mixtures of the two types, or any other chlorine
bleach stable types, or mixtures of mono- and di-esters of the
~ame type, may be employed. Especially preferred is a mixture
of mono- and di-CI6-Cl8 alkyl acid phosphate esters such as
monostearyl/distearyl acid phosphates 1.2/1, and the 3 to 4
~30 mole ethylene oxide condensates thereof. When employed,
proportions of 0.05 to 1.5 weight percent, preferably 0.1 to
0.5 weight percent, of foam depressant in the composition is
typical, the weight ratio of detergent active component (d) to
foam depressant (e) generally ranging from 10:1 to 1:1 and
~35 preferably 5:1 to 1:1. Other defoamers which may be u~ed
24
..
" `'~ ' ~
20~9845
include, for example, the known silicones, such as available
from Dow Chemicals. In addition, it i9 an advantageoùs
feature of this invention that many of the stabilizing salts,
such as the stearate salts, for example, aluminum stearate,
~hen included, are also effective as foam killers.
Although any chlorine bleach compound may be employed in
the compositions of this invention, such as dichloro-
isocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP,
alkali metal or alkaline earth metal, e.g. potassium, lithium,
magnesium and especially sodium, hypochlorite is preferred.
The composition should contain sufficient amount of chlorine
bleach compound to provide 0.2 to 4.0~ by weight of available
chlorine, as detenmined, for example by acidification of 100
parts of the composition with excess hydrochloric acid. A
solution containing 0.2 to 4.0% by weight of sodium
hypochlorite contains or provides roughly the same percentage
of available chlorine. 0.8 to 1.6~ by weight of available
chlorine is especially preferred. For example, sodium
hypochlorite (NaOCL) solution of from 11 to 13~ available
chlorine in amounts of 3 to 20~, preferably 7 to 12~, can be
advantageously used.
Detergent active material useful herein should be stable
in the presence of chlorine bleach, especially hypochlorite
bleach, and for this purpose those of the organic anionic,
amine oxide, phosphine oxide, sulphoxide or betaine water
dispersible surfactant types are preferred, the first
mentioned anionics being most preferred. Particularly
preferred surfactants herein are the linear or branched alkali
206984~
metal mono- and/or di-(C8-C,4) alkyl diphenyl oxide mono- and/or
di-sulphates, commercially available for example as DOWFAX
(regi~tered trademark) 3B-2 and DOWFAX 2A-1. In addition, the
surfactant should be compatible with the other ingredients of
the composition. Other suitable organic anionic, non-soap
surfactants include the primary alkylsulphates,
alkylsulphonates, alkylarylsulphonates and sec.-
alkylsulphates. Examples include sodium ClO-C~8 alkylsulphates
such as sodium dodecylsulphate and sodium tallow
alcoholsulphate; sodium C~O-Cl8 alkanesulphonates such as sodium
hexadecyl-1-sulphonate and sodium Cl2-C~8
alkylbenzenesulphonates such as sodium
dodecylbenzenesylphonates. The corresponding potassium salts
may also be employed.
As other suitable surfactants or detergents, the amine
oxide surfactants are typically of the structure R2RINO, in
which each R represents a lower alkyl group, for instance,
methyl, and Rl represents a long chain alkyl group ha~ing from
8 to 2a carbon atoms, for instance a lauryl, myristyl,
palmityl or cetyl group. Instead of an amine oxide, a
corresponding surfactant phosphine oxide R2RIPO or sulphoxide
RRISO can be employed. Betaine surfactants are typically of
the structure R2RIN+R~COO-, in which each R represents a lower
alkylene group having from 1 to 5 carbon atoms. Specific
~25 examples of these surfactants include lauryl-dimethylamine
oxide, myristyl-dimethylamine oxide, myristyl-dimethylamine
oxide, the corresponding phosphine oxides and sulphoxides, and
the corresponding betaines, including dodecyldimethylammonium
20698~5
acetate, tetradecyldiethylammonium pentanoate,
hexadecyldimethylammonium hexanoate and the like. For
biodegradability, the alkyl groups in these surfactants should
be linear, and such compounds are preferred.
i Surfactants of the foregoing type, all well known in the
art, are described, for example, in U.S. Patents 3,985,668 and
4,271,030. If chlorine bleach is not used than any of the
well known low-foaming nonionic surfactants such as
alkoxylated fatty alcohols, e.g. mixed ethylene oxide-
propylene oxide condensates of C8-C22 fatty alcohols can also be
used.
The chlorine bleach stable, wa~er dispersible organic
detergent-active material (surfactant) will normally be
present in the composition in minor amounts, generally 1% by
weight of the composition in minor amounts, generally 1% by
weight of the composition, although smaller or larger amounts,
such as up to 5~, such as from 0.1 to 5~, preferably form 0.3
or 0.4 to 2~ by weight of the composition~ may be used.
Alkali metal (e.g. potas~ium or sodium) silicate, which
provide~ alkalinity and protection of hard surfaces, such as
flne china glaze and pattern, i9 generally employed in an
amount ranging from 5 to 20 weight percent, preferably 5 to
15 weight percent, more preferably 8 to 12~ in the
composition. The sodium or potassium silicate is generally
25~ added in the form of an aqueous solution, preferably having
Na2O:SiO2 or K2O:SiO2 ratio of I:1.3 to 1:2.8, especially
preferably 1:2.0 to 1:2.6. At this point, it should be
mentioned that many of the other components of this
27
.
..
,
206984~
composition, e~pecially alkali metal hydroxide and bleach, are
also often added in the form of a preliminary prepared aqueous
dispersion or solution.
In addition to the detergent active surfactant, foam
lnhibitor, alkali metal silicate corrosion inhibitor, and
detergent builder salts, which all contribute to the cleaning
performance, it is also known that the effectiveness of the
liquid automatic dishwasher detergent compositions is related
to the alkalinity, and particularly to moderate to high
alkalinity levels. Accordingly, the compositions of this
invention will have pH value~ of at least 9.5, preferably at
least 11 to as high as 14, generally up to 13 or more, and,
when added to the aqueous wash bath at a typical concentration
level of 10 grams per liter, will provide a pH in the wash
bath of at least 9, preferably at least 10, such as 10.5,
11, 11.5 or 12 or more.
The alkalinity will be achieved, in part by the alkali
metal ions contributed by the alkali metal detergent builder
salts, e.g. sodium tripolyphosphate, tetrapotassium
pyrophosphate, and alkali metal silicate, however, it is
usually necessary to include alkali metal hydroxide, e.g. NaOH
or KOH, to achieve the desired high alkalinity. Amounts of
alkali metal hydroxide in the range of (on an active basis) of
from 0.5 to 8%, preferably from 1 to 6%, more preferably from
1.2 to 4~, by weight of the composition will be sufficient to
achieve the desired pH level and/or to adjust the K/Na weight
ratio.
28
20698g5
Other alkali metal salts, such as alkali metal carbonate
may also be present in the compositions in minor amounts, for
example from O to 4~, preferably O to 2~, by weight of the
composition.
' Other conventional ingredients may be included in these
compositions in small amounts, generally le~s than 3 weight
percent, nuch as perfume, hydrotropic agents such as the
sodium benzene, toluene, xylene and cumene sulphonates,
preservatives, dyestuffs and pigments and the like, all of
course being stable to chlorine bleach compound and high
alkalinity. Especially preferred for coloring are the
chlorinated phythalocyanines and polysuphides of
aluminosilicate which provide, respectively, pleasing green
and blue tints. TiO2 may be employed for whitening or
neutralizing off-shades.
Although for the reasons previously discussed excessive
air bubbles are not often desirable in the invention
compositions, depending on the amounts of dissolved solids and
liquid phase densities, incorporation of small amounts of
finely divided air bubbles, generally up to 10~ by volume,
preferably up to 4~ by volume, more preferably up to 2~ by
volume, can be incorporated to adjust the bulk density to
approximate liquid phase density. The incorporated air
bubbles should be finely divided, such as up to 100 microns
~25 in diameter, preferably from 20 to 40 microns in diameter,
to assure maximum stability. Although air is the preferred
gaseous medium for adjusting densities to improve physical
;', '
206984~
stability of the composition other inert gases can also be
used, such as nitrogen, carbon dioxide, helium, oxygen, etc.
The amount of water contained in these compositions
should, of course, be neither so high as to produce unduly low
~isco~3ity and fluidity, nor so low as to produce unduly high
viscosity and low flowability, linear viscoelastic properties
in either case being diminished or destroyed by increasing tan
1. Such amount i~ readily determined by routine
experimentation in any particular instance, generally ranging
from 30 to 75 weight percent, preferably 35 to 65 weight
percent. The water should also be preferably deionized or
softened.
The manner of formulating the invention compositions is
also important. As discussed above, the order of mixing the
}5 ingredients as well as the manner in which the the mixing is
performed will generally have a significant effect on the
properties of the composition, and in particular on product
density (by incorporation and stabilization of more or less
air) and physical stability (e.g. phase separation). Thus,
according to the preferred practice of this invention the
compositions are prepared by first forming a dispersion of the
polyacrylic acid-type thickener in water under moderate to
high shear conditions, neutralizing the dissolved polymer to
cause gelation, and then introducing, while continuing mixing,
~25 the detergent builder salts, alkali metal dilicates, chlorine
bleach compound and remaining detergent additives, including
any previously unused alkali metal hydroxide, if any, other
than the surface-active compounds. All of the additional
2069845
ingredients can be added simultaneously or sequentially.
Preferably, the ingredients are added sequentially, although
it is not necessary to complete the addition of one ingredient
before beginning to add the next ingredient. Furthermore, one
~r more of these ingredients can be divided into portions and
added at different times. These mixing steps should also be
performed under moderate to high shear rates to achieve
complete and uniform mixing. These mixing steps may ~e
carried out at room temperature, although the polymer
thickener neutralization (gelation) is usually exothermic.
The composition may be allowed to age, if necessary, to cause
dissolved or dispersed air to dissipate out of the
composition.
The remaining surface active ingredients, including the
anti-foaming agent, organic detergent compound, and fatty acid
or fatty acid salt stabilizer is post-added to the previously
formed mixture in the form of an aqueous emulsion (using from
1 to 10~, preferably from 2 to 4~ of the total water added to
the composition other than water added as carrier for other
ingredients or water of hydration) which is pre-heated to a
temperature in the range of from Tm+5 to Tm-20, preferably
from Tm to TM-10, where Tm is the melting point temperature
of the fatty acid or fatty acid salt. For the preferred
stearic acid stabilizer the heating temperature is in the
range of 50C to 70C. However, if care is taken to avoid
excessive air bubble incorporation during the gelatin step or
during the mixing of the detergent builder salts and other
additives, for example, by operating under vacuum, or using
206984~i
low shearing conditions, or special mixing operatatus, etc.,
the order of addition of the surface active ingredients should
be less important.
In accordance with an especially preferred emkodiment,
the thickened linear viscoelastic aqueous automatic dishwasher
detergent composition of this invention includes, on a weight
basis:
(a) 10 to 35~, preferably 15 to 30~, alkali metal
polyphosphate detergent builder;
(b) 5 to 15, preferably 8 to 12%, alkali metal silicate;
(c) 1 to 6~, preferably 1.2 to 4~, alkali metal
hydroxide;
(d) 0.1 to 3%, preferably 0.5 to 2~, chlorine bleach
stable, water-dispersible, low-foaming organic detergent
active material, preferably non-soap anionic detergent;
(e) 0.05 to 1.5~, preferably 0.1 to 0.5~, chlorine
bleach stable foam depressant;
(f) chlorine bleach compound in an amount to provide
0.2 to 4~, preferably 0.8 to 1.6%, of available chlorine;
(g) high molecular weight hydrophilic cross-linked
polyacrylic acid thickening agent in an amount to provide a
linear viscoelasticity to the formulation, preferably from
0.4 to 1.5%, more preferably from 0.4 to 1.0%;
(h) a long chain fatty acid or a metal salt of a long
chain fatty acid in an amount effective to increase the
: physical stability of the compositions, preferably from 0.08
to 0.4%, more preferably from 0.1 to 0.3%; and
20698~
(i) balance water, preferably from 30 to 75%, more
preferably from 35 to 65~; and wherein in (a) the alkali
metal polyphosphate includes a mixture of from 5 to 30~,
preferably from 12 to 22~ of tetrapotassium pyrophosphate,
and from 0 to 20~, preferably from 3 to 18~ of sodium
tripolyphosphate, and wherein in the entire composition the
ratio, by weight, of potassium ions to sodium ions is from
1.05/1 to 3/1, preferably from 1.1/1 to 2.5/1, the
compositions having an amount of air incorporated therein such
that the bulk density of the composition is from 1.32 to 1.42
g/cc, preferably from 1.35 to 1.40 g/cc.
The compositions will be supplied to the consumer in
suitable dispenser containers preferably formed of molded
plastic, especially polyolefin plastic, and most preferably
polyethylene, for which the invention compositions appear to
have particularly favorable slip characteristics. In addition
to their linear viscoelastic character, the compositions of
this invention may also be characterized as pseudoplastic gels
(non-thixotropic) which are typically near the borderline
between liquid and solid viscoelastic gel, depending, for
example, on the amount of the polymeric thickener. The
invention compositions can be readily poured from their
containers without any shaking or squeezing, although
squeezable containers are often convenient and accepted by the
consumer for gel-like products.
The liquid aqueous linear viscoelastic automatic
dishwasher compositions of this invention are readily employed
in known manner for washing dishes, other kitchen utensils and
20698~5
the like in an automatic dishwasher, provided with a suitable
detergent dispenser, in an aqueous wash bath containing an
effective amount of the composition, generally sufficient to
fill or partially fill the automatic dispenser cup of the
~articular machine being used.
The invention also provides a method for cleaning
dishware in an automatic dishwashing machine with an aqueous
wash bath containing an effective amount of the liquid linear
viscoelastic automatic dishwasher detergent composition as
described above. The composition can be readily poured from
the polyethylene container with little or no squeezing or
shaking into the dispensing cup of the automatic dishwashing
machine and will be sufficiently viscous and cohesive to
remain securely within the dispensing cup until shear forces
are again applied thereto, such as by the water spray from the
dishwashing machine.
The invention may be put into practice in various ways
and a number of specific embodiments will be described to
illustrate the invention with reference to the accompanying
ex&~ples.
All the amounts and proportions referred to herein are by
weight of the composition unless otherwise indicated.
Example 1
The following formulations A-K were prepared as described
below:
~ .
34
2069~5
1 ~ ~
~ In ~ ~ U~ l ~ ~1 ~ . l a~
1~ m N _ N . N , ~ ~1 O ~` N , ~
_ _ _ _ _
. O
;¦ l d~ l l N m .
~; , . , Ul rf) ~1 , . . N
H m ,N , ~,, N ,~) ~1 ~1 r r~ ,
_ _ _ _ _ _ _
. o
1:l O~ l ~r l l N ~_1 Il) . l
~; . l . ~ l l q~ . . . ~ l 1-')
~: m O _ (~, N _ ~ ~1 O t` A _
. ~d' , , , N -1 Lt~ O
v m ON , N , N , ~ ~1 O ~` N
_ _ __ _ ___
. O U~
~! l In l O Il~ ~` l l ~ ~ N l ~
~ m l ~ l N ~` ~1 l l rt l a~ A l ~1
_ _ _ __ _ _ _ 11
. O U~
~3 IJ~~ O 11~C` , l , ~1 N, 0~
~4~ ~~_ N ~ ~1 _ ~1 _ V _ ~1
O 1~1~1 l N ~1 ~ Nl a~
ON_ N N ~ ~1 O V _ ~i
. ~~ l l N ~1 Il) O
,,l In N .1 l . . . N
ua _ O N _ '1 N ') ~ O V _ ~1
. ~ er l l N ,_1 Il~ O ~`
. . l Irl ~) ~1 l . . N .
m a~ O N l ~ ~ N l ~ ~1 O ~` V O rl
. (~ ~ l l N ~1 15~ O
~: m O _ _ _ ,, N _ _ _ O r V _ _
1 ~
20698~5
1~ ~r~ ~
O O .
. r~ . . ~ 0
~ ~ ~ O O
H l i4 O O .C~
~ o o ~ a O
l ~ O O L~ X ~
--_~1 A A O IJ
~ ~1 .~ o o o~
_ - ~ V
l o o
l ~1 ~1 '~ ~I tJ) ~1
1~ _ A A ,_~ $ 0,~ a)
_ ri _ A A ~1 t/l ~
_ b- o o v~
. .,1 . . ~ ~1 0 ~
~ ~1 ~4 O O ~ U
_ ~ ~av~
~Jl O O ~ V~
U . O O .~ V~
_ av) ~ ~ ~0
o c~ m ~ ,vd v~ N
m ,1 _ O O qO ~
_ rl ~ ~ ~ ~ V
.~ O O ~ rO~ P~ o ~
,~c ~ o o ~ v~ ~ $~ ~
_ _ _ o ~ S~ ~ h
~ O~
~ ~ E~ ~ gtO~O~
O H i~ H U ~ 3 ~ ~Q
~i3 ~ ~o~o~
_ ~ ~ a~ rl~ ...
~I N ~
20698~5
Formulation~ A, B, C, D, E, G, J, and K are prepared by
first forming a uniform dispersion of the Carbopol 941 or 940
thickener in 97~ of the water (balance). The Carbopol is
slowly added to deionized water at room temperature using a
~ixer equipped with a premier blade, with agitation set at a
medium shear rate, as recommended by the manufacturer. The
dispersion is then neutralized by addition, under mixing, of
the caustic soda (50% NaOH or KOH) component to form a
thickened product of gel-like consistency.
To the resulting gelled dispersion the silicate,
tetrapotassium pyrophosphate (TKPP), sodium tripolyphosphate
TP(TPP, Na) and bleach, are added sequentially, in the order
stated, with the mixing continued at medium shear.
Separately, an emulsion of the phosphate anti-foaming
agent (LPKN), stearic acid/palmitic acid mixture and detergent
(Dowfax 3B2) is prepared by adding these ingredients to the
remaining 3% of water (balance) and heating the resulting
mixture to a temperature in the range of 50C to 70C.
This heated emulsion is then added to the previously
prepared gelled dispersion under low shear conditions, such
that a vortex is not formed.
The remaining formulations F, H and I are prepared in
essentially the same manner a~ described above except that the
heated emulsion of ~PKN, stearic acid and Dowfax 382 i9
directly added to the neutralized Carbopol dispersion prior to
the addition of the remaining ingredients. As a result,
formulations F, H and I, have higher levels of incorporated
air and densities below 1.30 g/cc.
20698~
The rheograms for the formulations A, C, D, G and J are
shown in figure~ 1-5, respectively, and rheograms for
formulations H, I and K are shown in figures 6, 7 and 8
respectively.
' These rheograms are obtained with the System 4 Rheometer
from Rheometrics equipped with a Fluid Servo with a 100 grams-
centimeter torque transducer and a 50 millimeter parallel
plate geometry having an 0.8 millimeter gap between plates.
All measurements are made at room temperature (25C+1C) in a
humidity chamber after a 5 minute or 10 minute holding period
of the sample in the gap. The measurements are made by
applying a frequency of 10 radians per second.
All of the composition formulations A, ~, C, D, G and J
according to the preferred embodiment of the invention which
include Carbopol 941 and stearic acid exhibit linear
viscoelasticity as seen from the rheograms of figure 1-5.
Formulation E which includes Carbopol 941 but not ~tearic acid
showed no phase separation at either room temperature or 100F
after 3 weeks, but exhibited 10~ phase separation after 8
weeks at room temperature and after only 6 weeks at 100F.
Formulation K, containing Carbopol 940 in place of
Carbopol 941, as seen from the rheogram in figure 8, exhibits
substantial linearity over the strain range of from 2% to 50~
(G' at 1~ strain-G' at 50~ strain 500 dynes/sq.cm.) although
tan ~ at a strain above 50~.
Example 2
38
.
206g8~
This example demonstrates the importance of the order of
addition of the ~urface active component premix to the
remainder of the composition on product density and stability.
The following formulations are prepared by methods A and
~:
Ingredient
Water, deionized Balance
Carbopol 941 0.5
NaOH (50~) 2.4
Na Silicate (47.5%) 21
TKPP 15
TPP, Na 13
Bleach (1~) 7.5
~PKN O.16
Stearic Acid 0.1
Dowfax 3B2
Method A:
The Carbopol 941 is dispersed, under medium shear rate,
using a premier blade mixer, in deionized water at ambient
temperature. The NaOH is added, under mixing, to neutralize
and gel the Carbopol 941 dispersion. To the thickened mixture
the following ingredients are added sequentially while the
stir~ing is continued: sodium silicate, TKPP, TPP, and
bleach.
Separately, an emulsion is prepared by adding the Dowfax
3B2, stearic acid and LPKN to water while mixing at moderate
shear and heating the mixture to 65C to finely disperse the
emulsified surface active ingredients in the water phase.
This emulsion premix is then slowly added to the Carbopol
dispersion while mixing under low shear conditions without
forming a vortex. The results are shown below.
Method B:
2069845
Method A is repeated except that the heated emulsion
premix i9 added to the neutralized Carbopol 941 dispersion
before the sodium stearate, TKPP, TPP, and bleach. The
results are also shown below.
i Method A Method B
Density (g/cc) 1.38 1.30
Stability (RT-8 weeks) 0.00~ 7.00~
Rheogram Fig. 9 Fig.10
From the rheograms of figures 9 and 10 it is seen that
both products are linear viscoelastic although the elastic and
viscous moduli G~ and G~ are higher for Method A than for
Method B.
From the results it is seen that early addition of the
surface active ingredients to the Carbopol gel significantly
increases the degree of aeration and lowers the bulk density
of the final product. Since the bulk density i9 lower than
the density of the continuous liquid phase, the liquid phase
undergoes inverse separation (a clear liquid phase forms on
the bottom of the composition). This process of inverse
separation appears to be kinetically controlled and will occur
faster as the density of the product becomes lower.
; Example 3
This example shows the importance of the temperature at
which the premixed surfactant emulsion is prepared.
Two formulations, L and M, having the same composition as
in Example 2 except that the amount of stearic acid was
increased from 0.1~ to 0.2~ are prepared as shown in Method A
2069~45
for formulation L and by the following Method C for
formulation M.
Method C
The procedure of Method A i9 repeated in all details
'except that emulsion premix of the surface active ingredients
is prepared at room temperature and i9 not heated before being
post-added to the thickened Carbopol dispersion containing
silicate, builders and bleach. The rheograms for formulations
L and M are shown in figures 11 and 12, respectively. From
these rheograms it is seen that formulation ~ is linear
viscoelastic in both G' and G" whereas formulation M is non-
linear viscoelastic particularly for elastic modulus G' (G' at
1% strain-G' at 30% strain > 500 dynes/cm2) and also for G" (G"
at 1% strain-G" at 30~ strain 300 dyne9/cm2).
Formulation L remains stable after storage at RT and 100F
for at lea8t 6 weeks whereas formulation M undergoes phase
~eparation.
ComE~arative Example 1
The following formulation is prepared without any
potassium salts:
Weight
~ater ~alance
Carbopol 941 0.2
NaOH (50%) 2.4
TPP, Na (50~) 21.0
Na Silicate (47.5~) 17.24
13leach (1~) 7.13
Stearic Acid 0.1
LPKN (59c) 3.2
Dowfax 3~32 0.8
Soda Ash 5.0
Acrysol ~W 45-N 2.0
41
,~ , .. . .
2069845
The procedure used is analogous to Method A of Example 2
with the soda ash and Acrysol LMW 45-N (low molecular weight
polyacrylate polymer) being added before and after,
respectively, the silicate, TPP and bleach, to the thickened
~arbopol 941 dispersion, followed by addition to the heated
surface active emulsion premix. The rheogram is shown in
figure 13 and is non-linear with G~/G~ (tan~ ) > 1 over the
range of strain of from 5~ to 80%.
Example 4
Formulations A, ~, C, D and K according to this invention
and comparative formulations F and a commercial liquid
automatic dishwasher detergent product as shown in Table 1
above were subjected to a bottle residue test using a standard
polyethylene 28 ounce bottle as used for current commercial
liquid dishwasher detergent bottle.
Six bottles are filled with the respective samples and
the product is dispensed, with a minimum of force, in 80 gram
dosages, with a 2 minute rest period between dosages, until
flow stops. At this point, the bottle was vigorously shaken
to try to expel additional product.
The amount of product remaining in the bottle is measured
as a percentage of the total product originally filled in the
bottle. The results are shown below.
42
2~6~845
Bottle Residue
Formulation Residue
A 8
B 10
C 6
D S
K 7
F* 4
Commercial Product 20
*The sample separates upon aging
Example V
The following formulas (A - K ) were prepared according
to the following procedure:
AB C D E
Carbopol 614 1.0 1.0 1.0 0.75 0.75
NlOHi O. 5 ~ ~ ~ ~77
A um na 0.2 1.6 0.5 1.5 ¦
(Dispal T23 )
Water~ ~1:~ 98 . 375 ~7~7
;~ Figure Nos.14,15 16,17 18,19 . 20,21 ~ 22,23
-5 : : = = ~ = =
'~
:
43
.
~0698~5
F G H I J K
Carbopol 614 0.5 0.5 0.5 1.0 0.75 0.5 1¦
NaOH 0.25 0.25 0.25 0.5 0.375 0.25 ¦¦
Stearic Acid
.- . .
Alum1na O.5 2.0 1.O 1.O 2.5 O.5
(Dispal T23)
Water 98.75 97.25 98.25 ~97.5 96.375
Figure Nos. 24,25 26,27 28,29 30,31 32
===== = . ~
2~6984~
The Carbopol polymer was added to water at 75 - 80C with
mixing. To the solution of the Carbopol polymer and water was
added with mixing the sodium hydroxide to neutralize the
Carbopol polymer so that the solution has a pH of 7 to 10.
~he dispersion of the alumina (Dispol T23) was added with
mixing to the solution of water and neutralized Carbopol
polymer to form formulas (A - K ). The polymer solutions
were tested on the System 4 Rheometer as in Example 1. The
Brookfield viscosities were run at room temperature using a #4
spindle at 20 rpms. Rheograms ( Figure 14-24)
depict the G/ and G for formulas A-K, wherein for each formula
a plot of G/ and G is illustrated.
