Thixotropic aqueous compositions containing long chain saturated fatty acid stabilizers

The physical stability of liquid gel-like compositions based on thixotropic thickener is greatly improved by incorporating in the composition small amounts of long chain fatty acids and salts thereof. The aqueous compositions containing inorganic builder salts and other functional inorganic salts, chlorine bleach, bleach stable detergent, at least one thixotropic thickener and a fatty acid or a metal salt of the fatty acid as a physical stabilizer exhibit a significant increase in apparent viscosity and remain stable against phase separation for an extended period of time. The thixotropic properties can be retained or improved using smaller levels of the thixotropic thickener than in the absence of the physical stabilizer. The stability, chlorine-bleach loss and cleaning ability of the compositions is further improved, when the composition pH is at least 11.2, when added to an aqueous wash both at a concentration of about 10 grams per liter. Use as liquid gel-like automatic dishwasher compositions are described.

FIELD OF INVENTION 
The present invention relates to thixotropic aqueous suspensions with 
improved physical stability. More specifically, the invention relates to 
the use of long chain fatty acids and salts thereof as physical 
stabilizers for polymeric thixotropic aqueous compositions. 
The present invention specifically relates to automatic dishwashing 
detergent compositions having thixotropic properties, improved chemical 
and physical stability, and with increased apparent viscosity, and which 
are readily dispersible in the washing medium to provide effective 
cleaning of dishware, glassware, china and the like. 
BACKGROUND OF THE INVENTION 
Commercially available household-machine dishwasher detergents provided in 
powder form have several disadvantages, e.g. non-uniform composition; 
costly operations necessary in their manufacture; tendency to cake in 
storage at high humidities, resulting in the formation of lumps which are 
difficult to disperse; dustiness, a source of particular irritation to 
users who suffer allergies; and tendency to cake in the dishwasher machine 
dispenser. 
Recent research and development activity has focused on the gel or 
"thixotropic" form of such compositions. Dishwasher products so provided 
are primarily objectionable in that they are insufficiently viscous to 
remain "anchored" in the dispenser cup of the dishwasher, and moreover 
yield spotty residues on dishware, glassware, china and the like. Ideally, 
thixotropic cleansing compositions should be highly viscous in a quiescent 
state, Bingham plastic in nature, and have relatively high yield values. 
When subjected to shear stresses, however, such as being shaken in a 
container or squeezed through an orifice, they should quickly fluidize and 
upon cessation of the applied shear stress, quickly revert to the high 
viscosity/Bingham plastic state. Stability is likewise of primary 
importance, i.e. there should be no significant evidence of phase 
separation or leaking after long standing. 
U.S. Pat. No. 4,752,409 and U.S. Pat. No. 4,801,395, which are assigned to 
applicants' assignee and of which the present application is a 
continuation in part, are directed to thixotropic aqueous suspension 
dishwashing detergent compositions containing long chain fatty acids and 
metal salts of long chain fatty acids such as aluminum stearate and sodium 
stearate as physical stabilizing agents. These compositions show 
improvement in the physical stability of the detergent composition and 
improvement against phase separation over those containing compositions 
that do not contain the aluminum stearate. Although polymeric thickeners 
are disclosed, they are not exemplified in the specifications even though 
they are well known in the art. 
The provision of automatic-dishwasher compositions in gel form having the 
afore-described properties, other than for the improvements described in 
the above mentioned Patent, has thus far proven problematical, 
particularly in home dishwasher machines. For effective use, it is 
generally recommended that the automatic dishwashing detergent, 
hereinafter also designated ADD, contain (1) sodium tripolyphosphate 
(NaTPP) to soften or tie up hard-water minerals and to emulsify and/or 
peptide soil; (2) sodium silicate to supply the alkalinity necessary for 
effective detergency and to provide protection for fine china glaze and 
pattern; (3) sodium carbonate, generally considered to be optional, to 
enhance alkalinity; (4) a chlorine-releasing agent to aid in the 
elimination of soil specks which lead to water spotting; and (5) 
defoamer/surfactant to reduce foam, thereby enhancing machine efficiency 
and supplying requisite detergency. See, for example, SDA Detergents in 
Depth, "Formulations Aspects of Machine Dishwashing," Thomas Oberle 
(1974). Cleansers approximating to the afore-described compositions are 
mostly liquids or powders. Combining such ingredients in a gel form 
effective for home-machine use has proved difficult. Generally, such 
compositions omit hypochlorite bleach, since it tends to react with other 
chemically active ingredients, particularly surfactant. Thus, U.S. Pat. No 
4,115,308 discloses thixotropic automatic dishwasher pastes containing a 
suspending agent, e.g. CMC, synthetic clays or the like; inorganic salts 
including silicates, phosphates and polyphosphates; a small amount of 
surfactant and a suds depressor. Bleach is not disclosed. U.S. Pat. No. 
4,147,650 is somewhat similar, optionally including C1-(hypochlorite) 
bleach but no organic surfactant or foam depressant. The product is 
described, moreover, as a detergent slurry with no apparent thixotropic 
properties. 
U.S. Pat. No. 3,985,668 describes abrasive scouring cleansers of gel-like 
consistency containing (1) suspending agent, preferably the Smectite and 
attapulgite types of clay at a relatively high concentration of preferably 
3-5% by weight; (2) abrasive, e.g. silica sand or perlite, and (3) filler 
comprising light density powdered polymers, expanded perlite and the like, 
which has a buoyancy and thus stabilizing effect on the composition in 
addition to serving as a bulking agent, thereby replacing water otherwise 
available for undesired supernatant layer formation due to leaking and 
phase de-stabilization. The foregoing are the essential ingredients. 
Optional ingredients include hypochlorite bleach, bleach stable surfactant 
and buffer, e.g. silicates, carbonates, and monophosphate. Builders, such 
as NaTPP, can be included as further optional ingredients to supply or 
supplement building function not provided by the buffer, the amount of 
such builder not exceeding 5% of the total composition, according to the 
patent. Maintenance of the desired (greater than) pH 10 levels is achieved 
by the buffer/builder components. High pH is said to minimized 
decomposition of chlorine bleach and undesired interaction between 
surfactant and bleach. Foam killer is not disclosed. 
In U.K. Patent GB No. 2,116,199B and GB No. 2,140,450B, both of which are 
assigned to Colgate-Palmolive, liquid ADD compositions are disclosed which 
have properties desirably characterizing thixotropic, gel-type structure 
and which include each of the various ingredients necessary for effective 
detergency with an automatic dishwasher. The normally gel-like aqueous 
automatic dishwasher detergent composition having thixotropic properties 
includes the following ingredients, on a weight basis: 
(a) 5 to 35% alkali metal tripolyphosphate; 
(b) 2.5 to 20% sodium silicate; 
(c) 0 to 9% alkali metal carbonate; 
(d) 0.1 to 5% chlorine bleach stable, water dispersible organic detergent 
active material; 
(e) 0 to 5% chlorine bleach stable foam depressant; 
(f) chlorine bleach compound in an amount to provide about 0.2 to 4% of 
available chlorine; 
(g) thixotropic thickener in an amount sufficient to provide the 
composition with thixotropy index of about 2.5 to 10; 
(h) sodium hydroxide, as necessary, to adjust pH; and 
(i) balance water. 
Add compositions so formulated are low-foaming; are readily soluble in the 
washing medium and most effective at pH values best conducive to improved 
cleaning performance, viz, pH 10.5-14. The compositions are normally of 
gel consistency, i.e. a highly viscous, opaque jelly-like material having 
Bingham plastic character and thus relatively high yield values. 
Accordingly, a definite shear force is necessary to initiate or increase 
flow, such as would obtain within the agitated dispenser cup of an 
energized automatic dishwasher. Under such conditions, the composition is 
quickly fluidized and easily dispersed. When the shear force is 
discontinued, the fluid composition quickly reverts to a high viscosity 
Bingham plastic state closely approximating its prior consistency.

SUMMARY OF THE INVENTION 
The present invention relates to thixotropic aqueous suspensions with 
improved physical stability. More specifically, the invention relates to 
the use of long chain fatty acids and salts thereof as physical 
stabilizers for polymeric thixotropic aqueous compositions as well as 
inorganic thixotropic aqueous compositions as well as mixtures thereof 
which compositions can contain either phosphate builder systems or 
non-phosphate builder systems. 
The present invention specifically relates to automatic dishwashing 
detergent compositions having thixotropic properties, improved chemical 
and physical stability, and with increased apparent viscosity, and which 
are readily dispersible in the washing medium to provide effective 
cleaning of dishware, glassware, china and the like. 
Accordingly, it is an objective of the invention to provide anti-settling 
additives for thixotropic aqueous compositions. 
It is another object of the invention to provide liquid ADD compositions 
having thixotropic properties with improved physical stability and 
rheological properties by using fatty acids and salts thereof as well as 
those being formed in situ in the compositions from the fatty acids. 
It is still another object of the invention to provide thixotropic liquid 
ADD compositions having reduced levels of inorganic thixotropic thickener 
without adversely effecting the generally high viscosities at low shear 
rates and lower viscosities at high shear rates which are characteristic 
of the desired thixotropic properties, wherein a minor amount of a fatty 
acid or salt thereof is incorporated into the aqueous suspension to 
increase the apparent viscosity of the formulation and to inhibit the 
settling of the suspended particles and to prevent phase separation. 
In particular, the linear viscoelastic aqueous liquid automatic dishwasher 
detergent compositions of this invention will, at least in the preferred 
embodiments, satisfy each of the following stability criteria over the 
aging temperature-time schedule shown by the following Table A: 
TABLE I 
______________________________________ 
Aging Temperature 
Duration (weeks) 
(.degree.F.) Minimum Preferred 
______________________________________ 
140 1 2 
120 6 8 
100 13 16 
Ambient 24 24 
______________________________________ 
More specifically, the compositions are considered stable if each of the 
following stability criteria is satisfied for at least the minimum number 
of weeks for each aging temperature shown in Table I: 
no visible phase separation (i.e. no solid/liquid separation) 
no significant change (e.g. less than 10%) in viscosities, yield stress or 
other dynamic-mechanical properties 
no crystal growth, if not irreversible, under repeated heating-cooling 
cycles over a temperature range of at least 7.degree. F. to 140.degree. F. 
no decolorization or significant color change 
In addition to the above stability criteria, the compositions of this 
invention are further characterized by their low bottle residue. 
Specifically, for the preferred cross-linked polyacrylic acid thickened 
compositions of this invention, bottle residues, under the usual use 
conditions, will be no more than about 6 to 8%, preferably no more than 
about 4 to 5%, of the original bottle contents, on a weight basis. 
According to another aspect the present invention there is provided a novel 
aqueous liquid automatic dishwasher detergent composition employing a 
polymeric thixotropic thickener or a mixture of a polymeric thixotropic 
thickener and an inorganic thixotropic thickener. The composition is 
characterized by its linear viscoelastic behavior, substantially 
indefinite stability against phase separation or settling of dissolved or 
suspended particles, low levels of bottle residue, relatively high bulk 
density, freedom from fish eyes, absence of crystal formulation and growth 
resistance to cup leakage, substantial absence of unbound or free water as 
compared to clay based formulations having high amounts of free water and 
a 3 dimensional structure of the polymeric formulations as compared to the 
two dimensional structures of clay formulations. This unique combination 
of properties is 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 at least one high molecular weight cross-linked polyacrylic acid type 
thickening agent, a physical stabilizing amount of a long chain fatty acid 
or salt thereof, and optionally, a source of potassium ions to provide a 
potassium/sodium weight ratio in the range of from about 1:1 to about 
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 
by a bulk density of at least about 1.32 g/cc, such that the density of 
the polymeric phase and the density of the aqueous (continuous) phase are 
approximately the same. 
A still further object of the instant invention is to provide a 
non-phosphate composition containing an inorganic thixotropic thickener 
which can optionally include a polymeric thixotropic thickener. 
These and other objects of the invention which will become more readily 
understood from the following detailed description of the invention and 
preferred embodiments thereof are achieved by incorporating in a normally 
gel-like aqueous liquid composition a small amount of a physical 
stabilizer which is a long chain fatty acid or salt thereof which 
increases the apparent viscosity of the formulation and inhibits settling 
of the suspended particles. 
DETAILED DESCRIPTION OF THE INVENTION 
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. 
In accordance with this particular aspect, the present invention provides a 
normally gel-like aqueous automatic dishwasher detergent composition 
having thixotropic properties which include, on a weight basis: 
(a) 5 to 35% of at least one inorganic phosphate builder salt such as an 
alkali metal tripolyphosphate; 
(b) 2.5 to 20% sodium silicate; 
(c) 0 to 9% alkali metal carbonate; 
(d) 0 to 5% organic detergent active material; 
(e) 0 to 5% chlorine bleach stable foam depressant; 
(f) chlorine bleach compound in an amount to provide about 0.2 to 4% of 
available chlorine; 
(g) thixotropic thickener, preferably an inorganic or organic thixotropic 
thickener, in an amount sufficient to provide the composition with 
thixotropy index of about 2.5 to 10; and 
(h) 0 to 8% alkali metal hydroxide; 
(i) a long chain fatty acid or salt thereof in an amount effective to 
increase apparent viscosity and the physical stability of the composition; 
and 
(j) balance water, 
Most preferably, the total amount of (b) sodium silicate, (c) alkali metal 
carbonate and (d) alkali metal hydroxide providing a pH sufficiently high 
such that when the composition is diluted in an aqueous wash bath to 
provide a concentration of 10 grams per liter the pH of the aqueous wash 
bath becomes at least 11.2. 
Also related to this specific aspect, the invention provides a method for 
cleaning dishware in an automatic dishwashing machine with an aqueous wash 
bath containing an effective amount of the liquid automatic dishwasher 
detergent (LADD) composition as described above. According to this aspect 
of the invention, the LADD composition can be readily poured into the 
dispensing cup of the automatic dishwashing machine and will thicken to 
its normal gel-like or pasty state 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 advantageous characteristics of the polymeric compositions of this 
invention made with a polymeric thickening agent, including physical 
stability, low bottle residue, high cleaning performance, e.g. low 
spotting and filming, dirt residue removal, and so 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 at least one 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) optionally, potassium ion to sodium ion weight ratio K/Na in the range 
of from about 1:1 to 45:1, especially from 1:1 to 3:1, and (4) a product 
bulk density of at least about 1.32 g/cc, such that the bulk density and 
liquid phase density are about the same, (5) maintaining the pH of the 
neutralized polymeric thickener at a pH of at least 11, preferably at 
least 11.5, and (6) that all the water in the composition is substantially 
bound to the polymeric thickening agent. 
Accordingly, in one aspect the present invention provides an improved 
linear viscoelastic aqueous liquid automatic dishwasher detergent 
polymeric composition comprising water, up to about 2% by weight of long 
chain fatty acid or salt thereof, from about 0.1 to 5% by weight of 
low-foaming chlorine bleach stable, water dispersible automatic dishwasher 
non-soap organic detergent, from about 10 to 35 by weight of alkali metal 
detergent builder salt, from about 3 to 20% by weight of a chlorine bleach 
compound, and at least one cross-linked polycarboxylate thickening agent 
having a molecular weight of at least about 500,000. The compositions 
preferably have a bulk density of from about 1.28 g/cm.sup.3 to about 1.42 
g/cm.sup.3. The aqueous phase may also include both sodium and potassium 
ions at a K/Na weight ratio of from about 1/1 to about 45/1. 
In one of the preferred embodiment, the linear viscoelastic aqueous liquid 
automatic dishwasher polymeric detergent comprises, approximately, by 
weight, 
(a) 10 to 35% metal tripolyphosphate detergent builder such as sodium 
tripolyphosphate or potassium tripolyphosphate and mixtures thereof; 
(b) 0 to 15% alkali metal silicate; 
(c) 0 to 6% alkali metal hydroxide; 
(d) 0.1 to 3% chlorine bleach stable, water-dispersible organic detergent 
active material; 
(e) 0 to 1.5% chlorine bleach stable foam depressant; 
(f) chlorine bleach compound in an amount to provide about 0.2 to 4% of 
available chlorine; 
(g) 0.4 to 1.5% of at least one hydrophilic cross-linked water insoluble 
polycarboxylate thickening agent having a molecular weight of from 500,000 
to 4,000,000 to provide said linear viscoelastic property; 
(h) 0.08 to 0.4% of long chain fatty acid or a metal salt of a long chain 
fatty acid; 
(i) 0 to 10% of a non-cross-linked polyacrylic acid having a molecular 
weight in the range of from about 800 to 200,000; and 
(j) water which is substantially bound. 
In another aspect of the invention, a novel method for preparing the 
aqueous linear viscoelastic composition is provided. According to this 
aspect, the method comprises the steps of 
I. (a) fully hydrating the cross-linked polycarboxylate thickener by slowly 
adding the thickener to heated water while moderately agitating the 
mixture, 
(b) slowly adding a neutralizing amount of caustic soda to the mixture from 
(a) while continuing agitation to obtain a dispersion of the neutralized 
thickener; 
II. (c) forming an aqueous mixture of surface active agents; 
(d) heating the mixture in (c) to a temperature higher than that of the 
heated water in (a) and mixing until a homogeneous smooth premix is 
obtained; 
III. (e) uniformly mixing alkali metal builder salts with the dispersion 
(b), 
(f) uniformly mixing the heated premix (d) with the mixture (e), 
(g) cooling the mixture (f) to a temperature above the temperature of the 
heated water in step (a), and 
(h) adding bleach to the mixture (g). 
In a preferred embodiment of the invention process, the pH of the aqueous 
slurry of the cross-linked polycarboxylate thickener after the 
neutralization in step (b) and in each succeeding step is maintained at a 
value of at least 11. Although for the reasons subsequently discussed 
excessive air bubbles are not often desirable in the invention 
compositions containing polymeric thickening agent, depending on the 
amounts of dissolved solids and liquid phase densities, incorporation of 
small amounts of finely divided air bubbles, generally up to about 10% by 
volume, preferably up to about 4% by volume, more preferably up to about 
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 about 100 microns in diameter, preferably 
from about 20 to about 40 microns in diameter, to assure maximum 
stability. Although air is the preferred gaseous medium for adjusting 
densities to improve physical 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 viscosity 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 is readily determined by routine 
experimentation in any particular instance, generally ranging from 30 to 
75 weight percent, preferably about 35 to 65 weight percent. The water 
should also be preferably deionized or softened. 
The manner of formulating the invention compositions made with polymeric 
thickening agent is also important. As discussed above, the order of 
mixing the ingredients as well as the manner in which 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, the detergent builder salts, alkali 
metal silicates, 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 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 or 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 be 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 about 1 to 10%, preferably from about 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 about Tm+5 to Tm+20, preferably from 
about Tm to Tm-10, where Tm is the melting point temperature of the fatty 
acid. For the preferred stearic acid stabilizer the heating temperature is 
in the range of 50.degree. to 70.degree. C. However, if care is taken to 
avoid excessive air bubble incorporation during the gelation step or 
during the mixing of the detergent builder salts and other additives, for 
example, by operating under vacuum, or using low shearing conditions, or 
special mixing operations, etc., the order of addition of the surface 
active ingredients should be less important. 
In accordance with an especially preferred embodiment, the thickened linear 
viscoelastic aqueous automatic dishwasher detergent composition containing 
polymeric thickening agent 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 to 1.5%, preferably 0.1 to 0.5%, chlorine bleach stable foam 
depressant; 
(f) Chlorine bleach compound in an amount to provide about 0.2 to 4%, 
preferably 0.8 to 1.6%, of available chlorine; 
(g) at least one high molecular weight hydrophilic cross-linked polyacrylic 
acid thickening agent in an amount to provide a linear viscoelasticity to 
the formulation, preferably from about 0.4 to 1.5%, more preferably from 
about 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 
(i) balance water, preferably from about 30 to 75%, more preferably from 
about 35 to 65%; and wherein in (a) the alkali metal polyphosphate 
includes optionally, a mixture of from about 5 to 30%, preferably from 
about 12 to 22% of tetrapotassium pyrophosphate, and from 0 to about 20%, 
preferably from about 3 to 18% of sodium tripolyphosphate, and wherein in 
the entire composition the optional ratio, by weight, of potassium ions to 
sodium ions is from about 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 about 1.32 to 1.42 g/cc.sup.3, 
preferably from about 1.35 to 1.40 g/cc.sup.3. A density of about 1.42 
g/cc.sup.3. is essentially equivalent to zero air content. 
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 
nonthixotropic as measured by dynamic rheological measurements (frequency 
sweep measurements) which is especially true in the case of compositions 
not containing fatty acid stabilizer. However, the instant polymeric 
compositions do have a thixotropic index (TI) of 2.5 to 10 as measured by 
a ratio of Brookfield viscosities at 30 rpm and 3 rpm, 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. 
A still further attribute of the polymeric compositions made with a 
polymeric thickening agent contributing to the overall product stability 
and low bottle 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 matrix. 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 is again subjected to a stress or 
strain. As a result of the absence of unbound or free water, there is 
virtually no phase separation-between the aqueous phase and the polymeric 
matrix or dissolved solid particles. This characteristic is manifested 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 determined by phase separation). In order to 
maximize physical (phase) stability, the density of the composition should 
be controlled such that the bulk density of the liquid phase is 
approximately the same as the bulk density of the entire composition, 
including the polymeric thickening agent. This control and equalization of 
the densities is achieved, according to the invention, by providing the 
composition with a bulk density of at least 1.32 g/cc.sup.3, preferably at 
least 1.35 g/cc.sup.3, up to about 1.42 g/cc.sup.3. 
Furthermore, to achieve these relatively high bulk densities, it is 
important to minimize the amount of air incorporated into the composition 
(a density of about 1.42 g/cc is essentially equivalent to zero air 
content). Generally, LADD effectiveness is directly related to (a) 
available chlorine levels; (b) alkalinity; (c) solubility in washing 
medium; and (d) foam inhibition. It is preferred herein that the pH of the 
LADD composition be at least about 11.5. The presence of carbonate is also 
often needed herein, since it acts as a buffer helping to maintain the 
desired pH level. Excess carbonate is to be avoided, however, since it may 
cause the formation of needle-like crystals of carbonate, thereby 
impairing the stability, if not reversible, as well as impairing the 
dispensibility of the product from, for example, squeeze tube bottles. The 
alkali metal hydroxide such as caustic soda (NaOH) services the further 
function of neutralizing the phosphoric or phosphonic acid ester foam 
depressant when present. About 0.5 to 6 wt % of NaOH and about 2 to 9 wt % 
of sodium carbonate in the LADD composition are typical, although it 
should be noted that sufficient alkalinity may be provided by the alkali 
metal tripolyphosphate and sodium silicate. 
In accordance with an especially preferred embodiment, the present 
invention provides a phosphate free aqueous automatic dishwasher detergent 
composition which is a solution and includes, approximately on a weight 
basis: 
(a) 5 to 20% of a low molecular weight non-crosslinked polyacrylate polymer 
such as SOKALAN PA-30CL; 
(b) 15 to 45% alkali metal silicate; 
(c) 2 to 10.0% alkali metal carbonate; 
(d) about 0 to about 10% alkali metal hydroxide; 
(e) 0 to 5% chlorine bleach stable organic detergent active material; 
(f) 0 to 1.5% stable foam depressant; 
(g) chlorine bleach compound in an amount to provide about 0.2 to about 4% 
of available chlorine; 
(h) 0.05 to 1.0%, more preferably 0.02 to 1.0% of a polyvalent or 
transition metal salt of a long chain fatty acid in an amount effective to 
increase the viscosity of the composition; 
(i) 0 to 0.6% of a fatty acid; 
(j) 0.1 to 5.0% of an inorganic thixotropic thickener; 
(k) 0 to 1% of a polymeric thixotropic thickener; and 
(l) 0 to 10% phosphonates; 
(m) 0 to 10% of entrained air bubbles; 
(n) the balance being water, wherein the ingredients (a) through (h) are 
dissolved in water and the total amount of (b) sodium silicate, (c) alkali 
metal carbonate and (d) alkali metal hydroxide provides a pH sufficiently 
high such that when the composition is diluted in an aqueous wash bath to 
provide a concentration of 10 grams per liter the pH of the aqueous wash 
bath becomes at least 11.2. 
The alkali metal silicate such as sodium silicate or sodium disilicate, 
which provides alkalinity and protection of hard surfaces, such as fine 
china glaze and pattern, is employed in the phosphate free composition in 
an amount ranging from about 15 to 45 weight percent, preferably about 20 
to 40 weight percent. The sodium silicate or sodium disilicate is 
generally added in the form of an aqueous solution, preferably having 
Na.sub.2 O:SiO.sub.2 ratio of about 1:1.3 to 1:2.8, especially preferably 
1:2.0 to 1:2.6. At this point, it should be mentioned, especially NaOH and 
sodium hypochlorite, are also often added in the form of a preliminary 
prepared aqueous dispersion or solution. 
The phosphate free liquid automatic dishwashing detergent composition 
contains about 2 to about 10% by weight of an alkali metal carbonate 
selected from the group consisting essentially of lithium carbonate, 
potassium carbonate and sodium carbonate and mixtures thereof, more 
preferably about 2 to about 8% by weight, and most preferably about 2 to 
about 5% by weight. Alkali metal gluconates and nitrolacetic acid salts 
can be used in conjunction with the alkali metal carbonates. 
In conjunction with the sodium carbonate in the phosphate free composition 
is used a low molecular weight non-crosslinked polyacrylate polymer such 
as SOKALAN PA-30CL which is a chlorine resistant polyacrylate builder and 
is available from BASF under the tradename of SOKALAN PA-30CL. The use of 
the SOKALAN PA-30CL which is low molecular weight non-crosslinked 
polyacrylate in the instant composition is critical because of its 
effective resistance against degradation by the chlorine contained in the 
composition. Previously used low molecular polyacrylates such as 
Sokalan.TM. CP45 sold by BASF and Norasol LMW 45ND are not resistant to 
chlorine degradation and when used in a composition containing chlorine. 
They are not as effective as is the SOKALAN PA-30CL. Another improved 
chlorine resistant polyacrylate builder is Norasol QR1014 having a 
molecular weight of about 10,000. 
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 sufficiently reduced 
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 inorganic or organic 
builder salt which has a water softening effect may aid in providing the 
desired degree of foam inhibition. However, it is generally preferred to 
include a chlorine bleach stable foam depressant or inhibitor. 
Particularly effective are the alkyl phosphoric acid esters of the 
formula: 
##STR1## 
and especially the alkyl acid phosphate esters of the formula: 
##STR2## 
In the above formulas, one or both R groups in each type of ester may 
represent independently a C.sub.12 -C.sub.20 alkyl or ethoxylated alkyl 
group. The ethoxylated derivative 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, 
such 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 diesters of the same type, may be employed. Especially 
preferred is a mixture of mono- and di- C.sub.16 -C.sub.18 alkyl acid or 
ethoxylated alkyl phosphate esters such as monostearyl/distearyl acid 
phosphate 1.2/1, and the 3 to 4 mole ethylene oxide condensates thereof. 
When employed, proportions of 0 to 1.5 weight percent, preferably 0.1 to 
1.0 weight percent, of foam depressant in the phosphate free composition 
is typical. Other defoamers which may be used include, for example, the 
known silicones, such as available from Dow Chemicals. In addition, it is 
an advantageous feature of this invention that many of the stabilizing 
salts, such as the stearate salts, for example, sodium stearate, are also 
effective as foam killers. 
Although any chlorine bleach compound may be employed in the phosphate free 
compositions of this invention, such as dichloroisocyanurate, 
dichloro-dimethyl handantoin, 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 
chlorine bleach compound to provide about 0.75 to about 2.0% by weight of 
available chlorine, as determined, for example, by acidification of 100 
parts of the composition with excess hydrochloric acid. A solution 
containing about 0.15 to 15.5% by weight of sodium hypochlorite (13% of 
available chlorine) contains or provides roughly the same percentage of 
available chlorine. About 0.8 to 1.6% by weight of available chlorine is 
especially preferred. 
Detergent active material which may be, useful herein in the phosphate free 
compositions must be stable in the presence of chlorine bleach, especially 
hypochlorite bleach, and 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. They are 
used in amounts ranging from about 0 to 5%, preferably about 0.1 to 5.0%. 
Particularly preferred surfactants herein are the linear or branched 
alkali metal mono- and/or di-(C.sub.8 -C.sub.14) alkyl diphenyl oxide 
disulphonated, commercially available for example as DOWFAX.TM. 3B-2 and 
DOWFAX.TM. 2A-1. Alkyl ether esters (C.sub.12 -C.sub.14 3EO SO.sub.3 
-N.sub.a.sup.+) are also useful surfactants. In addition, the surfactant 
should be compatible with the other ingredients of the composition. Other 
suitable surfactants include the primary alkylsulphates, alkylsulphonates, 
alkylarylsulphonates and sec.-alkylsulphates. Examples include sodium 
C.sub.10 -C.sub.18 alkylsulphates such as sodium dodecylsulphate and 
sodium tallow alcoholsulphate; sodium C.sub.10 -C.sub.18 alkanesulphonates 
such as sodium hexadecyl-1-sulphonate and sodium C.sub.12 -C.sub.18 
alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The 
corresponding potassium salts may also be employed. 
As other suitable surfactants or detergents, the amine oxide surfactants 
are typically of the structure R.sub.2 R.sub.1 N.fwdarw.O, in which each R 
represents a lower alkyl group, for instance, methyl, and R.sub.1 
represents a long chain alkyl group having from 8 to 22 carbon atoms, for 
instance a lauryl, myristyl, palmityl or cetyl group. Instead of an amine 
oxide, a corresponding surfactant phosphine oxide R.sub.3 R.sub.2 R.sub.1 
PO or sulphoxide RR.sub.1 SO can be employed. Betaine surfactants are 
typically of the structure R.sub.2 R.sub.1 N.rarw.R"COO--, in which each R 
represents a lower alkylene group having from 1 to 5 carbon atoms. 
Specific examples of these surfactants include lauryl-dimethylamine oxide, 
myristyl-dimethylamine oxide, the corresponding phosphine oxides and 
sulphoxides, and the corresponding betaines, including 
dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, 
hexadecyldimethylammonium hexanoate and the like. For biodegradability, 
the alkyl groups in these surfactants should be linear, and such compounds 
are preferred. 
Surfactants of the foregoing type, all well-known in the art, are 
described, for example, in U.S. Pat. Nos. 3,985,668 and 4,271,030. 
The preferred polyvalent or transition metal salts of the long chain fatty 
acids are the higher aliphatic fatty acids having from about 8 to 20 
carbon atoms, more preferably from about 10 to 20 carbon atoms, and 
especially preferably from about 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, etc., or from synthetic sources 
available from industrial manufacturing processes such as mixtures of 
stearic acid and palmitic acid. 
Thus, examples of the fatty acids from which the polyvalent or transition 
metal salt stabilizers can be formed include, for example, decanoic acid, 
dodecanoic acid, palmitic acid, myristic acid, stearic acid, isostearic, 
oleic acid, eicosanoic acid, tallow acid, coco fatty acid, soya fatty 
acid, mixtures of these acids, etc. Stearic acid and mixed fatty acids are 
preferred. The preferred metals are the alkali metals of Group IIIA, 
wherein aluminum is especially preferred. 
The amount of the polyvalent or transition metal fatty acid salt thickener 
to achieve the desired enhancement of viscosity will depend on such 
factors as the nature of the fatty acid salt, the nature and amount of the 
detergent active compound, inorganic salts and other LADD ingredients, as 
well the synergistic reaction between, the fatty acid and the polyacrylate 
builder. 
Other conventional ingredients may be included in these phosphate free 
compositions in small amounts, generally less than about 3 weight percent, 
such as perfume, preservatives, dyestuffs and pigments and the like, all 
of course being stable to chlorine bleach compound and high alkalinity 
(properties of all components). Especially preferred for coloring are the 
chlorinated phthalocyanines and polysulphides of aluminosilicate which 
provide, respectively, pleasing green and blue tints. 
The inorganic thixotropic thickeners used in the phosphate free 
compositions are identical to those previously described inorganic 
thixotropic thickeners which can be used in the phosphate containing 
compositions. The inorganic thixotropic thickeners used it the phosphate 
free systems are used at a concentration level of about 0.1 to 5.0 weight 
percent and more preferably at a concentration of about 0.2 to 3.0 weight 
percent. The polymeric thixotropic thickeners which can be optionally used 
in conjunction with the inorganic thixotropic thickeners in the phosphate 
free compositions are identical to those previously described polymeric 
thixotropic thickeners which can be used in the phosphate containing 
compositions. The polymeric thixotropic thickeners used in the phosphate 
free systems are used at a concentration level of 0 to about 1 weight 
percent and more preferably about 0.01 to 0.5 weight percent. 
The inorganic builder salt such as sodium tripolyphosphate (NaTPP) or 
potassium tripolyphosphate (KTPP) is employed in the phosphate containing 
LADD composition in a range of about 8 to 35 wt %, preferably about 20 to 
30 wt %, should preferably be free of heavy metals which tends to 
decompose or inactivate the preferred sodium hypochlorite and other 
chlorine bleach compounds. The NaTPP may be anhydrous or hydrated, 
including the stable hexahydrate with a degree of hydration of 6 
corresponding to about 18% by weight of water or more. Especially 
preferred LADD compositions are obtained, for example, when using a 0.5:1 
to 2:1 weight ratio of anhydrous to hexahydrated NaTPP, values of about 
1:1 being particularly preferred potassium tripolyphosphate can be 
employed alone or in combination with the sodium tripolyphosphate as an 
inorganic builder salt. Other useful builder salts are 
potassium-hexametaphosphate, potassium pyrophosphate, sodium citrate and 
sodium carbonate which can be used alone or in combination with sodium 
tripolyphosphate and/or potassium tripolyphosphate. Examples of preferred 
phosphate builders are Thermophos NW and Thermophos N Hexahydrate sold by 
Knapsack. 
In addition to or in place of part or all of the NaTPP detergency builder, 
other phosphorus or non-phosphorus inorganic or organic detergency builder 
salts can also be used in the composition. Examples of suitable detergency 
builders-sequestrants include, for instance, trisodium nitrilotriacetate, 
tetrasodiumethylenediamine tetraacetate, sodium citrate, and the 
corresponding potassium salts. Tetrapotassium or tetrasodium pyrophosphate 
can also be used. However, sodium tripolyphosphate is highly preferred 
where phosphorus-containing detergents are permitted. 
In one embodiment with the present invention, the detergent builder salts 
can comprise mixtures of at least potassium tripolyphosphate (KTPP) and 
sodium tripolyphosphate (NaTPP) (especially hexahydrate). Typical ratios 
of KTPP to NaTPP are from about 1.4:1 to 10:1, especially from about 2:1 
to 8:1. The total amount of detergent builder salts is preferably from 
about 10 to 35% by weight, more preferably from about 15 to 35%, 
especially from about 18 to 30% by weight of the composition. 
Also contributing to the physical stability and low bottle residue of the 
invention compositions made with polymeric thickening agent is the 
optional use of 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.sup.+) ions requires less water of hydration 
than the sodium (Na.sup.+) 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 is 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. loss 
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. 
The compositions of this invention optionally 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 about 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 to form a highly translucent product whereas when the 
K/Na ratio is more than 45, especially when it is greater than about 3, 
the product has a tendency to become too liquid and phase separation could 
begin to occur. When the K/Na ratios become much larger than 45, such as 
in an all or mostly potassium formulation, the polymer thickener could 
lose its absorption capacity and could begin 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 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 anionic detergent, bleach or other ionizable salt compound additive, 
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 metaphosphate, and the like, for example, sodium or potassium 
tripolyphosphate (hydrated or anhydrous), 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 builders, where not precluded due to local 
regulations, are preferred and mixtures of tetrapotassium pyrophosphate 
(TKPP) and sodium tripolyphosphate (NaTPP) (especially the hexadydrate) 
are especially preferred. Typical ratios of NaTPP to TKPP are from about 
2:1 to 1:8, especially from about 1:1.1 to 1:6. The total amount of 
detergent builder salts is preferably from about 5 to 35% by weight, more 
preferably from about 15 to 35%, especially from about 18 to 30% by weight 
of the composition. 
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 sufficiently reduced 
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 NaTPP which has a water 
softening effect may aid in providing the desired degree of foam 
inhibition. However, there may optimally be included a chlorine bleach 
stable foam depressant or inhibitor where a low foam LADD is desired. 
Particularly effective are the alkyl phosphoric acid esters of the formula 
##STR3## 
available, for example, from Hooker (SAP), Atochem Inc. (formerly PCUK) 
and Knapsack (LPKn-158), in which one or both R groups may represent 
independently a C.sub.12-20 alkyl or ethoxylated alkyl group. Mixtures of 
the two types, or any other chlorine bleach stable types, or mixtures of 
mono-and di-esters of the same type may be employed. Especially preferred 
is a mixture of mono and di-C.sub.16-18 alkyl acid phosphate esters such 
as monostearyl/distearyl acid phosphates 1.2/1 (Knapsack) or 4/1 (UGINE 
KULH-PLAN). When employed, proportions of 0.1 to 0.5 wt %, of foam 
depressant in the composition is typical, the weight ratio of detergent 
active component (d) to foam depressant (e) generally ranging from about 
10:1 to 1:1 and preferably about 5:1 to 1:1. In addition, it is an 
advantageous feature of this invention that many of the stabilizing long 
chain fatty acids, such as stearic acid and behenic acid also act as foam 
killer depressants. 
Although any chlorine bleach compound may be optionally employed in the 
compositions of this invention, such as chlorinated TSP, alkali metal, 
e.g. potassium, lithium, magnesium and especially sodium, hypochlorite is 
preferred. The composition should contain sufficient chlorine bleach 
compound to provide about 0.15 to 2.0% by weight of available chlorine, as 
determined for example, by acidification of 100 parts of the composition 
with excess of hydrochloric acid. A solution containing about 0.15 to 2.0% 
by weight of sodium hypochlorite contains or provides roughly the same 
percentage of available chlorine. About 0.8 to 1.6% by weight of available 
chlorine is especially preferred. For example, sodium hypochlorite (NaOCl) 
solution of from about 11 to about 14% available chlorine in amounts of 
about 3 to 20%, preferably about 7 to 12%, can be advantageously used. 
The alkali metal silicate such as potassium silicate or sodium silicate, 
which provides alkalinity and protection of hard surfaces, such as fine 
china glaze and pattern, is employed in an amount ranging from about 2.5 
to 30 wt %, preferably about 5 to 25 wt %, in the composition. The sodium 
silicate is generally added in the form of an aqueous solution, preferably 
having an Na.sub.2 O:SiO.sub.2 ratio of about 1:2 to 1:2:8. 
In accordance with the present invention the types and amounts of the 
alkaline components are chosen so that when the composition is added to an 
aqueous wash bath to provide a concentration of 10 grams of composition 
per liter of wash bath the pH of the wash bath becomes at least 11.2, 
preferably at least 11.5, such as from 11.5 to 13.5, preferably at least 
11.5 to 12.5. By operating at these high than normal alkalinity levels the 
cleaning performance is improved and at the same time the rheological 
properties, and particularly, physical stability, are also improved 
because of the increased alkalinity reserve of the composition due to the 
increase concentration of the basic components in the composition. 
Furthermore, in the preferred embodiment in which a chlorine bleach 
compound is included in the LADD composition, the additional benefit of 
reduction of loss of active chlorine is also obtained. 
Detergent active material useful herein must be stable in the presence of 
chlorine bleach, especially hypochlorite bleach, and those of the organic 
aromatic anionic, organic aliphatic anionic, amine oxide, phosphine oxide, 
sulphoxide or betaine water dispersible surfactant types can be used, the 
first mentioned anionics being most preferred. They are used in amounts 
ranging from about 0 to 5%, preferably about 0.3 to 2.0%. Particularly 
preferred surfactants herein are the alkali metal di-(C.sub.8-14) alkyl 
diphenyl oxide disulfonates commercially available for example as DOWFAX 
(Registered Trademark) 3B-2 and DOWFAX 2A-1. In addition, the surfactant 
should be compatible with the other ingredients of the composition. Other 
suitable surfactants include the primary alkylsulphates, alkylsulphonates, 
alkylaryl-sulphonates and sec.-alkylsulphates. Examples include sodium 
C.sub.10 -C.sub.18 alkanesulphonates such as sodium dodecylsulphate and 
sodium tallow alcoholsulphate; sodium C.sub.10 -C.sub.18 
hexadecyl-1-sulphonate and sodium C.sub.12 -C.sub.18 alkanesulphonates 
such as sodium alkylbenzenesulphonates and sodium 
dodecylbenzenesulphonates. Sodium benzoate may also be used. The 
corresponding potassium salts may also be employed. 
As other suitable surfactants or detergents, the amine oxide surfactants 
are typically of the structure R.sub.2 R.sub.1 N--R'COO--, in which each R 
represents a lower alkylene group having from 1 to 5 carbon atoms. 
Specific examples of these surfactants are lauryl-dimethylamine oxide, 
myristyldimethylamine oxide, the corresponding phosphine oxides and 
sulphoxides, and the corresponding betaines, including 
dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, 
hexadecyldimethylammonium hexanoate and the like. For biodegradability, 
the alkyl groups in these surfactants should be linear, an such compounds 
are preferred. Surfactants of the foregoing type, all well known in the 
art, are described, for example, in U.S. Pat. Nos. 3,985,668 and 
4,271,030. 
Thixotropic thickeners, i.e. thickeners or suspending agents which provide 
an aqueous medium with thixotropic properties, are known in the art and 
may be organic or inorganic water soluble, water dispersible or 
colloid-forming, and monomeric or polymeric as for example polycarboxylate 
thickener polymers exemplified in prior art U.S. Pat. No. 4,226,736 and 
U.S. Pat. No. 3,996,152 and should of course be stable in these 
compositions, e.g. stable to high alkalinity and chlorine bleach 
compounds, such as sodium hypochlorite. Those especially preferred 
generally comprise the inorganic, colloid-forming clays of smectite and or 
attapulgite types. These materials were generally used in amounts of about 
1.0 to 10, preferably 1.2 to 5 wt %, to confer the desired thixotropic 
properties and Bingham plastic character in the assignee's prior disclosed 
LADD formulations of the aforementioned GB No. 2,116,199A and GB No. 
2,140,450A. It is one of the advantages of the clay LADD formulations of 
the present invention that the desired thixotropic properties and Bingham 
plastic character can be obtained in the presence of the fatty acid 
stabilizers with lesser amounts of the thixotropic thickeners. For 
example, amounts of the inorganic colloid-forming clays of the smectite 
and/or attapulgite types in the range of from about 0.1 to 3%, preferably 
0.1 to 2.5%, especially 0.1 to 2%, are generally sufficient to achieve the 
desired thixotropic properties and Bingham plastic character when used in 
combination with the physical stabilizer. 
Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, 
smectite, saponite, and the like. Monmorillonite clays are preferred and 
are available under tradenames such as Thixogel (Registered Trademark) No. 
1 and Gelwhite (Registered Trademark) GP, H, etc., from Georgia Kaolin 
Company; ECCAGUM (Registered Trademark) GP, H, etc., from Luthern Clay 
Products; and Vasagel AP (Registered Trademark) from Sud Chemie. 
Attapulgite clays include the materials commercially available under the 
tradename Attagel (Registered Trademark), i.e. Attagel 40, Attagel 50 and 
Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of 
smectite and attapulgite types in weight ratios of 4:1 to 1:5 are also 
useful herein. Thickening or suspending agents of the foregoing types are 
well known in the art, being described, for example, in U.S. Pat. No. 
3,985,668 referred to above. 
Abrasives or polishing agents should be avoided in the LADD compositions as 
they may mar the surface of fine dishware, crystal and the like. 
The polymeric thixotropic thickeners of the instant invention can be used 
in conjunction with the clay thixotropic thickeners but are preferably 
used alone. The polymeric thixotropic thickener is preferably a 
polycarboxylate polymer having a molecular weight of about 500,000 to 
about 4,000,000, but the polymeric thickener can be a water soluble or 
water dispersible sulfonated polystyrene polymer or a 
hydrophobic/hydrophilic copolymer such as copolymer of polyacrylic acid 
and as dialkylacrylamide. The polycarboxylate polymers are disclosed in 
U.S. Pat. No. 2,798,053, issued on Jul. 2, 1957, which is hereby 
incorporated by reference. 
Exemplary of the polycarboxylate type thickening agents are cross-linked 
polyacrylic acid-type thickening agents sold by B. F. Goodrich under their 
Carbopol trademark, including both the 900 series resins, especially 
Carbopol 941, which is the most ion-insensitive of this class of polymers, 
and Carbopol 940 and Carbopol 934, and the 600 series resins, especially 
Carbopol 614. It is also contemplated within the scope of this invention 
that mixtures of Carbopol resins can be used. The Carbopol 600 and 900 
series resins are hydrophilic high molecular weight, cross-linked linear 
acrylic acid polymers having an average equivalent weight of 76, and the 
general structure illustrated by the following formulas: 
##STR4## 
wherein R can be hydrogen or an alkyl chain. Carbopol 941 has a molecular 
weight of about 1,250,000; Carbopol 940 has a molecular weight of 
approximately 3,000,000. The Carbopol 900 series resins are essentially 
linear copolymers which are highly branch chained and highly cross-linked 
with polyalkenyl polyether, e.g. about 1% of a polyalkyl ether of sucrose 
having an average of about 5.8 allyl groups for each molecule of sucrose. 
The preparation of this class of cross-linked carboxylic polymers is 
described in U.S. Pat. No. 2,798,053, the disclosure of which is 
incorporated by reference. Further detailed information on the Carbopol 
900 series resins is available from B. F. Goodrich, see, for example, the 
B. F. Goodrich catalog GC-67, Carbopol (Registered Trademark) Water 
Soluble Resins. 
In general, these thickening resins are preferably copolymers of a water 
dispersible copolymer of an alpha-beta monoethylenically unsaturated lower 
aliphatic carboxylic acid cross-linked with a polyether of a polyol 
selected from oligo saccharides, reduced derivatives thereof in which the 
carbonyl group is converted to an alcohol group and pentaerythritol, the 
hydroxyl groups of the polyol which are modified being etherified with 
allyl groups, there being preferably at least two such allyl groups per 
molecule. Other useful contemplated polymeric thickening agents are water 
soluble ionic polymers such as sulfonated polymers and complexes thereof 
with an amine containing copolymer. 
More recently, B. F. Goodrich has introduced the Carbopol (Registered 
Trademark) 600 series resin. These are high molecular weight, non-linear 
moderate branched chain polyacrylic acid cross-linked with polyalkenyl 
ether. In addition to the non-linear or branched nature of these resins, 
they are also believed to be more highly cross-linked than the 900 series 
resins and have molecular weights between about 1,000,000 and 4,000,000. 
Most especially useful of the Carbopol 600 series resins is Carbopol 614 
which is the most chlorine bleach stable of this class of thickening 
resins. Carbopol (Registered Trademark) 614 is also highly stable in the 
high alkalinity environment of the preferred liquid automatic dishwasher 
detergent compositions and is also highly stable to any anticipated 
storage temperature conditions from below freezing to elevated 
temperatures as high as 120.degree. F., preferably 140.degree. F., and 
especially 160.degree. F., for periods of as long as several days to 
several weeks or months or longer. 
While the most favorable results have now been achieved with Carbopol 614 
moderate branched chain polyacrylic resin, other branched cross-linked 
polycarboxylate-type thickening agents can also be used in the 
compositions of this invention. As used herein "polycarboxylate-type" 
refers to water-soluble carboxyvinyl polymers of alpha, beta 
monoethylenically unsaturated lower aliphatic carboxylic acids, which may 
be linear or non-linear, and are exemplified by 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 or 
their salts, esters or amides with each other or with one or more other 
ethylenically unsaturated monomers, such as, for example, styrene, maleic 
acid, maleic anhydride, 2-hydroxethylacrylate, acrylonitrile, vinyl 
acetate, ethylene, propylene, and the like, and which have molecular 
weights of from about 500,000 to 10,000,000 and are cross-linked or 
interpolymerized with a multi-vinyl or multi-allylic functionalized 
cross-linking agent, especially with a polyhydric compound. It is fully 
contemplated within the scope of this invention that mixtures of the 
Carbopol 900 Series and the Carbopol 600 Series can be employed in the 
formulations. 
These homopolymers or copolymers are characterized by their high molecular 
weight, in the range of from about 500,000, especially from about 
1,000,000 to 4,000,000, and by their water solubility, generally at least 
to an extent of up to about 5% by weight, or more, in water at 25.degree. 
C. 
The thickening agents are used in their 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 monomer mixture 
to be polymerized of known chemical cross-linking monomeric agents, 
typically polyunsaturated (e.g. diethylenically unsaturated) monomers, 
such as, for example, divinylbenzene, divinylether of diethylene glycol, 
N,N'-methylenebisacrylamide, polyalkenylpolyethers (such as described 
above), and the like. Typically, amounts of cross-linking agent to be 
incorporated in the final polymer may range from about 0.01 to about 5 
percent, preferably from about 0.05 to about 2 percent, and especially, 
preferably form about 0.1 to about 1.5 percent, by weight of cross-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 or non-linear polymeric 
compound while maintaining the cross-linked polymer at least water 
dispersible and highly water-swellable in an ionic aqueous medium. 
It is 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 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 in water or inhibit or prevent the uncoiling of the 
polymer molecules in the presence of the ionic aqueous system. 
The amount of at least one high molecular weight, cross-linked polymeric 
acid or other high molecular weight, hydrophilic cross-linked 
polycarboxylate thickening agent used to impart the desired rheological 
property of linear viscoelasticity will generally be in the range of from 
about 0.1 to 3.0%, preferably from about 0.1 to 2.5%, 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 polymeric thickening agents contribute to the linear viscoelastic 
rheology of the invention compositions. As used herein, "linear 
viscoelastic "or" linear viscoelasticity" means that the elastic (storage) 
moduli (G') and the viscous (loss) moduli (G") are both substantially 
independent of strain, at least in an applied strain range of from 0-50%, 
and preferably over an applied strain range of from 0 to 80%. More 
specifically, a composition is 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 100 dynes/sq.cm., preferably at least 250 
dynes/sq.cm., and varies less than about 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 loss 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.delta.) 
is 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 shear strain.times.100. 
By 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 (loss) modulus G" is a measure of the amount of 
energy dissipated as heat when strain is applied. Therefore, a value of 
tan.delta., 
EQU 0.05&lt;tan .delta.&lt;1, 
preferably 
EQU 0.2&lt;tan .delta.&lt;0.8 
means that the compositions will retain sufficient energy when a stress or 
strain is 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 is tilted, thereby contributing to the physical (phase) 
stability of the formulation and the low bottle residue (low product loss 
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. 
In conjunction with the polycarboxylate polymeric thixotropic thickener in 
either phosphate or nonphosphate composition can be used a low molecular 
weight polymeric thixotropic thickener such as polyacrylic acid polymers 
and salts thereof. The polyacrylic acid polymers and salts thereof that 
can be used comprise water soluble low molecular weight polymers having 
the formula: 
##STR5## 
wherein the R.sub.1, R.sub.2 and R.sub.3 can be the same or different and 
can be hydrogen, C.sub.1 -C.sub.4 lower alkyl, or combinations thereof. 
The value of n is 5 to 1000, preferably, 10 to 500, and more preferably 20 
to 100. M represents hydrogen, or an alkali metal such as sodium or 
potassium. The preferred substituent for M is sodium. 
The preferred R.sub.1, R.sub.2 and R.sub.3 groups are hydrogen, methyl, 
ethyl and propyl. Preferred acrylic acid monomer is one where R.sub.1 to 
R.sub.3 are hydrogen, e.g. acrylic acid, or where R.sub.1 and R.sub.3 are 
hydrogen and R.sub.2 is methyl, e.g. methyl acrylic acid monomer. 
The degree of polymerization, i.e. the value of n, is generally determined 
by the limit compatible with the solubility of the polymer in water. The 
terminal or end groups of the polymer are not critical and can be H, OH, 
CH.sub.3 or a low molecular weight hydrocarbon. 
The low molecular, non-crosslinked polyacrylic acid polymers and salts 
thereof can have a molecular weight of 500 or 1,000 to 200,000, preferably 
1,500 to 50,000 and especially preferably 2,000 to 10,000. 
Specific polyacrylic acid polymers which can be used include the Acrysol 
LMW acrylic acid polymers from Rohm and Haas, such as the Acrysol LMW,45N, 
a neutralized sodium salt, which has a molecular weight of about 4,500 and 
Acrysol LMW-20NX, a neutralized sodium salt, which has a molecular weight 
of about 2,000. Other polyacrylic acid polymers or salts thereof that can 
be used are: Alcosperse 149, molecular weight 2000, Alcosperse 123, 
molecular weight 4500, Alcosperse 107, molecular weight 3000, Alcosperse 
124, molecular weight 2000, and Alcosperse 602N molecular weight 4500, all 
of which are available from Alco Chemical Corp. The low molecular weight 
acrylic acid polymers can, for example, have a molecular weight of about 
1,000 to 10,000. Another polyacrylic acid polymer that can be used is 
Alcosperse 110 (from Alco) which is a sodium salt of an organic 
polycarboxylate and which has a molecular weight of about 100,000. 
The above non-crosslinked polyacrylic acid polymers and salts thereof can 
be made using procedures known in the art, see for example U.S. Pat. No. 
4,203,858, herein incorporated by reference. 
Generally, the amounts of the non-crosslinked polyacrylic acid polymer or 
salt anti-spotting agent that can be used are in the range of from about 0 
to 12%, preferably from about 0.5 to 4%, especially preferably about 0.75 
to 3%. 
The amount of water contained in these compositions should, of course, be 
neither so high as to produce unduly low viscosity and high fluidity, nor 
so low as to produce unduly high viscosity and low flowability, 
thixotropic properties in either case being diminished or destroyed. Such 
amount is readily determined by routine experimentation in any particular 
instance, generally ranging from about 30 to 75 wt %, preferably about 35 
to 65 wt %. The water should also be preferably deionized or softened. 
The LADD products of the prior U.K. patent application GB No. 2,116,199A 
and GB No. 2,140,450 exhibit improved rheological properties as evaluated 
by testing product viscosity as a function of shear rate. The compositions 
exhibited higher viscosity at a low shear rate and lower viscosity at a 
high shear rate, the data indicating efficient fluidization and gelation 
well within the shear rates extant within the standard dishwasher machine. 
In practical terms, this means improved pouring and processing 
characteristics as well as less leaking in the machine dispenser-cup, 
compared to prior liquor or gel ADD products. For applied shear rates 
corresponding to 3 to 30 rpm, viscosities (Brookfield) correspondingly 
ranged from about 10,000 to 50,000 cps to about 3,000 to 7,000 cps, as 
measured at room temperature by means of an LVT Brookfield viscometer 
after 3 minutes using a No. 4 spindle. A shear rate of 7.4 sec-.sup.1 
corresponds to a spindle rpm of about 3. An approximate ten-fold increase 
in shear rate produces about a 3- to 9-fold reduction in viscosity. 
With prior ADD gels, the corresponding reduction in viscosity was only 
about two-fold. Moreover, with such compositions, the initial viscosity 
taken at about 3 rpm was only about 2,500 to 2,700 cps. The compositions 
of the assignee's prior invention thus exhibit threshold fluidizations at 
lower shear rates and of significantly greater extent in terms of 
incremental increases in shear rate versus incremental decrease in 
viscosity. This property of the LADD products of the prior invention is 
summarized in terms of a thixotropic index (TI) which is the ratio of the 
apparent viscosity at 3 rpm and at 30 rpm. The prior compositions have a 
TI of from 2 to 10. The LADD compositions tested exhibited substantial and 
quick return to prior quiescent state consistency when the shear force was 
discontinued. 
The present invention is based upon the discovery that the physical 
stability, i.e. resistance to phase separation, settling, etc., of the 
U.K. patent applications GB No. 2,116,199A and GB No. 2,140,450 and the 
U.S. Pat. No. 4,752,409 liquid aqueous ADD compositions can be 
significantly improved or not adversely affected while at the same time 
significantly increasing the apparent viscosity and improving the physical 
stability of the formulations and at lower cost, by adding to the 
composition a small amount of a fatty acid anion moiety such as a (RCOO--) 
wherein R is about C.sub.8 to about C.sub.24 such as a salt of a long 
chain fatty acid or a long chain fatty acid which can form an alkali metal 
salt of the fatty acid in situ in the composition. 
As an example of the improvement in rheological properties, it has been 
found that the viscosities at low shear rates, e.g. with a #4 spindle at a 
spindle rpm of about 3, apparent viscosities may often be increased from 
two- to three-fold with the incorporation of as little as 0.2% or less, 
e.g. 0.16%, of the fatty acid stabilizer. At the same time, the physical 
stability may be improved to such an extent that even after a long time, 
the compositions containing the fatty acid stabilizers do not undergo any 
visible phase separation. 
The preferred long chain fatty acids are the higher aliphatic fatty acids 
having from about 8 to about 24 carbon atoms, more preferably from about 
10 to 24 carbon atoms, and especially preferably from about 12 to 22 
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 and may contain substituted functional groups 
affixed to the aliphatic chain. 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, etc., or from synthetic sources available from industrial 
manufacturing processes. 
Thus, examples of the fatty acids which can be used as stabilizers include, 
for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, 
stearic acid, behenic acid, oleic acid, eicosanoic acid, tallow fatty 
acid, coco fatty acid, soya fatty acid, mixtures of these acids, etc. 
Behenic acid, stearic acid and mixed fatty acids are preferred. 
Salts such as metal or ammonium of the fatty acids can be used and are 
added directly to the composition or in the alternative are formed in situ 
from the fatty acid reacting with basic materials in the composition. 
Examples of alkali metal salts are lithium stearate, sodium stearate 
and/or potassium stearate. The alkali metal salts can be used alone in the 
phosphate compositions or in combination with a fatty acid or in 
combination with a polyvalent metal salt of the fatty acid, wherein the 
polyvalent metal salt of the fatty acid can be used alone or in 
combination with the fatty acid. 
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 alkali 
metal salts of the fatty acids are preferred fatty acid salts. 
The preferred polyvalent metals are the di- and trivalent metals of Groups 
IIA, IIB and IIIA, such as magnesium, calcium, aluminum and zinc, although 
other polyvalent metals including those of Groups IIIB, 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 into 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 taking into consideration the toxicity of the metal. 
For this purpose, the alkali metal and calcium and magnesium salts as well 
as stearic and behenic acid are especially higher preferred as generally 
safe food additives. Another distinct advantage of the use of the fatty 
acids as stabilizers is their lower cost as compared to the fatty acid 
metal salts. 
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. 
Naturally, for LADD compositions, as well as any other applications where 
the invention composition will or may come into contact with articles used 
for the handling, storage or serving of food products or which otherwise 
come into contact with or be consumed by people or animals, the use of the 
fatty acids as the stabilizing agent are of particular advantage because 
of their known low toxicity. For this purpose, the stearic acid and 
behenic acid are especially preferred as generally safe food additives. 
Another distinct advantage of the use of the fatty acids as stabilizers is 
their lower cost as compared to the fatty acid metal salts. 
Many of these fatty acids are commercially available. For example, the 
stearic acid and behenic acid are readily available. 
Mixed fatty acids, such as the naturally occurring acids, e.g. coco acid, 
as well as mixed fatty acids resulting from the commercial manufacturing 
process are also advantageously used as an inexpensive but effective 
source of long chain fatty acids. 
Generally, for compositions made with clay thickening agents however, 
amounts of the fatty acid stabilizing agents in the range of from about 
0.02 to 1%, preferably from about 0.06 to 0.8%, especially preferably from 
about 0.08 to 0.4%, provide the increase in apparent viscosity and the 
long term stability and absence of phase separation upon standing or 
during transport at both low and elevated temperatures as are required for 
a commercially acceptable product. 
Generally, however, amounts of the fatty acid or fatty acid salt 
stabilizing agents used in compositions made with polymeric thickening 
agents in the range of from about 0.02 to 2%, preferably 0.04 to 1%, more 
preferably from about 0.06 to 0.8%, especially preferably from about 0.08 
to 0.4%, provide a long term stability 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 about 
0.08-0.4 weight percent fatty acid salt and from about 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. 
Besides the fatty acid compounds carboxylic containing compounds such as 
polycarboxylic acids selected from the group consisting of adipic acid, 
azelaic acid and dimers and trimers of C.sub.18 to C.sub.20 unsaturated 
fatty acids such as Empol 1010, Empol 1018, Empol 1022, Empol 1024, Empol 
1040, Empol 1041 and Empol 1052 can be readily employed. 
The polycarboxylic acids that can be used in accordance with the present 
invention are the dimers and trimers of fatty acids, preferably the 
unsaturated fatty acids. The C.sub.8 to C.sub.22 fatty acids can be used. 
The dimers and trimers are preferably from the C.sub.16 -C.sub.20 
unsaturated fatty acids. The most preferred dimer and trimer acids are 
prepared from C.sub.18 unsaturated fatty acids, e.g. oleic acid and 
linoleic acid. 
The monovalent metal salts and the polyvalent metal salts of the dimers and 
trimers of the fatty acids, preferably the unsaturated fatty acids, can 
also be used in the present invention. The ammonium salts of the dimers 
and trimers of the unsaturated fatty acids can also be used in the present 
invention. 
A particular preferred group of polycarboxylic acids are the dimers and 
trimers of C.sub.18 unsaturated fatty acids that are available from Emery 
Industries, Division of National Distillers & Chemical Corp. These 
materials are available under the following trade names: 
______________________________________ 
Dimers Trimers Polybasic Acid 
______________________________________ 
Empol 1010 Empol 1040 
Empol 1052 
Empol 1018 Empol 1041 
Empol 1022 
Empol 1024 
______________________________________ 
The Empol 1040 and Empol 1052 are of particular interest. The Empol 1040 
Trimer Acid typically contains 80% polybasic acids, 18% dibasic acid and 
2% monobasic acid. The Empol 1052 Polybasic Acid contains 63% tribasic, 
tetrabasic and higher acids with about 34% dibasic acid. 
In addition to the dimer and trimer acids, the adipic and azelaic 
polycarboxylic acids and their mono metal and ammonium salts and 
polyvalent metal salts can also be used as stabilizing agents in the 
present invention. 
When the polycarboxylic acid is used in the LADD composition, it is 
neutralized "in situ" in the LADD composition to form the metal salt of 
the polycarboxylic acid. 
The monovalent metal salts that can be used are the Group IA metals of the 
Periodic Table Of The Elements, and in particular the alkali metal salts. 
The Group IA monovalent metals that are included are Li, Na, K, Rb, Cs and 
Fr. The preferred monovalent alkali metals are Na and K. 
The chlorine bleach compounds are, however, not to be used with the 
ammonium fatty acid salt stabilizers, since they are not compatible with 
chlorine bleach compounds. In the formulations in which the ammonium fatty 
acid stabilizers are used, the chlorine bleach can be omitted or an 
oxidizing enzyme can be substituted for the chlorine bleach. 
The enzymes can be used in amounts of about 0.5 to 3%, preferably about 0.5 
to 2.0% and more preferably about 0.5 to 1.5%. 
The preferred polyvalent metals are the polyvalent metals of Groups IIA, 
IIB and IIIA, such as magnesium, calcium, aluminum and zinc, although 
other polyvalent metals, including those of Groups IIIB, IVA, VA, VIA, 
VIIA, 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. The 
use of the polycarboxylic acids and metal salts thereof as the stabilizing 
agent are of particular advantage because of their known low toxicity. For 
this purpose, the polycarboxylic acids per se, e.g. dimers and trimers of 
C.sub.18 unsaturated fatty acid, the monovalent Na and K and the NH.sub.4 
salts and the polyvalent Ca and Mg metal salts thereof are especially 
preferred as generally safe because of their known low toxicity and/or 
known use as food additives. Another distinct advantage of the use of the 
polycarboxylic acids and metal salts thereof as stabilizers is their lower 
cost as compared to the polyvalent fatty acid metal salts. 
Many of the polycarboxylic acids and metal salts thereof are commercially 
available. For example, the dimers and trimers of the C.sub.18 unsaturated 
fatty acids, and adipic and azelaic acids are readily available. 
The amount of the polycarboxylic acids and metal salts thereof stabilizers 
used to achieve the desired enhancement of physical stability and apparent 
viscosity increase will depend on such factors as the nature of the 
polycarboxylic acids and metal salts thereof, the nature and amount of the 
thixotropic agent, detergent active compound, inorganic salts, especially 
TPP, other LADD ingredients, as well as the anticipated storage and 
shipping conditions. 
Generally, however, amounts of the polycarboxylic acids or metal salts 
thereof stabilizing agents in the range of from about 0.001 to 1.0%, for 
example 0.01 to 1.0%, preferably from about 0.01 to 0.2%, especially 
preferably from about 0.05 to 0.2%, provide the increase in apparent 
viscosity and the long term stability and absence of phase separation upon 
standing or during transport at both low and elevated temperatures as are 
required for a commercially acceptable product. 
The redox enzymes, also known as oxidoreductase enzymes, can be used in the 
present invention. These enzymes catalyze chemical reductions and 
oxidations and are involved in the chemical breakdown of foods remaining 
on the dishware and utensils that are to be cleaned. Suitable enzymes that 
can be used are glucose oxidase, catalase and lipoxidase enzymes. 
There can also be used in the formulations of the present invention 
proteolytic and amylolytic enzymes and mixtures thereof. The proteolytic 
enzymes suitable for use include liquid, powder or slurry enzyme 
preparations. Suitable liquid enzyme preparations include "Alcalase" and 
"Esperase" sold by Novo Industrie, Copenhagen, Denmark. Liquid protease 
and liquid amylase enzymes can be used. Suitable alpha-amylase liquid 
enzyme preparations are those sold by Novo Industries and Gist-Brocades 
under the trade names "Termamyl" and "Maxamyl", respectively. 
From the examples to be given below, it will be seen that, depending on the 
amounts, proportions and types of physical stabilizers and thixotropic 
agents, the addition of the fatty acids or polycarboxylic acid in the case 
of clay compositions not only increases physical stability but also 
provides a simultaneous increase in apparent viscosity. Ratios of fatty 
acid to thixotropic agent in the range of from about 0.08 to 0.4 weight 
percent fatty acid and from about 0.1 to 2.5 weight percent thixotropic 
agent are usually sufficient to provide these simultaneous benefits and, 
therefore, the use of these ingredients in these rations is most 
preferred. 
One preferred method for mixing the ingredients of the LADD phosphate 
formulations or non phosphate containing compositions containing a clay 
thickening agent involves first forming a mixture of the water, foam 
suppressor (when employed), detergent, physical stabilizer or salt thereof 
such as aluminum stearate and optionally stearic acid and thixotropic 
agent, e.g. clay. These ingredients are mixed together under high shear 
conditions, preferably starting at room temperature, to form a uniform 
dispersion and passed through an in-line homogenizer. To this premixed 
portion the remaining ingredients are introduced under mixing conditions. 
For instance, the required amount of the premix is introduced into a mixer 
and thereafter the remaining ingredients are added, with mixing, either 
sequentially or simultaneously. Preferably, the ingredients are added 
sequentially, although it is not necessary to complete the addition of all 
of one ingredient before beginning to add the next ingredient. 
Furthermore, one or more of the ingredients can be divided into portions 
and added at different times. Good results have been obtained by adding 
the remaining ingredients in the following sequence: sodium hydroxide, 
alkali metal carbonate, sodium silicate, alkali metal tripolyphosphate 
(hydrated), alkali metal tripolyphosphate (anhydrous or up to 5% water), 
bleach (preferably, sodium hypochlorite) and sodium hydroxide. The final 
composition is passed through an in-line homogenizer. 
The compositions containing the polymeric thixotropic thickeners can be 
made forming a solution of the polymeric thixotropic thickener either at 
room temperature or at elevated temperatures. An aqueous premix dispersion 
of the surfactant, foam depressant and fatty acid or salt thereof is 
formed. The solution of the polymeric thixotropic thickener and the premix 
dispersion are mixed together to which is added with stirring at room 
temperature or at elevated temperatures the following ingredients in 
sequential order: alkali metal hydroxide, alkali metal carbonate, alkali 
metal silicate, alkali metal phosphates and bleach. The density of the 
formed composition is about 1.28 grams/ml to about 1.42 grams/ml, wherein 
the density of the composition can be varied by the amount of air 
incorporated into the composition during the shear mixing process. The 
composition has a Brookfield viscosity at room temperature after 24 hours 
after 3 minutes with a #4 spindle at a spindle rpm of 3 of about 4,000 cps 
to about 60,000 cps. 
In order to achieve the desired benefit from the fatty acid or fatty acid 
salt stabilizer for compositions made with polymeric thickening agent 
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 fatty 
acid or fatty acid salt and other surface active ingredients, it is 
usually necessary to heat the emulsion (or preheat the water) to an 
elevated temperature. For example, for stearic acid having a melting point 
of 68.degree.-69.degree. C., a temperature in the range of between 
50.degree. C. and 70.degree. C. will be used. For lauric acid 
(m.p.=47.degree. C.) an elevated temperature of about 35.degree. to 
50.degree. C. 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 droplets 
throughout the composition. 
In contrast, as will be shown in the examples which follow, for the 
polymeric compositions if the fatty acid is simply post-added at ambient 
temperature, the composition is not linear viscoelastic as defined above 
and the stability of the composition is clearly inferior. 
In addition to the detergent active surfactant, foam inhibitor, 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 
values of at least about 9.5, preferably at least about 11 to as high as 
14, generally up to about 13 or more, and, when added to the aqueous wash 
bath at a typical concentration level of about 10 grams per liter, will 
provide a pH in the wash bath of at least about 9, preferably at least 
about 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 (on an active basis) of from about 0.5 to 8%, 
preferably from 1 to 6%, more preferably from about 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. 
Other alkali metal salts, such as alkali metal carbonate may also be 
present in the phosphate compositions in minor amounts, for example from 0 
to 10%, preferably 0 to 6%, by weight of the composition. 
Other conventional ingredients may be included in these compositions in 
small amounts, generally less than about 3 weight percent, such as 
perfume, hydrotropic agents such as the sodium benzene sulphonate, toluene 
sulphonates, xylene sulphonate and cumene sulphonate, preservatives, 
dyestuffs and pigments and the like, all of course being stable to 
chlorine bleach compound and high alkalinity (properties of all the 
components). Especially preferred for coloring are the chlorinated 
phthalocyanines and polysulphides of aluminosilicate which provide, 
respectively, pleasing green and blue tints. TiO.sub.2 may be employed for 
whitening or neutralizing off-shades. 
In accordance with an especially preferred embodiment, the thickened linear 
viscoelastic aqueous automatic dishwasher detergent composition of this 
invention includes, on a weight basis: 
(a) 10 to 35%, preferably 10 to 20%, detergent builder such as potassium 
tripolyphosphate, or sodium tripolyphosphate and mixtures thereof; 
(b) 0 to 15%, preferably 8 to 12%, alkali metal silicate; 
(c) 0 to 6%, preferably 1.0 to 4%, alkali metal hydroxide; 
(d) 0 to 3%, preferably 0.1 to 3%, chlorine bleach stable, 
water-dispersible, low-foaming organic detergent active material, 
preferably non-soap anionic detergent; 
(e) 0 to 1.5%, preferably 0.05 to 1.5% chlorine bleach stable foam 
depressant; 
(f) chlorine bleach compound in an amount to provide about 0.2 to 4%, 
preferably 0.8 to 1.6%, of available chlorine; 
(g) a non-linear, water-dispersible polyacrylic acid thickening agent 
comprising at least one high molecular weight crosslinked hydrophilic 
polycarboxylate having a molecular weight of from 750,000 to 4,000,000, 
preferably 800,000 to 3,000,000, in an amount to provide a linear 
viscoelasticity to the formulation, preferably from about 0.2 to 2%, 
especially preferably from about 0.4 to 1.5%, more preferably from about 
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 
(i) 0 to 10%, preferably 1 to 8%, especially 2 to 6% of a non-crosslinked 
polyacrylic acid having a molecular weight in the range of from about 800 
to 200,000, preferably 1000 to 150,000, especially 2,000 to 100,000; and 
(j) balance water, preferably from about 30 to 75%, more preferably from 
about 35 to 65%, wherein the water is bound to the polymeric thickening 
agent. The compositions may also have an amount of air incorporated 
therein such that the bulk density of the composition is from about 1.28 
to 1.42 g/cc, preferably from about 1.32 to 1.42 g/cc, more preferably 
from about 1.35 to 1.40 g/cc. 
In accordance with another especially preferred embodiment, the present 
invention provides a thickened aqueous automatic dishwasher detergent 
composition which includes, on a weight basis: 
(a) 5 to 35% alkali metal tripolyphosphate; 
(b) 2.5 to 30% alkali metal silicate; 
(c) 0 to 9% alkali metal carbonate; 
(d) 2 to 10% alkali metal hydroxide; 
(e) 0.1 to 5% chlorine bleach stable, water dispersible organic detergent 
active material; 
(f) 0 to 5% chlorine bleach stable foam depressant; 
(g) chlorine bleach compound in an amount to provide about 0.2 to 4% of 
available chlorine; 
(h) 0.1 to 10% of inorganic colloid-forming clay; 
(i) a metal salt of a long chain fatty acid in an amount effective to 
increase the physical stability of the composition; and 
(j) balance water; 
the total amount of (b) sodium silicate, (c) alkali metal carbonate and (d) 
alkali metal hydroxide providing a pH sufficiently high such that when the 
composition is diluted in an aqueous wash bath to provide a concentration 
of 10 grams per liter the pH of the aqueous wash bath becomes at least 
11.2. When the composition is added to an aqueous wash bath to provide a 
concentration of 10 grams of composition per liter of wash bath the pH of 
the wash bath becomes at least 11.2, preferably at least 11.5, such as 
from 11.5 to 13.5, preferably 11.5 to 12.5. By operating at these higher 
than normal alkalinity levels the cleaning performance is improved and at 
the same time the rheological properties, and particularly, physical 
stability, are also improved. Furthermore, in the preferred embodiment in 
which a chlorine bleach compound is included in the LADD composition, the 
additional benefit of reduction of loss of active chlorine is also 
obtained. 
Therefore, in accordance with an especially preferred embodiment of this 
invention, the high alkalinity is achieved in a phosphate free, 
clay-thickened, fatty acid salt stabilized, chlorine-bleach containing 
liquid automatic dishwasher detergent composition wherein the alkaline 
compounds include, on an active basis, based on the total composition, 
from about 3 to 25 weight percent alkali metal silicate, from about 1.0 to 
4.5 weight percent alkali metal hydroxide 0 to 22 wt. % of a low molecular 
weight non-crosslinked polyacrylic polymer, and from 0 to about 8 weight 
percent alkali metal carbonate, with the provision that the total amount 
of alkali metal hydroxide and alkali metal carbonate is no more than about 
9 weight percent and the total amount of alkali metal silicate and alkali 
metal carbonate is not more than about 30 weight percent, the pH of the 
composition being at least 12.8, and the pH of 1 liter of aqueous wash 
bath containing 10 grams of the composition being at least 11.5. 
Although the alkali metal of the alkaline compounds: silicate, carbonate 
and hydroxide, is preferably sodium, the corresponding potassium 
compounds, or mixtures of sodium and potassium compounds, or mixtures of 
sodium and potassium compounds can also be used. 
A preferred example of the present invention provides for a composition 
comprising the following ingredients on a weight basis unless specified 
otherwise: 
(a) 5 to 35% of at least one alkali metal tripolyphosphate; 
(b) 0 to 20% sodium silicate; 
(c) 0 to 9% alkali metal carbonate; 
(d) 0 to 5% chlorine bleach stable, water dispersible organic detergent 
active material; 
(e) 0 to 5% chlorine bleach stable foam depressant; 
(f) chlorine bleach compound in an amount to provide about 0.2 to 4% of 
available chlorine; 
(g) thixotropic thickener in an amount sufficient to provide the 
composition with a thixotropy index of about 2.0 to 25, more preferably 
2.0 to 10; 
(h) alkali metal hydroxide, as necessary, to adjust the pH to a sufficient 
level; 
(i) a long chain fatty acid or its salt as a physical stabilizer in an 
amount effective to increase the physical stability of the composition; 
(j) optionally, a fragrance in an amount effective to provide a scent and 
to avoid destruction of the desired thixotropy and physical stability of 
the composition; 
(k) water in the amount effective to avoid destruction of the desired 
thixotropic properties; and 
(l) optionally, air in an amount ranging from about 2% to 10% by volume, 
effective to provide the composition with a bulk specific gravity of about 
1.20 to about 1.35. 
According to the process of the present invention, a phase stable, 
thixotropic liquid automatic dishwashing detergent composition is produced 
by optionally, entraining air into the composition so as to effect an 
equilibration of the specific gravities of the bulk and liquid phases of 
the composition. 
It has been found that concentrated dispersions which contain both liquid 
and solid phases, such as the liquid automatic dishwashing detergent 
compositions, can be stabilized by dispersing an appropriate amount of air 
in the form of micron size bubbles throughout the liquid phase of the 
composition. It has also been found that the air can be dispersed and 
stabilized as bubbles throughout the liquid phase by employing a 
stabilizing system categorized generally as, physical stabilizers, foam 
depressants or defoamers and surfactants. While not wishing to be bound by 
any theory to explain how the stabilizing system and air interact in the 
liquid automatic dishwashing detergent compositions, it is believed that 
these three components interact at the air/liquid interface such that the 
hydrophobic groups of the three components are oriented towards the air 
bubbles while the hydrophilic groups are oriented towards the aqueous 
phase. The hydrophilic groups, in turn, interact with the solid particles 
of the suspension either through hydrogen bonding or through electrostatic 
interaction. In other words, the liquid/air interface consists of the 
three components of the stabilizing system and solid particulates giving 
rise to a liquid crystalline type structure for the interphase. 
According to the preferred process of present invention, a three-part 
stabilizing system produces a highly stable liquid automatic dishwashing 
detergent composition by stabilizing the micron size air bubbles 
throughout the composition such that the bulk specific gravity of the 
liquid automatic dishwashing detergent composition is about equal to the 
specific gravity of the liquid phase only, in the liquid automatic 
dishwashing detergent composition. It is at this condition that the liquid 
automatic dishwashing detergent composition exhibits high stability, i.e., 
there is little or no tendency for phase separation due to density 
variations in the composition. 
In order to effectively disperse the air throughout the liquid automatic 
dishwasher detergent composition it has been discovered that the size of 
the entrained air bubbles must be greater than the size of any dispersed 
solid particles. The bubble size generally may vary from about 5 to about 
80 microns and preferably from about 20 to about 60 microns. Air bubble 
size can be controlled, generally, by varying the blade tip speed of the 
dispersers or agitators during the mixing operations. It has also been 
found that air entrainment from about 2 to about 10% by volume produces 
phase stable compositions, the preferred range being from about 4.0 to 
about 9.0% by volume, the most preferred range being from about 6.5 to 
about 8.5% by volume. 
As best seen in the drawing, the process of the present invention for a 
clay containing composition can be performed in a blending system 
incorporating predispersion vessel 2, premix vessel 4, main batch vessel 
6, homogenizers 8, 10, 19 and 21 heat exchanger 12, in-line mixer 14 and 
storage tank 16. 
A predispersion mix comprising the stabilizing system is prepared in a 
predispersion vessel 2 then fed to the premix vessel 4 through line 18 and 
homogenizer 19 via pump 20 where it is added to a thixotropic thickener to 
prepare a thickener premix. The thickener premix is then fed to the main 
batch vessel 6 through line 22 and homogenizer 21 via pump 24 wherein the 
remaining components of the liquid automatic detergent composition are 
added. 
The detergent composition from vessel 6 is then fed through homogenizers 8 
and 10 and thereafter cooled in the exchanger 12. If a scented dishwasher 
detergent composition is desired, the cooled product is fed through an 
in-line static mixer 14 where a fragrance is added. The liquid dishwasher 
detergent composition is then fed to tank 16 where it is stored. 
In one of the preferred process of the present invention, a liquid 
detergent predispersion mix is first prepared including the selected 
physical stabilizer, foam inhibitor and surfactant components of the 
liquid automatic dishwasher detergent composition as well as a portion of 
the total liquid automatic dishwasher detergent water content. Depending 
on the selection of stabilizing components, one or more of the components 
may initially be solid, requiring either the addition of heat to form a 
melt or the addition of water to form a solution or emulsion. The amount 
of water added to the predispersion mix should be limited so as to 
maintain a highly viscous mix. The predispersion mix is subjected to 
mixing, preferably high-shear mixing, for about 5 minutes during which 
time the predispersion mix temperature may exceed 100.degree. F. 
High-shear mixing, as used herein, is defined in terms of shear rates and 
is dependent on a number of variables, the most important being the 
configuration of the mixing vessel and the impeller tip speed. For 
example, the pre-dispersion mix is preferably high-shear mixed in a Myers 
HSD.TM. using an 8 inch impeller at an impeller speed of about 4500 
ft/min. The "high shear" rate at this condition is approximated to be of 
the order of 100 sec.sup.-1. 
The predispersion mixing step may be accomplished in other conventional 
milling or high-shear mixing equipment for example, roller mills, colloid 
mills and Premier mills. 
The predispersion mixing step is followed by a second mixing step during 
which a thixotropic thickener, e.g., clay, and an additional portion of 
the total liquid automatic dishwasher detergent water content is added to 
the predispersion mix to form a thickener premix. The thickener premix is 
preferably subjected to low shear mixing for about 20 minutes during which 
time the thickener is hydrated, deagglomerated and dispersed throughout 
the thickener premix. Low-shear mixing, as used herein, is also defined in 
terms of shear rates and as discussed above with respect to high-shear is 
a function of a number of variables including mixing vessel configuration 
and impeller tip speed. Equipment suitable for low-shear mixing of the 
thickener premix includes conventional paddle blade mixers wherein average 
shear rates are on the order of about 10 sec.sup.-1. 
The amount of water added to each of the first two mixing steps is somewhat 
arbitrary within the limits of the total water content of the final liquid 
automatic dishwasher detergent composition. However, it has been found 
that the amount of water added to the predispersion mix should not be so 
high as to produce an unduly low viscosity and high fluidity mixture since 
such a condition would adversely affect the mixing, particularly under 
high-shear mixing conditions. 
The second mixing step is followed by a main batch mixing step during which 
the thickener premix, the balance of the total liquid automatic 
dishwashing detergent water content and other desired liquid automatic 
dishwashing detergent ingredients are mixed preferably under high-shear 
conditions, to form a main batch composition. During this mixing step the 
remaining liquid automatic dishwashing detergent ingredients are 
preferably added. Shear rates on the order of 100 sec.sup.-1 are achieved 
during this mixing step. The remaining liquid automatic dishwashing 
detergent ingredients which may be added include the following: sodium 
hydroxide, sodium carbonate, silicates, alkali metal tripolyphosphates, 
chlorine bleach compounds, and other suitable ingredients which comprise 
the desired liquid automatic dishwashing detergent composition. 
Equipment suitable for the high-shear mixing operation include roller 
mills, colloid mills, Premier mills and Myers HSD, among others. 
The main batch composition from the high-shear mixing step is then 
subjected to a series of coarse and fine homogenizing steps until the 
solid and liquid phases of the liquid automatic dishwashing detergent 
composition are thoroughly homogenized. The homogenizing steps are carried 
out under high-shear conditions wherein shear rates on the order of about 
10.sup.4 sec.sup.-1 are achieved. The homogenizing steps are complete when 
the bulk specific gravity of the liquid automatic dishwashing detergent 
composition is about equal to the specific gravity of the liquid automatic 
dishwashing detergent liquid phase only. Homogenization of the liquid 
automatic dishwashing detergent composition may be accomplished in 
conventional homogenizers, such as high speed Dispax.TM., available from 
IKA-Works, Inc. 
According to the invention, the liquid automatic dishwashing detergent 
composition is preferably subjected to mixing at a sufficient rate which 
ensures air entrainment in an amount of about 2% to about 10% by volume, 
preferably 4 to 9% and most preferably 6.5 to 8.5% by volume in the 
dishwasher composition. In the preferred embodiment of the invention, the 
air is entrained in the composition during the light-shear mixing of the 
dishwasher detergent ingredients. However, according to the invention, air 
may be introduced to the composition at any point in the process by 
conventional means to produce a phase stable composition. 
The presence of a bulk specific gravity about equal to the liquid phase 
specific gravity is indicative of air entrainment and high product 
stability. Generally, it has been found that specific gravities within the 
range of 1.20 to 1.35 provide a phase stable liquid automatic dishwashing 
detergent composition, the preferred specific gravity being within the 
range from about 1.26 to about 1.32. 
In an alternate embodiment of the present invention, the liquid and solid 
components of the thixotropic detergent composition, as described above, 
are added sequentially to a high-shear mixer while continuously mixing, 
until all desired ingredients are included. Thereafter, the detergent 
composition is subjected to high-shear mixing for about 15 minutes to 
produce a homogeneous air entrained thixotropic detergent composition. The 
high-shear mixing step is complete when the bulk specific gravity of the 
composition is about equal to the liquid phase specific gravity. 
While the process of the invention has been described in terms of preferred 
ingredients and amounts, it would be understood to those skilled in the 
art that a highly stable thixotropic detergent composition could be 
achieved in the absence of one or more of the ingredients by appropriate 
adjustment of the remaining ingredients. For example, it may be possible 
to formulate a phase stable composition in the absence of a foam 
depressant by minimizing the surfactant level and increasing the amount of 
physical stabilizer in the composition. 
The liquid ADD compositions of this invention are readily employed in known 
manner for washing dishes, other kitchen utensils and the like in an 
automatic dishwasher, provided with a suitable detergent dispenser, in an 
aqueous wash bath containing an effective amount of the composition. 
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 examples. 
All amounts and proportions referred to herein are by weight of the 
composition unless otherwise indicated. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION 
EXAMPLE 1 
In order to demonstrate the effect of the fatty acid stabilizer a liquid 
ADD formulation is prepared as follows: 
______________________________________ 
Percent Percent 
______________________________________ 
Deionized water 41.10 
Caustic soda solution (50% NaOH) 
2.20 
Sodium carbonate, anhydrous 
5.00 
Sodium silicate, 47.5% 15.74 
solution of Na.sub.2 O:SiO.sub.2 ratio of 1:2.4 
Sodium TPP (substantially anhydrous - i.e. 
12.00 
0.5%, especially 3%, moisture) 
(Thermphos NW) 
Sodium TPP (hexahydrate) 12.00 
(Thermphos N hexa) 
______________________________________ 
The mixture is cooled at 25.degree.-30.degree. C. and agitation maintained 
throughout, and the following ingredients at room temperature are added 
thereto: 
______________________________________ 
Percent 
______________________________________ 
Sodium hypochlorite 9.00 
solution (11% available chlorine) 
Monostearyl phosphate 0.16 
DOWFAX 3B-2 (45% Na monodecyl/ 
0.80 
didecyl diphenyl oxide 
disulphonate aqueous solution) 
Physical stabilizer X 
(fatty acid or fatty acid salt) 
Pharmagel H 2.00 
______________________________________ 
There are three formulations prepared in which X=0%, X=0.10% calcium 
stearate and X=0.16% behenic acid. 
The monostearyl phosphate foam depressant (when employed) and Dowfax 3B-2 
detergent compound fatty acid stabilizer are added to the mixture just 
before the Pharmagel H thickener. 
The Run 1 is a control formulation which includes the monostearyl phosphate 
anti-foam agent, but which does not contain a fatty acid stabilizer. 
The Run 2 is a formulation of Run 1 to which has been added to a calcium 
stearate stabilizing agent of application Ser. No. 744,754. 
The Run 3 is a formulation of the present invention in which behenic acid 
(CH.sub.3 (CH.sub.2).sub.20 COOH is used as the stabilizing agent and the 
monostearyl phosphate antifoam agent is optionally omitted. 
Each of the resulting liquid ADD formulation as shown in the Table are 
measured for apparent viscosity at 3 and 30 rpm. The results obtained are 
also shown in Table. 
From the data reported in the Table the following conclusions are reached: 
The incorporation of 0.1% calcium stearate in a 2.0% Pharmagel H containing 
formula Run 3 (invention) leads to a significant increase in the apparent 
viscosity as compared to both the control Runs 1 and 2. 
______________________________________ 
BROOK LVT 
VISCOSITY 
(KCPS) (1) 
RUN FORMULATION 3 RPM 30 RPM 
______________________________________ 
1 H.sub.2 O = 41.10% 18 4.9 
Monostearyl Phosphate = 0.16% 
Stabilizer = 0% 
Pharmagel H = 2.0% 
2 H.sub.2 O = 41.0% 24 3.8 
Monostearyl Phosphate = 0.16% 
Ca Stearate = 0.1% 
Pharmagel H = 2.0% 
3 H.sub.2 O = 41.0% 87 10.2 
Monostearyl Phosphate = 0% 
Behenic Acid = 0.16% 
Pharmagel H = 2.0% 
______________________________________ 
(1) Measured with spindle 4 after three minutes at 3 and 30 rpm on 24 hou 
old samples. 
EXAMPLE 2 
The following gel-like thixotropic liquid ADD is prepared following the 
same general procedure as in Example 1. 
______________________________________ 
Ingredient Amount (A.1.) Wt % 
______________________________________ 
Sodium silicate (47.5% 
7.48 
solution of Na.sub.2 O:SiO.sub.2 
ratio of 1:2.4) 
Monostearyl phosphate 
0.16 
Dowfax 3B-2 0.36 
Thermphos NW 12.0 
Thermphos N hexa 12.0 
Behenic Acid 0.1 
Sodium carbonate, anhydrous 
5.0 
Caustic soda solution (50% NaOH) 
3.1 
Pharmagel H 1.5 
Sodium hypochlorite solution (11%) 
1.0 
Water balance 
______________________________________ 
Minor amounts of perfume, color, etc. can also be added to formulation. 
EXAMPLE 3 
The following gel-like thixotropic liquid ADD was prepared following the 
same general procedure as in Example 1. 
______________________________________ 
Ingredient Amount (A.I.) Wt % 
______________________________________ 
Sodium silicate (47.5% 
7.48 
solution of Na.sub.2 O:SiO.sub.2 
ratio of 1:2.4) 
Monostearyl phosphate 
0.16 
Dowfax 3B-2 0.36 
Thermphos NW 12.0 
Thermphos N hexa hydrate 
12.0 
Stearic Acid 0.2 
Sodium carbonate, anhydrous 
5.0 
Caustic soda solution (50% NaOH) 
3.1 
Pharmagel H 1.0 
Sodium hypochlorite solution (11%) 
1.0 
Water balance 
______________________________________ 
Minor amounts of perfume, color, etc. can also be added to formulation. 
EXAMPLES 4-9 
The following general procedure was used to prepare thixotropic polymeric 
compositions. 
Step 1: The Carbopol polymer in the acid form was dispersed in distilled 
water at ambient temperature using Premier blade mixer under medium shear 
condition. The complete dispersion of polymer was evaluated by visual 
inspection i.e. absence of Macroscopic gel particles or fish eyes. The 
above dispersion was neutralized slowly by adding 50% NaOH, with constant 
mixing. The neutralization step is exothermic and temperature increases in 
the range from 110.degree. F.-130.degree. F. The neutralization resulted 
in liquid translucent gel phase. 
Step 2: Preparation of Predispersion: 
An emulsion consisting formula level of Dowfax 3B2, Stearic Acid or sodium 
stearate and LPKN158 was prepared by the following procedure. 
To a 250 ml. pyrex beaker was added small quantity of water and these above 
components were added, and the resulting heterogeneous mixture was heated 
to a temperature above 160.degree. F. until an opaque emulsion was 
obtained. This emulsion mixture is viscous and solidifies when cooled at 
ambient temperature. 
Step 3: The predispersion obtained in step 2 was added to the gel of Step 1 
with constant shearing. The temperature of the gel and predispersion were 
about 110.degree. F. and 140.degree. F. temperature. Excessive shear was 
usually avoided to minimize air incorporation in the resulting Gel. 
To the above formed gel phase, the following ingredients were added with 
stirring sequentially i.e. color, soda ash, silicate, phosphates, followed 
by bleach. When the low molecular weight polymer Acrysol LWN45-N or the 
silicone defoamer were incorporated in the formula, they were added after 
bleach addition. In some cases the batch was cooled to 80.degree. F. prior 
the addition of bleach. 
EXAMPLE 4 
______________________________________ 
4-A 4-B 4-C 4-E 4-F 
______________________________________ 
LPKn-158 
0.16 0.16 0.16 0.16 0.16 
Dowfax 0.6 0.6 0.6 0.6 0.6 
3B2 (45%) 
Sodium 0.03 0.03 -- -- 0.03 
Stearate 
NaOH 2.4 2.4 2.4 2.4 2.4 
(50%) 
Sodium 13.74 13.74 13.74 
13.74 
25 
Silicate 
(47.5%) 
Na.sub.2 CO.sub.3 
7 7 7 7 7 
Thermphos 
12 -- -- -- -- 
NH 
Thermphos 
12 24 24 24 24 
NW 
NaOCL 7.62 7.62 7.62 7.62 7.62 
11% 
Carbopol 
0.1 0.1 0.2 0.2 0.01 
940 
Water balance balance balance 
balance 
balance 
Viscosity 
5320 11420 14320 9100 14,580 
standing 
cps.sup.1 
Viscosity 
4220 11660 17360 10560 10,900 
shaken cps 
______________________________________ 
.sup.1 Standing means 1-2 days in a plastic bottle or container 
EXAMPLE 5 
______________________________________ 
5-A 5-B 5-C 5-D 5-E 
______________________________________ 
LPKn-158 
0.16 0.16 0.16 
0.16 
0.16 
Dowfax 0.8 0.8 0.8 0.8 0.8 
3B2 (45%) 
Stearic 0.1 0.1 0.1 0.1 0.1 
Acid.sup.2 
NaOH 2.4 2.4 2.4 2.4 2.4 
(50%) 
Na.sub.2 Co.sub.3 
4 4 4 4 4 
Sodium 24 24 24 24 24 
Silicate 
(47.5%) 
TTP Hexa- 
12 -- -- -- -- 
hydrate 
(FMC 
Chemical 
Co.) 
TTP Oxy- 
12 22 22 22 22 
anhydrous 
(Oxy 
Chemical 
Co.) 
Zeolite 1.0 1.0 -- 1.0 1.0 
NaOCL 7 7 7 7 7 
11% 
Acrysol 2 2 2 2 2 
LMW45N 
Carbopol 
0.1 0.2 0.2 0.2 0.2 
940 
Potassium 
-- -- -- -- 5 
Carbonate 
Water balance balance balance 
balance 
balance 
Density 1.30 1.29 1.31 
1.17 
1.22 
g/ml 
Viscosity 
10,400 16,100 14,100 8,400 9,450 
standing 
cps 
______________________________________ 
5-F 5-G 5-H 5-I 5-J 
______________________________________ 
LPKn-158 
0.16 0.16 0.16 
0.16 
0.16 
Dowfax 0.8 0.8 0.8 0.8 0.8 
3B2 (45%) 
Stearic 0.1 0.1 0.1 0.1 0.1 
Acid.sub.2 
NaOH 2.4 2.4 2.4 2.4 2.4 
(50%) 
Na.sub.2 CO.sub.3 
-- 5 5 5 5 
Sodium 24 24 24 24 24 
Silicate 
(47.5%) 
TTP Hexa- 
-- 24 24 24 24 
hydrate 
(FM Chem- 
ical Co.) 
TTP Oxy- 
22 -- -- -- -- 
anhydrous 
(Oxy 
Chemical 
Co.) 
Zeolite 1.0 1.0 1.0 1.0 1.0 
NaOCI 7 7 7 7 7 
(11%) 
Acrysol 2 -- 2 2 2 
LMW45N 
Carbopol 
0.2 0.2 0.3 0.5 0.1 
940 
Potassium 
-- -- -- -- -- 
Carbonate 
Water balance balance balance 
balance 
balance 
Density 1.22 1.24 1.25 
1.22 
1.30 
g/ml 
Viscosity 
7,750 5,900 7,750 13,700 3,480 
standing 
cps 
______________________________________ 
.sup.2 Triple pressed stearic acid 
EXAMPLE 6 
______________________________________ 
6-A 6-B 6-C 6-D 6-E 
______________________________________ 
Carbopol 
1.0 1.0 0.5 0.75 
0.75 
941 
NaOH 2.4 2.4 2.4 2.4 2.4 
(50%) 
LPKN-158 
0.16 0.16 0.16 
0.16 
0.16 
Stearic 0.1 0.1 0.1 0.1 0.1 
Acid 
Dowfax 0.8 0.8 0.8 0.8 0.8 
3B2 (45%) 
Sodium 1 6.8 21 21 21 
Silicate 
(47.5%) 
TKPP (te- 
10 15 15 15 20 
trapotas- 
sium pyro- 
phosphate) 
TTP Hexa- 
17 12 12 12 7 
hydrate 
Acrysol -- 2 2 2 2 
LMW 45N 
Potassium 
6.78 -- -- -- -- 
Silicate 
NaOCI 9.10 9.10 9.10 
9.10 
7.5 
(11%) 
Water balance balance balance 
balance 
balance 
Viscosity 
8,100 10,400 6,200 8,000 10,000 
standing 
cps 
Density -- 1.31 -- 1.29 
-- 
g/ml 
______________________________________ 
EXAMPLE 7 
______________________________________ 
7-A 7-B 7-C 7-D 7-E 7-F 
______________________________________ 
Sodium 17.24 24 20 30 30 30 
Silicate 
(47.5% 
solution 
of 
Na.sub.2 O-- 
SiO.sub.2 
ratio of 
1:2.4) 
LPKN- 0.16 0.16 0.16 
0.16 
0.16 
0.16 
158 
Dowfax 0.8 0.8 0.8 0.6 0.6 0.8 
3B-2 
(45%) 
Therm- 12.0 12 10.5 -- -- -- 
phos NW 
Therm- 12.0 12 10.5 -- -- 
phos N 
Hexa- 
hydrate 
Stearic 
0.1 0.1 0.05 
0.1 0.1 0.1 
Acid 
Na.sub.2 Co.sub.3 
5.0 5.0 4 4 4 4 
NaOH 2.4 2.4 2.4 2.4 2.4 2.4 
(50%) 
Carbopol 
0.3 0.1 0.2 
1.0 1.0 0.8 
940 
Acrysol 
-- -- 2.0 2.5 2.5 -- 
LMW 
45N 
NaOCI 7.0 7.0 7 7 7 7 
11% 
Antifoam 
-- 0.05 0.05 
-- -- -- 
T-H 
(Silicone 
Defoamer) 
Water 43 36.39 42.3 24.2 29.2 
31.7 
Density 
1.35 1.39 1.34 
1.29 
1.17 
1.22 
g/ml 
Viscosity 
thick -- 7,800 7,950 10,100 9,900 
cps 
______________________________________ 
EXAMPLE 8 
______________________________________ 
8A 8B 8C 8D 
______________________________________ 
Distilled Water 
41.08% 41.03% 40.93% 
40.83% 
Carbopol 940 0.05 0.10 0.20 0.30 
Carbopol 941 -- -- -- -- 
Sodium Hydroxide 
2.40 2.40 2.40 2.40 
(50%) 
LPKN (158%) 3.20 3.20 3.20 3.20 
Dowfax 3B2 (45%) 
0.80 0.80 0.80 0.80 
Stearic Acid 0.10 0.10 0.10 0.10 
Soda Ash 5.00 5.00 5.00 5.00 
PO Silicate 17.24 17.24 17.24 
17.24 
FMC Hexahydrate 
-- -- -- -- 
TPP 
Oxy Anhydrous TPP 
21.00 21.00 21.00 
21.00 
TKPP -- -- -- -- 
NaOCI (14.03%) 
7.13 7.13 7.13 7.13 
Acrysol LWM 45-N 
2.00 2.00 2.00 2.00 
Density g/ml 1.29 1.29 1.27 1.25 
Viscosity cps 
6950 8050 10200 13800 
Foam Test avg. rpm 
X X X 25.0 
Cup Leakage (%) 
30.2 24.5 38.6 19.6 
______________________________________ 
8E 8F 8G 
______________________________________ 
Distilled Water 
40.73% 33.65% 33.65% 
Carbopol 940 0.40 -- -- 
Carbopol 941 -- 0.75 0.75 
Sodium Hydroxide 
2.40 2.40 2.40 
(50%) 
LPKN (158%) 3.20 3.20 3.20 
Dowfax 3B2 (45%) 
0.80 0.80 0.80 
Stearic Acid 0.10 0.10 0.10 
Soda Ash 5.00 -- -- 
PO Silicate 17.24 21.00 21.00 
FMC Hexahydrate 
-- 12.00 7.00 
TPP 
Oxy Anhydrous TPP 
21.00 -- -- 
TKPP -- 15.00 20.00 
Bleach (14.03%) 
7.13 9.10 9.10 
Acrysol LWM 45-N 
2.00 2.00 2.00 
Density g/ml 1.24 1.29 1.27 
Viscosity cps 
16200 8000 7350 
Foam Test avg. rpm 
23.6 X X 
Cup Leakage (%) 
19.2 12.1 14.1 
______________________________________ 
EXAMPLE 9 
______________________________________ 
9A 9B 9C 9D 
______________________________________ 
Distilled Water 
26.9076 26.9676 27.0076 
27.0076 
Carbopol 940 
0.10 0.20 0.10 -- 
Caustic 6.38 6.38 6.38 6.38 
Graphtol Green 
0.0024 0.0024 0.0024 
0.0024 
Dye 
LPKn-158 0.16 -- 0.16 0.16 
Stearic Acid 
0.12 0.12 -- 0.12 
Dowfax 3B2 
1.00 1.00 1.00 1.00 
(45%) 
Distilled Water 
3.50 3.50 3.50 3.50 
Sodium 4.00 4.00 4.00 4.00 
Carbonate 
Sodium Silicate 
20.83 20.83 20.83 20.83 
(47.5%) 
TPP Anhydrous 
22.00 22.00 22.00 22.00 
NaOCI (11%) 
14.80 14.80 14.80 14.80 
Dow Corning 
0.20 0.20 0.20 0.20 
1400 
Density g/ml 
1.32 1.36 1.37 1.23 
Viscosity cps 
15600 Off Scale 
8350 9200 
Chlorine level 
1.623 1.628 1.641 
1.638 
(%) 
Chlorine level 
1.457 1.439 1.493 
1.638 
(%) 
Aged 1 month - 
Slight (1 m) top 
Slight Stable 
RT top sep sep top sep 
Chlorine level 
0.992 0.987 1.025 
0.987 
(%) 
Aged 1 month - 
(1 ml) top sep 
Stable Top sep 
Sit Bottom 
100.degree. F. 
Bottle Residue 
Doses Left At - 
7% level 1.24 1.24 0.87 1.21 
15% level 2.20 2.41 1.07 1.54 
20% level 2.51 2.59 1.21 1.48 
______________________________________ 
9E 9F 9G 
______________________________________ 
Distilled Water 
26.9576 27.2376 27.1876 
Carbopol 940 0.05 0.05 0.10 
Caustic 6.38 6.38 6.38 
Graphtol Green Dye 
0.0024 0.0024 0.0024 
LPKn-158 0.16 -- -- 
Stearic Acid 0.12 -- -- 
Dowfax 3B2 (45%) 
1.00 1.00 1.00 
Distilled Water 
3.50 3.50 3.50 
Sodium Carbonate 
4.00 4.00 4.00 
Sodium Silicate (47.5%) 
20.83 20.83 20.83 
TPP Anhydrous 22.00 22.00 22.00 
NaOCI (11%) 14.80 14.80 14.80 
Dow Corning 1400 
0.20 0.20 0.20 
Density g/ml 1.26 1.29 1.34 
Viscosity cps 12200 5800 6800 
Chlorine level (%) 
1.991 1.986 1.999 
Chlorine level (%) 
1.790 1.810 1.840 
Aged 1 month - RT 
Stable Bottom sep 
Top sep 
Chlorine level (%) 
1.190 1.320 1.280 
Aged 1 month - 100.degree. F. 
Stable Bottom sep 
Top sep 
Bottle Residue 
Doses Left At - 
7% level 2.09 0.91 1.03 
15% level 2.31 0.89 1.27 
20% level 2.10 0.94 1.31 
______________________________________ 
EXAMPLE 10 
Thixotropic aqueous stearate formulation (10A-10I) were prepared by adding 
Graphtol green to water and Carbopol was then sprinkled or sived into 
heated water (100.degree.-110.degree. F.) while stirring slowly so that 
there was no vortex generated and no lumping formed during stirring. 
Sufficient stirring was allowed so that the Carbopol polymer was 
completely swelled or hydrated. Sodium hydroxide was slowly added to the 
hydrated polymer while stirring and allowed to neutralize the polymer 
mixture. Liquid silicate was then added, followed by slow addition of 
phosphates slowly while stirring and mixing. Sodium polyacrylate liquid 
was then added. LPKN 158 and stearic acid melted in Dowfax and water was 
added to the mixture and stirred for about 5 minutes to uniformly mix all 
the ingredients. The batch was cooled to ambient temperature and sodium 
hypochlorite added and then stirred for 5 minutes. 
EXAMPLE 10 
______________________________________ 
10A 10B 10C 
______________________________________ 
Deionized Water 
41.427 41.427 41.427 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous- 
13.000 13.000 13.000 
Estimate 
Potassium TPP- 3.000 5.000 7.000 
Anhydrous-Estimate 
Sodium Polyacrylate - 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKn 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Total Formula Amounts 
100.000 100.000 100.000 
Physical Properties 
Density 1.24 1.3 1.29 
pH (1% Solution) 
Viscosity, 1 WK - Ambient 
7200 7225 6700 
Aged, 1 Month - Ambient 
7880 7000 6420 
Temp. 
Aged, 1 Month - 100.degree. F. 
8140 7000 6720 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, 
1.16 1.21 1.19 
Initial 
Aged, 1 Month - Ambient 
1.09 1.12 1.07 
Temp. 
Aged, 1 Month - 100.degree. F. 
0.95 1 0.98 
Temp. 
Aged, 4 Months - Ambient 
Temp. 
Laboratory Performance 
Cup Leakage (Current 
53 (36) 53 (36) 64 (36) 
PADD), % 
Rel. Foam Generation 
25 (48) 36 (48) 19 (48) 
(PADD CONTROL), to 
Soft Water 
Egg Cleaning % (PADD 
7 (7) 6 (7) 14 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
78 (49) 25 (49) 76 (49) 
(PADD CONTROL), 300 
ppm, 120.degree. F. 
Filming Rating (PADD 
2.4 (2.8) 1.6 (2.8) 2.6 (2.8) 
Control), 
300 ppm, 120.degree. F. 
Spotting Rating (PADD 
2.4 (3.0) 2.6 (3.0) 1.6 (3.0) 
Control), 
300 ppm, 120.degree. F. 
______________________________________ 
10D 10E 10F 
______________________________________ 
Deionized Water 
37.427 37.427 37.427 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
15.000 13.000 11.000 
Potassium TPP-Anhydrous 
5.000 7.000 9.000 
Sodium Polyacrylate 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Density 1.09 1.26 1.25 
pH (1% solution) 
Viscosity, 1 WK - Ambient 
10450 9275 8050 
Aged, 1 Month - Ambient 
11060 9260 8480 
Temp. 
Aged, 1 Month - 100.degree. F. 
10720 9520 9420 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, 
1.24 1.19 1.17 
Initial 
Aged, 1 Month - Ambient 
1.22 1.07 1.03 
Temp. 
Aged, 1 Month - 100.degree. F. 
0.97 1.1 0.94 
Temp. 
Aged, 4 Months - Ambient 
Temp. 
Cup Leakage (Current 
41 (36) 52 (36) 55 (36) 
PADD), % 
Rel. Foam Generation 
22 (46) 25 (48) 22 (48) 
(PADD Control) to Soft 
Water 
Egg Cleaning, % (PADD 
9 (7) 7 (7) 7 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
82 (49) 82 (49) 86 (49) 
(PADD Control), 
300 ppm, 120.degree. F. 
Filming Rating (PADD 
1.8 (2.8) 2.3 (2.8) 2.4 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.3 (3.0) 1.6 (3.0) 1.5 (3.0) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
10G 10H 10I 
______________________________________ 
Deionized Water 
41.867 41.867 41.867 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
15.000 13.000 11.000 
Potassium TPP-An- 
5.000 7.000 9.000 
hydrous Estimate 
Sodium Polyacrylate - 
0.000 0.000 0.000 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKn 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Density 1.26 1.27 1.29 
pH (1% Solution) 
Viscosity, 1 WK - Ambient 
9050 7350 7100 
Aged, 1 Month - Ambient 
9420 8820 7600 
Temp. 
Aged, 1 Month - 100.degree. F. 
9300 8140 7900 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, 
1.18 1.42 1.17 
Initial 
Aged, 1 Month - Ambient 
1.1 1.14 1.09 
Temp. 
Aged, 1 Month - 100.degree. F. 
1.07 0.99 0.96 
Temp. 
Aged, 4 Months - Ambient 
Temp. 
Cup Leakage (Current 
52 (36) 57 (36) 60 (36) 
PADD), % 
Rel. Foam Generation 
31 (48) 33 (48) 33 (48) 
(PADD Control) 
to Soft Water 
Egg Cleaning, % (PADD 
18 (7) 15 (7) 11 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
34 (49) 43 (49) 72 (49) 
(PADD Control), 300 
ppm, 120.degree. F. 
Filming Rating (PADD 
3.3 (2.8) 3 (2.8) 3 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.5 (3.0) 2.6 (3.0) 2.8 (3.0) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
EXAMPLE 11 
Thixotropic aqueous stearate formulations (11A-11F) were prepared according 
to the procedure of Example 10. 
______________________________________ 
11A 11B 11C 
______________________________________ 
Deionized Water 39.327 39.327 39.327 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 1.000 1.000 1.000 
Sodium Hydroxide (50%) 
6.380 6.380 6.380 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
12.000 10.000 8.000 
Potassium TPP-Anhydrous 
4.000 6.000 8.000 
Sodium Polyacrylate - 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 5016 
0.120 0.120 0.120 
Sodium Hypochlorite (12%) 
11.100 11.100 11.100 
Density 1.2 1.32 1.29 
pH (1% Solution) 11.54 11.54 11.48 
Viscosity, 1 WK - Ambient 
7550 6150 6450 
Aged, 1 Month - Ambient Temp. 
9200 8950 13400 
Aged, 1 Month - 100.degree. F. Temp. 
9300 9000 11900 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, Initial 
1.19 1.22 1.19 
Aged, 1 Month - Ambient Temp. 
1.17 1.18 1.15 
Aged, 1 Month - 100.degree. F. Temp. 
1.05 1.03 1.04 
Aged, 4 Months - Ambient Temp. 
Cup Leakage (Current PADD), 
32 (28) 35 (28) 20 (28) 
Rel. Foam Generation (PADD 
Control) to Soft Water 
Egg Cleaning, % (PADD 
29 (10) 21 (10) 17 (10) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % (PADD 
73 (68) 77 (68) 56 (68) 
Control), 300 ppm, 120.degree. F. 
Filming Rating (PADD 
2 (2.8) 
2 (2.8) 
1.1 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
2.1 (2.5) 
2.3 (2.5) 
2 (2.5) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
11D 11E 11F 
______________________________________ 
Deionized Water 35.347 35.347 35.347 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 1.000 1.000 1.000 
Sodium Hydroxide (50%) 
6.380 6.380 6.380 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
15.000 12.500 10.000 
Potassium TPP-Anhydrous- 
5.000 7.500 10.000 
Estimate 
Sodium Polyacrylate - 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 5016 
0.100 0.100 0.100 
Sodium Hypochlorite (12%) 
11.100 11.100 11.100 
Density 1.3 1.34 1.33 
pH (1% Solution) 11.43 11.54 11.57 
Viscosity, 1 WK - Ambient 
6950 4760 6100 
Aged, 1 Month - Ambient Temp. 
12400 10700 11200 
Aged, 1 Month - 100.degree. F. Temp. 
11200 10600 14200 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, Initial 
1.05 1.19 1.08 
Aged, 1 Month - Ambient Temp. 
1.01 1.12 1.21 
Aged, 1 Month - 100.degree. F. Temp. 
0.93 0.92 0.92 
Aged, 4 Months - Ambient Temp. 
Cup Leakage (Current PADD), 
20 (28) 29 (28) 24 (28) 
Rel. Foam Generation (PADD 
Control) to Soft Water 
Egg Cleaning, % (PADD 
23 (10) 25 (10) 23 (10) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % (PADD 
64 (68) 75 (68) 30 (68) 
Control), 300 ppm, 120.degree. F. 
Filming Rating (PADD 
1.5 (2.8) 
1.6 (2.8) 
1.8 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.8 (2.5) 
2.1 (2.5) 
2.8 (2.5) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
EXAMPLE 12 
Thixotropic aqueous stearate formulations (12A-12F) were prepared according 
to the procedure of Example 10. 
______________________________________ 
12A 12B 12C 
______________________________________ 
Deionized Water 
32.68 32.68 32.68 
Graphtol Green 0.00 0.00 10.00 
Carbapol 614 0.00 0.00 0.00 
Carbopol 940 0.50 0.00 0.50 
Sodium Hydroxide (50%) 
6.38 6.38 6.38 
Sodium Silicate (47.5%) 
20.83 20.83 20.83 
Sodium TPP-Anhydrous 
22.45 22.45 22.45 
Sodium Polyacrylate - 
LMW 45N (45%) 5.00 5.00 5.00 
Dowfax 3B2 (45%) 
0.80 0.80 0.80 
LPKN 158 - Defoamer 
0.16 0.16 0.16 
Stearic Acid - Witco 
0.10 0.10 0.10 
Fragrance - BBA 
0.00 0.00 0.05 
Highlights 
Sodium Hypochlorite 
11.10 11.10 11.10 
(12%) 
Solids Content, % 
39.55 39.55 39.50 
Density 1.37 1.36 1.34 
pH (1% Solution) 
11.60 11.59 11.59 
Viscosity, 1 WK, - 
14800.00 15000.00 13800.00 
Ambient 
Aged, 1 Month - Ambient 
14300.00 14000.00 13900.00 
Temp. 
Aged, 1 Month - 100.degree. F. 
12900.00 12000.00 12700.00 
Temp. 
Aged, 2 Months - Ambient 
14400.00 11700.00 11600.00 
Temp. 
Aged, 2 Months - 100.degree. F. 
13400.00 11300.00 13200.00 
Temp. 
Aged, 4 Months - Ambient 
12000.00 11200.00 11000.00 
Temp. 
Aged, 4 Months - 100.degree. F. 
10000.00 8700.00 8950.00 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
4 Months - Ambient Temp. 
4 Months - 100.degree. F. Temp. 
OK (0) OK (0) OK 
(Few 
Drops) 
Available Chlorine %, 
1.32 1.33 1.30 
Initial 
Aged, 1 Month - Ambient 
1.24 1.26 1.19 
Temp. 
Aged, 2 Months - Ambient 
1.20 1.20 1.10 
Temp. 
Aged, 4 Months - Ambient 
0.96 1.05 0.92 
Temp. 
Bottle Residue (PADD 
Control) % 
Aged, 1 Month - 
5.7 (6.2) 
7.1 (6.2) 
5.1 (6.2) 
Method A 
Aged, 1 Month - 
2.7 (5.5) 
3.4 (5.5) 
2.5 (5.5) 
Method B 
Aged, 2 Months - 
10.9 (9.4) 
12.4 (9.4) 
8.0 (9.4) 
Method A 
Aged, 2 Months - 
4.8 (7.5) 
6.5 (4.5) 
5.5 (7.5) 
Method B 
Aged, 4 Months - 
4.8 (16.4) 
4.8 (16.4) 
4.9 (16.4) 
Method A 
Aged, 4 Months - 
2.6 (9.1) 
3.3 (9.1) 
2.3 (9.1) 
Method B 
Av. Bottle Res. Redu. (4 
Month) 
68% (A), 69% (B) 
Cup Leakage (Current 
18 (24) 15 (24) 20 (24) 
PADD), % 
Rel. Foam Generation 
29.00 24.00 19.00 
(PADD Control) 
to Soft Water 
Egg Cleaning, % (PADD 
36 (16) 33 (16) 39 (16) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
90 (90) 90 (90) 90 (90) 
(PADD Control), 300 
ppm, 120.degree. F. 
Filming Rating (PADD 
2 (3) 1.9 (3) 1.9 (3) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.4 (2.6) 
1.0 (2.6) 
1.3 (2.6) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
12D 12E 12F 
______________________________________ 
Deionized Water 
32.63 32.58 32.58 
Graphtol Green 0.00 0.00 0.00 
Carbopol 614 0.50 0.00 0.50 
Carbopol 940 0.00 0.50 0.00 
Sodium Hydroxide (50%) 
6.38 6.38 6.38 
Sodium Silicate (47.5%) 
20.83 20.83 20.83 
Sodium TPP-Anhydrous 
22.45 22.45 22.45 
Sodium Polyacrylate - 
LMW 45N (45%) 5.00 5.00 5.00 
Dowfax 3B2 (45%) 
0.80 0.80 0.80 
LPKN 158 - Defoamer 
0.16 0.16 0.16 
Stearic Acid - Witco 
0.10 0.10 0.10 
Fragrance - BBR 
0.05 0.10 0.10 
Highlights 
Sodium Hypochlorite 
11.10 11.10 11.10 
(12%) 
Solids Content, % 
39.50 39.45 39.45 
Density 1.37 1.36 1.31 
pH (1% solution) 
11.67 11.68 11.65 
Viscosity, 1 WK - Ambient 
13400.00 12800.00 13200.00 
Aged, 1 Month - Ambient 
13680.00 11000.00 12700.00 
Temp. 
Aged, 1 Month - 100.degree. F. 
8720.00 10940.00 10570.00 
Temp. 
Aged, 2 Months - Ambient 
12000.00 12700.00 13200.00 
Temp. 
Aged, 2 Months - 100.degree. F. 
10140.00 10560.00 10650.00 
Temp. 
Aged, 4 Months - Ambient 
11800.00 11200.00 11300.00 
Temp. 
Aged, 4 Months - 100.degree. F. 
11800.00 11600.00 10100.00 
Temp. 
Stability (Separation), 
OK (Few OK (0) OK (Few 
4 Month - Ambient Temp. 
Drops) Drops) 
4 Months - 100.degree. F. Temp. 
OK (0) OK (Few OK (Top 
Drops) 
Available Chlorine %, 
1.30 1.27 1.32 
initial 
Aged, 1 Month - Ambient 
1.23 1.24 1.19 
Temp. 
Aged, 2 Months - Ambient 
1.08 1.02 1.05 
Temp. 
Aged, 4 Months - Ambient 
0.96 0.94 0.94 
Temp. 
Bottle Residue 
(PADD control) % 
Aged, 1 Month - 
9.9 (6.2) 6.3 (6.2) 6.9 (6.2) 
Method A 
Aged, 1 Month - 
6.1 (5.5) 2.9 (5.5) 4.8 (5.5) 
Method B 
Aged, 2 Months - 
6.2 (9.4) 8.6 (9.4) 5.3 (9.4) 
Method A 
Aged, 2 Months - 
3.6 (7.5) 1.8 (7.5) 3.6 (7.5) 
Method B 
Aged, 4 Months - 
5.3 (16.4) 
6.9 (16.4) 
4.8 (16.4) 
Method A 
Aged, 4 Months - 
3.6 (9.1) 2.6 (9.1) 2.2 (9.1) 
Method B 
Av. Bottle Res. Redu. (4 
Month) 68% (A), 69% (B) 
Cup Leakage (Current 
16 (24) 23 (24) 21 (24) 
PADD), % 
Rel. Foam Generation 
-- -- -- 
(PADD Control) 
to Soft Water 
Egg Cleaning, % (PADD 
-- -- -- 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
-- -- -- 
(PADD Control), 
300 ppm, 120.degree. F. 
Filming Rating (PADD 
-- -- -- 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
-- -- -- 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
EXAMPLE 13 
Thixotropic aqueous stearate formulations (13-A-13-I) were prepared 
according to the procedure of Example 10. 
______________________________________ 
13A 13B 13C 
______________________________________ 
Deionized Water 
41.427 41.427 41.427 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
13.000 11.000 9.000 
Potassium TPP-Anhydrous 
3.000 5.000 7.000 
Sodium Polyacrylate - 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Solids Content, % 
Density 1.24 1.3 1.29 
pH (1% Solulion) 
Viscosity, 1 WK - Ambient 
7200 7225 6700 
Aged, 1 Month - Ambient 
7880 7000 6420 
Temp. 
Aged, 1 Month - 100.degree. F. 
8140 7000 6720 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK(0) 
Available Chlorine %, 
1.16 1.21 1.19 
Initial 
Aged, 1 Month - Ambient 
1.09 1.12 1.07 
Temp. 
Aged, 1 Month - 100.degree. F. 
0.95 1 0.98 
Temp. 
Av. Bottle Res. Redu. (4 
Month) 68% (A), 69% (B) 
Cup Leakage (Current 
53 (36) 53 (36) 64 (36) 
PADD), % 
Rel. Foam Generation 
25 (48) 36 (48) 19 (48) 
(PADD Control) to Soft 
Water 
Egg Cleaning, % (PADD 
7 (7) 6 (7) 14 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
78 (49) 25 (49) 76 (49) 
(PADD Control), 
300 ppm, 120.degree. F. 
Filming Rating (PADD 
2.4 (2.8) 1.6 (2.8) 2.6 (2.8) 
control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
2.4 (3.0) 2.6 (3.0) 1.6 (3.0) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
13D 13E 13F 
______________________________________ 
Deionized Water 
37.427 37.427 37.427 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
15.000 13.000 11.000 
Potassium TPP-Anhydrous 
5.000 5.000 5.000 
Sodium Polyacrylate - 
4.440 4.440 4.440 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Density 1.09 1.26 1.25 
Viscosity, 1 WK - Ambient 
10450 9275 8050 
Aged, 1 Month - Ambient 
11060 9260 8480 
Temp. 
Aged, 1 Month - 100.degree. F. 
10720 9520 9420 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, 
1.24 1.19 1.17 
Initial 
Aged, 1 Month - Ambient 
1.22 1.07 1.03 
Temp. 
Aged, 1 Month - 100.degree. F. 
0.97 1.1 0.94 
Temp. 
Av. Bottle Res. Redu. (4 
month) 68% (A), 69% (B) 
Cup Leakage (Current 
41 (36) 52 (36) 55 (36) 
PADD), % 
Rel. Foam Generation 
22 (48) 25 (48) 22 (48) 
(PADD Control) to Soft 
Water 
Egg Cleaning, % (PADD 
9 (7) 7 (7) 7 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
82 (49) 82 (49) 86 (49) 
(PADD Control), 
300 ppm, 120.degree. F. 
Filming Rating (PADD 
1.8 (2.8) 2.3 (2.8) 2.4 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.3 (3.0) 1.6 (3.0) 1.5 (3.0) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
13G 13H 13I 
______________________________________ 
Deionized Water 
41.867 41.867 41.867 
Graphtol Green 0.003 0.003 0.003 
Carbopol 614 0.800 0.800 0.800 
Sodium Hydroxide (50%) 
4.500 4.500 4.500 
Sodium Silicate (47.5%) 
20.830 20.830 20.830 
Sodium TPP-Anhydrous 
15.000 13.000 11.000 
Potassium TPP-Anhydrous 
5.000 7.000 9.000 
Sodium Polyacrylate - 
0.000 0.000 0.000 
LMW 45N (45%) 
Dowfax 3B2 (45%) 
0.600 0.600 0.600 
LPKN 158 - Defoamer 
0.200 0.200 0.200 
Stearic Acid - Hystrene 
0.100 0.100 0.100 
5016 
Sodium Hypochlorite 
11.100 11.100 11.100 
(12%) 
Density 1.26 1.27 1.29 
Viscosity, 1 WK - Ambient 
9050 7350 7100 
Aged, 1 Month - Ambient 
9420 8820 7600 
Temp. 
Aged, 1 Month - 100.degree. F. 
9300 8140 7900 
Temp. 
Stability (Separation), 
OK (0) OK (0) OK (0) 
1 Month - Ambient Temp. 
1 Month - 100.degree. F. Temp. 
OK (0) OK (0) OK (0) 
Available Chlorine %, 
1.18 1.42 1.17 
Initial 
Aged, 1 Month - Ambient 
1.1 1.14 1.09 
Temp. 
Aged, 1 Month - 100.degree. F. 
1.07 0.99 0.96 
Temp. 
Av. Bottle Res. Redu. (4 
Month) 68% (A), 69% (B) 
Cup Leakage (Current 
52 (36) 57 (36) 60 (36) 
PADD), % 
Rel. Foam Generation 
31 (48) 33 (48) 33 (48) 
(PADD Control) to Soft 
Water 
Egg Cleaning, % (PADD 
18 (7) 15 (7) 11 (7) 
Control), 300 ppm, 120.degree. F. 
Oatmeal Cleaning, % 
34 (49) 43 (49) 72 (49) 
(PADD Control), 
300 ppm, 120.degree. F. 
Filming Rating (PADD 
3.3 (2.8) 3 (2.8) 3 (2.8) 
Control), 300 ppm, 120.degree. F. 
Spotting Rating (PADD 
1.5 (3.0) 2.6 (3.0) 2.8 (3.0) 
Control), 300 ppm, 120.degree. F. 
______________________________________ 
EXAMPLE 14 
In order to demonstrate the effect of the polycarboxylic acid stabilizer, 
polycarboxylic acid containing liquid ADD formulation were prepared as 
follows: 
Using a high shear mixer the following premix was made: 
______________________________________ 
Part I - Premix 
Grams 
______________________________________ 
Deionized water at room temperature 
442.8 
Glass H.sup.1 10.0 
Adipic Acid 10.66 
LPKN-158 Defoamer.sup.2 
341.2 
Dowfax 3B2.sup.3 85.3 
______________________________________ 
187.5 grams of the premix was transferred into a low shear mixer and the 
following ingredients were added with stirring to the 187.5 grams of the 
premix. 
______________________________________ 
Part II Post Added Ingredients 
Grams 
______________________________________ 
Deionized water 717.8 
Color 0.024 
NaOH 50% (solution in water) 
48.0 
Sodium Silicate 47.5% of Na.sub.2 O Si O.sub.2 
139.8 
Ratio of 1:2.4 
Thermphos N hexa 240.0 
Thermphos NW 240.0 
Sodium Hypochlorite Solution 
152.2 
(11% available chlorine) 
______________________________________ 
.sup.1 Glass H is a linear polyphosphate containing approximately 26 
phosphate groups. 
.sup.2 Dowfax 3B2 is a 45% Na monodecyl/didecyl diphenyl oxide 
disulphonate aqueous solution. 
.sup.3 LPKN158 is an antifoam agent comprising a 2:1 molar mixture of 
mono,di-(C.sub.16 -C.sub.18) alkyl esters of phosphoric acid. 
The initial Brookfield viscosity of the composition using a #4 spindle at 
20 rpm at room temperature was 4,340 cps. The Brookfield viscosity at 
100.degree. F. after three weeks was 4,200 cps and after three weeks at 
room temperature was 4,680 cps. The formulation was tested for percentage 
of the formulation which settled from solution after standing both at 
100.degree. F. and at room temperature for three weeks. Both samples 
exhibited 0.0% settling. 
EXAMPLE 15 
A formulation was prepared according to the procedure of Example 14 except 
that azelaic acid was used instead of adipic acid. The Brookfield 
viscosity at room temperature using a #4 spindle at 20 rpm was 5400 cps 
and was 4260 at 100.degree. F. after three weeks and 5640 cps after three 
weeks at room temperature. The percent settling after three weeks both at 
room temperature and 100.degree. F. was 0.0%. 
EXAMPLE 16 
In order to demonstrate the effect of the metal salt stabilizer liquid ADD 
formulations are prepared with varying amounts of stabilizer and 
thixotropic thickener, 
______________________________________ 
Deionized water 41.10 + y - x 
Caustic soda solution 
2.20 
(50% NaOH) 
Sodium carbonate, 5.00 
anhydrous 
Sodium silicate, 47.5% 
15.74 
solution of Na.sub.2 O:SiO.sub.2 
ratio of 1:2.4 
Sodium TPP (substantially 
12.00 
anhydrous-i.e. 0-5%, 
especially 3%, moisture) 
(Thermphos NW) 
Sodium TPP (hexahydrate) 
12.00 
(Thermphos N hexa) 
______________________________________ 
The mixture is cooled at 25.degree.-30.degree. C. and agitation maintained 
throughout, and the following ingredients at room temperature are added 
thereto: 
______________________________________ 
Sodium hypochlorite 9.00 
solution (11% available chlorine) 
Monostearylphosphate 0.16 
DOWFAX 3B-2 (45% Na 0.8 
monodecyl/diphenyl oxide 
disulphonate-aqueous solution) 
Physical stabilizer x 
(fatty acid salt) 
Gel White H 2.00 - y 
______________________________________ 
The monostearyl phosphate foam depressant and Dowfax 3B-2 detergent active 
compound are added to the mixture just before the aluminum tristearate or 
zinc distearate stabilizer or right before the Gel White H thickener. 
Each of the resulting liquid ADD formulations as show in the following 
Table are measured for density, apparent viscosity at 3 and 30 rpm, and 
physical stability (phase-separation) on standing and in a shipping test. 
The results are also shown in Table I. 
From the data reported in the Table, the following conclusions are reached: 
The incorporation of 0.2% A1 stearate in a 1.5% Gel White H containing 
formula, as well as the incorporation of 0.1% A1 stearate or of 0.1% zinc 
stearate in a 2% Gel White H containing formula leads to a simultaneous 
increase of the physical stability and of the apparent viscosity Runs 1 
(control), 2, 6, and 9. 
Similar results are observed with 0.1% calcium distearate or 0.1% Radiastar 
1100 incorporated with 2% Pharmagel H (a bentonite clay) (Runs 12 
(control), 13 and 14). 
The incorporation of 0.1% or 0.2% A1 stearate in a 1% Gel White H 
containing formula, of 0.2% A1 stearate in a 0.5% Gel White H containing 
formula, and of 0.3 to 0.4% A1 stearate in a 0.25% Gel White H containing 
formula leads to an increase of the physical stability without any drastic 
viscosity increase Runs 1 (control), 3, 4, 7, 10 and 11). 
For the combination of 0.1% A1 stearate and 0.5% Gel White H (Run 8) the 
apparent viscosity values remain acceptable but no significant improvement 
in physical stability is obtained. 
The polyvalent metal salts of short chain fatty acids do not provide or in 
fact impair physical stability (Runs 15 and 16). 
__________________________________________________________________________ 
UNSHAKEN 
BROOK. LVT LIQUID SEATION 
VISCOSITY (%) (AFTER 12 WEEKS) 
(KCPS) (1) 
4.degree. C. IN 
RT IN 35.degree. C. IN 
43.degree. C. 
RT IN SHIPPING 
DENSITY 
3 30 GLASS 
GLASS GLASS 
GLASS PLASTIC 
TEST % 
RUN FORMULATION 
(g/cm.sup.3) 
RPM RPM (2) (2) (2) (2) (3) (4) 
__________________________________________________________________________ 
1 H.sub.2 O = 41.1% 
1.28 15 4 2-8 0-8 0-4 0 6-16 9-12 
(Con- 
Stabilizer = 0+/-0.002 
+/-5 
+/-1 
trol) 
(X = 0) 
Gel 
White H = 2.0% 
(Y = 0) 
2 H.sub.2 O = 41.4% 
1.29 43 5.9 0 0 0 0 0 0 
Al Stearate = 0.2% 
(X = 0.2%) 
Gel White H = 1.5% 
(Y = 0.5) 
3 H.sub.2 O = 41.9% 
1.30 26 6.1 0 0 0 0 0 0 
Al Stearate = 0.2% 
(X = 0.2) 
Gel White H = 1% 
(Y = 1.0) 
4 H.sub.2 O = 42.4% 
1.33 11 3.8 &lt;1 0 5 0 2 0 
Al Stearate = 0.2% 
(X = 0.2) 
Gel White H = 0.5% 
(Y = 1.5) 
5 H.sub.2 O = 42.65% 
1.35 4 1.7 0 0 0 0 2 0-13 
Al Stearate = 0.2% 
(X = 0.2) 
Gel White H = 0.25% 
(y = 1.75) 
6 H.sub.2 O = 41.0% 
1.26 36 9 0 0 0 0 2 0-13 
Al Stearate = 0.1% 
Gel White H = 2% 
7 H.sub.2 O = 42.0% 
1.30 17 5 0 0 0 0 0-5 -- 
Al Stearate = 0.1% 
+/-0.01 
+/-4 
+/-2 
Gel White H = 1% 
8 H.sub.2 O = 42.5% 
1.31 10 3.5 8 4 &lt; 2 &lt;2 9 -- 
Al Stearate = 0.1% 
Gel White H = 0.5% 
9 H.sub.2 O = 4.5% 
1.25 40 4.6 0 0 0 0 0 -- 
Zn di- 
stearate = 0.1% 
Gel White H = 2% 
10 H.sub.2 O = 42.55% 
1.35 6 2.6 0 0 0 0 0 0 
Al Stearate = 0.3% 
Gel White H = 0.25% 
11 H.sub.2 O = 42.45% 
1.35 10 2.9 0 0 0 0 0 0 
Al Stearate = 0.4% 
Gel White H = 0.25% 
12 H.sub.2 O = 41.1% 
1.25+ 13+ 
4+ 2+ 7+ 0 0 
(Con- 
Stabilizer = 0(x = 0) 
0.02 4 2 7 7 2 2 
trol) 
Pharmagel H = 2.0% 
(Bentomic clay) 
13 H.sub.2 O = 41.1% 
1.22 24 3.8 0 0 0 0 0 0 
Ca Distearate = 0.1% 
Pharmagel H = 2.0% 
14 H.sub.2 O = 41.1% 
1.25 26 7.5 0 0 0 0 0 0 
Radiastar 
1100(5) = 0.1% 
Pharmagel H = 2.0% 
15 H.sub.2 O = 41.1% 
1.31 10 1.9 Unshaken liquid separation = 8% 
Zinc di After 2 weeks at RT in glass 
acetate = 0.1% 
Pharmagel H = 2.0% 
16 H.sub.2 O = 41.1% 
-- phase separation after 1 day 
Mg diacetate = 0.1% 
Pharmagel H = 2.0% 
__________________________________________________________________________ 
Notes to Table I 
(1) Measured with spindle 4 after 3 minutes on 24 hour old samples. 
(2) In Height (RT = room temperature = 20 + 2.degree. C.) 
(3) In weight (RT = room temperature = 20 + 2.degree. C.) 
(4) Liquid separation measured after 6 weeks and 3000 Kms is a private ca 
(in weight in a plastic bottle). 
(5) Radiastar 1100 is an industrial grade mixture of saturated fatty acid 
in the form of their magnesium salts (trademarked product of Olefina). 
EXAMPLE 17 
Using the same composition and preparation method as in Example 16 except 
that in place of Gel White H as the thixotropic thickener, 2% of Attagel 
50 (an attapulgite clay) or 0.4% of Bentone EW (a specifically processed 
Hectorite clay) was used with (Runs 2 and 4) or without (control Runs 1 
and 3) aluminum tristearate. The apparent viscosities and physical 
stabilities were measured in the same manner as described for Example 16. 
The results are shown in The following Table. 
From the results shown in the Table, it can be seen that small amounts of 
aluminum stearate are equally effective in increasing the physical 
stability of attapulgite clay and hectorite clay based liquid thixotropic 
automatic dishwasher detergent compositions, with the degree of physical 
stability increase again being dependent on the amounts of stabilizer and 
thickening agent. 
__________________________________________________________________________ 
BROOK. LVT UNSHAKEN LIQUID SEATION 
VISCOSITY (%) (AFTER 12 WEEKS) 
(KCPS) (1) 
4.degree. C. IN 
RT IN 35.degree. C. 
43.degree. C. IN 
DENSITY 
3 30 GLASS 
GLASS GLASS GLASS 
RUN FORMULATION 
(g/cm.sup.3) 
RPM RPM (2) (2) (2) (2) 
__________________________________________________________________________ 
1 H.sub.2 0 = 42.7% 
1.30 liq. sep. 
25 32 32 17 
(Control) 
Bentone EW = 0.4% 
after 1 day 
instead of Gel White 
2 As above 0.1% 
1.33 5 2.1 4 5 6 8 
but with 
Al tristearate 
just before 
Bentone 
H.sup.2 O 42.6% 
3 H.sub.2 O = 41.1% 
1.33 4 1.3 12 17 14 24 
(Control) 
Attagel 50 = 2% 
instead of Gel 
White H 
4 As above 0.1% 
1.36 6 1.7 3 0 0 0 
but with Al 
tristearate just 
before Attagal 
H.sub.2 O = 41.0% 
__________________________________________________________________________ 
(1) Measured with Spindle 4 after 3 minutes (24 hours after making); 
(2) In height; 
(3) In weight; 
EXAMPLE 18 
This example shows that inorganic aluminum and zinc salts, including 
Al.sub.2 O.sub.3, ZnSO.sub.4 and Al.sub.2 (SO.sub.4).sub.3 and sodium 
stearate do not provide improved physical stability to the liquid 
thixotropic ADD compositions. Using the same formulation as in Run 6 of 
Example 16, 0.1% of each of Al.sub.2 O.sub.3, ZnSO.sub.4, Al.sub.2 
(SO.sub.4).sub.3 or sodium stearate was used in place of 0.1% aluminum 
stearate. The results of the measurement of apparent viscosity and 
physical stability are shown in the following Table. 
__________________________________________________________________________ 
UNSHAKEN 
BROOK. LVT LIQUID SEATION 
VISCOSITY (%) (AFTER 12 WEEKS) 
(KCPS) (1) 
4.degree. C. IN 
RT IN 
35.degree. C. IN 
43.degree. C. 
RT IN SHIPPING 
DENSITY 
3 30 GLASS 
GLASS 
GLASS GLASS 
PLASTIC 
TEST % 
RUN FORMULATION 
(g/cm.sup.3) 
RPM RPM (2) (2) (2) (2) (3) (4) 
__________________________________________________________________________ 
1 H.sub.2 O = 42.1% 
1.28 15 4 2-8 0-8 0-4 0 6-16 9-12 
(Control) 
+/-0.002 +/-5 +/-1 
(X = 0) 
Gel White H = 2.0% 
2 H.sub.2 O = 41.0% 
1.30 10 4 Strong decantation after 4 
--eks 
Al.sub.2 (SO.sub.4).sub.3 = 0.1% 
instead of Al Stearate 
Gel White H = 2.0% 
3 H.sub.2 O = 41.0% 
1.32 8 2.9 Strong decantation after 4 
--eks 
ZnSO.sub.4 = 0.1% 
instead of Al Stearate 
Gel White H = 2.0% 
4 H.sub.2 O = 41.0% 
1.29 15 4.1 Strong decantation after 4 
--eks 
Al.sub.2 O.sub.3 = 0.1% 
instead of Al Stearate 
Gel White H = 2.0% 
5 H.sub.2 O - 41.0% 
1.27 22 6.2 Strong decantation after 6 
--eks 
addition of 0.1% 
Al.sub.2 O.sub.3 in the first 
part of caustic soda 
Gel White H = 2.0% 
6 H.sub.2 O = 41.0% 
1.30 26 4.8 4 4 0 0 8 -- 
Stearic acid Na 
salt = 0.1% 
instead of Al Stearate 
Gel White H = 2.0% 
__________________________________________________________________________ 
Notes: 
(1)-(4) same as in Table 1 
EXAMPLE 19 
The following gel-like thixotropic liquid ADD is prepared following the 
same general procedures as in Example 16: 
______________________________________ 
Ingredient Amount (A.1.) wt % 
______________________________________ 
pH = 13 to 13.4 
Na.sub.2 O/SiO.sub.2 = 1/2.4) 
Monostearyl phosphate 
0.16 
Dowfax 3B-2) 0.36 
Thermphos NW 12.0 
Thermphos N hexa 12.0 
Aluminum tristearate 0.1 
Sodium Carbonate, anhydrous 
5.0 
Caustic soda solution 
3.1 
(50% NaOH) 
Pharmagel Euroclay 1.25 
Sodium silicate (47.5% sol'n 
7.48 
MG/Al Silicate clay) 
Sodium hypochlorite solution (11%) 
1.0 
Water balance 
______________________________________ 
Minor amounts of perfume, color, etc. can also be added to formulation. 
EXAMPLE 20 
This example shows the preparation of liquid ADD formulations using a 
different preparation technique. The following formulation is prepared 
using a high shear mixer. 
______________________________________ 
Part 1 - Premix 
Weight percent 
______________________________________ 
Deionized water (at room temp.) 
37.75-41.75 
Phosphoric (defoamer) 0.16 
Detergent (e.g. Dowfax 3B-2 
0.80 
(45% active) 
Physical Stabilizer (e.g. calcium 
0.10 
stearate) 
Thixotropic agent (e.g. Gel White USP) 
1.25 
______________________________________ 
The premix, in the required amount, is transferred into a low shear mixer. 
The following ingredients are then added sequentially, while stirring, to 
Part 1. 
______________________________________ 
Part II - Post Added Ingredients 
______________________________________ 
Sodium hydroxide (50% solution) 
1.00 
Sodium carbonate 5.00 
Sodium silicate (47.5% solution) 
15.74 
Thermphos N hexa 12.00 
Thermphos NW 12.00 
Sodium hypochlorite (13% solution) 
9.00 
Sodium hydroxide (50% solution) 
1.20-5.20 
______________________________________ 
EXAMPLE 21 
In order to demonstrate the effect of the alkalinity on the fatty acid 
metal salt stabilized clay thickened liquid ADD formulations, compositions 
as shown in the following Table are prepared with varying amounts of 
alkaline compounds. 
__________________________________________________________________________ 
Amount (Weight/%) 
Ingredient Control 
1 2 3 4 5 6 
__________________________________________________________________________ 
Water, deionized 
41.75 
41.75 
41.75 
37.75 
35.75 
38.05 
34.24 
Caustic soda, sol'n 
2.20 5.20 
7.20 
6.20 
8.20 
2.20 
2.20 
(50% NaOH) 
Na.sub.2 CO.sub.3 
5.00 2.00 
-- 5.00 
5.00 
-- -- 
Na.sub.2 O.SiO.sub.2 
(47.5% sol'n, 
Na.sub.2 O:SiO.sub.2 = 1:2.4) 
15.74 
15.74 
15.74 
15.74 
15.74 
15.74 
-- 
(57.5% sol'n, 
Na.sub.2 O:SiO.sub.2 = 1:2.4) 
-- -- -- -- -- 8.70 
-- 
(55.9% sol'n, 
Na.sub.2 O:SiO.sub.2 = 1:2) 
-- -- -- -- -- -- 28.25 
Sodium tripolyphosphate, 
12.00 
12.00 
12.00 
12.00 
12.00 
12.00 
12.00 
anhydrous 
Sodium tripolyphosphate, 
12.00 
12.00 
12.00 
12.00 
12.00 
12.00 
12.00 
hexahydrate 
Sodium hypochlorite 
9.00 9.00 
9.00 
9.00 
9.00 
9.00 
9.00 
11% available chlorine) 
Monostearyl phosphate 
0.16 0.16 
0.16 
0.16 
0.16 
0.16 
0.16 
Dowfax 3B-2 
(45% Na monodecyl/didecyl 
0.80 0.80 
0.80 
0.80 
0.80 
0.80 
0.80 
diphenyl oxide disulfonate- 
aqueous solution) 
Aluminum tristearate 
0.10 0.10 
0.10 
0.10 
0.10 
0.10 
0.10 
Pharmagel H, clay 
1.25 1.25 
1.25 
1.25 
1.25 
1.25 
1.25 
TOTAL 100.00 
100.00 
100.00 
100.00 
100.00 
100.00 
100.00 
ph of 10 g/liter 
10.9 11.4 
11.7 
-- 11.8 
-- -- 
__________________________________________________________________________ 
In preparing these formulations, the monostearyl phosphate foam depressant 
and Dowfax 3B-2 detergent active compound are added to the mixture just 
before the Pharmagel H clay thickener; all of the NaOH is added after the 
clay. The resulting liquid ADD formulations as shown below are measured 
for cleaning performance; and for density, and physical stability (phase 
separation) on standing and in a shipping test. The results are shown as 
follows. 
______________________________________ 
CLEANING PERFORMANCE 
Composition 
Average Rating On 
Average Rating On 
Run No. Mixed Soils Starchy Soils 2) 
______________________________________ 
1 5.71 3.80 
2 5.85 4.00 
Control 5.12 3.50 
Powder 1) 6.11 4.61 
______________________________________ 
1) Commercially available powdery ADD, pH = 12.2 
2) Dishes with rice and cuttery with rice and porridge 
__________________________________________________________________________ 
Unshaken Liquid Separation Measured 
After 12 Weeks 
Glass Bottle CT Type Bottle 100 Days 
Shipping Test 2) 
Composition 
Density 
(% height) (% in weight 1) % Separation 
Run No. 
g/cm.sub.3 
4.degree. C. 
RT3) 
35.degree. C. 
43.degree. C. 
4.degree. C. 
RT3) 
35.degree. C. 
43.degree. C. 
RT3) (by weight) 
__________________________________________________________________________ 
1 1.27 0 0 0 0.2 
&lt;0.1 
0.4 0.5 1-0.5 
0.7 
2 1.27 &lt;2 0 0 0 1.4 
0.3 3.0 5.0 1-0.5 
0.7 
3 1.30 &lt;2 0 0 0 0 0 0 0 0 0 
4 1.31 3 0 0 0 2 0.2 0 0 0 1.5 
5 1.30 0 0 0 0 0 0 0 0 0 0 
6 1.28 3 0 0 0 0 0 0 0 0 0 
__________________________________________________________________________ 
1) Average measurement with 5 different CT bottles 
2) Liquid separation measured after 6 weeks and 3000 kms in a private car 
in plastic bottles 
3) Room temperature = 20-2.degree. C. 
EXAMPLE 22 
The example 21 control composition and the compositions of Run Nos. 3 and 5 
were aged at 4.degree. C., room temperature (RT), 35.degree. C. or 
43.degree. C. and the viscosity of each sample was measured after storage 
in a plastic bottle for 1, 4, 6 and 12 weeks with a Brookfield LVT 
viscometer using a No. 4 spindle at 3 rpm. The results are shown as 
follows: 
__________________________________________________________________________ 
Viscosity (kcps) 
Composition 
Temp (.degree.C.) 
4 RT 35 43 
Run No. 
Time (weeks) 
2 4 6 12 
2 4 6 12 
2 4 6 12 
2 4 6 12 
__________________________________________________________________________ 
CONTROL 19 
23 
25 
29 
24 
34 
53 
70 
36 
48 
-- 
68 
-- 
74 
120 
180 
3 25 
27 
26 
18 
30 
48 
28 
23 
40 
23 
22 
31 
38 
24 
28 18 
5 28 
23 
17 
20 
27 
12 
20 
15 
18 
20 
18 
25 
26 
20 
29 24 
__________________________________________________________________________ 
EXAMPLE 23 
The Example 21 control composition and the compositions of Run Nos. 3 and 5 
and a referential example in which the aluminum stearate of the control 
composition was omitted and the amount of clay increased to 2% were tested 
to measure rheological properties after standing at room temperature for 
10 days, 6 weeks and 3 months. The results are shown as follows: 
__________________________________________________________________________ 
Low Shear 
High Shear 
3 rpm 30 rpm Apparent Viscosity 
Aging 60 nl 60 nl Thixotropy 
1.58 s-1 
25 s-1 
1585 
Composition 
Time (Pa) 
(Pa.S) 
(Pa) 
(Pa.S) 
(Pa/S) 
(Pa.S) 
(Pa.S) 
(Pa.S) 
__________________________________________________________________________ 
Reference 
10 days 
-- -- -- -- -- -- -- -- 
6 weeks 
6.2 
28.9 
34.0 
0.014 
766 21.5 
1.65 
0.33 
3 months 
6.3 
21.1 
19.0 
0.007 
269 15.6 
0.93 
0.19 
Control 
10 days 
6.9 
35.1 
34.0 
0.001 
1665 22.6 
1.47 
0.24 
6 weeks 
-- -- -- -- -- -- -- -- 
3 months 
5.6 
33.6 
33.7 
0.001 
1450 22.2 
1.42 
0.23 
Run No. 3 
10 days 
6.6 
41.4 
38.7 
0.012 
1971 23.0 
1.86 
0.34 
6 weeks 
6.8 
37.9 
39.2 
0.013 
1938 21.2 
1.89 
0.35 
3 months 
7.4 
28.0 
35.2 
0.017 
1397 18.1 
1.73 
0.35 
Run No. 5 
10 days 
7.5 
30.8 
37.5 
0.003 
1665 21.2 
1.66 
0.29 
6 weeks 
7.1 
31.8 
34.1 
0.008 
1538 19.9 
1.58 
-- 
3 months 
6.3 
21.7 
31.6 
0.008 
1215 16.4 
1.43 
0.28 
__________________________________________________________________________ 
EXAMPLE 24 
Using the Example 21 control composition, and the compositions of Run Nos. 
1, 3 and 5 the available chlorine levels remaining after storage at room 
temperature, 35.degree. C. and 43.degree. C. for 2, 4, 6 or 12 weeks was 
measured. The results are shown as follows: 
______________________________________ 
RESIDUAL CHLORINE LEVELS 
(% OF ORIGINAL) 
RT 35.degree. C. 
43.degree. C. 
Weeks 
Composition 
2 4 6 12 2 4 6 12 2 4 6 
12 
______________________________________ 
Control 96 94 90 77 85 80 75 55 66 51 35 
18 
Run No. 1 98 96 95 88 -- -- 92 68 96 74 64 40 
4 
Run No. 3 91 92 89 74 84 78 72 52 57 55 30 22 
Run No. 5 98 95 93 84 92 92 90 64 76 66 59 33 
______________________________________ 
EXAMPLE 25 
The following formulations A-K were prepared as described below: 
__________________________________________________________________________ 
INGREDIENT/ 
FORMULATION A B C D E F G 
__________________________________________________________________________ 
DEIONIZED WATER 
BALANCE 
BALANCE 
BALANCE 
BALANCE 
BALANCE 
BALANCE 
BALANCE 
CARBOPOL 941 0.9 0.9 0.9 0.9 1 -- 0.9 
NaOH (50%) 2.4 2.4 2.4 2.4 3.5 3.5 2.4 
KOH (50%) -- -- -- -- -- -- -- 
TKPP 15 15 15 20 20 20 28 
TPP HEXAHYDRATE, 
13 13 12 7.5 7.5 7.5 -- 
Na SILICATE 21 21 21 21 17 17 21 
(47.5%) (1:2.3) 
K SILICATE -- -- -- -- -- -- -- 
(29.1%) (1:2.3) 
LPKN (5%) 3.2 3.2 3.2 3.2 -- -- 3.2 
DOWFAX 3B2 1 1 1 1 1 1 1 
FATTY ACID.sup.2 
0.1 0.1 0.1 0.1 -- -- 0.1 
BLEACH 7.5 7.5 7.5 7.5 9.1 9.1 7.5 
(13.0% CL) 
AIR.sup.3 (VOL. %) 
&lt;2.0 &lt;2.0 &lt;2.0 &lt;2.0 &lt;2.0 &gt;2.0 &lt;2.0 
FRAGRANCE -- 0.17 -- -- -- -- -- 
K/Na RATIO 1.12 1.12 1.16 1.89 1.95 1.95 4.16 
DENSITY (g/cc) 
1.37 1.37 1.35 1.37 1.36 -- 1.37 
RHEOGRAM FIG. 1 FIG. 2 FIG. 3 FIG. 4 FIG. 6 FIG. 7 
STABILITY RESULTS 
0.0 0.0 0.0 0.0 &gt;10.0 &gt;10.0 0.0 
ROOM TEMP. 8 WEEKS 
(%) 
STABILITY RESULTS 
0.0 0.0 0.0 0.0 &gt;10.0 &gt;10.0 0.0 
100.degree. F., 6 WEEKS 
(%) 
__________________________________________________________________________ 
INGREDIENT/FORMULATION 
H I J K 
__________________________________________________________________________ 
DEIONIZED WATER BALANCE BALANCE BALANCE BALANCE 
CARBOPOL 941 0.9 -- 1.5 0.91 
NaOH (50%) -- 2.4 2.4 2.4 
KOH (50%) 2.4 -- -- -- 
TKPP 28 15 20 15 
TPP HEXAHYDRATE, -- 13 7.5 13 
Na SILICATE -- 21 21 21 
(47.5%) (1:2.3) 
K SILICATE 34 -- -- -- 
(29.1%) (1:2.3) 
LPKN (5%) 3.2 3.2 3.2 3.2 
DOWFAX 3B2 1 1 1 1 
FATTY ACID.sup.2 0.1 1 0.1 0.1 
BLEACH (13.0% CL) 7.5 7.5 7.5 9 
AIR.sup.3 (VOL. %) &gt;2.0 &gt;2.0 &lt;2.0 &lt;2.0 
FRAGRANCE -- -- -- -- 
K/Na RATIO 45.15 -- 1.89 -- 
DENSITY (g/cc) -- -- 1.37 1.37 
RHEOGRAM FIG. 6 FIG. 7 FIG. 5 FIG. 8 
STABILITY RESULTS &gt;20.0 &gt;5.0 0.0 0.0 
ROOM TEMP. 8 WEEKS 
(%) 
STABILITY RESULTS &gt;20.0 &gt;5.0 0.0 0.0 
100.degree. F., 6 WEEKS 
__________________________________________________________________________ 
1. Carbopol 940 
2. Emersol 132 (Mixture of stearic and palmitic acid 1:1 ratio. 
3. All the formulations are aerated to a certain degree depending upon th 
shear condition employed for the preparation, typically the volume of air 
does not exceed 7-8% by volume, the preferred degree of aeration (2% by 
volume) resulting in the indicated densities; the air bubbles average 
between 20 and 60 microns in diameter. 
Formulations 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 about 97% of 
the water (balance). The Carbopol is slowly added to deionized water at 
room temperature using a mixer 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 50.degree. 
C. to 70.degree. C. 
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 as described above except that the heated emulsion of LPKN, stearic 
acid and Dowfax 3B2 is 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.sup.3. 
The rheograms for the formulations A, C, D, G and J are shown in FIGS. 1-5, 
respectively, and rheograms for formulations H, I and K are shown in FIGS. 
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 
(25.degree.+1.degree. C.) 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, B, 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 
FIGS. 1-5. Formulation E which includes Carbopol 941 but not stearic acid 
showed no phase separation at either room temperature or 100.degree. F. 
after 3 weeks, but exhibited 10% phase separation after 8 weeks at room 
temperature and after only 6 weeks at 100.degree. F. 
Formulation K, containing Carbopol 940 in place of Carbopol 941, as seen 
from the rheogram in FIG. 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 .delta. at a strain above 50%. 
EXAMPLE 26 
This example demonstrates the importance of the order of addition of the 
surface active component premix to the remainder of the composition on 
product density and stability. 
The following formulations are prepared by methods A and B: 
______________________________________ 
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 
LPKN 0.16 
Stearic Acid 0.1 
Dowfax 3B2 1 
______________________________________ 
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 stirring 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 about 65.degree. C. 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 
Method A is repeated except that the heated emulsion premix is added to the 
neutralized Carbopol 941 dispersion before the sodium silicate, TKPP, TPP, 
and bleach. The results are also shown below. 
______________________________________ 
METHOD A METHOD B 
______________________________________ 
Density (g/cc.sup.3) 
1.38 1.30 
Stability (RT-8 weeks) 
0.00% 7.00% 
Rheogram FIG. 9 FIG. 10 
______________________________________ 
From the rheograms of FIGS. 9 and 10 it is seen that both products are 
linear viscoelastic although the elastic and viscous module 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 is 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 27 
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 26 
except that the amount of stearic acid was increased from 0.1% to 0.2% are 
prepared as shown in Method A for formulation L and by the following 
Method C for formulation M. 
Method C: 
The procedure of Method A is repeated in all details except that emulsion 
premix of the surface active ingredients is prepared at room temperature 
and is 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 FIGS. 11 and 12, respectively. From 
these rheograms it is seen that formulation L 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&gt;500 
dynes/cm.sub.2) and also for G" (G" at 1% strain-G" at 30% strain=300 
dynes/cm.sub.2). 
Formulation L remains stable after storage at RT and 100.degree. F. for at 
least 6 weeks whereas formulation M undergoes phase separation. 
Comparative Example 27 
The following formulation is prepared without any potassium salts: 
______________________________________ 
Weight % 
______________________________________ 
Water Balance 
Carbopol 941 0.2 
NaOH (50%) 2.4 
TPP, Na (50%) 21.0 
Na Silicate (47.5%) 
17.24 
Bleach (1%) 7.13 
Stearic Acid 0.1 
LPKN (5%) 3.2 
Dowfax 3B2 0.8 
Soda Ash 5.0 
Acrysol LMW 45-N 2.0 
______________________________________ 
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 Carbopol 941 dispersion, followed by addition of the heated 
surface active emulsion premix. The rheogram is shown in FIG. 13 and is 
non-linear with G"/G' (tan .delta.)&gt;1 over the range of strain of from 
about 5% to 80%. 
EXAMPLE 28 
Formulations A, B, C, D and K according to this invention and comparative 
formulations F and a commercial liquid automatic dishwasher detergent 
product as shown in the Table 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. 
______________________________________ 
Bottle Residue 
Formulation Residue 
______________________________________ 
A 8 
B 10 
C 6 
D 5 
K 7 
F* 4 
Commercial Product 
20 
______________________________________ 
*The sample separates upon aging. 
EXAMPLE 29 
The following formulations A-F were prepared as described below: 
______________________________________ 
FORMULATION 
INGREDIENT A B C 
______________________________________ 
WATER Q.A Q.A Q.A 
CARBOPOL 941 0.9 -- -- 
CARBOPOL 940 -- 0.9 -- 
CARBOPOL 614 -- -- 0.9 
NaOH (50%) 2.4 4.5 4.5 
Na-SILICATE (47.5%) (1:2.4) 
21 21 20.83 
TKPP 15 15 -- 
KTPP -- -- 20.35 
NaTPP (ANHYDROUS) 13 13 5.26 
DOWFAX 3B2 1 0.8 0.8 
LPKN (ANTI-FOAMING 
0.16 0.16 0.16 
AGENT) 
FATTY ACID 0.10(2) 0.20(1) 0.15(3) 
BLEACH (13.1%) 8.1 11.1 10.13 
GRAPTHOL GREEN 0.0025 0.003 0.003 
CI DIRECT YELLOW 28 
-- -- -- 
AIR (Vol. %) APPROX. 
&lt;2 &lt;2 &lt;2 
ACRYSOL LMW 45-N (45.0%) 
-- -- -- 
HIGHLIGHTS -- -- 0.05 
(FRAGRANCE) 
K/Na 0.98 0.98 1.61 
DENSITY 1.35 1.37 1.37 
STABILITY AMBIENT 8 WKS 8 WKS 24 WKS 
STABILITY 100.degree. F. 
2 WKS 2 WKS -- 
STABILITY 120.degree. F. 
-- -- -- 
STABILITY 140.degree. F. 
-- -- -- 
CRYSTAL GROWTH (100.degree. F.) 
YES YES NO 
RHEOGRAM FIG. 1 FIG. 2 FIG. 3 
______________________________________ 
FORMULATION 
INGREDIENT D E F 
______________________________________ 
WATER Q.A Q.A Q.A 
CARBOPOL 941 -- -- -- 
CARBOPOL 940 -- -- -- 
CARBOPOL 614 0.9 0.9 0.9 
NaOH (50%) 4.0 4.5 4.5 
Na-SILICATE (47.5%) (1:2.4) 
20.83 20.83 20.83 
TKPP -- -- -- 
KTPP 20.35 13 20.35 
NaTPP (ANHYDROUS) 5.26 3 5.26 
DOWFAX 3B2 0.8 0.8 0.8 
LPKN (ANTI-FOAMING 
0.16 0.16 0.16 
AGENT) 
FATTY ACID 0.15(2) 0.15(2) 0.15(2) 
BLEACH (13.1%) 10.13 10.13 10.13 
GRAPTHOL GREEN 0.003 0.003 -- 
CI DIRECT YELLOW 28 
-- -- 0.003 
AIR (Vol. %) APPROX. 
&lt;2 &lt;2 &lt;2 
ACRYSOL LMW 45-N (45.0%) 
-- 4.4 -- 
HIGHLIGHTS 0.05 0.05 0.05 
(FRAGRANCE) 
K/Na 1.61 1.17 1.61 
DENSITY 1.37 1.28 1.37 
STABILITY AMBIENT 24 WKS 12 WKS 4 WKS 
STABILITY 100.degree. F. 
20 WKS 8 WKS 4 WKS 
STABILITY 120.degree. F. 
8 WKS 8 WKS 4 WKS 
STABILITY 140.degree. F. 
2 WKS 2 WKS 2 WKS 
CRYSTAL GROWTH (100.degree. F.) 
NO NO NO 
RHEOGRAM FIG. 4 FIG. 5 FIG. 6 
______________________________________ 
(1) Syncrowax C24-26 
(2) Stearic Acid 
(3) Syncrowax C18-36 
Formulations A, B, C, D, E and F are prepared by first forming a uniform 
dispersion of the Carbopol 614 or 940 thickener in about 97% of the water 
of the total formula water. The Carbopol is slowly added by sprinkling it 
into the vortex of previously colored deionized water preheated to a 
temperature of 105.degree. F. using a mixer equipped with a premier blade, 
with agitation set at a medium shear rate, as recommended by the 
manufacturer. After mixing for about 15 minutes, the dispersion is then 
neutralized by addition, under the same mixing, of the caustic soda (50% 
NaOH) component until a thickened product of gel-like consistency is 
formed (about 10 minutes). 
To the resulting gelled dispersion the silicate, sodium tripolyphosphate 
(NaTPP), tetrapotassium pyrophosphate (TKPP), or potassium 
tripolyphosphate (KTPP), the surfactant emulsion (described below) and 
bleach and color, are added sequentially, in the order stated, with the 
mixing continued at medium shear for several minutes before adding the 
next ingredient. After the addition of the surfactant emulsion (at 
160.degree. F.), the mixture is cooled from 90.degree.-95.degree. F. 
before the bleach is added. 
Separately, the surfactant emulsion of the phosphate anti-foaming agent 
(LPKN), stearic acid or fatty acid mixture and detergent (Dowfax 3B2) is 
prepared by adding these ingredients to the remaining 3% of water and 
heating the resulting mixture to a temperature in the range of 160.degree. 
F. (71.degree. C.). In formulation E, the Acrysol LMW 45-N may be added at 
this stage. 
The rheograms for the formulations A, B, C, D, E and F are shown in FIGS. 
10-15, 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 
(25.degree.+1.degree. C.) 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 C, D and F exhibit linear 
viscoelasticity as seen from the rheograms of FIGS. 21-25. No phase 
separation at from ambient temperature to 140.degree. F. were observed for 
any of the formulations for at least the minimum number of weeks required 
to satisfy the criteria stability as shown above. 
However, in the control formulations A and B maintained at 100.degree. F., 
the TKPP crystallized in the aqueous phase and eventually formed 
sufficiently large size crystals which separated to the bottom of the 
composition. Also, as seen in FIGS. 1 and 2 formulations A and B are not 
linear viscoelastic, at least within the preferred criteria as previously 
described. Formulations C, D, E and F, according to the invention did not 
undergo any crystal growth. 
For the bottle residue test, each formulation is allowed to age for about 1 
week at ambient temperature in a standard 32 ounce small necked 
polyethylene bottle. An amount of product is poured from the bottle to 
fill a standard sized dispenser cup of an automatic dishwasher. The bottle 
is then replaced in an upright position and is retained in the upright 
position for at least 15 minutes. This procedure of filling the dispenser 
cup, placing the container in the upright position and waiting at least 15 
minutes is repeated until no more product flows from the bottle. At this 
time, the weight of the bottle is measured. Bottle residue is calculated 
as: 
##EQU1## 
Wo is the initial weight of the filled bottle and Wf is the final weight 
of the filled bottle. The bottle residue for each formulation A-F is about 
4 to 5%. Formulations C-F have viscosities of from 10,000 to 20,000 
measured at 80.degree. F. All of these products are easily pourable from 
the polyethylene bottle. 
EXAMPLE 30 
A Carbopol 614 slurry is formed as described in Example 29 except that the 
coloring agent is first added to the deionized water (about 92% of the 
total added water) and the amounts of the ingredients are changed as shown 
below. The premix (surfactant emulsion) of the surface active ingredients 
is also formed as in Example 29 using stearic acid as the fatty acid 
stabilizer and the remaining 8% of the total added water. 
The ingredients are then mixed together with the Carbopol 614 slurry in the 
following order: alkali metal silicate, NaTPP (powder), KTPP (powder), 
surfactant emulsion, bleach and perfume. The resulting composition is 
obtained with the following ingredients in the following amounts: 
______________________________________ 
Ingredient Amount (wt %) 
______________________________________ 
Deionized Water Balance 
Carbopol 614 1.00 
NaOH (38% Na2O) 6.38 
Na silicate (1:24) (47.5%) 
20.83 
KTPP (anhydrous) powder 
20.35 
NaTPP (3% H2O) powder 
5.26 
Dowfax 3B2 0.80 
LPKN 0.16 
Stearic Acid 0.15 
Bleach (Na hypochlorite - 13%) 
9.23 
CI Pigment Green 7 (CI 74260) 
0.0024 
Highlights (fragrance) 
0.05 
______________________________________ 
The composition has a pH of 11.3+0.2 and density (sp.gr.) of 1.39+0.03. The 
viscosity at 80.degree. F. measured with a Brookfield LVT viscometer at 20 
rpm with a #4 spindle is 12,000.+-.2,000. 
All of the preferred criteria as set forth in the above are satisfied. 
EXAMPLE 31 
The following formulation G was prepared according to the procedure of 
Example 29. 
______________________________________ 
Component Weight Percent 
______________________________________ 
Water, deionized 43.0% 
LPKN (pure) 0.16% 
Dowfax 3B2 0.8% 
Stearic Acid 0.1% 
Caustic (50%) 2.4% 
Soda Ash 5.0% 
Na Silicate (47.5%) (1:2.4) 
17.24% 
Na PP (FMC Hexahydrate) 
12.0% 
Na TPP (Oxy Anhydrous) 
12.0% 
Bleach (Na Hypochlorite) 
7.07% 
Carbopol 940 0.3% 
Density = 1.35 g/ml. 
______________________________________ 
EXAMPLE 32 
A scented thixotropic liquid automatic dishwashing detergent composition 
having the formulation described below, was prepared using the preferred 
process of the present invention. 
______________________________________ 
STAGE COMPONENT WEIGHT 
______________________________________ 
PREDISPERSION 
Water (Softened) 41.44 
(I) LPKN 158 .TM. 8.84 
Al stearate 5.52 
DOWFAX .TM. 3B-2 .TM. 
44.20 
Total 100.00 
PREMIX Water (Softened) 82.37 
(II) Predispersion (I) 10.43 
Gel White .TM. H 7.20 
Total 100.00 
MAIN BATCH Water (Softened) 25.69 
(III) Premix (II) 17.53 
Sodium hydroxide (50% A.I.) 
2.42 
Sodium carbonate 5.05 
Sodium silicate (43.5% A.I.) 
17.42 
Thermphos NH .TM. 12.12 
Thermphos NW .TM. 12.12 
Sodium hypochlorite 
7.48 
(13% A.I.) 
Subtotal 99.83 
HOMOGENIZE, Fragrance 0.17 
COOL & MIX Total 100.00 
(IV) 
______________________________________ 
According to the preferred process of the invention, a predispersion mix 
was prepared in a vessel equipped with a high speed dispenser, e.g., Myers 
HSD.TM.. The amount of water included in the predispersion vessel was 
limited so that the mixture remained viscous and susceptible to high-shear 
dispersing. The high-shear dispersing was carried out for about 5 to 10 
minutes at which point the predispersion mix was conveyed through an 
homogenizer to a premix vessel where the clay thickener and water were 
added to the predispersion mix under low-shear conditions. A paddle blade 
type mixer, e.g., baffled crutcher, was used in the premix vessel which 
mechanically deagglomerated the clay as it was hydrated. The preparation 
of the premix generally lasts for about 20 minutes depending on the mixer 
speed. The resultant premix was removed and homogenized, then added with 
water to the main batch vessel where is was subjected to high-shear 
dispersing using a Myers HSD.TM.. During the high-shear mixing, the 
remaining liquid and solid ingredients were sequentially added to the main 
batch vessel. 
As additional ingredients were added, particularly, the solid ingredients, 
the mixture became more viscous and the high speed dispenser ground the 
particles to a fine particle size which, in turn, caused an increase in 
temperature, i.e. to about 125.degree. F.-150.degree. F. The continuous 
high-shear dispersing also resulted in entrainment of a substantial 
portion of air. The high-shear dispersing continued for a total of about 
20 minutes during which visible lumps of solid material disappeared and 
the particle size of the undissolved particles was reduced so that a phase 
stable dispersion was formed. 
Thereafter, the main batch material was fed through a series of coarse and 
fine homogenizers, where the material was milled at high speeds for 
relatively short times to further deagglomerate any remaining solids 
particles. The resultant product was a phase stable thixotropic liquid 
automatic dishwashing detergent composition. 
When it was desired to add a fragrance to the detergent composition, as in 
the present example, the main batch material was cooled from the main 
batch temperature which is generally greater than 100.degree. F., 
typically, 105.degree. F. to 125.degree. F., to a temperature of about 
85.degree. F. or less. The cooled main batch material and fragrances were 
then fed through a series of in-line static mixers and the resultant 
product was a scented thixotropic liquid automatic dishwashing detergent 
composition. 
It has been found that the addition of fragrance to the composition 
according to this method does not have an adverse effect on the 
rheological properties of the composition or on the long-term phase 
stability of the composition. The specific gravity, viscosity and phase 
stability, i.e., phase separation, of the scented detergent composition 
were measured (Example A). For comparison, a sample of the main batch 
material (Example B) was removed for analysis prior to the fragrance 
addition. Specific gravity measurements of the bulk and liquid phases were 
made by conventional techniques known to those skilled in the art. For 
example, the specific gravity of the bulk composition was determined by 
weighing a known volume of the bulk composition and an identical volume of 
water. The ratio of the bulk composition weight to the weight of the water 
is termed the "bulk specific gravity". 
The liquid phase specific gravity was determined by first loading a sample 
of the liquid automatic dishwashing detergent composition into a 
conventional centrifuge, e.g. Ivan Sorvall, then spinning the centrifuge 
at a speed of about 2000 rpm to remove a sufficient amount of supernatant 
(clear liquid phase) for weighing. 
The centrifugation step requires approximately 1-11/2 hours to separate a 
sufficient amount of supernatant for several measurements. Thereafter, the 
supernatant specific gravity was calculated by dividing the weight of an 8 
ml vial of the supernatant by the weight of an identical volume of water, 
the ratio being defined as the "liquid phase specific gravity." 
The viscosity of the compositions were measured using a Brookfield HATDV II 
Model viscometer with a #4 spindle (Brookfield Labs, Stoughton, Mass.). 
The viscosity was recorded after the compositions were sheared for 90 
seconds at a shear rate of 20 rpm. The results are summarized below. 
______________________________________ 
A B 
______________________________________ 
Specific gravity (BULK) 
1.28 1.28 
Specific gravity (LIQUID) 
1.28 1.28 
Viscosity (cP) - 1 day after preparation 
5060 4760 
Viscosity (cP) - 12 weeks after preparation 
5150 6350 
Separation (%) - 12 weeks after preparation 
0 0 
______________________________________ 
The above data demonstrates that the process of the present invention 
produces a thixotropic liquid automatic dishwashing detergent composition 
which is highly stable and not subject to phase separation after long 
periods of storage. 
EXAMPLE 34 
The following liquid automatic dishwashing detergent compositions, having 
the formulations described in the following table, were prepared in a 
single mixer according to the alternate embodiment of the process of the 
invention. 
TABLE 
______________________________________ 
Component Example A Example B 
______________________________________ 
Water 36.90 36.15 
LPKn 158 .TM. (5%) 
3.20 3.20 
DOWFAX .TM. 0.80 0.80 
Stearic acid 0.10 0.10 
Gel White .TM. H 1.25 0. 
Caustic (50% A.I.) 
2.40 2.40 
Soda ash 5.00 5.00 
Silicate (45% A.I.) 
17.34 17.34 
Thermphos .TM. NH 12.00 12.00 
Thermphos .TM. NW 12.00 12.00 
Bleach (11% A.I.) 9.00 9.00 
Acrysol .TM. LMW-45N 
0. 2.00 
Air (BALANCE) 0.01 0.01 
TOTAL 100.00 100.00 
______________________________________ 
All of the above ingredients were mixed in a Premier.TM. Mill Mixer at room 
temperature In the examples, a 5% aqueous dispersion of defoamer (LPKn) is 
initially prepared by heating and mixing the defoamer in water until 
dispersed. Similarly, the surfactant (DOWFAX.TM.) and a physical 
stabilizer (stearic acid), are heated to form an emulsion prior to and 
during addition to the mixer. 
After addition of the surfactant and physical stabilizer, the mixture is 
allowed to cool and the remaining ingredients were added sequentially as 
shown in Table I, while subjecting the ingredients to constant high-shear 
mixing. 
Upon adding the final ingredient, typically a bleach compound, the 
composition is subjected to additional high-shear mixing until air in the 
amount of about 2% to about 10% is entrained in the thixotropic detergent 
composition. This highly stable condition is evidenced by the presence of 
a bulk specific gravity about equal to the liquid phase specific gravity. 
As seen in the above examples, a three component air stabilizing system, 
i.e. a physical stabilizer, foam depressant (defoamer) and surfactant is 
employed in each composition. 
Each of the resulting liquid detergent compositions were measured for 
specific gravity, degree of aeration and phase stability, i.e., phase 
separation upon standing. 
The degree of aeration is calculated as follows: 
##EQU2## 
The density of the de-aerated product is determined by centrifuging the 
composition to remove all entrained air, then measuring the density of the 
centrifuged composition by conventional means. The results obtained are 
summarized below. 
EXAMPLE 35 
______________________________________ 
PROPERTY A B 
______________________________________ 
Specific 1.28 1.29 
gravity (bulk) 
Specific 1.28 1.28 
gravity (liquid) 
Degree of 7.91 7.91 
aeration (%) 
Nature of 0.00* 0.00* 
separation 
______________________________________ 
*Age 8 wks after Sample Preparation 
The above data demonstrates that liquid automatic dishwashing detergent 
compositions comprising a three component stabilizing system according to 
the present invention exhibit excellent stability. As shown, the air 
stabilized composition of Example A has a bulk specific gravity (1.28 
g/cc) identical to the liquid phase specific gravity (1.28 g/cc) of the 
composition. Under these conditions the composition exhibits excellent 
phase stability. 
Substantially identical results were obtained in the composition of Example 
B in the absence of a thixotropic thickener, e.g. clay, where a bulk 
specific gravity of 1.29 g/cc was achieved, almost identical to the liquid 
phase specific gravity of the composition. Example not only demonstrates 
that clay is not required for producing an acceptable stabilized 
composition, but is further advantageous in that all of its ingredients 
are completely water soluble, resulting in superior spotting and filming 
performance compared to clay based thixotropic detergents. 
EXAMPLE 36 
A phosphate-free composition having the following formulas were prepared: 
______________________________________ 
Ingredients A B C D E 
______________________________________ 
NaOH (50%) 5 5 5 5 5 
Sodium Carbonate 
4 4 6 4 4 
Sodium Silicate (44%; 
SiO.sub.2,; Na.sub.2 O = 2.1) 
39 39 39 45 39 
Sokolan 0 CL 
17 17 17 17 17 
(45%) 
Sodium Hypochlorite 
9 9 9 9 9 
(13%) 
Dye .0012 .0012 0.0012 
.0012 .0012 
Dowfax 3B2 1 1 1 1 1 
Aluminum Stearate 
0.3 0.5 0.5 0.5 0.3 
Vasagel Clay 0.5 0.5 0.5 0.5 0.75 
Stearic Acid -- -- -- -- -- 
Water 24.7988 23.9988 21.9988 
17.9988 
23.9488 
Viscosity.sup.2 Standing.sup.1 
400 1420 1400 1960 860 
(cps) 
Density (g/ml) 
1.34 1.34 1.37 1.36 1.33 
______________________________________ 
______________________________________ 
Ingredients F G H I J 
______________________________________ 
NaOH (50%) 6 6 6 6 6 
Sodium Carbonate 
4 4 4 4 4 
Sodium Silicate (44%; 
39 39 39 39 39 
SiO.sub.2 ; Na.sub.2 O = 2.1) 
Sokolan 0 CL 
17 17 17 17 17 
(45%) 
Sodium Hypochlorite 
9 9 9 9 
(13%) 
Dye .0012 0.0012 0.0012 
0.0012 
0.0012 
Dowfax 3B2 1 1 1 1 1 
Aluminum Stearate 
0.3 0.3 0.3 0.4 0.3 
Vasagel Clay 1.0 1.5 1 1 1.5 
Stearic Acid -- -- 0.05 0.05 0.05 
Water 22.6988 22.1988 22.6488 
22.5488 
22.1488 
Viscosity.sup.2 Standing.sup.1 
950 1220 1150 162 142 
(cps) 
Density (g/ml) 
1.36 1.35 1.37 1.35 1.36 
______________________________________ 
Formula A to G were prepared by making a premix A with all the formula 
amounts of water, dye, Dowfax 3B2, aluminum stearate and clay (stainless 
steel vessel of 30 cm in diameter and 40 cm in with a Cowles dispersing 
plate of 9 cm in diameter working at 400 rpm 68 RT for 10 minutes; premix 
batch size=4.5 kg). This premix was ground through an in line homogenizer 
before to be re-introduced in the same stainless steel vessel after 
cleaning) and the other ingredients were then added in the order shown in 
the table with the Cowles dispersing plate working at 800 rpm (batch 
size=6 kg). All the finished products were ground trough the in line 
homogenizer just after batching. 
Formulae H to J were made by the same procedure as formulae A to G except 
that a second premix B was made by heating (up to 80.degree. C.) a blend 
containing the formula amount of stearic acid plus part of the formula 
amount of water plus part of the formula amount of caustic. This second 
premix B was then added to the main batch vessel just before the bleach 
incorporation. 
This invention in its broader aspects is not limited to the specially 
described embodiments or examples and departures may be made therefrom 
without departing from the principles of the invention and without 
sacrificing its chief advantages.