Linear viscoelastic automatic dishwasher compositions containing a crosslinked methyl vinyl ether/maleic anhydride copolymer

A linear viscoelastic aqueous liquid automatic dishwasher detergent composition comprising water; up to about 2% by weight of long chain fatty acid or salt thereof; from about 0 to 5% by weight of organic detergent; from about 5 to 40% by weight of alkali metal detergent builder salt; up to about 20% by weight of a chlorine bleach compound; and 0.1 to 5.0% of a cross-linked copolymer of methyl vinyl ether and maleic anhydride which is crosslinked with at least about 0.5 weight % of an aliphatic diene having about 6 to about 20 carbon atoms.

FIELD OF THE INVENTION 
The invention relates to aqueous linear viscoelastic (gel-like) liquid 
compositions which are especially useful as automatic dishwashing 
detergent compositions. 
BACKGROUND OF THE INVENTION 
Liquid automatic dishwashing detergent compositions have recently received 
much attention, and the aqueous products have achieved commercial 
popularity. 
The acceptance and popularity of the liquid formulations as compared to the 
more conventional powder product stems from the convenience and 
performance of the liquid products. However, even the best of the 
currently available liquid formulations still suffer form two major 
problems: product phase instability and bottle residue, and to some 
extent, cup leakage from the dispenser cup of the automatic dishwashing 
machine. 
Representative patent art in this area includes Rek U.S. Pat. No. 
4,556,504; Bush et al. U.S. Pat. No. 4,226,736; Ulrich U.S. Pat. No. 
4,431,559; Sabatelli U.S. Pat. No. 4,147,650; Paucot U.S. Pat. No. 
4,079,015; Leikhem U.S. Pat. No. 4,116,849; Milora U.S. Pat. No. 
4,521,332; Jones U.S. Pat. No. 4,597,889; Heile U.S. Pat. No. 4,512,908; 
Laitem U.S. Pat. No. 4,753,748; Sabatelli U.S. Pat. No. 3,579,455; Hynam 
U.S. Pat. No. 3,684,722. Other patents relating to thickened aqueous 
detergent compositions include Ginn U.S. Pat. No. 3,060,124, U.S. Pat. No. 
3,985,668; U.K. Patent Applications GB 2,116,199A and GB 240,450; U.S. 
Pat. No. 4,511,487; Drapier, et al. U.S. Pat. No. 4,752,409; U.S. Pat. No. 
Drapier, et al. 4,801,395; Ahmed et al. U.S. Pat. No. 4,889,653. Commonly 
assigned co-pending patents include, for example, Ser. No. 427,912 filed 
Oct. 24, 1989; Ser. No. 924,385, filed Oct. 29, 1986; Ser. No. 323,138, 
filed Mar. 13, 1989; Ser. No. 328,716, filed Mar. 27, 1989; Ser. No. 
323,137, filed Mar. 13, 1989; Ser. No. 323,134, filed Mar. 13, 1989. 
The solubilizing effect of potassium salts on sodium tripolyphosphate in 
aqueous detergent compositions is described in Smeets U.S. Pat. No. 
3,720,621. This patent describes homogeneous liquid compositions 
containing 14 to 35 percent sodium tripolyphosphate, 0.1 to 50 percent of 
potassium and/or ammonium salt of an inorganic or organic acid, water, and 
optional surfactants, solubilizing agent, organic sequestering agent and 
other adjuvants. 
Corring U.S. Pat. No. 4,836,948 discloses a viscoelastic gel detergent 
composition characterized by its viscosity under low and high shear 
conditions, pH, and steady state viscoelastic deformation compliance. The 
composition requires the presence of a polycarboxylate polymeric 
thickener, preferably a cross-linked polyacrylic acid. The compositions of 
this patent also, however, require a trivalent metal containing material, 
especially an aluminum containing material such as alumina. The 
compositions may further include a structuring chelant which may be a salt 
of carbonate, pyrophosphate or mixture thereof, and preferably the 
potassium salts. 
The recently issued U.S. Pat. No. 4,859,358 discloses the incorporation of 
metal salts of long chain hydroxy fatty acids, as anti-tarnishing agents, 
which do not affect the viscosity of the compositions in thickened aqueous 
automatic dishwasher detergent compositions. The thickeners for these 
compositions may be a high molecular weight polycarboxylate polymer, such 
as those sold under the Carbopol trade name, and specific 600 and 900 
series resins are mentioned. It is also disclosed that the compositions 
include entrained gas, e.g. air bubbles to further ensure stability. 
Amounts of air in the range of from about 1% to 20%, preferably from about 
5 to 15% by volume, will lower the specific gravity of the overall 
composition to within from about 5% more than to about 10% less than, 
preferably from 1% more than to 5% less than, the specific gravity of the 
aqueous phase. In Example III of this patent, the specific gravity of the 
composition was stated to be 1.32 g/cm.sup.3. The compositions are not 
described as being linear viscoelastic and as exemplified do not include 
any potassium salts. 
While the compositions disclosed in U.S. Ser. No. 353,712 provided a 
satisfactory solution to the problems of phase instability, bottle residue 
and cup leakage, it has now been found that under some storage and 
handling conditions and/or processing conditions, additional improvements 
would be desirable. Specifically, if the viscoelastic composition is 
subjected to repeated heating and cooling cycles, growth of crystals and 
product thinning and/or precipitate formation has been observed. 
As a result of these problems, the finished product not only may be 
perceived as unaesthetic but, more importantly, the product viscosity is 
often lowered which in turn may lead to cup leakage and corresponding 
degradation in cleaning performance. 
SUMMARY OF THE INVENTION 
The present invention related to an improved aqueous liquid automatic 
dishwashing detergent composition (abbreviated LADD) which is 
characterized by its linear viscoelastic behavior, excellent stability 
against phase separation, excellent stability against settling of 
dissolved or suspended particles under high and low temperature 
conditions, low levels of bottle residue, relatively high bulk density, 
substantial absence of loosely bound water, superior aesthetics, improved 
optical properties, freedom from fish-eyes, absence of crystal formation 
and growth, and resistance to cup leakage of less than about 10 wt %. 
The present invention relates to an automatic dishwashing composition which 
contains a cross-linked, methyl vinyl ether/maleic anhydride polymeric 
thickening agent (referred to as cross-linked Gantrez) that is 
exceptionally stable to the high bleach, salt, and alkali levels found in 
automatic dishwashing detergent. In addition, the composition formed is 
temperature-stable. Furthermore, by controlling the conditions of mixing 
the ingredients of the compositions, and by controlling the method of 
dispersion, and by controlling the pH and temperature of the aqueous 
solution of the polymeric thickener, the formation of fish-eyes and loss 
of viscosity with time can be minimized. 
It is thought that if the gel forming polymer were surface active, in 
addition to its function as a structuring agent, that it would make a 
contribution toward reduced spotting and filming on glassware. This would 
be possible if nonionic-like groups were appended to the polymer, causing 
it to have increased surfactant properties. Ordinarily it is not possible 
to incorporate classical nonionics into a liquid automatic dish detergent 
because the nonionics react with the hypochlorite bleach. In the case of 
cross-linked Gantrez, the OCH.sub.3 groups on every repeating unit 
contribute a chemical functionality like that of the ethoxy groups on 
ethoxylated nonionic surfactants. For example, a dilute solution (0.05%) 
of cross-linked Gantrez shows a lower surface tension, by about 4 
dynes/cm, than a solution of Carbopol 614 under the same circumstances. 
Surprisingly, these groups do not contribute to loss of available 
chlorine, but rather compositions containing them show the same chlorine 
stability as those without. 
Another advantage the the cross-linked Gantrez polymer used in the instant 
compositions has over Carbopol is that it is much easier to disperse. It 
is well known that Carbopol is hard to disperse. BF Goodrich suggests the 
use of an eductor and other specialized procedures to get good 
dispersions. The problem arises because Carbopol is so hydrophilic that 
the individual particles swell and the particles clump to form aggregates. 
When dispersion is attempted, the outside of the aggregate hydrates and 
swells. The inside is no longer readily contacted with water. This causes 
fish eyes and regions of inhomogeneity that are very hard to remove by 
further mixing. The fish eyes and inhomogeneous dispersion persist in the 
final product. The result is decreased control over the final rheological 
properties of the product and increased batch to batch variation. These 
variations are readily perceived by the end user and are interpreted as 
poor quality product. 
In contrast, in cross-linked Gantrez the aggregates, if any, that form are 
readily broken up by mechanical action before the particle swells and 
gelation occurs. The reason, it is believed, is the presence of the maleic 
anhydride ring in the polymer. 
This causes a great decrease in the water seeking character of the polymer 
and permits preliminary dispersion to occur by mechanical action. In time, 
the maleic anhydride ring hydrolyzes, the carboxylate groups are freed, 
and the polymer swells and gels into a viscoelastic substance. The ease of 
dispersion is reflected in lack of fish eyes, more homogeneous final 
product, and a more reliable manufacturing process. 
Accordingly, the present invention provides an improved linear viscoelastic 
aqueous liquid automatic dishwashing detergent composition comprising 
water; up to about 2% by weight of long chain fatty acid or salt thereof; 
from about 0 to 5% by weight of low foaming, chlorine bleach stable 
surfactant; from 0 to 3% by weight of a chlorine bleach-stable foam 
depressant; from about 5 to about 40% by weight of alkali metal detergent 
builder salt; from about 0 to about 20% by weight of a chlorine bleach 
compound; and from about 0.1 to about 5% by weight of a cross-linked 
polymeric thickening agent, wherein the compositions preferably have a 
bulk density of from about 1.28 g/cm.sup.3 to about 1.42 g/cm.sup.3. 
in a preferred embodiment, the linear viscoelastic aqueous LADD comprises, 
approximately, by weight, 
(a) 5 to 40% phosphate detergent builder such as sodium tripolyphosphate; 
(b) 5 to 15% alkali metal silicate; 
(c) 0 to 8% alkali metal hydroxide; 
(d) 0 to 5% water-dispersible organic detergent active material of the type 
that is stable to chlorine bleach; 
(e) 0 to 1.5% chlorine bleach stable foam depressant; 
(f) chlorine bleach compound in an amount sufficient to provide about 0.2 
to 4% of available chlorine; 
(g) 0.1 to 5.0% hydrophilic cross-linked water-dispersible thickening agent 
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 to increase the physical stability of the composition; 
(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 
wherein the entire composition has a cup leakage of less than 10 wt %, more 
preferably less than 8 wt %, and most preferably less than 6 wt %.

DESCRIPTION AND PREFERRED EMBODIMENTS 
The compositions of this invention are thickened aqueous liquids containing 
various cleansing active ingredients, detergent builder salts and other 
detergent adjuvants, structuring and thickening agents and stabilizing 
components, although some ingredients may serve more than one of these 
functions. 
The advantageous characteristics of the compositions of this invention 
include: 1) improved optical properties, 2) physical stability such as 
manifested by little or no phase separation, solid settling or viscosity 
change over time, 3) little or no settling and/or viscosity change 
resulting from temperature variations, 4) low bottle residue, 5) low cup 
leakage of less than 10 wt %, 6) high cleaning performance, e.g. low 
spotting and filming, low dirt residue, 7) consistency in product 
characteristics performance, 8) superior aesthetics, 9) easier 
manufacturing process conditions than compositions made with Carbopol 
resins, and 10) improved biodegradability. These characteristics are 
believed to be attributed to several interrelated factors such as low 
undissolved particulate content, product density and linear viscoelastic 
rheology. These factors are, in turn, dependent on several critical 
compositional components and processing conditions of the formulations, 
namely, (1) the inclusion of a cross-linked polymeric thickening agent 
that is stable to alkali, bleach and salt, in an amount effective for 
thickening and that has a high water absorption capacity, exemplified by a 
copolymer of methyl vinyl ether/maleic anhydride which is cross-linked 
with a diene such as Octadiene (2) inclusion of a physical stabilizing 
amount of a long chain fatty acid or salt thereof, and (3) a product bulk 
density of at least about 1.28 g/cc, especially at least 1.32 g/cc and (4) 
maintaining the pH of the neutralized polymeric thickener at a pH of at 
least 11, more preferably at least 11.5. 
In particular, the linear viscoelastic aqueous liquid automatic dishwashing 
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 I: 
TABLE I 
______________________________________ 
Aging Temperature (.degree.F.) 
Minimum Duration (Weeks) 
______________________________________ 
140 &gt;1 
120 &gt;4 
100 &gt;12 
77 &gt;21 
______________________________________ 
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 in viscosities, yield stress or other 
dynamic-mechanical properties, 
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 and cup 
leakage. Specifically, for the preferred 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. 
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) 
modulus (G') and the viscous (loss) modulus (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 
modulus 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 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 
modulus 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 S 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 compositions to 
cause it to flow, the surrounding portions will follow. As a result of 
this cohesiveness of the linear viscoelastic characteristic, 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 characterized the compositions of this invention. 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. Linear 
viscoelasticity also contributes to the elimination of dripping of the 
contents, when the product is poured from a bottle and hence reduction of 
formation of drops around the container mouth at the conclusion of pouring 
the product from a container. 
It has previously been found in connection with other types of thickened 
aqueous liquid automatic dishwashing detergent compositions that 
agglomeration or escape of incorporated air bubbles could be avoided by 
incorporating certain surface active ingredients, especially higher fatty 
acids and the salts thereof, such as stearic acid, behenic acid, palmitic 
acid, sodium stearate, aluminum stearate, and the like. 
Therefore, in the present invention, in order to avoid stabilization of air 
bubbles which may become incorporated into the compositions during normal 
processing, such as during various mixing steps, the surface active 
ingredients are post-added to the remainder of the composition, under low 
shear conditions using mixing devices designed to minimize cavitation and 
vortex formation. 
The surface active ingredients present in the composition will include the 
main detergent surface active cleaning agent, and will also preferably 
include anti-foaming agent (e.g. phosphate ester) and higher fatty acid or 
salt thereof as a physical stabilizer. 
Certain classes of polymers can be lightly cross-linked to give gels in 
aqueous systems. These gels have strong elastic character, are able to 
suspend solids, resist syneresis on aging, and have other desirable 
physical properties for use in consumer products. Desirable properties for 
an automatic dishwasher detergent include: 1) ease of dispensing from a 
bottle (easily shear-thinned) 2) high yield value (so the product will not 
run out of the detergent dispenser cup in the door of the dishwasher 3) 
good maintenance of viscosity on aging, especially in the presence of a 
high concentration of inorganic salts and 4) resistance to oxidation by 
components of the formula containing available chlorine. The preferred 
polymers to impart these properties are lightly cross-linked so that they 
tend to swell and form strong three-dimensional networks in aqueous 
systems. 
One such class of polymers is based on methyl vinyl ether/maleic anhydride 
copolymers and terpolymers. Examples of useful polymers are: methyl vinyl 
ether, maleic anhydride, acrylic acid, cross-linked; methyl vinyl ether, 
maleic anhydride, vinyl pyrrolidone, cross-linked; and methyl vinyl ether, 
maleic anhydride, isobutene, cross-linked. The cross-linking agent is 
essential to establish the kind of polymer network useful in this 
invention. The cross-linking agent can be any hydrocarbon with a chain 
length of four or more carbon atoms containing at least two carbon-carbon 
double bonds. The cross-linking agent is mainly a hydrocarbon with 
optional halogen and oxygen-containing substituents and linkages such as 
ester, ether and OH groups. These cross-linking agents can vary in amount 
from 0.01 to 30% by weight of the total quantity of polymer used. Examples 
of cross-linking agents are 1,7-Octadiene, 1,9 Decadiene, non-terminal 
dienes, Divinyl Glycol, Butane Divinylether, polyallyl pentaerythritol and 
polyallyl sucrose. Cross-linking can also be achieved through the maleic 
anhydride after the polymer is formed, via ester or amide formation using 
polyols and polyamines such as 1,4 butane diol and polyethylene glycols. 
The most useful polymers of these inventions are the Gantrez AN 
cross-linked with aliphatic dienes such as 1,7 octadiene and 1,9 
decadiene. 
Gantrez AN polymers cross-linked from 0.01 to 10% by weight of 1,7 
octadiene were shaken overnight in order to hydrolyze the maleic anhydride 
ring. The polymer solutions were neutralized to pH 7 to fully ionize the 
carboxyl groups. The results show that 5% by weight of cross-linking agent 
is necessary before a gel is formed. If Gantrez AN is cross-linked with 
1,9 decadiene then a gel is formed at 3-4% cross-linking. 
The cross-linking causes the formation of a polymer that disperses in water 
to form a gel with a yield point. Table II gives typical yield points for 
the polymer cross-linked with 1,9 decadiene. 
TABLE II 
______________________________________ 
Yield Point.sup.a as a Function of Polymer Concentration in Water 
for Cross-linked Gantrez (Gantrez ACV-4006 cross-linked with 
1,9 Decadiene). 
Polymer Concentration 
(Weight %) pH Yield Point, Pa 
______________________________________ 
0.125 7 37 
0.250 7 64 
0.500 7 176 
______________________________________ 
.sup.a Measurements were made using the Haake Rotoviscometer RV12 with MV 
IP sensor system. Shear rate was varied from 0 to 10 sec.sup.-1. 
Brookfield viscosity measurements were made using cross-linked Gantrez 
polymers, and results are summarized in Table III. Results show that even 
at very low concentrations, cross-linked Gantrez yield highly viscous 
polymer solutions. These viscosities characterize the degree of 
polymerization of the polymers. 
TABLE III 
______________________________________ 
Brookfield Viscosity.sup.a of 0.5% Cross-linked Gantrez 
(ACV-4006) in water at pH 7. 
Brookfield Viscosity 
Spindle # RPM (cps) 
______________________________________ 
T-C 1 376 .times. 10.sup.3 
T-C 2.5 180 .times. 10.sup.3 
T-C 5 105 .times. 10.sup.3 
T-C 10 59 .times. 10.sup.3 
______________________________________ 
.sup.a The measurements were taken with a Brookfield Model DV II. 
The copolymer of methyl vinyl ether/maleic anhydride is illustrated by the 
following formula: 
##STR1## 
wherein x is about 50 mole %. 
The copolymer is cross-linked with about 0.5 to about 20.0 wt % of a diene 
monomer having about 6 to about 20 carbon atoms, more preferably about 7 
to 16 and most preferably about 8 to 12, wherein preferred diene monomers 
are 1,7 Octadiene and 1,9 decadiene. These water-dispersible, cross-linked 
thickening resins were obtained from the GAF corporation. The amount of 
the cross-linked polymeric thickening agent or other high molecular 
weight, hydrophilic cross-linked polycarboxylate thickening agent to 
impart the desired rheological property of linear viscoelasticity will 
generally be in the range of from about 1.5 to 5%, preferably from about 
0.5 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 inorganic detergent builder salts that are employed in the compositions 
of the instant invention are selected from the group consisting of sodium 
and potassium salts of polyphosphates, orthophosphates, carbonates, 
bicarbonates, sesquicarbonates and borates and aluminosilicates, wherein 
sodium tripolyphosphate (NaTPP) and potassium tripolypolyphosphate (KTPP) 
are especially preferred. 
Organic detergent builders maybe used alone or in combination with the 
inorganic builder salts, wherein the organic builder salts are selected 
from the group consisting of sodium and potassium salts of citrates, 
nitrilotriacetates, oxydyacetates, carboxymethoxysuccinates, 
tetracarboxylates, and starch. 
In accordance with the present invention, however, the detergent builder 
salts will be comprised of mixtures of at least potassium tripolyphosphate 
(KTPP) and sodium tripolyphosphate (NaTPP). Typical ratios (based upon 
weight) 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% and most preferably from about 15 to 30% by weight of the 
composition. Of this total amount of the detergent builders at least 50% 
by weight (preferably at least about 8% by weight of the composition) will 
be KTPP and preferably at least 5% by weight (preferably at least 2% by 
weight of the composition) will be NaTPP. More preferably, the alkali 
metal detergent builder salt will be comprised of from about 65 to 95% by 
weight of KTPP, especially 75 to 90% of KTPP and from about 5 to 35% of 
NaTPP, especially 10 to 25% of NaTPP. In terms of the total composition, 
the amount of KTPP will be in the range of from about 8 to 25% by weight, 
preferably 15 to 22%, and the amount of NaTPP will be in the range of from 
about 2 to 10% by weight, preferably 3 to 8%. 
When other alkali metal detergent builder salts are present in the 
formulation, they will usually be present in amounts less than 5% by 
weight based on the total composition and, in any case, in amounts to 
maintain the K/Na ratios to within the above described range. 
The linear viscoelastic compositions of this invention may, and preferably 
will, contain a small, but effective, amount of a long chain fatty acid or 
monovalent or polyvalent salt thereof to stabilize the composition. 
Although the manner by which the fatty acid or salt contributes to the 
rheology and stability of the composition has not been fully elucidated it 
is hypothesized that it may function as a hydrogen bonding agent or 
cross-linking agent for the polymeric thickener. 
The preferred long chain fatty acids are the higher aliphatic fatty acids 
having from about 10 to 50 carbon atoms, more preferably from about 12 to 
40 carbon atoms, and especially preferably from about 14 to 40 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, wherein the aliphatic radical can have functional 
groups can be attached to the aliphatic radical, wherein the functional 
groups are selected from the group consisting of hydroxyl, ester, tertiary 
amines and dialkyl substituted amide groups. 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 include, for example, decanoic acid, 
dodecanoic acid, palmitic acid, myristic acid, stearic acid, isostearic 
acid, behenic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco 
fatty acid, soya fatty acid, mixtures of these acids, etc. Stearic acid 
and mixed fatty acids, e.g. stearic acid/palmitic acid, are preferred. 
Further improvements in phase stability, particularly under elevated 
temperature storage conditions, and maintenance of product viscosity 
levels can be obtained by using longer chain length fatty acids in the 
range of from C.sub.18 to C.sub.40. Either individual or mixtures of these 
longer chain length fatty acids can be used, however, the average chain 
length should be in the range of from about 20 to 32 carbon atoms, 
especially 24 to 30 carbon atoms and mixture of fatty acids encompassing 
this range are preferred. Suitable mixed fatty acids are commercially 
available, for instance those sold under the trade name Syncrowax by 
Croda. 
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 tri- valent metals of Groups 
IIA, IIB and IIIB, such as magnesium, calcium, aluminum and zinc, although 
other polyvalent metals, including those of Groups IIIA, IVA. VA. IB, IVB, 
VB, VIB, VIIB and VIII of the Periodic Table of the Elements can also be 
used. Specific examples of such other polyvalent metals include Ti, Zr, V, 
Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. Generally, the metals may be 
present in the divalent to pentavalent state. Preferably, the metal salts 
are used in their higher oxidation states. Naturally, for use in automatic 
dishwashers, as well as any other applications where the invention 
composition will or may come 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 are 
especially preferred since they are generally safe food additives. 
The amount of the fatty acid or fatty acid salt stabilizer to achieve the 
desired enhancement of physical stability will depend on such factors as 
the nature of the fatty acid or its salt, the nature and amount of the 
thickening agent, detergent active compound, inorganic salts, other 
ingredients, as well as the anticipated storage and shipping conditions. 
Generally, however, amounts of the fatty acid or fatty acid salt 
stabilizing agents in the range of from about 0.02 to 2% by weight, 
preferably 0.04 to 1%, more preferably from about 0.06 to 0.8%, most 
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 polycarboxylate thickening agents, the addition 
of the fatty acid or salt not only increases physical stability, but also 
provides a simultaneous increase in apparent viscosity. From about 
0.08-0.4 weight percent of the metal salt of the fatty acid salt or the 
fatty acid and from about 0.4-1.5 weight percent of the polymeric 
thickening agent is usually sufficient to provide these simultaneous 
benefits and, therefore, the use of these ingredients in these amounts is 
most preferred. 
In order to achieve the desired benefit from the fatty acid or fatty acid 
salt stabilizer, without stabilization of excess incorporated air bubbles 
and consequent excessive lowering of the product bulk density, the fatty 
acid or salt is preferably 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 near the melting temperature of the fatty acid or its 
salt. 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 71.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. 
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 reduced by suitable 
selection of the type and/or amount of detergent active material. The 
degree of foam is also somewhat dependent on the hardness of the wash 
water in the machine whereby suitable adjustment of the proportions of the 
builder salts, such as NaTPP which has a water softening effect, may aid 
in providing a degree of foam inhibition. However, it is generally 
preferred to include a chlorine bleach stable foam depressant or 
inhibitor. Particularly effective are the alkyl phosphoric acid esters of 
the formula: 
##STR2## 
and especially the alkyl acid phosphate esters of the formula: 
##STR3## 
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 derivatives of each type of ester, for example, the 
condensation products of one mole of ester with from 1 to 10 moles, 
preferably 2 to 6 moles, more preferably 3 or 4 moles, ethylene oxide can 
also be used. Some examples of the foregoing are commercially available, 
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 diethers of the same type, may be employed. Especially 
preferred is a mixture of mono- and di-C.sub.16 -C.sub.18 alkyl acid 
phosphate esters such as monostearyl/distearyl acid phosphates 1.2/1, and 
the 3 to 4 mole ethylene oxide condensates thereof. When employed, 
proportions of 0.05 to 1.5 weight percent, preferably 0.1 to 0.5 weight 
percent, of foam depressant in the composition is typical. The weight 
ratio of detergent active component to foam depressant generally ranges 
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 
salts, such as the stearate salts, when included, are also effective as 
foam depressants. 
Although any chlorine bleach compound may be employed in the compositions 
of this invention, such as dichloroisocyanurate, dichloro-dimethyl 
hydantoin, or chlorinated TSP, alkali metal or alkaline earth metal, e.g. 
potassium, lithium, magnesium and especially sodium, hypochlorite is 
preferred. The composition should contain sufficient amount of chlorine 
bleach compound to provide about 0.2 to 4.0% by weight 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 13% available chlorine in amounts of about 3 to 20%, 
preferably about 7 to 12%, can be advantageously used. 
Detergent active material useful herein should be low-foaming and stable in 
the presence of chlorine bleach, especially hypochlorite bleach. For this 
purpose those of the organic aromatic anionic, organic aliphatic anionic, 
nonionic, amine oxide, phosphine oxide, sulphoxide or betaine water 
dispersible surfactant types are preferred, wherein anionic surfactants 
are most preferred. Particularly preferred surfactants are the linear or 
branched alkali metal mono- and/or di-(C.sub.8 -C.sub.14)alkyl diphenyl 
oxide mono- and/or di-sulphates, 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 organic anionic, non-soap 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 hexadecylbenzenesulphonates. 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.3 R'NO, in which each R represents a 
lower alkyl group, for instance, methyl, and R' 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.2 R'PO or sulphoxide RR'SO 
can be employed. Betaine surfactants are typically of the structure 
R.sub.2 R'N 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, myristyldimethylamine oxide, the 
corresponding phosphine oxides and sulphoxides, and the corresponding 
betaines, including dodecyldimethylanmonium 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. If 
chlorine bleach is not used than any of the well known low-foaming 
nonionic surfactants such as alkoxylated fatty alcohols, e.g. mixed 
ethylene oxide-propylene oxide condensates of C.sub.8 -C.sub.22 fatty 
alcohols can also be used. 
The chlorine bleach stable, water dispersible or water soluble organic 
detergent-active material (surfactant) will normally be present in minor 
amounts, generally about 1% by weight of the composition, although smaller 
or larger amounts, such as up to about 5%, such as from 0 to 5%, 
preferably from 0.3 or 0.4 to 2% by weight of the composition, may be 
used. 
Alkali metal (e.g. potassium or sodium) silicate, which provides alkalinity 
and protection of hard surfaces, such as fine china glaze and pattern, is 
generally employed in an amount ranging from about 5 to 20 weight percent, 
preferably about 5 to 15 weight percent, more preferably 8 to 12 weight 
percent in the composition. The sodium or potassium silicate is generally 
added in the form of an aqueous solution, preferably having Na.sub.2 
O:SiO.sub.2 or K.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. 
Many of the other components of this composition, especially alkali metal 
hydroxide and bleach, are also often added in the form of a preliminary 
prepared aqueous dispersion or solution. However, unless otherwise noted, 
when amounts of a particular ingredient are given, the reference is to an 
active ingredient basis, i.e. does not include the aqueous carrier. 
In addition to the detergent active surfactant, foam inhibitor, alkali 
metal silicate corrosion inhibitor, and detergent builder salts, all of 
which 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, potassium tripolyphosphate and alkali metal silicate, 
however, it is usually necessary to include alkali metal hydroxide, e.g. 
NaOH or KOH, to achieve the desired high alkalinity. Amounts of alkali 
metal hydroxide in the range of from about 0 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 compositions in minor amounts, for example from 0 to 4%, 
preferably 0 to 2%, by weight of the composition. 
Another often beneficial additive for the present liquid automatic 
dishwasher detergent compositions is a relatively low molecular weight, 
non-crosslinked polyacrylic acid, such as the commercial product Acrysol 
LMW=45N, which has a molecular weight of about 45,000. The low polyacrylic 
acids can provide additional thickening characteristics but are primarily 
introduced for their ability to function as a builder or chelating agent. 
In this capacity, the low molecular weight polyacrylic acids can 
contribute to reduced spotting or streaking and reduced filming on dishes, 
glassware, pots, pans and other utensils and appliances. Generally, a 
suitable molecular weight ranges for the non-crosslinked polyacrylic acid 
is from about 800 to 200,000, preferably 1000 to 150,000, and more 
preferably from about 2,000 to 100,000. When present in the formulation, 
the non-crosslinked polyacrylic acid can be used in amounts up to about 
10% by weight, preferably from about 0 to 8% by weight, especially 2 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 sodium benzene sulfonate, toluene 
sulfonate, xylene sulfonate and cumene sulfonate, preservatives, dyestuffs 
and pigments and the like, all of course being stable to chlorine bleach 
compound and high alkalinity. Especially preferred for coloring are the 
chlorinated phthalocyanines and polysulphides of aluminosilicate which 
provide, respectively, pleasing green and blue tints. To achieve stable 
yellow colored products, the bleach stable mixed dyes C.I. Direct Yellow 
28 (C.I. 19555) or C.I. Direct Yellow 29 (C.I. 19556) can be added to the 
compositions. TiO.sub.3 may be employed for whitening or neutralizing 
off-shades. 
Although for the reasons previously discussed excessive air bubbles are not 
often desirable in the invention compositions, depending on the amounts of 
dissolved solids and liquid phase densities, incorporation of small 
amounts of finely divided air bubbles, generally up to 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 visual appearance, product 
density and flowability. The incorporated air bubbles should be finely 
divided, such as up to about 100 microns in diameter, preferably from 
about 20 to 40 microns in diameter. Other inert gases can also be used, 
such as nitrogen, helium, argon, 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 S. The amount of water is readily determined by routine 
experimentation and generally will range from 30 to 75 weight percent, 
preferably about 35 to 65 weight percent. Preferably, the water should 
also be deionized or softened. 
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) 
(i) 0 to 35%, preferably 5 to 30% potassium tripolyphosphate detergent 
builder; 
(ii) 0 to 35% sodium tripolyphosphate, preferably 5 to 15% 
(b) 0 to 15, preferably 5 to 12%, alkali metal silicate; 
(c) 0 to 8%, preferably 1.0 to 6%, alkali metal hydroxide; 
(d) 0 to 5%, preferably 0.3 to 5%, chlorine bleach stable, organic 
detergent-active material, preferably non-soap anionic detergent; 
(e) 0 to 1.5%, preferably 0.1 to 0.5%, 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) 0.1 to 5% of a crosslinked copolymer of methyl vinyl ether/maleic 
anhydride which is cross-linked with 0.5 to 2.5 weight percent of an 
aliphatic diene having about 6 to about 20 carbon atoms; 
(h) 0.02 to 2.0% of a metal salt of a fatty acid or a fatty acid; and 
(i) water. 
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) 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, i.e. have a 
sufficiently low yield stress value to flow under their own weight 
(gravity), although squeezable containers are often convenient and 
accepted by the consumer for gel-like products. 
The liquid aqueous linear viscoelastic automatic dishwasher compositions of 
this invention are readily employed in known manner for washing dishes, 
other kitchen utensils and the like in an automatic dishwasher, provided 
with a suitable detergent dispenser, in an aqueous wash bath containing an 
effective amount of the composition, generally sufficient to fill or 
partially fill the automatic dispenser cup of the particular machine being 
used. 
The invention also provides a method for cleaning dishware in an automatic 
dishwashing machine with an aqueous wash bath containing an effective 
amount of the liquid linear viscoelastic automatic dishwasher detergent 
composition as described above. The composition can be readily poured from 
the polyethylene container with little or no squeezing or shaking into the 
dispensing cup of the automatic dishwashing machine and will be 
sufficiently viscous and cohesive to remain securely within the dispensing 
cup until shear forces are again applied thereto, such as by the water 
spray from the dishwashing machine. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
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. 
EXAMPLE I 
A typical synthesis of cross-linked Gantrez is set forth as follows: 
In a one liter pressure reactor charge the following (all parts by weight): 
404.4 parts cyclohexane, 269.6 parts ethyl acetate, 6 parts 1,7 octadiene. 
The initiator t-butylperoxypivalate, is added at 58.degree. C. in three 
increments of 0.1 part each. Each portion is added all at once, not over a 
period of time. Initiator is added as 0.1 part at times: 0, 60, and 120 
minutes of the reaction. Seventy-five parts of molten maleic anhydride and 
49.0 parts of methyl vinyl ether are mixed together and added to the 
reaction vessel at 58.degree. C. and 65 psi. They are fed in over a period 
of time for 2 to 3 hours. The reaction mixture is held at 58.degree. C. 
for two hours after the last addition of the initiator. The presence of 
maleic anhydride is followed by testing with triphenyl phosphene. The 
product precipitates out of solution (slurry polymerization). After the 
reaction is complete, the product is filtered and dried in a vacuum oven. 
EXAMPLE II 
Formulations A-F (Table IV) were prepared by first forming a uniform 
dispersion of the crosslinked Gantrez AN polymer from Example 1 in about 
90% of the water to be added as water in the formula. The Gantrez AN was 
added to deionized water with agitation. The dispersion was then 
neutralized by addition of the caustic soda (50% NaOH) component until a 
thickened product of gel-like consistency was formed. 
To the resulting gelled dispersion the silicate, sodium tripolyphosphate 
(NaTPP), potassium tripolyphosphate (KTPP), the surfactant emulsion 
(described below), bleach and color, were 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 was cooled to 90.degree. F. from 
90.degree.-110.degree. F. before the bleach was added. 
The surfactant emulsion of the phosphate anti-foaming agent (LPKN), stearic 
acid or fatty acid mixture and detergent (Dowfax 3B2) was prepared 
separately by adding these ingredients to the remaining 3% of water (that 
was not used to disperse the polymer) and heating the resulting mixture to 
a temperature of about 160.degree. F. (71.degree. C.). 
The aging data at 100.degree. F. and 120.degree. F. (Table V) indicates 
that Formula E is the best out of all the cross-linked Gantrez 
compositions. Formula F, which contains 5% linear Gantrez separated after 
2 weeks, indicates that cross-linking is necessary to achieve stability 
against separation. All the cross-linked Gantrez formulas had not 
separated at 77.degree. F., even after almost 5 months. 
Table VI contains a summary of available chlorine data of LADD with 
cross-linked Gantrez. Formula E (most stable against separation per wt of 
polymer used) exhibits only a 20% loss in available chlorine after 6 weeks 
at room temperature, and a 30% loss after 3 weeks at 100.degree. F. 
Viscosity measurements of the various LADD formulas are summarized in Table 
VII as a function of time. Viscosity of the cross-linked Gantrez formulas 
show little or no viscosity loss experienced as a function of aging. 
Table VIII contains data on the amount of bottle residue obtained for 
liquid automatic dishwashing detergent with cross-linked Gantrez and two 
different versions of a standard commercial automatic dishwashing 
detergent. The residue left for samples C and D is considerably more (2 
times and 1.4 times, respectively) than that of the cross-linked Gantrez 
when no force is used to dispense the product. 
The method for determining the bottle residue was to put test samples in 50 
oz Polyethylene bottles. All samples were shaken before being left to 
equilibrate overnight. Eighty grams is dispensed repeatedly with 2 min 
rests between doses. The sample is capped and stood upright during the 
rest periods. No excess force is used until the point when no more product 
can be dispensed easily. At this time the bottle is shaken and the product 
is forced out. Grams of bottle residue is reported a) without force and b) 
with force. 
TABLE IV 
__________________________________________________________________________ 
LADD Compositions Containing Gantrez Polymer 
A B C D E F 
__________________________________________________________________________ 
wt polymer 2.5 2 1 1.2 1.2 .5 
NaOH 50% 4.5 4.5 4.5 4.6 4.5 4.5 
Na Silicate (1/2.4) 
21.5 21 21 21 
TKPP 14.3 14.3 
KTPP 15 15 15.1 15 15 
STPP 11.5 10 10 10 10 11.5 
Graphtol Green 
0.0008 
0.0012 
0.0012 
0.0012 
0.0012 
0.0008 
Bleach 11 11 11 11 10 11 
Dowfax 3B2 (45% ai) 
1 1 1 1 1 
LPKN 0.16 0.16 0.16 0.16 0.16 
Stearic Acid 
0.1 0.1 0.1 0.1 0.1 
wt water qs qs qs qs qs qs 
__________________________________________________________________________ 
Tetrapotassium Pyrophosphate (TKPP) 
Tetrasodium Pyrophosphate (TSPP) 
Sodium tripolyphosphate (STPP) 
Potassium Tripolyphosphate (KTPP) 
Composition 
Polymer Description 
A Gantrez AN cross-linked with 10 wt. % 1,7 Octadiene 
B Gantrez AN crosslinked with 5 wt. % 1,7 Octadiene 
C Gantrez AN crosslinked with 5 wt. % 1,7 Octadiene 
D Gantrez AN/Acrylic Acid Terpolymer crosslinked with 5 wt % 1,7 
Octadiene 
E Gantrez AN crosslinked with 5 wt. % 1,7 Octadiene 
F Linear Gantrez 
TABLE V 
______________________________________ 
Stability of LADD Formulas Containing Cross-linked Gantrez 
Current status or days to failure 
Formula % Polymer 
140.degree. F. 
120.degree. F. 
100.degree. F. 
77.degree. F. 
______________________________________ 
(A) 2.5% XL Gantrez OK 164 (RT) 
(B) 2.0% XL Gantrez 
4 14-21 63-84 ok 150 
(C) 1.0% XL Gantrez 
4 17-21 63-84 OK 150 
(D) 1.2% XL Gantrez 
7 not tested 
40 Marginal 
150 
(E) 1.2% XL Gantrez 
7 32-40 OK 85 OK 150 
(F) 5% Linear Gantrez 14 (RT) 
______________________________________ 
OK = continuing to age 
n-m = failed between these two times 
TABLE VI 
__________________________________________________________________________ 
Percent Available Chlorine of LADD Made With Cross-linked 
__________________________________________________________________________ 
Gantrez 
Formula, polymer 
init. Chl 
1 wk, 77 F. 
3 wk, 77 F. 
4 wk, 77 F. 
6 wk, 77 F. 
__________________________________________________________________________ 
A. 2.5% XL Gantrez 
1.18 1.09 
B. 2% XL Gantrez 
1.24 1.17 1.05 
C. 1% XL Gantrez 
1.24 1.17 1.1 
D. Terpolymer 
1.37 1.27 1.16 1.01 
E. 1.2% XL Gantrez 
1.34 1.23 1.17 1.07 
__________________________________________________________________________ 
Formula, polymer 
1 wk, 100 F. 
3 wk, 100 F. 
4 wk, 100 F. 
6 wk, 100 F. 
__________________________________________________________________________ 
B. 2% XL Gantrez 
1.24 0.96 0.71 
C. 1% XL Gantrez 
1.24 1.04 0.83 
D. Terpolymer 
1.37 1.12 0.72 
E. 1.2% XL Gantrez (E) 
1.34 1.15 0.79 
__________________________________________________________________________ 
TABLE VII 
______________________________________ 
Viscosity of LADD Containing XL Gantrez 
Viscosities in thousands of centipoises 
______________________________________ 
Number, polymer 
init. visc 
visc, 77 F., 1 wk 
3 wk, 77 F. 
______________________________________ 
B. 2% XL Gantrez 
37.6 37.6 31.6 
C. 1% XL Gantrez 
12.4 12 12.4 
D. 1.2% XL Gantrez 
11.6 13.6 17.2 
______________________________________ 
Number, polymer visc. 100 F. 3 wk, 100 
______________________________________ 
B. 2% XL Gantrez 30.8 22.4 
C. 1% XL Gantrez 9.6 8.4 
D. Terpolymer AA 
E. 1.2% XL Gantrez 16 10.8 
______________________________________ 
TABLE VIII 
__________________________________________________________________________ 
Bottle Residue of LADD Containing XL Gantrez Compared to commercially 
available LADD. 
LADD w/1.2% 
#2-Lemon XL Gantrez 
Commercial LADD Sample #1-Regular 
Commercial LADD 
__________________________________________________________________________ 
Sample 
wt resid (grams), no force 
117 231 162 
wt resid (grams), force 
48 76 65 
__________________________________________________________________________