Processes for making a granular detergent composition containing a crystalline builder

A process for preparing high density detergent compositions is provided. The process comprises the steps of: (a) continuously mixing a detergent surfactant paste and dry starting detergent material into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the surfactant paste to the dry detergent material is from about 1:10 to about 10:1; (b) mixing the detergent agglomerates in a moderate speed mixer/densifier to further densify and agglomerate the detergent agglomerates; and (c) drying said detergent agglomerates so as to form the high density detergent composition. The dry detergent material may contain a builder material including a crystalline microstructure in which a carbonate anion, a calcium cation and at least one water-soluble cation are contained. The process may include one or more additional processing steps such as adding a coating agent such as the builder material described herein after the moderate speed mixer/densifier to facilitate and control agglomeration.

FIELD OF THE INVENTION 
The present invention generally relates to processes for producing a 
granular detergent composition. More particularly, the invention is 
directed to processes during which detergent granules or agglomerates are 
produced from starting detergent materials, one of which is a crystalline 
builder material. The builder material includes a crystalline 
microstructure in which a carbonate anion, a calcium cation and at least 
one water-soluble cation are contained. The process produces a free 
flowing, granular detergent composition which can be commercially sold as 
a modern compact detergent product. 
BACKGROUND OF THE INVENTION 
Recently, there has been considerable interest within the detergent 
industry for laundry detergents which are "compact" and therefore, have 
low dosage volumes. To facilitate production of these so-called low dosage 
detergents, many attempts have been made to produce high bulk density 
detergents, for example with a density of 600 g/l or higher. The low 
dosage detergents are currently in high demand as they conserve resources 
and can be sold in small packages which are more convenient for consumers. 
Generally, there are two primary types of processes by which detergent 
granules or powders can be prepared. The first type of process involves 
spray-drying an aqueous detergent slurry in a spray-drying tower to 
produce highly porous detergent granules. In the second type of process, 
the various detergent components are dry mixed after which they are 
agglomerated with a binder such as a nonionic or anionic surfactant. In 
both processes, the most important factors which govern the density of the 
resulting detergent granules are the density, porosity and surface area of 
the various starting materials and their respective chemical composition. 
There has been interest in the art for providing processes which increase 
the density of detergent granules or powders. Particular attention has 
been given to densification of spray-dried granules by post tower 
treatment. For example, one attempt involves a batch process in which 
spray-dried or granulated detergent powders containing sodium 
tripolyphosphate and sodium sulfate are densified and spheronized in a 
Marumerizer.RTM.. This apparatus comprises a substantially horizontal, 
roughened, rotatable table positioned within and at the base of a 
substantially vertical, smooth walled cylinder. This process, however, is 
essentially a batch process and is therefore less suitable for the large 
scale production of detergent powders. More recently, other processes have 
developed for increasing the density of "post-tower" or spray dried 
detergent granules. Typically, such processes require a first apparatus 
which pulverizes or grinds the granules and a second apparatus which 
increases the density of the pulverized granules by agglomeration. These 
processes achieve the desired increase in density by treating or 
densifying "post tower" or spray dried granules. The art is also replete 
with disclosures of processes which entail agglomerating detergent 
compositions. For example, attempts have been made to agglomerate 
detergent builders by mixing zeolite and/or layered silicates in a mixer 
to form free flowing agglomerates. 
Furthermore, it has been long-established practice for detergent 
formulators to use builder materials and combinations thereof in detergent 
compositions. By way of example, certain clay minerals have been used to 
adsorb hardness cations, especially in fabric laundering operations. 
Further, the zeolites (or aluminosilicates) have been suggested for use in 
various cleaning situations as detergency builders. For example, 
water-insoluble aluminosilicate ion exchange materials have been widely 
used in detergent compositions throughout the industry. While such builder 
materials are quite effective and useful, they account for a significant 
portion of the cost in most any fully formulated detergent composition. 
Therefore, it would be desirable to have a builder material which performs 
as well as or better than the aforementioned builders, and importantly, is 
also less expensive. 
Accordingly, there remains a need in the art for a process which produces a 
granular and/or agglomerated detergent composition from starting detergent 
ingredients including an improved builder material which can improve the 
flow properties and the cleaning performance of the composition. Also, 
there remains a need for such a process which is more efficient and 
economical to facilitate large-scale production of low dosage or compact 
detergents. 
BACKGROUND ART 
The following references are directed to densifying spray-dried granules: 
Appel et al, U.S. Pat. No. 5,133,924 (Lever); Bortolotti et al, U.S. Pat. 
No. 5,160,657 (Lever); Johnson et al, British patent No. 1,517,713 
(Unilever); and Curtis, European Patent Application 451,894. The following 
references are directed to producing detergents by agglomeration: Beerse 
et al, U.S. Pat. No. 5,108,646 (Procter & Gamble); Hollingsworth et al, 
European Patent Application 351,937 (Unilever); Swatling et al, U.S. Pat. 
No. 5,205,958; and Capeci et al, U.S. Pat. No. 5,366,652 (Procter & 
Gamble). 
The following references are directed to builders for cleaning 
compositions: Atkinson et al, U.S. Pat. No. 4,900,466 (Lever); Houghton, 
WO 93/22411 (Lever); Allan et al, EP 518 576 A2; (Lever); Zolotoochin, 
U.S. Pat. No. 5,219,541 (Tenneco Minerals Company); Garner-Gray et al, 
U.S. Pat. No. 4,966,606 (Lever); Davies et al, U.S. Pat. No. 4,908,159 
(Lever); Carter et at, U.S. Pat. No. 4,711,740 (Lever); Greene, U.S. Pat. 
No. 4,473,485 (Lever); Davies et al, U.S. Pat. No. 4,407,722 (Lever); 
Jones et al, U.S. Pat. No. 4,352,678 (Lever); Clarke et at, U.S. Pat. No. 
4,348,293 (Lever); Clarke et al, U.S. Pat. No. 4,196,093 (Lever); Benjamin 
et al, U.S. Pat. No. 4,171,291 (Procter & Gamble); Kowalchuk, U.S. Pat. 
No. 4,162,994 (Lever); Davies et at, U.S. Pat. No. 4,076,653 (Lever); 
Davies et al, U.S. Pat. No. 4,051,054 (Lever); Collier, U.S. Pat. No. 
4,049,586 (Procter & Gamble); Benson et at, U.S. Pat. No. 4,040,988 
(Procter & Gamble); Cherney, U.S. Pat. No. 4,035,257 (Procter & Gamble); 
Curtis, U.S. Pat. No. 4,022,702 (Lever); Child et al, U.S. Pat. 4,013,578 
(Lever); Lamberti, U.S. Pat. No. 3,997,692 (Lever); Cherney, U.S. Pat. No. 
3,992,314 (Procter & Gamble); Child, U.S. Pat. No. 3,979,314 (Lever); 
Davies et al, U.S. Pat. No. 3,957,695 (Lever); Lamberti, U.S. Pat. No. 
3,954,649 (Lever); Sagel et al U.S. Pat. No. 3,932,316 (Procter & Gamble); 
Lobunez et al, U.S. Pat. No. 3,981,686 (Intermountain Research and 
Development Corp.); and Mallow et al, U.S. Pat. No. 4,828,620 (Southwest 
Research Institute). 
The following references relate to crystalline minerals: Friedman et al, 
"Economic Implications of the Deuterium Anomaly in the Brine and salts in 
Searles Lake, Calif.," Scientific Communications, 0361-0128/82/32, pp. 
694-699; Bischoff et al, "Gaylussite Formation at Mono Lake, Calif.," 
Geochimica et Cosmochimica Acta, Vol. 55, (1991) pp. 1743-1747; Bischoff, 
"Catalysis, Inhibition, and The Calcite-Aragonite Problem," American 
Journal of Science, Vol. 266, February 1968, pp. 65-90; Aspden, "The 
Composition of Solid Inclusions and the Occurrence of Shortite in Apatites 
from the Tororo Carbonatite Complex of Eastern Uganda," Mineralogical 
Magazine, June 1981, Vol. 44, pp. 201-4; Plummer and Busenberg, "The 
Solubilities of Calcite, Aragonite and Vaterite in CO.sub.2 --H.sub.2 O 
Solutions Between 0.degree. and 90.degree. C., and an Evaluation of the 
Aqueous Model for the System CaCO.sub.3 --CO.sub.2 --H.sub.2 O," 
Geochimica et Cosmochimica Acta, Vol. 46, pp. 1011-1040; Milton and 
Axelrod, "Fused Wood-ash Stones: Fairchildite (n.sp.) K.sub.2 CO.sub.3 
CaCO.sub.3, Buetschliite (n.sp.) 3K.sub.2 CO.sub.3 2CaCO.sub.3 6H.sub.2 O 
and Calcite, CaCO.sub.3, Their Essential Components," U.S. Geological 
Survey, pp. 607-22; Evans and Milton, "Crystallography of the Heating 
Products of Gaylussite and Pirssonite," Abstracts of ACA Sessions on 
Mineralogical Crystallography, pp. 1104; Johnson and Robb, "Gaylussite: 
Thermal Properties by Simultaneous Thermal Analysis," American 
Mineralogist, Vol. 58, pp. 778-784, 1973; Cooper, Gittins and Tuttle, "The 
System Na.sub.2 CO.sub.3 --K.sub.2 CO.sub.3 --CaCO.sub.3 at 1 Kilobar and 
its Significance in Carbonatite Petrogenesis," American Journal of 
Science, Vol. 275, May, 1975, pp. 534-560; Smith, Johnson and Robb, 
"Thermal Synthesis of Sodium Calcium Carbonate-A Potential Thermal 
Analysis Standard," humica Acta, pp. 305-12; Fahey, "Shortite, a New 
Carbonate of Sodium and Calcium," U.S. Geological Survey, pp. 514-518. 
SUMMARY OF THE INVENTION 
The present invention meets the aforementioned needs in the art by 
providing a process which produces a granular and/or agglomerated 
detergent composition directly from an improved builder material and other 
starting detergent ingredients. The builder material can also serve as a 
coating agent to improve the flow properties of the detergent composition. 
As a consequence of the process, the detergent composition also exhibits 
improved performance and is less expensive. 
As used herein, the term "agglomerates" refers to particles formed by 
build-up agglomeration of starting detergent ingredients (particles) which 
typically have a smaller median particle size than the formed 
agglomerates. As used herein, the phrase "crystalline microstructure" 
means a crystal form of molecules having a size ranging from a 
molecular-size structure to larger combinations or aggregations of 
molecular-size crystal structures. The crystal microstructure can be 
uniformly layered, randomly layered or not layered at all. All percentages 
and ratios used herein are expressed as percentages by weight (anhydrous 
basis) unless otherwise indicated. All documents are incorporated herein 
by reference. All viscosities referenced herein are measured at 70.degree. 
C. (.+-.5.degree. C.) and at shear rates of about 10 to 100 sec.sup.-1. 
In accordance with one aspect of the invention, a process for preparing a 
crisp, free flowing, high density detergent composition is provided. The 
process comprises the steps of: (a) continuously mixing a detergent 
surfactant paste and dry starting detergent material into a high speed 
mixer/densifier to obtain detergent agglomerates, wherein the ratio of the 
surfactant paste to the dry detergent material is from about 1:10 to about 
10:1 and the dry detergent material contains a builder material including 
a crystalline microstructure in which a carbonate anion, a calcium cation 
and at least one water-soluble cation are contained; (b) mixing the 
detergent agglomerates in a moderate speed mixer/densifier to further 
densify and agglomerate the detergent agglomerates; and (c) drying the 
detergent agglomerates so as to form the high density detergent 
composition. 
One preferred embodiment entails processing the agglomerates such that the 
density of the detergent composition is at least 650 g/l. In another 
preferred embodiment, the process further comprises the step of adding a 
coating agent in and/or after the moderate speed mixer/densifier (e.g. 
between the moderate speed mixer/densifier and drying apparatus, in the 
moderate speed mixer/densifier or between the moderate speed 
mixer/densifier and drying apparatus), wherein the coating agent is 
selected from the group consisting of aluminosilicates, carbonates, 
silicates, the instant crystalline builder material and mixtures thereof. 
Other embodiments include maintaining the mean residence time of the 
detergent agglomerates in the high speed mixer/densifier in range from 
about 2 seconds to about 45 seconds; and/or maintaining the mean residence 
time of the detergent agglomerates in the moderate speed mixer/densifier 
in range from about 0.5 minutes to about 15 minutes. 
In still other aspects of the invention, the ratio of the surfactant paste 
to the dry detergent material is from about 1:4 to about 4:1; the 
surfactant paste has a viscosity of from about 5,000 cps to about 100,000 
cps; and the surfactant paste comprises water and a surfactant selected 
from the group consisting of anionic, nonionic, zwitterionic, ampholytic 
and cationic surfactants and mixtures thereof. An optional embodiment of 
the process contemplates having the high speed and moderate speed 
mixer/densifier together imparting from about 5.times.10.sup.10 erg/kg to 
about 2.times.10.sup.12 erg/kg of energy at a rate of from about 
3.times.10.sup.8 erg/kg-sec to about 3.times.10.sup.9 erg/kg-sec. Other 
embodiments of the invention are directed to a step of adding a coating 
agent in the moderate speed mixer/densifier, and/or a step of adding a 
coating agent between the mixing step and the drying step. 
In an especially preferred embodiment of the invention, the process 
comprises the steps of: (a) continuously mixing a detergent surfactant 
paste and a dry starting detergent material into a high speed 
mixer/densifier to obtain detergent agglomerates, wherein the ratio of the 
surfactant paste to dry detergent material is from about 1:10 to about 
10:1; (b) mixing the detergent agglomerates in a moderate speed 
mixer/densifier to further densify and agglomerate the detergent 
agglomerates; (c) drying the detergent agglomerates; and (d) adding a 
coating agent to the detergent agglomerates so as to obtain said high 
density detergent composition having a density of at least 650 g/l; 
wherein the coating agent is a builder material including a crystalline 
microstructure in which a carbonate anion, a calcium cation and at least 
one water-soluble cation are contained. The invention also provides a high 
density detergent composition made according to the process of the 
invention and its various embodiments. 
In another aspect of the invention, a process involving spray drying and 
agglomeration of detergent ingredients to provide a high density detergent 
composition is provided. More particularly, the process comprises the 
steps of: (a) spray drying an aqueous slurry containing a builder material 
including a crystalline microstructure in which a carbonate anion, a 
calcium cation and at least one water-soluble cation are contained, a 
detergent surfactant, and a supersaturated aqueous solution of the 
water-soluble cation or salt thereof to form spray dried granules; (b) 
continuously mixing a detergent surfactant paste and dry starting 
detergent material into a high speed mixer/densifier to obtain detergent 
agglomerates, wherein the ratio of the surfactant paste to the dry 
detergent material is from about 1:10 to about 10:1; (c) mixing the 
detergent agglomerates in a moderate speed mixer/densifier to further 
densify and agglomerate the detergent agglomerates; and (d) blending the 
granules and the detergent agglomerates together so as to form a high 
density detergent composition. Optionally, the builder material can be 
coated with a nonionic surfactant prior to the spray drying step. 
In yet other aspects of the invention, additional process embodiments are 
provided. One process entails continuously preparing a granular detergent 
composition by spray drying an aqueous slurry containing a builder 
material including a crystalline microstructure in which a carbonate 
anion, a calcium cation and at least one water-soluble cation are 
contained, a detergent surfactant, and a supersaturated aqueous solution 
of the water-soluble cation or salt thereof to form spray dried granules. 
Another process involves preparing a detergent composition comprising the 
steps of: (a) forming a particulate material in the form of agglomerates, 
granules or combinations thereof, wherein the particulate material 
contains a detergent surfactant; and (b) coating the particulate material 
with a crystalline microstructure in which a carbonate anion, a calcium 
cation and at least one water-soluble cation are contained. 
Accordingly, it is an object of the present invention to provide a process 
for producing a granular and/or agglomerated detergent composition 
directly from starting detergent ingredients which includes an improved 
detergency builder. It is also an object of the invention to provide such 
a process which is not limited by unnecessary process parameters so that 
large-scale production of low dosage or compact detergents is more 
economical and efficient. These and other objects, features and attendant 
advantages of the present invention will become apparent to those skilled 
in the art from a reading of the following drawing, detailed description 
of the preferred embodiment and the appended claims.

EXAMPLE I 
This Example illustrates the process of the invention which produces free 
flowing, crisp, high density detergent composition. Two feed streams of 
various detergent starting ingredients are continuously fed, at a rate of 
2800 kg/hr, into a Lodige CB-30 mixer/densifier, one of which comprises a 
surfactant paste containing surfactant and water and the other stream 
containing starting dry detergent material containing aluminosilicate and 
sodium carbonate. The rotational speed of the shaft in the Lodige CB-30 
mixer/densifier is about 1400 rpm and the mean residence time is about 10 
seconds. The contents from the Lodige CB-30 mixer/densifier are 
continuously fed into a Lodige KM 600 mixer/densifier for further 
agglomeration during which the mean residence time is about 2-3 minutes. 
The resulting detergent agglomerates are then fed to a fluid bed dryer and 
then to a fluid bed cooler, the mean residence time being about 10 minutes 
and 15 minutes, respectively. A coating agent, aluminosilicate, is fed 
about midway down the moderate speed mixer/densifier 16 to control and 
prevent over agglomeration. The detergent agglomerates are then screened 
with conventional screening apparatus resulting in a uniform particle size 
distribution. The composition of the detergent agglomerates exiting the 
fluid bed cooler is set forth in Table I below: 
TABLE I 
______________________________________ 
Component % Weight of Total Feed 
______________________________________ 
C.sub.14-15 alkyl sulfate/C.sub.14-15 
29.1 
alkyl ethoxy sulfate (EO = 0.6) 
Na.sub.2 Ca(CO.sub.3).sub.2 
29.4 
Aluminosilicate 5.0 
Sodium carbonate 17.5 
Polyethylene glycol (MW 4000) 
1.3 
Misc. (water, etc.) 
17.7 
100.0 
______________________________________ 
Additional detergent ingredients including perfumes, enzymes, and other 
minors are sprayed onto the agglomerates described above in the finishing 
step to result in a finished detergent composition. The relative 
proportions of the overall finished detergent composition produced by the 
process of instant process is presented in Table II below: 
TABLE II 
______________________________________ 
(% weight) 
Component A 
______________________________________ 
C.sub.14-15 alkyl sulfate/C.sub.14-15 
16.3 
alkyl ethoxy sulfate (EO = 0.6) 
Neodol 23-6.5.sup.1 
3.0 
C.sub.12-14 N-methyl glucamide 
0.9 
Polyacrylate (MW = 4500) 
3.0 
Polyethylene glycol (MW = 4000) 
1.2 
Sodium Sulfate 8.9 
Na.sub.2 Ca(CO.sub.3).sub.2 
23.5 
Aluminosilicate 2.8 
Sodium carbonate 27.2 
Protease enzyme 0.4 
Amylase enzyme 0.1 
Lipase enzyme 0.2 
Cellulase enzyme 0.1 
Minors (water, perfume, etc.) 
12.4 
100.0 
______________________________________ 
.sup.1 C.sub.12-13 alkyl ethoxylate (EO = 6.5) commercially available fro 
Shell Oil Company. 
The density of the resulting detergent composition is 796 g/l, the median 
particle size is 613 microns. 
EXAMPLE II 
This Example illustrates another process in accordance with the invention 
in which the steps described in Example I are performed except the coating 
agent, aluminosilicate, is added after the fluid bed cooler as opposed to 
in the moderate speed mixer/densifier. The composition of the detergent 
agglomerates exiting the fluid bed cooler after the coating agent is added 
is set forth in Table III below: 
TABLE III 
______________________________________ 
Component % Weight of Total Feed 
______________________________________ 
C.sub.14-15 alkyl sulfate/C.sub.14-15 
21.3 
alkyl ethoxy sulfate (EO = 0.6) 
C.sub.12-13 linear alkylbenzene sulfonate 
7.1 
Na.sub.2 Ca(CO.sub.3).sub.2 
29.2 
Aluminosilicate 5.0 
Sodium carbonate 18.3 
Polyethylene glycol (MW 4000) 
1.4 
Misc. (water, perfume, etc.) 
17.7 
100.0 
______________________________________ 
Additional detergent ingredients including perfumes, brighteners and 
enzymes are sprayed onto the agglomerates described above in the finishing 
step to result in a finished detergent composition. The relative 
proportions of the overall finished detergent composition produced by the 
process of instant process is presented in Table IV below: 
TABLE IV 
______________________________________ 
(% weight) 
Component A 
______________________________________ 
C.sub.12-16 linear alkylbenzene sulfonate 
9.0 
C.sub.14-15 alkyl sulfate/C.sub.14-15 
7.3 
alkyl ethoxy sulfate (EO = 0.6) 
Neodol 23-6.5.sup.1 3.0 
C.sub.12-14 N-methyl glucamide 
0.9 
Polyacrylate (MW = 4500) 
3.0 
Polyethylene glycol (MW = 4000) 
1.2 
Sodium Sulfate 8.9 
Na.sub.2 Ca(CO.sub.3).sub.2 
24.6 
Aluminosilicate 1.7 
Sodium carbonate 27.2 
Protease enzyme 0.4 
Amylase enzyme 0.1 
Lipase enzyme 0.2 
Cellulase enzyme 0.1 
Minors (water, perfume, etc.) 
12.4 
100.0 
______________________________________ 
.sup.1 C.sub.12-13 alkyl ethoxylate (EO = 6.5) commercially available fro 
Shell Oil Company. 
The density of the resulting detergent composition is 800 g/l, the median 
particle size is 620 microns. 
EXAMPLE III 
Calcium Sequestration and Rate of Sequestration Test 
The following illustrates a step-by-step procedure for determining the 
amount of calcium sequestration and the rate thereof for the builder 
material used in the compositions described herein. 
1. Add to 750 ml of 35.degree. C. distilled water, sufficient water 
hardness concentrate to produce 171 ppm of CaCO3; 
2. Stir and maintain water temperature at 35.degree. C. during the 
experiment; 
3. Add 1.0 ml of 8.76% KOH to the water; 
4. Add 0.1085 gm of KCl; 
5. Add 0.188 gm of Glycine; 
6. Stir in 0.15 gm of Na.sub.2 CO.sub.3 ; 
7. Adjust pH to 10.0 using 2N HCl and maintain throughout the test; 
8. Stir in 0.15 gm of a builder according the invention and start timer; 
9. Collect an aliquot of solution at 30 seconds, quickly filter it through 
a 0.22 micron filter, quickly acidify it to pH 2.0-3.5 and seal the 
container; 
10. Repeat step 9 at 1 minute, 2 minutes, 4 minutes, 8 minutes, and 16 
minutes; 
11. Analyze all six aliquots for CaCO.sub.3 content via ion selective 
electrode, titration, quantitative ICP or other appropriate technique; 
12. The Sequestration rate in ppm CaCO.sub.3 sequestered per 200 ppm of 
builder is 171 minus the CaCO.sub.3 concentration at one minute; 
13. Amount of sequestration (in ppm CaCO.sub.3 per gram/liter of builder) 
is 171 minus the CaCO.sub.3 concentration at 16 minutes times five. 
For the builder material particle sizes according to the instant invention 
which are on the low end of the particle size range, a reference sample is 
needed which is run without hardness in order to determine how much of the 
builder passes through the filter. The above calculations should then be 
corrected to eliminate the contribution of the builder to the apparent 
calcium concentration. 
EXAMPLES IV-VI 
Several detergent compositions made in accordance with the invention and 
specifically for top-loading washing machines are exemplified below. The 
base granule is prepared by a conventional spray drying process in which 
the starting ingredients are formed into a slurry and passed though a 
spray drying tower having a counter current stream of hot air 
(200.degree.-300.degree. C.) resulting in the formation of porous 
granules. The admixed agglomerates are formed from two feed streams of 
various starting detergent ingredients which are continuously fed, at a 
rate of 1400 kg/hr, into a Lodige CB-30 mixer/densifier, one of which 
comprises a surfactant paste containing surfactant and water and the other 
stream containing starting dry detergent material containing 
aluminosilicate and sodium carbonate. The rotational speed of the shaft in 
the Lodige CB-30 mixer/densifier is about 1400 rpm and the median 
residence time is about 5-10 seconds. The contents from the Lodige CB-30 
mixer/densifier are continuously fed into a Lodige KM-600 mixer/densifier 
for further agglomeration during which the mean residence time is about 6 
minutes. The resulting detergent agglomerates are then fed to a fluid bed 
dryer and to a fluid bed cooler before being admixed with the spray dried 
granules. The remaining adjunct detergent ingredients are sprayed on or 
dry added to the blend of agglomerates and granules. 
______________________________________ 
IV V VI 
______________________________________ 
Base Granule 
Na.sub.2 Ca(CO.sub.3).sub.2 
3.0 16.0 11.0 
Aluminosilicate 15.0 2.0 11.0 
Sodium sulfate 10.0 10.0 19.0 
Sodium polyacrylate polymer 
3.0 3.0 2.0 
Polyethylene Glycol (MW = 4000) 
2.0 2.0 1.0 
C.sub.12-13 linear alkylbenzene sulfonate, Na 
6.0 6.0 7.0 
C.sub.14-16 secondary alkyl sulfate, Na 
3.0 3.0 3.0 
C.sub.14-15 alkyl ethoxylated sulfate, Na 
3.0 3.0 9.0 
Sodium silicate 1.0 1.0 2.0 
Brightener 24.sup.6 0.3 0.3 0.3 
Sodium carbonate 7.0 7.0 25.7 
DTPA.sup.1 0.5 0.5 -- 
Admixed Agglomerates 
C.sub.14-15 alkyl sulfate, Na 
5.0 5.0 -- 
C.sub.12-13 linear alkylbenzene sulfonate, Na 
2.0 2.0 -- 
NaKCa(CO.sub.3).sub.2 
-- 7.0 -- 
Sodium Carbonate 4.0 4.0 -- 
Polyethylene Glycol (MW = 4000) 
1.0 1.0 -- 
Admix 
C.sub.12-15 alkyl ethoxylate (EO = 7) 
2.0 2.0 0.5 
Perfume 0.3 0.3 1.0 
Polyvinylpyrrilidone 0.5 0.5 -- 
Polyvinylpyridine N-oxide 
0.5 0.5 -- 
Polyvinylpyrrolidone-polyvinylimidazole 
0.5 0.5 -- 
Distearylamine & Cumene sulfonic acid 
2.0 2.0 -- 
Soil Release Polymer.sup.2 
0.5 0.5 -- 
Lipolase Lipase (100.000 LU/I).sup.4 
0.5 0.5 -- 
Termamyl amylase (60 KNU/g).sup.5 
0.3 0.3 -- 
CAREZYME .RTM. cellulase (1000 CEVU/g).sup.4 
0.3 0.3 -- 
Protease (40 mg/g).sup.5 
0.5 0.5 0.5 
NOBS.sup.3 5.0 5.0 -- 
Sodium Percarbonate 12.0 12.0 -- 
Polydimethylsiloxane 0.3 0.3 -- 
Miscellaneous (water, etc.) 
balance balance balance 
Total 100 100 100 
______________________________________ 
.sup.1 Diethylene Triamine Pentaacetic Acid 
.sup.2 Made according to U.S. Pat. 5,415,807, issued May 16, 1995 to 
Gosselink et al 
.sup.3 Nonanoyloxybenzenesulfonate 
.sup.4 Purchased from Novo Nordisk A/S 
.sup.5 Purchased from Genencor 
.sup.6 Purchased from CibaGeigy 
EXAMPLE VII 
Index of Surface Activity 
This Example illustrates detergent compositions in accordance with the 
Index of Surface Activity aspect of the invention. A detergent formulation 
is contemplated in which C.sub.12-13 linear alkylbenzene sulfonate (LAS), 
acrylic acid/maleic acid (PAMA) co-polymer and possibly a sugar (for 
example those sugars disclosed in U.S. Pat. No. 4,908,159, Davies et al, 
issued Mar. 13, 1990) are intended to be used along with Na.sub.2 
Ca(CO.sub.3).sub.2. 
The following illustrates a step-by-step procedure for determining the 
amount of LAS and PAMA that can be used in the detergent formulation. 
1. Add to 500 ml of 35.degree. C. water with a calcium carbonate hardness 
of 5 grains per gallon, sufficient Na.sub.2 Ca(CO.sub.3).sub.2 to produce 
a 300 ppm solution of Na.sub.2 Ca(CO.sub.3).sub.2. 
2. Stir and maintain water temperature at 35.degree. C. during the 
experiment; 
3. Record the pH of the solution at 30 second intervals for up to 15 
minutes. 
4. Repeat steps 1 through 3 with LAS added to the solution of step 1 at the 
concentration indicated by the intended usage conditions of the detergent 
formulation (e.g. 100 ppm of LAS). 
5. Subtract the pH values in step 4 from the pH values in step 3 and record 
the largest positive difference. This value normalized as below then 
becomes the constant A in the Index of Surface Activity equation. 
6. Steps 4 and 5 are then repeated with PAMA added at the concentration 
indicated by the intended usage conditions of the detergent formulation in 
addition to LAS added at the concentration indicated by the intended usage 
conditions of the detergent formulation (e.g. 50 ppm of PAMA). 
7. If the Index of Surface Activity is satisfied in both Steps 5 and 6, 
then use of LAS and PAMA at the intended levels is satisfactory. If the 
Index is not satisfied, then the concentrations of the LAS and/or the PAMA 
must be decreased in order to satisfy the Index. Alternatively, a process 
aid such as a sugar (for example those sugars disclosed in U.S. Pat. No. 
4,908,159, Davies et al, issued Mar. 13, 1990) can be added to the formula 
and step 6 repeated at increasing levels of sugar until the Index is 
satisfied. 
8. The pH difference value is normalized by the following equation: 
EQU A=(.DELTA.pH max for ingredient)/(.DELTA.pH max for C.sub.12-13 LAS@100 
ppm )!*0.5 
If the normalized value of A is zero, it is assumed the Index is satisfied. 
Having thus described the invention in detail, it will be clear to those 
skilled in the art that various changes may be made without departing from 
the scope of the invention and the invention is not to be considered 
limited to what is described in the specification.