DETERGENTS
Evaluation of Anti-Redeposition
Aids on Laundry Detergents
An Effective Screening Methodology and its
Correlation with Consumer’s Visual Perception
ABSTRACT
Redeposition of soil during domestic and institutional laundry
washing processes is a relevant issue for consumers and it is well
known that a good anti-redeposition performance is dependent
upon the balance among surfactants, builders and other
ingredients of the formulation. An effective and easy-to-perform
screening tool has been developed for the evaluation of anti-
redeposition polymers and new molecules currently available on
the market. The proposed methodology allows the formulator to
evaluate the visual impact of different types of soils, washing
conditions and additives in a short period of time. Results from
this new methodology are statistically treated via parametric (for
colorimetric readings) and non-parametric (for visual panel)
approaches and correlations are made with consumer visual
results.
INTRODUCTION
Soil redeposition is one of the undesirable phenomena that take
place during the washing process and it plays an important role
on whiteness loss of a cloth that has been submitted to
consecutive washings.
Laundry detergents are expected to not only remove soil from the
cloth but to also prevent the removed soil from redepositing on
the fabric. There are a variety of products available for this
purpose, but reliable data proving the efficiency of these products
is not widely available in the literature and is not easy to
generate.
The aim of this work is to propose an effective and easy-to-
perform method that allows the formulator to evaluate the visual
impact of different types of soils, washing conditions and
additives in a short period of time.
HISTORICAL BACKGROUND
The oldest literary reference to soap is a Sumerian tablet from
2200 BC giving a soap formula consisting of water, alkali and
cassia oil, but it is not known exactly when it was discovered(1). It
is believed that it was accidentally discovered in Rome. Romans
used to make animal sacrifices to their Gods at Mount Sapo and
over time, the fat from the animals and the alkali from wood
ashes mixed and flowed downhill to the Tiber River where it
accumulated in the clay soil. Local women soon found that the
clay around Mount Sapo had special properties that made their
clothes easier to wash(1).
The industrial production of soap (boiling fats and oils with an
alkali) remained basically the same until 1916, when the first
synthetic detergent was developed in Germany in response to a
World War I-related shortage of fats for making soap(2).
Soaps have an advantage over unbuilt-synthetic surfactant
systems regarding soil redeposition and whiteness maintenance:
it acts as its own water softener and therefore when there is
12
enough soap to form suds and wash, the water has already been
softened(3). The need of anti-redeposition agents began with the
introduction of multi-component laundry detergents based on
synthetic surfactants (in Europe, Fewa since 1932 and in USA,
Dreft since 1933)(4): although synthetic surfactants help to prevent
the soil redeposition to some extent, this effect is not very
pronounced, making a whiteness retention aid a necessity.
FACTORS AFFECTING SOIL REDEPOSITION
During textile washing, several processes, reactions and
interactions among different components take place
simultaneously making the determination of the contribution of a
single variable a rather difficult task. Some of the variables are
washing time, temperature, agitation, rinsing conditions,
surfactant type and concentration, water hardness, particle size,
shape and surface charge of particulate soil, viscosity and
surface tension of liquid soil and nature of the fabric(5). In that
context, it is necessary to control as many variables as possible in
order to isolate and study the desired factors and effects. High
intensity agitation tends to deflocculate suspended soils, breaking
them into smaller particles. Since small particles diffuse more
rapidly into the fabric, the higher the intensity of agitation, the
higher the soil redeposition(6). As the washing temperature rises,
so does the solubility of anionic surfactants enhancing both
washing and anti-redeposition power. For nonionic surfactants,
higher temperatures make them less hydrated which improves the
adsorption on both fibre and soil and, consequently, avoids soil
redeposition. On the other hand, high temperatures can also
favour the redeposition of particulate soils by increasing their
kinetic energy and Brownian motion(6).
MECHANISMS OF SOIL REDEPOSITION – COLLOIDS
THEORY
The theory of colloid stability is commonly applied to explain the
soil redeposition process. Therefore, it is important to review the
main concepts regarding colloidal systems to better interpret
experimental data and develop new technologies and methods in
this field. The most common definition of a colloidal dispersion is
a system where particles from 1nm to 1µm of any nature (solid,
liquid or gas) are dispersed in a continuous phase of a different
composition (or state)(7). In such systems, the particles are
continuously undergoing Brownian motion, colliding with each
other. The stability of the colloid is given by the interaction
between the particles during these collisions, which is a
combination of attractive and repulsive forces. If attractive forces
are dominant, the particles will adhere and the colloid will
coalesce. If the repulsive forces are dominant, the dispersion will
be stable. So, in order to maintain a stable colloidal dispersion, it
is necessary to keep a repulsive force strong enough to overcome
the attractive forces between the particles. There are basically 3
Household and Personal Care TODAY • nr. 0/2006

mechanisms for colloid stabilization: steric, electrostatic and
electrosteric (a combination of the two previous mechanisms and
the most commonly found) effects.
Steric Stabilization(7)
Steric stabilization of a colloidal system occurs when
macromolecules are adsorbed at the particle surface. Depending
on the macromolecule concentration, stabilization or aggregation
may occur:
– Low macromolecule concentration: the macromolecule first
adsorbs partly onto one particle, loops around it and then
this same macromolecule becomes attached to a second
particle, holding them together.
– Medium macromolecule concentration: the interaction
between the macromolecules releases solvent molecules to the
media leading to an entropic stabilization.
– Medium macromolecule concentration and in the presence
of free macromolecule: the flocculation is facilitated by non-
adsorbing polymers based on differences in the osmotic
pressure.
– High macromolecule concentration: in the presence of an
excess of macromolecules, depletion stabilization and its
mechanism is still under study.
Steric stabilization is insensitive to the presence of electrolytes and
works in both aqueous and non aqueous media. Normally the
flocculation of steric-stabilized dispersions is reversible.
Electrostatic Stabilization
-The DLVO Theory(7)
Developed in the 1940’s by four scientists (Derjaguin, Landau,
Verwey and Overbeek), the DLVO theory states that the stability
of a particle in solution depends on the total potential energy
function VT:
where V T = VA + VR + VS
VS = potential due to the solvent
VA = attractive potential due to van der Waals interaction
VR = repulsive potential due to the electrical double layer
Since water is the most used solvent and so far there are no
satisfactory theories for its structure, VS is usually not considered.
The attractive component VA is given by:
where:
A = Hamaker constant
VA = –
A
(
12π D2 ) The Effect of the pH(6)
D = distance between the two centres of the sphere
VR can be expressed as:
where: VR = 2πεaζ2 exp(–κD)
a = particle radius
ε = dielectric constant of the medium
κ = Debye-Hückel parameter
ζ = zeta potential
The equation above shows that zeta potential is the factor that
has the highest effect on VR .The higher the zeta potential, the
higher the repulsive potential and the colloid stability.
Consequently, high values of zeta potential lead to lower soil
redeposition.
-The Zeta Potential(8)
A charged particle immersed in an electrolyte solution forces the
orientation of ions present in the solution. The concentration of
ions with opposite charges will be high near the particle. As the
distance from the charged particle increases, the concentration of
oppositely charged ions will decrease. In a similar, but opposite
way, the concentration of ions with the same charge of the
original particle gradually increases with the increasingly
distance. At a certain distance from the charged particle, the
Household and Personal Care TODAY • nr. 0/2006
DETERGENTS
concentrations of both ions reach the concentration of the bulk
solution. This arrangement of the ions around a charged particle
is the diffuse electrical double layer and its length depends on the
electrolyte concentration and the type and charge of the particle.
The first counter-ion layer that is firmly attached to the charged
particle is called the Stern layer. When the charged particle
moves, it also drags some ions, creating a shear plane inside the
diffuse electrical double layer. The zeta potential is the potential
at this shear plane but, for practical purposes, the zeta potential
is measured at the Stern layer.
The main factors affecting the zeta potential are(7):
– Concentration of the potential determining ions (pdi): pdi
are ions that will affect the charge of the particle. For
instance, for a system of AgBr, the concentration of H+ or
OH- will not affect the charge of Ag+ or Br–. For a colloidal
system consisting of a metal oxide, however, the hydroxide
layer around the oxide is capable of adsorbing or losing a
proton, depending on the pH. Thus, H+ and OH– are pdi for
a metal oxide system but not for AgBr.
– Size of the electrical double layer: the electrical double layer
length is predicted by the Debye-Hückel theory which was
developed to determine the activity coefficient of an ion on a
solution with a certain ionic strength. The double layer length
is given by the inverse Debye-Hückel parameter, κ.
8p · NA · I · e2
where:
(
κ = 1000 · ε · k · T
B
)
NA = Avogadro’s number
I = ionic strength
e = electron charge
ε = solvent dielectric constant
κB = Boltzmann constant
T = temperature
According to this equation, a high ionic strength will generate a
high value of κ and consequently a shorter double layer. Thus, a
high particle charge (high or low pH values) and a large
electrical double layer (low ionic strength) will generate a high
zeta potential which stabilizes the colloid and avoids soil
redeposition.
CONTROLLING SOIL REDEPOSITION
The pH of the washing liquor will induce a positive or negative
charge on both the fibre and soil surfaces by protonating the
amino or imino groups of the amphoteric fibers or ionizing
carboxyl groups of proteins, polyamines, polyester and cellulosic
fibers. The point of highest colloid instability (highest soil
redeposition) is the point of electroneutrality or isoeletric point.
Therefore, in order to avoid soil redeposition, it is necessary to
make the potential of both the soil and the fibres more negative
by keeping a high pH during the washing.
The Effect of Surfactants(4)
– Anionic Surfactant: due to the adsorption of long-chain
negative ions, there is an increase on the negative potential
which will reduce the soil redeposition.
– Cationic Surfactant: at low concentrations, the cationic
surfactant will neutralize the negative surface charge,
whereby increasing the soil redeposition. With increasing
concentration, electroneutrality (point of maximum instability)
is reached. At high cationic concentrations, there is a charge
reversal and the potential becomes highly positive, inhibiting
soil redeposition.
– Nonionic Surfactant: the adsorption of nonionic surfactant on
soil and substrate surfaces produces no changes on the
potential. Instead, it prevents the soil redeposition by forming
an adsorption layer(3) (steric effect).
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 DETERGENTS
The Effect of Inorganic Electrolytes(9)
Normally used as builders, inorganic salts play an important role
in detergent formulations, but can also favour soil redeposition.
The presence of electrolytes favours soil redeposition by
increasing the ionic strength of the medium, reducing the
electrical double layer size and reducing the soil-fabric repulsion.
The higher the cation valence, the higher the ionic strength, so
monovalent salts are preferred to di- or trivalent salts. By adding
a sequestrant and choosing the appropriate salts, it is possible to
overcome the negative effect of electrolytes on soil redeposition.
The Effect of Anti-Redeposition Agents
-Carboxymethyl Cellulose (CMC)(3, 10-14)
CMC was the first anti-redeposition agent to be used in the
industry and is still widely present in laundry detergent
formulations. During washing, it is adsorbed on both the fabric
and the soil, generating repulsion between them. The colloidal
system generated by CMC in water also helps keep the soil
suspended. Due to its similarity to cotton (molecular weight and
position of carboxylic groups), CMC preferably deposits on this
kind of fibre while its performance on synthetic fibres is limited.
-Polycarboxylates(2)
Polycarboxylates can adsorb on fabric (even at a pH where both
are negatively charged) and serve to increase the surface charge.
A polymer with a high level of carboxylic acid functionality does
not necessarily generate the most efficient anti-redeposition effect.
In the presence of a high concentration of divalent cations, a
polymer with a high level of carboxylic acid groups can
precipitate as a polymer-metal salt. Thus, it is necessary to have a
balance between the charge density and the molecular weight for
a satisfactory anti-redeposition effect.
-Nonionic Polymers(3)
Adsorbed on soil particles, nonionic polymers keep the particles
in solution by steric effects. Polyvinylpyrrolidones of molecular
weight from 15,000 to 40,000 are very effective regarding soil
redeposition while molecular weights higher than 250,000 are
less effective. Polyvinyl alcohols with low molecular weights and a
low degree of hydrolysis are more efficient.
AN EFFECTIVE ANTI-REDEPOSITION SCREENING
TEST
The first steps of product development normally generate a large
number of samples that are pared down as the development
moves forward. The decision of which sample(s) should move
forward is critical to the success of the development, making a
fast, reproducible and reliable screening methodology a
necessity.
Regarding the development of anti-redeposition aids, domestic
washing machine studies would not be the best option as a
screening tool. Washing machine studies are not only time and
sample consuming, but continuous exposure of the internal parts
of the machine to carbon black* could damage the equipment.
To fulfil the requirements mentioned above, a new laundry
screening test apparatus was developed: the modified Jar Test.
This equipment was originally used for flotation tests in the water
treatment field, but was modified at Clariant’s
Global Development Centre - Laundry (São Paulo,
Brazil). Several mechanical alterations were made Soil Type
and a heating system was added to the original jar
test, which enabled determination of the anti- Organic Particulate
redeposition effect at different conditions and Particulate - Oily
temperatures. The geometry of the stirrers and its Naturally Colored Oily
rotation direction were also modified to better
Artificially Colored Oily
(6)
* although carbon black is not a realistic system , its Inorganic Particulate
effects have good correlation with natural soil(9) and it is
Table 1: Soil concentration for single cycle tests
widely used for anti-redeposition evaluation.
14
Figure 1: Modifications on the original jar test made by Clariant’s GDC
simulate the mechanical work of a domestic top loading washing
machine. The main modifications are shown on figure 1.
The Methodology – Principles and Procedures
Basically, the developed methodology consists of suspending the
test soil in a laundry detergent solution and washing unsoiled
white swatches in this suspension for a determined period of time
under controlled conditions. Since soil redeposition can be
defined as the adsorption of soil removed from a substrate back
onto that same substrate or onto accompanying substrates(6), the
proposed methodology is a deposition test to evaluate
redeposition. The method was validated using commercial
laundry detergents. The detergents were tested as purchased and
also with the addition of anti-redeposition aids. The anti-
redeposition aids were anionic modified polyesters with
pronounced anti-redeposition effect, developed at Clariant’s
Competence Center for Additives (Frankfurt, Germany). During
the laundry process, a variety of soils are present and those soils
can be liquid (mainly oils), solid (either organic or inorganic) or a
mixture of both. The most realistic soil present in domestic and
institutional laundry would be a complex mixture of liquid and
solid components. For investigation purposes, however, the use of
a complex mixture of soil presents reproducibility problems,
among others(5). Thus, the present methodology was validated on
soils of different natures (oily liquid, organic and inorganic
particulate) separately and in a two-component mixture (oil-
organic particulate). For each soil and substrate, the best soil
concentration was determined in order to avoid a soil over-
dosage that could compromise the detergent performance and
the final evaluation. Two different approaches were considered:
– A single cycle test performed with a highly concentrated soil
suspension. Despite the fact that it is less representative of
real-world conditions, it provides a very quick indication of
which anti-redeposition aids perform most effectively.
– A multi-cycle test performed with a low soil concentration,
which better represents the soil concentration of real-world
laundry conditions. While this approach is more time
consuming, it provides a more realistic evaluation of the loss
of whiteness after several cycles.
The different soils and concentrations used for each method are
found on the tables 1 and 2.
Substrate
Soil Knit 50% CO – Knit 100%
50% PES PES
Carbon Black 0.5 g/L 0.5 g/L
Carbon Black – Olive Oil 0.8 g/L 0.5 g/L
Raw Palm Oil 0.5 g/L 0.3 g/L
Olive Oil – Dye 4.0 g/L 2.0 g/L
Red Earth (tennis court type) 3.0 g/L 3.0 g/L
Household and Personal Care TODAY • nr. 0/2006
 DETERGENTS

Substrate Multi Cycle Test

Soil Type Soil Knit 50% CO – 50% PES
In general, after consecutive washing cycles with low soil
concentration, test swatches are still relatively white. Therefore,
Particulate - Oily Carbon Black – Olive Oil 100 L/L colorimetric (CIE Whiteness Degree) and visual analyses are
needed to define which product has the best performance.
Table 2: Soil concentration for multi-cycle tests
-The Visual Panel
Since the efficiency of a laundry product is given by the
consumer’s perception of cleanliness, a product evaluation during
Single Cycle Test
the development process must be as close as possible to the real-
As mentioned previously, the single cycle test is performed with a
world condition. For that purpose, a visual analysis panel was
high concentration of soil to quickly identify the most efficient
developed by Clariant’s Global Development Centre for Laundry
anti-redeposition products, without the need for colorimetric or
(figure 4).
further analyses.
The replicates of each formulation are grouped into tiles and
Figure 2 shows the comparative results of a laundry detergent
presented to 12 untrained panelists to simulate the evaluation of
with no anti-redeposition aid and the same product with an
the final consumer. The panelists analyze the tiles under the same
anionic-modified polyester additive. The anti-redeposition
conditions (light, background, distance from the swatches and
performance enhancement provided by the polymer is clearly
temperature) and are asked to organize them from the cleanest to
observed.
the dirtiest; each tile receives a grade (the dirtiest receives grade
1). At the end, the grade average of each product is calculated
and submitted to the non-parametric Friedman-Modified Dan’s
statistical analysis.

Figure 2: Results for single cycle tests on knit 50% CO – 50% PES

Figure 4: The Visual Panel – (a) Front view of the visual panel15 (b) Lateral view of
the visual panel15
(c) Tiles containing the replicates of each test product

-Test Results
Graph 1 shows the colorimetric results for three sets of swatches:
Swatches that have been washed with laundry powder detergent;
Swatches that have been washed with the same laundry powder
detergent plus Clariant’s anionic-modified polyester;
Unwashed white swatches that serve as a reference of the initial
whiteness degree.

Figure 3: Test results for (a) a laundry detergent with no anti-redeposition

additive.
The same laundry detergent with (b) commercial CMC and with (c) an
anionic modified polyester

This methodology also makes it possible to compare different

additives for anti-redeposition in a fast and simple way. Figure 3
shows the comparative anti-redeposition effect of CMC and
Clariant’s anionic-modified polyester, using the same powder Graph 1: Colorimetric results for multi-cycle tests (substrate knit 50% CO
– 50% PES, soil carbon black – olive oil)
detergent base.

15
Household and Personal Care TODAY • nr. 0/2006
 DETERGENTS
Statistical analysis of colorimetric data: Anova
After seven consecutive cycles, it is possible to observe that both
set of swatches have significantly lost whiteness. However, the set
of swatches washed with the detergent plus the anti-redeposition
agent has lost less whiteness than the set washed with the laundry
detergent with no additive. A statistical differentiation appears
after five cycles.
Graph 2 and 3 show the results of the visual analysis of the
swatches after three and five consecutive washings. After three
cycles, the panelists were able to separate the 3 sets of swatches
into two groups: the set of white unwashed swatches as the
cleanest and the other two sets in another group, as the dirtiest.
No difference between the two formulations was detected after
three cycles.
Graph 2: Visual Analysis Results after 3 Washing Cycles
Substrate: Knit 50% CO – 50% PES, Soil: Carbon black – olive oil;
Statistical analysis of visual data: Friedman-Modified Dan
Graph 3: Visual Analysis Results after 5 Washing Cycles
Substrate: Knit 50% CO – 50% PES, Soil: Carbon black – olive oil;
Statistical analysis of visual data: Friedman-Modified Dan
GEORGE NUNES*1, ANA REGINA COIMBRA1,
MANLIO GALLOTTI1, ALEXANDER LERCH2,
ROMAN MORSCHHAEUSER2
*Corresponding author
1. Clariant SA
Av. das Nações Unidas
18.001, zip code 04795-900
São Paulo, SP, Brazil
2. Clariant Produkte (Deutschland) GmbH
Industriepark Höchst, D 562, D-65926
Frankfurt am Main
16
The panel was able to separate the sets into three statistically
different groups after five consecutive cycles: the panellists
perceive the unwashed white fabric as the cleanest, followed by
the set washed with the laundry detergent plus the anti-
redeposition aid. The set of swatches washed only with the
laundry detergent was classified as the dirtiest one.
CONCLUSIONS
A versatile, time-saving and resource-conserving method was
developed for laundry products anti-redeposition performance
testing. With the modified equipment and method described
herein, the researcher is able to evaluate several variables
(product, type of soil, substrate, washing conditions, etc)
simultaneously.
Two approaches for anti-redeposition evaluation were established
and validated:
– A single cycle test with a high soil concentration that makes it
possible to compare different additives for soil anti-
redeposition in very short time. This approach is very useful
in the early stages of laundry product development to screen
several potential formulations for anti-redeposition
performance.
– A multi-cycle test with a soil concentration closer to real-world
conditions. Although this methodology is more time-
consuming, it is a useful procedure during the final stages of
product development to prove the efficacy of a selected
formulation.
The results obtained from the visual panel analysis proved the
negative impact of soil redeposition on the consumer perceived
final cleanliness and whiteness of fabrics. Untrained evaluators
were able to perceive and differentiate swatches submitted to
successive washes in the presence or absence of anti-redeposition
additives, even under low soil concentration conditions.
This work has also confirmed the importance of having a reliable
method to help the researcher design a balanced formulation and
choose the correct additive(s) to minimize the whiteness loss
caused by soil redeposition during the laundry process.
ACKNOWLEDGMENT
The authors would like to acknowledge the assistance and
support received from B. Albrecht, C. Barge, G. Borchers, V.
Carvajal, E. Fernandes, S. Heuser, J. Himmrich, E. Horikoshi,
G.H. Kume, D. Moss, K. Podrasky, G. Reinhardt, K.H.
Schoenwaelder, H.J. Scholz, H. Shimizu, C.E. Sousa, C. Tani, M.
Trautmann.
REFERENCES AND NOTES
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3. “Surface Active Agents and Detergents”, Vol. 3, A.M.Schwartz, J.W.Perry
and J.Berch, Interscience Publishers Inc., 1958
4. “Detergents and Textile Washing: Principles and Practice”, G.Jakobi and
A.Löhr, VCH Velagsgesellschaft mbH, 1987
5. “Detergency: Theory and Technology”, Surfactant Science Series, Vol. 20,
Edited by W.G.Cutler and E.Kissa, Marcel Dekker Inc., 1987
6. “Detergents: Theory and and Test Methods”, Surfactant Science Series, Vol.
5, Edited by W.G.Cutler and R.C.Davis, Marcel Dekker Inc., 1972.
7. “Foundations of Colloid Science”, Vol. 1, R.J.Hunter, R.Lee, Oxford Science
Publications
8. “Physical Chemistry”, P.W.Atkins, 6th edition, Oxford University Press, 1998
9. H.B. Trost, JAOCS, 40(11), 699-374 (1963)
10. J.G. Jarrel and H.B.Trost; Soap Sanit. Chem., 28(7), 40-43, 155; (8), 50-
52, 162 (1952)
11. K.J.Niewenhuis; Meded. Proefstn. Wasind., 66, 10 (1947)
12. F.J. Pollock; Perfum. Cosmet., 24, 991-995 (1951)
13. H.R.Suter and M.G.Kramer, Soap Sanit. Chem. 27 (8), 33-36, 149 (1951)
14. A.S. Weatherburn; Text. Res. J., 20, 510-513 (1950)
15. AATCC Test Method 88C-1996, “Retention of Creases in Fabrics after
Repeated Home Laundering”
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