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 antiredeposition 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-toperform 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. 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. 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).




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

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

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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 nonadsorbing 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

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 κ = 1000 · ε · k · T B

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: A where: VA = – 12π D2 A = Hamaker constant 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.

where: 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.





The Effect of the pH(6) 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).

-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

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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.
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 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, Soil Type Brazil). Several mechanical alterations were made and a heating system was added to the original jar Organic Particulate test, which enabled determination of the antiredeposition 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
* although carbon black is not a realistic system , its effects have good correlation with natural soil(9) and it is widely used for anti-redeposition evaluation.

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 antiredeposition 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 (oilorganic particulate). For each soil and substrate, the best soil concentration was determined in order to avoid a soil overdosage 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 Carbon Black Carbon Black – Olive Oil Raw Palm Oil Olive Oil – Dye Knit 50% CO – Knit 100% 50% PES PES 0.5 g/L 0.8 g/L 0.5 g/L 4.0 g/L 0.5 g/L 0.5 g/L 0.3 g/L 2.0 g/L 3.0 g/L

Artificially Colored Oily Inorganic Particulate

Red Earth (tennis court type) 3.0 g/L

Table 1: Soil concentration for single cycle tests

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Substrate Soil Type Particulate - Oily Soil Carbon Black – Olive Oil Knit 50% CO – 50% PES 100 L/L

Table 2: Soil concentration for multi-cycle tests

Single Cycle Test As mentioned previously, the single cycle test is performed with a high concentration of soil to quickly identify the most efficient anti-redeposition products, without the need for colorimetric or further analyses. Figure 2 shows the comparative results of a laundry detergent with no anti-redeposition aid and the same product with an anionic-modified polyester additive. The anti-redeposition performance enhancement provided by the polymer is clearly observed.

Multi Cycle Test In general, after consecutive washing cycles with low soil concentration, test swatches are still relatively white. Therefore, colorimetric (CIE Whiteness Degree) and visual analyses are needed to define which product has the best performance. -The Visual Panel Since the efficiency of a laundry product is given by the consumer’s perception of cleanliness, a product evaluation during the development process must be as close as possible to the realworld condition. For that purpose, a visual analysis panel was developed by Clariant’s Global Development Centre for Laundry (figure 4). The replicates of each formulation are grouped into tiles and presented to 12 untrained panelists to simulate the evaluation of the final consumer. The panelists analyze the tiles under the same conditions (light, background, distance from the swatches and temperature) and are asked to organize them from the cleanest to 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 detergent base.

Graph 1: Colorimetric results for multi-cycle tests (substrate knit 50% CO – 50% PES, soil carbon black – olive oil)

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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.

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 antiredeposition aid. The set of swatches washed only with the laundry detergent was classified as the dirtiest one.


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

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 antiredeposition 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 timeconsuming, 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.


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.
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
1. 2. 3. 4. L.Spitz, “Soap and Technology for the 1990’s”, American Oil Chemist’s Society, 1990 “Handbook of Detergens Part A: Properties”, Surfactant Science Series Vol. 82, Edited by G. Brooze, Marcel Dekker Inc., 1999 “Surface Active Agents and Detergents”, Vol. 3, A.M.Schwartz, J.W.Perry and J.Berch, Interscience Publishers Inc., 1958 “Detergents and Textile Washing: Principles and Practice”, G.Jakobi and A.Löhr, VCH Velagsgesellschaft mbH, 1987 “Detergency: Theory and Technology”, Surfactant Science Series, Vol. 20, Edited by W.G.Cutler and E.Kissa, Marcel Dekker Inc., 1987 “Detergents: Theory and and Test Methods”, Surfactant Science Series, Vol. 5, Edited by W.G.Cutler and R.C.Davis, Marcel Dekker Inc., 1972. “Foundations of Colloid Science”, Vol. 1, R.J.Hunter, R.Lee, Oxford Science Publications “Physical Chemistry”, P.W.Atkins, 6th edition, Oxford University Press, 1998 H.B. Trost, JAOCS, 40(11), 699-374 (1963) J.G. Jarrel and H.B.Trost; Soap Sanit. Chem., 28(7), 40-43, 155; (8), 5052, 162 (1952) K.J.Niewenhuis; Meded. Proefstn. Wasind., 66, 10 (1947) F.J. Pollock; Perfum. Cosmet., 24, 991-995 (1951) H.R.Suter and M.G.Kramer, Soap Sanit. Chem. 27 (8), 33-36, 149 (1951) A.S. Weatherburn; Text. Res. J., 20, 510-513 (1950) AATCC Test Method 88C-1996, “Retention of Creases in Fabrics after Repeated Home Laundering”

*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

5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

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