Handbook of detergents part d

Get Books. Part A of this handbook describes the raw materials and potential interactions of detergent products before, during and after use, focusing on the development and mechanisms of action of cleaning components.

Handbook of Detergents, Part D. Beyond use in the consumer markets, detergents affect applications ranging from automotive lubricants to remediation techniques for oil spills and other environmental contaminants, paper and textile processing, and the formulation of paints, inks, and colorants. Faced with many challenges and choices, formulators must choose the composition of detergents carefully.

Handbook of Detergents, Part B. The second installment of the multivolume Handbook of Detergents deals with the potential environmental impact of detergents as a result of their production, formulation, usage, consumption, and disposal.

To that end, Chapter 2 provides an overview of the use of statistical mixture design in detergent formulations. This book should serve as a useful reference for scientists, engineers, technicians, managers, policymakers, and students having an interest in detergents and emerging technology trends and formulations that will sustain the industry for years to come.

I would like to thank the contributing authors for their time in preparing the highly authoritative individual chapters for this volume, Dr. Uri Zoller for his helpful suggestions and guidance, and Helena Redshaw for her patience, encouragement, and support. Michael S. He is author or coauthor of a number of articles, book chapters, and presentations on the use of enzymes in laundry and cleaning products.

Mike received a B. Watson, Beijing, P. Introduction to Detergents Michael S. Showell 1 2. Ashrawi and George A. Smith 27 3. Laundry Detergent Formulations Randall A. Watson 51 4. Scheper, Mark R. Sivik, Glenn T. Song 5. Sabatini, Robert C. Knox, Jeffrey H. Harwell, and Ben Shiau Paints and Printing Inks Krister Holmberg Surfactant Formulations in Polymerization Gianmarco Polotti Passut Dispersing Polymers Builders and Chelants Bleaching Systems Performance Enhancing Minor Ingredients Representative Detergent Formulations Laundry Detergent Formulations Dishwash Detergent Formulations Hard Surface Cleaning Formulations Agricultural Detergent Formulations Automobile Detergent Formulations Detergent Formulations for Metal Component Cleaning Detergency Theory and Mechanisms Removal Mechanisms Suspension Mechanisms Promote removal of material from a surface, e.

By far the most common and familiar detergents are those used in household cleaning and personal care. These products can be grouped into four general categories: 1. Laundry detergents and laundry aids. These comprise mainframe laundry detergents in powder, liquid, tablet, gel, and bar form, fabric conditioner products typically in liquid or sheet form, and an array of specialty products like pretreaters as sticks, gels, sprays, bars , presoaks liquids, powders , and bleaches liquids, powders.

Typical laundry detergents are formulated to provide general cleaning, which includes removal of soils and stains as well as the ability to maintain whiteness and brightness. Dishwashing products. These include detergents for hand and machine dishwashing and are typically provided in liquid, gel, powder, or tablet form. Hand dish wash products are formulated to remove and suspend food soils from a variety of surfaces.

They also must deliver long-lasting suds, even at high soil loads, and they must be mild to skin. Rinse aids are specialty detergent formulations for automatic dishwashing designed to promote drainage of water from surfaces via lowering of surface tension. Household cleaning products.

Because no single product can provide the range of cleaning required on the various surfaces found in the home a broad range of household cleaning products are currently marketed. These are typically formulated either in liquid or powder form although gel, solid, sheet, and pad products are also available.

Many of these products also contain low levels of antibacterial actives like Triclosan to sustain disinfectancy claims. Powdered abrasive cleaners remove heavy accumulations of soil via the use of mineral or metallic abrasive particles. Some of these products may also bleach and disinfect through the incorporation of a bleach precursor like sodium perborate, sodium percabonate, or sodium dichloroisocyanurate.

These include products for hand and body washing as well as shampoos, conditioners, and toothpastes. They are marketed primarily in bar, gel, and liquid forms. A major consideration in formulation of such products is the desired consumer aesthetic such as lather, skin feel, rinsability, smell, and taste. In addition to these familiar consumer products, detergent formulations are used in a number of other applications and industries.

These include: 1. Environmental remediation. Surfactant systems have been developed to aid in the clean up of contaminated groundwater supplies [1]. Enhanced oil recovery. Researchers have used the phase behavior of surfactants to generate self-assembling nanosystems [3].

Formulation of paints and printing inks. Paints and inks comprise formulations wherein a pigment is dispersed into a liquid phase. Preparation and application of synthetic polymers. Emulsion polymerization and the preparation of latexes represent one of the largest uses for surfactants outside the cleaning arena [5]. Detergent compositions based on a CO2 bulk phase have application in the cleaning of microelectronic components [1]. Medical applications.

Mimics of human lung surfactants have been developed to treat respiratory distress syndrome in premature infants [1].

Textile processing. Agricultural preparations. This diversity of application of detergents presents a rather formidable challenge when compiling a volume such as this on detergent formulations.

Accordingly, rather than try to cover authoritatively all aspects of detergent formulations—a monumental task in its own right— I have elected instead in this chapter to provide some general background on detergency, the common ingredients used in detergent formulations, and general approaches to detergent processing or manufacture. This should provide a solid framework for the more in-depth discussions found in later chapters of this book.

In addition, there are several good reference books available on the topic of detergent formulations [7— 9]. It is not within the scope of this chapter to provide an extensive review of the myriad ingredients used in detergent formulations. Rather, the intent of this section is to provide a general overview of the more common elements— surfactants, dispersing polymers, builders and chelants, bleaching systems, solvents, and performance enhancing minors — in order to familiarize the reader with the general chemistry of detergent formulation.

Surfactants Surfactants are arguably the most common ingredient of the detergent formulations described in this book. Their primary function is to modify the interface between two or more phases in order to promote the dispersion of one phase into another. In cleaning formulations, for example, surfactants serve to wet surfaces and reduce the interfacial tension between soil and water such that the soil is removed from the surface to be cleaned and dispersed in the aqueous phase.

The ability of surfactants to concentrate at interfaces derives from their amphiphilic character—the combination of hydrophilic and hydrophobic moieties within the same molecule. The nonionic surfactants have a hydrophilic component that is not ionized. Typical nonionic groups consist of polyoxyethylene, polyoxypropylene, alkanolamides, or sugar esters. As the name implies, the hydrophilic component of anionic surfactants comprises an anionic group, typically a sulfate, sulfonate, or carboxylate moiety.

Likewise, the cationic surfactants comprise molecules containing a positively charged group such as a quaternary amine. The amphoteric surfactants are perhaps the most unique in that they comprise a hydrophilic group containing both anionic and cationic character such as the amino acids. Typical hydrophobes for surfactants are the alkyl chains between C10 and C Examples of common surfactants are shown in Table 1.

Until the s detergents were formulated principally with the sodium or potassium salts of C12—C18 chain length fatty acids. The synthesis of surfactants from petroleum feed stocks in the late s spurred the development of soap-free synthetic detergents that proved much more effective for cleaning in cooler wash temperatures and in hard water. Today, the linear alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, and alkyl ether ethoxylates are the workhorse surfactants for most detergent formulations.

Alkyl polyglucosides, alkyl glucosamides, and methyl ester sulfonates are also widely used [13]. Recent attention has been given to the use of internal methyl branched alkyl chains as the hydrophobe for certain anionic surfactants [14]. Such branching promotes improved solubility, particularly in cold, hard water. For systems where water is not the continuous phase a variety of specialty surfactants are used. Examples include the polydimethylsiloxane-based surfactants for use in highly hydrophobic media and the acrylate-polystyrene co-polymers designed by DiSimone and colleagues for applications in cleaning systems utilizing condensed phase CO2 [15].

Dispersing Polymers The suspension of solids or liquids in a continuous phase is a critical aspect in the formulation of paints, inks, coatings, and agricultural products such as herbicides.

In order to keep the dispersed phase stable it is important to adsorb functional actives at these surfaces to prevent aggregation. This is one of the critical functions of surfactants. However, another class of detergent actives has been developed to assist in particle suspension—the polymeric dispersants.

Typical of the ionic dispersing polymers are the homopolymers of acrylic acid and copolymers of acrylic and maleic acids which are widely used in laundry detergent formulations: H H C C Z COOH n where Z is either hydrogen, in the case of homopolymers of acrylic acid, or a carboxyl group in the case where the monomer unit is maleic acid.

Polymers of this type are commonly found in powdered laundry detergent formulations where they assist in cleaning by acting as a dispersant for soil and inorganic salts, provide alkalinity control, and serve as crystal growth inhibitors [17].

Anionic dispersing polymers comprising carboxyl and sulfonate groups in the same backbone have been developed for use in water treatment where they act to prevent formation of inorganic scale. C and D are optional but can include acrylamide, vinyl acetate alcohol , acrylate esters, cationics, or phosphonates [18]. Examples include polyamino acid polymers such as polyaspartate prepared from the catalytic condensation of polyaspartic acid [22] and functionalized polysaccharides such as oxidized starches [23].

Recently, a novel process was reported for the preparation of functionalized polyaspartic acid polymers that expands the utility of these materials as dispersants for a variety of applications [24]. Graft copolymers of polyalkylene oxide and vinyl acetate are reported to be effective antiredeposition agents for hydrophobic surfaces like polyester fabric [27].

Builders and Chelants Metal ion control is a common need in many detergent formulations. Fatty acids can precipitate as calcium soaps resulting in the formation of soap scum on hard surfaces, and many soils, especially inorganic clays, will precipitate with calcium leading to redeposition of the soil onto the surface being cleaned.

Sodium tripolyphosphate STPP is among the best known and widely used detergent builder. However, environmental concerns associated with large-scale release of phosphates into the environment lead to the development of a number of substitutes.

Insoluble builders include the zeolites and layered silicates, which bind calcium via an ion exchange mechanism [28]. Citric acid is also an excellent chelant for metal ions other than calcium and can be employed where the removal of transition metals such as copper, zinc, and iron is important.

Bleaching Systems Bleaches are common components of laundry, automatic dish wash, and hard surface cleaning detergent formulations where they act to destroy chromophoric groups responsible for color in soils via oxidative attack. Four basic technology approaches have been taken to deliver bleaching in these products—chlorine-based bleaches, peroxide-based bleaches, activated peroxide systems, and metal catalysts. Chlorine-based systems are common in some powdered abrasive hard surface cleaners and automatic dishwashing products.

NOBS reacts in much the same way but generates the more hydrophobic pernonanoic acid. A frequently studied approach to bleaching involves the use of transition metal catalysts [29]. Complexes of metals like Mn, Fe, Cu, and Co with certain organic ligands can react with peroxygen compounds to form reactive intermediates, which can potentially result in powerful bleaching action. Solvents The selection of solvents for use in detergent formulation depends on the nature of the actives being formulated, the intended application of the detergent, and economics.

Water is the dominant solvent in most household and industrial cleaning formulations. Generally speaking, water-based detergents are less toxic, more environmentally friendly, cheaper, more surface compatible, and easier to handle than petroleum-based solvents.

Typical co-solvents used in household cleaning formulations include ethanol, glycerol, and 1,2-propanediol. Common hydrotropes are sodium xylene sulfonate, sodium toluene sulfonate, and sodium cumene sulfonate. A typical liquid dishwashing formulation, shown below in Table 2, is a good example of a surfactant-rich aqueous-based detergent system comprising both a co-solvent in this case ethanol and a hydrotrope sodium cumene sulfonate : Of course there are applications where water must be avoided.

Concerns that such solvents may represent human and environmental safety hazards has recently lead to the development of alternative processes utilizing condensed phase CO2 [30] and certain silicone oils like cyclic decamethylpentasiloxane, D5 [31]. Detergent formulations for use in such systems will typically comprise a solvent compatible with the bulk phase e.

Here chlorinated hydrocarbons like perchloroethylene or methylene chloride, or volatile organics like methyl ethyl ketone have historically been used but regulatory pressure has resulted in a shift to more environmentally friendly solvents like terpenes and dibasic esters.

Proteases enzymes that degrade protein are the most common of all the detergent enzymes but amylases starch degrading , lipases lipid degrading , and cellulases cellulase degrading are also used [32].

Typical whitening actives are built from direct linkage or ethylenic bridging of aromatic or heteroaromatic moieties. Among the most commonly used whiteners in laundry detergents are the derivatives of 4,4-diaminostilbene-2,2-disulfonic acid. Foam boosters. In some applications, most notably hand dishwashing and shampoos; it is desirable for the detergent formulation to generate a large-volume, stable foam.

While most surfactants are capable of generating and sustaining foam in the absence of soil, these foams rapidly collapse in the presence of soil, especially particulate and fatty soils. Proteins have been shown to promote foaming in certain systems [33] especially in food and beverage applications [34]. Polymeric foam boosters of the type shown below have also proved effective in hand dish wash applications [35]: n N O 4.

O Antifoam agents. In many applications it is desirable to minimize foam generation. For example, in automatic dishwashing foam generation can interfere with rotation of the spray arm leading to degradation in the performance of the dishwasher. Antifoam agents act to reduce or eliminate foams. They either prevent formation of the foam or accelerate its collapse. Alkyl ethoxylate nonionic surfactants are commonly used as foam control agents in detergents where application temperatures exceed the cloud point of the surfactant—the temperature at which the surfactant becomes insoluble.

The insoluble nonionic-rich surfactant phase acts to break foam lamella promoting foam collapse. The calcium soaps of long-chain fatty acids are effective at foam control as are hydrophobic silica particles.

Particularly effective antifoams are comprised of colloidal hydrophobic silica particles suspended in a silicone oil like polydimethyl siloxane. For example, gel-type automatic dishwashing detergents are thickened to help suspend phosphate and other solids that would otherwise separate out from the liquid phase. Thickening can be achieved through the use of inorganic electrolytes, e. Soil release polymers. Carboxymethyl cellulose CMC is the archetypical soil release polymer.

Once absorbed, the carboxyl moiety creates a high net negative charge on the fabric surface effectively repelling negatively charged soils, especially clays [7]. This is by no means an exhaustive compilation. Rather, the intent is to illustrate the variety of detergent formulations and how the composition of the formulation varies depending on the intended use. Laundry Detergent Formulations Examples of granular laundry detergent formulations are shown in Table 3.

Table 4 illustrates typical liquid laundry detergent formulations. Dishwash Detergent Formulations Examples of typical liquid hand dishwash formulations are provided in Table 5. Examples of granular detergent formulations for use in automatic dishwashing applications are illustrated in Table 6. Hard Surface Cleaning Formulations Examples of liquid hard surface cleaning formulations are illustrated in Table 7.

Personal Care Detergent Formulations Table 8 provides examples of typical shampoo formulations. Examples of body washes are provided in Table 9. Examples of Toothpaste formulations are provided in Table In the toothpaste formulations illustrated in Table 11 note the use of silica as an abrasive cleaning agent.

Agricultural Detergent Formulations Herbicidal compositions typically comprise an aqueous emulsion of the active with appropriate surfactants to insure effective spreading and penetration of the herbicide into plants. Typical compositions comprising the well-known herbicidal active glyphosphate are illustrated in Table Automobile Detergent Formulations A variety of detergent compositions are used in the care and maintenance of automobiles.

Chapter 8 provides an extensive review of the components used in such formulations. A formulation designed to remove grease from automobile engines and engine compartments is illustrated in Table Source: From U.

Patents 6,, B1 and 6,, B1. Detergent Formulations for Cleaning Food Processing Equipment Processing of food contaminates surfaces with lipids, carbohydrates, and proteins. Table 15 provides an example of one such detergent utilizing high alkalinity as the major detersive component: More user friendly and environmentally compatible formulations can be built around enzyme technology to facilitate the removal of protein bound to surfaces.

Examples are illustrated in Table Patent 6,, B1. Detergent Formulations for Metal Component Cleaning Industries involved in repair and replacement of mechanical parts often require that those parts be cleaned prior to inspections, repair, or replacement. Generally, mechanical parts have been exposed to a wide variety of contaminants including dirt, oil, ink, and grease that must be removed for effective repair or service.

A variety of metal cleaners have been developed to clean such surfaces. For example, solvent-based cleaners containing either halogenated or nonhalogenated hydrocarbons are common. However, the use of these cleaners carries certain environmental and worker safety issues. Where appropriate, aqueous-based cleaners are preferred for cost, safety, and environmental concerns.

Table 17 provides example formulations of aqueous-based metal cleaning formulations: IV. Patents 5,, and 6,, B1. Patents 6,, and 6,, Patent 5,, W to be done on the system. In general, surface-active agents like surfactants promote removal from surfaces by lowering the interfacial energy between the substrate and the bulk phase.

Generally, suspension is achieved either by electrostatic repulsive effects or steric stabilization. Subsequent chapters of this book provide extensive detail on how to remove and suspend materials via chemical means. The purpose of this section is to provide a general thermodynamic underpinning to the phenomena of soil removal and particulate suspension so that the reader can better understand the mechanisms by which detergent chemicals function.

Patent 6,, Removal Mechanisms For simplicity, in the following discussion, materials to be removed from a surface will be generically referred to as soils. S Patent 3,, Patent 4,, to Ecolab Inc. Patent 6,, B1 to Ecolab Inc. Soil removal mechanisms can be considered to comprise several steps: 1. Surfactant transport to an interface. The kinetics of surfactant transport and adsorption at the interface can be measured via dynamic interfacial tensiometry [37—41].

From this equation it can be seen that the work required to remove soil from a surface is reduced when the interfacial tensions between the surface and bulk phase and soil and bulk phase are minimized and the interfacial tension of the soil-surface is increased.

This is exactly the effect that surfactants have. By adsorbing at the surface, bulk-phase, and soil interfaces surfactant lowers interfacial energies, decreasing the free energy associated with moving the soil from the surface into the bulk phase. One aspect of the above that is often ignored is step one, transport of surfactant to the various interfaces. The presence of monomeric surfactant is critical to rapid transport of surfactant to the interface and rapid lowering of the interfacial tensions IFT.

However, solubilization is dependent on the presence of micelles. The formation of micelles reduces the capacity of the surfactant to adsorb at the interface and reduce IFT that is critical in step 2.

This optimum is dependent on the nature of the soil being removed, the substrate hydrophobicity , and the surfactant system used. The mechanism outlined above is generally applicable for oily soils.

For particulate soils consideration of the electrostatic and van der Waals forces of attraction between the particle and the surface need to be considered because most particulate dirt and most surfaces tend to be charged due to the presence of surface exposed silicic acid, hydroxyl, or carboxyl groups [43].

Again, the process can be described in a series of steps [44]. The process requires work input, w1, to overcome the van der Waals attraction between P and S. Then detergent solution penetrates the space between P and S, allowing surfactant to adsorb at the solution-particle interface and the surface-solution interface, and a net sum of work, w2 , is obtained.

According to Eq. The addition of surfactant reduces both gsw and gpw such that w2 increases, which helps to lower the total work of removal.

In addition, the total potential energy of the system jd is the sum of the attractive van der Waals interactions, jd,A, and the repulsive interactions, jd,R, due to surface charges. The adsorption of surfactant, especially anionic surfactant, at the surface-solution and particle-solution interfaces serves to decrease the attractive force and increase the repulsive force thereby promoting removal to a distance where there are no longer any attractive forces between particle and surface. Suspension Mechanisms Once material is removed from a surface it must be suspended in the bulk phase to avoid redeposition.

For hydrophobic liquid soils in aqueous media, suspension is typically accomplished by entrapment of the soil within the surfactant micelle or vesicle.

There are two general mechanisms for suspending soil in solution— electrostatic repulsion and steric stabilization. In polar media, most substances will acquire a surface electric charge as a result of ionization of surface chemical groups, ion adsorption, and ion dissolution [16].

In aqueous solutions most surfaces and most soil particles are negatively charged. As a result both soil and surface possess an electrical double layer. The electrical double layer is comprised of a compact layer of ions of opposite charge to the surface and a more diffuse double layer comprised of counter- and co-ions distributed in a diffuse manner in the polar medium.

As described in Section IV A, the total potential energy for a system comprised of a particle at some distance, d, from a surface is the sum of the attractive force, jd,A, and the repulsive force jd,R. When two particles of the same net surface charge approach one another, or when a particle approaches a charged surface, they repel each other as their double layers start to overlap. The particles have to overcome this electrical barrier in order to get close enough for van der Waals attraction to take over.

When the potential energy barrier jd,R is high particles tend to stay dispersed in the bulk phase. However, if the electrical double layer is compressed by high ionic strength or shielded by adsorption of an organic layer coalescence and aggregation can occur resulting in redeposition of soil particles back onto the surface.

Electrostatic repulsion is best achieved in low ionic strength media where the electrical double layer on particles and surfaces is diffuse. An alternative strategy is to adsorb a charged polymer, such as the acrylic acid polymers described in Section II B, or a charged surfactant onto the surface.

When particles having adsorbed layers polymer or surfactant collide, their adsorbed layers may be compressed without penetrating. Stabilization can therefore come either as a result of a positive change in enthalpy or a decrease in entropy.

Steric stabilizers are usually block copolymers that make up a hydrophobic part e. These four factors combined determine the ultimate effectiveness of the detergent formulation. Gogarty, Petroleum Techn. Zheng, Y. Xie, L. Zhu, X. Jiang, and A. Yan, Ultrasonics Sonochem. Bassemir, A.

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