75 Surfactants, Dispersants, and Defoamers for the Coatings, Inks, and Adhesives Industries 75.1. Introduction 75-1 75.2. Wetting and Dispersing Process. 75-2 The Wetting and Dipersing Process Waterborne Systeme" Solvent Based Systems» Clasication + Summary 75.3 Silicones and Surface Flow Control Agents. 75-6 Background + Chemical Steuctue of Sicones" + Surface Phenomena and the Elimination of Defects» Summary 754. Deloaming Additives 75-9 The Nature of Foam + Defeamers versus Air Release Agents = The Mechanisms of Defoaming and Aie Relese» Defoamers for Aqueous Systems» Defoamers for Slvent-Based Systems + Selection Criteria and Test Methods © Sunny John W Du 753 Conclusion. 75-12 BYK-Chemie USA References. 75-12 75.1 Introduction Over the history of coatings, inks, and adhesives, many evolutionary changes have occurred; not only have the ingredients used to make the formulations been changed, but also the physic of the formulations along with their application, cure, and performance parameters have changed. Of course, each trend poses challenges to both raw material suppliers and formulators alike, Because additives are used to enable and enhance system performance, the evolution of resins, pigments, solvents, application technologies pose special challenges for additive suppliers. Resin and solvent combinations used in the good old days were typically quite low in surface tensions in comparison to modern formulations. Today's mote environmentally friendly formulations with litle fr no solvents, or in the case of aqueous formulations, with litle or no cosolvents, require increased use of interfacially active materials in order to provide adequate substrate wetting, surface flow, and the prevention of foaming and air entrapment. characteristics75.2. Coatings Technology Handbook, Third Edition Interfaces play in important role in the production and application of coating systems. For the coatings chemist the following interfaces are of particular interest: solidair, solid/liquid, liquid/air, and iquidsiquid. During the pigment wetting and dispersion stage, ai atthe pigment surface is displaced by the resin solvent solution; the soid/air(pigment/ai) interface at the pigment surface is replaced by a solid/liquid (pigment/resin solution) interface. During manufacturing and application, additional interfaces become important: solid/liquid (substrate/liquid, others), liquid/liqud (il contamination, wet-on-wet applica- tion, mixing, etc), as well as liquid/air (foam, entrapped air, surface leveling, etc). The selection of the proper additive chemistry and concentration provides the coatings formulator with the means to manip- tlate and control these interfaces. ‘As environmentally friendly coatings, inks, and adhesive systems have evolved, additives have also evolved in chemistry, structure, and effectiveness. This overview strives to present these new additive technologies in three areas: surfactants, dispersants, and defoamers. The chemical nature of these additives and subsequent performance in a variety of systems will be described, ‘While there is significant overlap of the three phenomena being discussed, this chapter will attempt to establish some clear delineation between the chemical structure ofthe additives and their performance as surfactants, defoamers, and dispersants. ‘This chapter will strive to develop a unified approach to describe the phenomena of the following: 1, Wetting and dispersing additives 2, Silicone and surface flow control agents 3, Defoaming additives 75.2 Wetting and Dispersing Process Wetting and dispersing additives are designed to prevent defects such as flocculation, gloss reduction, ooding and floating, formation of Bénard cells, pigment setting, and theology problems. 75.2.1 The Wetting and Dispersing Process uring the initial phase of the pigment wetting process the air and adsorbed water atthe pigment surface must be displaced by the binder solution. This means that the solid/gas interface (pigment/air) needs to make the transition to become a solid/liquid (pigment/binder) interface. In order to successfully complete the wetting phase, the interfacial tension difference between the pigment and binder solution must be bridged over, so to speak. This bridging process can be enhanced by the use of appropriate wetting agents Homogeneous particle distribution enhances the transition process and is crucial to improved per- formance; interfacially active substances, which bridge the boundaries between solid and liguid media, are therefore essential. From a practical standpoint, proper distribution is necessary not only during. ‘manufacturing and application but also for storage. ‘The transition process is pictured in Figure 75.1. As shown, the pigment agglomerates are dispersed by mechanical energy (impact/shear) so that their particle sizes are reduced. The technology of the equipment (in combination with properly adjusted millbase formulations and grinding media) is para ‘mount to the success of the dispersion (grinding) process. Through the input of mechanical energy, the dispersed pigment particles are brought to a higher energy state than the starting agglomerates. These dispersed pigment particles continually strive to reach their lowest energy state, so they will try to flgcculate or agglomerate unless a means for stabilization is introduced, Inadequately stabilized pigmented coating systems will exhibit sedimentation, a reduction of gloss, a change of color when rubbed, and. possible looding and floating, Dispersing or dispersion stabilizing additives prevent the dispersed pig. ‘ment particles from flocculating or agglomerating by attaching themselves to the surface ofthe dispersed pigment particles. The stabilizing additive on the pigment surface spaces the pigment particles from each other, thus preventing flocculation or pigment-to-pigment contactSurfactants, Dispersants, and Defoamers 753 1 2 3 wetting Dispersing ‘tabilzng Dispersing Additive FIGURE 75.1. ‘The wetting and dispersion stabilization proces 75.2.2. Waterborne Systems 75.2.2.1 Wetting Additives for Waterborne Systems Wetting additives reduce interfacial tension and, as a result, increase the spreading pressure of the liquid continuous phase. Characteristic of such substances is ther highly surface-active structure (pola, hydro- philic structural elements along with nonpolar hydrophobic structural elements combined into a single ‘molecule). Such substances migrate to the pigment/binder solution interface. In waterborne systems, there is often a specific additive used for the wetting process. Ina solvent-based system, the additive is typically responsible for both wetting and dispersing (this will be discussed later). Iniluental factors in this wetting process include the polarities of the pigment surface and solution, the viscosity of the liquid phase, as well asthe geometry of the empty spaces (or pores) within the pigment agglomerate structures. OF utmost importance is the interfacial tension in the exact areas where the wetting additive performs — between the pigment surface and the resin solution. inder 75.2.2.2 Dispersing Additives for Waterbome Systems ‘There are two principle mechanisms for stabilizing dispersed pigments into a resin solution, These spacing techniques are electrostatic repulsion and steric hindrance. In electrostatic repulsion, the pigment particles inthe liquid carry electrical charges on ther surfaces. With the use of special additives, it is possible to strengthen these charges and, furthermore, to make all of the pigment particles equally charged. Counterions concentrate around the pigment particles o that an electrical double-layer is formed; stabilization increases with layer thickness. This particular electro- static repulsion stabilizing mechanism is especially useful in waterborne latex systems. Chemically speak ing, the additives used for dispersion in such systems are polyelectrolytes — tailored higher molecular weight products with electrical charges in their side chains. In addition to polyphosphates, many poly- carboxylics and derivatives are used as polyelectrolytes in the coatings industry. These adsorb onto pigment surfaces and consequently transfer their charge to pigment particles. Through electrostatic repulsion between equally charged pigment particles, the deflocculated state is stabilized. This isthe primary mechanism of pigment stabilization in many waterborne systems. Dispersion stabilizing additives that function by steric hindrance display two special structural features. First, these additives contain one or more so-called pigment-afinic groups (anchoring or adhesive 20ups),all of which provide strong adsorption onto pigment susfaces. Second, these additives contain resin-compatible chains (hydrocarbon entities), which following adsorption of the additive's pigment affinie groups onto the pigment, protrude as far as possible from the pigment surface into the surrounding resin solution. This layer of adsorbed additive molecules with protruding chains produces steric hindrance or “entropic stabilization” Newly developed specialized additive chemistries make use of the above stabilization mechanism. Furthermore, this mechanism is accentuated by the interaction of the polymeric segments of the additive ©2009 Tyr Ar Gap.