Formulation associative thickeners

Resin Solubilizers. In general, water-soluble resins ate amine salts of acidic polymers. Water-soluble coatings formulated with AMP-95 and DMAMP-80 exhibit superior performance (15,16) (see Water-SOLUBLE polymers). AMP-95, used in conjunction with associative thickeners (17) or hydroxy-ethylceUulose, provides for the most efficient utilization of such thickeners. It also is the neutralizer of choice for use with hair spray resins. 

The specific nature of the interactions among hydrophobes would suggest that the associative thickeners will vary in performance with the different latices and components used in coatings formulations. This has been observed(29) in... 

HMHEC polymers are improved rheological modifiers for latex paints. They retain the benefits of traditional cellulosic ethers (compatibility with a wide range of coatings ingredients, storage stability, better sag resistance, etc.) but overcome many deficiencies of synthetic associative thickeners (sensitivity to latex systems and pH of paint formulations, poor sag resistance, etc.). The combined advantages offered by HMHEC are best suited for interior and exterior flat paints (5). 

X HE RELATIVE COST OF MANUFACTURING hydrophobically modified, water-soluble polymers is the primary determinant in their market acceptance. The lowest-cost associative thickeners used in coating formulations are hydrophobically modified, alkali-swellable emulsions (HASE). The extensive history leading to the development of this technology is reviewed in the preceding chapter their utilization and limitations are discussed in Chapters 27 and 28. 

Viscosity Maxima. The low-shear-rate viscosities of both commercial and model associative thickeners below their c /, values will increase with the addition of conventional low molecular weight surfactants or coalescing aid (22). With HEUR polymers, solution viscosities are observed to increase, achieve a maximum value, and then decrease with continued increase in surfactant concentration (23). This type of behavior is illustrated (Figure 5) for four commercial HEURs with a nonionic surfactant (typical of that used in coating formulations). A similar behavior has been observed (24) with a classical anionic surfactant and hydrophobically modified (hydroxy-ethyl)cellulose (HMHEC) and is reviewed in Chapter 18. Intermicellar networks, formed by the participation of one or more hydrophobes from different polymers in the micelles of conventional surfactants, were again recently suggested (25) to affect viscous solutions. 

The studies just discussed do not address one of the significant contributions associative thickeners make to coatings rheology minimizing LSVs in small-particle latex formulations. 

Syneresis. This chapter began with consideration of the depletion layer effect. This phenomenon can be seen in coatings that contain large latices (>300 nm) not highly stabilized by surface-attached (hydroxy-ethyl)cellulose fragments (16), and is in part the problem observed in the last sections of Chapter 27. The phenomenon is not necessarily restricted to HEC-thickened formulations and depletion flocculation. In our studies, syneresis is observed in thickened aqueous solutions and in dispersed systems containing the model trimer associative thickener (Scheme II) it can be overcome by addition of conventional surfactants. Syneresis in HMHEC-thickened solutions is discussed in Chapter 19 in the absence of a dispersed phase. Syneresis is discussed in the following chapter where additives that substantially enhance low shear viscosities are added to inhibit syneresis. 

In HEC-thickened formulations, low-shear-rate viscosities increase with decreasing latex particle size. This effect has been a major limitation in formulating small-particle latices. The phenomenon appears to arise from electro viscous, hydration, or flocculation effects, not a depletion layer mechanism. Associative thickeners achieve efficient viscosity in coating formulations via participation in synthesis and formulation surfactant micelles to form pseudo macromolecules and via an ion-dipole interaction between the cations of surface carboxylate groups on the latex and the ether linkages of the associative thickener. Generally, an excess of synthesis surfactant is found in the production of small-particle latices. The achievement of lower viscosities in small-particle ( 100 nm) latex coatings thickened with associative thickener appears to occur by extensive disruption of the polymer hydrophobe s participation in intermicellar networks. 

Depletion layer effects occur in associative thickener formulations when the latex is larger in size ( 500 nm) and not highly stabilized with surface (hydroxyethyl)cellulose fragments. Syneresis is also observed in simple aqueous solutions and in latex dispersions when the hydrophobicity of the associative thickener is high. 

PRACTICAL ASPECTS OF FORMULATING WITH ASSOCIATIVE THICKENERS Isabelle Mussard... 

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