Spray applications: Part IV. Compositional influences of HEUR thickeners on the spray and velocity profiles of waterborne latex coatings

In this study, the focus is on the spray behavior of latex coatings thickened with structurally different surfactant-modified, water-soluble polymers (associative thickeners of the hydrophobically modified, ethoxylated urethane [HEUR] type). Particle image velocimetry (PIV) profiles are considered in the perspective of the dynamic uniaxial extensional viscosity (DUEV) of the coatings and an effort to understand the results in terms of the structural aspects of the thickener molecules is undertaken. A high-M _v hydroxyethyl cellulose (HEC) thickened formulation, with a significant DUEV, does not atomize well. Among the HEUR thickeners, the addition of larger hydrophobes in the terminal positions requires less thickener to achieve a 90 KU viscosity and produces lower DUEVs and lower viscosities at high-shear rates. This is necessary to produce formulations with acceptable spray characteristics (i.e., good atomization). The sprayability of these systems is reflected in their velocity profiles and particle size/particle size distributions. Poorer spray characteristics are reflected in ligaments and broad particles size distributions. This study highlights the ability to control the particle size/size distribution and velocity profiles of coatings formulations through the use of structurally different HEUR associative thickeners. Variations in sprayability among different nozzle geometries are also studied. Presented at the 2006 FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006.     

Waterborne latex coatings of color: I. Component influences on viscosity decreases

For almost two decades, it has been known that the addition of colorants to a waterborne latex coating thicknened with an associative thickener will result in a viscosity loss. The influence of surfactants on viscosity variations in waterborne latex coatings, as discussed in our most recent JCTCoatingsTech article,¹ is the source of the viscosity decreases. To evaluate this problem, aqueous solutions containing large quantities of five different surfactants, and the smallest particle size of the colorants, carbon black (CB), were prepared. Large quantities of surfactant were used to allow for adsorption on, and stabilization of, CB. When traditional associative polymers (HMHEC, HASE, and a telechelic HEUR) were used to thicken carbon black dispersions, viscosity decreases were not observed, for most of the surfactnat is adsorbed on the CB’s surface. There is enough surfactant, however, to promote viscosity decreases in comb-HEUR thickened CB dispersions. Moving beyond the colorant dispersions, the CB, yellow, or red colorants were then added to a commercial latex paint that contains many surfactants, glycol ether, and coalescing aids, and significant viscosity decreases were observed. The decreases were very dramatic as the colorant concentration was increased to obtain deeper color tones, due to the additional excess surfactant added to the coating. Reduction in total surfactant levels in the colorant was an obvious solution, but this led to rub-up incompatibility. The conflict between viscosity retention and rub-up incompatibility was resolved when the surfactant concentration was reduced by adding to the colorant formulation compositionally different hydrophobically-modified poly(oxyethylenes) and hydrophobe-modified maleic acid co-oligomers. Presented in part at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2003 in Philadelphia, PA     

Associative polymer/latex dispersion phase diagrams II: HASE thickeners

The colloidal interactions of HASE associative polymers and latexes in the presence of surfactant are complicated and subject to a number of variables. Both bridging and depletion flocculation can occur, in addition to good particle dispersion. Dispersion phase diagrams have been developed to help visualize these interactions. The various dispersion states can have a significant effect on coating formulations and film properties. Examples of dispersion phase diagrams are presented for a model HASE anionic associative thickener and various model latexes in the presence of sodium dodecyl-sulfate and nonionic surfactants. The major variables affecting dispersion behavior are associative polymer concentration, latex particle size, latex surface hydrophobicity, electrolyte concentration, and surfactant concentration. The dispersion phase behavior of the HASE systems is compared to that of HEUR thickened systems reported previously. A significant difference is that much less bridging flocculation is observed in the HASE systems. In addition, nonionic surfactants induced depletion flocculation in the HASE systems but not in the HEUR systems.     

Waterborne latex coatings of color: II. Surfactant influences on color development and viscosity

A matrix of coating variables, nonassociative versus associative thickeners, different latex median particle sizes, individual surfactants and colorants [carbon black (CB), red, and yellow pigments], was examined for their influence on variances in coatings rheology and color development. Within the different coating groups, the variable of interest in this study was the surfactant added to the colorant formulation. In all three colorant formulations, sodium dodecyl sulfate (an anionic surfactant) provided poorer color development (CD) than in applied formulations containing an equivalent nonylphenol oxyethylene (EO) surfactant. In CB formulations, nonionic surfactants with higher EO content provide improved color development at low (2 mM) concentrations, but near equality in CD is achieved with low EO surfactants at higher concentrations. In contrast to CB formulations, red and yellow colorants exhibit good color development with high EO content nonionic surfactants only at low nonionic surfactants concentrations. This variance appears to be related to the interactions of surfactants with inorganic pigments (talc and laponite) in the colorant formulation. The coating’s rheology is related to latex, thickeners, and surfactant components of the paint, as has been noted in previous studies, but not to the nature of the color pigment. The viscosity of the hydroxyethyl cellulose (nonassociative type) and HEUR (associative type) thickened paint decreased with colorant addition due to dilution effects. There were no unusual deviations with the NP(EO)_x surfactants, except when a large hydrophobe nonionic surfactant [e.g., C₁₈H₃₇(EO)₁₀₀] is added. In HEC thickened coatings, the viscosity decreases when C₁₈H₃₇-(EO)₁₀₀ is in the colorant due to that surfactant inhibiting depletion flocculation. In the C₁₈H₃₇(EO)₁₀₀ coatings containing the HEUR thickener, significant increases in viscosity were observed, above the dilution values observed with the colorant addition. This is related to the viscosity maximum in the low concentration of HEUR with the C₁₈H₃₇(EO)₁₀₀ surfactant. Color development is independent of the viscosity profile of the coating. Presented in part at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2003 in Philadelphia, PA.     

Using dispersion/flocculation phase diagrams to visualize interactions of associative polymers, latexes, and surfactants

The colloidal interactions of associative polymers and latexes in the presence of surfactant are complex. This is because, in addition to good particle dispersion, both brid-ging and depletion flocculation can occur. Therefore, we have developed phase diagrams to help visualize these interactions. The various phases have a significant effect on coatings and applications properties. Examples of phase diagrams are presented for a model HEUR nonionic associative polymer and latexes in the presence of sodium dodecylsulfate. The major variables affecting phase behavior were found to be associative polymer concentration, latex particle size, latex surface hydrophobicity, and electrolyte, cosolvent, and surfactant concentrations. Presented at the PMSE Waterborne Coatings Symposium at the ACS Meeting, August 26–30, 2001, in Chicago IL. P.O. Box 904, Spring House, PA 19477-0904, E-mail: ekostansek@rohmhaas.com.     

Phase behaviors and film properties of dispersions and coatings containing associative and conventional thickeners

Phase-separation behaviors of latex dispersions, using commercial latices of three different median sizes, and pigmented coatings are examined. Both the dispersions and pigmented coatings at a 0.32 volume fraction of total dispersed phase were thickened with water-soluble polymers, with and without surfactant hydrophobes. Latex dispersions thickened with water-soluble polymers without hydrophobe modification follow the phase-separation behavior described by the volume restriction flocculation (VRF) concept (i.e., molecular weight of the thickener or particle size of the latex). This is surprising since commercial latices contain a variety of surface-stabilizing moieties, in addition to surfactant. Latex dispersions thickened with commercial and model hydrophobically modified ethoxylated urethane (HEUR) polymers do not follow the phase-separation behavior predicted by the VRF concept. The lack of correlation of phase behavior with latex median size in HEUR-thickened formulations led to an examination of four secondary thickeners, noted for providing high viscosities at low shear rates. With an all-acrylic, large median-size latex, the combinations of commercial HEURs with secondary thickeners are effective in eliminating phase separation; only partial reduction in phase separation is observed with a vinyl acetateacrylic large-particle latex. The influence of HEUR/secondary thickener blends on the film properties also is discussed. © 1993 John Wiley & Sons, Inc.     

Control of rheology of water-borne paints using associative thickeners

Water-borne decorative topcoats generally show inferior leveling and open time compared to solvent-based paints. Basically, this behavior is caused by the divergent viscosity–solid content relationship for dispersions and emulsions and by the relatively high evaporation rate of water. Employment of associative thickeners may improve leveling and open time of latex paints only if they introduce a substantial amount of ‘network viscosity,' characterized by a short relaxation time and little dependence on solid content. This network viscosity enables one to formulate a paint with sufficient high-shear viscosity at a particle-packing density far below the value where low-shear viscosity starts to diverge. Addition of an associative thickener not only affects rheology, but also the interaction between latex particles: Associative HEUR thickeners may induce undesired phase separation by strong bridging between the latex particles. The influence of HEUR thickeners on latex particle interaction has been studied by turbidity measurements. The experimental results could qualitatively be interpreted very well by two-particle interaction potentials computed using the Self-Consistent-Field theory of Scheutjens and Fleer. It is demonstrated how viscosity, created by the addition of an associative thickener to a highly concentrated latex, can be split up into a polymer network viscosity and a contribution to (relative) dispersion viscosity. According to these analyses, reduction of the molecular weight of tri-block HEUR thickeners yields an increase of the favorable network viscosity and a reduction of the unfavorable dispersion viscosity. However, reduction of the molecular weight of the HEUR thickener is limited by the introduction of undesired phase separation (bridging flocculation) below a certain molecular weight.     

Unifying model for associative thickener influences on waterborne coatings: II. Competitive adsorption of nonionic surfactants and HEUR thickeners on titanium dioxide pretreated with inorganic stabilizers and organic oligomeric dispersants

Size exclusion chromatography in tandem with UV absorbance of the surfactant is used to separate and quantify the amount of nonionic surfactant and model hydrophobically modified ethoxylated urethane (HEUR) thickeners adsorbed on different organic oligomeric polyacid, metal oxide-treated TiO₂ surfaces. The isoelectric point imposed on TiO₂ by the metal oxide surface treatment determines the amount of organic dispersant adsorbed. The size of the α-olefin on the maleic acid dispersant is also important in the adsorption of the dispersant. The size of the α-olefin on the organic acid dispersant, in turn, determines the amount of surfactant and HEUR thickener adsorbed. The surfactant, unlike the HEUR thickener, exhibits a dependence on the metal oxide treatment in neutral media, independent in several aspects of the amount of organic dispersant adsorbed. The adsorption dependence of HEUR thickeners and nonionic surfactant on the hydrophobe size of the HEUR is discussed. Presented at the 69th Annual Meeting of the Federation of Societies for Coatings Technology, on October 23, 1996 in Chicago, IL Polymers and Coatings Dept., Dunbar Hall, Fargo, ND 58105. Chestnut Run, Building 709, Wilmington, DE 19898.     

Controlling particle dispersion in latex paints containing associative thickeners

Latex paints contain several types of particles including polymer binder, primary pigment, extenders, and colorants. When the paints contain associative thickeners, control of particle dispersion can be very complicated due to the interaction of the particles with dispersants, surfactants, and the associative thickener itself. In particular, dispersion of the pigments can act independently of dispersion of the binder particles. The consequences of this situation are manifested in the physical properties of the paint and of the films it forms. This paper describes these interactions in terms of their colloid chemistry and shows the consequences of additive choices on the particle dispersion and also the optical properties of model paint films. Presented at the 2006 FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006.     

Interaction between styrene/butylacrylate latex and water soluble associative thickener for coalescent free wall paints

The effect of water soluble hydrophobically modified ethylene oxide urethane (HEUR) thickener on coalescent free wall paints was studied. Three systems were looked at: latex/thickener blends, model paints (containing no fillers that could have an effect on paint rheology) and satin paints (PVC 30%). The latexes used were a styrene/butylacrylate copolymer, designed for coalescent free wall paints. A full factorial statistical experimental design was employed to study the effect of latex and formulation variables on the viscosity response for the full range of shear rates encountered in paint application. The factors considered in the design were total latex surface area, polymerization surfactant level, thickener type and thickener concentration. The surfactant level was varied between 0.85 and 1.71 parts. The two HEUR thickeners were selected based on the manufacturer's claim that they exhibited good performance at different shear rates. The thickener levels were the extremes recommended by the manufacturer. Measurements were done on Haake, Rheometrics, Brookfield and ICI Cone & Plate rheometers. Total latex surface area and the thickener level are the two significant parameters for latex thickener blends and for model paints at the same significance level, this indicates good correlation between the two systems. The introduction of clay as a filler decreases the effect of all parameters studied.     

Preparation and characterization of waterborne epoxy latexes and epoxy/(silica sol) composites

A series of waterborne epoxy latexes was synthesized, and epoxy/(silica sol) composite latexes were prepared. The effects of functional monomer methacrylic acid (MAA) and silica sol on the latex particle size, morphology, and stability were investigated. With increasing amounts of MAA, the conversion rate increased, the particle size reduced, and the viscosity of the epoxy latexes increased. The epoxy latexes had storage stability and could be stored at room temperature for more than 6 months with a solid content variation of less than 1%. For the (silica sol)‐modified waterborne epoxy latexes, the effects of preparation techniques and silica sol content on the latexes and latex films were investigated. When the silica sol content increased, the particle size of the composite latexes decreased. The morphology investigation showed that when the silica sol content increased, the uneven surface level of the latex films was increased. The increase of elemental silica on the surface was in accord with the improvement of the water resistance of the composite latex films. The heat resistance of these films was improved as well, and their overall performance was better than that of the epoxy latex films. J. VINYL ADDIT. TECHNOL., 20:57–64, 2014. © 2014 Society of Plastics Engineers     

Interactions in associative thickener/220 nm methyl methacrylate latex dispersions

The rheology of commercial associative thickener dispersions containing 220 nm ‘model’ methyl methacrylate (MMA) latices have been examined. These high T_g MMA latices were synthesized by a semicontinuous process with variable percentages of methacrylic acid (MAA). The latex surface without monomer acid segments was only 70% saturated. The latices stabilized with neutralized methacrylic acid segments provided surfactant-saturated surfaces and uniform dispersions when thickened. With the acid-monomer-free latex, the addition of surfactant to saturate the surface of the latex and to increase the free surfactant concentration in the aqueous phase to the level needed to optimize viscosity by intermicellar participation did not effect viscosities equivalent to those noted in associative thickener dispersions containing acid-stabilized latices. These observations support the ion—dipole associative thickener mechanism previously proposed.

The viscoelastic behavior of associative thickener dispersions containing stabilized MMA/MAA latices neutralized with ammonium and alkali metal hydroxides has also been examined. The viscosities of all dispersions containing associative thickeners were highest with NH₄OH-neutralized latices. These results are interpreted in terms of the greater solubilizing power and lower pK_a value of the ammonium salt. The viscosity of hydroxy-ethylcellulose (HEC) thickened dispersions was found to be insensitive to the free surfactant concentration and the nature of the base cation, with only minimal changes in low shear rate viscosities (LSVs) being observed with increasing latex surface acids. These variables notably influence the LSV of the associative thickeners (AT), the magnitude of the latter variations being specific to the AT employed.

In oscillatory experiments, dispersions containing commercial associative thickeners, used predominately with acrylic latices in the U.S. and Australian markets, were observed to exhibit large viscous components. A large elastic component, reflecting thickening via network formation, was noted with commercial associative thickener used largely with commercial vinyl/acrylic latices.     

Study of the rheology of aqueous radiation curable polyurethane dispersions modified with associative thickeners

The chemistry of radiation curable polyurethane dispersions is outlined with an emphasis on the microstructure of the aqueous polymer dispersion and the possible interactions with associative thickeners. The steady-shear flow was studied for two model dispersions prepared from the same unsaturated polyurethane but showing significantly different particle size distributions. A hydrophobically modified ethoxylated urethane (HEUR) associative thickener with a linear structure was incorporated at different amounts to the dispersions with varying particle volume fractions. The steady-state viscosity at 25 and 10 °C was always reached quickly after instant flow rate changes so that no significant thixotropic effects were reported within the experimental timescale. Without thickener, the flow curves of the two model dispersions exhibited a Newtonian behavior except at the highest volume fractions where shear thinning became apparent. The maximum packing values determined from the Krieger–Dougherty relationship were essentially the same for the two systems. In the presence of thickener, the flow curves were characterized by a Newtonian plateau followed by a marked shear thinning region even at low particle volume fractions. This behavior typically suggests the formation of a physical network between polyurethane particles and thickener molecules partly adsorbed onto the polymer surface. The zero-shear viscosity of the two dispersions was compared with respect to: (i) particle volume fraction and (ii) particle surface area at different HEUR concentrations. At a given volume fraction, the particle size affects the viscosity of thickened models. As a corollary, a relationship is found between the particles size and the level of thickener required to reach a target viscosity. This study offers practically relevant data in terms of application conditions and provides a better insight into the thickening protocol.     

Study of the effect of PEG length in Uni‐HEUR thickener behavior

Four new models of Uni‐HEUR associative thickener were designed and synthesized using various molecular weights of poly(ethylene glycol) (PEG) as hydrophilic segments. The PEG chain ends were capped with octadecyl isocyanate as hydrophobic segments. The structure of the prepared Uni‐HEUR thickeners was confirmed by infrared spectroscopy. The steady shear viscosity measurements of aqueous solution of HEUR models showed that the relative size of hydrophilic segments to hydrophobic segments is very important. Oscillatory measurements confirmed the steady shear viscosity results. It is found, there is an optimum relative size of hydrophilic segments to hydrophobic segments to achieve the thickener with a good performance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Syneresis and rheology mechanisms of a latex-HEUR associative thickener system

This study focuses on the phase behavior, rheology, and interactions of polymer latex particles and a hydrophobically modified ethoxylated urethane (HEUR) associative thickener in water. At constant 0.25 latex particle volume fraction, increasing HEUR caused stable, followed by phase separated (syneresis), and stable mixtures as HEUR concentration increased from 0% to 2.0% (by weight) in the latex-thickener aqueous mixture. The mixtures that underwent syneresis were flocculated. The relationship between the flocculation behavior and the composition of the latex-HEUR mixtures is consistent with previous work reported by other investigators. However, detailed rheological data on systems like these that have undergone syneresis have not been reported. This paper presents detailed viscosity vs shear rate data and correlates viscosity trends with the both flocculation and syneresis behavior. The stable latex-HEUR mixtures at low HEUR levels show Newtonian or shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased to levels at which syneresis is observed, erratic rheological profiles with shear thinning as well as thickening are observed. This type of shear thickening has been attributed to bridging flocculation by other investigators. When HEUR level is further increased to levels at which no syneresis is observed, low-shear Newtonian plateaus re-appeared, albeit at higher viscosities. Detailed analysis of syneresis and shear-thickening behavior of a latex-HEUR mixture containing 0.5% (by weight) HEUR showed two shear-thickening regions, one between 0.1 and 0.5 s^?1 shear rate range and another between 30 and 100 s^?1 shear rate range. Molecular weight distribution (MWD) of the HEUR thickener indicates that the two shear-thickening regions are related to the bi-modal nature of the thickener’s MWD.     

Flooding and floating in latex paint

Flooding and floating are problems in many paint applications. If pigment concentration is uniform on the surface but not through the thickness of the film, one refers to ‘flooding’ (horizontal separation). If, however, concentration differences are visible across the surface of the paint film, one refers to ‘floating’ (vertical separation). In this article, the influence of pigment, filler, additives, and processing conditions on the flooding and floating of colored latex paint were investigated. It was discovered that too broad a distribution of pigment and filler particle size can lead to flooding and floating. Different levels of pigment (TiO₂) or filler (kaolin) loading cause diverse degrees of flooding and floating. Waterborne coatings that do not exhibit flooding or floating may show these conditions when diluted. Using dispersants or thickeners with hydrophobic constituents, increasing viscosity, reducing surface tension, etc., all help to prevent or reduce flooding and floating. Comparison tests revealed little influence of processing conditions on flooding or floating.     

Tailoring HASE rheology through polymer design: Effects of hydrophobe size, acid content, and molecular weight

Hydrophobically modified alkali-soluble emulsion (HASE) polymers are an important class of rheology modifiers for waterborne coatings applications. They are typically prepared as terpolymers by emulsion polymerization of ethyl acrylate (EA), methacrylic acid (MAA), and an associative macromonomer. The viscosity development and shear responses of HASE solutions depend on a number of factors. This article presents rheological data reflecting the impacts of three key variables: hydrophobe size, acid content, and molecular weight, on model HASE thickening and rheological performance. The relative contributions of hydrophobic association, chain expansion, and polymer chain length are discussed. In steady shear flow, all thickener solutions approached some constant low-shear viscosity at small deformation rates. At the same molar composition, larger hydrophobe size resulted in higher viscosity development and greater shear thinning behavior. The amount of acid monomer in HASE polymers can influence the balance between hydrophobic attraction and electrostatic repulsion forces. It was found that a minimum of 15 wt% MAA was required to effect dissolution and thickening of the model HASE polymers. Increasing the MAA level yielded higher zero-shear viscosity and storage modulus G’ with maximal values being obtained at 40% MAA. The molecular weight of the model thickeners was controlled by the amount of chain transfer agent (CTA) added during polymerization. When the CTA level was below 0.1 wt% based on total monomers, the polymer solutions displayed shear-thinning behavior. A small increase in CTA concentration beyond 0.1% resulted in a dramatic change to Newtonian flow, and the solution viscosity was nearly two orders of magnitude lower. The model thickeners were also tested in a vinyl acrylic architectural paint formulation. The effects of each individual factor on paint thickener efficiency, high-shear, and low-shear properties are discussed and compared with solution rheology for predictive relationships. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 11–12, 2003, in Philadelphia, PA.     

聚氨酯缔合型增稠剂的合成及其应用性能研究

介绍了两款聚氨酯缔合型增稠剂(HEUR)的制备方法,包括一款假塑型增稠剂(增稠剂-万华A)和一款牛顿型增稠剂(增稠剂-万华B),并在乳胶漆配方中考察了这两种增稠剂的增稠性能、配方稳定性、色浆稳定性及展色性;并考察了自制增稠剂B的增稠效率及其在水性木器涂料中的应用。研究表明:合成的自制增稠剂A具有优异的增稠剂效率、良好的配方稳定性、色浆稳定性及展色性。自制增稠剂B具有高效的高剪切增稠效率,在水性木器涂料中性能表现优异,性能良好。     

Influence of the Chemical Structure of Urethane-Based Thickeners on the Properties of Waterborne Polyurethane Adhesives

To analyse the parameters that influence the thickening mechanism of waterborne polyurethane adhesives, different hydrophobically modified ethoxylated polyurethane based thickeners (HEUR) were used. The thickeners were characterized by proton nuclear magnetic resonance (¹H-NMR) and gel permeation chromatography (GPC). The thickened adhesive solutions were characterized by flow rheology, pH, particle size measurements, solids content, and confocal microscopy. The thickened solid adhesive films were characterized by ATR-IR spectroscopy, parallel plate rheology, dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC). The adhesion was measured by a T-peel test of leather/polyurethane adhesive/SBR rubber joints. The addition of the different HEUR thickeners increased the viscosity of the polyurethane dispersion to different degrees. Furthermore, whereas the un-thickened polyurethane dispersion showed a Newtonian rheological behaviour, a shear-thinning rheological behaviour was observed in the thickened dispersions due to thickener-thickener and polyurethane-thickener interactions. The viscosity of the thickened polyurethane adhesive solutions increased with the degree of hydrophobicity and the molecular weight of the thickener. The addition of different thickeners increased the pH values due to the ionic adsorption, which is one of the interactions that contribute to the thickening mechanism of the polyurethane thickeners, besides hydrogen bonding and van der Waals hydrophobic interactions (micelles). The entanglement of the thickened polyurethane adhesives was studied by confocal microscopy. Although the addition of the thickeners did not affect the thermal properties of the polyurethanes, the T-peel strength of leather/adhesive/SBR rubber joints was influenced by the rheological properties of the thickened adhesives.