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Avoiding Viscosity

Loss on Tinting
New rheology modifier technology for reducing viscosity loss on
tinting while maintaining an excellent flow/sag balance.

T
wo trends are evident in architec-
tural paints today. Waterborne, or
latex, paints continue to grow in
use, and today’s homes are increas-
ingly being painted with deep,
vibrant colors, both inside and out. While experi-
ence has shown that the best overall balance of
rheology in waterborne coatings is achieved by using
non-ionic associative rheology modifiers, when such
coatings are tinted with high levels of colorants they
often exhibit a significant decrease in viscosity. This
decreased viscosity can manifest itself in a number of
ways, including low sag resistance, poor brush load-
ing and a “thin” appearance in the can. Although a
number of approaches to formulating around these
issues exist, there continues to be a need for viscosity-
stable rheology modifiers. A new development in
HEUR thickening offers significant improvements in
these performance parameters.

Associative Thickening
Associative rheology modifiers consist of a water-
soluble polymer backbone that contains two or more
hydrophobic groups. This general structure is shown
in more detail in Figure 1 for the specific case of
the HEUR (hydrophobically modified ethylene oxide-
based polyurethane) composition. The function of
the hydrophobes is to associate with hydrophobes
from other rheology modifier polymers as well as
with the surface of the binder latex particles. Figure
2 illustrates how such associations can result in the
formation of a network structure that links together
individual latex particles, thereby restricting their
motion and thus increasing the viscosity.

By Dr. Daniel Saucy, Research Group Leader, Paints and Coatings Materials | Rohm and Haas Company, Philadelphia, PA

Reprinted with permission from the August 2008 issue of Paint & Coatings Industry magazine
O N N O nO N N O
OH HO OH HO m
R' R O R R'
ON N O nO N N O
O H HO OH HO
Avoiding
Alkyl R'ViscosityRLoss on Tinting
Urethane P(EO)
O Urethane
R
m
R' Alkyl
O N N O n O N N O
H H H H m
Alkyl Urethane P(EO) Urethane Alkyl

Alkyl Urethane P(EO) Urethane Alkyl Effect of Colorant Addition


FIGURE 1 | Structure of HEUR non-ionic associative rheology modifier.
Colorants, especially the universal type, contain high
surfactant concentrations. The hydrophobes from
O O O O
R' R O R R' these surfactants compete for adsorption sites on the
O N N O nO N N O latex surface and will thereby displace some of the rhe-
H H H H m ology modifier from that surface. The net effect of this
competition is that there will be fewer thickener hydro-
Alkyl Urethane P(EO) Urethane Alkyl phobes adsorbed, resulting in a weaker network and
lower viscosity. The surfactant will also decrease the
Water-soluble Polymer
association between rheology modifier chains them-
FIGURE 2 |LATEX
Mechanism of associative thickening. Hydrophobic groups associate with selves, also contributing to a decrease in viscosity.
the latex surfaces to form a network structure. Water-soluble Polymer Various approaches exist to mitigate these effects of
colorant addition. The simplest approach is to mini-
LATEX Water-soluble Polymer mize the use of associative thickeners, and in their
LATEX place use non‑associative thickeners. This approach
LATEX
tends to result in poor flow, a direct consequence of the
LATEX volume-depletion flocculation mechanism by which
non‑associative thickeners work. This phenomenon is
LATEX LATEX shown in the transmission electron microscope (TEM)
Hydrophobes images shown in Figure 3, where the left side shows
LATEX uniformly distributed latex particles in a mixture con-
Water-soluble Polymer
Hydrophobes taining only latex and water. However, when a non-
LATEX LATEX associative thickener is added, there is flocculation of
Hydrophobes the latex particles, resulting in regions of high latex
concentration and regions of low concentration. This
LATEX flocculation creates high viscosity at low shear rates,
FIGURE 3 | Transmission electron micrograph showing volume depletion floccula- which leads to poor flow and leveling of the coating.
tion of latex particles that is caused by cellulosic thickeners. A second approach to mitigating the viscosity loss
problem is to overthicken the untinted base paint, so
LATEX that after tinting, the viscosity drops to the desired
Hydrophobes final viscosity. This approach adds cost to the formu-
lation, can make handling of the unthickened paint
during manufacturing and filling more difficult,
and gives a wide range of final, tinted viscosities that
depend on the color formula.
Latex only Latex with
In summary, as the colored paint market contin-
Non-Associative Thickener
Latex with
ues to grow, the currently available approaches to
Latex only mitigating viscosity drop all have weaknesses. Thus
Non-Associative Thickener
the need continues to exist for a rheology modifier
Latex only Latex with that provides significantly better viscosity stability
Non-Associative Thickener
upon colorant addition.
FIGURE 4 | Adsorbed species on latex particle surface at low levels of surfactant.
New Viscosity-Building Mechanism
A new rheology modifier technology has now been
cle

developed that significantly reduces the viscosity loss


rti

upon tinting. This new type of thickener is of the


xPa
le

Latex with
te

HEUR, non-ionic type and in addition to viscosity


tic

Latex only
La

ar

Non-Associative Thickener stability, it delivers the excellent flow and leveling and
xP
te

other properties for which non-ionic rheology modifi-


cle
La

rti

ers are well known. It is also free of solvent for compli-


xPa

High Shear Builder ance with current and future regulations.


te
La

Mid Shear Builder The improved viscosity stability is achieved through


High Shear Builder
Surfactant a new viscosity-building mechanism. To understand
Mid Shear Builder Latex Particle this new mechanism, one needs a slightly more
Surfactant
High Shear Builder Latex Particle
Mid Shear Builder
cle
rti

Surfactant
Pa
detailed model of how associative thickeners build
FIGURE 5 | Difference in hydrodynamic volume of low- and high-molecular-weight
the networks that develop their viscosity. Figure 4 thickeners adsorbed on the surface of a latex particle hinders access to the lower-
shows the surface of two latex particles and a number molecular-weight thickener.
La
of interactions that contribute to the network. There te
xP
are high-shear building (HS) (also called ICI-build- ar
tic
ing) and mid-shear building (MS) (also called KU- La le
te
building) thickeners adsorbed on the surface of the High MW xP
ar
latex particles. Since there is typically a higher level Low MW tic
le
of HS than MS in a coating, the figure shows more HS High MW
adsorbed than MS. Note the existence of both looped
and single-ended adsorption of the MS thickener. Low MW
The new technology has been designed to have a
lower molecular weight than the high-shear thick-
ener. This difference in molecular weight leads to
the two components occupying different volumes Latex Particle
of space when adsorbed on the latex surface (shown
schematically in Figure 5), thus hindering access to Latex Particle
the lower-molecular-weight, new-technology com-
ponent. This steric crowding makes some of the
hydrophobes on the new technology polymer inac- FIGURE 6 | Adsorbed species on latex particle surface at elevated surfactant levels,
i.e., after addition of universal colorant.
cessible for network building and, in effect, inacti-
vates a fraction of these thickener polymers.
When colorant is added, its surfactants will dis-
place both HS and MS chains from the latex surface.
This change results in a decrease of the steric crowd-
ing at the surface, and allows some of the previously
inaccessible mid-shear chains to now participate in
le
tic

network building. Furthermore, the displaced chains


ar
xP

can participate in building the multi-link connec-


te
La

le

tions necessary for effective network building. This


tic
ar

effect is illustrated by comparing the schematic prior


xP
te

to the addition of the colorant (Figure 4) to the situa-


La

tion after colorant addition (Figure 6). High Shear Builder


In summary, with the new technology, the colo- Mid Shear Builder
rant activates a new mechanism that increases vis- Surfactant
High Shear Builder
cosity upon the addition of surfactant. The result is Latex Particle
Mid Shear Builder
significantly less viscosity loss upon the addition of Surfactant
colorant to the paint base.
FIGURE 7 | Viscosity loss from conventional and new technology thickener with
Latex Particle
8 oz/gal of universal phthalo blue and red iron oxide colorants. Paint is 34VS/30PVC
Benefits of New Technology neutral base with Rhoplex VSR-1050.
The viscosity stability delivered by this new technol- Viscosity Loss on Tinting
ogy, embodied in Acrysol RM-895 rheology modi-
Universal Blue Universal Red Oxide
fier, will be of greatest benefit in paints that exhibit 0
Viscosity Change (Krebs units)

the largest viscosity loss with colorant, i.e., medium -5


to deeply tinted paints (4% or more tint). Thus, we -10
compared the performance of the new technology to -15
current HEUR products in a 100%-acrylic Rhoplex -20
VSR-1050, semigloss neutral base formulated at 34%
-25
volume solids and 30 PVC of calcium carbonate.
-30
The viscosities of each initial, untinted base paint
-35
were adjusted so that after tinting with 8 oz/gal of
-40
either phthalo blue or red iron oxide, the viscosities
-45
were approximately 95 KU. The viscosity losses exhib- Conventional Acrysol Conventional
ited by the three paints are shown in Figure 7. Clearly, HEUR #1 RM-895 HEUR #2
-45
Conventional Acrysol Conventional
HEUR #1 RM-895 HEUR #2

Avoiding Viscosity Loss on Tinting

unexpected result is that even the 120 KU Acrysol RM-895


FIGURE 8 | Leneta sag resistance of tinted neutral bases. Paints on the left
side of the figure are all approximately 95 KU after tinting. Paints on the paint has flow that is only slightly poorer than the 100 KU
right side of the figure are 120 KU after tinting. All paints have excellent paint, thus giving an excellent flow/sag balance to the tinted
flow and leveling. paint. The improved sag resistance also translates into excel-
Sag Resistance of Tinted Paints lent brush and roller loading.
Universal Blue Universal Red Oxide
25 Because of the need to establish a wide array of associa-
100 KU after tinting 120 KU
Leneta Sag Rating (mils)

tions between rheology modifiers, surfactants, dispersants,


20
latex particles and other hydrophobic components of the
15 formulation, it is common for viscosities to take several
hours, and sometimes overnight, to reach their final val-
10 ues. This new technology typically achieves its final viscos-
5
ity within approximately 1 hour, potentially spurring a
significant increase in plant productivity.
0
Conventional Acrysol Conventional Acrysol
HEUR #1 RM-895 HEUR #2 RM-895 Conclusion
The new technology for non-ionic thickeners described
the new technology gives a much lower viscosity drop on above acts through a new mechanism to provide three
tinting. The new technology has sag resistance comparable desired properties to tinted paints: 1) improved resistance
to or better than the conventional HEUR products (left side of to viscosity loss, 2) improved sag resistance, and 3) preser-
Figure 8). The right side of the figure shows the increased sag vation of excellent flow. n
resistance obtained when the initial KU, and hence the tinted
KU, of the new technology paint is deliberately higher. An For more information, visit www.rohmhaas.com.