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IN ORGANIC
COATINGS
ELSEVIER
Received 15 July 1996: received in revised form 14 August 1996; accepted 26 August 1996
Abstract
In-can rheology was studied for sixteen model acrylate latexes and a commercial vinyl/acrylate copolymer latex. Following the model of
Quemada, the shear thinning behaviour, the effects of latex neutralisation and the copolymer composition could be described. Furthermore,
the rheological effects of coalescing agents and thickeners (a cellulose and hydrophobically modified types thereof (HEC and HMHEC), as
well as associative urethanes (HEUR)) were studied. A special apparatus (the TNO Filmviscometer) was shown to be suitable to follow the
theological changes during drying of latex films. Effects of binder type, coalescent and thickener were investigated. The rheological effects
of coalescents during drying could be related to the evaporation kinetics and latex particle swelling, while the effects of thickeners reflect
the initial in-can rheology. The rheological changes during drying correlate to sagging and levelling behaviour and to the adsorption
behaviour of associative thickeners onto latex particles. 1997 Elsevier Science S.A.
Keywords." Rheology in-can; Rheology during drying; Acrylate latexes; Coalescing agents: Associative thickeners (HMHEC, HEUR);
Adsorption of thickeners onto latex: Film drying; Evaporation kinetics; Sagging/levelling
1. Introduction
affect the in-can theology of latex coatings, a wide systematic series of model acrylate latexes and a commercial vinyl/
acrylate latex were studied. It was, furthermore, investigated whether the results could be interpreted according to
the theological model of Quemada. The pure latexes were
studied by measuring flow curves to evaluate the effects of
the shear stress applied, the neutralisation of the latexes
(pH) and the copolymer composition of the binder. Subsequently, the effects of different types of coalescing agents
and thickeners were investigated. This concerns both hydrophilic, volatile coalescents and hydrophobic, slowly evaporating coalescents. The thickener types studied were a
representative hydroxyethyl cellulose (HEC), two hydrophobically modified hydroxyethyl cellulose thickeners
(HMHEC) and four hydrophobically modified ethoxylated
urethanes (HEUR).
In understanding practical paint properties that are related
to rheology (sagging, levelling, open time), often the rheological changes which occur during film formation (drying)
are overlooked, or not measured due to the experimental
difficulties when studying freely evaporating, drying latex
films. An apparatus specially developed to follow these
theological changes during drying was used in this study
(TNO filmviscometer, Section 4). The effects of different
142
Table I
Tablc 3
Binder compositions (percentages by weighil and characteristics: temposition of the model acrylate latices
Code
Co nlOllonlel's a
BMA
BA
MFFT
St),
MMA
AA
MAA
(CI
31
33
33
34
32
35
4O
27
23
23
23
25
29
29
28
28
28
B 108
B75
B76
B77
B78
B79
BSO
B125
BI26
BI27
B 128
B129
BI3I
B135
B137
B138
B139
100
99
97.5
95
99
97.5
95
39
54
69
84
91.5
39
54
69
84
91.5
In general
1.0
2.5
5.0
1.0
2.5
5.0
2O
15
10
5
2,5
20
15
I(I
5
2.5
40
30
20
10
5
40
30
2(I
1(I
5
Component/properly
Methyl inethacrylale
2-ethyl hexyl acrylate
VeoVa 9
Acrylic acid
Anionic sur factanl
Non-ionic surfactant
Biocidc Proxcl XL 12
18
2(1
60
2
0.5
1.0
0.001
Solids content
MFFT
pH
Mean particle size
46
26C
S.5
126 nm
Characteristic
Type of alkyd
Solids content
pH
Mean particle size
2. Experimental
2. I. Materials
Table 5
Overview of the thickeners studied
Abbreviation/
thickener type
Description
Remark
HEC
HMHEC- l '
Hydrophobically
Modilied
Hydroxy Ethyl Celhflose
HMHEC-2"
Hydrophobically
Modified
Hydroxy Ethyl Cellulose
Aliphatic HEUR Hydrophobically Modified
Ethoxylated URrethane
Aromatic HEUR Hydrophobically Modified
Ethoxylated URrethane
HEUR-U1
HEUR-U2
~'Experimenta[ product.
the pH was adjusted to 9 and the ionic strength was 0.01 M
(NaCI). The zeta-potentials were measured as a function of
thickener level. In special cases extra emulsifier was added
to the latex.
143
The determinations were carried out in 12-fold (two series of six). The latexes were applied by an applicator with a
clearance of 150/,m on tin-plated steel strips.
2.2.3.5. Sag resistam'e. The latexes were applied horizontally in narrow (6 ram), parallel and equidistant (6 mm)
streaks on degreased glass plates using a block shaped
applicator. The applicator clearance varied from 50 to
200 /,m. The coated substrate was positioned vertically l
rain after application. The sag resistance is defined as the
maximum applicator clearance that does not lead to
coincidence of the corresponding streak with an adjacent
streak.
2.2.3.6. Levelling. According to A S T M D 2801-69. This
standard is analogous to the sagging method described
above, however, it makes use of different dimensions of
the applicator geometry, and the full drying occurs
horizontally; scale: 0 means very poor flow and 10 is
excellent levelling.
2.2.3. Film/brmation
2.2.3.1. hi general. All film formation experiments (TNO
Filmviscometer, weight loss measurements, sagging,
levelling, etc.) were carried out in a climate room (50%
RH, 23C).
2.2.3.2. TNO fihm'iscometer. The experimental method to
follow the viscosity change of a drying film as a function of
drying time, is described in Section 4 and references [ 1-31.
The air speed velocity above the film was 5 cm/s. The angle
of the coated panel and the diameter of the steel ball used
per individual case, are mentioned in Section 4. The
substrate was degreased tin plated steel (20 x 20 cm) and
the applicator clearance was 150/,m.
2.2.3,3. Weight loss meclmtrements. The gravimetric
determinations were carried out in the measuring box of
the TNO fihnviscometer at an air speed above the coated
panel of 5 cm/s (23C, 50% RH) after the same application
procedure as mentioned for the Fihnviscometer experiments.
2.2.3.4. Do'ing time and opelt time. These properties were
determined with a standard BK drying recorder (Mickle
Laboratory Engineering Co,. UK). The drying time is
characterised at the moment the scratching tip of the
needle starts to cause film wrinkling in a V-shaped
pattern. The open time is taken as the time after which
the trace of the moving needle is becoming visually
much more apparent due to insufficient flow.
144
Next to the various effects occurring in pure binder systems, the rheological effects of the addition of different
types of coalescing agents and thickeners, as used in paint
formulation, were studied. In Section 3 only the effects in
the can are described, while the theological effects occurring during film drying and as observed in dried films, are
described in Sections 4 and 5.
k - ko + k~(q,/~,c)
1 + ('~/~'cY'
(2)
3.2. P u r e b i n d e r s - a c r y l a t e l a t e x e s
Table 6
Rheologieal parameters according to the Quemada model for non-neutralised (*pH = 2) and neutralised latices (pH = 9)
Latex
4~,.,o
0 .....
ko
k~
'~c
B75
B75
B76
B76
B77"
B77
B78 ~
B78
B79'
B79
B80"
B80
0.435
0.394
0.406
0,406
0.391
0.391
0.404
0.398
0.394
0.393
0.403
0.393
0.894
0.690
0.856
0.653
0.888
0.581
0.899
0.719
0.864
0.770
0.873
0.791
4.60
5.08
4.92
4.92
5.12
5.12
4.95
5.07
5.08
5.09
4.97
5.09
2.24
2.90
2.34
3.06
2.25
3.44
2.22
2.78
2.32
2.60
2.29
2.53
0.61
0.65
0.58
0.55
0.48
0.61
{).59
0.52
0.56
0.55
0.56
0.53
193
83.4
72.9
23.5
34.0
3 I. 2
66.4
39.6
74.4
47.5
06.5
62.0
B 125 ~
B 125
B 126*
B 126
B 127~
B 127
B 128*
B 128
B 129'
B 129
B 131"
B 131
B 135
B 135
B 137
B 137
B 138
B 138
B 139 ~
B 139
0.411
0.425
0.425
0,383
0,426
0,425
0,425
0,424
0.411
0,410
0,425
0.404
0.410
0.418
0.427
0.425
0.425
0.434
0.425
0.426
0,772
0.756
0.769
{I.763
0,783
0.710
0.800
0.683
0.770
0.707
0.877
0.854
0.799
0.742
[).976
0.845
{).826
0.758
0.857
I).761
4.87
4.70
4.70
5.21
4.69
4.70
4.70
4.71
4.86
4.88
4.70
4.95
4.88
4.78
4.68
4.70
4.70
4.61
4.70
4.69
2.59
2.64
2.60
2.62
2.55
2.81
2.50
2.93
2.60
2.83
2.28
2.34
2.50
2.69
2.05
2.37
2.42
2.64
2.33
2.63
0.46
0.55
0.44
0.52
0.43
0.46
0.37
0.52
0.41
0.50
0.52
0.57
0.50
0.62
0.51
0.45
0.47
0.53
0.38
0.52
23.3
18.6
17.9
49.8
37.7
16.1
6.4
32.5
16.3
16.3
43.7
23.6
9.7
12.9
159
21.2
7.3
14.4
4.5
24.3
VV/Acryl
0.47
215
~Not determined.
145
q ~ e n _ l + _3A
_
4)
R
(3)
146
Table 7
Effect of coalescing agents on the maximum packing fraction at high shear (6,,,.+.-) for neutralised laticcs (pH = 9)
Latex
B125
Coalescent
no (Rel)
DBA a
PnB
HPV ~
TEX
aliph. HC ~
PnBA ~
PM
B131
no (Refi
DBA a
PnB
HPV L"
TEX
aliph. HC r
PnBA ~
PM
Level (%b.w))
(J.....
Volume increase
Rheology h
Ultra-centrifugation '
0
5
10
10
5
5
10
5
I0
10
10
0.756
0.732
0.722
0.698
0.739
0.722
0.668
0.721
0.700
0.681
0.696
3.2
4.7
8.3
2.3
4.7
13.2
4.6
8.0
11.0
8.6
4.5
8.7
8.2
5.0
4.9
9.2
5.9
I 1.2
8.7
4.4
0
l0
II)
I0
5
10
10
10
10
0.854
0.780
0.766
0.722
0.805
0.708
0.763
0.751
0.781
9.5
I1.5
18.3
6. I
20.6
I 1.9
13.7
9.3
8.7
8.4
9.2
5.0
10.5
11.2
9.0
1.5
147
!04
10'~
n'
G', G"
(Pa.s)
(14.=-2)
10a
10a
102
102
.A
/ /
" ,o,"Ao....o~...
10~
to~
-o..~
10;-2
, ,,,,,.
, ,. .............
iO-t
,0o
i0
13 I
Frequency (Hz)
Fig. 2. Dynamic properties of thc VV/Acryl latex thickened with the aromatic HEUR (0.2c)} by weight based on water phase). O: ~1'; D: G': A: G".
i0 s
ZOS
Visccsity
(Pa s)
'0 2
-
104
iL.o-o,,
I
+~
t04
G', G"
10~
+'x o
(?as)
+..0~
\ b%,0,
,
0'
103
I01
*.,'o.
%"0,
(Nra-2)
AI "~
103
.+x o
10c
10
102
\+
[C -i
lC-:
I0i
10.2
:0-2
&
gL
10-i0-1
10c
&
10:
10~
shear rate (s-i)
Fig. I. Flow curves of the thickened VV/Acryl latex, showing the synergy
in thickening efficiency when combining an aqueous solution of an associative HEUR thickener with a latex. : solution of the aliphatic HEUR
thickener (0.5%): DI: VV/Acryl latex: + : VV/Acryl latex with 0,2% aliphatic HEUR (5~ b.w. based on water phase): O: VV/Acryl latex with
0.4% aliphatic HEUR (% based on water weight).
',;%
V'"
'
.....
I0
....
i0o
.....
?0t0
Frequency (Hz)
148
104
lO 4
n'
(N.m-2)
(Pa.s)
103
t0 3
10 2
I0 2
101
IC i
10c
10-2
. . . . . . . . . . . . .
lO-1
, .....
i0 o
qO 0
10r
Frequency (Hz)
Fig. 4. Dynamic properties of the VV/Acryl latex thickened with H E U R UI (0.2 and 0.4% by weight based on water phase). @: r/(0.2%): 0 :
r/(().4%): E: G ' (0.2%): a : G' (11.4%): & : G " (0.2%); i,: G " (0.4%).
103
10 3
103
103
10 2
Gt, G"
102
102
(N.rn ~)
(Pas
" ,.l~
tO~
tan 5
10i
tO 1
1,0o - . '
,, - u,
tO
z
j3""
10
"~Q~----o~o...
.~'
i0
"-~-.I --- ~
.....
r'" j / "
t
:i;-~
. . . . . . . . . . . . . . .
lo-'
'M
-]
Frequency (Hz)
10-1
10 -2
.......................
10 -I
Frequency
I0 0
logo 1
(Hz)
Fig. 5. Loss factor tan 6 of the VV/Acryl latex thickened v/ith different
149
tan
tO 3
lo 3
1'32 i
lOa
lower, see Fig. 7), the viscosity 07') of the VV/Acryl latex is
much higher (roughly one decade) and the G" is 10-100times as high. Realising that G' can be related to the structure build-up of associative thickeners in latex systems, it
can be concluded that the aliphatic HEUR and the urea
modified HEUR-U1 are much more effective in the hydrophobic VV/Acryl latex than in the hydrophilic alkyd emulsion. It can be assumed that the surface of the emulsion
droplets contains a lot of polar groups (hydroxy and/or carboxylic) and a high amount of surfactant molecules. These
polar moieties are unfavourable for interaction with the
thickener hydrophobes via adsorption. Furthermore, the
total surface area of the alkyd emulsion droplets is smaller
than that of the VV/Acryl latex particles (the particle diameters are 370 and 126 nm respectively, while the solids
contents are comparable; Tables 1-3).
<5
101
101
_-4D.
l
o
0~i
]0 - 2
......
o .o
,,i
qll.
......
10 -!
...... q O -i
10
Frequency
10:
(Hz)
4. R h e o l o g y
Fig. 7. Colnparisonof the loss factor tan6 between the alkyd emulsionand
the VV/Acryl latex when thickenedwith HEUR thickener((I.4% on water
content). The thickenedalkyd emulsionis much more viscous(less elastic)
in nature than the thickened VV/Acryl latex. : VV/Acry[ latex with
aliphatic HEUR; O: alkyd emulsion with aliphatic HEUR; D: VV/Acryl
latex with HEUR-UI" i : alkyd emulsion with HEUR-U1.
of drying
results
4. l . M e t h o d
(4)
=
V
V i s c o s i t y in Pa,s
100
90
2]
80
70
60
50
40
30
20
i,, , ~ , , ~ - , ~
60
120
180
240
300
360
420
480
540
600
-660
720
Fig. 8. Change of the viscosity (Pa.s) o1' the pure B75 latex (neutralised at pH = 9) as a function of the drying time Is), as measured with the TNOFilmviscometer(conditions:23C, 50% RH; rolling ball diameter: 1.5 ram; slope: 15).
150
Table 8
Comparison of initial viscosities measured witl~ a conventional stress controlled rheometer (measured by CoRI, at 10.3 s i) and with the TNO
Filmviscometer (in a drying fihn, extrapolated to time zero): the formulations contain the latex B I25~ a HEUR thickener, titanium dioxide at 9.9
and 18% PVC, respectively, and the coalescents indicated (level: 10cA
based on binder weight)
PVC
Coalescent
9.9c7~
PnB
EB
TEX
PnB
EB
TEX
18%
Viscosity (Pa.s)
fihnviscometer
2,0
1.5
3.0
2,0
1.7
4.0
Viscosity (Pa.s)
conventional
2.4
1.9
2.7
1.8
1.4
4.5
Acid
Level
t(rt,~,,~,~) (s)
l0 ~4.o-"
B75
B76
B77
B78
B79
B80
AA
AA
AA
MAA
MAA
MAA
I c7~
2.5',;~
5eli
1C4
2.59~
5~,/~
680
660
520
630
640
590
2.9
4.3
8.8
2.2
2.2
3.4
;'o. Surface charge density: the number of electrical surface charges on the
latex particles per m 2, determined with polyelectrolyte titration using the
streaming potential method after three months of storage of the neutralised
latices.
Table I0
TNO Fihnviscometer results of several latices (binder/coalescent systemsl
showing the effect of coalescents at a level of 49;, on total httcx weight
(t('~lll~lX): time to reach ball fixation (in seconds): differences between par
cntheses h)
Coalescent
B76
B79
B 125
VVtacryl
BMAIAA BMA/MAA Sts/acryl vinyl/acryl
No (reference)
TEX
660
590
(+70) ~
630
(+30)
650
(+10)
670
i-10i
PnB
PM
EB
151
158
640
520
(+1201
580
(+6(})
68(I
(40)
700
1-60i
380"
420
(-4(I)
470
(-90)
580
1-160)
Hydroxy propyl
versatate
High boiling
aliphatic hydrocarbon
230"
160
(+70}
310
(80)
300
(-7(1)
360
1-1301
280
(50)
200
(+30i
Measuring conditions: 23C, 50~k RH: ball diameter, slope o< B76, B79:
1.5 ram, 15: B125:2.5 Illri], 15: VVtAcryl latex: 2.0 ram, 20 c.
Difference of l(~nla\j between latices without and with coalescent: +, acceleration; , delay of the viscosity peak.
Viscosity in Pa.s
350
300
250
200
15o
/'
10o
t
/
I
5O
O
60
120
180
240
300
drying time
152
-{7
900
800
700
600
500
400
I
300
200
//
100
0
0
60
120
180
240
300
360
420
480
540
600
D r y i n g time ( s e c o n d s )
Fig. 10. Change of the viscosity (Pa.s) of the pure alkyd emulsion as a function of the drying time (s), as measured with the TNO-Fihnviscometer (conditions:
23C, 50% RH; rolling ball diameter: 3.0 ram: slope: 45).
addition of
coalescing agents to the pure latexes, the slopes of the
viscosity increase remain roughly unchanged. However,
the effects of coalescent expressed as t(r/m,0, are large
(see Table 10 and Fig. 11).
Viscosity in Pa.s
l no coalesent
=PM<EB
The t(r/max) values for non-thickened binder/coalescent systems are not mainly determined by the initial in-can viscosity (see Table 11). This can be best shown by comparing
the data for TEX with those for EB. At the shear rates close
to those relevant to the filmviscometer at the onset of the
measurement ( 1 0 - 2 0 s ~) the TEX containing latexes B76
and B79 have a much lower viscosity than the EB counterparts. If the initial viscosity were the determining para-
-~ P n B
250
TEX<PnB<
Table I 1
35O
j ,, EB
200 q
Latex
shear
rate (s a)
B76
5
10
50
100
200
5
I0
20
50
100
200
150
i
100
B79
50
60
120
180
240
300
360
420
480
540
600
Fig. I1. Effect of addition of coalescing agents to the latex B125 on the
viscosity (Pa.s) as a function of the drying timc (s), as measured with the
TNO-Fihnviscometer (conditions: 23C, 50% RH: rolling ball diameter:
1.5 mm: slope: 15; coalescent level: 10% b.w. on solids).
PM
PnB
EB
0.0227
0.0127
0.0105
0.0093
0.0420
0.0150
0.0120
0.0110
0.0099
0.0960
0.0132
0.0098
0.0081
0.0071
TEX
O.029O
0.0200
0.0130
0.0131 0.0110
0.0091 0.0094
0.0829
0.0337
0.0149
0.0098
HPV
0.0220
0.0160
0.0175
0.0219
0.0216
0.0114
0.0110
0.0084
0.0076
0.0130
0.0100
0.0088
The values discussed in the text are in italics and show that the viscosity at
the lower shear rates is substantially lower for the TEX than for the EB
containing latices, in spite of the much stronger latex particle swelling by
TEX.
--i ~> T e x + H E U R
300
' - PnB+HEUR
,!
153
Table 12
Comparison of TNO Fihnviscometer results (t(~,,,,~O) with in-can viscosity
measurements at a shear rate of 1 s ~ (rlr(t = 0): see text) and dynamic
viscosity results (at 0.1 Hz) for the thickened VV/Acryl latices (thickener
level: 0.1% b.w. on total weight: 0.2% on water content)); also, the tendency of thickener adsorption onto the latex particles is indicated
Addition
t(rl,,,~J ~/,
(see) ~ (t = 0)
Pure
+ 5% Water (RefS)
HEC
Aliph. HEUR
Arom. HEUR
HMHEC-I
HMHEC-2
HEUR-UI
HEUR-U2
370
470
380
300
450
520
500
310
430
38
16
<l
< 1
26
l0
88.0
17.1
61
4.0
46.4
34.7
43.7
35
+ + + +
++
+
+
+ + +
+ + +
of t(rtm~), although the relative order for the respective coalescents is the same for this binder (Fig. 11). It is possible
that the degree of sintering of the latex particles during the
drying process, on the time scale of the measurement with
the filmviscometer, also plays a role according to the drying
mechanism proposed by Winnik and Feng [16]. This means
that the lower Tg particles (of B125 containing TEX)
deform to a larger extent in the region close to the drying
front, which leads to narrower capillaries between the latex
particles resulting in a lower rate of water transport and a
lower rate of evaporation. Due to this contribution, the overall effect of TEX in B 125 apparently results into a delay of
the viscosity peak, i.e., an increased t(rlm~x) as compared to
the pure latex.
4.2.3. Effect of thickener
* EB+HEUR
250
iI
200
150
1 O0
,>4
50
i'
,/
.,
,'
j
[
I
. .,,.~..~/%
0
0
60
120
180
240
300
360
420
480
Fig. 12. Effect of addition of the aliphatic HEUR Ihickener and additionally different coalescing agents to the latex B 125 on the viscosity (Pa.s) as
a function of the drying time (s), as measured with the TNO-Filmviscomeler (conditions: 23C, 50% RH: rolling ball diameter: 2.5 mm; slope:
15 " coalescent level: 10% b.w. on solids: thickener level: (I.5% on total
weight).
154
AA
0 &
-i0
-.~0
oa
-50
o
70
90-
-ll0
0,0
o:2
o:4
o18
t,o
t ~]lfltK ) (S)
VV/Acr,,I latex'
Pure
+ 5qf waler i' Reference
8(10
990
370
47(1
HI:.("
HMHEC I
HMHEC-2
Aliphatic H E U R
Aromatic H E U R
HEUR UI
630
931)
720
910
,821)
,850
,830
3,8(1
52(1
51)(1
30(}
450
HELIR-U2
310
43()
~'Measurin,_,+ condilit'n'~s: __
v3 :~C. 5 0 q RH: ball d i a n l e t e r = 3 . 0 ram. slope = 45 ~
hDihlted with ,aater to the same solids contcnl as the thickened binders.
HEUR to the lowest and the two urea modified HEURs are
intermediate in this series. This was indeed measured (see
Table 12).
in smnmary, the thickening efficiency did not change
during fihn drying and could be related to the initial rheological behaviour of the thickened latexes.
In the case of an alkyd emulsion, HEC. and to a lesser
extent, the HMHEC (i.e. HMHEC-2) were found to reduce
t(r/ ......) substantially more strongly than the HEUR associative thickeners (Table 13), which is in contrast to the acrylate or vinyl/acrylate type latexes. This is due to the
difference of thickening mechanism combined with the
hydrophobic/hydrophilic nature of the binder particles: the
associative thickeners are more efficient in case of hydrophobic and snlall size binder particles Ithe alkyd emulsion
droplets arc relatively polar and signilicantly larger),
whereas the HEC acts ~ia the continuous water phase via
hydrogen bridges, coiling and chain entanglements,
mechanisms which are principally independent of the nature
of the surface of the polymer particles.
,1
350
300
i
,I
250
155
,k
,i
200
150
100
j,
,P
,,1'
50
Tex
I PnB
EB
T
6O
120
180
240
300
360
420
480
I~
"
540
600
Fig. 14. Efiecl of the addition of coalescing agents to a pigmented, thickencd formulation based on the latex B I 2 5 . on Ihe viscosity (Pa.s) as a
function of the drying time {s), as measured with the T N O - F i l n w i s c o m e t e r
(conditions: 2 3 ' C . 5(I<A RH: rolling ball diameter: 2.5 ram: slope: 15;
pigment: titaniuln dioxide. I(YA PVC: thickener: the aliphatic HEUR,
1.29k b.w. based on tile water phase: level of coalescents: 109i on binder
"a cigh! I.
156
Table 14
Practical coating properties for thickened latex formulations (based on the
BMA/MAA latex B79:0.2~,4 thickened, on water phase weighl) demonstrafing the gnud correlation between sagging/levelling and ti~,,,~,), as
opposed lo the findings for the drying time and open time as measured
with a standard drying recorder, which seem contradictory to the sagging/
levelling data: also, coalescents are shown to act as rheology modifiers
Thickener Coalescent Drying Open z(rl,,,~,,! Sag
Levelling
time
time (s)
tvsistance (ASTM)"
(sl
(s)
(#m)
HMHEC-2
TEX
PnB
EB
HEUR-U2
TEX
PnB
EB
1630
1610
1290
1320
1150
1480
1I 10
1040
h
l l(I
1010
430
950
710
740
680
i,
<150
1250
290
56[)
400
690
490
175
>200
175
75
>200
>200
>200
175
9
7
10
10
0
0
I
3
Table 15
General trends observed for the effects of coalescing agents on acrylate
and vinyl/acrylate latex furmulations (see text).
Coalescent
EB
PM
PnB
TEX
Relative
t07,,,~0
evaporation rat&
Slow
Medium
Fast
Variable
>
+
_+
<
Levelling
+
_+
_+
-
Sag
resistance
-_+
+
6. Conclusions
6.1. Rheology in-can
6.1.1. Pure latexes
The Q u e m a d a model is very suitable to describe and
interpret the rheological in-can behaviour of latex systems.
A wide systematic series of acrylate c o p o l y m e r latexes was
studied (T,~: 2 4 - 4 1 C, stabilised with one fixed type of anionic emulsifier at a constant level). It was shown that the
157
158
or modify the effective latex particle T,g by absorption/desorption. In these systems the in-can theology is relatively
preserved during drying.
Acknowledgements
The investigations were carried out in the framework of a
BRITE/EURAM programme (PL41911. We gratefully
acknowledge the support of the European Union, the Swedish National Board for Industrial and Technical Development (NUTEK), and each of the 21 sponsoring companies
from all over Europe. We have appreciated the intense and
pleasant cooperation and many constructive discussions
with the EU, especially with Prof. C. Kiparissides and Dr.
C. Tokamanis, the project partners (CoRk Forbairt, PRA,
TNO, YKI), and the participating companies. With respect
to the rheology work presented here, the authors like to
mention the valuable contributions of Mr I. Szigetvari
(CoRI), H. van Bracht, R.M. Meertens, P. Vink (TNO)
and Dr. M. Boutonnet Kizling (YKI).
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