Low VOC Binder Development: Exploration of Morphology and Crosslinking Erin Vogel│ Dow Coating...
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Transcript of Low VOC Binder Development: Exploration of Morphology and Crosslinking Erin Vogel│ Dow Coating...
Low VOC Binder Development: Exploration of Morphology and Crosslinking
Erin Vogel│ Dow Coating Materials Dow Coating Materials
Partha Majumdar, David Conner, Yuanqin Liu, Sonya Eberly, Gary W Dombrowski
Western Coatings Symposium, October 25-28, 2015
®Trademark of The Dow Chemical Company
Outline
• Overview of Low VOC Driver
• Key Unmet Needs in Low PVC High Gloss and Deep Tone Space
• Technical Challenges and Approaches
• Investigation of Variables Hard Phase and Crosslinker Level
Crosslinker Level and Binder MFFT
Effect of Particle Size of Binder
• Performance of Optimized Binder
• Summary
2
Low VOC: Continuous Journey over Decades
VOC reduction in architectural paints over time:
• Initially driven by convenience and cost: water clean-up, odor
• Later driven by regulations and social awareness
Source: Coatingstech, Vol 11, No 4, April 2014 ; 2007 ARB SCM for Architectural Coatings; RAL-UZ 102 Low Emission Wall Paints
3
0
200
400
600
800
VO
C G
ram
s/L
ite
r
VOC ContentArchitectural Wall Paint
Low VOC Drive: Regulations and Eco Labels
Source: Adapted from Paint Quality Institute (PQI)
Environmental Agency/Rule CoverageCurrent VOC limit (g/l) by agency for FLAT paints
US EPA National AIM Rule (1999) All US 250
Ozone Transport Commission (OTC) AIM Rules
CT, DE, PA, NY, NJ, DC, VA, ME, NH 100
California Air Resources Board (CARB) All of CA except SCAQMD areas 100
South Coast Air Quality Management District (SCAQMD) Rule 1113
Los Angeles & surrounding basin 50 (2008)
LADCO/MRPO WI, IL, IN, MI, OH N/A
Environment Canada Canada N/A
This independent, nonprofit organization identifies and promotes green products and services and provides certification for EPA’s environmentally preferable purchasing. Have standards for low VOC, anti-corrosive and recycled paints, and adhesives
Develops standards and certifies low emitting interior products. Greenguard offers a specific program for paints and coatings.
MPI has as its vision; a paint & coatings industry that develops and uses paints and coatings with balanced performance, safely and appropriately EVERY TIME!
Offers two levels of certification for paints and coatings – Indoor Advantage and Indoor Advantage Gold. Products must meet strict indoor air quality performance standards to achieve certification, and must be re-examined annually to maintain certification.
4
®Trademark of UL LLC ®Trademark of Scientific Certification Systems, Inc.
Key Unmet Needs in Low PVC High Gloss and Deep Tone Space
5
• Technologies Enabling Lower VOC Potential
• Technologies that Enable Higher Early Hardness
• Improved Tackiness, Block Resistance and Feel Properties
• Alkyd-like Appearance without some of the Drawbacks
• Lower Emphasis Placed on common Broad Wall Properties
Challenges
6
Harder PolymersSofter Polymers
Block/TackDirt Pick UpResistance
Low Temp Film Form.Reduced Coalescent
Flexibility
Standard VOC Conventional Ultra Low VOC
• Excellent Film Formation • Good Properties
Hard Polymer + Solvent
• Excellent Film Formation• Poor Properties
• Poor Film Formation
• Poor Properties
Soft Polymer Hard Polymer
Plasticization
Approach
7
Compositions- Hard/Soft Monomer Choice & Combination
-Functional Monomer/Specialty
Monomer
Process
Unique Polymer Morphology with
Functionality
Hard Stage
Soft Stage
Initiator
Surfactant, etc
Hard Phase and Crosslinker Level
8
Design Outline: Hard Stage Content: Low to High Crosslinker Level: Low to High Center Points
• Crosslinker level has maximum impact on scrub resistance
• Konig hardness effected by hard phase content (primarily). Some impact from crosslinker level
Prediction Profiler
20
24
28
32
Ko
nig
1D
30.8
02
94
2428323640
Ko
nig
7D
38.3
67
65
900
1200
1500
Scr
ub
116
7.4
41
00
.51
De
sira
bilit
y
0.857052
26
28
30
32
33
Hard Phase
1
1.5 2
2.5 3
3
Crosslinker
00
.25
0.5
0.7
5 1
Desirability
Low→High Low→High
Responses Konig-1 Day
Konig-7 Day
Scrub
Factors Prob > F values are shown
Hard phase 0.0095* 0.0039* 0.3105
Crosslinker 0.0957 0.0151* 0.0082*
[(Hard phase) x
(Crosslinker)]
0.3301 0.5320 0.5674
Formulations-White Gloss (20 PVC) No coalescing agent
* Indicates significant factor
Crosslinker Level and Binder MFFTFormulations-White Gloss (20 PVC) : No coalescing agent except High MFFT- (2% Texanol)
• Crosslinker level has an impact on hardness profile-requires at least a threshold level
• Higher MFFT has more impact on Konig hardness at 7 day
Ko
nig
-1d
(se
c) &
Kon
ig-7
d (
sec)
18
21
24
27
30
33
X-link None Low High High
MFFT Low Low High
Konig-1d (sec)Konig-7d (sec)
Pri
nt-
1d &
Pri
nt-
7d
4
6
8
10
X-link None Low High High
MFFT Low Low High
Print-1dPrint-7d
9
Print rating 1 to 10, 10 = best. Embroidery cloth was used
Pri
nt
Re
sis
tan
ce
Ko
nig
Ha
rdn
es
s (
se
c)
Crosslinker Level and Binder MFFT
10
Formulations-White Gloss (20 PVC) : No coalescing agent except High MFFT- (2% Texanol)
• Significant impact on scrub resistance based on crosslinker level
Scr
ub
0
500
1000
1500
MFFT Low Low High
X-link None Low High High
Sc
rub
Cy
cle
s
10
Crosslinker Level and Binder MFFT
11
Formulations-Deep Base: No coalescing agent except High MFFT-(1.5% Optifilm enhancer 400)
• Crosslinker conc. increases Konig hardness and print resistance in deep base.• Coalescing agent had an impact on initial hardness profile in high MFFT.
Print-1d & Print-7d vs. Coatings
Pri
nt-
1d
& P
rin
t-7d
0
1
2
3
4
5
6
7
8
0% D
AAm
1% D
AAm
2% D
AAm
3% D
AAm-Low
MFF
T
3% D
AAm-H
igh M
FFT
Pri
nt-
1d &
Pri
nt-
7d
Print-1dPrint-7d
Konig-1d (sec) & Konig-7d (sec) vs. Coatings
Ko
nig
-1d (
sec)
& K
onig
-7d
(se
c)
12
14
16
18
20
0% D
AAm
1% D
AAm
2% D
AAm
3% D
AAm-L
ow M
FFT
3% D
AAm-H
igh
MFF
T
Ko
nig
-1d
(se
c) &
Konig
-7d
(sec)
Konig-1d (sec)Konig-7d (sec)
X-link None Low High High
MFFT Low Low High
X-link None Low High High
MFFT Low Low High
Pri
nt
Re
sis
tan
ce
Ko
nig
Ha
rdn
es
s (
se
c)
Print rating 1 to 10, 10 = best. Embroidery cloth was used
Crosslinker Level and Binder MFFT
12
Formulations-Deep Base: No coalescing agent except High MFFT-(1.5% Optifilm enhancer 400)
• Significant impact on tack resistance after threshold crosslinker conc. Hard phase content drives tack resistance below threshold crosslinker conc.
• Coalescing agent had an impact on initial tack in high MFFT.
Tack
-1d
(Z
apo
n-g
) &
Tack-
7d
(Z
apo
n-g
)
0
200
400
600
800
1000
Tack
-1d
(Z
ap
on
-g)
& T
ack
-7d
(Z
ap
on
-g)
Tack-1d (Zapon-g)Tack-7d (Zapon-g)
X-link None Low High High
MFFT Low Low High
Higher is better
Tac
k R
es
ista
nc
e (
g)
13
Effect of Particle Size
Connecting Letters Report
LevelSmallMediumLarge
AA
BB
Mean918.87500827.62500731.37500
Levels not connected by same letter are significantly different.
• Decrease in gloss, Konig, and scrub with increasing PS• No significant effect on block and print with increasing PS
Formulations-White Gloss (20 PVC): No coalescing agent
600
700
800
900
1000
1100
Scr
ub
Small Medium Large
Binder PS
All PairsTukey-Kramer
0.05
Overlay Plot
Pro
be T
yp
e
EX
P-4
76
6
30
31
32
33
34
35
36
37
38
Glo
ss-2
0d
eg (
1d
)
14
16
18
20
22
24
Ko
nig
-se
c (1
d)
Overlay Plot
Pro
be T
yp
e
Left Scale: Gloss-20deg (1d)
Right Scale: Konig-sec (1d)
Particle Size
Small Medium Large
Scr
ub
Cyc
les
14
Effect of Particle Size
• Decrease in Konig hardness with increasing particle size and rheology modifier demand
Mean(Konig (sec)-1day) & Mean(Konig (sec)-7 day) vs. Particle size
Ko
nig
(se
c)-1
da
y &
Kon
ig (
sec)-
7 d
ay
6
9
12
15
18
70 80 90 100 110 120 130
Mean(Konig (sec)-1day)Mean(Konig (sec)-7 day)
Mean(Konig (sec)-1day)Mean(Konig (sec)-7 day)
8
9
10
11
12
13
14
15
Ko
nig
(sec)-
1d
ay
3 4 5 6 7 8 9 10Total RM (dry lb/100 gallon)
Summary of FitRSquareRSquare AdjRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)
0.8552640.8345870.84028711.11111
9
11
12
13
14
15
16
Ko
nig
(se
c)-7
day
3 4 5 6 7 8 9 10Total RM (dry lb/100 gallon)
Summary of FitRSquareRSquare AdjRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)
0.8740210.832028
0.6972713.02222
9
Formulations-Deep Base: No coalescing agent
Particle SizeSmall Medium Large
Ko
nig
Ha
rdn
es
s (
se
c)
Optimized Binder in Deep Base
15
Optimized Binder
Internal Binder A Competitive Binder A
Typical formulation VOC 0 50 0-50
Coalescing agent demand + = +
Gloss = = =
Tack -1day(Zapon/feel) ++ = ++
Tack -7day(Zapon/feel) ++ = ++
Block-1day (RT/Hot) =/+ = =/+
Block-7day (RT/Hot) =/+ = =/+
Print (1d/7d) ++/++ = ++/++
Konig (1d/7d) +/+ = +/+
Colorant amount = 12 oz/gal• Optimized binder shows significantly less leaching of water-soluble materials compared to Competitive
Binder A
“++” = Significantly better, “+” = Better
16
Optimized Binder in White GlossOptimized
BinderInternal
Binder A Competitive
Binder ACompetitive
Binder B
Typical formulation VOC 0-25 50 0-50 0
Coalescing agent demand + = + +
Gloss - = - =
Block-1day (RT/Hot) +/+ = +/+ --/--
Block-7day (RT/Hot) +/+ = +/+ --/--
Print (1d/7d) ++/++ = ++/++ NA
Konig (1d/7d) ++/++ = +/+ NA
Scrub + = + ++
Hydrophobic Stain - = - --
Hydrophilic Stain - = -- --
• Optimized binder shows better dry alkyd adhesion and oil softening resistance compared to Competitive Binder A
“++” = Significantly better, “+” = Better, “-” = Weaker, “--“ = Significantly weaker
17
Leaching of Water-Soluble Materials
ASTM
Method:• Followed ASTM method• Drawdown (7 mil) over black leneta chart• Cured in CTR for 4 hr and 1 day test• Water streaking test• Visual appearance ranking: 1 = best to 6 = worst
Binders Rating in Deep Base Paint
Optimized Binder 1
Competitive Binder A 5
Optimized binder shows less leaching of water-soluble materials compared to Competitive Binder A, especially in deep base
Binders Rating in White Gloss Paint
Optimized Binder 3
Competitive Binder A 5
Exposure Series (October 2014)
18
Optimized Binder Competitive Binder A
Pictures taken in July 2015
Two coats of paint over chalky latex cedar board
Exposure Series (October 2014)
19
Optimized Binder Competitive Binder A
Pictures taken in July 2015
Two coats of paint over yellow pine board
Summary
• Hard phase content and crosslinker level in binder composition drive early hardness development and resistance properties.
• Increase in the particle size of binder can lower hardness and scrub resistance.
• Optimized binder provides exceptional early hardness development, maintains balance of properties, and requires no coalescing agent to formulate deep tone and high gloss paints.
20
21
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