Transcript LZ Blue external - Pacific Northwest Society for Coatings Technology

Low VOC High Performance
1K Waterborne Polyurethanes
For Wood Coatings
Kevin Quinn
Pacific Northwest Society for Coating Technology
October 9, 2014
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Outline
• Introduction and background of topic
• Factors affecting PUD performance and VOC’s
Process
Polyurethane structural characteristics
Morphology
Raw materials/composition
Crosslinking
• Comparison of 1K and 2K PUD attributes and performance
• Summary
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Introduction and Background
- Thermoplastic Waterborne Finishes for Wood Flooring
•
Inadequate mar and black heel mark resistance
•
Poor alcohol/ polar solvent resistance
- 2K Waterborne Finishes for Wood Flooring
•
Commercial approach typically using polyaziridines or polyisocyanates as crosslinking
components with polyurethane dispersions
•
Excellent chemical, mar and black heel mark resistance
- Many Performance grade Floor Finishes for Wood Flooring are
typically high VOC
• Solventborne Polyurethanes
• Waterborne Polyurethane at >270 g/L and may contain NMP as cosolvent.
Target = Low VOC High Performance 1K PUD Resins that offer properties
required for wood flooring applications & improved user friendliness
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Introduction and Background
Generation I = Soft 1K PUD containing NMP
Generation II = Soft 1K PUD without NMP
Generation III = Harder 1K PUD containing NMP
Generation IV = Harder 1K PUD without NMP and capable of
formulations at <140 g/L VOC coatings.
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Factors Affecting PUD Coating
VOC’s & Performance
• Synthetic process
• Polyurethane structural
characteristics
• Particle morphology
• Raw materials/composition
• Crosslinking
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PUD Prepolymer Process
COOH
HO
OH + OCN
Polyol
OH + Diluent
NCO + HO
Poly-isocyanate
1) Neutralize
Water Dispersing
Process Aid
Group
(viscosity control)
2) Water
OCN
NCO
Urethane Formation
x
H 2N
NH2
Urea Formation
Waterborne Polyurethane Dispersion
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x
z
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Polyurethane Block Copolymer Structure
and Phase Separation
Hard segment
(HS)
or
urethane block
Diisocyanate
Chain extender
or
Diol
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Soft segment (SS)
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Raw Material Options for
Balanced Performance
• Polyisocyanate: aromatic, aliphatic, functionality
• Polyol: polyesters, polyethers, polycarbonates
• Diols (hard segment modifiers): butane diol, cyclohexyl
dimethylol, etc.
• Crosslinking Functionality: acetoacetonate, carbonyl,
unsaturation (other options with applied energy)
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Diisocyanates (Hard Segment)
Type
Advantages
Aromatic
TDI - Toluene Diisocyanate
Hardness &
MDI - Diphenylmethane Diisocyanate
Low Cost
Aliphatics
HDI - Hexamethylene Diisocyanate
Flexibility &
TMXDI - Tetramethyl Xylene Diisocyanate
Light Stability
IPDI - Isophorone Diisocyanate
H12MDI - Hydrogenated Diphenylmethane Diisocyanate
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Polyols (Soft Segment)
Type
Advantages
Disadvantages
Polyethers
(excluding PEO)
Softness
Flexibility
Hydrolytic Stability
Solvent Resistance(PTMEG)
Low Cost (PPG’s)
Adhesion to plastics
Weatherability (oxidizable)
Poor solvent resistance(PPG’s)
Polyesters
Adhesion
Toughness
Abrasion Resistance
Exterior Durability
Synthetic Flexibility
Hydrolytic Stability
Polycarbonates
Hydrolytic Stability
Weatherability
Abrasion Resistance
Cost
Availability
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1K and 2K
Ambient Crosslinked Coatings
-Helpful for obtaining required performance while maintaining low VOCs
 2K Crosslinked Polymer:
 Applicator mixes (1) crosslinker
+ (2) polymer base on the job:
requires proper measurement
and mixing, potential exposure
 Chemical reaction typically
starts when crosslinker is added
 Mixture needs to be used
before pot life expires
 1K Self-Crosslinking Polymer:
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 Crosslinking mechanism is built
into the polymer
 Chemical crosslink reaction is
activated as finish dries
 For on-site floor finishes this is
at low or ambient temperatures
(4˚-32˚C)
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Chemical Resistance
Test
1K PUD LZ-1
(140g/L)
1K PUD LZ-1
(50g/L)
2K Aziridine
(275g/L)
2K NCO
(275 g/L)
Water (16 hr)
5
5
5
5
1.4% Ammonia (1 hr)
4
3
5
4
1% Spic and Span (4h)
5
4
5
5
Red Wine (6 hr)
5
5
5
4
Mustard (6 hr)
3
3
3
3
MEK (1 hr)
5
5
5
5
50% Ethanol (1 hr)
5
5
5
4
IPA (1 hr)
5
4
5
5
MEK Double Rubs (100)
Ethanol Double Rubs
(100)
Overall Total
5
5
5
5
5
4
5
4
47
43
48
44
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Solvent Swells (Degree of Crosslinking)
Cure Time at RTSolvent
1K PUD LZ-1
1K PUD LZ-1
without crosslink with crosslink
(140 g/L)
(140 g/L)
(% Increase)
(% Increase)
2K Aziridine
PUD
(275g/L)
(% Increase)
2K NCO
PUD
(275g/L)
(% Increase )
1 Day RT Cure
MEK
108
28
18
24 (slight white)
IPA
36
16
11
14 (slight white)
dissolved
52
46
62
MEK
100
28
17
24 (slight white)
IPA
36
16
11
12 (slight white)
dissolved
50
42
52
NMP
7 Day RT Cure
NMP
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Black Heel Mark (Scuff) Resistance
Black Heel Mark Resistance for Low VOC 1K PUD (LZ-1) versus High VOC 2K PUDs
10
8
6
1day cure BHMR
7day cure BHMR
4
2
0
1K Low VOC
(50g/L)
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1K Low VOC
(140g/L)
NCO 2K (275
g/L)
Aziridine 2K
(275 g/L)
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Black Heel Mark Appearance on Wood
non-crosslinked PUD
(275g/L)
2K NCO Crosslinked
(275g/L)
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1K LZ-1 PUD
(140g/L)
2K Aziridine Crosslinked
(275g/L)
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Wear/Abrasion Resistance
Taber Abrasion
100
900
80
70
Milligrams Wt. Loss/1000 Cycles
60
Low Value
Average
50
High Value
40
30
20
10
0
0
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High VOC 1K PUD
(with NMP)
<140g/L
1K PUD
2K PUD
( Aziridine)
2K PUD
(NCO)
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Adhesion: Solventborne Wood Stain
Solventborne Stained Wood Panel
1K PUD LZ-1
Top Coat
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Competitive PUD
Top Coat
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Summary: Low VOC High Performance 1K
Waterborne Polyurethanes
 Engineered for low VOC NMP-free formulation as a 1K wood floor
finish comparable to two component PUD performance.
»
No additional crosslinker required – no pot-life issues, no mixing
issues, no handling issues, reduced waste and disposal cost
»
»
Target: NMP free, <140g/L, 2K performance
Easy to apply, user friendly, quick dry – multiple coats per day
 Polymer crosslinks upon application as it dries – as a result
coating produced have:
»
»
»

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Rapid hardness development and abrasion resistance
Cleaners- and alcohol- resistance on-par with 2K WB systems
Comparable sport floor wear to commercial 2K crosslinked PUDs
Excellent Adhesion to solventborne stains
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Thank You For Attending
and To The People Who Helped Make it Happen:
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Anthony Pajerski
George Ahrens
Jonathan Bird
Svetlana Lerner
Diawn Jones
Tony Kropinak
Matt Haney
Lisa Blevins
Charles Nelson
Naser Pourahmady
Bob Samelson
Vic Stanislawczyk
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Disclaimer
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© The Lubrizol Corporation 2014, all rights reserved