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© The Lubrizol Corporation 2014, all rights reserved Low VOC High Performance 1K Waterborne Polyurethanes Kevin Quinn Pacific Northwest Society for Coating Technology October 9, 2014 For Wood Coatings
© The Lubrizol Corporation 2014, all rights reserved 2 Definitions: PUD = Polyurethane dispersion (waterborne) 1K = 1 component coating PUD 1K PUD LZ-1 = 1K low VOC (<140g/L) self-crosslinking (at R.T.) PUD 2K = 2 component coating (polymer + crosslinker) 2K NCO = 2K commercial PUD coating with polyisocyanate crosslinker 2K Aziridine = 2K commercial PUD coating with polyaziridine crosslinker
© The Lubrizol Corporation 2014, all rights reserved 3 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
© The Lubrizol Corporation 2014, all rights reserved 4 - 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. Introduction and Background Target = Low VOC High Performance 1K PUD Resins that offer properties required for wood flooring applications & improved user friendliness
© The Lubrizol Corporation 2014, all rights reserved 5 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. Introduction and Background
© The Lubrizol Corporation 2014, all rights reserved 6 Factors Affecting PUD Coating VOC’s & Performance Synthetic process Polyurethane structural characteristics Particle morphology Raw materials/composition Crosslinking
© The Lubrizol Corporation 2014, all rights reserved 7 PUD Prepolymer Process
© The Lubrizol Corporation 2014, all rights reserved 8 Polyurethane Block Copolymer Structure and Phase Separation
© The Lubrizol Corporation 2014, all rights reserved 9 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)
© The Lubrizol Corporation 2014, all rights reserved 10 Diisocyanates (Hard Segment) Aromatic TDI - Toluene Diisocyanate Hardness & MDI - Diphenylmethane DiisocyanateLow Cost Aliphatics HDI - Hexamethylene DiisocyanateFlexibility & TMXDI - Tetramethyl Xylene Diisocyanate Light Stability IPDI - Isophorone Diisocyanate H12MDI - Hydrogenated Diphenylmethane Diisocyanate Type Advantages
© The Lubrizol Corporation 2014, all rights reserved 11 Polyols (Soft Segment) Type Advantages Disadvantages Polyethers Softness Adhesion to plastics (excluding PEO) Flexibility Weatherability (oxidizable) Hydrolytic Stability Poor solvent resistance- Solvent Resistance- (PPG’s) (PTMEG) Low Cost (PPG’s) Polyesters Adhesion Hydrolytic Stability Toughness Abrasion Resistance Exterior Durability Synthetic Flexibility Polycarbonates Hydrolytic Stability Cost WeatherabilityAvailability Abrasion Resistance
© The Lubrizol Corporation 2014, all rights reserved 12 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: 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)
© The Lubrizol Corporation 2014, all rights reserved 13 Chemical Resistance Test1K PUD LZ-1 (140g/L) 1K PUD LZ-1 (50g/L) 2K Aziridine (275g/L) 2K NCO (275 g/L) Water (16 hr) 5555 1.4% Ammonia (1 hr) 4354 1% Spic and Span (4h) 5455 Red Wine (6 hr) 5554 Mustard (6 hr) 3333 MEK (1 hr) 5555 50% Ethanol (1 hr) 5554 IPA (1 hr) 5455 MEK Double Rubs (100) 5555 Ethanol Double Rubs (100) 5454 Overall Total 47434844
© The Lubrizol Corporation 2014, all rights reserved 14 Solvent Swells (Degree of Crosslinking) Cure Time at RT- Solvent 1K PUD LZ-1 without crosslink (140 g/L) (% Increase) 1K PUD LZ-1 with crosslink (140 g/L) (% Increase) 2K Aziridine PUD (275g/L) (% Increase) 2K NCO PUD (275g/L) (% Increase ) 1 Day RT Cure MEK108281824 (slight white) IPA36161114 (slight white) NMPdissolved524662 7 Day RT Cure MEK100281724 (slight white) IPA36161112 (slight white) NMPdissolved504252
© The Lubrizol Corporation 2014, all rights reserved 15 DMA Comparison of 1K and 2K PUDs
© The Lubrizol Corporation 2014, all rights reserved 16 Black Heel Mark (Scuff) Resistance
© The Lubrizol Corporation 2014, all rights reserved 17 Black Heel Mark Appearance on Wood non-crosslinked PUD (275g/L) 2K NCO Crosslinked (275g/L) 1K LZ-1 PUD (140g/L) 2K Aziridine Crosslinked (275g/L)
© The Lubrizol Corporation 2014, all rights reserved 18 Wear/Abrasion Resistance 0 10 20 30 40 50 60 70 80 900 100 0High VOC 1K PUD (with NMP) <140g/L 1K PUD 2K PUD ( Aziridine) Milligrams Wt. Loss/1000 Cycles Low Value Average High Value 2K PUD (NCO) Taber Abrasion
© The Lubrizol Corporation 2014, all rights reserved 19 Adhesion: Solventborne Wood Stain 1K PUD LZ-1 Top Coat Competitive PUD Top Coat Solventborne Stained Wood Panel
© The Lubrizol Corporation 2014, all rights reserved 20 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: » 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
© The Lubrizol Corporation 2014, all rights reserved 21 Thank You For Attending and To The People Who Helped Make it Happen: Anthony Pajerski George Ahrens Jonathan Bird Svetlana Lerner Diawn Jones Tony Kropinak Matt Haney Lisa Blevins Charles Nelson Naser Pourahmady Bob Samelson Vic Stanislawczyk
© The Lubrizol Corporation 2014, all rights reserved 22 Disclaimer Trademarks owned by The Lubrizol Corporation © The Lubrizol Corporation 2014, All Rights Reserved, February 2014
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