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1、Evy KrisnawatyTechnical Service Specialist - Paint.Rheology ModifiersFor Decorative Latex PaintsContents1. Paint & Coatings2. Rheology3. Classes of Rheology Modifier- Cellulosic Thickeners- Associative Thickeners4. Competitors1. Paint & CoatingsCoating - A liquid composition that is converted to a s
2、olid protective, decorative, or functional adherent film after application as a thin layer. Paint - A pigmented coating which is converted to an opaque film after application. Architectural Coating - A coating intended for on-site application to interior or exterior surfaces of residential, commerci
3、al, institutional, or industrial buildings.Paint & CoatingsPigment-Binder RelationshipPVCPigmentVolumeConcentrationPVC =Pigment VolumePigment Volume + Binder VolumePaint & CoatingsPVCHighLowHigh HidingLow GlossPoor DurabilityLow HidingHigh GlossGood DurabilityPigment Volume ConcentrationSubstratePig
4、mentBinderVoidPaint & CoatingsPaint Ingredients:WaterPigment / ExtendersFilm FormerAdditives : dispersant, surfactant, defoamer, biocide, coalescing agent, co-solvent, rheology modifierPaint & CoatingsPrimary or Hiding Pigments Opacity Film Hardness DurabilityExtender Pigments Economy/Space Filling
5、Hiding Contribution Film Hardness DurabilityCalcium CarbonateClaySilicaTalcTitanium DioxideZinc OxidePaint & CoatingsFilm Former Binds Pigments to Substrate Protects SubstrateArchitectural Latex Paint Binder Chemistries1. Vinyl Acrylic2. Vinyl Acetate Ethylene (VAE)3. Vinyl Acetate-VeoVa4. Acrylic5.
6、 Styrene AcrylicPaint & CoatingsSurfactants Pigment Wetting Substrate Wetting Latex Stabilization Colorant StabilizationNonionicNonylphenol EthoxylatesAnionicAlkyl SulfosuccinatesAmphotericWater-Dispersible LecithinPaint & CoatingsDispersants Pigment DispersionPolyphosphateKTPPK5P3O10TKPPK4P2O7Calgo
7、n Nan(PO3)n PolyacrylateTamol, Colloid, Byk,Dispex, NopcosperseAmino AlcoholAMP-95Paint & CoatingsCo-solvent Anti-Freeze Control Drying Workability Coalescence Flow Touch UpEthylene GlycolPropylene GlycolPaint & CoatingsCoalescing Agents Film Formation Touch UpGlycol EthersButyl CarbitolEster Alcoho
8、lsTexanolUcar Filmer IBTPaint & CoatingsDefoamers Defoam/DeaerateSilicone OilsNon-SiliconeAlcoholsFatty AcidsFatty Acid EstersPhosphate EstersMetallic SoapsPaint & CoatingsPreservatives *Prevent in-can spoilage Prevent mildewIsothiazoline-One*Proxel GXL*Kathon LXSkane M-8Oxazolidine*Nuosept 95Carbam
9、ate*Troysan PolyphaseZinc OxideZnOPaint & CoatingsThickeners/Rheology Modifiers Viscosity/Thickening Pigment Suspension Syneresis Resistance Sag Resistance Film Build Applicator Loading WorkabilityCellulosic HEC, EHEC, MC, HMHEC, HMEHECSyntheticIonic (HASE), Nonionic (HEUR/HMPE)ClayAttapulgite, Bent
10、onitePaint & CoatingsPaint TypePVC, %60 GlossExtendersInteriorFlat40-800-10YesSheen30-403-20YesSemi-Gloss20-3530-70Yes/NoGloss2070-85NoHigh Gloss85NoExteriorFlat35-550-15YesSatin30-4010-20YesTrim20-3030-70Yes/NoGloss2070NoThings can be wrongFadingDirt Pick UpThings can be wrongBrush MarkRoller MarkT
11、hings can be wrongHiding PowerSaggingThings can be wrongEfflorescenceBlisteringThings can be wrongAlkali ResistanceFoam Cratering2. Paint - RheologyViscosity vs Shear RateViscosityShear RateNewtonian Flow Viscosity is independentof shear rate.Viscosity vs Shear RateViscosityShear RatePseudoplastic F
12、lowViscosity decreases withincreasing shear rate.ShearThinningTypes of Viscous FlowPaint - RheologyThixotropyTime-dependence of viscosity loss and recovery Viscosity vs TimeViscosityTimeConstantShearViscosity vs Shear RateViscosityShear RateRamping ShearUp and DownThixotropicLoopTypes of Viscous Flo
13、wPaint - RheologyPlastic FlowLittle or no deformation occurs until a certain minimum level of stress, called a yield stress or yield value, is exceeded.Shear Stress vs Shear RateShear StressShear RateViscosity vs Shear RateViscosityShear RateTypes of Viscous FlowPaint - RheologyViscosity vs Shear Ra
14、teViscosityShear RateDilatent FlowViscosity Increases with Increasing Shear Rate.ShearThickeningTypes of Viscous Flow3. Classes of Rheology ModifiersPaint properties are predominantly controlled by binder type.Within the additives group the Rheology modifiers have the largest influence. Control of:C
15、lasses of Rheology Modifiers NonionicPolymersAnionicPolymersAqualon Rheology Modifiers NonionicPolymersAnionicPolymersCellulosic Thickeners1. Chemistry2. Enzyme Resistance3. Incorporation4. Selection5. Associative Cellulosics Hydrophobically Modified HEC (HMHEC)6. Modified HEC - New ProductCellulosi
16、c ChemistryCH2OHOHHOHHHHOCH2OHOHOHOHHHHOCH2OHOOHHHHOOOHHCH2OHOOHHHHOOOHHCelluloseCH2H2COEthylene OxideHydroxyethylcelluloseEthylhydroxyethylcelluloseCH2H2COEthylene OxideEthyl ChlorideCH3ClHydroxypropylmethylcellulosePropylene OxideCH2H2COH3CMethyl ChlorideCH3ClCH2Reactants & ProductsCellulose Ether
17、 to Paint Properties Pigment DispersionHEC CMC EHEC MHEC Foaming HEC = CMC EHEC MHEC Thickening EfficiencyMHEC HEC EHEC CMC Storage StabilityHEC EHEC = MHEC CMC BiostabilityHEC EHEC MHEC CMC SpreadabilityHEC EHEC CMC MHECEnzyme ResistanceEnzymeEnzymeBacteriumEnzymeEnzyme ResistanceCH2OHOHHOHHHHOCH2O
18、HOHHHHOCH2OHOOHHHHOOOHHCH2OOHHHHOOOHCH2CH2OCH2CH2OHOCH2CH2OCH2CH2OHCH2CH2OOHOCH2CH2OCH2CH2OCH2CH2OHCH2OHHOHHHOCH2OHOHHHHOCH2OOHHHHOOOHHCH2OOHHHHOOOHCH2CH2OCH2CH2OHOCH2CH2OCH2CH2OHCH2CH2OOHOCH2CH2OCH2CH2OCH2CH2OHOCH2CH2OHCH2CH2OHCH2CH2OCH2CH2OOHCH2H2CORegular HECBiostable HECEnzyme ResistanceStormer
19、KUEnzyme Resistant HEC/EHECTime, DaysMethyl CelluloseNon-Enzyme Resistant HEC/EHECTypical Viscosity Losses inPaint on Exposure to EnzymeIncorporation Water(Glycol) Defoamer (Thickener) Surfactant(Preservative) Dispersant Amine/Ammonia PigmentGrind TankGrind StageLetdown TankLetdown Stage To Fill Lin
20、ePigment Bulk Liquids Water Latex Defoamer Thickener Amine/Ammonia Coalescent PreservativeCommon Paint Making ProcessIncorporation1. Addition to the GrindDirect Addition before Pigments2. Addition to the Letdown a. Addition as a Slurry, in Water Glycol Coalescent b. Addition as a Stock Solution1. Di
21、ssolve HEC2. Add Preservative c. Eductor AdditionEductor Addition To Letdown TankNatrosolWaterEductorEductorOperationEductor Addition1. HEC is Added to Funnel of Eductor2. Vacuum Created by Water Flow Draws HEC into the Water Stream3. HEC is Uniformly Dispersed in the Water StreamNatrosol - Selectio
22、n Low Mw High MwThickening-+Spatter Resistance+-Leveling-+Hiding Power+-Open time+-Water resistance-+Water retention+-Molecular Weight InfluenceNatrosol - SelectionNatrosol HECViscosity Grade/Molecular Weight Effects60-PVC Vinyl-Acrylic Flat Paint, 95 KUNatrosol - Selection Less Spatter Higher Brush
23、ing Viscosity Better Sag Resistance Longer Open TimeDecreasing Viscosity/Molecular WeightIncreasing Viscosity/Molecular Weight More Efficient Lower Cost in Use Better Leveling Better Water ResistanceAssociative CellulosicsHydrogenBondingNetworkChainEntanglementHydrophobeInteractionNatrosol Thickenin
24、g MechanismsNatrosol Plus 330Thickening MechanismsAssociative CellulosicsSpatter Resistance of Natrosol PlusInterior Flat Paint Thickened with Natrosol Plus 330Interior Flat Paint Thickened with Natrosol 250H4BRAssociative CellulosicsLow G PaintHigh G PaintAssociative CellulosicsNatrosol Plus 330 an
25、d Natrosol 250GRUcar 367 60-PVC Vinyl-Acrylic Flat Paint Thickening EfficiencyNatrosollb/ICI,SpatterSag, ScrubProductWt % 100 gal Poise Resistance Leveling mils Cycles250GR0.9010.51.6531490Plus 3300.56 6.51.28416135Associative CellulosicsNatrosol Plus 330 and Natrosol 250GRRhoplex AC-417M Acrylic Se
26、migloss Paint Thickening EfficiencyNatrosollb/ICI,Spatter Gloss ScrubProductWt % 100 gal Poise Resistance Leveling 60 Cycles250GR0.646.82.25245550Plus 3300.414.31.48242655Modified HEC - New ProductNonionic- Wide Compatibility- Excellent Water ResistanceModified HEC- High Efficiency- Improved Applica
27、tion Performance:LevelingSag ResistanceSpatter ResistanceModified HEC - New ProductProperties in Flat Emulsion PaintPVC 80 based on Styrene Acrylate as binderSynthetic Thickeners1. Chemistry and Nomenclature2. Thickening Mechanism3. Interactions in Paint4. AquaflowNomenclatureAcronymChemistryHASEHyd
28、rophobically Modified Alkali-Soluble EmulsionHMHECHydrophobically Modified HydroxyEthylCelluloseHEURHydrophobically Modified Ethoxylate UrethaneHMPEHydrophobically Modified PolyEtherHEUR and HMPE AreNonionic Synthetic Associative Thickeners (NSATs)ChemistryATHMPE/HEUR(NSAT)20-100HMHEC300HASE200-1,00
29、0MW x 103StructureOHOHOHOHOHOHOHOHOHOHCO2HCO2HCO2HCO2HCO2HCO2HCO2ROHThickening MechanismAssociative Thickening of Comb-Type ATLatexPigmentPaintHMHECor HASEThickening MechanismAssociative Thickening of Telechelic NSATPaintLatexHMPEor HEURInteractions in PaintAny Paint Ingredient Having Hydrophobic Ch
30、aracter Will Affect the Performance of Associative ThickenersLatexDispersantsDefoamersGlycolsCoalescentsSurfactantsSurfactants Are The Most Potent InteractorsInteractions with LatexLatex ChemistriesIncreasing HydrophobicityVinylAcrylicAcrylicStyreneAcrylicVA-VeoVaVAEInteractions with LatexInteractio
31、ns Between Associative Thickeners and the Latex Increase: As the Latex Becomes More Hydrophobic As Gloss Increases/Latex Concentration Increases /PVC Decreases As Latex Particle Size DecreasesInteractions with CoalescentWater-Miscible Coalescent (Butyl Carbitol) Partitions Between Aqueous Phase and
32、Latex Disrupts Hydrophobic Associations Reduces Associative Thickener EfficiencyWater-Immiscible Coalescent (Texanol) Partitions Entirely into Latex Particles Increases Latex Volume Decreases Surfactant Coverage Increases Associative Thickener EfficiencyCoalescent Type and Amount Will Impact Thicken
33、er Demand/Efficiency. Interactions with SurfactantHydrophobe-HydrophobeInteractionSimpleAdsorptionCompetitiveAdsorptionShieldingInteractions with SurfactantNetwork Enhancement andDisruption in Coatings cause by SurfactantEnhancersl Dialkyl Sulfosuccinatesl Low-HLB Nonionic Ethoxylatesl Alkylphenol E
34、thoxylate Sulfatesl Fatty Acid SaltsDisruptorsl High-HLB Nonionicsl Some DispersantsSurfactant02468101214161820LipophilicHydrophilicHydrophobicLipophobic4-6Water-in-Oil Emulsifiers7-9Wetting AgentsOil-in-Water Emulsifiers13-15Detergents10-18SolubilizersHydrophile-Lipophile Balance8-18The HLB Concept
35、LipophilicHydrophilicHLBNonylphenol and Octylphenol Ethoxylate SurfactantsSurfonicN-10N-31.5N-60N-100N-120N-200N-40N-1500246810121416182015MolesEO12341012206154070IgepalCO-210CO-430CA-420CO-530CO-660CO-720CO-850CO-730CO-890CO-987TergitolNP-4NP-6NP-10NP-20NP-15NP-40NP-70TritonN-17N-42X-35X-100X-15X-4
36、05X-705Interactions with Dispersant Compatibility of Synthetic Thickeners with Dispersants is Determined by the Acid and/or Counter Ion Content of the Dispersant. Dispersants are Commonly Supplied as Salts.Organic Polymeric DispersantsCarboxylate AnionPolyphosphate DispersantsPhosphate AnionCounter
37、IonsSodium, Potassium, AmmoniumInteractions with Dispersant High-Acid Content DispersantsHigh Ionic Strength Can Reduce the Solubility of Nonionic Synthetic Thickeners. Low-Acid Content DispersantsCan Adversely Affect Paints Thickened with HASE Thickeners. Co-Polymer DispersantsTend to Be Compatible
38、 with Nonionic SATs and HASE ThickenersDispersant RecommendationsNSAT = HMPE, HEURInteractions with DispersantNonionic SAT - High-Acid Dispersant Incompatibility Minimize Ion Content of the Paint Avoid Polyacid Homopolymer and Polyphosphate Dispersants. Lower-Acid Copolymer Dispersants Are Most Effe
39、ctive. Hydrophobic Copolymer Dispersants Can Have Advantages for Gloss, Leveling, and Syneresis Resistance. Avoid High Surfactant Levels.Synthetic Thickener - SummaryThe Effectiveness of Synthetic Associative Thickeners is Determined by Latex Type Latex Concentration Latex Particle Size Coalescent D
40、efoamer Glycol Surfactant DispersantChemical Type: Hydrophobically Modified PolyetherNLS-200NLS-210NHS-300AppearanceHazy White Liq.Hazy White Liq.Hazy White Liq.Solids, Weight %252520Carrier80:20 Water: 75:25 Water: WaterButyl Carbitol Butyl CarbitolViscosity, cP3,000-4,500 2,500-4,000 4,500-7,000Sp
41、ecific Gravity1.051.051.04N-Series Rheology ModifiersPaint Viscosity vs Shear Rate0.11101001000100000.0010.010.1110100100010000Shear Rate, s-1Viscosity, mPa sStorageDryingTransportationProcessingApplicationNLS-200NHS-300HECRoller / BrushNLS-210N-Series Rheology ModifiersNLS-200RM-825 NHS-300RM-2020N
42、PRThickener Ratio, Dry Basis8:924:96Total Thickener, wt %0.630.64Stormer KU101100ICI Viscosity, CP1.951.90Gloss, 608080Leveling, Brush87Sag Resistance, m10075Color Development, E0.91.4Viscosity Loss on Tinting*, %28446% Red OxideHG-74D Styrene-Acrylic Gloss Paint N-Series Rheology ModifiersCellulosi
43、c & Synthetic Thickeners70-PVC Interior Flat Tint Base8 Oz Red Iron Oxide per GallonViscosity Loss on Tinting ComparisonTinting Colorants ContainV DispersantsV DefoamersV GlycolsV SurfactantsAll of Which Can Reduce the Efficiency of Associative Thickeners-5-9-16-29HECHMHECHASEHEURHMPE-20Aqualons Rheology ModifiersApplicability by Paint Typeaqualon
