Biodegradable, Low Foam Surfactants for Automatic ...

1 Biodegradable, Low Foam SurfactantsBiodegradable, Low Foam Surfactantsfor Automatic dishwashing ApplicationsSeverine Ferrieux, Jan Shulman and Luis Madrigal*The Dow Chemical Company1 The Dow Chemical CompanyConference of SEPAWA Nordic Section (Malmo, Sweden)May 6, 2013 Biodegradable, Low Foam Surfactantsfor Automatic dishwashing applications Dish Care Global Trends Dish Care Global Trends Regulatory Drivers Challenges Formulating with Non-Phosphate Builders- Prototypical Formulations surfactant Design/Characteristics Performance in ADWs/Rinse Aids Summary/ConclusionsDish Care Global TrendsA large part of the world is still using hand dishwashingformats (mostly liquids)A large part of the world is still using hand dishwashingformats (mostly liquids)ADW sales are mostly in Europe and North America (~90%) : Eastern Europe is one of the major growth areas for ADWin volume and value Powders are still dominant but tablets gain quick marketshare in WE and North sales are mostly in Europe and North America (~90%).

2 Eastern Europe is one of the major growth areas for ADWin volume and value Powders are still dominant but tablets gain quick marketshare in WE and North value growth driver is machine penetration, availableincome and as a result increased penetration of premiumpriced-tablet format (Europe)Main value growth driver is machine penetration, availableincome and as a result increased penetration of premiumpriced-tablet format (Europe)priced-tablet format (Europe)priced-tablet format (Europe)The move toward more sustainable products is a globaltrend(Regulatory-driven reformulations move out of phosphates))The move toward more sustainable products is a globaltrend(Regulatory-driven reformulations move out of phosphates))Regulatory-Driven Innovation:Phosphate-Free FormulationsNorth America Regulatory driven re-formulations were initiated July 1, 2010. Law enforced limitation of total phosphorus content to in ADW Law enforced limitation of total phosphorus content to in ADWdetergents in 16 states.

3 Based on this regulation, many manufacturers voluntary removedphosphates for other European Parliament has approved phosphate ban:-Standard Phosphate dosage for Automatic dishwasher detergentswill be limited to on January 1, 2017-Standard Phosphate dosage for Automatic dishwasher detergentswill be limited to on January 1, 2017 Sweden moves to phosphate-free ADW formulations as of July 2011 Pressure on Baltic Sea countries to follow Sweden In France, a tax is paid on phosphates:-complete move to phosphate-free in 2012 When Phosphates (STPP/TKPP)are shineon glassesandsurfacesPoor shineon glassesandsurfacesWithPhosphateSTPPWithP hosphateSTPP andsurfacesandsurfaces-STPPR educedsoilremovalReducedsoilremovalIncre asedspottingandfilming onsurfacesIncreasedspottingandfilming onsurfaces-STPP-STPPF actors Influencing Inorganic/OrganicScale Formation and Deposition Washing Parameters-Water Hardness/Temperature-Water Hardness/Temperature- Type of Surface (Glass, Ceramic, Plastic)- Concentration of Food Soil Selection of the Builder/Polymer System-Detergent Concentration in the Wash Bath-Detergent Concentration in the Wash Bath Selection of the Low Foam Emulsifying surfactant - Structure/Functionality/ConcentrationDet ergent Builders(Precipitating/Non-Precipitating ) Phosphates (STPP, TKPP) Carbonates(Soda Ash, Bicarbonate) Carbonates(Soda Ash, Bicarbonate) Citrates Aminocarboxylates (MGDA, GLDA) Organics (NTA)

4 , Inorganics (HEDP) Silicates Silicates Polycarboxylates/Builder Assists (Acrylics,Acrylic/Maleics, Acrylic/Sulfonated Co/terpolymers)Phosphate vs. Phosphate-FreeAutomatic dishwashing ProductsComponentsPhosphateNon-Phosphate % (Actives)BuildersBuildersSTPP/TKPP5-350 Soda Ash5-2015-35+Sodium Bicarbonate0-150-15 Sodium Disilicate (Corrosion Inhibitor)2-102-10 Percarbonate (Peroxygen Bleach)0-150-15 TAED (Bleach Activator )0-40-3 Surfactants (Emulsification/Degreasing) (Protease/Amylase/Lipase)0-20-2 Polymers (Scale Inhibition)0-22-10 PEG (Tablet Binder), PVOH (Film)As NeededAs NeededFiller (Sodium Sulfate/NaCl)BalanceBalanceLow Foam Surfactants for ADW applications (Ideal Properties) Designed to facilitate the removal of baked on, burnt onfood soilsfood soils Emulsification of food soils Prevent redeposition of oily/greasy soils back onceramics and flatware. Rapid wetting, mitigate spotting/streaking on glassware Shine enhancement Shine enhancement Readily biodegradable (OECD 301) Control excessive foam formation (keep dishwasherjets clear to insure appropriate mechanical actionAlkyl/Block EO/PO/BO Surfactants Water solubility, oil insolubility High molecular weights Primary OH Solid products (at high EO content) Water insolubility, dispersibility Oil solubility, low foam Limited molecular weights Liquid productsEOPOBO10 Secondary OH Oil solubility, water insolubility Limited molecular weights Liquid products Secondary OHBOLow Foam surfactant StructuresDesignationChemistryHLBC loud Point#1 Tergitol L-61EO/PO/EO324#2 Tergitol L-64EO/PO/EO1562#2 Tergitol L-64EO/PO/EO1562#3 Ecosurf LF-20 Sec-alcoholalkoxylate:EO-BO10-1120#4 Ecosurf LF-30 Sec-alcoholalkoxylate:EO-BO11-1233#5 Dowfax 20B102 Linear-alcoholalkoxylate:EO-BO1132alkoxy late.)

5 EO-BO#6 BenchmarkAlcoholalkoxylate4-518#7 Triton CF-32 Alkyl amineEO/PO1125 Automatic dishwashing ConditionsWashing ParametersDishwasherSears KenmoreCycleNormal wash, 1-3 complete cyclesTemperature55oCDetergent Concentration20 grams ADW PowderSoil Load40 grams ASTM (Milk/Margarine),added at time zero (start of the pre-wash cycle)Water (2/1 Ca/Mg)GlasswareLibbey-CollinsBallast LoadCeramic plates, Fine China, StainlessSteel flatware, PlasticwareASTM Rating1 = clean, unwashed glass;5 = heavily filmed or cycleNon-Phosphate ADW Powder (Sachet)Kenmore Dishwashers, 55 C, 300 ppm WH (2/1 Ca/Mg), 3 wash cycles,ASTM Food Soil(40 grams milk/margarine), 20 grams ADW Powder/Load,ASTM Rating System (1 = clean glass, 5 = heavily filmed) cycle2 cycles3 PowderNo SurfactantTergitol L-61(#1) 3%Dowfax 20B102(#5) 3%Benchmark(#6) 3%Ecosurf LF-30(#4) 3% cycle2 cyclesNon-Phosphate ADW Powder (Sachet)Kenmore Dishwashers, 55 C, 300 ppm WH (2/1 Ca/Mg), 3 wash cycles,ASTM Food Soil(40 grams milk/margarine), 20 grams ADW Powder/Load,ASTM Rating System (1 = clean glass, 5 = heavily filmed) cycles3 CF-32(#7) 3%Dowfax 20B102(#5) 3%Tergitol L-64(#2) 3%ADW PowderNo SurfactantEcosurf LF-20(#3) 3% cycleNon-Phosphate ADW Powder (Sachet)Kenmore Dishwashers, 55 C, 300 ppm WH (2/1 Ca/Mg), 3 wash cycles,ASTM Food Soil(40 grams milk/margarine), 20 grams ADW Powder/Load,ASTM Rating System (1 = clean glass, 5 = heavily filmed)

6 Cycles3 20B102(#5) 20B102(#5) 3%Tergitol L-61(#1) L-61(#1) 3% cycleNon-Phosphate ADW Powder (Sachet)Kenmore Dishwashers, 55 F, 300 ppm WH (2/1 Ca/Mg), 3 wash cycles,ASTM Food Soil(40 grams milk/margarine), 20 grams ADW Powder/Load,ASTM Rating System (1 = clean glass, 5 = heavily filmed) cycle2 cycles3 PowderNo SurfactantEcosurf LF-30(#4) LF-30(#4) 3%Benchmark(#6) (#6) 3%US Non-Phosphate ADWs - Conclusions Dowfax 20B102 (#5) is clearly the best performingsurfactant for spotting inhibition Performance at surfactant solids is noticeably Performance at surfactant solids is noticeablybetter than the current base containing a conventionalnonionic alcohol alkoxylates (Benchmark, #6) Ecosurf LF-20 (#3) and Ecosurf LF-30 (#4) are also viablecandidates under this testing protocol (utilizing theASTM non-fat dry milk/margarine soil).ASTM non-fat dry milk/margarine soil).17 Rinse Aid EvaluationsSurfactant Pool high chemical varietyDow and competitive benchmark surfactants1.

7 Shine on glass2. Full Scale Test:1. Screening phase:Wetting characteristics small scale screenStarting pointformulation 50oCIntermediaterinse 55-70oCDryingSurfactant added in rinse cycle2. Plastic drying 12% surfactant Qsp water 50 CCleaningrinse 55-70 CFinalrinseSurfactants in the TestDesignationChemistryHLBT ergitol 15-S-7 Secondary alcohol EH-62- Ethyl hexanol LF-20 Secondary alcohol alkoxylate10-11 Different chemistries Different degree ofethoxylation in thesame LF-20 Secondary alcohol alkoxylate10-11 Ecosurf LF-30 Secondary alcohol alkoxylate11-12 Ecosurf LF-45 Secondary alcohol alkoxylate12-13 Dowfax 20A64 Linear alcohol alkoxylateDowfax 20B102 Linear alcohol alkoxylate11 Triton DF-12 Capped alcohol L-61EO/ PO/EO Tri-block3 Select best chemistry /properties inapplications testTergitol L-64EO/ PO/EO Tri-block15 Benchmark 1 Alcohol ethoxylatedpropoxylatedCloud point = 33oCBenchmark 2 Alcohol ethoxylatedpropoxylatedRinse Aid Studies - ResultsDow Surfactants .

8 Select best candidates from first screening roundTergitol L-61 Exceptional shine on glassStarting pointformulationTergitol L-61 Exceptional shine on glass(excellent wetting)Tergitol L-64 Excellent drying on plasticSurfactantDIDIDIDIDIC alculation of drying properties (drying index calculation)0 < drying index DI < 10 = wet dishes1 = dry dishesformulation anh. citric acid 12% surfactant Qsp waterSurfactantDIoverallDIporcelainDIgla ssDIcutleryDIplasticTergitol P-Free Detergent Study Evaluate rinse performance of non-ionic Surfactants inmulti-functional detergent vs. competitive samples FormulationSurfactant addedat beginningShine on glass 50oCCleaningIntermediaterinse 55-70oCFinalrinseDrying Formulation P-free powder formulation with organic builder MGDAM ultifunctional Phosphate-Free FormulationFormulaIngredients%Methylglyc inediaceticacid(MGDA) 100 Spotting ResultsWash conditionsMiele G1222 SC LaborWater hardness = , ratio Ca/Mg 3/1 Wash temperature = 50oC (without prewash)20g detergent per washWith STIWA food soil (50g)Rating: 1 = no spot; 5 = highly spottedReference withoutsurfactant3456 SpottingscoreSpotting on Glasswarespotting cycle 1spotting cycle 3spotting cycle 5 Dowfax20B102 Benchmark 1012/4% TergitolL-61E4% EcosurfLF-204% EcosurfLF-304% Dowfax20B1024%benchmark 14%benchmark 2 SpottingscoreER Non-Phosphate Formulation - ConclusionsWe have found low foam Surfactants with superiorperformance in Automatic dishwashing applications :1.

9 In a rinse aid In a rinse aid Tergitol L-61 and Tergitol L-64 provide for improvedplastic drying and shiny glassware2. In a multifunctional, phosphate-free Ecosurf LF-20 (#3) and Dowfax 20B102 (#5) deliverreducedreducedspotting and create shinier glasses- With a performance on par or better than benchmarknonionic Surfactants in the testBiodegradable, Low Foam Surfactantsfor Automatic dishwashing Applicationsfor Automatic dishwashing ApplicationsThank You!Severine Ferrieux, Jan Shulman and Luis Madrigal*The Dow Chemical CompanyThe Dow Chemical CompanyConference of SEPAWA Nordic Section (Malmo, Sweden)May 6, 2013 STIWA Food Soil CompositionIngredients for 1 kg (20 doses @ 50 grams/wash cycle) 25g ketchup 25g mustard 25g mustard 25g instant gravy 5g starch 1g benzoic acid 3g egg yolk 100g margarine 50g milk ( fat equivalent semi skimmed) 700g tap water26