Sustainable alkyd and epoxy based coatings
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1 Sustainable alkyd and epoxy based coatings Jonathan Huang Business Development Specialist, Croda Asia Pacific July 2016 Innovation you can build on
2 Making A Difference by Being Different The skill, know-how and dedication of our people are what drives our innovation, differentiates us from our competitors and fuels our success Steve Foots, Group Chief Executive Innovation you can build on
3 Our Highlights Since 2008 Since 2013 Since 2013 Awarded ,081.7m Revenue in 2015 with 26.1% of sales from NPP 24.2% Energy from non-fossil fuel 56.8% Reduction in waste to landfill since 2010 Eleven manufacturing sites have RSPO certification to support CSPO 66.1 % raw materials from renewable sources 6,321 hours 1% Club volunteering hours, equivalent to c. 120,000 3
4 What We Do Consumer Care Personal Care Sun Care & Biotechnologies Sederma Crodarom & Seatons Health Care Crop Care Performance Technologies Industrial Chemicals Lubricants Coatings & Polymers Home Care Geo Technologies Polymer Additives Industrial Chemicals
5 Our Leading Edge Brands Bio-Based Monomers (Building Blocks) Priplast Pripol Priamine Polyester polyols bring enhanced properties to polyurethane, polyamide and polyester applications Dimer diols and dimer acids improve epoxy, polyester and polyamide properties Dimer diamines for adhesives & coatings and curing agents for epoxy coatings Enhanced benefits include: Flexibility Protects substrate from moisture Universal adhesion Chemical resistance Excellent colour and durability HO H 2 N OH NH 2
6 Our Leading Edge Brands Speciality Additives B-Tough Maxemul Epoxy functional toughening agent for epoxy coatings/adhesives Polymeric surfactants for high quality, VOC free resin emulsions Synperonic LoVOCoat Multiwet Zephrym Crodacor EO/PO block copolymers for epoxies and polyurethanes Polymeric surfactants for low VOC alkyd paints with no compromise on performance Multi-functional wetting agents simplifying aqueous formulations Non/low VOC polymeric pigment dispersants for aqueous and nonaqueous applications Corrosion and flash rust protection for aqueous formulations
7 Maxemul Polymeric surfactants for high quality, low and VOC free resin emulsions Maxemul 5000/6000 Maxemul 7000 Maxemul 9107 Non-migratory surfactants in heterogeneous free radical polymerisation for acrylic, styrene acrylic, VAM systems Polymeric surfactants for alkyd Emulsions in VOC free alkyd paints Cost effective solution for Low to Zero VOC epoxy emulsions
8 Advanced Surfactant Technology for Alkyd Emulsions in VOC Free Alkyd Paints
9 Alkyd resins Popular binders for wood and metal protective coatings Fatty acid modified polyesters Long history Excellent balance between cost/performance High gloss finish Largely from renewable resource Traditionally solvent borne
10 Alkyd paint VOC reduction or elimination 2 Main Approaches Improved Alkyd based coatings Drivers for Change Solvent Borne (Low VOC) High Solids Alkyd Water Borne (No VOC) Water Reducible Cost Environmental Water-in-oil Alkyds Urethane Modified Health Emerging Legislations LoVOCoat EM500 Oil-in-water Alkyds Maxemul Advanced surfactant technology
11 The solution - Going waterborne 100 LoVOCoat EM500 Maxemul Total replacement of solvent with water % solvent water surfactant alkyd 10 0 Conventional High solids Water-in-oil alkyds Oil-in-water alkyds Alkyd emulsion Surfactant stabilised
12 Going waterborne stabilisation with Maxemul TM polymeric surfactants Performance benefits Conventional alkyd resins can be used Emulsification rather then diluting in solvent No polymer development required Oil phase Cost savings from solvent elimination Water phase Preferred production method The phase inversion technique Emulsification in stirred pot No high speed mixing equipment required Minimal investment cost Low energy consumption
13 Procedure Going waterborne Simple emulsification process The emulsifiers are preferably dissolved in the resin phase Water is added to the oil phase while stirring, initial formation of a W/O emulsion, viscosity increases with water addition At the inversion point (at viscosity maximum): spontaneous inversion from a W/O to an O/W emulsion upon further addition of water Water phase Oil phase O / W
14 Preferred impellers Intermig (Ekato) Surfactant reduction with optimum mixing efficiency
15 Formulation advice Emulsification advice Reaction vessel with heating and cooling capabilities Addition of 6-10% surfactant on resin generates emulsion with stable droplet size Surfactant is preferably mixed with resin at emulsification temperature for 1-2 hours before starting water addition Optimum temperature of emulsification depends on resin viscosity Water should be kept at emulsification temperature and added slowly and gradually Slow speed mixing giving axial flow is recommended; Intermig impeller shown Emulsion should be cooled down to ambient temperature while stirring before drumming *How to Formulation guide provides detailed information on equipment
16 Going waterborne Emulsifier selection Our leading edge alkyd emulsifiers, product offerings: Maxemul 7101, nonionic polymeric emulsifier, 100% a.i. All long & medium oil alkyds, up to emulsification temp. to 85 C Maxemul 7102, nonionic polymeric emulsifier, 100% a.i. For high temperature emulsification close to 100 C Maxemul 7201, anionic emulsifier, 100% a.i. Oil soluble, most versatile, up to emulsification temp. to 85 C
17 Going waterborne the role of the surfactant The role of the surfactant Interfacial tension reduction Facilitates droplet formation Stabilisation of formed polymer particles Protection against coalescence Control of shelf life Limitations of conventional surfactant technology Poor affinity to the oil/water interface Risk of preferential adsorption in pigmented systems High surfactant levels are required Desorption upon dilution Plasticization of film surface, poor blocking resistance, dirt pickup Lower efficiency of associative thickeners
18 Volume (%) VOC compliant alkyds alkyd emulsions stability Conventional long oil alkyd resin, 60% oil length and acid value < 10 mg KOH/g Stability monitoring via particle size measurements (Static laser light scattering) upon storage Formulation pbw Resin 50 Water 46.8 KOH (85%) 0.15 Maxemul Maxemul Total 100 Particle size (nm) d(0.5) d(0.9) Initial m/RT m/40 C m/50 C Particle Size Distribution Particle Size (µm) after 3 months aging at 50 C - Average, woensdag 16 oktober :21: after 3 months aging at 40 C - Average, woensdag 16 oktober :14: after 3 months aging at RT - Average, woensdag 16 oktober :09: Average, woensdag 3 juli :52:30
19 Waterborne alkyd paint formulation High gloss trim paint Matt wall paint Direct benefits over alternatives Improved gloss Improved drying times Cost effective Meeting VOC directives
20 High gloss trim paint starting formulation Low VOC high gloss trim paint starting formulation Grind Wt % Type Supplier 1. Demin. water 7.5 Carrier 2. Tego Airex 901W 0.3 Anti-foam Evonik 3. Zephrym PD Pigment dispersant Croda 4. Dupont TiPure R Pigment Dupont 5. Borchigel L75N (1:1 in water) 0.2 Rheology modifier OMG Borchers Let down 6. Alkyd emulsion 53 % solids 56.8 Binder* Croda 7. Dehydran Anti-foam BASF 8. Byk Levelling /flow Byk Chemie 9. Octa-Soligen 421 Aqua 1.8 Drier OMG Borchers 10. Rheolate Rheology modifier Elementis 11. Borchigel L75N (1:1 in water) 0.4 Rheology modifier OMG Borchers 12. Demin. water 2.7 Total 100 Physical properties VOC (g/l) 4.5 Vol. Solids (%) 41.3 PVC (%) 19 Krebs Stormer viscosity (K.U.) 93 High Shear Viscosity C&P (10,000s -1, 25 C) (mpa.s) 230 * Alkyd emulsion binder based on Croda Maxemul polymeric surfactants
21 Viscosity (mpa.s) High gloss trim paint wet film properties Excellent tropical storage stability and superior drying time vs solvent borne enamel Rheology after tropical storage BK Drying times, 1w/23 C 2,000 1,800 1,600 1,400 1,200 1, Shear rate (1/s) Initial 8 wks 50 C Solventborne enamel 2 Solventborne enamel 1 WB enamel Cobalt combi-drier WB enamel-iron complex drier Time (h) leveling basic trace rippled film surface trace The SB references are commercial VOC compliant high gloss trim paints, <300g/l VOC
22 Gloss units High gloss trim paint dry film properties Early water spot resistance (24 hrs), no damage after 3 hrs water spotting Gloss comparable to commercial SB enamel Good hardness development Gloss (initial) WB enamel-iron complex drier WB enamel Cobalt combidrier Solventborne enamel 20 60
23 Flat wall paint starting formulation Low VOC flat wall paint starting formulation Grind Wt % Type Supplier 1. Demin. water 17 Carrier 2. Propylene Glycol 0.7 Solvent 3. AMP Neutralizing agent DOW 4. Orotan 731-A-ER 1 Pigment dispersant DOW 5. Nuosperse FN Pigment dispersant Elementis 6. Byk Anti-Foam Byk Chemie 7. TiPure R Pigment Dupont 8. Omya Carb 5-GU 25.8 Filler Omya 9. Omya Carb 2-GU 17.9 Filler Omya 10. SteoPac 4.6 Filler Imerys 11. Natrosol HHBR (2% in water) 13.5 Rheology modifier Ashland Let down 12. Alkyd emulsion 53% solids 10.6 Binder* Croda 13. Byk Anti-foam Byk Chemie 14. Octa-Soligen 421 Aqua 0.3 Drier OMG Borchers 15. Natrosol HHBR (2% in water) 2 Rheology modifier Ashland Total 100 Physical properties VOC (g/l) 13.1 Vol. Solids (%) 37.6 PVC (%) 79.6 Specific gravity (g/ml) 1.55 * Alkyd emulsion binder based on Croda Maxemul polymeric surfactants
24 Flat wall paint - washability Tested according to DIN A 180µm wet film applied on black leneta chart Dried for 7 and 28 days at 23 C and 50% R.H. The film is continuously wetted with a 0.25% NaDBSA aqueous solution at 60cc/h Scrubbed with a pig bristles brush The nr of cycles is recorded when the paint is removed over 2 continuous strokes of over 100mm length Washability after 7d drying: cycles (L) Washability after 28d drying: >5000 cycles (R)
25 Conclusion Improved performance versus high solid alkyd paint No solvent emissions at workplace No alkyd resin development required / minimal investment costs Cost savings from solvent elimination Formulation of low to zero-voc coatings, excellent shelf life, easy to handle and apply Maxemul TM 7101 Maxemul TM 7102 Maxemul TM 7201 Polymeric nonionic surfactant Polymeric nonionic surfactant Polymeric anionic surfactant
26 What is available from Croda? Formulation Support Formulation Guides including dos and don ts Product Literature E-Seminars For more information, please contact us or visit our website at
27 Maxemul 9107 Cost effective solution for Low to Zero VOC liquid epoxy emulsions
28 Epoxy resins Binders for 2K protective coatings Used for: Chemical resistance Corrosion protection Adhesive strength Used with e.g. polyamine or polyamide hardeners Formulation flexibility Wall paints with enhanced chemical resistance Application areas Heavy duty flooring Composites Adhesives Direct-to-Metal Coatings
29 Epoxy resins in liquid paints Liquid epoxy Low MW epoxy resin, liquid at ambient conditions Highly crosslinked network after curing Zero to low VOC paints Excellent chemical resistance Very hard coating, brittle, poor crack resistance Application areas: Flooring, wall coatings Solid epoxy Low MW Type-1 solid type epoxy Lower density network Traditionally High VOC Good adhesion to metal Better flexibility Application areas: Direct-tometal coatings
30 The trend towards epoxy emulsions Legislation EU Deco paints directive Solvent emission directive Indoor air quality Cost effectiveness Solvent replacement, time saving (application on wet concrete), overcoatability Performance improvement Consistent quality, application ease Storage stability
31 Current water-based epoxy solutions Hardener stabilised water-based coating Water soluble hardener is used as emulsion stabiliser Skilled labourer required to prepare epoxy formulation Reproducibility issues Limited to liquid epoxies combinations with reactive diluents Commercial water-based epoxy emulsions Limited shelf life, challenging logistics Limited formulation flexibility
32 Water resistance Hardener stabilised formulation vs epoxy emulsion paint Epikote 828 O/W emulsions cured with Anquawhite 100 or Anquamine 721 Hardener stabilised, surfactant free reference paint Epikote 828/Anquamine 721 Films are dried for 1 week at ambient and immersed in water for 1w Emulsion based paint: films are slightly hazy, Defect free film with Anquawhite 100, some blisters with Anquamine 721 Hardener stabilised, surfactant free reference paint: blistering after 1h exposure to water. Hardener stabilised WB epoxy paint Established technology Film integrity depends on quality of mixing. Poor water resistance Water-based epoxy emulsions Surfactant stabilised Reproducibility, formulation flexibility, cost control
33 Maxemul TM 9107 Polymeric epoxy resin emulsifier Maxemul 9107 allows formulation of low to zero VOC epoxy emulsions: Versatile emulsifier for liquid, type-1 solid and solid-liquid blend epoxy emulsions Cost effective emulsifier Emulsions with enhanced storage stability No negative effect caused by surfactant on final film properties Good Chemical Resistance, Water Resistance
34 Choosing the right formulation Formulation A Low speed mixing (25 C) Pitch blade impeller Enhanced stability Formulation B Heating and cooling facilities (95 25 C) Enhanced stability Toughened film Formulation C Liquid Epoxy Resins High speed mixing (60degC) Cowles disc Formulation D Formulation E Without heating facility Enhanced Stability Formulation F Solid Epoxy Resins Solid/Liquid 50:50 Blend Epoxy Resins With heating facility With heating facility Formulation G Formulation H
35 Formulation advice Emulsification advice Reaction vessel with heating and cooling capabilities preferred* Addition of 5-10% surfactant on resin generates emulsion with stable droplet size Surfactant is preferably mixed with resin at elevated temperatures ( C) for 1-2 hours before starting water addition Optimum temperature of emulsification depends on resin viscosity Water should be kept at emulsification temperature and added slowly and gradually Slow speed mixing giving axial flow is recommended; Intermig impeller shown Emulsion should be cooled down to ambient temperature while stirring before drumming Formulation advice Dry film properties will depend largely on the hardener choice *How to Formulation guide provides detailed information on equipment
36 Ask for our guide formulations for more details! 36
37 Maxemul 9107 EU 10/2011 Food Contact Approvals FDA (adhesive application), , Individual statements are available upon request
38 Maxemul 9107 registration Country Compliant Country Compliant Europe Y Australia Y China Y South Korea Y USA Y Canada Y Japan Y Philippines Y
39 Maxemul Polymeric surfactants for high quality, low and VOC free resin emulsions Maxemul 5000/6000 Maxemul 7000 Maxemul 9107 Non-migratory surfactants in heterogeneous free radical polymerisation for acrylic, styrene acrylic, VAM systems Polymeric surfactants for alkyd Emulsions in VOC free alkyd paints Cost effective solution for Low to Zero VOC epoxy emulsions
40 Thank you! Contact: Yash Singh, Croda Australia Jonathan Huang, Croda Singapore,
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