Formulating cost-efficient & low to zero VOC alkyd based coatingsusingpolymeric surfactants technology

APAC Coatings show, JakartaJune 23-24th, 2010 J. Grade, Application Manager Croda Coatings and Polymers

Croda is a leading global supplier of speciality chemicals Personal care Lubricants Polymer additives Crop care Homecare and cleaning Coatings and Polymers

Coatings and Polymers product offerings Building blocks from oleochemical and synthetic origin for

condensation polymerisation Surfactants used as process aids during resin manufacture Surfactants as formulation aids Surfactants in alkyds and alkyd based coatings

Croda Plc

Alkyd resins

Popular binders for wood and metal protective coatings

Simple chemistry, Fatty acid modified polyesters Well established, long history Excellent balance between cost/performance High gloss finish/ Excellent protective properties Largely from renewable resource

Solvent-borne

VOC compliant alkydsDrivers for change

Origin Organic solvents are flammable Organic solvents catalyse photochemical synthesis of ozone in lower

regions of the atmosphere. OPS (Organo Psycho Syndrome), irreversible damage of the short

term memory.

Change driven by legislation (e.g.Deco paints directive) Distribution sector (safety, green image, carbon footprint)

EEC directive 2004/42/CE VOC or Decorative Paints directive Stricter VOC - regulations (Volatile Organic Compounds) at EU level Further amendments expected for 2013 - 2015

More stringent national regulations Indoor air quality

Maximum VOC content limit values for paints and varnishes (EU)

(*) DIRECTIVE 2004/42/CE OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 21April 2004; annex II

Technology options

Conventionalalkyd

Solventbornealkyds

Waterbornealkyds

Water reduciblealkydsHigh solids alkyds

Urethane modified alkydsWater in oil alkyds

Alkyd emulsions

Jan 2010

Technology options

Conventionalalkyd

Solventbornealkyds

Waterbornealkyds

Water reduciblealkydsHigh solids alkyds

Urethane modified alkydsWater in oil alkyds

Alkyd emulsions

Jan 2010

Drawbacks of high solids alkyds

Softer filmsFaster yellowingSlow drying

Higher cost

VOC compliant alkydsWater in oil alkyds

0%10%20%30%40%50%60%70%80%90%

100%

Conventional High solids W/O alkyd

watersolventalkyd

Partial replacement of solvent and/or resin with water

W/O alkydSurfactant stabilised

Water+ Surfactant

Pigments

Polymer

LoVOCoat polymeric W/O stabilisers

LoVOCoat Form 100/ LoVOCoat Stable 100 Surfactant/co-surfactant combination Liquid products, 20% active matter Recommended ratio Form100/Stable 100 60:40 Recommended concentration 15.5% min. on water

Use of polymeric surfactant combination guarantees

Fine droplet sizeAn excellent shelf life and tropical storage without phase separationHigh water loading with low formulation viscosityMinimal effect on flow, drying time or dry film properties

LoVOCoat the W/O concept starting formulation

W/O alkydRef Ref 06.33.045Formulation Water (1% MgSO4) 31

LoVOCoat Form 100 3.05LoVOCoat Stable 100 1.95Long oil alkyd, 78% in Exxsol D40 64

Properties Brookfield viscosity (mPA.s) 4200Particle size (nm) 350Storage stability

40C 5m55C 3m

Surfactants supplied as 20% solutions Recommended surfactant level min. 3.1% active matter, 15.5% as is on dispersed water phase Recommended ratio LoVOCoat Form100:LoVOCoat Stable 100 60:40 Excellent storage stability, even at higher temperatures Viscosity reduction vs high solids alkyd (formulations above use the same conventional alkyd) Optimisation of emulsification conditions is key to guarantee a small droplet size

LoVOCoat the W/O concept

Via direct emulsification

The emulsifiers are dissolved in the oil phase. A watersoluble salt or polymer is added to the water as osmotic pressure regulator Water is added to the oil phase with high shear stirring, a water in oil emulsion is formed Typical surfactant level, down to 3% surfactant, active matter on dispersed water phase Emulsification using high mechanical shear or low speed emulsification in a viscous continuous

phase

Water phase

Resin phase

LoVOCoat Water incorporation strategies

Water in solvent pre-emulsion

Let downMixing at low shear with finished paint

Water in alkyd pre-emulsion

Let downMixing at low shear with pigment concentrate

Water in pigment concentrate

Let downMixing at low shear with remaining alkyd

Rotor stator mixer Dissolver Dissolver

LoVOCoat Polymeric surfactants for W/O emulsion stabilisation

Low MW hydrophobes,C18max Weak hydrophylic interaction,

easy desorption

Polymeric hydrophobe Strong hydrophylic interaction, irreversible

adsorption, thick steric barrier

Pigment

Conventional surfactant Polymeric surfactant

Pigment

W/O alkydsEffects of stabiliserLoVOCoat vs conventional W/O technology

Effects on viscosity

0

2000

4000

6000

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10000

12000

20% 25% 32.60%

Water content (%)

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LoVOCoatConventional

Effects on formulation stability (40C)

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20% 25% 32.60%

Water content (%)S

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LoVOCoatConventional

W/O emulsions with polymeric surfactant technology have significantly lower viscosities and better shelf life vs oligomerics. All formulations have 50% L.O.Alkyd, from 20 to 32.6% of a 1% MgSo4 solution, 8% surfactant on water and Exxsol D40 to the balance

LoVOCoat stability >16W

W/O alkydsEffects of stabiliserLoVOCoat vs conventional W/O technology

W/O emulsions with polymeric surfactant technology have significantly lower viscosities and better shelf life vs oligomerics. All formulations have 50% Polymer solids, approx. 20% water in oil, 3.1% stabiliser active matter on water (1% MgSO4)

Approx. 50% polymer20% W/O emulsionLoVOCoat, 3.1% a.m.30d at 50degC

Approx. 50% polymer20% W/O emulsionComp., 3.1% a.m.7d at 50degC

W/O alkyd formulationsEffects on rheology

Flow properties are unaffected with up to 25% water incorporated (resin dependent). All formulations have 50% L.O.Alkyd, from 20% of a 1% MgSo4 solution, 8% surfactant on water and Exxsol D40 to the balance (cone & plate rheometer)

W/O alkyd formulationsEffects on rheologyLoVOCoat vs conventional W/O technology

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0.01 0.1 1 10 100 1000

Shear rate, log(1/s)

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Conventional

LoVOCoat

Oligomeric stabiliser shows viscosity increase at low shear rates which will affect levelling of the coating. LoVOCoat technology only shows this rheology at high water loading (32% and high surfactant level (8% on water). All formulations have 50% L.O.Alkyd, 20% of a 1% MgSO4 solution, 8% surfactant on water and Exxsol D40 to the balance

Drying times

Measured with a BK drying time recorder at standard conditions, 23C, 50% R.H.

Leveling basic trace - rippled film - surface trace - dry

W/O alkyd formulationsEffects on drying time, clearcoat

0 2 4 6 8 10

Reference

W/O alkyd8% surf

W/O alkyd6.2% surf

W/O alkyd3.1% surf

Conv. 8%

levellingbasic traceripped filmsurface trace

BK drying time (hrs), 50% alkyd, 32% water, 3.1 to 8% surfactant, active matter on dispersed waterphase, solvent to the balanceOnly moderate increase; stabilisers have no effect on drying; slower drying for oligomeric stabiliser

W/O alkyd formulationsEffects on dry film properties

Hardness Gloss 60 TransmittanceSurf conc Process 4W 4W 4W

- reference 21 96 93,38 W/O alkyd 18 97 92,6

8% surfactant, active matter on dispersed water phaseKonig hardness, gloss and transmittance measuredThe transmittance measurement on the clear film is a measure of its transparency. It is the ratio of transmitted light to the incident light.

W/O alkyd formulationsEffects on drying time, Formulations

Cetol TGL Plus (Akzo), varnish, 440g/l VOCResults show a reduction in drying time with water added!

Brookfield Viscosity(DV-II, 30rpm, spindle 18 Ambient)

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50

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200

250

0% water 10% water 20% water

m

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Visco 24hrs RT Visco 1 week RT Visco 1 week 50 C

BK drying time (ASTM 5895), hrs

1) Sikkens Cetol TGL Plus

0 2 4 6 8 10 12

0% water

10% water

20% water

leveling basic trace ripple surface trace

W/O alkyd formulationsEffects on drying time, Formulations

Rubbol AZ PLUS, white pigmented high gloss trim paint (Akzo)Results show a reduction in drying time with water added!

Brookfield Viscosity(DV-II, 30rpm, spindle 18 Ambient)

0

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300

400

0% water 10% water 20% water

m

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Visco 24hrs RT Visco 1 w eek RT Visco 1 week 50 C

BK drying time (ASTM 5895), hrs

0 2 4 6 8 10 12 14

0% water

10% water

20% water

leveling basic trace ripple surface trace

W/O alkyd formulationsEffects of ageing on drying time

Rubbol AZ plus High Gloss Finish (Max 300 g/ l VOC)

0,00 2,00 4,00 6,00 8,00 10,00 12,00 14,00

0% w ater

20% w ater

0% 8 w k 50C

20% 8 w k 50C

Time (hrs)

levelingbasic traceripplesurface trace

Rubbol AZ PLUS, white pigmented high gloss trim paint (Akzo)Ageing at elevated temperatures causes a moderate increase in drying time

W/O alkyd formulationsEffects of formulation ingredients

PVC (%) 13.66 14.43 14.43Volume solids (%) 64.78 51.15 49.88VOC (g/l) 258.46 224.40 239.23

Ti-Pure R-902+ 30.49 25.71 25.20Lovocoat Form 100 3.01 2.53 2.48Exxsol D40 12.28 10.36 10.15

Uralac HS233 Q-85 52.22 41.32 40.49Lovocoat Form 100 0.00 1.56 1.53Lovocoat Stable 100 0.00 1.00 0.98

Water, 1% MgSO4 0.00 16.09 15.77Octa-Soligen 141 Z 1.77 1.25 1.22MEKO 0.23 0.18 0.17Butylglycol 0.00 2.00Total 100.00 100.00 100.00

W/O alkyd formulationsEffects of formulation ingredients

Zephrym 3300B, no water

LoVOCoat Form 100, 16% water

LoVOCoat Form 100, no water

LoVOCoat Form 100, 16% water, 2% BG

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5Pa.s

0 100 200 300 400 500 600 700 800 1.0001/s

Shear Rate.

US 200 plate/plate Rheometer, MP 31 (50mm,0) d=1 mm

Resin free grind, surfactant stabilisedZephrym 3300B (anionic) or LoVOCoat Form 100 (polymeric)15% PVC, approx. 65 vs 50% volume solidsButylglycol for further viscosity reduction

W/O alkyd EmulsifiersPerformance benefits

LoVOCoat polymeric surfactant technology Allows for high water level incorporation Excellent tropical storage stability With minimal impact on drying rate and dry film properties

Formulation of VOC compliant alkyd based coatings Based on conventional SB alkyds No resin development required Complementary to HS alkyd development Improved drying time for HS alkyds Formulation flexibility Cost savings without compromise

Technology options

Conventional alkyd

Solventborne alkyds

Waterborne alkyds

Water reducible alkydsHigh solids alkyds

Urethane modified alkydsWater in oil alkyds

Alkyd emulsions

Jan 2010

Please visit our website at www.crodacoatingsandpolymers.com

Technology options

Conventional alkyd

Solventborne alkyds

Waterborne alkyds

Water reducible alkydsHigh solids alkyds

Urethane modified alkydsWater in oil alkyds

Alkyd emulsions

Jan 2010Water reducible alkydsPoor shelf life, hydrolysis in the canPoor barrier propertiesLow polymer solids

Urethane modified alkydsGood shelf lifeHard filmsExpensive

Alkyd emulsions

0%10%20%30%40%50%60%70%80%90%

100%

Conventional High solids Alkyd emulsion

watersurfactantsolventalkyd

Total replacement of solvent with water

Alkyd emulsionSurfactant stabilised

Alkyd emulsions

Developing alkyd emulsions using external emulsifiers

The technology offers the following performance benefits: Conventional alkyd resins can be used

Emulsification rather then diluting in solvent No polymer development required No co-solvent required Higher polymer solids (>50%)

Cost savings from solvent elimination

Preferred production method: The phase inversion technique Stirred pot, low stirring speed Low investment cost, low energy cost

Going waterborneSimple emulsification process

Procedure The emulsifiers are preferably

dissolved in the resin phase. Water is added to the oil phase

while stirring -> formation of a W/O emulsion.

After reaching the inversion point (surpassing viscosity maximum): spontaneous inversion from a W/O to an O/W emulsion upon further addition of water.

O / W

Water phase

Oil phase

Going waterborne 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 Plasticization of film surface Lower efficiency of associative thickeners

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 85C

Maxemul 7102, nonionic polymeric emulsifier, 100% a.i. For high temperature emulsification close to 100C

Maxemul 7201, anionic emulsifier, 100% a.i. Oil soluble, most versatile

Going waterborne Formulation optimisation

Emulsions stabilised by a combination of anionic and nonionic polymeric emulsifier Process and formulation optimisation is critical for succesful formulating

Anionic/nonionic surfactant ratio Surfactant level on resin, 6% on resin on average Neutralisation of the resin Stirring speed, approx. 250-300rpm and stirrer design Emulsification temperature, dependent on resin viscosity Speed of water addition

Emulsions have excellent storage stability, >2 yrs at ambient temperature No compromise on dry film properties

alkyd emulsionpbw

Long oil alkyd 50-55KOH relative to A.V.Surfactant 5-8% on resinWater up to 100

VOC compliant alkyds Alkyd emulsions, particle size

Medium oil alkyd emulsion Particle size after 1 month ageing at 40 and

50degC

Particle Size Distribution

0.01 0.1 1 10 100 1000 3000 Particle Size (m)

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20673-77/1 ~40 1 month, 08 October 2007 14:21:5120673-77/1 ~50 1 month, 08 October 2007 14:16:2020673-77/1 ~RT 1 month, 21 September 2007 11:14:00

pbw Resin 47.17Water 49.77KOH 0.23 Maxemul 7101 1.42 Maxemul 7201 1.42

VOC compliant alkyds Alkyd emulsions, dry film properties

Beck Kller drying time recording Conventional solventborne alkyd vs alkyd emulsion

Set Time

Touch Dry

Through Time

Discon-tinuous Track

Final Through Time

%Cobalt Stage1 Stage2 Stage3 Stage4 Stage

5

Solventborne 0.02

VOC compliant alkyds Alkyd emulsions, dry film properties

Konig hardness development Conventional solventborne alkyd vs alkyd emulsion

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Conventional solventborne alkyd coating

Non-VOC water bornealkyd coating

Going waterborne - the Maxemul benefits Maxemul advanced surfactant technology for alkyd resin emulsification

allows for total elimination of solvents in water borne alkyd based coatings No compromise on performance versus conventional alkyd coatings No solvent emissions at workplace No alkyd resin development work required Minimal investment costs Cost savings from solvent elimination Formulation of zero-VOC coatings, easy to handle and apply

Please visit our website at www.crodacoatingsandpolymers.com