Effect of Low Voc Coalescents on Film Formation, Dirt Pickup Resistance and Surfactant Leaching of Waterborne Paints Agenda

EFFECT OF LOW VOC COALESCENTS ON FILM FORMATION, DIRT PICKUP RESISTANCE AND SURFACTANT LEACHING OF WATERBORNE PAINTS AGENDA

OXITENO

TRENDS FOR ARCHITECTURAL COATINGS

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IMPORTANT TRENDS

WATERBORNE ARCHITECTURAL COATINGS

GHS VOC LOW APE-free Improve short-term and Deep Colors Compliance Reduction Odor long-term performances CHALLENGES FOR ARCHITECTURAL COATINGS

HIGH VOC LOW VOC COALESCENT COALESCENT OBJECTIVE

Develop a low VOC coalescent that alows...

↑ Hardness Evolution ↑ Manter propriedades Dirt Pickupimportantes ao longo da vida útil como cor, brilho e resistência á agua . OBJECTIVE

Develop a low VOC coalescent that maximizes LATEX FILM FORMATION

STAGE I STAGE II

STAGE III

MECHANICAL WATER WET SCRUB LEACHING PROPERTIES RESISTANCE RESISTANCE RESISTANCE QUESTIONS

Can low VOC coalescents enhance final film formation ?

Can low VOC coalescents generate paints with dirt pickup resistance as good as high VOC coalescents ?

Can coalescent reduce surfactant leaching of paints ? OXITENO LOW VOC COALESCENT´S PROPERTIES COALESCENT PROPERTIES

Coalescents Boiling Point Chemical nature: Aliphatic Ester

Oxiteno´s New 100% Renewable Coalescent 283°C Carbon

Polarity: Coalescent 1 254°C Hydrophobic 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate

Coalescent 2 344°C

Tri(ethylene glycol) bis(2-ethylhexanoate) VOC REGULATIONS

OXITENO ´S NEW COALESCENT 2 VOC CONCEPT TESTING REGULATIONS COALESCENT 1 COALESCENT METHODS 250 °C 2004/42/EC 0% 0% 0%

Boiling 280 °C GC 100% 0% 0% Point Green Seal

340 °C 100% 100%* 0% SCAQMD M313

Ozone US EPA (Aerosol 0.8 g O /g Reaticvity Formation Paints) 3 0.6 g O 3/g NA

Volatility Method 24 US EPA 100% 50% 0%

*Evaluation on going. SOLUBILITY IN WATER OXITENO´S LOW VOC COALESCENT

Property Value Partition coefficient in 4 octanol/water HANSEN SOLUBILITYPARAMETERS OXITENO´S LOW VOC COALESCENT

4δ δ δ δ +δ δ

R0 : radius of solubility sphere of polymers

RED = Ra/R 0 RED: Relative energy difference

LATEXES RED Values Styreneacrylic latex 0.9 R0 Acrylic latex 0.9 Vinyl acrylic latex 0.8

RED < 1 means that coalescent has high affinity with the polymers within latexes LATEX FILM FORMATION

STAGE I

STAGE II Continuous Transparent film T > Tg wet MFFT ↓↓↓ Mechanical resistance

Smooth film STAGE III No particle domains T > Tg dry ↑↑↑ Mechanical resistance EFFECT OF COALESCENT ON LATEX FILM FORMATION

Latex Particles Latex Particles + Coalescent MFFT Tg

STAGE II T > MFFT

STAGE III

T > Tg dry MINIMUM FILM FORMATION TEMPERATURE (MFFT)

Cold Hot 0°C 20°C

STAGE I T > MFFT STAGE II

Brittle film Continuous and transparent film EFFECT OF COALESCENT CONTENT ON MFFT

ACRYLIC LATEX

Coalescent 1 Coalescent 2 New Coalescent 20 15 10

MFFT MFFT (°C) 5 0 0 2 4 6 8 10 -5 Coalescent Content (php) EFFECT OF COALESCENT CONTENT ON MFFT

STYRENE-ACRYLIC LATEX

COALESCENT 1 ULTRAFILMLOW VOC COALESCENT 5000 25

MFFT(°C) 5

0 0 1 2 3 4 5 -5 Coalescent Content (wt%) ATOMIC FORCE Tapping Mode™ AFM MICROSCOPY (AFM) Laser Detector Oscilation response Cantilever + TIP Piezo Feedback Oscilation Driver

STAGE II Transparent T > Tg wet Continuous Film MFFT ↓↓↓ Mechanical resistance

STAGE III Smooth film No particle domains T > Tg dry ↑↑↑ Mechanical resistance AFM ACRYLIC LATEX WITHOUT COALESCENT

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days

Acrylic latex: MFFT ~ 17°C and Tg ~ 29°C AFM ACRYLIC LATEX + 6 php COALESCENT 1

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days AFM ACRYLIC LATEX + 6 php COALESCENT 2

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days AFM ACRYLIC LATEX + 6 php NEW COALESCENT

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days AFM OVERVIEW

New Coalescent 1 Coalescent 2 Properties Pure Latex Coalescent BP~254 °C BP~344 °C BP~283 °C

3D image

Are particle contours Yes Yes Yes Yes visible? Maximum height difference 35 20 12 12 (nm) Average height (nm) 22 10 7 7 Average roughness (nm) 3.5 2.6 1.1 0.9 Quadratic mean roughness 4.3 3.3 1.3 1.1 (nm) AFM STYRENE-ACRYLIC LATEX

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days

StyreneAcrylic latex: MFFT ~ 21°C and Tg ~ 28°C AFM STYRENE-ACRYLIC LATEX + 10 php COALESCENT 1

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days AFM STYRENE-ACRYLIC LATEX + 10 php LOW VOC COALESCENT

Film cast on Leneta, dried at 25 ± 5°C, 60 % RH, 7 days AFM OVERVIEW

New Coalescent 1 Properties Pure Latex Coalescent PE~254 °C PE~283 °C

3D image

Are particle contours Yes Yes No visible? Maximum height 18 12 3 difference (nm) Average height (nm) 9.3 7.4 1.7 Average roughness 2.6 1.2 0.4 (nm) Quadratic mean 3.2 1.6 0.5 roughness (nm) DIRT PICKUP HARDNESS EVOLUTION ASTM D4366

ACRYLIC LATEX Semi-gloss paints, PVC 30, containing different coalescents

CompetitorCoalescent 1 1 CompetitorCoalescent 2 2 LowNew VOC Coalescent Coalescent 40

10 Number of Cycles 0 0 5 10 15 20 25 30 35 40 45

Drying Time (days) HARDNESS EVOLUTION ASTM D4366

ACRYLIC LATEX Semi-gloss paints, PVC 30, containing different coalescents

COALESCENT 3 NEW COALESCENT 40 Coalescent 3

30 Boiling Point 282ºC

20 2,2,4-trimethyl-1,3-pentanediol diisobutyrate

Number ofCycles Number 10

0 0 5 10 15 20 25 30 Drying Time (days) EVALUATION OF DIRT PICKUP RESISTANCE Oxiteno´s Internal Methodology

1° Step: Standard Dirt 2° Step: Paint Application 5° Step: ΕΕΕ 200 g Water 0.5 g dispersant Thickness: 150 m

50 g Fe 2O3 (red) Substrates: glass or leneta

40 g Fe 2O3 (yellow) Temperature: 25 ± 5°C

10 g Fe 2O3 (black) RU: 60 ± 5 % Drying Time: 740 days

4° Step: Dirt Removal 3° Step: Dirt Application

Thickness: 20 m Temperature: 25 ± 5°C RU: 60 ± 5 % Drying Time: 1 day

* Dantas, N. Y. S.; Manual Descomplicado de Tecnologia de Tintas, Blucher 2017. DIRT PICK UP RESISTANCE

Paints dried for ~ 40 days at 25 °C, 60% RH 30

Delta E Delta 10

0 Coalescent 1 New Coalescent Coalescent 2 LEACHING LEACHING

Definition:

– Extraction of soluble species

• Surfactants – Extraction of pigments

• “Snail trail” Latex Content LEACHING atr htfvu ecigi aebrepaints inwaterborne leaching favour that Factors orcaecneo ae particles latex of coalescence Poor content latex Low fillers and pigments of dispersion Poor species hydrophilic of Excess : PERMEABILITY OF LATEX FILMS

↑ Coalescence ↓ Water Permeability

Stage II T > Tg Stage III

Continuous and Coalesced Film Transparent Film

Vanderhoff et. al., J. Pol. Sci. 1973 , 41, 155174. EFFECT OF LOW VOC COALESCENT ON LEACHING

OXITENO´S LOW COALESCENT 1 VOC COALESCENT

> LEACHING EVALUATION Oxiteno´s Internal Methodology

1° STEP 2° STEP Paint preparation Immersion in water

Thickness: 400 m Water mass: 20 g Immersion time: 4h Substrate: leneta Temperature: 25 ± 5°C Drying time: 7 days Area: 25 cm² Surface tension: 72mN/m Drying temperature: 25 ± 5°C Temperature: 5 ± 2°C Drying time: 1 day

3° STEP 4° STEP

Measure surface tension of Measure the color difference of paints immersion water After immersion ΕΕΕ Before immersion SBB17 LEACHING Internal Methodology

STYRENE-ACRYLIC LATEX FORMULATION

54 PVC ~ 55 % 52

Latex ~ 20 % 50 48

Coalescent ~ 1 % 46 44

Viscosity: 125 +/- 5 KU Surface Tension (mN/m) 42 40 CONCORRENTECOALESCENT 1 1LOW ULTRAFILMVOC COALESCENT 5000 pH: 8.5 – 9.0 Coalescents

↓↓↓ Surface Tension ↔ ↑↑↑ Surfactant Extraction ↔ ↓↓↓ Leaching Resistance Slide 42

SBB17 Silmar Balsamo Barrios; 18/10/2019 LEACHING COALESCENT 1 Internal Methodology

STYRENE-ACRYLIC LATEX

Low VOC Delta E Coalescent 1

0 CONCORRENTECOALESCENTCompetidor 11 1 LOW ULTRAFILMULTRAFILM VOC COALESCENT 5000® 5000 Coalescents

↑↑↑ Delta E ↔ ↑↑↑ Water Permeability, Surfactant & Pigment Extractions ↔ ↓↓↓ Leaching Resistance LOW VOC COALESCENT

IN PAINT FORMULATIONS THICKENER DEMAND IN PAINTS Reduction in thickener demand in up to 20 wt% in comparison to COALESCENT 1

VINYL-ACRYLIC LATEX

Semi-Gloss Paints, PVC 30%

3,5%

3,0%

2,5%

2,0%

1,5% Thickener Content (wt%) 1,0% COALESCENTCOMPETITOR 11LOW ULTRAFILMULTRAFILM® VOC COALESCENT 5000 5000 WET SCRUB RESISTANCE SCRUB RESISTANCE – Flat Paint

STYRENE-ACRYLIC, ASTM D2486 FORMULATION 400 348 PVC ~ 52.5 % 283 300 Latex Content ~ 22.5 wt% 200 Coalescent~ 1 wt% 100 Number of Cycles Viscosity: 100 +/- 5 KU 0 CONCORRENTECOALESCENT 1 LOW ULTRAFILM® VOC COALESCENT 5000 pH: 8.5 - 9.0 Coalescents SCRUB RESISTANCE – Flat Paint

VINYL-ACRYLIC LATEX, ASTM D2486 FORMULATION 600 18% 6% 479 PVC ~ 55 % 500 398 375 391 Latex ~ 20 wt% 400

300

Coalescent ~ 0,5 -1,0 wt% 5 pcp 10 pcp5 pcp 10 pcp 200 Number of Cycles Viscosity: 125 +/- 5 KU 100

0 pH: 8.5 - 9.0 COMPETITORCONCORRENTECOALESCENT 11 1 LOW ULTRAFILM® VOC COALESCENT 5000 Coalescents SCRUB RESISTANCE – Semi-Gloss Paint

ACRYLIC LATEX, ASTM D2486 FORMULATION 300

PVC ~ 30 % 250 233

200 Latex ~ 35 wt% 177 150

Coalescent ~ 2 wt% 100 10 pp

Number of Cycles 50 Viscosity: 125 +/- 5 KU 0 COMPETITORCONCORRENTECOALESCENT 11 1 LOW ULTRAFILM VOC COALESCENT 5000

pH: 8.5 - 9.0 Coalescents CONCLUSIONS

Can low VOC coalescents enhance film formation?

OXITENO´S LOW YES! VOC COALESCENT COALESCENT 1

StyreneAcrylic Latex 10 php Coalescents

All Acrylic Latex 6 php Coalescents CONCLUSIONS Can low VOC coalescents generate paints with dirt pickup resistance as good as high VOC coalescents ?

YES! 205

154

103

Delta E Delta 2 5 1 0 CONCORRENTE 1 ULTRAFILM ® 5000 Competitor 1 LowOxiteno´s VOC LowCoalescent VOC Coalescent CONCLUSIONS Can low VOC coalescent reduce surfactant leaching of paints?

AFM Oxiteno´s Low COALESCENT 1 VOC Coalescent

YES!

55 5 4 50 3

Delta E Delta 2 45 1

Surface Tension Surface (mN/m) 40 0 Oxiteno´s Low COALESCENTCompetitor 1 1 ULTRAFILMOxiteno´s LoW VOC Low® 5000 CompetitorCOALESCENT 1 1 ULTRAFILM Low VOC ® 5000 VOCCoalescent Coalescent VOCCoalescent Coalescent THANK YOU VERY MUCH FOR YOUR ATTENTION ! Further questions: [email protected] [email protected]