New Innovations in Development of Di- and

Mono- Benzoates in Coatings Applications

Marianne Conner, William D. Arendt, and Emily L. McBride

Emerald Kalama Chemical, LLCKalama, Washington

NW Coatings FestOctober 8-10, 2014Hood River, Oregon

© Copyright October 2014, Emerald Kalama Chemical, LLC. All rights reserved.

2

Presentation Outline

• Background– Historic benzoate overview– New products

• Goal

• Evaluation– Initial benzoate introduction– Physical properties, volatility, and VOC’s– Interior architectural paint with higher MFFT polymers

• Partitioning– Most recent developments in interior paint – Update on exterior paint performance

• Recap

3

Historical Development

4

Benzoate Coalescent Development

Benzoates: non-phthalates, commercially available for decades for coatings and other applications

•Recently created dibenzoate platform was presented in Waterborne 2011 conference

850S - low VOC diblend of two dibenzoates

975P - low VOC type with lower freeze point than most diblends, broader range of compatibility in polar polymers

•Global products– On inventories in the US, EU, and numerous others

around the world

5

New Products• In 2013, commercialized:

500P - Lowest VOC of the line of dibenzoates. Proprietary blend of diethylene and dipropylene glycol dibenzoates.

• Introducing new monobenzoates for coatings:613 (3–Phenylpropyl benzoate) – Significantly lower

in VOC than TMPDMIB. Listed as a flavor additive in EU.

BOB (Benzyl benzoate) – Also significantly lower in VOC than TMPDMIB. Listed as a flavor additive.

6

Goal

• Review previously presented information:– Interior architectural paint with harder polymer – Exterior paint

• Introduce and discuss most recent results on new dibenzoate coalescents for use in coatings:– Interior architectural paint

Coalescent VOC’s

8

VOC Measurement

• In the US, EPA 24 is the guideline on VOC measurement method– ASTM D2369 oven volatility method (110ºC for 1 hour)– 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate

(TMPDMIB) is 100% volatile as is the diisobutyrate (TMPDMDIB)

• ASTM D6886 under revision:– A modified version of D6885– Future of ASTM D6886 use of methyl palmitate boiling

point marker (b.p. 319-321 at standard atmospheric pressure). Compounds eluting before considered VOC.

8

9

Coalescents Evaluated

• 975P: DPG/DEG/PGDB dibenzoate triblend

• 850S: Second generation dibenzoate binary blend

• 500P: Third generation dibenzoate diblend

• 613: 3–Phenylpropyl benzoate

• BOB: Benzyl benzoate

• TEGDO: Triethylene glycol di-2-ethylhexanoate, competitive low VOC coalescent, primary control

• TMPDMIB: 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate

10

Coalescent Properties

10

CoalescentBoiling Point,

°C at 5 mm Hg [760 mm Hg])

Vapor Pressure(mm Hg at 25°C)

Flash Point(°C)

TMPDMIB 110 [254] 1.3 x 10-2 120

TEGDO 160 [344] < 1 x 10-4 195

850S 180 [>330] 9.0 x 10-5 193

975P 215 [>350] 3.6 x 10-6 202

X-613 191 [337] 5.0 x 10-5 193

BOB 156 [320] 8 x 10-3 148

500P 236 [>350] 1.0 x 10-8 232

11

Coalescent Vapor Pressurevs. Boiling Point Curve

1

10

100

1000

1.90E-03 1.95E-03 2.00E-03 2.05E-03 2.10E-03 2.15E-03

1/T, T in Kelvin

Pre

ssu

re (

mm

Hg

)

TMPDMIB 975P 850S X-613 BOB 500P TEGDO

11

12

VOC, 110ºC for 1 HourASTM D-2369, Part of EPA 24

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Vo

lati

lity

, %

We

igh

t L

os

t

TMPDMIB TEGDO 975P 850S 500P X-613 BOB

13

Volatility by Thermogravametric Analyzer

VOC

14

VOC, ASTM D6886

0

10

20

30

40

50

60

70

VOC

VO

C, g

/L

Control 0 VOC1.5% Wt TMPDMIB1.5% Wt TEGDO1.5% Wt 975P1.5% Wt 850S1.5% Wt 500P1.5% Wt X6131.5% Wt BOB

0

0.5

1

1.5

2

2.5

VOC

We

igh

t %

Lo

st

15

Proposed Modification of ASTM D6886 GC VOC Method - Methyl

Palmitate BP Marker

0.0

0.5

1.0

1.5

% W

t

TMPDMIB

TEGDO

975P

850S

500P

X613

BOB 0

10

20

30

40

50

VO

C (

g/L

)

In California, South Coast Air Quality Management District (SCAQMD) is considering adoption of this method to quantify VOC. TMPDMIB, TMPDDIB and many other coalescents will be 100% VOC by this definition. (Draft Method 313) if set to this marker.

Boiling Point at atmospheric pressure of methyl palmitate: 417ºC, 332ºC and 319 - 321ºC.

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ASTM D6886with Methyl Palmitate Marker

X-613

Initial Coatings Evaluation

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First Experimental Protocol• Goal

Provide data to demonstrate the utility of the new benzoate triblend for coatings

• Formulations–Three polymers

Vinyl acrylic type: MFFT = 9ºC, Tg = 12ºCSoft acrylic for low VOC applications: MFFT = 8ºC, Tg = 7ºCHarder acrylic copolymer: MFFT = 28ºC, Tg = 31ºC

–Three paints • Flat based on vinyl acrylic:

Volume solids = 34.8%, PVC = 58%, VOC = 50 g/L

• Semigloss based on acrylic:Volume solids = 33%, PVC = 29.8%, VOC = 50

g/L

• Gloss based on harder acrylic copolymer: Volume solids = 35%, PVC = 18%, VOC = 160

g/L

19

Total Coatings’ VOC andCalculated Contribution of

Coalescents

0

10

20

30

40

50

Flat, Vinyl Acrylic Semigloss, Acrylic

VO

C's

(g/

L)

Total Paint VOC

TMPDMIB

TEGDO

975P

850S

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Experimental Protocols: Tests

• Wet paint and filming – Viscosity, rheology, heat stability, leveling, freeze/thaw, wet edge/open time, dry to touch, mud cracking

• Dry paint – Adhesion, scrub resistance, blocking, wet adhesion, dry adhesion, accelerated dirt pick up, contrast ratio, reflectance, color, gloss

Not all tests run for each evaluation. Not all tests discussed.

21

Semigloss PaintBlocking Resistance

0

1

2

3

4

5

6

7

8

9

10

1 Day RT 7 Days RT 1 Day 120°F 7 Days 120°F

Rat

ing

(0-

10)

TMPDMIB TEGDO 975P 850S

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Gloss Paint Scrub Versus Coalescent

Concentration

1500

1700

1900

2100

2300

2500

2700

2900

15 20 25 30 35 40

Scru

b Cy

cles

Pounds Coalescent/100 gallons

TMPDMIB850S975P

Next Step: Interior Architectural

Paint Based on a Harder Polymer

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Paint Formulation VariablesVinyl Acrylic Flat

Polymer, 7°C MFFT, 22°C TgVolume Solids = 38.1%PVC = 53 %

Coalescent level = 6 pounds/100 gallonsControl TMPDMIB Low VOC coalescents of 850P, 975P and TEGDO

Acrylic Semigloss Polymer, 17°C MFFT, 19°C TgVolume solids = 34%, PVC = 22%,

VOC = 150 g/LCoalescent level = 12 pounds/100 gallonsControl TMPDMB with 150 g/L formula adjusted to < 50 g/LLow VOC coalescent paints adjusted to < 20 g/L

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ResultsThe following tests were equal or similar to the control,

TMPDMIB, in both the flat and the semigloss:– Wet Adhesion (1 week, gloss alkyd), Viscosity, ICI, Flow &

Leveling.– Hiding, Freeze / Thaw - 3 Cycles, Dry-to-Touch Time. – Block Resistance

But there were some positive performance improvements – Illustrated in the following slides─ Scrub resistance─ Scrub resistance versus coalescent concentration─ Gloss development

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Vinyl Acrylic Flat PaintScrub Versus Coalescent

Concentration

800900

10001100120013001400150016001700

0 2 4 6 8 10

Scru

b Cy

cles

Pounds Coalescent/100 gallons

TMPDMIB850S975P

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Acrylic SemiglossScrub Versus Coalescent

Concentration

2000

2500

3000

3500

4000

4500

4 6 8 10 12

Cycl

es

Pounds Coalescent/100 gallons

TMPDMIB

850S

975P

28

0

1

2

3

4

5

6

7

8

9

10

1 Day RT 1 Day 120F 7 Days RT 7 Days 120F

Ratin

g

TMPDMIB

TEGDO

975P

850S

Acrylic Semigloss Block Resistance

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Acrylic Semigloss Gloss development

50

60

70

80

60º G

loss

TMPDMIB

TEGDO

975P

850S

New BenzoatesInterior Architectural Paint

Based on Hard Polymer

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Paint Formulation Variables

• Vinyl Acrylic Flat– Polymer, 7°C MFFT, 22°C Tg– Volume Solids = 38.1%, PVC = 52.8– Coalescents all at 6 pounds/100 gallons

• Acrylic Semigloss – Polymer, 17°C MFFT, 19°C Tg– Volume solids = 34%, PVC = 22%– Coalescents all at 12 pounds/100 gallons– Control TMPDMIB, 50 g/L formula– Low VOC paints, < 20 g/L formula

32

Total Coatings’ VOC and Calculated Contribution of

Coalescent

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Results

• The following tests were equal or similar to the control, TMPDMIB in both the flat and the semigloss for 500P, 613 and BOB:

– WPG, pH, Viscosity, ICI, Sag

– Contrast Ratio - 3 Mils, Reflectance, Freeze / Thaw - 3 Cycles, Dry To Touch Time

• But there were some positive performance improvements:

– VOC reduction

– Better leveling and wet edge in the flat

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Vinyl Acrylic FlatOpen-time / Wet Edge Rating

0

1

2

3

4

5

6

7

8

9

10

5 min 6 min 7 min 8 min 9 min 10 min 11 min 12 min

Open-time

Wet

Edge R

ating:

10,

excellent TMPDMIB

TEGDO

BOB

X-613

500P

Blank

35

Vinyl Acrylic FlatScrub Resistance

0

100

200

300

400

500

600

700

800

TMPDMIB TEGDO BOB X-613 500P

Coalescent

Cy

cle

s

36

Semigloss AcrylicOpen-time / Wet edge Rating

0

1

2

3

4

5

6

7

8

9

10

1 min 2 min 3 min 4 min 5 min

Open-time

Wet E

dge R

ating: 10, excellent

TMPDMIB

TEGDO

BOB

X-613

500P

Blank

37

Semigloss AcrylicScrub Resistance

1500

1600

1700

1800

1900

2000

TMPDMIB TEGDO BOB X-613 500P

Cyc

les

Exterior Paint Evaluation

Florida Fence Data to Date

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Exterior Paint Test Protocol• Goal

Determine the performance of commercial dibenzoate blends in exterior paint

• Formulations–Polymer – Two base polymer emulsions

Low VOC acrylic type: MFFT = 8°C, Tg = 7°CAll acrylic exterior type: MFFT = 11°C, Tg = 9°C

–PaintExterior flat - all acrylic exterior type polymer

Volume solids = 38.2% PVC = 46.0% Coalescent at 7.7 pounds/100 gallons for each (10% excess)

Exterior semigloss - soft low VOC acrylic polymer Volume solids = 33.7%

PVC = 29.8% Coalescent at 3.5 pounds/100 gallons for each

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Three Year Fence Data: South and North Vertical

• South Vertical, Southern Pine, Flat paints dried at 4.4°C– General appearance, mildew: TMPDMIB – 5.5, TEGDO – 6, 850S

– 7.5, 975P – 6– Dirt pick up: all rated 8.5 - 9

• North Vertical, Southern Pine, Flat and Semi-gloss paint dried at RT– Flats

• General appearance and dirt pick up: all 8’s

• Cracking/delamination: all are still rated 10

• Mildew: all >8

– Semigloss

• All 2’s for mildew and general appearance

• Cracking/delamination: all are still rated 10

• Dirt pick up: all 7’s

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Fence Data: South 45°

• 45° South– General appearance and mildew growth fell below 8 at 18 months– Dirt pickup fell below 8 after 24 months

Partitioning

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Partitioning• Factors affecting the rate of partition into the polymer particles

– Water-insoluble versus water-soluble coalescent types.– Tg of the polymer, hardness.– Type of surfactant present. – Mixing and temperature during incorporation.

• Protocol to determine partitioning:– Mix emulsion. – Add coalescent at level recommended. – Take MFFT at different time intervals.– Consider surfactants – effect on MFFT, particularly HLB value.

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Minimum Film Formation Temperature

0

1

2

3

4

5

6

7

Initial, 1 hour 1 Day 2 Days 3 day

MFFT (°C

)

TMPDMIB

TEGDO

KF850S

KF975P

Coalescents at 3% on the polymer emulsion, or 16 #/ 100 gallons, Polymer MFFT = 16°C.

46

Partitioning with 850Sin Styrenated Acrylic Emulsion

0

1

2

3

4

5

500 RPM 2000 RPM HLB = 17.6 HLB = 13.4 HLB = 8.7

15 min

1 Day

3 Day

7 DayMFFT,

°C

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Recap and ConclusionsLow VOC alternates by any method of test, the new dibenzoate

blends (975P, 850S and 500P) and monobenzoates (613 and BOB) function well in architectural paint versus a common low VOC plasticizer/coalescent

Specifically in paint properties– With dibenzoate blends, scrub and block resistance tests are the

same as or better than the high VOC coalescent films – Tough films

– Monobenzoates are listed as flavor additives and while higher in VOC than dibenzoates are still quite low

– Similar in other properties

Exterior exposure data does not expose any deficiencies in the paints with the dibenzoate blends

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NextArchitectural Coating

• In late-2013 - began exterior exposure series in flat and semigloss in Kalama, Florida, and Southeast Asia.

Control, 975P, 500P, 613, and BOB.

Industrial Maintenance Coating• First quarter 2014 – began evaluation for DTM primer

and topcoat. Control, 975P, 850S, 500P, and 613.

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Acknowledgements• Permission to publish by Emerald Kalama Chemical LLC, Ed Gotch,

CEO

• Debbie Davidson, Sarah Strother, Ian Query, Emily McBride, and Dan Marschall for data development

49

Some of the Emerald Kalama Research Staff

in front of the lab

Emerald Kalama’s Research and Applications Lab Building.

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Disclaimer

The information contained herein is believed to be reliable, however is based upon laboratory work with small scale equipment and does not necessarily indicate end-product performance. Because of variations in methods, conditions and equipment used commercially in processing these materials, Emerald makes no representations, warranties or guarantees, express or implied, as to the suitability of the products for particular applications, including those disclosed, or the results to be obtained. Full-scale testing and end-product performance are the responsibility of the user. Emerald Performance Materials shall not be liable for and the customer assumes all risk and liability for use and handling of any materials beyond Emerald’s direct control. Nothing contained herein is to be considered as permission, recommendation nor as inducement to practice any patented invention without permission of the patent owner.

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Test MethodsTest Reference/Method

pH ASTM E70

Stormer Viscosity ASTM D562

ICI Viscosity ASTM D4287

Contrast Ratio, Reflectance, and CIE Values ASTM D2805, E97, D2244 – 3 mil wet film over a Leneta 3B chart dried for 5 days. Contrast ratio is reflectance of black over reflectance over white.

Gloss and Sheen ASTM D2243 – 3 mil wet film on Leneta 3B chartdried for five days.

Low Temperature Coalescence Paint and equipment conditioned at 40°F for 2 hours. Paint drawn down on a Leneta Form HK to 6 mils wet. The films were dried horizontal for 24 hours and rated (see lab rating system below).

Thermogravametic Analysis (TGA) TA Q-500 TGA employed. Isothermal under air with a flow rate of 160 ml/minute. 5 mg sample size

VOC, Oven method EPA 24, D-2369, 3 ml toluene used with 0.3 g sample.

Lab Rating System 10= Excellent, 0= Very poor

VOC, GC method ASTM D-6886, post add of 1.5% coalescent to a commercial zero VOC paint

VOC GC method ISO 11890-2

Boiling point, atmospheric or reduced pressure

Reported values as available reported for reduced pressure or atmospheric pressure. Most of atmospheric extrapolated for reduced pressure data

Flow and Leveling ASTM D4062 – Leneta test blade used to apply paint. Dried paint rated.

Dry Adhesion ASTM D3359B – Paint was applied to dried aged alkyd with a brush and dried for 7 days before testing by cross hatch tape adhesion.

52

Test Methods ContinuedTest Reference/Method

Scrubbability ASTM D2486 – Paint applied at 7 mils wet to a leneta P121-10N chart and dried at room temperature for 7 days. A 10 shim was employed with abrasive media (SC-2). Failure was a continuous thin line at the shim.

Wet adhesion ASTM D6900 - A gloss alkyd (ICI / Devoe Devguard 4308-6650 Medium Green) was applied by drawdown and cured for 6 to 12 weeks at room temperature on a Leneta P121-10N scrub chart. A drawdown of the test paint was made perpendicular to the gloss alkyd and allowed to dry for 24 hours. The coating was then crosshatched into squares with sufficient pressure to cut the latex paint film but not enough pressure to cut the alkyd film. The test panel was soaked for 5 minutes in water. The panel was placed in the scrub machine so that the squares were in the path of the nylon brush. The % removed after 500 cycles were reported.

Sag resistance ASTM D-4400

Dirt pick up 3 mil of paint applied to aluminum panel and dried for 24 hours. Then it was placed in the QUV chamber for 7 days of exposure. The top half of the panel was covered up and the synthetic dirt was spread evenly over the un-covered portion. The panel was placed in a 120’ oven for 30 minutes. The panels were removed from the oven and the loose dirt was removed by tapping on the panel. The top portion of the panel was uncovered. The % Y reflectance of the tested part and the untested part were read. The % Y reflectance retained was reported. The higher the %, the better the dirt pick up resistance.

Porosity Ratio ASTM D3793 – A 6 mil applicator was used to apply paint film to white Leneta WB charts. The ambient (dried 7-Days) and low temperature conditioned at 40ºF (dried 48 hours) were stained with 10 mils of Leneta Staining Medium for 5 minutes. The stain was washed off with mineral spirits and then air dried 3 hours. The difference in porosity of the unstained and stained was calculated for each the ambient and 40ºF conditioned panels. The ratio of the porosities of the 40ºF to the ambient was calculated.

53

Test Methods ContinuedTest Method

Flow and Leveling ASTM D4062 – Leneta test blade used to apply paint. Dried paint rated.

Dry Adhesion ASTM D3359B – Paint was applied to dried aged alkyd with a brush and dried for 7 days before testing by cross hatch tape adhesion.

Wet Edge/Open Time Paint applied with notched drawdown bar on Leneta WB chart. At 1 minute intervals ¼ of 1” brush was dipped into the paint and brushed 10 strokes across the line. The wet edge was rated with the lab system.

Scrubbability ASTM D2486 – Paint applied at 7 mils wet to a leneta P121-10N chart and dried at room temperature for 7 days. A 10 shim was employed with abrasive media (SC-2). Failure was a continuous thin line at the shim.

Blocking Resistance ASTM D4946 – 3 mil wet films applied to Leneta WB chart and the films were dried for 7 days. Blocking was tested face to face at ambient and 120°F with a 1 Kg weight in place. The samples were separated and rated.

Color Acceptance Tinted paint (with 2 ounces/gallon black) drawn down at 3 mils. After one minute the paint is rubbed up in the unsealed area. The color acceptance is then rated.

Touch Up Touch up was tested with the paint prepared for the color acceptance. Self primed Upsom was used and applied with a Linzer 2”Bristle and polyester brush at RT and 40°F and allowed to dry overnight. The test paint was applied and rated for sheen uniformity and color difference.

Low Temperature Touch-Up(Brush over Roll)

ASTM D7489 – Wet tinted paint was roller applied onto 1 sq.ft. Upson Board panels, all conditioned in constant temperature environmental room and dried for 24 hours. For touch up, the paint, brush, and panel conditioned at 40ºF for 4 hours, and immediately 5 strokes vertical and 5 strokes horizontal of the conditioned paint were applied as second coat onto panel. Panel replaced into 40ºF and condition for additional 24 hours. ASTM Standardized Scoring System used to rate for visual and instrumental: Rating of 1 = Poor, 3 = Good, 5 = Excellent.

Mudcracking Paint was applied with a Leneta Antisag meter (14-60 mils) on an HK chart at ambient and 40°F. After 24 hour dry the greatest mils without cracking noted.

54

Test Methods ContinuedTest Reference/method

Freeze/Thaw ASTM D2243 – Frozen at 0°C and thawed at ambient. 3 cycles used.

Heat Stability ASTM D1849 – Tested at 120°F for two weeks.Initial and final viscosities taken.

Drying Time ASTM D1640 – 3 mil wet film applied to Leneta 3B, set to touch determined at ambient.