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Jo Ann Arceneaux, Ph.D.

Mi6ga6on of Oxygen Inhibi6on to

Improve the UV LED Cure Process

Acknowledgements: Dr. Steven Capelle, Dr. Xavier Deruy=ere, David Martel, Dr. Stefan Smeets, S@jn Vrijsen

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AGENDA

•  Introduc6on

•  Low Energy, Long Wavelength Cure Systems

•  Oxygen Inhibi6on of Free Radical Polymeriza6on

•  Mi6ga6on of Oxygen Inhibi6on

•  Experimental Results & Discussion

•  Conclusions

INTRODUCTION

•  Air contains 21% Oxygen

•  UV LED is Low Intensity and/or Long Wavelength Cure: Exaggerates Oxygen Inhibi6on Effect

•  Problems -  Tacky surfaces -  Reduced coa6ng proper6es

•  Typical solu6ons add 6me and cost: $$$$ -  Addi6onal UV cure with Hg lamp, typically end-‐of-‐line -  Thermal cure via non-‐free radical mechanism

-  Removal of uncured layer via solvent wipe

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LOW ENERGY CURE SYSTEMS

Mercury Lamp and LED Emission Spectra

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*courtesy of Phoseon Technology

OXYGEN INHIBITION OF FREE RADICAL POLYMERIZATION

UV Ini6ated Free Radical Polymeriza6on

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OXYGEN INHIBITION OF FREE RADICAL POLYMERIZATION

Reac6ons of Oxygen in UV ini6ated Free Radical Polymeriza6on

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MITIGATION OF OXYGEN INHIBITION

Methods

•  Use chemicals that react with the peroxy radicals -  Easily abstractable hydrogens

!  Thiols: EBECRYL® LED 02

!  Amines: EBECRYL 80, 81, 83

!  Ethers: EBECRYL 8811, 8807, 5849 (5781)

!  Combina6ons of above

-  Acrylated compounds for improved performance !  Reduced migra6on/blooming !  Lower odor

March 14, 15 7

EXPERIMENTAL RESULTS & DISCUSSION

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UV LED Surface Cure with and without Thiol

Component %

EBECRYL® 1291 (6 func6onal urethane acrylate) 55 55 55

Dipropylene glycol diacrylate; dilu6ng monomer (DPGDA) 20 20 10

EBECRYL 853 (3 func6onal polyester acrylate) 25 -‐-‐ -‐-‐

EBECRYL LED 02 (mercapto modified polyester acrylate) -‐-‐ 25 35

Phosphine oxide based photoini6ator 5 5 5

Viscosity, cP @ 25°C 1020 1280 984

Reac6vity, # of passes at x m/min. Determined by surface marring by fingernail.

30 µ coa6ng on Leneta Chart. 395 nm, 8 W/cm2 UV LED lamp.

1 cm distance from lamp to substrate.

> 4 passes 2.5 m/min

4 passes 2.5 m/min

1 pass 5 m/min

EBECRYL LED 02 increases cure speed; higher concentra6on = faster cure


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Effect of Distance from UV LED Lamp to Substrate on Surface Cure

Component %

Distance (cm) LED to Substrate

EBECRYL® 8465 (3 func6onal urethane acrylate) 65

Dipropylene glycol diacrylate; dilu6ng monomer (DPGDA) 10

ADDITOL® LED 01 (EBECRYL LED 02) mercapto modified polyester acrylate 20

Phosphine oxide based photoini6ator 5

0.5 1.0 2.0

Reac6vity, # of passes at 5 m/min. Determined by surface marring by fingernail.


1 1 2

Reac6vity decreases with distance from LED lamp


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Effect of Coa6ng Thickness on Surface Cure with UV LED Lamps

Component %

Distance (cm) LED to Substrate

EBECRYL® 8465 (3 func6onal urethane acrylate) 65

Dipropylene glycol diacrylate; dilu6ng monomer (DPGDA) 10

ADDITOL® LED 01 (EBECRYL LED 02) mercapto modified polyester acrylate

20

Phosphine oxide based photoini6ator 5

0.5 1.0 2.0

Coa6ng Thickness (µ) on Leneta Chart

10 30 10 30 10 30


395 nm, 8 W/cm2 UV LED lamp.

3 x 5

1 x 15

3 x 5

1 x 15

4 x 5

1 x 15

Thicker coa6ngs cure faster


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Effect of Coa6ng Func6onality on Surface Cure with UV LED Lamps

Component %

EBECRYL® 8465 (3 func6onal urethane acrylate) 57 -‐-‐

Dipropylene glycol diacrylate; dilu6ng monomer (DPGDA) 18 -‐-‐

EBECRYL 8254 (6 func6onal urethane acrylate) -‐-‐ 75

ADDITOL® LED 01 (EBECRYL LED 02) mercapto modified polyester acrylate 20 20

Phosphine oxide based photoini6ator 5 5




1 x 10 1 x 40

Higher func6onality formula6ons cure faster


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Effect of Amine Modifica6on on Polyester Acrylate Cure Speed

Component Parts by Weight

EBECRYL® 810 (unmodified polyester acrylate) 100 -‐ -‐ -‐

EBECRYL 80 (amine modified polyester acrylate) 100 -‐ -‐

EBECRYL 81 (amine modified polyester acrylate) -‐ 100 -‐

EBECRYL 83 (amine modified polyester acrylate) -‐ -‐ 100

2-‐hydroxy-‐2-‐methyl-‐1-‐phenylpropanone 3 3 3 3

Benzophenone 2 2 2 2

Viscosity at 25°C, cP 504 3350 139 622

UV energy, mJ/cm2 640 <90 230 110

Cure speed, fpm 30 200 110 155

Amine modifica6on increases cure speed; Higher viscosity is also beser for surface cure


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Low Intensity Cure of Urethane Acrylates

Component %

EBECRYL® 8807 or EBECRYL 8811 (polyether based; 2 func6onal UA)

96.2

EBECRYL 8402 (polyester based; 2 func6onal UA) 96.2


EBECRYL 265 (polyether based; 2.3 func6onal UA) 96.2


EBECRYL 270 (polyether based; 2 func. UA, low Tg) 96.2

2-‐hydroxy-‐2-‐methyl-‐1-‐phenylpropanone 3.8 3.8 3.8 3.8 3.8 3.8

Surface cure; 20 min. exposure 0 = no surface tack or marring <1 <2 <3

<4 = wet surface

0 4 2 1 2 3

Polyether based UAs, especially EBECRYL 8811, provide faster cure


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Cure Time versus EBECRYL® 8807 or EBECRYL 8811

Content using Low Intensity UVA Lamp

Increasing EBECRYL 8807 concentra6on increases cure speed


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Effect of NEW Bio-‐Based Oligomer on Surface Cure with UV LED Lamps

Component %

EBECRYL® 5849 (2 func6onal bio-‐based oligomer) 50 -‐-‐

Dipropylene glycol diacrylate; dilu6ng monomer -‐-‐ 20

EBECRYL 1291 (6 func6onal urethane acrylate) 25 55

EBECRYL 853 (3 func6onal polyester acrylate) 25 25


Viscosity, cP @ 25°C 2480 1020




1 x 5 m/min > 4 x 2.5 m/min

2 func6onal bio-‐based oligomer cures faster than 6 func6onal UA


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Synergis6c Effect of Thiol and NEW Bio-‐Based Oligomer on Surface Cure Speed with UV LED Lamps


EBECRYL® LED 02 (mercapto modified polyester acrylate) 25 -‐-‐

EBECRYL 5849 (2 func6onal bio-‐based oligomer) 50 50

EBECRYL 1291 (6 func6onal urethane acrylate) 25 25

EBECRYL 853 (3 func6onal polyester acrylate) -‐-‐ 25


Viscosity at 25°C, cP 2870 2480

30 µ thickness; reac6vity, x m/min 15 5

10 µ thickness; reac6vity, x m/min 10 > 4 passes 2.5

EBECRYL LED 02 + EBECRYL 5849 faster at all thicknesses


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Synergis6c Effect of Thiol and Polyether Modifica6on on Surface Cure Speed with UV LED Lamps


EBECRYL® LED 02 (mercapto modified polyester acrylate) 25 25 25

EBECRYL 4666 (4 func6onal urethane acrylate) 55 30 30

EBECRYL 8811 (polyether based; 2 func6onal UA) -‐-‐ 25 -‐-‐

EBECRYL 271 (polyether based; 2 func6onal UA; low Tg) -‐-‐ -‐-‐ 25

Pentaerythritol tri/tetra acrylate (PETIA) 20 20 20

Phosphine oxide based photoini6ator 5 5 5

Viscosity at 25°C, cP 4350 8250 6550

30 µ thickness; reac6vity, x m/min 10 12.5 7.5

10 µ thickness; reac6vity, x m/min 5 10 2.5

EBECRYL LED 02 + EBECRYL 8811 especially effec6ve at low thickness

CONCLUSIONS

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•  In low energy cure applica6ons, such as UV LED cure, acrylates modified with thiols, amines, or ethers can be used to mi6gate oxygen inhibi6on.

•  Surface reac6vity increases with concentra6on of the modified acrylate.

•  Increasing the func6onality or thickness of the coa6ng improves surface reac6vity.

•  Decreasing the distance from the lamp to the substrate aids surface cure.

•  Using these chemical methods to mi6gate oxygen inhibi6on saves process 6me and money $$$

ALLNEX PRODUCTS TO MITIGATE OXYGEN INHIBITION

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RESIN TYPE PRODUCT NAME MODIFICATION TYPE

POLYESTER ACRYLATE EBECRYL® LED 02 THIOL EBECRYL 80 AMINE EBECRYL 81 AMINE EBECRYL 83 AMINE EBECRYL 5849 (5781) ETHER

URETHANE ACRYLATE EBECRYL 8807 ETHER EBECRYL 8811 ETHER

EPOXY ACRYLATE EBECRYL 3418 AMINE EBECRYL 3600 AMINE EBECRYL 3639 AMINE EBECRYL 3703 AMINE

LEO EBECRYL LEO 10551 AMINE EBECRYL LEO 10552 AMINE EBECRYL LEO 10553 AMINE

DILUTING ACRYLATE EBECRYL 110 ETHER EBECRYL 114 ETHER EBECRYL 40 ETHER EBECRYL 160 or TMPEOTA ETHER

PHOTOSYNERGIST EBECRYL P104 AMINE EBECRYL P115 AMINE EBECRYL P116 AMINE EBECRYL 7100 AMINE

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For more informa6on, please visit us at www.allnex.com.

Contact Name: Jo Ann Arceneaux Office Phone: 770-‐280-‐8302 E-‐mail: [email protected]

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