CPIPC September 2012 Meeting

UV/LED Curing in Graphic Arts Applications

Eileen Jaranilla-Tran
RAHN-Group

Introduction
UV/LED curing is recently-developed technology

Offering improved process speeds, capabilities and product performance

Enabling the use of thinner, more heat-sensitive substrates
Reducing harmful process byproducts such as ozone and mercury
Capable of reducing total cost of operations

395n
m

Presentation

UV Energy Curing Basics A verbal Introduction

The Light Spectrum

The UV/LED light source

Measurement of UV/LED Power

Photoinitiators for UV/LED

Example Formulations

Conclusion

The Light

UV radiation
25-30%

VIS light radiation

5-10%

IR radiation
60-65%

Photochemistry
The UV Spectrum
The UV Range
UVV

700-400 nm = visible light range

(dental applications)

UVA

400-315 nm = long wave lengths

(through cure of thick layers)

UVB

315-280 nm = medium wave lengths

(bulk cure)

UVC

280-200 nm = short wave lengths

(surface cure)

VUV

200-100 nm = vacuum UV, not useful in

energy curing due to atmospheric gas absorption

Where The UV Goes

- Relative Penetration
200-280nm

UVC

280-315nm

UVB

315-380nm

400-450nm

UVA

UVV

Ink, Coating, Adhesive Thickness

Substrate

Light-Emitting Diodes (LEDs)

LEDs are semiconductor diodes that emit light when an electric current is
applied in the forward direction of the device.

The output is a form of electroluminescence where incoherent* and

narrow-spectrum light is emitted.

LEDs are usually a small area (less than 1mm-2mm) light source, with
optics added on top of the chip to shape the radiation pattern and assist
in reflection.
* Electromagnetic radiant energy not all of the same phase, and possibly also consisting of
various wavelengths.22

Advantages of UV/LED
Technology

Size of 1 LED

SLM Technology
Advantages of SLM (Semiconductor Light Matrix) LEDs:

Cooler
More intense
Longer life
Precise control
The full-intensity lifetime of SLM devices is expected to be 15,000+ hours
compared to less than 2,000 hours with traditional mercury arc lamps

Power consumption is typically 30-40% less than that of equivalentlyintense Hg lamps, reducing heat generation and total power consumption

SLM arrays can be constructed to irradiate a wider area more uniformly

than traditional Hg lamps, enabling new applications such as web curing
of photopolymers using UV SLMs

Energy Efficiency:
UV/LED vs. Mercury Lamps

Barely over 25% of the radiant energy from a conventional arc lamp is
useful UV output

The majority of the energy is wasted as visible light (>10%) and heat
(>50%)

UV/LED Power
UV/LED units are modular and can be added together to increase
power output in a relatively small area (e.g. 3 x 8 W/cm2 LED blocks
together total 24 W/cm2)

Total power output depends on temperature control, life time, and

electrical control of the UV/LED lamp

Standard UV dose measurement devices have a gap from

390-395 nm

Distance of UV/LED lamp from substrate will influence total

power
available at the surface closer is better. This is not
problematic
because the UV/LED unit generates far less heat than
mercury arc
lamps and temperature is easily controlled. But, UV/LED lamps WILL
get hot!
365
nm

UV/LED Power

Power is a valid comparative parameter because all measurements

were collected over the same time

The UV/LED lamps produce significant power around the defining

wavelength with intensity being nearly equal

Introduction
The Challenge: Photoinitiator Choice

Most PIs have maximum absorbance below 395nm where the most
common and cost-effective UV/LED lamps irradiate

Unlike medium pressure mercury lamps, UV/LEDs have very narrow

output spectra:

The upside: UV/LED lamps do not have an entirely monochromatic

spectrum and PIs have broad absorbance bands including wavelengths
other than the maxima

Photoinitiators for UV/LED:

Which One?
Max. Absorption [nm]

GENOCURE* BDMM

230/325

GENOCURE* BAPO

365

GENOCURE* TPO

380

GENOCURE* LTM

253/368

GENOCURE* TPO-L

370

GENOCURE* CQ

470

GENOCURE* BDK

252

GENOCURE* PMP

307

GENOCURE* DMHA

247/277

GENOCURE* ITX

259/383

GENOCURE* EHA

228/311

GENOCURE* DETX

261/384

A thorough study of PI types,

amounts, lamp output, etc. was
undertaken.
1
Extinction

PI

0.8

Exctinction Spectrum G* BDMM

365 395

0.6
0.4
0.2
0
200

250

300

350

400

450

500

wavelength [nm]

Based on absorbance spectra, the

PI candidates chosen were:
TPO, BDMM, ITX and BAPO

Photoinitiator Absorbance
Spectra

Photoinitiators for UV/LED

The semi-quantitative study with both 365 nm and 395 nm Phoseon watercooled 8 W/cm2 units concluded the following:
Based on absorbance spectra, ITX>BAPO>TPO>BDMM
BAPO, TPO >> BDMM with much lower yellowing among Norrish Type I
candidates
ITX (Type II) is very reactive, but too yellow for OPV and whites
Surface cure is challenging for UV/LED in air

Photoinitiators for UV/LED

A detailed DOE was run in 2011 to fully quantify the results seen in the
previous study. A mixture design with center and axial points on a
benchmark CLEAR formulation was tested with a Phoseon 395 nm
8W/cm2 variable power, water-cooled curing unit. After all of the numbers
were crunched, Type I PI was better than Type II (ITX with MEA) and
BAPO was the best PI by far.

Pigment Transmission Spectra

Once pigment is introduced, trends change. Chemistry cannot trump
physics: where PI competes for light with pigment, reactivity suffers.

Figures from W. Arthur Green, Industrial Photoinitiators, CRC Press, 2010.

OPV
OPV, 12 mm; 6W/cm2 LED 395nm
Reactivity LED
Inert
[m/min]

Db

Run#

Reactivity LED air

[m/min]

OPV 37

40

1.9

300

0.9

OPV 33

90

4.0

n.m.

OPV 32

15

3.3

1.
2.
3.
4.
5.

Db

Reactivity UV
Fusion
[m/min]

> 200

Db

2.0

Inerting boosts reactivity and reduces yellowing

Reactivity for standard Hg-UV lamp is significantly higher
Sensitizer 1 improves reactivity significantly
ITX has a very strong boost effect, but yellowing is high
Highly reactive oligomers and monomers are also fast under UV/LED

OPV 37:
Ingredient

[%]

Cure: 40m/min; LED 395; 6W/cm2, (i.e. 100mJ/cm2)

G* 3456

42.5

Yellowing : Db 1.9

M500

35

G* TPO

7.5

Sensitizer1

15

Film thickness: 12mm

InkJet Ink
Inkjet Ink; 12mm, 6W/cm2 LED 395nm

Colour

Reactivity UV
Fusion [m/min]

IJ 16

Yellow

16

17

IJ 9

Magenta

18

33

IJ 17

Cyan

26

> 108

2.02

IJ 19

Black

17

20

1.70

Run#

Reactivity
Inert [m/min]

Colour
Density

Reactivity
air [m/min]

2.00
23

2.54

Surface cure is faster than through cure (adhesion and fingernail)

Color densities are not optimized and are, in general, too high
BAPO is approximately 5X more efficient than BDMM

Flexographic Ink
Flexographic Ink; 6W/cm2 LED 395nm, app. 1mm,
Run#

Colour

Reactivity air
[m/min]

Reactivity UV Fusion
[m/min]

Colour
Density

F27

Yellow

32

> 110

1.55

F31

Magenta

50

> 110

1.52

F29

Cyan

60

> 110

1.86

F36

Black

25

75

1.77

F35

White

35

65

b-value:5.5

Inerting has no effect in tested black flexographic ink

Raven Black 1060 shows a higher reactivity than Special Black 250
Low yellow, opaque white is feasible with some photoinitiator modification
Short Investigation of LED 395 vs. 365:
o Standard photoinitiator cocktail with BDMM with UV/LED 395 6X faster
o Standard photoinitiator cocktail with BAPO with UV/LED 395 10X faster

Conclusion
Fast acrylates under conventional UV lamps are also fast with UV/LED
Yellowing is problematic for OPV and white, but when the formulation is
optimized a reasonable cure can be realized

Black and Yellow colors are the most difficult to cure

Selection of black pigment is important
Norrish Type II Photoinitiator are effective to achieve good surface cure
Overall system cure speed is optimized by careful selection of
photoinitiators AND acrylate components!

Starting Point Formulations with competitive cure for OPV, Flexo and Ink Jet
Inks are available

Thank you for your attention!