Radiation curing: update and outlook

Sandy Morrison,Member of SpecialChem Technical Expert Team

Introduction
By way of a change from offering you my speculations on the future of our sector of the
coatings industry, I'd like to share with you the speculations of the industry experts at the
recent "Radiation curing: update and outlook" symposium held in Enfield, near London.
This one-day event on June 16th was a joint venture between the London Section of
OCCA and industry association RadTech Europe.

Photo: The symposium was held at the

historic Royal Chace Hotel in Enfield.

Six speakers provided an insight into several leading-edge developments in radiation

curing, showing that new raw materials and systems are breaking down what might once
have seemed insurmountable barriers to greater market penetration. The wide range of
developments on offer is notable - ours is by no means a 'mature' market, and projections
of continued rapid growth seem more plausible in the light of the information presented
here.

The proceedings were opened by John Bernie, former managing director of PRA, who
noted the rapid growth of radiation curing, but expressed surprise that the industry had
not made even greater inroads into the coatings market over the last 15 years. The most
optimistic estimates of future growth suggest that radcure may achieve a 7.5% share of
the total coatings market by 2010.
 Photo: Chairman John Bernie considers
some of the problems of radiation
curing.

Bernie concluded by observing that for this sector of the industry, "Legislation is going to
be your driving force - and possibly your best friend".

There are no problems - only opportunities

Professor R Stephen Davidson, who has had a long-standing involvement in radiation
curing, then presented an overview of 'Opportunities for radiation curing'.

Photo: Stephen Davidson presented the

most wide-ranging paper of the day.
radiation curing market, despite having significant advantages in terms of low shrinkage,
low viscosity, generally good adhesion to "difficult" substrates and a lack of oxygen
inhibition. Why should this be so? In his view, the higher cost of cationic materials was
the main obstacle to progress.

Other serious issues include the decomposition of vinyl ethers to produce acetaldehyde,
and the recognition a few years ago that all cationic photoinitiators produced benzene
under irradiation. However, recently developed photoinitiators may offer faster curing
and some avoid the problem of benzene production.

Oxetanes are another key area of interest in cationic systems. These cure by a ring-
opening mechanism similar to that of epoxides, but differences in the chemistry mean
that under the right circumstances they will cure much more rapidly - a point discussed in
greater detail by a later speaker. Likely areas of growth are coatings on plastics and glass,
graphic arts (particularly flexo and inkjet where low viscosity is advantageous), medical
application and optoelectronics.

Frontal polymerisation
With many cationic systems, a highly exothermic curing reaction takes place. In the case
of thick materials, this can propagate a "heat wave" from the surface curing zone into the
thickness of the material. Temperatures can briefly exceed 250°C, which is sufficient to
induce curing. Thus the process is of great potential interest in composites manufacture
and potting of electronic components, for example. It does, however, create the effect of a
very long induction time followed by very rapid curing.

Davidson posed the question of whether conventional methods of determining cure rate
reflect what will happen in practice with cationic systems. In laboratory tests, small
samples are usually cured relatively slowly, and thus the effects of any exotherm will not
be reproduced, due to heat losses from the small test samples.

Rapid growth for cationic systems

Next, continuing to place the emphasis on cationic cure, Jill Ross of DKSH presented a
paper co-authored with Richard Martin. Ross noted that Frost & Sullivan predicts growth
in radiation curing within Europe of some 7% per year over the period 2000-2007
(totalling 66% over seven years). By far the largest application areas are wood &
furniture finishes, and printing & packaging, each with more than 40% of the total
market. However, Ross predicted much more rapid growth for cationic systems,
indicating that the (still relatively small) volume of cationic-cure materials had more than
doubled each year from 2002 to 2005. The key growth areas are expected to be print,
packaging and coatings for plastics.
Achieving synergy in cationic coatings
Paralleling remarks by the previous speaker, Ross displayed some test results comparing
the radiation curing of oxetanes and epoxies. Notably, the initial stage of cure is faster for
epoxies, whereas oxetanes experience an extended induction period followed by rapid
reaction and the achievement of a higher conversion rate.

What is perhaps of greater interest is the cure speed of mixtures of the two monomers.
The addition of 5-10% of epoxy to an oxetane produces rapid initial curing and a final
conversion rate even higher than that of the pure oxetane. The molecular weight of the
cured system is higher than that of the pure epoxy and with a narrower distribution.

The mixtures also exhibited better adhesion to a wide range of substrates, faster
development of solvent resistance and caused less curling when applied as a coating to a
flexible plastic substrate. The last result is particularly intriguing, as oxetane actually
produced a slight increase in the shrinkage of the film during cure. It appears that despite
this, there is less build-up of internal stress within the film.

Thus, the use of oxetanes in conjunction with epoxides allows the level of photoinitiator
to be reduced, or cheaper types to be used, while still giving faster cure. In particular, it is
possible to replace antimony-based photoinitiators with phosphorus-based ones which are
both safer and cheaper.

Introducing the D-word

In any discussion of evolving technology, it is difficult to avoid mentioning the word
'dendrimer', and David James of Perstorp filled this gap. Boltorn W3000 is a non-ionic
amphiphilic dendrimeric surfactant - that is, it has a dendritic core with both hydrophobic
and hydrophilic attachments. As the structure is based on ethoxylated drying oils, it will
harden by an air-drying mechanism in coating films.

It can be used to convert almost any solvent-borne or 100% solids radcure formulation to
an emulsion via the inversion point method. According to James, it is much harder to
produce a stable emulsion of radcure materials in this way by using conventional
emulsifiers.

A key advantage of producing waterborne radcure coatings in this way is that it is

possible to mix them with almost any other waterborne coating to provide a wide range
of hybrid-cure systems. Examples were shown of acrylates mixed with polyvinyl acetate,
polyurethane dispersion and waterborne alkyd.

Emulsions produced using the dendrimer surfactant also appear to give a faster water
release during the initial stages of drying, reducing flash-off time. Coatings which are
entirely free of VOCs can be produced, since the acrylate part of the formulation is
capable of plasticising other materials at the film-forming stage.

Cytec - the new name for UV specialities

Following an excellent lunch, the afternoon session was introduced and chaired by Dawn
Skinner of Fusion UV, representing RadTech Europe.

The recent acquisition of UCB's extensive radiation-cure operations by Cytec has created
a new giant in the industry: Cytec Specialties, represented at this meeting by Paul
Gevaert. He discussed the use of radiation-curing inks in offset litho applications.
Radcure has the evident advantages of eliminating the twin risks of inks drying on the
press and failing to dry fast enough on the printed sheet. However, its press running
properties are generally less satisfactory, in terms of tack, misting and pigment wetting.
Currently, radcure has 2-3% of the offset litho inks market; Gevaert considered that the
probable limit to growth in this area is about 10% of the market.

The high ink viscosities required in letterpress and litho printing are ideal for radcure and
allow inks to be formulated with relatively low monomer diluent contents, but in litho,
the issue of the ink/water balance can be critical. Emulsification of water leads to a
reduction in ink viscosity, and after the initial stage, continuing emulsification (which can
be tested on a Lithotronic machine) results in further viscosity reductions for UV-acrylate
inks but some recovery for conventional inks.

UV litho inks are normally formulated using a mixture of polyester acrylate and epoxy
acrylate. (Epoxies give high cure speed and are relatively low in cost, while polyester
acrylates are better at retaining the required ink/water balance.)

A new higher molecular weight polyester acrylate has been developed by Cytec, and
Lithotronic tests showed that it exhibited an emulsification behaviour midway between
that of conventional inks and those based on standard acrylate oligomers. In addition,
tack and misting were reduced while pigment wetting and cure speed were improved.

Adhesives under pressure

Peter Palasz of National Adhesives next considered the prospects for radcure in pressure-
sensitive adhesives (PSAs). The standard for high-performance PSAs is set by solution
acrylics. However, the high flammability of the solvents, the requirements for large
coating machines and the necessity for solvent incineration or recovery mean that
alternatives are highly desirable. Hot melt PSAs are generally rubber-based. They are
more economic and avoid solvent use issues but have inferior performance.

UV-cure systems can combine the best of both these approaches, but have significant
drawbacks. National Adhesives has recently introduced a range of polymers which cure
by a polymer grafting process, reducing both the crosslink density and the residual
monomer level. The increased viscosity of these systems means that hot melt application
systems must be used. UVA for deep cure and UVC for surface cure must be combined
when using this system, and this has highlighted a problem in that different dose
measuring systems all give different readings under the same lamps. The problem seems
to be that UVC is measured as a narrow band, and discrepancies in the cutoff points will
produce large differences in measured intensity.

Test results on a number of adhesives based on these polymers were presented, showing
that it is possible to achieve adhesion properties comparable to those of solvent-based
acrylic PSAs. Critically (particularly in view of the difficulty of achieving accurate dose
monitoring) the effect of varying the UV dose over a range of 2:1 in the recommended
exposure range has only a small effect on adhesion properties.

Taking the flexible approach

Concluding the day, Sébastien Villeneuve of Ciba Specialty Chemicals examined the
scope of radiation curing in flexible packaging applications. In this market, solvent-based
inks still predominate, as both flexo and gravure processes require low viscosities, and
waterborne types have built a strong presence only for printing on paper and board
substrates. Particular problems for radcure are the extensive use of opaque white ink
(accounting for 40% of the total), the need to combine high adhesion with flexibility,
compatibility with lamination and sealing systems, odour and migration.

Photo: Sébastien Villeneuve of Ciba.

However, in narrow web and short-run applications, the higher raw material cost of
radcure inks has less of an impact on the total cost of a job, and inks which are essentially
radcure inks are recognised as providing the best print quality, especially where finely
detailed halftones are to be reproduced.

What can be done to offset some drawbacks? Ciba has developed PrimeIT, a pretreatment
system in which plastic surfaces are first activated by (for example) corona treatment,
then coated with a monolayer of grafted photoinitiator. In this state, the substrate can be
stored for an extended period prior to final coating with a free radical ink or coating
which will bond firmly to the photoinitiator. In addition, it has been shown that even
partial inertisation can provide considerable benefits in terms of enhancing cure speed
and/or reducing photoinitiator levels.

A successful event - with quiet dissent

For both OCCA and RadTech Europe, this joint venture can be considered a success. It
attracted a good-sized audience which received the presentations enthusiastically, and the
organisation ran smoothly. The only dissenting note was heard off-stage from a couple of
experienced formulators, critical not so much of what was being said as of possible gaps
in the knowledge of some researchers. Moving staff from one position to another creates
the wrong kind of 'fast-moving industry', in which there is a constant risk of reinventing
the wheel. 'No one is at the coal-face for a long enough time to develop in-depth
knowledge', said one.

At the back of the hall, a small table-top exhibition by three companies drew attention in
the time between the papers. DKSH and Kromachem provided information on the wide
range of specialist raw materials each offers for the radiation curing industry. Able
Instruments is an agent for a wide range of instrumentation, but for this event naturally
placed the emphasis on radiometers. David Quelch of Able expressed satisfaction with
the event, noting that from a relatively small audience he had received three firm requests
to make company visits.

About the organisers

OCCA is an international professional organisation whose members are employed in, or
associated with, the world-wide surface coatings industries. It publishes Surface Coatings
International, runs several symposia each year mostly in the UK, and is associated with
the UK's major coatings exhibition, Surfex.

For the industry association RadTech Europe, the symposium provided a foretaste of the
wide range of papers that will be on offer at its biennial conference and exhibition. This
will be held on 18-20 October 2005 in Barcelona, Spain.
The next Surfex exhibition is in 2006 - see www.surfex.net

For the industry association RadTech Europe, the symposium provided a foretaste of the
wide range of papers that will be on offer at its biennial conference and exhibition. This
will be held on 18-20 October 2005 in Barcelona, Spain. See www.radtech-europe.com
or for information on the event only, www.coatings.de

I hope you found this extended newsletter interesting and that you'll join me for further
thoughts on the future of radiation curing technology later in the year.