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Sandy Morrison,Member of SpecialChem Technical Expert Team
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 ringopening 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.
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 pressuresensitive 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.
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