Technical Paper

New UV-Curable Coatings for the Resilient Flooring Industry

By Dirk Bontinck and Mike Idacavage
n many industries, growing concerns on ecological issues have lead to the development of technologies having a lesser chemical impact on occupational health and environment. Although the chemical industry has acted upon these concerns by allocating a growing amount of resources to projects with an ecological background, the switch from existing to these new technologies is difficult and slow. Among the reasons why industries are somewhat reluctant to make this switch, a higher initial cost and a potential loss of performance can be regarded as the most important drawbacks.

The aim of this paper is to give an insight in the present and future developments of high performance, yet environmentally and economically viable resilient flooring coating systems. These developments may vary geographically; cultural differences will put emphasis on different functional and esthetical aspects of the end product, as perceived by the consumer. Although the chemical industry has been globalizing to a high extent, it will have to find ways to meet local demands.

Resilient Flooring
Next to other flooring materials such as hardwood, ceramic tiles, carpets and fabrics, the global resilient flooring market is estimated at 800 million m2it covers vinyl, polyolefin, rubber and linoleum. These resilient floorings have their specific advantages and drawbacks, and vary in popularity in different parts of the world. Their general characteristics are shown in Table 1. Resilient flooring is often preferred because it is easy to install and to clean, comes in many different colors and designs, and is relatively inexpensive. However, two major drawbacks are that many household materials and dyes can create severe stains, and that many shoe sole types can leave scuff marks. To overcome these drawbacks, resilient flooring is protected with an overcoat. The first coating systems

During the last decade, solvents, hazardous crosslinkers, coalescents and free monomers have been questioned; the development of waterborne, ultraviolet-curable coatings can offer a way out.
This paper will focus on UV-curable polyurethane dispersions used by the resilient flooring industry, their chemistry, performance and relative cost. During the last decade, solvents, hazardous crosslinkers, coalescents and free monomers have been questioned; the development of waterborne, ultraviolet-curable coatings can offer a way out. The way these waterborne UV-systems can overcome cost and performance drawbacks will be addressed, as well as how this chemistry could develop in the future.
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Table 1
Different types of resilient flooring
Type Vinyl Composition PVC Heterogeneous Homogeneous PE/PP blends Vulcanized rubber SBR Linseed oil (1/3) Limestone (1/3) Wood/Cork flour (1/3) On jute backing Advantage Low cost Flame retardant Cl-free No shrinkage Low cost No plasticisers No shrinkage Natural product No shrinkage Disadvantage Contains 10-30% CI Shrinkage Primer needed Overall higher cost Low performance Poor design freedom Not flame retardant Long term flexibility Maintenance Linseed monopoly

Polyester Rubber

Linoleum

involved solventborne nitrocellulose, followed by polyaziridine crosslinked waterborne polyurethane dispersions, and 100% solids UV-cured systems. Radiation-curable systems are widespread in the United States, because their ability to reach very high-gloss values, whereas the polyurethane dispersions are used primarily in Europe because of their low-gloss possibilities. The performance, as well as the design demands for this type of flooring, has been increasing over the past decade. An increasing fraction of the resilient flooring production is now being lacquered for improved stain and abrasion resistance.

neutralizing agent for the carboxylate functions. Prepolymer chain length and functionality of the hydroxy acrylate can be varied in order to come up with the desired crosslink density. The use of non-irritating acrylating oligomers

enables the manufacturing of low-irritation coating systems. A comparison of UV-PUD with PUD and 100% UV systems is shown in Table 2 (following page). It is clear that waterborne UV benefits from the

Figure 1
Chemistry of UV-PUD
0 0 0 + + 0 + 0 0 0

UV-Curable Polyurethane Dispersions

The combination of polyurethane dispersions and radiation-curable technology has led to the development of waterborne UV-curable polyurethane dispersions (UV-PUD). The chemistry is outlined in Figure 1. Anionic, isocyanate-terminated polyurethane prepolymer is reacted with a hydroxylated acrylate, and is then dispersed into water using a tertiary amine as a

+ + 0 + 0

 0 =?HO =JAI M=JAH JHEAJDO = E A

0-J!

0-J !

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Table 2
Comparison of technologies
100 % UV Organic co-solvent-free Monomer/Oligomers 96% EtOH resistance Stain resistance Hard yet flexible Sprayable Thickness control Tack free before cure 60 gloss range Monomer deep-cure Adhesion to PVC OK Reactive diluents OK OK Limited Limited Limited Limited 20-90% Problematic Problematic UV-PUD OK Water OK OK OK OK OK OK 5-80% OK OK PUD 3-14%NMP Water Limited OK OK OK OK OK 5-70% NA OK

advantages of both 100% UV and PUD systems, without suffering from any of their obvious disadvantages. Waterborne UV-PUD exhibits a superior balance in chemical resistance and cold flexibility. The improved flexibility can be explained by the fact that their UV-crosslink density is lower than for 100% UV systems, meaning that the average molecular weight between crosslinks is higher (Figure 2). This

enables the design of UV-PUD that is tack-free before cure, meaning that they are non-blocking after water flash-off and before UV curing. This feature is very interesting for the resilient flooring manufacturerthe surface can be embossed thermally before curing, without sticking to the embossing rolls. If necessary, the flooring material can even be wound up at another time or at another place.

The use of UV-PUD results in a higher degree of freedom in both process and design as gloss, thickness and surface embossing can be arranged on the same coating equipment. The lack of crosslink density, necessary to obtain good solvent and chemical resistance, is balanced by the presence of polyurethane. The typical urethane hard domains provide excellent chemical resistance.

Figure 2
Relative crosslinking density representation of a 100% UV system and a UV-PUD

100% UV system

UV-PUD

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Table 3
Formulation for waterborne UV-PUD
UV-PUD TS100 Byk 346 Aquamat 266 Irgacure 500 Ucecoat XE430 UCB Degussa Byk Byk Ciba UCB 100.0 1.0 0.4 1.0 1.5 0.7

dyes, dissolved in various carriers (mineral oil, absolute ethanol and water) for 16 hours under a cover glass. Then, the excess dye is removed, the sample is cleaned with water and isopropanol. The remaining stain is reported on a scale from 1 to 5. (1 meaning a severe stain, 5 means that no trace of the dye can be observed.) An average of several stains is reported per carrier. The results clearly indicate that solvent and stain resistance improve dramatically as the crosslink density increases. The alcohol-based stains are very hard to pass; 96% ethanol softens the coatings considerably, making it a vehicle for the dyes. Only the UV-PUD with the highest crosslink density can withstand these alcoholbased stains. Although the crosslink density increases drastically in this range, surface hardness does not seem to increase accordingly. However, the flexibility is lost rapidly as the UV network becomes denser. The performance of uncoated PVC flooring is included as a reference. Because of the presence of plasticizers, PVC itself acts as an excellent carrier for dyes.

A typical formulation for waterborne UV-PUD is shown in Table 3. Next to the binder itself, a matting agent, a wetting agent, a wax, a photoinitiator and a rheological modifier are being used. This formulation results in a Brookfield viscosity of 1,000 mPa.s and a 60 gloss of 25%. Application on resilient flooring is preferably done by roller coating in reverse mode. Flash-off for a 23 g/m2-wet coating is achieved in 30 seconds at 100C. Curing is carried out with two Hg-lamps at 80 W/cm, at a typical line speed of 10 m per minute.

Influence of Crosslink Density

It is obvious that a UV-cured coating becomes harder and more rigid as the number of acrylic double bonds increases. The chemical and solvent resistance should be expected to increase accordingly. A range of UV-PUD with an increasing level of crosslink density was synthesized and is presented in Table 4. For comparison, the crosslink density for a 100% UV system can be 8 milli-equivalents of acrylic double bonds per g of solid and higher. The stain results were obtained after exposing the coating to a range of

Table 4
Performance of 10 m UV-PUD coatings on PVC resilient flooring with increasing crosslink density
Uncoated PVC Meq. acrylic per g of solid coating Knig hardness (s) Taber CS17/1 kg (mg) @ 1000 cyc. Cold flexibility (impact test) (C) MEK double rubs Stain resistance (5 = best) Oil based stains Alcohol based stains Water based stains Shoe polish Liquid tar NA 48.6 <-20 10 1 1 2 1 1 UV-PUD # 1 1.00 120 28.8 <-20 60 3 1 3 2 2 UV-PUD # 2 2.00 145 26.1 -10 85 4 1 4 3 3 UV-PUD # 3 2.75 170 22.5 0 125 5 1 5 4 4 UV-PUD # 4 3.50 180 19.5 20 160 5 3 5 5 5

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Table 5
Performance of 1O m UV-PUD coatings on PVC resilient flooring with increasing Mw between crosslinks
Uncoated PVC Meq. acrylic per g of solid coating Molecular weight between crosslinks Knig hardness (s) Taber CS17/1 kg (mg) @ 1,000 cyc. Cold flexibility (impact test) (C) MEK double rubs Stain resistance (5 = best) Oil based stains Alcohol based stains Water based stains Shoe polish Liquid tar NA 48.6 <-20 10 1 1 2 1 1 UV-PUD # 5 2.56 2,000 170 24.1 5 130 5 1 5 3 4 UV-PUD # 6 2.49 4,000 165 25.6 0 125 5 2 5 3 4 UV-PUD # 7 2.43 8,000 160 25.0 -10 125 5 1 5 4 4

Influence of Molecular Weight between Crosslinks

In Table 5, a range of UV-PUD with increasing molecular weight between crosslinks, is presented. The overall crosslink density was kept as a constant by increasing the functionality of the hydroxylated acrylate with increasing chain length between crosslinks. Increasing chain length does not have a significant effect on most properties. The crosslink density has been shown to have a greater influence. However, the cold flexibility does changethe UV network becomes less rigid with increasing chain length between crosslinks.

Economical Considerations
In addition to the technical advantages, waterborne UV-PUD systems have a clear advantage over many competing technologies in relation to occupational health and environmental issues. However, their penetration into the resilient flooring market will only happen when the price is right. As process and design benefits are hard to break down in dollars and cents, the cost of the lacquer itself was analyzed and what the raw material cost per m2 of produced flooring could be. Table 6 shows a number of cost simulations. At identical coating weight, UV-PUD will

suffer from its emerging technology status. The price for aliphatic diisocyanates, a key raw material for UV-PUD, remains a serious threat to the development of competitive polyurethane systems. However, when taking into consideration the outstanding stain performance of UV-PUD, it can be argued that a higher coating weight of 100% UV is needed to catch up with UV-PUD. As shown in Table 6, this puts the waterborne technology in a whole different perspective; the cost difference is not at all what it appeared to be at first sight.

Future Developments in UV-PUD

Further improvements in the balance of flexibility vs. chemical resistance are to be expected. The incorporation of mixed isocyanates and extenders looks promising at this point. A lot of effort is also being made in the development of dendrimer technologya more efficient use of acrylic double bonds and secondary crosslinking mechanisms should also be beneficial.

Table 6
Raw material coating cost per m2 of resilient flooring
100% UV Cost per kg of solid (USD) g/m (dry coating weight) Cost per m (USD cents)
2 2

UV-PUD 11.75 12 14

PUD 11.2 12 13

6.98 12 8

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The development of acrylated acrylic resins can bring the raw material cost down to an acceptable level. Acrylic resins as such do bring a cost reduction, but are extremely susceptible to stains. Any technology that can reduce or eliminate the level of aliphatic isocyanate needed in waterborne UV-systems should be examined with great interest. Another interesting topic is the development of self-curing UV-systems, omitting the rather expensive photoinitiator.

Conclusion
It has been shown that UV-PUD brings performance, process and design benefits. The relationship between crosslink density, chain length between crosslinks, chemical resistance and cold flexibility was studied. A raw material cost comparison was made between existing technologies for the resilient flooring application.

Water-based UV may never fully replace 100% UV systems. Nevertheless, they could well be an interesting alternative in terms of improved gloss control and process freedom with only one type of UV lamps and one coating roll. The tack-free before cure properties of UV-PUD allow for the separation of coating and curing. Since the bottleneck obviously is the PVC calandering or foaming, all UV curing could be reduced to one dedicated line at higher speeds, avoiding the installation of UV lamps on all production lines. UV-PUD should be regarded as complimentary to 100% UV systems. Depending on technological and market demands, one or the other will prevail. In Europe, many resilient flooring producers have switched or are now switching to waterborne UV systems. They are moving away from solvents such as N-methyl-pyrrolidone and hazardous crosslinkers such as polyaziridines, present in PUD, and are

reluctant to move into an oligomer related technology as 100% UV. As the resilient flooring industry suffers globally from overcapacity, those manufacturers with the most versatile and flexible operation might well have the best chance for survival. Clearly, UV-PUD can offer those options. Dirk Bontinck is Radcure research manager at Surface Specialties UCB, Drogenbos, Belgium. Mike Idacavage is vice president of research and technology at Surface Specialties UCB, Smyrna, Ga.

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