EPA-600/2-91-035

J u l y 1991

RADIATION-CURABLE COATINGS

Prepared by:

Stephen A. Walata 111

C.R. Newman
Alliance Technologies Corporation
100 Europa Drive, Suite 150
Chapel Hill, NC 27514

EPA Contract NO. 68-D9-0173

Work Assignment OR02 and 1/130

Project Officer

Charles H. Datvln
Air and Energy Engineering Research Laboratory
U.S. Envlronmental ProtectionAgency
Research TrlanglePark, NC 2771 1

Prepared for:

Control Technology Center

U.S. Environmental ProtectionAgency
Research TrianglePark, NC 2771 1
 CONTROL TECHNOLOGY CENTER

SPONSORED BY:

Emission Standards Division

Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711

Air and Energy Engineering Research Laboratory

Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711

Center for Environmental Research Information

Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268 -

PREFACE

EPAs Control Technology Center (CTC) was established by EPAs Office of Research and
Development (ORD) and Office of Air Quality Planning and Standards(OAQPS) to provide technical
assistance to State and local air pollution control agencies. Three levels of assistance are available
through the CTC. First, a CTC HOTLINE has been established to provide telephone assistance on
matters relating to air pollution control technology. Second, more in-depth engineering assistance
can
be provided when appropriate. Third, the CTCcan provide technical guidance through publicationof
technicalguidancedocuments,development of personalcomputersoftware,andpresentation of
workshops on control technology matters.
The technical guidance projects, such of nationalor regional interest
as this one, focus on topics
that are identified through contact with State and local agencies. In this case, the CTC assisted the
Bay Area Air Quality Management District in San Francisco, CA, in identifying the scope and nature
of radiation-curable coatings and inks being used in industry. This document discusses advantages
and disadvantagesof radiation-curables as well as potential future use.

ii
 TABLE OF CONTENTS

Page

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
List of Figures ................................................ iv
ListofTables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
Executive
Summary ................................................ V

INTRODUCTION
1.0 ................................................ 1

BACKGROUND
2.0 ................................................ 2
2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.3CuringandDryingEquipment
2.4LiteratureSources .
....................................
.............. .............................
4
6

3.0RADIATION-CURABLESYSTEMS IN INDUSTRY . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1CurrentUsage in Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2AdvantagesofRadiation-CurableSystems ........................... 9
3.3
Limitations
Radiation-Curable
of Systems ............................ 12
3.3.1OxygenInhibition ........................................ 12
3.3.2CurePenetration ........................................ 13
3.3.3
Viscosity .............................................. 14
3.4
Potential
Applications
for
Radiation-Curable Systems ................... 15

4.0
TOXICITY
DATA .................................................. 17
4.1 GeneralToxicologicalData ...................................... 17
4.2PermissibleExposureLimits ..................................... 18
4.3 SafetyandRadiation-CurableSystems ............................. 19

5.0 EMISSIONSDATA ................................................ 22

5.1 TheoreticalEmissionsRate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.2 AirborneHazard of Radiation-CurableSystems . . . . . . . . . . . . . . . . . . . . . . . 24
5.3 V O C ReductionPotential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

6.0
COST
COMPARISON .............................................. 27
6.1 Costs Associated with
Curing
Equipment ............................ 27
6.2 CostsAssociatedwithCoatingandInkMaterial ....................... 27
6.3 Costs Associated
with
Controlling VOC Emissions . . . . . . . . . . . . . . . . . . . . . 30
6.4OtherCostIssues ............................................. 34
6.5
Summary ................................................... 34

CONCLUSIONS
7.0 .................................................. 35

8.0
REFERENCES ................................................... 37

iii
 LIST OF FIGURES

Number Page

2-1
UV-Curable
System .Continuous
Web
Configuration ........................ 7

2-2
UV-Curable
System .Sheet-Fed
Configuration ............................ 7

2-3
EB-Curable
System .Continuous
Web
Configuration ........................ 8

2-4
EB-Curable
System .Sheet-Fed
Configuration ............................ 8

6-1 Cost of Coating a 1,000.Squar e.Foot Area with Various Types of

Fiat
Line
Finishing
Equipment .................................... 29

6-2 Pounds of VOCs Emitted While Coating a 1,000.Squar e.Foot Area with
VariousTypesofFlatLineFinishingEquipment ....................... 33

LIST OF TABLES

Number Page

2-1Comparison of
the MainCharacteristics of
Radiation-Curable
Systems ........... 5

2-2
Literature
Sources
for
Radiation-Curable
Systems .......................... 6

3-1
Current
Applications of UV-Curable
Systems .............................. 10

3-2 A SelectSampleofCompaniesUsingRadiation-CurableSystems .............. 11

3-3
Viscosity
Ranges
for
Various
Printing
Processes ........................... 15

4-1
Permissible
Exposure
Limits
of
Radiation-Curable
Material ..................... 19

4-2
Permissible
Exposure
Limits
of
Organic
Solvents ........................... 21

5-1 VOCEmissionsReductionResultingfromConversionto
Radiation-Curable
Coatings ..................................... 26

6-1CapitalCostElementsandFactors for SelectAdd-onControlSystems ........... 31

6-2TypicalItemsIncluded in AnnualCosts of Add-onControlSystems ............. 32

iv
 EXECUTIVE SUMMARY

This report presents the resultsof an evaluation of radiation-curable coatingsas a technology

for reducing volatile organic compound (VOC) emissions from surface coating operations. A survey
of the literature was conducted to assess the state of the technology and emissions from radiation-
curable processes. The data collectedin the literature survey were usedto evaluate the engineering
and economic concerns associated with radiation-curable systems andto identify technical problems
requiring future resolution.
Radiation-curablecoatingsandinksmaybeconsideredhighersolidsformulationsthan
conventional coatings and, consequently from an air pollution viewpoint, are considered
to be a well
suited substitute for solvent-based thermal-curable systems. The radiation source for these systems
is either an ultraviolet (UV) light or an accelerated electron beam (EB). A radiation-cured surface
coating or printing process emits reduced levels of VOC-emissions in comparison to solvent-based,
to the solventless nature of mosf radiation-curable systems. Radiation-
thermal-curable processes due
curable systems also require less energy to achieve a cured film and operate at lower temperatures
thanthermal-curablesystems.Thisallows radiationcurable systems to be used on temperature
sensitive substrates and can yield a75 to 90 percent savings in energy costs. The curing equipment
50 to 75 percent less floor space than thermal-curing
for radiation-curable compounds typically requires
ovens. Higher production rates than thermalcurable systems are potentially achievable due to the
rapid curing ratesof radiation-curable systems. Fourtypes of polymerizable systems commonly used
for radiation-curable applications include unsaturated polyester resins, multifunctional acrylates, thiol-
polyenesystemsandcationicpolymerizedepoxides.ThephotoinitiatorsrequiredforUV-curable
systemsformtheinitiatingradicalbyeitherphotocleavage,hydrogenabstraction or cationic
photoinitiation.
Radiation-curablesystemshaveseveralinherentlimitationswhichmaylimitimmediate
applications in some commercial environments. Atmospheric oxygen has a retarding effect on the
curing rateof free radical polymerization processes due
to molecular oxygen's affinity for free radicals.
Thepresence of air in theradiation-curableprocesscanresult in coatingswithtackysurfaces.
Practical solutions to oxygen interference will differ between UV- and EBcuring systems due to the
inherent differences in the way the two forms of energy interact with the coating material.UV energy
of free
tends tobe strongly absorbedat the syrfaceof the coating. This generates a higher proportion
radicals at the surface in relation to the rest of the coating. With proper formulation, UV-curing can
be conducted in ambient conditions. The fairly uniform distribution of energyfor EBcurable systems
requires the cure zone to be kept free of oxygen by blanketing with an inert gas. Due to the higher
solids content, radiation-curable formulations have a higher viscosity than thermal-curable systems.
The high viscosity of radiation-curablesystemsmayrestrictpotentialapplicationmethods.The

V
viscosity problem can
be minimized by the addition
of a reactive diluent or additional heat
by thinning
or
withanorganicsolvent. In addition,someearlyradiation-curablesystemswereconsideredtoxic.
Current materials, however, have been classified as only slightly toxic. Acrylate materials used in
of the irritation depends
radiation-curable systems are considered skin and eye irritants. The seventy
on the material being used.
Costpervolumeofcoatingformulationtraditionallyhasbeenaneconomicfactorused to
determine whether radiation-curable systems are an acceptable alternativeto conventional thermal-
curable systems. The cost differential on this unit basis between radiation-curable and thermal-curable
systems is relatively largein favor of thermalcurable systems. The higher unit cost
of radiation-curable
systemsresultsintheuser’sperceptionthatradiation-curablesystemsarenotaneconomically
attractive alternative printing or coating process. However, when the costs of the two systems are
compared on the basisof cost per unit areaof substrate coverage, a better indication of the true cost
of the coating or printing process
is given. Limited available data on cost per area coated indicate the
costdifferential to be infavor of radiationcurablesystems. ~

Available data indicate that some monomer emissions could be present in the exhaust for
processes using radiation-curable systems. Additional investigation to determine the quantity and
composition of emissions resultingfrom the useof radiation-curable coatings and inks would define and
determine the extentof the problem, if any. All other potential problem areas might be addressed by
good engineering and operating practicesof the installed system.

Vi
 ¶

1.O INTRODUCTION

This report presents the resultsof an evaluation of radiation-curable coatingsas a technology

for reducing volatile organic compound (VOC) emissions from surface coating operations. Traditionally,
surface coating operations (e.g., furniture finishes, paper varnishes, protective varnishes on aluminum
cans) have used coating formulations consisting of a functional part, a solid polymer, dissolved in an
if required with more solvent (e.g., methyl ethyl
organic solvent. The formulation may be further diluted
ketone, ethyl acetate, toluene, alcohols) to reduce the viscosity in order to facilitate application to a
substrate. After the coating has been applied, the solvent is removed by evaporation. Traditional
thermal-curing methods use a heat source to speed solvent evaporation and trigger the polymerization
reaction. The solvent evaporates into theair currents and is carried away from the substrate, leaving
a dry film. The solvent-laden air is then exhausted through a stack or a vent with or without being
subject to some vapor removal control system (Lankford,-1983). The polymer network formed by the
coating may require a thermally sensitive catalyst to initiate the polymerization reaction.
Radiation-curable coatings may
be considered higher solids formulations used
in various surface
coating industries as an alternative to energy- and solvent-intensive coatings and inks. Radiation-
curable coatings and inks are composed
of organic material (i.e., polyesters, acrylates, epoxies) and,
unlike thermal coatings, use ultraviolet (UV) or electron-beam (EB) energy to initiate the reaction to
form a polymer network. Since the formulations contain little or no organic solvents, use
of radiation-
curablesystemsmayallowsurfacecoatingoperations to complywithcurrent VOCemissions
restrictions. Although radiation-curable systems have beeninused
commercial operations for
20 years,
little information is available to allow local air pollution control agencies to assess the technology's
to reduce VOC emissions.
effectiveness as a process material change
The Bay Area Air Quality Management Districtin San Francisco, CA, requested the assistance
of EPAs Control Technology Center (CTC)in compiling informationon radiationcurable coatings for
the purpose of evaluating this technology as a process change to achieve VOC reduction. CTC is
l o c a l air pollution control agenciesin the implementationof their
responsible for supporting State and
programs. Work has involved: (1) a suwey of the literature to assess the stateof the technology and
emissions from radiation-curable coating processes; (2) an evaluation of engineering and economic
concerns associated with radiation-curable systems; and (3) an identification of technical problems
preventing universal adoptionof this coating and printing technology.

1
 2.0 BACKGROUND

2.1 HISTORY
The use of radiation-curable coatings dates backat least 4,000 years. The ancient Egyptians
used a type of UV-curable coating in the preparation of mummies which cured when exposed to
sunlight(AFWSME,1986).An asphatbased oil coating that polymerized upon exposure to solar
radiation was also used by the ancient Egyptians as a sealant for ships (Decker, 1987).
In the modern era, scientific interest in developing radiation-curable systems began onlyin the
1940’s. At that time, the first patent was granted for an unsaturated polyester styrene printing ink that
polymerized underUV exposure (Decker, 1987). One of the first attempts at applying radiation-curable
systems to a manufacturing system was made in the late 1960’s. This high-energy electron beam
curing system developed by the Ford Motor Company, however, was abandonedtodue
complexities
of the process and associated high costs (Lawson and- Kaminsky, 1982). Successful commercial
application of radiation-curable systems did not evolve until th3 early 1970’s. The publicized driving
forces behind the development of commercially viable systems were the energy crisis of the early
1970’s and the growing environmental concerns about VOC emissions resulting from conventional
thermal-curable systems (Kubisen, et
al., 1984; Lankford, 1983). However, the primary motivations for
the use of radiation-curable systems are improved product performance and productivity (Lawson and
Kaminsky, 1982).
The early applicationsof radiation-curable systems were limited
to flat line processes mainlyin
the lumber and printing industries (AFP/SME, 1986). This was primarily because radiation-curable
processes of that time could only be cured whenin the line-of-sight of the radiative source. Starting
in 1974,UV-curableinksandovervarnisheswereusedfordecoratingaluminumbeveragecans
(LeFevre, 1980). Improvements in plant engineering, such as rotating conveyers and adjustments
to
the curing equipment, have allowed the three-dimensional application
of radiationcurablecoatings and
inks(LawsonandKaminsky,1982). In addition,advances in thefield of polymersciencehave
provided a wide variety
of materials for formulations whichcan exhibit the characteristics required by
an end-user in specific industrial applications (Decker, 1987).

2.2 CHEMISTRY
The basic chemistry ofradiationcurable systems involvestwo components which makeup the
polymer network of a coating or ink formulation. One component of a formulation is reactive resins,
which form the backboneof the coating. Usually referredto as oligomers, these compounds typically
A second component in a formulation
have a relatively high molecular weight and are highly viscous.
is the reactive diluents. Reactive diluents are low molecular weight materials used to reduce the
viscosity of a formulation (Danneman, 1988). These reactive diluents become part of the polymer

2
network and enhance or add to the physical properties
of the coating or ink. The formulation may also
contain other components such as pigments, flow modifiers, and fillers.
The polymer network is formed by either bridging existing polymer chains
(e.g., vulcanization of
two compatible reactive
of compounds that contain at least
rubbers) or by promoting the polymerization
functionalities in their molecules. The latter characteristic results in a chain reaction which develops
rapidly when radiation (UVor EB) is usedto produce the initiating species andcan ultimately leadto
a network exhibiting a very high crosslink concentration (Decker, 1987). In EB-curable formulations,
the radicals required for crosslinking the oligomers and/or monomers are generated through electron
bombardment (Lankford, 1983). UV-radiation, on the other hand, does not have enough energy to
produce initiating species in sufficient quantity and thus requires a photoinitiator to initiate the chain
reaction. Photoinitiators are compounds which absorb incident light and produce initiating species with
high efficiency.
The various photoinitiators in use are classified into three major categories dependingon the
mechanism involved in their photolysis. The most efficient category of photoinitiators forms radicals
byphotocleavage,aprocessbywhichthephotointitiatormoleculeisfragmentatedbyuse of
electromagnetic energy. UV radiative energy dissociates abond in the photoinitiator, resulting in the
formation of two radicalmolecules.Included in thiscategoryarearomaticcarbonylcompounds,
benzoin derivatives, benzilketals, acetophenone derivatives, and hydroxyalkylphenones, where the
benzoylradicalisthemajorinitiatingspecies.Otherinitiators of thephotocleavagetypeinclude
acylophosphine oxides and the substituted a-amino ketones (Decker,
1987).
Thenextcategoryofphotoinitiatorsgeneratesradicalsbyhydrogenabstraction.Aromatic
ketones,whenpromoted to anexcitedstate by UV-radiation,abstractahydrogenatomfroma
hydrogen-donor moleculeto the oxygenin the carbonyl group, which generatesketyl
a radical and the
donor radical. The hydrogen-donor molecules most often used in this type of initiation are tertiary
amines. In this case, the hydrogen-donor radical initiates the polymerizationof the formulation. The
ketyl radicals are consumed mainly through a radical coupling process. Compounds included
in this
type of photoinitiation are benzophenone and thiozanthone.
The last category of photoinitiators are cationic photoinitiators. Aryldiazonium salts undergo a
fast fragmentation under UV-radiation with formationof free Lewis acids which are efficient initiators
for the polymerizationof epoxy monomers (Decker, 1987).
Fourdifferenttypes of polymerizablesystemsarecommonlyusedforradiation-curable
applications.Early radiationcurable systemswerebasedonunsaturatedpolyesterresins.The
reactivediluentused in thesetype ofsystems isusuallystyrenemonomer.Theresultingcured
material is very hard and solvent-resistant. The curing rate
of this system, however, is relatively slow,
and problems with air pollution may arise from the volatility of the styrene diluent. Due to their low
cost, polyester resins are used mostly
in industries where large tonnages are involved (Decker,
1987).

3
 Multifunctional acrylates are the most widely used compound in
class
radiation-curable systems
1984). The varietyof multifunctional
due to their high reactivity, moderate cost, and low volatility (Bean,
acrylates allows this type of compound class to be used as both an oligomer and a reactive diluent.
Multifunctionaldy of acompoundmeansthatithasmorethanonepotentialreactionsiteforthe
polymerization process (AFP/SME, 1986). A large variety of prepolymer material is available to the
end-user, allowing for the creation of polymer networks with tailor-made properties. Because of the
high viscosityof the oligomers, reactive diluents must be added to the formulation. These are usually
low volatility mono- or multifunctional acrylates that provide good application properties and increase
the cure speed (Decker,1987). The diluent material reacts with the oligomers to become part of the
coating. However, depending on the vapor pressure of the material, a small fraction may be emitted
into the surroundings before the curing process is completed.
Thiol-polyene systems use the photochemically-induced addition of a thiol to an olefinic double
bond as the network-forming reaction, provided multifunctional materials are involved. Using hydrogen
abstraction photoinitiators, thiol-polyene systems are not very sensitive to oxygen inhibition because
radicals formed by oxygen scavenging can still abstract hydrogen from a thiol group and continue the
chain reaction. A broad range of properties can be obtained for the cured material by varying the
functionaldy and the backbone structure of both the polyene and polythiol.
Thelasttypeofpolymerizablesystemdiscussed is theuseofcationicpolymerizationof
epoxides.Thesesystemsinvolvethecationicringopeningpolymerizationofepoxyresins,when
catalyzed by a Lewis acidor protonic acid. Such systems are less sensitive to oxygen inhibition than
unsaturated polyester or multiiunctional acrylate systems but have a relatively slow cure rate. Claims
have been made that systems using cationic polymerization of epoxides cause less skin irritation than
acrylate systems (Vrancken, 1980; Decker, 1987). The main characteristics of the various radiation-
curable systems are compared in Table 2-1.

2.3 CURINGANDDRYINGEQUIPMENT
When a coating or ink has been applied to a substrate, the "wet" coating or ink must be cured
before proceeding in the manufacturing process. Conventional thermal-curable systems use a dryer
tunnel. Frequently, high velocity heated airis used to drive off solvents from the coating, leaving a dry
film (Lankford, 1983). In the case of solution and reactive coatings, the temperature initiates the
polymerization reaction. Radiationcurable systems,
on the other hand, cure at room temperature using
radiative energyin the form of accelerated electron energy (EB)or electromagnetic energy (UV-light)
to cause the formation of the polymer network (AFP/SME, 1986).

4
 TABLE 2-1. COMPARISON OF THE MAIN CHARACTERISTICS OF RADIATION-CURABLESYSTEMS

OXYGEN EB uv
REACTIVITY
SYSTEM
INHIBITION
DURABILITY
CURABLE
CURABLE
~ ~~

Low
Polyester/styrene High Poor No Yes

Acrylates High Moderate High Yes Yes

Thiol-polyene High
High Low Yes Yes

Cationic Epoxies Fair

Medium Low No Yes
Sources: Decker, C..‘UV-CuringChemistry: Past, Present, and Future,’ J. ol C08thp Tech.,59(751):97-108,1987.
Vrandcen. A, ’Market Trends for IrradiationCurable Coatings and Printing Inks in Eumpe,”fmm the pmceedings of Radiation Curing V; A L& to the
80’s. ksoaation of Finishing Processes of M E , Sept. 23-25, Boston,MA. 1980.

UV-curable systems typically use medium-pressure meicury vapor lamps to generate the UV
of 200 to
radiation energy for curing. These lamps provide electromagnetic energy with a wavelength
400nanometers(Frecska,1987;Garratt,1984).UV-radiation in thisrangeprovidestherequisite
A UV-curable
energy to the photoinitiators to form the radicals which begin the polymerization process.
systemalsohasreflectorstoenhancethefocusanddistribution of UV-lightontothesubstrate.
Shutters may be a part of the UV-curing system to protect heat-sensitive substrates which may be
under the lamp when the conveyor stops. These shutters are normally linked with a press or belt
switch and close automatically when the coating or printing line stops (Knight, 1979). UV-curing
systems require shielding
to minimize exposureto UV-radiation by the curing process personnel. Since
UV-light is not visible to the eye, workers may not be aware of its presence or related dangers. The
skin and eyes are particularly vulnerable
to injury caused by overexposureto UV-radiation. Common
injuries caused by overexposure are skin erythema
(i.e., sunburn), heat stress, eye conjunctivitis, and
lesions on thecorneaknownasphotokeratitis.Chronicoverexposure can result in skincancer,
cataracts, retinal damage, keratoconjunctivitis, genetic alteration, and asthenopia (Kovachik, 1987b).
UV-curing systems also may require a ventilation system for the irradiation area to remove ozone
generated when short wavelength
UV photons are absorbed by oxygen. Ozone generation by the UV-
curing system canbe minimized with the use
of quartz filters fitted
to the lamp which filter out the short
wavelength photons (Kovachik, 1987b):
Most EB-curable systems include a power supply, vacuum system, and an electron beam gun,
which is used to bombard the coated substrate with accelerated electrons (Lankford, 1983). As the
electrons lose their energy in the coated material, the energy from the electron beam interacts with the
unsaturated prepolymer material, forming the radical required for the polymerization process to begin.
The amount of energy lost
by the electrons is directly related to the curing completeness
of the coating.

5
Personnel can receive ionizing radiation exposure from both electrons and x-rays. Protection from
ionizing radiation from electrons
can be achieved by preventing direct exposure
to the fluxof electrons
from the electron gun. Protection from x-rays is normally achieved by lining the unit with materialof
low atomic number followed by material having high atomic number. Current federal guidelines for
occupationalexposurelimitthedose-equivalenttothewholebody to 3 remsperyear,andan
accumulated occupational dose-equivalent to the whole body not exceeding 5(N-18) rem, where N
equals the individual agein years.
Radiation-curable system equipment is generally operated
as either a continuous web or sheet-
fed configuration. Figures2-1 to 2-4 provide the outlines
of the basic configurations usedin radiation-
curable systems with roll coating application.

2.4 LITERATURE
SOURCES
Table 2-2 lists literature sources that were reviewed in this project. This list represents the
sources available during the literature search and should not be considered an all inclusive list of
information sources on radiation-curable systems.

TABLE 2-2. LITERATURE SOURCES FOR RADIATION-CURABLE SYSTEMS

Radiation Curing (periodical)

Journal of Radiation Curing (periodical)
Journal of Coatings Technology (periodical)
Modern Paint and Coatings(periodical)
Furniture Design and Manufacturing (periodical)
Paint and Resin (periodical)
Conference Proceedingsand Literature published by the Association for Finishing
Processes of the Society of Manufacturing Engineers

6
 Coating
Reservoir

Roll

Unwind Roll Rewind

Roll
Station Station

-
Figure 2-1. UV-curable system continuous web configuration.

Feed
Conveyor

0 Feed
nStacking

-
Figure 2-2. UV-curable system sheet-fed configuration.

7
 Electron
lnotina Chamber /- Beam Gun

Roll

Beam
Collector
Unwind Roll Rewind Roll
Station Station

-
Figure 2-3. EB-curable system continuous web configuration.

Coating
Reservoir 7

Feed Stacking

-
Figure 2-4. EB-curable system sheet-fed configuration.

a
 3.0 RADIATION-CURABLE SYSTEMS IN INDUSTRY

3.1 CURRENTUSAGE IN INDUSTRY

Radiation-curable systems became a generally viable commercial process
in the early 1970’s.
Among the early successful radiation-curing processes were printing operations and wood processing
operations (Bean, 1984; Garratt, 1984; Currier, 1989; AFP/SME, 1986). Since their introduction into
in many applicationsin the surface coating
manufacturing, radiation-curable systems have been used
and printing industries. Table 3-1 provides a general overview of the main applications of radiation-
curable systems. One of the primary uses of radiation-curable systems isin resilient flooring, where
no-wax floor coatings are radiatively cured onto vinyl tiles (Pincus and Sickinger, 1988; Pincus, 1983;
Prane, 1980). The graphic arts industry is anotherlargeuser of UVcurable inksandvarnishes,
accounting for almost 50 percentofthe radiationcurable market (Decker, 1987; Morris, 1984). A
relatively new, yet quickly growing, industry using radiation-curable systems is the microelectronics
industry (Frecska, 1987).
After the initial success of UV systems in wood processing, no-wax resilient floors, and printing
inks, experts predicted radiation-curable technology would soon capture at least 20 percent of the
overall surface coating and ink market. However, the facilities using radiation-curable systems have
been limited to 2 to 3 percent of the overall surface coating and ink market (Schessler, 1984).
Intense competition among equipment manufacturers and material suppliers has led to dollar and
product volumes being regarded as proprietary information, which makes
it difficutt to assess market
size (Pincus, 1983). However, hundreds of companies, ranging from large corporations to small job-
shops, use radiation-curable systems
in manufacturing processes. Table3-2 provides a small sample
of companies which are currently using radiation-curable technologies.

3.2 ADVANTAGES OF RADIATION-CURABLESYSTEMS

Radiation-curablesystemshaveadvantagesoverconventional thermalcurable systems in
energy efficiency, operating environment(i.e., working condiiions), facility usage, and productivity.In
general, the majorityof current radiation-curable systems contain none
of the organic solvents found
in conventional coatings and inks.In fact, the film forming componentsin a radiationcurable system
may be consideredto be essentially 100 percent reactive, which means
all of the materialis converted
into the polymer network, and nothing evaporates before the or
coating
ink is considered dry (Lankford,
1983). The exception to this is some photoinitiators for UVcurable systems, which may not become
part of the formed polymer system of the film and are available for migration, extraction, and/or
absorption(Bean,1984).Consequently, no additionalenergyisrequired to volatilizeanorganic
solvent. This results in EB and UV systems using only about 20 percentof the energy consumed by
of heat energy,in contrast to the thermal systems, means
thermal systems (Clark, 1990). The absence

9
 TABLE 3-1. CURRENT APPLICATIONS OF UV-CURABLE SYSTEMS

Estlmated Process in
1985
(million pounds)

Surface Treatment
Graphic Arts'
Wood Finishes 13
Metal Coatings 10
Plastic Coatings N/A
Paper Varnishes 15
Resilient Flooring 16

Electronics 142
Printed Circuits (negative photoresists)
Sealants (encapsulation)-
Protective Coatings (optical fibers)
Patterning (video disks, compact disks)

Pigmented Resins
UV-Curable Inks 11
Print Plates 14
Dental Material N/A

Adhesives
Laminates N/A
Sealants N/A
Bonding N/A
Pressure Sensitive N/A

'Gnphic Arts usage is retleded in Metal and Plastic Coatings. Paper Varnishes. UV-Curable Inks and Print Plates.
b a a nflect industry-wide usage.
-
-
NIA Data not available
1 pound , 4 5 4 kilogrpm

Dedcer, C.. 'UV-Curing Chemistry: Past, Present. and Future,' J. of Coati- Tdmobgy, 59(751)97-106,1987. Prane, J.W.,
-
'Ultraviolet Curable 'halings and Inks Markets and Pmjediom,' fmm the pmceedings of R d W n Curing V: A Lodc lo the
BO!! Association of Finishing Pmcesws of W E . Sept. 23-25. Boston. MA, 1980.

that the radiation-curable systems operate

at or near room temperature. Becauseof the low operating
temperature,radiation-curablesystemscanbeusedontemperature-sensitivesubstrates(e.g.,
polyethylene,
polypropylene,
polyzgstyrene,
wood,
lowquality
paper).
Thereduced
energy
requirements result in a 75 to 90 percent savings on energy costs over thermal-curable systems
(AFPISME, 1986; Lawson and Kaminsky, 1982).

10
 TABLE 3-2. A SELECT SAMPLE OF COMPANIES USING RADIATION-CURABLE SYSTEMS

Company Usage

Coors Container Company Metal Coating

Loewenstein, Inc. Furniture
The Stanley Works Metal Coating
Corning Glass Fiber Optics
Solder Woodworking Furniture
Universal Wood Furniture
Westvaco Paper Coating
Metalized Products Thermal Blankets
American Telephone & Telegraph Fiber Optics
Doubleday Paper Coating
Armstrong World Color Resilient Flooring
General Motors Sealants and Adhesives
James River C o p Graphic Arts
Hallmark Graphic Arts

Sources:Proceedings of Radation Curing V: A Look to the 80s,Association of FinishingProcesses of SME, 1980.

Proceedings of Radcure ‘84 Conference, Association of Finishing Processes of SME, 1984.

The second advantage of radiation curing systems over thermal equipment is the different facility
space requirements. The basic requirement of the curing equipment, regardless of type, is to provide
a sufficient residence time for the requisite energy to cure the coating or ink. In thermally-cured
systems, the coated material is subject to heat transfer rates. Time is required to heat the substrate
and coating to the proper temperature to vaporize the solvent and cause chemical crosslinking.
Depending on the volatility of the solvent, the initial temperature of the coating and the speedof the
production line, the length required for the dryer tunnel to evaporate and exhaust the solvent and cause
15 and 230 feet (4.6 and 70.2 meters),
potential curing reactions to be completed can vary between
(Lankford, 1983; Clark, 1990). Radiation-curable systems, on the other hand, require a short time
period for the radiative energy to generate the initiating species.
A chain reaction then takes place to
curethecoating.Consequently,UV- or EB-curingequipmentismorecompactthanthethermal

11
counterpart and requires less space. For example Coors Container Corporation replaced a 230-foot
thermal oven used to cure paint on beer cans with a six-foot UV curing system (Clark, 1990). Such
an example may be extreme, but, on average, radiation curing systems require50 to 75 percent less
space than thermal-curing systems (Arnold,1984).
Another advantageof radiation-curable systemsis the potentialfor higher production rates than
1984; Lawson and Kaminsky,1982).
thermal-curable systems due to their rapid curing rates (Morris,
The more rapid curing rate
of radiation-curable systems allows for faster production throughputs, either
from faster line speeds, elimination
of an oven pass, or more rapid handling
in subsequent operations.

The highly crosslinked nature of radiation-curable systems provides advantageous characteristics

for the resulting coating film. Characteristics, such as solvent and heat resistance, provide the coated
substrate with better stain resistance and resistance to any possible heating operation than most
conventional coatings (AFPISME,1986). High scratch resistance and improved resistance to natural
weathering over conventional coatings can be achieved with systems that have high crosslink density
characteristics (Morris, 1984; Decker, 1987).
The fact that radiation-curable coatings anddo
inks
not cureuntil exposed to the proper radiation
source provides a distinct advantage overthermal-curable systems. This allows for easier maintenance
of theapplicationandcuringequipment,sincethecoatingorinkwillnotcureintheproduction
equipment during normal operations. The absence of heatin the process allows for a more rapid and
efficient maintenanceof the curing equipment. Since radiation curing equipment systems are “instant
on” systems, there is no need for lengthy cool-down and warm-up periods as required by thermal
ovens (LeFevre, 1980).

3.3 LIMITATIONS OF RADIATION-CURABLESYSTEMS

Although radiation-curable systems have advantages over conventional coatings and inks, they
alsohavesomeinherentlimitations,whichmayrestrictpotentialapplications to commercial
environments. The more severe limitations are examined in the following pages.

3.3.1 OxygenInhibition
Some coatings lose some of their reactivity when exposed to air. Such
inhibition has a retarding
effect on the curing process due to molecular oxygen’s affinity
for the free radical, forming a peroxide
(Decker, 1987). Such reactions deplete the number of free radicals. They are therefore no longer
to continue the polymerization chain reaction. Further, such
available to react with unsaturated bonds
copolymerization of oxygen into the polymer network presents potential reactive sites for subsequent
photodegradation. Relatively small amounts
of oxygen can result in a coating with a tacky surface after
curing because of reduced chain length or molecular weight (Vrancken, 1980). UVcurable systems

12
 a

typically are not as sensitive to oxygen inhibition as EB-curable systems, because a high concentration
of photoinitiatedradicalsisfound atthesurface. A highconcentration of radicals atthesurface
interface is required to offset the competition from molecular oxygen (Vrancken, 1980). If oxygen
inhibition becomes a problem for UVcurable
a system, increasing the light intensity or the addition
of
oxygen barriers, such as nitrogen blanketing, can minimize the undesired effects (Decker, 1987).
Oxygen inhibition is more of a problem in EB-curing systems. Unlike UV-curable systems, radical
formation in EB-curable systems is not higherat the surface. This means that an insufficient quantity
of free radicals is present at the surface to surmount the effect of molecular oxygen. To solve the
oxygen inhibition problem, EB-curing is typically carried out within an inert cure zone using a nitrogen
gas blanket as the oxygen barrier (Vrancken,1980).

3.3.2 Cure Penetration

One of the major limiting factors of UV-curable systems is the thicknessof the film which can
becured,due to boththelight’sinabilitytopenetratetheorganicmatterwhichcomprisesthe
prepolymer material and the depletion of light energy due to absorption by surface photoinitiators
(Decker, 1987). Studieshaveshownthat as thepercentageofphotoinitiator in anUV-curable
formulation increases, the quantity of light energy penetrating the coating decreases (Lewarchik and
Hurwitz, 1984). Most of the applications of UV-curable systems, therefore, have been restricted
thin to
films and coatings. Another limitation of UV-curing involves the curing of pigmented coatings. The
pigment in a formulation blocks the light and restricts the spectral region available for efficient utilization
by photoinitiators (Garratt, 1984). Most UV-curable systems operate in the wavelength range of 200
to 400 nanometers. Successful applications of clear UV-curable systems have
been achieved with film
thicknesses of 130 to 250 pm (0.005 to 0.01 inches) (Lewarchik and Hurwitz, 1984). Pigmented UV-
curable systems, however, have been cured with film thicknesses up to only 50 pm (0.002 inches)
(Bean, 1984).
Cure penetration can be improved by reducing the concentration of the photoinitiator in the
coating formulation, which improves the depth of cure penetration,
but lengthens the cure rate. High
intensity light, such as pulsed sourcesor lasers, may improve the depth of penetrationof the light in
someapplications.Developmentofphotoinitiatorswhichbecometransparentto UV lightupon
1987). Pigments with good hiding power have
photolysis would also improve cure penetration (Decker,
also been developed for printing inks of 10 to 15 pm (0.0004 to
a 9 can be cured at film thicknesses
0.0006 inches) at practical line speeds (Garratt, 1984). Increasing the number of lamps is another
means of improving the
curing processfor pigmented coatings. However, this compromises the space-
saving and energy cost advantages to some extent (Schessler, 1984).

13
3.3.3 Viscosity
Thehighviscositycharacteristic of radiation-curablecoatingsorinks is notwellsuitedfor
traditional coating equipment. Over two-thirdsof traditional, thermally-cured finishes are applied by a
spray process which requires a relatively low viscosity (Lawson and Kaminsky,
1982). The application
of inks in various printing processes also requires a specific viscosity
as shown in Table 3-3.
Typically, before a reactive resin can be applied to a substrate in an industrial process, the
viscosity must be reduced to meet the requirementsof the application equipment. Several viscosity
reductionmethodshavebeendevised,includingamethodinvolvingtheaddition of low-viscosity
reactive diluents. Instead of evaporating during curing like solvent diluents in conventional systems,
most reactive diluent materials react with the growing polymer chain to become part of the finished film
(Danneman, 1988). Thus, only a fraction of these reactive diluents are emitted to the atmosphere.
Use of reactive diluents, however, does have potential limitations. One such limitation is that these
reactive diluents may resultin unwanted physical changes
(e.g., brittleness, yellowing)in the resulting
film (Lawson and Kaminsky,1982). The reactive diluentsmay also possibly cause problems with the
cure rate of the system because some low-viscosity reactive diluents have poor curing rates (Bean,
1984). Emissions problems may also arise, since the reactive diluents with the lowest viscosities are
likely to be the most volatile, hence a greater fraction evaporates before reaction
(AFPBME, 1986).
Another methodof reducing the viscosityof a radiation-curable coating or ink
is the application
of 15°C would frequently
of heat to the formulation. Studies have shown that a temperature increase
reduce the viscosity of a formulation by half (Lawson and Kaminsky, 1982; Bean, 1984). As with
adding reactive diluent, heating the formulation
to reduce the viscosity also has limitations. For highly
viscous formulations, heating may not reduce the viscosity
to a degree necessaryfor the application
equipment. In addition, applying too much heat may cause the formulation
to decompose and to emit
acrid smoke and irritating ortoxic fumes (Sax and Lewis, 1989). Furthermore, heating increases the
evaporation rate and may resutlin greater VOC emissions.
Reducing the viscosity of radiation-curable coatings or inks can also be accomplished by the
addition of an organic solvent to the formulation. This method has been gaining wide acceptancein
many application processes, especiallyin the furniture and wood processing industries (Riedell,
1989;
Currier, 1989). This method incorporates a quantity
of conventional solvent into the formulation
in order
to adjust rheological properties(i.e., viscosity) to permit the use of spray equipment (Garratt, 1984).
The solvents used are usually fast evaporating (i.e., ketones and alcohols) and provide the proper
viscosity for good atomization and rapid flow over on the substrate when using spraying equipment
(Lawson and Kaminsky,1982). Before the formulationcan be exposed to the radiation source, flash
time is required to remove the solvent (FDM, 1989b). Sprayable UV-curable systems used in the
furniture industry generally contain
47 percent by volume (40 percent by weight)

14
 TABLE 3-3. VISCOSITY RANGES FOR VARIOUS PRINTING PROCESSES

Printing Process Viscosity at 25°C

(Centipoise)

Letterpress 1,000 - 50,000

Lithography 10,000 - 80,000
News Ink 200 - 1,000
Flexography 50 - 500
Gravure 30 - 200
Screen Printing 1,000- 50,000

Source: RadiationCuring:AnIntroduction to Coatings,Varnishes,Adhesives and Inks,SecondEdition,TheAssociation

for Finishing Processes of the Society of Manufacturing Engineers, 1986.

conventional volatile organic solvents.

A conventional thermal-curable coating for similar use contains
85 percent by volume (79 percent by weight) organic solvent (Currier, 1989). In addition, there are a
fewspray applications of radiation-curable systems which require high organic solvent contents
in the
rangeof70 to 80percentbyvolume.Whentheseorganicsolvent-containing,radiation-curable
systems are used, removal of the organic solvents from the coating must be conductedin a manner
similar to thermal-curablecompounds.Additionalsafetyfactorsmust be includedsincemost
UV-curable units are not equipped for handling solvent laden atmospheres (Lawson and Kaminsky,
1982). An alternative may be found in water-based UV-curable acrylate resins being developed in
Europe for low-viscosity, low VOC-emitting inks and top coats (Ashcroft, 1987). Similarly, there are
waterborne radiation-curable nitrocellulose systems are availablein the United States.
Theuseoforganicsolvents to reducetheviscosityofradiation-curablecoatingsandinks
compromises some of the advantages inherent to the systems. For example, increased space would
be required and a potential for increased energy demand for the coating process to evaporate the
organic solvent priorto initiating the polymerization process. Additionaliy, an undesired effect
of using
organic solvents as a viscosity reducing agent is the need
to control VOC emissions. Likely sources
of VOC emissions resulting from organic solvent-containing, radiation-curable systems wouldbe the
to install an emissions controls system
spray booths and drying areas and may require the facility to
meet local regulations.

3.4 POTENTIALAPPLICATIONS FOR RADIATION-CURABLESYSTEMS

Radiation-curable systems have the potential to be used in nearly every application which
employs conventional thermal-curable coatings and inks. In most cases, the application equipment
used for the thermal-curable systems can be used with some modifications for the radiation-curable
systems. The more promising usesof radiation curable systems involve application techniques which
apply materials having relatively high viscosity. Among such application techniques are roll coating,
offset lithographic printing and screen printing. Roll coating processes are used in the wood industry
for applying fillers and top coatings andin the paper, plastics, and metal industries for applying clear
protective top coats (Jones, 1980). Roll coating applications can operatein either a continuous web
or sheet-fed configuration. Offset lithographic processes are being used with radiation-curable inks in
the metal decorating industry (e.g., two-piece beverage cans) (Schessler, 1984). The use ofUV-
in the electronics industry.
curable inks in conjunction with screen printing processes has been used
Spray and dip-coating applicationsof radiation-curable systems are possiblewith the addition
of a volatile organic solventto control the viscosity. Spray applicationof UV-curable top coats with a
low VOC content 3 to 5 pounds per gallon (360 to 600 grams per liter) is currently being usedin the
wood furniture industry (FDM, 1989a).

16
 4.0 TOXICITYDATA

4.1 GENERALTOXICOLOGICALDATA
Unstable chemistryof formulations and dermatitis problems from formulations used in graphic
arts left early radiation-curable systems with a reputation
high
fortoxicity (Pincus and Sickinger,
1988).
This perception continues to the present time to some degree and may be the resultof workers not
1986). More recently developed
fully understanding or respecting the materials being used (AFPISME,
radiation-curable systems have shown a continuing shift towards lower toxicity levels. Today, the
toxicity of a radiation-curable system depends greatly on the formulation technique.
As a general tule,
manufacturers try
to exclude from use those ingredients which are suspected carcinogens, tumorogens,
1982). This, however, is not always possible. Some functional
and mutagens (Lawson and Kaminsky,
1989). As a whole, most
acrylic-based polymers or copolymers may exhibit toxic properties (Currier,
acrylicunsaturatedcompoundsarenotconsideredtoxic(Vrancken, 1980). In general,reactive
diluents and some oligomers are skin and eye irritants (AFP/SME, 1986). Draize scores, a measure
of skin and eye irritation, range between1.5 and 6.2 for monomers usedin radiation-curable systems
(Bean, 1984; Kubisen et al., 1984). A draize scoreof 8.0 constitutes a severe skin irritant.In addition
to beingskinirritants, someradiation-curablematerialshavebeenshownto be oncogenic or
carcinogenic. A skin study with male mice indicated that 2-ethylhexyl acrylate and neopentyl glycol
diacrylate are oncogenic (DePass, 1982). Other skin painting tests have shown tetraethylene glycol
diacrylate,triethyleneglycoldiacrylate,and 2-ethylhexylglycoldiacrylate to be veryweakskin
carcinogens(AFP/SME, 1986). However,duetothelowvolatility of radiation-curablesystems,
inhalation risks to workers can be minimized (Vrancken,1980; AFP/SME, 1986).
The solvents used
in conventional thermal-curable systems have their own
of risks.
set The high
volatility of these solvents requires worker protection from inhalation
of the compounds. Methyl ethyl
ketone,acommonlyusedsolvent,causesirritation of theeyesandnoseand is consideredan
experimental teratogen(Sax and Lewis, 1989). Nearly all of the ketones used as solvents for paints,
varnishes, and lacquers are considered eye and nose irritants (Sittig, 1985). Methanol, an industrial
solvent for inks, can cause mild dermatitis upon contact. Systemic effects of chronic exposure to
methanol include optic nerve damage(Siig, 1985). Glycol ethers, a classof solvents used for inks,
1984). The cleaning chemicals
paints, lacquers, and varnishes are suspected carcinogens (Schessler,
for radiation-curable systems shouldbe similar to those used in thermal-curable systems and should
present no increased risks.
Enactment of the Toxic Substance Control Act (TSCA) in 1977 gave EPA broad authority to
regulate new and existing chemicals. Under this Act, EPA is charged with assessing the risks posed
by toxic chemicals to human health and ecosystems (Plamondon and Keener, 1984). Most of the
materials usedin radiation-curable systems are under the jurisdiction
of this Act. The development of

17
new compounds for radiation-curable systems is regulated under Section 5 of TSCA, which requires
manufacturersorimporters of achemicalnotincluded in the TSCA inventory to submita
Premanufacturing Notice (PMN) for new to its manufacture
a chemical substance (NCS) 90 days prior
(Svoboda and Schwebke, 1987). During the 90-day period, EPA must decide whether or not the NCS
presents an unreasonable risk. If EPA takes no action within 90 days after the PMN submission, the
NCS is presumed not to pose an unreasonable risk, and the submitter is free to manufacture the
substance (Plamondon and Keener, 1984). Over the past few years, the safety of acrylate material
has been questioned and, thus, few if any new acrylate materials have cleared the PMN regulatory
process (Kovachik, 1987a). EPA has increasingly invoked Section 5(e) of TSCA for radiation-curable
materials which allowsEPA to ban or place limits on the NCS that may pose the unreasonable risks
(Plamondon and Keener, 1984). As a result, the industry feels that TSCA regulations have inhibited
innovations (Nelson, 1987). Industry groups (Basic Acrylic Monomer Manufacturers Association and
Specialty Acrylates and Methacrylates Program) have been working with to resolve the regulatory
EPA
differences, but some regulatory problems still remain (Clark, B90).
The recently passed Clean Air Act Amendments (CAAA)
of 1990 may also have an impact on
Ill of the CAAA, EPAis requiredto develop emissions standards
radiation-curable systems. Under Title
forailstationarysourcecategorieswhichhaveemissions of 189 listed hazardousairpollutants.
Several ofthecompounds used in radiationcurablesystemsareincluded on thislist(e.g.,
to reduce the
acetophenone, benzophenone, styrene). The list also includes several compounds used
viscosity of radiation-curable formulations, such as methanol, methyl ethyl ketone, toluene, and xylene.
The emission standards developed byEPA for new and existing sources of hazardous air pollutants
will require the maximum degree
of reduction in emissions after considering the cost
of achieving the
emission reduction, any nonair quality health and environmental impacts, and energy requirements.
Emissions standards for all 189 compounds are to be promulgated by the year 2000.

4.2 PERMISSIBLE EXPOSURE LIMITS

TheOccupationalSafetyandHealthAdministration(OSHA),theNationalInstitutefor
Occupational Safety and Health (NIOSH), and the American Conferenceof Governmental Industrial
Hygienists (ACGIH) have developed exposure limits for workers for a variety of chemicals used in
industrial settings. Some of the componentsof radiation-curable systems have permissible exposure
limits(PEL)determinedbytheseagencies.Table 4-1 provides PELvalues for radiation-curable
materials. This list should not be considered all inclusive given the large quantityof material usedin
radiation-curable processes. Table 4-2 provides PEL values for potential organic solvents used in
conventional thermal-curing processes.

18
 TABLE 4-1. PERMISSIBLE EXPOSURE LIMITSOF RADIATION-CURABLE MATERIAL

Compound &hour time

weighted average limit

Acetophenone No Standard Available

Benzophenone No Standard Available
Caprolactone acrylate No Standard Available
2,2-Dimethyltrimethylene acrylate No Standard Available
1 ,CDivinyl benzene 10PPm
Epoxy acrylate No Standard Available
Ethoxyethoxyethylacrylate No Standard Available
Ethoxyethyl acrylate No Standard Available
2-Ethylhexyl acrylate 50 PPm
2-Ethylhexyl methacrylate No Standard Available
Glycerolpropoxytriacrylate No Standard Available
Hexanediol diacrylate '- No Standard Available
Hydroxypropyl acrylate 0.5 ppm'
Methylcarbamoyloxyethyl acrylate No Standard Available
Pentaerythritol triacrylate No Standard Available
Phenyl glycidyl ether 10 PPm
Styrene 100 ppm
Trimethylolpropane triacrylate No Standard Available
Trirnethylolpropane tri(3-mercaptopropionate) No Standard Available
Tripropyleneglycoldiacrylate No Standard Available
Vinyl cyclohexene dioxide 10 PPm
n-Vinyl pyrrolidone No Standard Available

4.3 SAFETY AND RADIATION-CURABLESYSTEMS

Thecompoundsused in radiation-curablesystemscan be handledsafely if thepersonnel
involvedfullyunderstandthenature of thehazards.Oneprincipalsource of informationonthe
chemicals used in aformulationisthematerialsafetydatasheet (MSDS). Requiredbythe
for chemicals usedin the workplace,MSDS's
Occupational Safety and Health Administration (OSHA)
contain product hazard and safety information aimed
at helping workers and customers use products
safely(Kovachik,1987b).Asageneralrule,radiation-curablesystems can be handledsafely if

19
measures are taken to eliminate dermal contact with the compounds. The protective clothing used
should be compatible with the compound being handled. Proper eye protection should always
be used
when handling radiation-curable materials in liquid form. Good hygiene practices should be followed
includinguse of barriercreambeforestartingwork,neverusingasolvent to wash,andproper
housekeeping of the work area (Scott, 1987).

20
 TABLE 4-2. PERMISSIBLE EXPOSURE LIMITS OF ORGANIC SOLVENTS

Compound &hour time

weighted average limit (ppm)

n-Butoxyethanol 50
Butyl acetate 150
n-Butyl glycidyl ester 50
Butyl lactate 5-
p-tert-Butyl toluene 10
Carbon tetrachloride 10
Diisopropyl ether 500
N,N-Dimethylacetamide 10
Dipropylene glycol methyl ether 100
Dipropyl ketone 50
2-Ethoxyethanol 200
2-Ethoxyethyl acetate 100
Ethyl acetate 400
Ethyl butyl ketone 50
Ethyl ether 400
sec-Hexyl acetate 50
lsophorone 25
Isopropanol 400
Isopropyl acetate 250
Mesityl oxide 25
Methyl acetate 200
Methylal 1,000
Methyl alcohol 200
Methyl n-amyl ketone 100
Methyl n-butyl ketone 100
Methylcyclohexane 500
Methyl ethyl ketone 200
5-Methyl-3-heptane 25
Methyl isoamyl ketone 50'
n-Propyl alcohol 200
Propylene glycol monomethyl ether 100'
1,I,2,2-Tetrachloroethane 5
Tetrahydrofuran 200
Toluene 200
Xylenes 100

'Note: No Federalstandard, value recommended by ACGIH.

Source: Sittig, M., HandbookofToxicand Hazardous ChemicalsandCafcinogens, 2ndedition, Noyes Publications, Park
Ridge, NJ. 1985.

21
 5.0 EMISSIONS DATA

There is a general lack

of published data about the volatile organic compound (VOC) emissions
from radiation-curable systems. One study reported the volatile component emitted by a traditional
100 percent reactive radiation-curable system comprised about
2 percent of the formulation (Lawson
and Kaminsky, 1982). This volatile component consisted largely of monomers and dimers. Another
1 percent loss after UV-curing
study evaluating aUVcurable coating on metal showed approximately
and a total8.5 percent loss after a subsequent baking (AFP/SME,1986). The study, however,did not
identify the composition of the volatile components. One study, which included sampling with a gas
chromatograph in the neighborhood of a printing press using an UV-curable varnish, detected an
ambient concentration of less than 3 ppm of monomer (Vrancken, 1980). This would be expected,
since a majority of the compounds associated with radiation-curable systems have low vapor pressures
(AFPSME, 1986). Low vapor pressures are an indication that a compound will not readily volatilize
at ambient temperatures.
Another obstacle in evaluating emissions from radiation-curable systems is the lack of data
regarding the type and quantity most part, the formulations
of chemicals used by the industry. For the
used in radiation-curable systems are considered proprietary and are only described
in general terms
or by the trade name in the literature. The formulations provided in the literature did not include the
extent to which each is used by the industry. There are, however, several general statements which
can be made about emissions resultingfrom the application of radiation-curable systems.

5.1 THEORETICAL EMISSIONS RATE

The flux (emissions rateper unit area) of a compound into the air is definedby Fick's law and
can be expressed as (Shewood et al., 1975):

where
N, = Flux [(g mole/(sec)(cm2)],
DAB = Diffusioncoefficient(cm2/sec),
P = Pressure(atm),
R = Idealgasconstant((cm3(atm)/(gmole)(K)],
T = Temperature (K),
Ye,, YE, = Mole fraction of compound in air, and
yo = Distance in direction of diffusion(cm).

This equation assumes that a thin layerof stagnant air is in contact with the coating and that the air
does not dafuse into thecoating.Assumingtheenvironmentalconditions (i.e., temperatureand

22
pressure) do not change, the driving forces
of the flux are the diffusion coefficient and the mole fraction
difference from the coating surface to the edge
of the stagnant layer. This equation shows that there
is a proportional relationship between the flux and diffusion coefficient and the natural logarithm
of the
difference in the mole fractions. The diffusion coefficient of a compound can be calculated by the
theoretical equation derived by Chapman and Enskog (Lyman
et al., 1982):

where
DAB = 1.858x l o 3
[ 1
T1 .5(M,)0.5

M, (MA + MB)/MAMB
MA = Molecularweightofair; 28.97g/gmole,
MB = Molecular weight of the compound of interest (g/g mole),
CAB = Collisiondiameter,and
L? = Collision
integral.

The collision diameter and collision integral are functions of ‘iemperatureandarebasedonthe

Lennard-Jones potential (Weltyet al., 1976).A solution to this equation has been proposed by Fuller,
Schettler and Gibbings and
is based on the temperature, molecular weights and molar volumes (Lyman
et al., 1982). This solution is expressed as:

1 0-3 ~ 1 . 7 5~ , 0 . 5
DAB (5-3)
P ( V p + Vp)’
where
VA = Molarvolume of air; 20.1 cm3/gmole,and
V, = Molarvolume of thecompoundofinterest(cm3/gmole).

This relationship shows that the heavier compounds

will have a smaller diffusion coefficient and thus,
be less likely to volatilize from the surface.
To simplify the Equation5-1, the mole fractionat the edge of the stagnant layer is assumedto
approach zero. The mole fractionat the interface of the coating and air
can be estimated as (Lyman,
et al., 1982):
YB, = H/RT(&MW~/XX,MW,) (5-4)

where
H = Henry’slawconstant(atmm3/gmole),and
X = Weightfraction ofcomponent in coating.

Substituting Equations 5-3 and 5-4 into Equation 5-1 shows that the highly volatile organic solvents
used in thermal-curing systems will have a large flux. Conversely, the high molecular weight and low

23
volatility compounds used in radiation-curable systems will have a small flux. Although
some reactive
diluents may be highly volatile, they will have a relatively small flux, because they only make up a small
percentage of the formulation.

5.2 AIRBORNEHAZARD OF RADIATION-CURABLESYSTEMS

An airborne hazard from radiationcurable systems results from the potential overspray from
spray applications techniques. A buildup of overspray inside the plant should be avoided sinceit will
probably not cure and will become a source of worker contamination and skin irritation (Lawson and
Kaminsky, 1982). The exposure to facility personnel can be minimized through the
of an
useenclosed
automatic spray system. Robotics can be utilized in the enclosed area when complex or unusual
shapes are being coated (Lewarchik and Hunrvitz, 1984). Useofelectrostaticsprayequipmentis
another meansof reducing the amountof overspray (Riedell, 1989). The overspray can be recovered
for reuse in the coating operation, or the exhaust from the spray booth canbe treated with a water
wash or dry filters to remove overspray particles depending on the economics
of the recovery process
or waste disposal.

5.3 VOC
REDUCTION
POTENTIAL
As a means of reducing VOC emissions from surface coating operations, radiation-curable
coating can be very effective. For facilities involved with flat coating process (e.g., flatwood production,
100 percent reductionin VOC emissions over
paper coating, metal decoration, fabric coating), a near
conventional coatingscan be achieved by using radiation-curable coatings. These are processes for
which radiation-curable systems have traditionally been well suited (Schessler, 1984). Even when
organic solvents are used
to modify the viscosity of a radiation-curable system, a substantial reduction
to reduce coatings
in VOC emissions is possible in some applications. However, organic solvents used
to a sprayable viscositycan constitute up to 80 percent by volume of a sprayable UV-curable system.
This translates into a VOC content of approximately 720 kg/m3 (6.0 Ib/gal) of coating. This is nearly
the same degree as conventional nitrocellulose lacquer which typically has an organic solvent content
of 80 percent by weight or780 kg/m3 (6.5 Ib/gal) of coating (Riedell, 1989).
The degreeof VOC reductionto be achieved from converting to radiation-curable systems can
be estimated by comparing emissions from various formulations. The base case for this comparison
is one metricton (1.1 short ton)of conventional nitrocellulose lacquer finish a material commonly used
in spray applications in the wood furniture industry with an organic solvent content of 85 percent by
volume (Currier, 1989). The resulting uncontrolled emissions from this material are approximately
790 kg (1738 Ib)ofVOC.Emissions fromthreeUV-curableformulationswerecomparedwith
in Table 5-1. Case 1 is a sprayable UV-curable
emissions from this thermally-cured coating as shown
system diluted to a sprayable viscosity with reactive diluents. It is assumed that only 2 percent by

24
weight will evaporate from the formulation during the curing process. Case 2 represents the typical
solvent-containing UV-curable system used
in the wood furniture industry. This sprayable formulation
of percent by volume. Case3 illustrates the worst case
has an organic solvent content 47 for solvent-
containingradiation-curablesystems.Thishigh-solventradiation-curablecoatinghasanorganic
solvent content of 80 percent by volume.
For the purpose of the comparison, it is assumed that equal quantities of solid material are
contained in each of the coating formulation cases and that each coatingwill cover equal areas with
anequalfilmthickness. It shouldbenotedthatthissituationmaynotconformwithrealworld
conditions. However, this assumption can provide a crude approximationto show the potential VOC
emissions reduction for each radiation-curable system and illuminate a few interesting facts. As one
would expect, a conversionto the 100 percent reactive UV-curable formulation (Case
1) provides the
greatest VOC emissions reduction over the thermal-curable coating. Depending on the compounds
to a 100 percent reactive UV-curable formulation might eliminate the necessity
emitted, the conversion
of VOC control devices. A conversion to the high-solvent UV-curable formulation (Case
3) affords only
a relatively small improvement in VOC emissions over the thermalcurable coating. This means the
high-solvent UV-curable formulationwill require approximately the same size VOC control device as
the thermal-curable systemto meet VOC emission standards. A conversion to the typical sprayable
UV-curable formulation (Case2) would provide an 82 percent reduction in VOC emissions over the
thermal-curable system even though this formulationis nearly half organic solvent. The VOC device
be smaller and less costly than that needed
required to handle the evaporating organic solvents would
for thethermalarable coating.

25
 TABLE 5-1. VOC EMISSIONS REDUCTION RESULTING FROM CONVERSION
TO RADIATION-CURABLE COATINGS

CondRion
Estimated
Emissions
VOC Projected Percent Reduction'
in Kilograms (Pounds) due to UV-Curable Conversion

Base Case2 790

(1,738)

Case i3 4 (36) 99

Case z4 (308)
140 82

Case 35 630
(1,386) 20

-
Thermal Coating Emissions Radiation Coating Emissions
duction- 'Percent ~ x100
Thermal Coating Emissions
b n e metric ton of conventinal nitrocellulose lacquer lopcoatused in the furniture industry containing85 percent by
volume organic solvent.

'A sprayable UV-curable formulation dilutedto a spray viscosity withreactive diluents and has an evaporation rateof
two percent for the mixture.

'A sprayable UVwable formulation typically used in the furniture industry and diluted to a spray viscosity with
conventional solventsto 47 percent VOC by volume.

'A sprayable UVGurable formulation diluted with conventional solvents0 80 percent VOC by volume.

26
 6.0 COSTCOMPARISON

Another obstacle to widespread use of radiation-curable systems has been the perception of
higher costs than
for conventional thermalcurable systems.
In some cases, a cursory cost review may
have led facility management to conclude that radiation-curable systems are notas cost-effective as
conventional thermal systems. The emergence of competing technologies such as water-borne, high
solids, and powder systems has seemingly reduced the economic effectiveness of converting to a
radiation-curablesystem.However,thereareseveralintrinsiccharacteristics of radiation-curable
systems which may outweigh the perceivedcost disadvantage.

6.1 COSTSASSOCIATEDWITHCURINGEQUIPMENT
The cost of curing and application equipment form the basis of the total capital expenditure
or radiation-curable equipmentwill dictate, to a
required for the facility. The choice between thermal-
certain extent, some faciliy design features including size, suppbrt structures, utility requirements and
auxiliarysystems(e.g.,ventilationsystems). It hasgenerallybeentheperception in the thermal-
curable coating industry thatradiationcuring equipment is more expensive than conventional thermal
ovens. Industry literature, however, indicates that this is not always the case. The cost for a UV-curing
oven can range from $25,000 to $100,000(Pincus, 1983). The cost of a conventional thermal-curing
system is generally twice the cost of UV-curing equipment (LeFevre, 1980). EB-curing equipment,
$500,000 per unit, is more expensive than or
which costs approximately UV-
thermal-curing equipment
(Newcomb, 1985).
Radiation-curing equipment, however, has a distinct advantage over thermal equipment. In
costs for UV systems, radiation-curing equipment, for both
addition to lower actual equipment EB and
UVsystems, requires 50 to 75 percent less space than comparable thermal-curing systems. This
translates into the need for a smaller faciliiy to house the UV or EB equipment. This can be viewed
as an advantage when both converting an existing thermal process to a radiation-curable system or
constructing new production capacity. Radiation-curing systems generallycan be housed in existing
facilities, whereas increasing capacity using thermal systems may require construction
of a complete
facility, including all auxiliary physical plant equipment. When the Coors Container Company converted
to a UVcurable ink, for example, the 230-foot long thermal-curing oven was replaced with a six-foot
long UV-curing oven (LeFevre, 1980).

6.2 COSTSASSOCIATEDWITHCOATINGANDINKMATERIAL
The cost of coating or ink material is a major component of the annual operating cost of any
surface coatingor printing operation. Some literature indicates that radiation-curable material, on a unit
basis, normally costs more than thermal-curable material. This has resutted in many considering a

27
conversiontoradiation-curablesystemstoconcludethatthesetypes of systemsarenotan
economically attractive substitute material.
The cost of a radiation-curable coating can be up
to four times the cost of an equal quantity
of
thermally-curableformulation(Currier,1989).Thecost of radiation-curableinksmaybe 25 to
75 percent greater than conventional inks. This higher material cost may have prevented their use
in
newspaper,magazine,andbookproductionandhaslimitedtheuse of radiation-curableinksto
specialty applications (Schessler, 1984). On an overall economic basis, the Coors Container Company
experienced a 20 percent increase in ink costs after converting to a UV-curable system (LeFevre,
1980). The cost differential between radiationcurable and thermally-cured systems generally seems
to be relatedto the viscosityof the formulation. The lower the viscosity requirement
of the application
equipment,thegreaterthecostdifferentialbetweenbothtypes of systems.Itshouldbenoted,
however, that the major componentof a thermally-cured coatingor ink is a solvent that, once cured,
is no longer presentin the film. On an equal material basis, radiation-curable systems frequently have
two to four times the coverage of conventional systems (FDM,'1989b). Thus, less radiation-curable
material is required to obtain the same results as a thermal-curable system. This ability to provide
greater coverage can negate the disadvantage caused by the higher material costs.A study for the
wood furniture industry used costs
of $5.80 per unit volume
of nitrocellulose lacquer topcoat and $22.00
per unit volumeof UV-curable clear topcoat. Thisis a cost differentialof nearly four times. However,
of coating a 1,000-square-foot ( 91 square meters) area with an equally thick
when comparing the cost
film, the cost for the UV-curable system was only slightly more expensive than the thermal system
thisdifferential was between 6 12
(Currier, 1989). For various application techniques,cost andpercent.
in cost for thetwo coating systemsfor different application techniques.
Figure 6-1 shows the difference
Depending on theapplicationtechnique,thecoatingcost for aUV-curablesystem in a flat line
installation varies from approximately $28 to $52 per square foot ($307 to $571 per square meter).
Coating costs for a comparable thermal systemcan vary from approximately $25to $49 per square
foot ($274 to $538 per square meter) (Currier, 1989). Although data are currently available for only
into other industrial applications
the wood furniture industry, investigations of radiation-curable systems
may result in the similar comparisons.
Another cost associated with the type of material used is the energy required to cure the coating
or ink.Asstatedearlier,theenergyrequiredbyradiation-curablesystemsisused to initiate the
polymerization chain-reaction. In contrast, energy required by thermal-curable systems is used to
evaporate the organic solvent
in the formulation as well to
ascure the material. When Coors Container
Company converted to UV-curable inks, the energy savings achieved by the switch was 60 percent
(LeFevre, 1980). The energy savings of60 to 80.percent per square foot of surface coated with
cost savings can fluctuate with changes in
radiation-curable systems is significant. However, the total
energy costs.

28
1 1 I 1
0 0
LD

29
6.3 COSTASSOCIATEDWITHCONTROLLINGVOCEMISSIONS
One of the most common means of reducing VOC emissions
for specific operationsto meet air
emissions standards are add-on control systems. A number of variables affects the investment cost
and annualized operating costof add-on control systems and must be accounted forin the planning
process. Tables 6-1 and 6-2 show typical items to consider for add-on control systems. The purchase
from $100,000to $3,000,000
cost of this typeof equipment for surface coating operations can range
depending on the volumeof solvent-laden exhaust air and operating conditions
of the facility and on
regulatoryrequirements(Lankford, 1983). ThecostofpurchasingandmaintainingVOCcontrol
equipment can significantly add to the operating costs of applying each pound
of coating or ink to the
substrate. In the past, such increased operating costs have made smaller facilities using conventional
coatings and inks uncompetitive (Lankford, 1983). Radiation-curable systems have the potential for
greatly reducing the necessity VOC
for control equipment. The available data suggest that only a small
quantity of material will volatilize from a radiation-curable system consisting of 100 percent reactive
material (Lawson and Kaminsky, 1982; Vrancken, 1980). These emissions should only be a small
fraction of the VOC emissions resulting from a thermal-curable system. However,isthis
not substantial
proof of the reduced VOC control requirements extended by radiation curable systems.
As discussed in Section 3.3.3, organic solvents are sometimes usedto reduce the viscosity of
radiation-curable systems (Lawson and Kaminsky, 1982). This is a common practice in the wood
furniture industry, allowing the use of UV-curable topcoats in spray application techniques (Garratt,
1984). The organic solvents in these formulations generally comprise 47 percent of the formulation
up toof80 percent
by volume, although some solvent-containing radiation-curable formulations consist
by volume of organic solvents for some spray processes (Currier, 1989). Even with a substantial
percentage of the formulation consisting of organic solvent, some radiationcurable systems emit
substantially fewer VOCs than conventional coatings because of the superior coverage radiation
curable systems offer on a square-foot basis. A study of VOC emissions from the wood furniture
industry compared a conventional nitrocellulose lacquer topcoat with an UV-curable clear topcoat
containing 47 percent by volume organic solvents.
VOC emissions from the coating
of a 1,000-square-
foot area with a UV-curable system emitted only20 percent of the VOC emitted by the conventional
coating (Currier, 1989). Figure 6-2 shows the difference in VOC emissions for these coating systems
for various application techniques. The lower emissions generated by such a UV-curable system would
result in less-intensiveVOC control requirements because less air would
be requiredto carry theVOC
from the process, resultingin lower overall operating and capital costs.
 TABLE 6-1. CAPITAL COST ELEMENTS AND FACTORS FOR SELECT
ADD-ON CONTROL SYSTEMS'

Cost Element Incinerators

Adsorbers
Absorbers Condensers

DIRECT COSTS
Purchased Equipment Cos* 1.oo 1.oo 1.oo 1.oo

Other Direct Costs:

Foundation and Support 0.08 0.08 0.1 2 0.08
Erection and Handling 0.14 0.14 0.40 0.14
Electrical 0.04 0.04 0.01 0.08
Piping 0.02 0.02 0.30 0.02
Insulation 0.01 0.01 0.01 0.10
Painting 0.01 0.01 0.01 0.01

Total Direct Cost 1.30 1.30 1.85 1.43

INDIRECT COSTS
Engineering and Supervision 0.10 .0.10 0.10 0.10
Construction and Field Expenses 0.05 0.05 0.1 0 0.05
Construction Fee 0.1 0 0.1 0 0.1 0 0.05
Start up 0.02 0.02 0.01 0.02
Performance Tests 0.01 0.01 0.01 0.01

Total Indirect Cost 0.28 0.28 0.32 0.28

CONTINGENCY 0.05 0.05 0.07 0.05

TOTAL" 1.63 1.63 2.24 1.76

Note: A
' s fractions of total purchased equipment cost. They must be applied to the total purchased equipment cost
qotal of purchased costs of major equipment and auxiliary equipment and others, which include instrumentation and
controls at 10 percent, taxes and freight at 8 percent of the equipment purchase cost
Tor retrofit applications, multiply the total by 1.25

SOurCe: U.S. Environmental

Protection
Agency. Handbook - Control
Technologies for Hazardws Air Pollutants.
EPA/625/6-86X)14. AirandEnergyEngineeringResearchLaboratory.ResearchTrianglePark, NC. 1976.

Other means of reducing

VOC emissions from surface coating
or printing operations include the
substitution of coating or ink material. Among the possible materials are water-borne and high solids
coatingandinks.However,thesematerialsalsohavedrawbackslimitingtheiruse.Water-borne
systems require more energy to cure than the current thermal-curable systems. In addition, water-
borne systems cannotbe used with several application techniques, such as screen printing, because
to stick to the substrate. Highersolid systems
they become tacky and cause the application equipment
have a lower organic solvent content than current thermal-curable systems, but are more expensive
on a costper gallon basis but nearly identical oncost
a per square-foot coated basis. They do require

31
higher temperatures and slower line speeds to cure (Schessler, 1984). This would restrict their use
with more temperature-sensitive substrates.

TABLE 6-2. TYPICAL ITEMS INCLUDED IN ANNUAL COSTS OF ADD-ON

CONTROL SYSTEMS

Direct Operating Costs

Utilities (where applicable)

Natural Gas
Fuel Oil
Water
Steam
Electricity
Solvent

Operating Labor:

Operating Labor
Operating Labor Supervision

Maintenance:

Labor
Maintenance Material and Operating Supplies (e.g., lubricants, paper)

Replacement:

Parts
Labor

indirect Operating Costs

Overhead (80 percent of operating, maintenance and replacement labor)

Property Tax (One percent of Total Capital Cost)
Insurance (One percent of Total Capital Cost)
Administration (One percent of Total Capital Cost)
Capital Recovery (Based on average interest rate)

Credits
Salable product or energy recovered by control system

Source: US. Environmental

Protection
Agency. Handbook - Control
Technologies for Hazardous Air Pollutants.
EPA1625/6-86/014.Air and EnergyEngineeringResearchLaboratory.ResearchTrianglePark, NC. 1976.

32
 O
I" I-

c
m

1"

IW

0 0 0 0 0 0 0
co 10 d- m cv 7

33
6.4 OTHER COST ISSUES
Converting to radiation-curable processes, as with any process conversion, results
in equipment
and personnel training costs. The application equipment used at the facility may need modification
before beginning the applicationof radiation-curable systems. Such components as rollers, blankets,
plates,anddoctorbladeswillrequireexaminationtoensurecompatibilitywithradiation-curable
systems(Schessler, 1984). Specialattentionisrequiredtoensurethatpersonnelinvolved in
application and curing processes understand exactly the hazards associated with each compound being
used. Protective clothing worn by the facility personnel also will needtobecompatiblewiththe
compounds in use.
Oneadditionalcostissuemayeventuallyrestricttheuseofradiation-curableinks.The
crosslinked nature of radiation-curable inks has shown to advantageous in improved chemical and
abrasion resistance. This crosslinking, however, becomes a disadvantage when trying
to de-ink prints
and makes recycling paper difficult (Schessler, 1984). The widespread use of radiation-curable inks
may substantially increase in the cost of recycling paper, thereby reducing the economic benefitsof
using recycled paper products. More information, however, is required to adequately address this
issue.

6.5 SUMMARY
In the past, radiation-curable systems have not been perceived as an economically attractive
replacement for conventional thermal-curable systems. This perception
is based on the relatively large
difference in the cost per gallon of radiationcurable and thermal-curable materials. This perception
doesnotaccountforadvantages in coverageandenergysavingsprovidedbyradiation-curable
materials. When these factors are included
in the cost analysis and examinedon a square-foot basis,
radiation-curable systems are only slightly more costly
than thermal systems. The additional operating
cost associated with the larger
VOC control equipment required for conventional coatings may provide
a cost differentialin favor of higher solids radiation-curable materials. For the same area
of coverage,
pure radiation-curable formulations and solvent-containing higher solids radiation-curable formulations
wil generate less VOC emissions than conventional thermal systems.

34
 7.0 CONCLUSIONS

Radiation-curable coatings and inks have found uses within various surface coating and printing
processes.Althoughradiation-curables,likeanyothersingletechnology,maynotbeuniversally
applicable to all industrial applications, they have the potential to replacethermalcurable systems in
a substantial number of industrial processes to cost-effectively reduce VOC emissions. Radiation-
curable systems are currently being used
in metal-decorating, flatwood production, and paper coating
processes. Depending on the operation and formulation, radiation-curable coatings and inks have
at least an 80 percent reductionin VOC emissions over thermal-curable
shown thepotential to provide
coatings and inks. Other advantages of radiation-curable systems over thermal-curables include a
reduction in the energy required to cure the material, a reduction in the space requirements, and an
increase in productivity. The low-temperature nature
of radiationcurable systemsmay allow for a wider
use on substrates considered unsuitable for thermal-curable systems. The polymer films formed by
the radiation-curable systems have also been found more dwable than films from thermal-curable
systems in terms of hardness, solvent resistance, and heat resistance.
Radiation-curable systems, however, have several disadvantages, which are currently restricting
wider use in surface coating and printing processes. The high viscosity of many radiation-curable
compounds has tendedto limit their use to application techniques such as roll coating, curtain coating,
lithographic, and screen printing. The majority
of conventional industrial finishes, however, are applied
through spray techniques. In nearly all cases, the viscosityof radiation-curable systems is unsuitable
for use in spray applications. The current practice in the wood furniture industry is to modify the
viscosity of a radiationcurable system by adding organic solvents (upto 40 percent by volume and
more). This can compromise the environmental benefits
of potentialVOC emissions reduction through
use of radiation-curable systems. However, data exist which indicate that solvent-containing higher
solidsradiation-curablesystemsstillprovideasubstantialreduction in VOC emissionsover
conventional thermal-curable systems.
The early radiationcurable systems were foundto be fairly toxic dueto unstable formulations
and resulting dermatitis problems. Mostof these problems have been addressed by the industry.
Formulations have since been developed that remain stable for lengthy periods of time. Problems
associated with dermatitiscan be avoided through afull understanding of the hazards involved and a
minimizationof exposure to radiation-curable material. The industry has made great strides
in reducing
the toxicity of radiationcurable systems, but like most industrial chemicals, some hazard
will remain.
The perceived disadvantage of radiationcurable systems in terms of cost may be the most
difficult to resolve. The main issue of cost involves the fact that radiation-curable materials
cost more
on a unit basis than thermal-curable material.
The capital expense of radiation-curing equipment has
also been cited as a reason for rejecting radiation-curable systems. This view ignores the fact that

35
radiation-curable systems can provide improved coverage on the substrate, substantial reduction in
energy costs and floor space, and reduction in the size or in some cases, the need for VOC control
equipment. In addition, some data show UV-curing equipment actuallycosts less than thermal-curing
equipment. Data in the literature suggest that, on acost-per-areacoatedbasis, the expenditures are
essentially the same for
both radiation-curable and thermal-curable systems. This conclusion is based,
however, on only one industrial use for radiationcurable systems. Additional investigations on a cost-
per-area-coated basis could resolve this issue ofcost.
Two issues have not been fully resolved. The first is the impact that greater use of radiation-
curableinks will haveonpaperrecycling.Thedifficulty in de-inkingradiation-curedpaper may
significantly increase the cost to recycle this paper. The second issue is the question of volatile
emissions from radiationcurable systems. There is a general lack of data presented in the literature
concerning reactive components which may evaporate from the coating or ink. Only limited data are
available for determining which radiation-curable systems are environmentally suitable.

36
 8.0 REFERENCES

1. Arnold, H.S., Sr., "Three-Dimensional UV Finishing in Practice," from the proceedingsof Radcure
'84 Conference, Association of Finishing Processes of SME, September 10-13, Atlanta, GA,
1984.

2. Ashcroit,W.R., 'Water-Based UVCurableAcrylateResins," PaintandResin, 57(5):4-6,1987.

3. AssociationforFinishingProcessesofSME, RadiationCuring:An introduction toCoatings,

Varnishes, Adhesives and Inks, Second Edition, 1986.

4. Bean, A.J., "The Technology of Using UV and EB Curable Inks and Coatings for Decorative and
Protective Packaging," fromthe proceedings ofRadcure '84 Conference,Association of Finishing
Processes of SME, September 10-13, Atlanta, GA, 1984.

5. Clark,K.,"High-SolidsCoatings,ElectronBeamCuringandUltravioletCuring," Proceedings of
the Conference "Waste Reduction-Pollution Prevention: Progress and Prospects within North
Carolina,"NorthCarolina Department of Natural Resources and Community Development, 1990.

6. . Currier, G.,"Interest in UV-Curable Coatings on the Rise,"furniture Design and Manufacturing,

61(6):54-58,1989.

7. Danneman, J., "UV Process Provides Rapid Cure for Compliant Wood Finishes," ModernPaint
and Coatings, 78(2):28-29,1988.

8. Decker,C.,"UV-CuringChemistry:Past,Present,andFuture," J. ofCoatingsTechnology,
59(751):97-106,1987.

9. DePass, L.R., "Carcinogenicity Testing of Photocurable Coatings," Radiation Curing, 9(3):18-23,

1982.

10. Frecska, T., "UV Curing: The Process and the Equipment," J. of Radiation Curing, 14(4):26-28,
1987.

11. Furniture Design and Manufacturing, "Atop the Technology Wave," 61 (6):44-52,1989a.

12. Furniture Design and Manufacturing, "UV Coatings Update," 61 (1 2):llO-118, 1989b.

13. Garratt, P.G., "The Use of Unsaturated Polyester Resins in UV Curable Paint Formulations for
Use in the Furniture Industry," from the proceedings
of Radcure '84 Conference,Association of
Finishing Processes of SME, September 10-13, Atlanta, GA, 1984.

14. Jones,D.T., "Roll CoatingEquipment - ApplicationandLimitations,"fromtheproceedingsof

Radiation Curing V: A Look to the80's, Association of Finishing Processes of SME, Sept.
23-25,
Boston, MA, 1980.

15. Knight, R.E., "UV-drying Equipment, Design and Installation," J. of Radiation Curing, 6(1):14-18,
1979.

16. Kovachik, C.R., "Radiation Curing: A Market Overview," RadiationCuring, 14(1):18-19,1987a.

17. Kovachik,C.R.,"RadiationCuring - SafetyReferenceGuide," RadiationCuring, 14(2):6-14,

1987b.

37
18. Kubisen, S.J., G.S. Peacock, J.V.
and Koleske, "Functionalized Acrylates Based on Caprolactone
forRadiationCuredCoatingSystems,"fromtheproceedings of Radcure '84 Conference,
Association of Finishing Processes of SME, September 10-13, Atlanta, GA, 1984.

19. Lankford, A.P., II, "History and Growthof Radiation Curing in the Converting Industry,"
Radiation
Curing, 1O(3) 120-27,1983.

20. Lawson, K.R., and M.I. Kaminsky, "Radiation Curable Coatings for Three-Dimensional Shapes,"
Radiation Curing, 9(2):28-35, 1982.

21. LeFevre,P.H.,"UVCureofTwo-PieceCanDecoration,"fromtheproceedingsof Radiation

Curing V: A Look to the 80k,Association of Finishing Processesof SME, Sept. 23-25, Boston,
MA, 1980.

22. Lewarchik, R.J., and D.A. Hurwitz, "New Developments in UV Curables for Automotive and
Product Finishes," from the proceedings of Radwre '84 Conference, Association of Finishing
Processes of SME, September 10-13, Atlanta, GA, 1984.

23. Lyman,W.J.,W.F.Reehl,andD.H.Rosenblatt, Handbookof ChemicalPropertyEstimation

Methods - Environmental Behavior of Organic Compounds, McGraw-Hill, Inc., New York, NY,
. 1982.

24. Morris, W.J., "Formulation of High Performance Urethane UV/EB Curable Systems," from the
proceedings of Radwre '84 Conference,Association of Finishing Processes of SME, September
10-13, Atlanta, GA, 1984.

25. ry...Working Toward a Common Goal,"

Nelson, PC., "The Government and the Indust Radiation
Cudng, 14(2):4-5, 1987.

26. Newcomb, W.T., "Graphic Arts Research and Radiation Curing," Radiation Curing, 12(1):2-6,
1985.

27. Pincus, A.H., "Radiation Curing Markets and Marketing Data," Radiation Curing, 10(1):13-16,
1983.

28. Pincus, A.H., and G. Sickinger, "Two Curing Leaders Radiate Ideas About Their Industry,"
J. of
Radiation Curing, 15(2):8-10, 1988.

29. Plamondon, J., and R.L.Keener,"RecentDevelopments in theRegulation of Industrial

ChemicalsunderTSCA,"fromtheproceedingsof Radwre '84 Conference, Association of
Finishing Processes of SME, September 10-13, Atlanta, GA, 1984.

30. Prane, J.W., "UltravioletCurableCoatingsandInks - MarketsandProjections,"fromthe

proceedings of Radiation Curing V: A Look to the 803, Association of Finishing Processes of
SME, Sept. 23-25, Boston, MA, 1980.

31. Riedell, A.,"Back toBasics to BeatVOCEmissionProblems," Furniture

Design
and
Manufacturing, 61(1):32-34, 1989.

32. SantaAna,M.M.,"PrintingUVCurableInks on NarrowWebs,"fromtheproceedingsof

Radiation CuringV: A Look tothe 803, Association of Finishing Processes of SME, Sept.
23-25,
Boston, MA, 1980.

38
33. Sax, N.I., and R.J. Lewis,
Sr., Dangerous Pmpertiesof lndustrialMaterials,Seventh Edition, Van
Nostrand Reinhold, New York, NY, 1989.

34. Schessler, P.G., "Printing Ink - A Changing Industry," Radiation Curing, 11(1):17-22, 1984.

35. Scott, LC., "Hazardous Raw Materials Used in the Paint and Ink Industries," Radiation Curing,
14(2) :20-22, 1987.

36. Shewood, T.K., R.L. Pigford, and C.R. Wilke, Mass Transfer,McGraw-Hill, Inc., New York,NY,
1975.

37. Sittig, M., HandbookofToxicandHazardousChemicalsandCarcinogens, Second Edition,

Noyes Publications, Park Ridge, NJ, 1985.

38. Svoboda,G.R.,andG.Schwebke, "Is A 5(e) Consent Order Workable?" RadiationCuring,

14(2):24-25,1987.

39. U.S. Environmental Protection Agency. Handbook - ControlTechnologiesforHazardous Air

Pollutants. EPN625/6-86/014. AirandEnergyEngineeringResearchLaboratory.Research
Triangle Park, NC, 1976.

40. Vrancken, A., "Market Trends for Irradiation Curable Coatings and Printing Inks in Europe," from
the proceedings of Radiation Curin0 V: A Look to the ~ O ' S Association
, of Finishing Processes
of SME, Sept. 23-25, Boston, MA, 1980.

41. WeRy,J.R.,C.E.WicksandR.E.Watson, Fundamentals of Momentum, Heat, andMass

Transfer, Second Edition, John Wiley andSons, Inc., New York, NY, 1976.

39
 (Plcasc read Iurtructiom on lhe reverse beforc- compIcIiq)
O. 1 . REPORT 2. 3. RECIPIENT'S ACCESSION N O .

EPA-600 /2-91-035
4. T I T L E A N 0 S U B T I T L E 5 . REPORT DATE
Radiation- Curable Coatings July 1991
6. P E R F O R M I N G O R G A N I Z A T I O N C O D E

7. A U T H O R G ) NO O R G A N8.
REPORT I ZP
AETR
I OFN
ORMING
Stephen A. Walata, 111, and C. R. Newman

9. P E R F O R M I N G O R G A N I Z A T I O N N A M E A N D A D D R E S S
Alliance Technologies Corporation
100 Europa Drive, Suite 150
Chapel
Hill,
North
Carolina 27514 68- D9-0173, Tasks 0 /702
and 1/130
SPONSORING
12. AGENCY
ADDRESS
TYPE
NAME
AND
13. OF R E
PPA
ECO
N
ROR
D
IO
VTD
ER
EPA,
Office of Research and DevelopmentTask
Final; 6/90 - 5/91
A i r andEnergyEngineeringResearchLaboratory 14.SP0NS0R1NG
AGENCY

I Research Triangle Park, North Carolina 27711

I E P A / 600 / 13
I
15.SUPPLEMENTARY NOTES AEERL project officer is Charles H. Darvin, Mail Drop 61,91!
541-7633.

16.AesTRAcTThe report gives results of an evaluation of radiation- curable coatings as

technology for reducing volatile organic compound (VOC) emissions from surface
coating operations. A survey of the literature was conducted to a s s e s s the state of
the technology and emissions from radiation- curable processes. The information
collected from the literature was used to evaluate the engineering and economic
issues associated with radiation-curable systems and to idenitify the requirements
for implementing the technology and any problems arising from its use. Topics dis
cussed in the report include coating characteristics, potential VOC reduction capa-
bility, potential health problems associated with the use of ultraviolet (UV) coating:
and the economic impacts of conversion to U V coatings. The report provides infor-
mation to permit an informed judgement on when and how to apply radiation-curabll
technologies for industrial application. Radiation- curable coatings - and inks are
higher solids formulations than conventional coatings and, consequently from an ai:
pollution viewpoint, are considered to be well suited substitutes for solvent-based
thermal-curable systems. The radiation source for these systems is either an U V
light or an accelerated electron beam (EB).

~ ~~

a. DESCRIPTORS ).IDENTIFIERS/OPEN ENDED TERMS . COSATI Field/Group

Pollution Pollution Control 13B 14E
Ultraviolet
Coatings
Radiation Stationary Sources 11C 20F
Radiation
Beams
Electron Volatile Organic Com- 14G 20H
Curing pounds(VOCs) 13H
Organic Compounds 07C
Volatility 20M
18. D I S T R I B U T I O N S T A T E M E N T 19. SECURITY CLASS (ThisReport). !1. NO. OF PAGES
Release to Public Unclassified - 46
!O. SECURITY CLASS (Thispage)
~. !2. PRICE
Unclassified
EPA Form 2220-1 (9-73) 40