OVERVIEW ON BASIC CHEMISTRY OF UV- CURING

TECHNOLOGY

Vipin Shukla* and Madhu Bajpai

Oil and Paint Department
H.B. Technological Institute
Kanpur – 208002 (India).

Key words : Oligomers, Dilents/Monomers, Photoinitiators

ABSTRACT

The market for ultraviolet technology has been growing at double-digit

rate the last 10 years. A significant reason for the technology’s growth

is its unique process characteristics, which allow UV-coating to be

applied on virtually any substrates. Plastic, metal, composite, wood,

paper, leather, vinyl, glass, magnetic recording tape and even human

teeth are substrates finished with this technology.

The original driving forces behind the commercialisation of UV-

technology were energy saving and freedom from solvents. These

benefits are complemented by high productivity and subsequently higher

profits that can be obtained with the process ever increasing line speeds,

just-in-time benefits and immediate “pack and ship” capabilities.

* To whom correspondence should be made.

[email protected]
INTRODUCTION

The “Curing” of the surface coating means its conversion from

the liquid state to the solid state. In essence is the chemical drying (i.e.
by chemical bond formation) of the material where by crosslinking or
polymerization occurs throughout the film. This is contrast to simple
hardening of films, which is physical drying whereby solvent is
removed from the polymer solution. A new technology has now
emerged whereby this curing may be achieved by using light energy
instead of heat. UV-inks and varnishes are composed of 100% reactive
material and contain no volatile solvents as complared to conventional
materials. Their mechanism of drying depend upon some of their
chemical constituents being sensitive to UV-light of certain
wavelengths1.

In general system which is cured by UV-light may consist of the

following ingredients, where the first three are found in almost all
formulation.

(i) Prepolymer (or oligomers)

(ii) Diluents (or monomers)
(iii) Photoinitiator
(iv) Coinitiator
Reducing agent
Chain transfer agent
Spectral sensitiser
(v) Light stabiliser
(vi) Thermal stabiliser
(vii) Colourants, plasticisers and additives2-4

2
OLIGOMERS (RADIATION CURABLE BINDER)
Classes of resin used in UV-curing
It can be classified as follows
(i) Unsaturated polyester/acrylated polyester
(ii) Acrylated epoxy resin
(iii) Acrylated urethanes (both aliphatic and aromatic)
(iv) Acrylated silicone resins
(v) Acrylated polyethers
(vi) Acrylated melamines
(vii) Acrylated oils
(viii) N-vinyl urethanes
(ix) Thiolene system
a) Acrylated Polyesters
Polyester acrylates can be produced in a wide range of viscosities
and reactivities to adopt to end uses in printing inks, wood and paper
coatings. One of the major advantages offered by polyester acrylates
over the other prepolymers is their low viscosity for example the basic
recipe reported by Rybny has a viscosity of 1:660 centipoise at a
molecular weight of around 1000 compared with an epoxy acrylate
which will be 5-10 time higher in viscosity. As the molecular weight of
the polyester decrease, its acrylated counterpart becomes more monomer
like. It should be appreciate from the low molecular weight polyester
the presence of pure di acrylate from the glycol used in preparation base
polyester becomes a statistically significant probability one of the major
problems associated with the use of the low molecular weight polyester
acrylates is the reduction in reactivity and increased surface inhibition
observed and found that this can be compensated for by a number of

3
techniques, e.g. incorporation of pendent aromatic group and ether
grouping with in the polyester backbone. It is possible prepare polyester
acrylate using transesterification technique with an acrylic monomer
such as ethylacrylate.5,6

It is relative economy compared with other acrylated

prepolymers. By varying the molecular weight of polyester, it is
possible to obtain acrylates from low viscosity, to hard solids, at
ambient temperature, compatibility with other prepolymer is good, so
they can be used in many formulation. Polyester acrylate are mainly
used in UV roller coat varnishes for paper and board and UV-wood
coating.

HO Polyester OH + 2 CH2 = CH COOH

(Acrylic acid)

O O
CH2 CH C O Polyester O C CH CH2

(b) Acrylated Epoxies

Epoxy acrylates are extensively used in UV curing in litho inks
and varnishes, roller coating varnishes for paper and board, printed
circuit board, wood and plastic coatings. They offer good all round
properties combined with cure rate. Both aromatic and aliphatic epoxies
and epoxy novolacs are used.7
The reaction of an epoxy group with other acrylic or methacrylic
monomers will give rise to an epoxy acrylate (or methacrylate). There

4
are a wild range of epoxy acrylate available including acrylates of
DGEBA, acrylates of epoxidised oils such as soya or linseed and
acrylates of epoxy novolacs.

CH2 CH R CH CH2 + 2CH2 = CH COOH

O O
(Epoxy) (Acrylic acid)

O OH O
CH2 CH C O CH2 CH R CH CH2 O C CH = CH2
OH

CH3
Where R= O C O CH2 CH CH2
CH3 OH n

Epoxy acrylates having a higher skin irritancy careful processing

and formulation is an essential feature in preparation of epoxy acrylate
very low acid values are necessary since unlike other coating resins such
as alkyds or polyesters, any residual acid is present as molecular weight
(e.g. Epikote 1001 and 1004) have been prepared but are not used
widely. Epoxidised oils are also acrylated and provide good flexibility,
lower viscosity, good pigment wetting properties and very low skin
irritancy. Molecular weight of acrylated oils fall in the region of 800.

Epoxy novolac acrylate are harder materials and have superior

resistance properties to the standard epoxy acrylates. They find use in
some screen printing application also in UV solder-resist formulations
for the electronic industry.8

5
© Acrylated Urethanes

The reaction between hydroxyl and isocyanate group proceeds

efficiently at low temperature without the evolution of volatile by
products. The well known properties of hardness, chemical resistance,
toughness and light stability normally associated with the urethanes can
be build into a radiation curable prepolymer and acrylated urethane
would be formed by the reaction of 2-mole of EHA
(Ethylhydroxylacrylate) with one mole of a diisocyanate. Such a
product will be highly viscous and produce cured films which are very
hard and inflexible but also highly chemical resistant.

Colour retentive properties achieved will depend on the type of

isocyanate chosen. Two main classes are available, aromatic, e.g.
toluene digsocyanate and aliphatic, e.g. isophorone-di-isocyanate.
Aromatic isocyanates result in higher viscosities and poorer colour. The
colour is seen in prepolymer as supplied as well as in the light and heat
stability of coating based on them and improvement in flexibility may
be achieved by chain extension using long chain diol to produce a higher
molecular weight isocyanate functional prepolymer which is
subsequently capped by a hydroxy acrylic monomer.9

2 CH2 = C R OH + OCN R1 NCO

Y

O H O
CH2 C R O C R1 N C O R C = CH2
Y Y

6
 O
Where R = C O (CH2)n , n = 1 or 2

R1 = OCN R1 NCO can be TDI, HMDI, IPDI, MDI

Y = H or CH3

TDI = Toluene diisocyanate

HMDI = Hexamethylene diisocyanate
IPDI = Isophorone diisocyanate
MDI = Diphenyl methane diisocyanate

(d) Acrylated Silicones

Incorporation of silicone into radiation curable prepolymers is of
interest in a number of area. Silicone are well known for their release
properties, heat and weather resistance. The advantages of silicone
acrylates in the protection of optical fibers where their excellent
flexibility and extensibility properties, particularly at low operating
temperatures are used to advantages. At present state of development
silicone acrylates appear to be far more sensitive to air inhibition than
other UV curable systems and curing under inert gas is often
recommended.
O
Si CH2 CH2 CH2 O C CH = CH2

O H
Si CH2 CH CH2 O C C CH = CH2
R

7
 O
Si O R O C CH = CH2

R R
R O Si O Si O R
Si Si
HO O Si O Si O OH
R R

(Silicon containing intermediates)

(e) Acrylated Polyethers

Polyether acrylates are lower viscosity resin compared with the
polyester type and are relatively inexpensive to prepare. In the
acrylation of polyether however, a transesterification technique is used
to prevent the polyether links from degrading. Polyethers may also be
reacted with the isocyanate groups and this is often an easier method to
introducing polyether linkages into an acrylated system since the
problems of removing the by products of transesterification such as
ethanol are eliminated.
The reaction of ethylene or propylene oxide with a polyol in the
presence of basic or acidic catalyst such as BF3 or NaOH will give a
polyether. Where secondary hydroxyl is available in complete
etherification may occur. The total degree of etherification will depend
upon the ratio of propylene oxide and polyol. Many other common
polyethers have been acrylated. Amongst them are ethoxylates and
propoxylates of trimethylolpropane, pentaetythritol and polyethers or
1,4-butane diol. These form the basic of the new generation of low

8
viscosity, low toxicity monomers which are rapidly gaining in
importance.10

CH3
CH2-OH CH2 (O CH CH2 )n OH
O
CH-OH (i) Pressure CH3
+ 3n CH2 CH CH3 CH (O CH CH2 )n OH
(CH2)3 (ii) heat
CH2OH (iii) Catalyst (CH2)3
(Propylene oxide)
CH3
(1,2,6-hexane triol) CH2 (O CH CH2 )n OH
(Polyether)

(f) Acrylated oils

Normally acrylated oil are derived from natural products such as
castor or fish oils. They all contain triglyceride oils generally, acrylated
oils are highly flexibility or soft, due firstly to their flexible aliphatic
acrylic backbone and to their low level of acrylic unsaturation.
The oil that has the highest consumption, about 90% of the
acrylated oils in the market in soyabean, due to its relatively low cost
and ready availability. It consists of about 50% linoleic acid, 25% oleic
acid, 10% palmitic and linolenic acid and about 5% stearic acid. These
acids contain a relatively high level of unsaturated groups which can be
oxidised by the reaction with peracids and hydrogenperoxide on the
other hand, even though less linseed oils are used than soyabean oils,
they are used extensively due to their reasonable cost and relatively
higher level of unsaturation that revents in a higher number of epoxy
groups. Acrylation is usually performed with acrylic acid under similar
conditions to epoxy acrylate manufacture.11 The viscosity and degree of

9
unsaturation of acrylated oils is lower than epoxy acrylate and
consequently, it is not necessary to use a reactive diluent to decrease
viscosity.

(g) Thiolene system

Free radical addition of mecaptans to olefins has been known for

many years. As presently understood, mercaptan olefin polymerization
occur according to given reaction.

HS R SH + n CH2 = CH CH = CH2

(Ph)2 CO hν

HS R S CH2 CH2 CH2 CH2 S R SH

n

The company W.R. Grace carried out much of the original work
in this area and they are consequently very heavily patented there are
two advantages to the thiol/polyene system.

1) They are non-air inhibited, and

2) Flexibile cured films can be obtained from relatively low

viscosity mixture without the need to incorporate a diluents
polyfunctional thiol compound gives very tough abrasive-
resistant coating which are ideal for application such as
flooring compounds. It is also possible to modify acrylic UV
curable formulation with polythiol polymer to improve their
properties.12

10
 Table-1 : General film properties of acrylated oligomer

S. Cured film
Acrylic Polyester Urethane Epoxy
No. properties
1 Tensile strength Low Moderate Variable High
2 Flexibility Good Variable Good Poor
3 Chemical Low Good Good Excellent
resistance
4 Hardness Low Moderate Variable High
5 Non yellowing Excellent Poor Variable Moderate
to poor
DILUENT/MONOMER

As all the currently available aligomers (e.g. acrylated epoxy,

acrylated urethane etc.) are two viscous to be applied an conventional
coating equipment, most formulators now dilute the oligomer down to
application viscosity (from 10,000 cps to 100 cps depending on the
method of application)13. They have to be added to a system so as to act
as crosslinking agents and to give system a workable viscosity. To
obtained low viscosity, much monomer has to be added. However, to
retain good reactivity in the mixture, earlier literature indicates that as
little monomer as possible should be used. As little monomer as possible
should be added to a system for toxicolosic reason, such as skin
irritation which is largely determined by amount of monomer
present.14,15

It is obvious that, with a higher functionality monomer, the cure

rate of formulation is to increase. The monomer selected for a system
depends upon its.

11
(i) Photoresponse
(ii) Contribution to the photopolymerized film properties
(iii) Relative volatility
(iv) Odour and toxicity
(v) Solvating efficiency
(vi) Cost

(a) Vinyl based diluent

1) Styrene and derivative such as α-methyl styrene and vinyl

toluene

CH = CH2 CH3 CH3 CH3

CH = CH2

CH = CH2
CH = CH3
Styrene ortho meta para-vinyl toluene

They have low cost, give hardness and slow cure and are volatile,
but have good copolymerisation characteristics with many resins
and other monomer.

2) Vinyl acetate

CH2 = CH COOCH3

This is excellent reducer but is volatile and inflammable also

have poor weatherability and water resistance.

12
 3) N-vinyl pyrrolidone

N O
CH = CH2

This is excellent reducer with low reported toxicity. It has no

acrylate functionality but copolymerise with acrylates when
used at the optimum mole ratio. Also it is reported to improve
flexibility of the cure film.

(b) Acrylics

(I) Monoacrylates

(1) n-Butyl acrylate (BA) : This has slow cure and poor solvent
resistance but is a good viscosity reducer and has good
flexing action. It is volatile and mainly used in wood coating.
Isobutyl acrylate may also be used but again is very volatile.

O
H3C CH2 CH2 CH2 C O CH = CH2

(2) 2-Ethyl hexyl acrylate (EHA)

This is probably the most widely used diluent. It is volatile

and has odour but is slowish in cure and give poor solvent
resistance. It has good flexing action in films.

O C2H5
CH2 = CH C O CH2 CH (CH2)3 CH3

13
(3) Iso decyl acrylate (IDA)

This is good viscosity reducer, being less volatile than EHA.

It is reported to increase flexibility owing to long aliphatic
chains.

CH3 O
CH3 CH (CH2)7 C O CH = CH2

(4) Iso bornyl acrylate (IBA)

A strong odour is the main disadvantage of this monomer,

which has low toxicity and volatility, imparts a hardness
comparable to MMA, but with the fast cure rate of acrylate,
and has a low shrinkage rate.

CH3 CH3

O
CH3
O C CH = CH2

(5) 2-Hydroxy ethyl acrylates (HEA)

Although it is widely used at present, it high toxicity has

forced people to formulate around this material.

O
HO CH2 CH2 O C CH = CH2

14
 (6) 2-Hydroxy propyl acrylate (HPA)

It is good reducer but highly toxic.

O
H3C CH CH2 O C CH = CH2
OH

(II) Diacrylates

They have stronger odour, are skin irritants and same are
carcinogenic methacrylic analogues are also available but they suffer
from the disadvantage of having slow reactivity as a result of oxygen
inhibition and also exhibit strong odour. The only major area where the
methacrylates are used is in the UV-adhesive industry.

1) 1,4-Butanedioldiacrylate (BDDA)

CH2 = CH C O CH2 CH2 CH2 CH2 CH2 C CH = CH2

O O

It is widely used in wood coating area.

2) 1,6-Hexanedioldiacrylate (HDDA)

CH2 = CH C O CH2 (CH2)4 CH2 O C CH = CH2

O O

With its lower volatility, is increasingly replacing neopentyl glycol

diacrylate, although both are suspected skin irritation sensitisers. They
are relatively good viscosity reducers.

15
3) Neopentylglycoldiacrylate (NPGDA)

O CH3
CH2 = CH C O CH2 C CH2 O C CH = CH2
CH3 O

4) Diethyleneglycoldiacrylate (DEGDA)

O O
CH2 = CH C O . CH2 CH2 O CH2 CH2 O C CH = CH2

(III) Triacrylates

1) Pentaerythritoltriacrylate (PETA)

It is widely used in the printing area since it give rapid cure response.
However product is a severe eye irritant and suspect to be carcinogenic.

CH2OOCCH = CH2
HO CH2 C CH2 OOCCH = CH2
CH2 OOC CH = CH2

2) Trimethylolpropanetriacrylate (TMPTA)

It has low volatility and is attractive in the ink field.

CH2OOCCH = CH2
CH2 = CH COOCH2 C CH2CH3
CH2OOCCH = CH2

16
(IV) Tetracrylates

Pentaerythritoltetracrylate

CH2 CH2 - OOCCH = CH2

HCCOO CH2 C CH2 - OOCCH = CH2
CH2OOCCH = CH2

(V) Pentacrylates
Dipentaerythritol (monohydroxy) pentaacrylate

OOCCH = CH2
O CH2 CH2 - OOCCH = CH2
CH2 = CH C O CH2 C CH2 OCH2 C CH2OH
OOCCH = CH2 CH2 - OOCCH = CH2

© Allylic Monomers
(1) Triallyl cyanurate

O CH2 CH = CH2
C
N N

C C
CH2 = CH CH2O N O CH2 CH = CH2

(2) Trimethylol propane trially ether

CH2 - O CH2 - CH = CH2

CH3 CH2 C CH2 - O CH2 - CH = CH2
CH2 - O CH2 - CH = CH2

17
PLASTICIZING DILUENTS

These are numerous plasticizing diluents. Some examples are given

below:

(i) Butyl acetate (ii) Butyl cellosolve (iii) Butyl carbitol acetate (iv)
Dipentene or pine oil (v) Tributyl phosphate (vi) Hexadecanol (vii)
Diallyl phthalate (viii) Sucrose acetate isobutyrate (viscous material that
cut viscosity) (ix) Epoxy ester of iso-octyl tallate (x) Benzophenone (a
solid photoinitiator that causes viscosity reduction). Many of these are,
however very volatile.16

Table-2: Some properties of monomers used in UV-curing

S. Average Visco- Acrylic Acid BP (0ºC) Primary
No. mol. sity function value (at y mm Irritation
Wt. (Cp) -ality Hg) Index
Mn - FA (PII)
Neopentyl glycol
1 212 8 2 <1 96 6.0
diacrylate
Hexanediol
2 226 8 2 <1 125 6.0
diacrylate 1,6
Polyethylene
3 310 30 2 <2 >120 4.9
glycol diacrylate
Trimethylol-
4 propane 296 250 3 <2 >200 5.1
triacrylate
Pentaerythritol
5 300 2500 3 <2 >200 5.2
triacrylate
Dianol 2,2
6 400 8000 2 <5 >200 0.4
Diacrylate
UV E70 Polyester
7 450 300 2 <15 >200 4.4
acrylate

PHOTOINITIATORS
Acrylic monomers do not absorb UV-light in a very efficient way
and will not initiate radical polymerization fast enough. So a
photopolymerizable coating essentially consists of a polymerizable

18
vehicle (oligomer) and light sensitive compound able to convest
absorbed light energy into another useful form capable of causing the
binder to polymerise into a hard solid mass. This compound may be
called a photo-initiator/sensitizer. Therefore a photoinitiator is added
which produces initiator radicals either directly by the fragmentation of
the photo-excited state, or in two steps, by hydrogen transfer from a
suitable substrate to the photo-excited state.17

The photoinitiator is of paramount importance in these systems.

It is selective to light of specific wavelengths and during selection for
formulation is matched in absorption characteristics to the beak
wavelengths present in the lamp source.18 Therefore the choice of
photoinitiator is of prime importance in the light induced polymerization
since it directly governs the cure rate. A suitable photoinitiator system
must first present high absorption in the emission range of the light
source, usually a medium pressure mercury lamp. In addition, the
excited states thus formed must both have a short lifetime to avoid
quenching by oxygen or the monomer, and split into reactive radicals or
ionic species with the highest possible quantum yield.

The selection of photoinitiator mixture depend on a number of factors

Line speed to be obtained with given curing oven

Coating thickness

Transparency of the coating material, presence of pigments
and filler

Surface properties to be obtained such as hardness and glass

Non yellowing, odourless, low volatility good thermal stability

19

Non toxic, low migration and cost effective

High absorptivity in the region of activation

High quantum yield for free radical formulation

A distinction is necessary between the term photoinitiator and

photosensitizer, which are often commonly incorrectly regarded as
interchangeable. A photoinitiator absorbs the incident light directly and
split up or fragments to form free radicals. These than attack the
monomer (generally by hydrogen atom abstraction) to initiate the
photopolymerisation reaction. In contrast, a photosensitizer absorbs the
incident light but does not fragment itself, but ‘transfers’ the energy it
has obtained to another compound (which may be the monomer).
Which will then procure initiation of the polymerisation reaction.

Some common type of photoinitiators fall into the class of :

Aromatic ketones and synergistic amines

Alkyl benzoin ethers

Thioxathones and derivatives

Benzil ketals

Acylphosphine oxide

Ketoxime ester or α acyloxime esters

Cationic curing quaternary ammonium salts

Acetophenone derivatives

(1) Aromatic ketones and synergistic amines

Benzophenone : Benzophenone react by hydrogen abstraction and is

photo reduced to benzopinacol in the presence of hydrogen donors like
amino alcohols or N,N-dialkylamino benzene derivatives.

20
Benzophenone undergo photoinduced excitation predominantly at 340
nm to form a singlet excited stated (which is an isomer of ground state).
The siglet state converted by intersystem crossing in a fraction of second
in to relatively longer lived excited triplet state. This time period
permits the excited electrons adequate time to collide with other atoms.
The hydrogen atom is a particularly mobile atom and is readily attracted
by this kind of triplet state and radicals of the surrounding monomer and
benzohydrophenone are produced. The monomers polymerise whereas
the benzohydrophenone radical reacts with another benzohydrophenone
radical to form benzopinacol or it may react with another radical to form
an electro neutral and saturated compound.19-21

O O⋅ S* O⋅⋅ T*

C C⋅ C⋅
hγ
λ =340 nm

Singlet excited state Triplet excited state

T*
O
OH
C C⋅
+ Reactive + Free radical
R⋅
Matrix
(RH)

(Benzohydrophenone)

21
 OH
C OH OH
⋅
2 C C

(Benzopinacol)

OH RI
O
RIII
C C C C RI H RIII
⋅ RII RIIII
+ C C
⋅ RIIII
RII

This later compound can be considered an independent primary

photoinitiator as being used as a synergist or secondary photoinitiator.
Amines such as small amounts of triethylamine have been found
to enhance the photopolymerisation rate in benzophenone/ acrylate
system probably via the formation of the exciplex, which gives rise to
free radicals.
Michler’s Ketone has markedly improved light response
sensitivity for most UV systems when used with mixture with
benzophenone, benzil, benzoin alkylethers and/or amines, pre-ground
mixtures of the solids to an inks appear to be more efficient than it they
are added individually and milled straight into ink.
(2) Benzoin alkyl ethers
To obtain better performance, modification of the benzoin
molecules has thus induced α-alkylation. These compounds are the
benzoin alkyl ethers α-methylolation has also been tried.

22
 O R O CH2 - OH O OR
C C C C C C
, ,
OH OH H

As opposed to benzoin which undergoes fragmentation from the

excited triplet state, these were thought to fragment from singlet excited
states. This may be the cause of benzoin exhibiting higher quantum
efficiencies for fragmentation in monomers having high triplet energies
than it would in low triplet energy monomers, where triplet-triplet
energy transfer may be in direct competition with fragmentation of the
excited benzoin. Quantum yields for the photo- initiation by benzoin
derivatives are often in the region 0.2-0.3. Later work however,
indicates a reactive triplet state.
Norrish type 1 cleavage of benzoin, benzoin alkyl ethers and α-alkylated
benzoins will form benzoyl radicals. Which can be expected to be
reactive entities a efficient photoinitiators. Photoinitiation is though to
proceed as follows22

O OR O OR OR OR
hν
Ph C C Ph Ph C ⋅ + ⋅ C Ph Ph CH CH Ph
H H
(alkoxy benxyl radical)
RH

Ph CHO + Ph C C Ph + R⋅
O O

The two radicals are formed : (i) benzoyl radical (ii) alkoxy benzyl
radical are of different reactivity.

23
Benzoyl radicals are the main cause of polymer chain initiation α-
alkoxy benzyl radicals are less reactive and partially dimerize. Benzoin
ethers lead to poor pot stability probably owing to the activated
hydrogen in the α-position of the ether group. Ethers with this structure
readily react with oxygen forming hydroperoxides. This intermediate
may result in thermal stability. Particularly in the presence of transition
metals which are often present in filler materials. The substituted
pattern of benzoin ether can also effect the pot life, shot chain alkyl or
non branched ether such as benzoin methylether, being the worst. A
reasonable compromise between reactivity and shell life is benzoin
isopropyl ether. Stabilizers can also be incorporated as along as cure
rate is not effected.
(3) Thioxanthone and Derivatives
Many photoinitiator can be regarded as derivatives of
benzophenone in particular thioxanthane and its substituted compounds.
The table over leaf shows some of these which can be seen to have a
derivation from the formula.
O
1
C 2 Y

3
X 4

[Y may occupy any one of the positions 1, 2, 3, 4. If it represents a Cl-

atom replacing on hydrogen atom, or it may itself be a hydrogen atom]
Substituted thioxanthones have been developed for white pigmented
coating as two chief problems occur with these relatively thick coatings.
i) The pigment can reflect or absorb incident UV light,
diminishing the available light to the photoinitiator.

24
 ii) The opacity of thickner pigmented films can result in a poor
through cure23.
Titanium dioxide has high reflectivity through the visible range of
spectrum and strong adsorption at wavelength <340 nm. As the region
350-400 nm represents a transition between the reflection and
absorption of light, this window can be used for photo-sensitizer such
thioxanthone derivatives. The main properties needed from a
photoinitiator from a formulation aspect are :
1) UV-curing response
2) Colour of final film
3) Stability/ease of incorporation
4) Pot stability of the formulation
5) Physiological aspects (toxicity, odour, etc.)
6) Cost effectiveness
Of particular use are
(i) 2-chlorothioxanthone (2-CTX)
O
C Cl

S
(ii) 2-isopropyl thioxanthone
O CH3
CH
CH3
S
The latter has good stability (as it is a liquid) in many solvents and
former is however, a solid.

25
2-CTX probably reacts by a hydrogen abstraction methods

O O * OH
Cl Cl Cl
hν RH
+ R⋅
S S

2-CTX excited state

2-CTX has absorption band at 260 nm and 385 nm. Some synergistic
agent (or photoactivators) often used with thioxanthone and its
derivatives (or any other convenient photoinitiator responsive to these
compounds are :

a) Ethyl para-dimethyl amino benzoate

b) Ethyl ortho-dimethyl amino benzoate
c) 2(n-butoxy) ethyl-para dimethyl amino benzoate

(4) Benzil Ketals

Benzil ketals represent a versatile family of photoinitiators. 2,2-

dimethoxy 2-phenyl acetophenone (DMPA) is one of the most important
commercial photoinitiators of the α-cleavage family.

It’s mode of action is thought to be primarily a Norrish type I cleavage.

O O - CH3 O O - CH3
hν ⋅ C Ph (dimethoxybenzyl radical)
Ph C C Ph Ph C ⋅ +
O - CH3 (benzoyl radical O - CH3

O O
2 Ph CO⋅ Ph C C Ph (benzil)
(recombination reaction)

26
 OMe O
Ph C ⋅ ⋅
Ph C O CH3 + CH3
OMe (benzoic acid (methyl
methyl ester) radical)

This ester formation is strongly temperature dependent.

O
Ph C ⋅ + RH Ph CHO + R ⋅
(benzaldehyde)

O O
Ph ⋅
C ⋅ + CH3
Ph C CH3
(acetophenone)

Here, acetophenone is a cage collaps product of benzoyl and methyl

radical. The pot stability of this compound relative to benzoin ethers is
reported to be for greater.24

The manor drawback of this compound is its considerable yellowing.

Acrylate based inks and coating for metal, paper, plastic and wood
commonly make use of these types of photoinitiators.

(5) Acyl phosphine Oxide

Acylphosphine oxide were introduced some year ago as a new

class of α-cleavage photoinitiators, derived from DEAP by replacing C-
H by P=O alkoxy by aryl groups. A relatively high oxygen inhibition
may decrease their reactivity in the curing of thin films.

Mono-acyl phosphine (MAPO eg. Lucirin TPO) and bis acylphosphine

oxides such as BAPOI (Irgacure 1700 and 1800) and BAPO 2 (Irgacure

27
819) have absorption band in the near UV/visible region, and so are
specially indicated for use in pigmented system. Additionally
acylphosphine oxides bleach on irradiation, hence there is a decrease of
absorptivity in the near UV-visible range and radiation can penetrate
into deeper layers. Acylphosphine oxides produce little yellowing
immediately after curing and no long term exposure, therefore, they
have been used in applications where low yellowing is required as in
white and ale inks. Acyl phosphine oxide possess short-lived excited
state and present low quenching characteristics being suitable in styrene-
based coating for the furniture manufacturing industry25.

(6) α-Acyloxime esters

A Norrish type I cleavage reaction occurs to form a benzoyl radical and

another which undergoes further cleavage.

Ph
O Ph O ⋅C
O
Ph C C N O C R
hν
Ph C⋅ + N O Ph - CN + CO2 + R⋅
O C R

A useful (0-acylated-α-oximino ketone) derivatives that has been used

in 1-phenyl-1, 2-propane dione-2-(0-ethoxy carbonyl oxime)

O
C C CH3
N O
O C OC2H5

It is white/off white crystalline solid, odourless stable for at least one

year at room temperature and soluble in many solvent like Trimethoxyol

28
propane triacrylate, 1-6-Hexanedioldiacrylate, MMA (Methyl
methacrylate), Hexane, CCl4, Acetone, Ethanol, Methanol, Toluene.

(7) Acetophenone Derivatives

Dialkoxy acetophenone can be regarded as benzoin ethers. The most

popular used is DEAP (diethoxy acetophenone). DEAP undergoes a
Norrish type II cleavage yielding a biradical as the chain initiating
species.

O O⋅ OH
C⋅
C OC2H5
hν
C
⋅ ⋅
CH OC2H5 CH OCH CH3
CH
OC2H5
OC2H5 OC2H5

CH3 O
OH ⋅ CH O C
CH CH3
C CH CH2 OC2H5
⋅
C
O OH OC2H5
CH
+ CH3 CHO
OC2H5

If no reactive double bond are available, the biradical undergoes initial

coupling to form an oxetanol intermediate which disproportionates
thermally to acetaldehyde an ω-ethoxy acetophenone.

Chlorinated acetophenone derivatives

Substituted di- and tri-chloroacetophenone undergo photolysis. Such as

p-tert-butyl trichloroacetophenone (in the general formula below for this
type of compound R = (CH3)3C. β-cleavage is the prime reaction. X
may be either an H or another CI-atoms.

29
 O O
R C CXCl2
hν ⋅ ⋅
R C CXCl + Cl

Cl ⋅ + R1 H HCl + R1 ⋅

The liberated chlorine radical is particularly highly reactive and initiates

polymerization efficiently especially ionic curable binders. A
disadvantage is that this radical can form hydrochloric acid by hydrogen
abstraction from a hydrogen donor and this presents an obvious
disadvantage in many areas. Such as metal decorating and may also lead
to poor pot stability.26,27

30
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1. Roffey, C G; Journal of Oil & Colour Chemist Association;
1986, 69, (11), 288.
2. Berner, G; Kirchmayr, R and Rist, G; Journal of Oil & Colour
Chemist Association; 1978, 61, (4), 105.
3. Pappas, S P; Progress in Organic Coating, 1973, 74, (2), 333.
4. Ledwith, A; Journal of Oil & Colour Chemist Association,
1976, 59, 157.
5. Micheli de P.; Journal of Oil & Colour Chemist Association,
2000, 83, (9), 457.
6. Hara, K O; Journal of Oil and Colour Chemist Association,
1985, 68, (4), 254.
7. Aggrawal, D. and Maithani, A.; Paint India, 2002, 52, (4), 43.
8. Randell, D R; Radiation Curing of Polymer, 1986, 121 (P)
Great Britain by Whitstable Litho Ltd., The Royal Society of
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9. Roffey, C G; Photopolymerisation of Surface Coatings, 1982,
146 (P), A Wiley-Interscience Publication, John Wiley and
Sons.
10. Roffey, C G; Photopolymerisation of Surface Coatings, 1982,
156 (P), A Wiley-Interscience Publication, John Wiley and
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12. Irene, O B; Paint India, 1996, (2), 25.
13. Pelgrims, J; Journal of Oil and Colour Chemist Association,
1978, 61, (9), 114.

31
 14. Neerbos, A V; Journal of Oil and Colour Chemist Association,
1978, 61, (7), 241.
15. Durgval, S.V.; Paint India, 2002, 52, (4), 38.
16. Roffey, C G; Photopolymerisation of Surface Coatings, 1982,
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18. Decker, C; Journal of Coating Technology, 1987, 59, (8), 97.
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Colour Chemist Association, 1978, 61, (4), 105.
20. Gamble, A A; Journal of Oil and Colour Chemist Association,
1976, 59, (4), 240.
21. Hulme, B E; Journal of Oil and Colour Chemist Association,
1976, 59, (7), 245.
22. Allen, S N; Edge, M; Journal of Oil and Colour Chemist
Association, 1990, 73, (1), 438.
23. Pappas, S P; Progress Organic Coating, 1973/74, 2, 333.
24. Hageman, H J; Progress Organic Coating, 1985, 13, 123.
25. Studer, K. and Roniger, R.;; European Coating Journal, 2001,
(1-2), 110.
26. Pappas, S P and McGinniss, V D; “UV-Curing Science and
Technology”, Vol-I, Technology Marketing Corp., USA,
1978.
27. Holman, R and Oldering P; UV and EB Curing Formulation
for Printing Inks, SITA-Technology, 1988, 203(P), Gardiner
House Broomhill Road, London SW18, England.

32

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