Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3-11498/DIV IV
This Application is a divisional of Application 318,328 filed
December 20th, 1978.
The invention relates to the use of aromatic aliphatic
ketones which are substituted in the a-position as sensitizers
for the photopolymerisation of unsaturated compounds or for the
photochemical crosslinking of polyolefins, as well as to the
photopolymerisable and crosslinkable systems which contain such
sensitizers.
Photochemical polymerisation processes have attained
substantial importance in the art, especially in those cases where
thin layers have to be hardened in a shor-t time, for example
in the hardening of varnish coatings or in the drying of printing
inks. Compared with conventional hardening methods, UV irradia-
tion in the presence of photosensitizers has a number of advantages,
the most important of which is the great speed of the photoharden-
ing. The speed is heavily dependent on the photosensi tizer
employed and -there has been no lack of attemps to replace the
conventional sensitizers by ever better and more effec-tive com-
pounds. Among the most effective photosensitizers are derivatives
of benzoin, in particular the benzoin ethers described for example
in German Patent Specification 1,694,149, derivatives of
a-hydrox.ymethylbenzoin described in German Offenlegungsschrift
1,923,266, and the dialkoxyacetophenones and benzil monoketals
- 1- ~.~
~2~ )2~
described for example in German Offenlegungsschrift 2,261,383 or
2,232,365. ~-Aminoacetophenones and ~-diaminoacetophenones have
recently been proposed as pho-tosensitizers in United States
Patent Specification 4,048,034 and c~-hydroxy-~-alkylolacetophenones
and their ethers in German Offenleg-mgsschrift 2,357,866. The
shortcomings of these known photosensitizers are in some cases an
insufficient storage life in the dark of the photopolymerisable
systems mixed with such sensitizers. A number of benzoin deriva-
tives tend to cause yellowing of the hardened compositions. Other
sensitizers are insufficiently reactive - a feature which is
observed in the rela-tively lengthy hardening times - or their
solubility in the photopolymerisable systems is too low or they are
rapidly rendered inactive by atmospheric oxygen. There is there-
fore a need in the art for photosensitizers whicn are readily
soluble in the substrate and, while having a good storage li fe in
the dark, initiate the photopolymerisation more rapidly and give
a higher polymer yield per unit of time than the known photo~
sensitizers. By using such improved photosensitizers it would be
possible to exploit be tter the expensive industrial UV irradiation
plants.
It has been found that compounds of the following
formula I possess the required properties as photosensitizers.
In particular, they effect a rapid photopolymerisa-tion and do not
have the shortcomings referred to or possess them to a much lesser
degree than the known photosensitizers. Furthermore, they are
suita;~le for the photochemical crosslinking of polyolefins. The
invention relates to the use of the colnpounds of the following
formula I R
~2
wherein:
Ar represents (a) phenyl substjtu-ted wi-th -CN, -OH, -alk,
-Oalk, -O phenyl, -Salk, -SO2alk, -SO2phenyl, -COOalk, -SO2NH2,
-SO2N(alk)2, -NHalk, -N(alk)2 or -NHCOalk, or
(b) naphthyl, thienyl, pyridyl, furyl, indanyl,
or te'rahydronaphthyl;
R represents Cl to C8 alkyl which is unsubstituted or sub-
stituted by -OH, -Oalk, C2-C8acyloxy, -NR R5, -COOalk, -CN-C3-
C3-C4alkenyl, C3-C6cycloalkyl, or C7-Cgphenylalkyl;
R has one of the meanings assigned to Rl or represents a
-CH2CH2R group, or, together with R , represents a C2-C8 alkyl-
ene, C3-Cg-oxa-alkylene or C3-Cg-aza-alkylene group;
R4 represents Cl-C12 alkyl, C2-C4alkyl substituted by -OH,
-CN or -Oalk, or C3-C5 alkenyl, cyclohexyl, C7-Cgphenylalkyl,
phenyl, or phenyl substituted by -Cl, -alk, -OH, -Oalk, or -COOalk;
R5 represents Cl-C12 alkyl, C2-C4alkyl substituted by -OH,
-CN or -Oalk; or C3-C5alkenyl, cyclohexyl or C7-Cgphenylalkyl, or
together T"ith R4 represents C4-C5alkylene which can be interrupted
by -O- or -NR14-, or together with R2 represents Cl-Cgalkylene or
phenylalkylene or C2-C3-oxa or aza-alkylene;
-- 3 --
V~Z~
R13 represents -CON~2, CONHalk, -CON(alk)2, -P(O)(Oalk)2,
2-pyridyl or 2-oxo-1-pyridyl;
R represents Cl-C4alkyl, -CH2CH2CN or -CH2CH2COOalk; and
alk represents a lower alkyl radical of 1 to 4 carbon a-toms.
These compounds are accordingly aromatic-aliphatic
ketones, the ~-carbon atom of which is tertiary and which is
substituted by an amino group. The aliphatic residue can also be
cycloaliphatic or araliphatic or linked to the aromatic residue
with ring closure, which corresponds to the benzocyclic ketones
of the formula IV.
Of the substituents listed above, Rl and R2, can be
alkyl of 1 to 8 carbon atoms, for example methyl, ethyl, propyl,
butyl, hexyl or octyl. R4 and R5 as alkyl can be unbranched or
branched alkyl of 1 to 12 carbon atoms, for example methyl, ethyl,
isopropyl, tert -butyl, isoamyl, n-hexyl, 2-ethylhexyl, n-decyl
or n-dodecyl. Alk represents a lower alkyl radical of 1 to 4
carbon atoms, for example methyl, ethyl, isopropyl, n-butyl or
tert -butyl.
R and R2 as hydroxyalkyl, alkoxyalkyl or acyloxyalkyl
can be for example hydroxymethyl, l-hydroxyethyl, 2-hydroxyethyl,
2-isopropoxyethyl, l-hydroxyisobu-tyl, l-acetyloxybu-tyl, l-acryloyl-
oxyhexyl, l-hydroxyoctyl, 3-benzoyloxypropyl, methoxymethyl or
isobutyloxymethyl. The acyl racical can be the radical of an
aliphatic or arornatic carboxylic acid. Preferably they are
l-hydroxyalkyl radicals and their e-thers or esters. R4 and R5
as hydroxyalkyl or alkoxyalkyl can be for example 2-hydroxyethyl,
2-butoxyethyl, 2-methoxypropyl, 3-hydroxypropyl or 2-e-thoxybutyl.
-- 4
Preferably they are 2-hydroxyalkyl radicals and the ethers there-
of.
R and R as alkyl whieh is subs-tituted by -NR R ean
be for example dibutylaminomethyl, 2-piperidinoethyl or 2-dimethyl-
aminopropyl.
Rl, R , R or R as CN-substitu-ted alkyl ean be for
example 2-eyanoe-thyl, 2-cyanopropyl or 4-cyanobutyl, whilst Rl,
R2 and R4 ean also be for example cyanomethyl, 2-eyanohexyl or
4-eyanooctyl. The 2-cyanoethyl radical is preferred.
Rl and R2 as alkyl substituted by -COOalk can be for
example -CH2COOC2H5, -CH2CH2COOCE13, -(CH2)3-COOCH3 or -CH2-
CH(C H )-COOC4H9
R , R2, R and R as alkenyl can be for example allyl,
methallyl or 2-butenyl.
Rl and R as cycloalkyl can be cyclopentyl or eyelohexyl.
Rl, R2, R4 and R5 as phenylalkyl ean be for example ben~yl,
phenylethyl or dimethylbenzyl.
Ar as aryl or substituted phenyl ean be for example
phenyl, naphthyl, isopropylphenyl, phenoxyphenyl, cyanophenyl,
hydroxyphenyl, -tolyl, tert -butylphenyl, xylyl, methoxyphenyl,
ethoxyphenyl, phenoxyphenyl, methylthiophenyl, butylsulfophenyl,
phenylsulfophenyl, ethoxycarbonylphenyl, tert -butoxyearbonyl-
phenyl, methylaminosulfophenyl, dipropylaminosulfophenyl,
dimethylaminophenyl or acetylaminophenyl.
~, _
~,Z~
Rl and R2 together can represent alkylene or oxaalkylene
or azaalkylene. In this case, Rl and R2 together with the carbon
atom to which they are attached form a cyclopropane, cyclobutane,
cyclopentane, cyclohexane, cycloheptane, tetrahydrofurane, tetra-
hydropyrane, pyrrolidine or piperidine ring.
R and R5 together can represent alkylene or phenyl-
alkylene of 1 to 9 carbon atoms or oxaalkylene or azaalkylene. In
this case, R and R5 -together wi-th the carbon atom to which R2
is attached and the nitrogen atom to which R5 is attached form a
3- to 6-membered ring, for example an aziridine, azetidine,
pyrrolidine, imidazolidine, piperidine, piperazine or morpholine
ring.
R and R together can represent alkylene of 4 to 5
carbon atoms which can be interrupted by -O- or -NR14-. In this
case, R4 and R5 together with the nitrogen atom to which they are
attached form a pyrrolidine, piperidine, morpholine, 4-alkylpiper-
azine, 4-cyanoethylpiperazine or 4-alkoxycarbonylethylpiperazine
ring.
Ar can be arylene of 6 to 12 carbon atoms~ for example
phenylene or naphthylene.
Most preferably, the invention is concerned with the
use of compounds of the formula I, wherein Ar represents phenyl
~,lhich is unsubstituted or substitu-ted by Cl-C4 alkyl or Oalk,
or represents indanyl or tetrahydronaph-thyl, Rl represents
Cl-C8-alkyl, R represents Cl-C8alkyl or C3-C4alkenyl, R
represents Cl-C12alkyl, R5 represents Cl-C12alkyl or -together with
-- 6
2~325
R represents C4-C5alkylene which can be interrupted by -O-
or -NR -and R represents Cl-C4alkyl-
The most preferred compound according to this inventionis 2-~1orpholino-2-methyl-p-(methylthio)-propiophenone.
These novel compounds can be prepared by methods analo-
gous to those for obtaininy the known compounds, whereby different
methods are possible.
Accordingly, the compounds of the formula I can be
prepared from aromatic-aliphatic ketones by the following reaction
steps:
(a) by bromination of a suitable propiophenone; -the bromo
compound is converted to the epoxide, which is reacted with an
amine:
ArCOCRlR2H ~ Ar-CO-CRlR2Br ,
Ar-f/ - \CRlR2.__~ ArCOCR R-NR R
OCH3
(b) as an alternative to (a), the corresponding propiophe-
none can be chlorinated rather than bromina-ted, the remaining
steps being the same;
(c) by chlorination of a suitable propiophenone, followed
by direct reaction witn an amine;
ArCOCRlR2H ~ ArCOCR R Cl -, ArCOCRlR-NR R ;
and
(d) as an alternative to (c), the bromo compound can be used.
3.~
Compounds of the formula I, wherein Rl is a subs-titu-ted
alkyl group, can be obtained from the compounds of the formula
ArCOCR R -NR R by reaction with aldehydes (R = hydroxyalkyl)
or with a vinyl compound which is capable of addition, for example
with acrylates or acryloni-trile. In the same way, a -Cll2Ci~2-R
group can be introduced as R2, star-ting from a compo~md
A-CoCHRl-NR4R5. If both Rl and R are substituted alkyl, then
both substituents can be introduced jointly by reaction of a
compound ArCOCRlR2NR R5 with at least 2 moles of an aldehyde or
a vinyl compound. The corresponding alkoxyalkyl and acyloxyalkyl
groups can be obtained from the hydroxyalkyl groups Rl and/or R2
by etherification or esterification.
Compounds in which X together with Rl is a -O-CH (R9)
group are ~-oxydoketones and can be obtained by epoxidation of
the corresponding ~-vinyl ketones. Reaction of the oxydoketones
with secondary amines affords compounds in which either X is OH
and R is an aminoalkyl group, or in which X is NR R and R is
a hydroxyalkyl group.
Addition of bromine to the ~-vinyl ketones yields
~J~,e-dibromoketones of the formula ArCOCBrRl-CBralk.
P~eaction of the dibromoketones with one mole of a primary
amine yields the corresponding ~-aziridinoketones [J. Am. Chem.
Soc. 65 (lg43), 312], and reaction with 2 moles of a secondary
amine yields compounds of the formula I, wherein R is an amino-
alkyl radical [J. Am. Chem. Soc. 74 (1952), 1886].
8 ~
Aminoalkyl groups K and/or R can also be introduced
by the Mannich reaction, wherein ketones of the formula
Ar-CO-CHRl-X or Ar-CO-CH2-X are reacted with 1 or 2 moles of
formaldehyde and a secondary amine.
Whereas all these methods of synthesis start from an
aromatic-aliphatic ke-tone into which a substituent is introduced
in a different manner, it is also possible in specific cases to
introduce the substituent during the ketone synthesis by the
Friedel-Crafts reaction in accordance with the reaction scheme:
Rl R-
X - C - COCl ~ ArH AlC13 Ar- CO -C -X
R2 12
This presupposes that the substituent X is not attacked
under the conditions of the Friedel-Crafts reaction. In this
way it is possible for example by using heterocyclic carboxylic
acid chlorides to prepare compounds of -the formula I, in which
X and R together with the carbon atom to which they are attached
form a heteroring.
According to the invention, the compounds of the
formula I can be used as sensitizers for the photopolymerisation
of unsaturated compounds or systems which contain such compounds.
Such compounds are for example unsaturated monomers,
such as esters of acrylic or methacrylic acid, for example
methylacrylate, ethylacrylate, n- or tert-butylacrylate, isooctyl-
acrylate or hydroxyethylacrylate, methyl- or ethylmethacrylate,
g
3~2~
ethylene diacrylate, neopentyl diacrylate, trime-thylolpropane
trisacrylate, pentaerythritol tetraacrylate or pentaery-thritol
trisacrylate; acrylonitrile, methacrylonitrile, acrylamide,
methacrylamide, N-substituted acrylamides and methacrylamides;
vinyl esters, such as vinyl acetate, vinyl propionate, vinyl
acrylate or vlnyl succinate; other vinyl compounds, such as vinyl
ethers, s-tyrene, alkyl styrenes, ha:Lostyrenes, divinyl benzene,
vinyl naph-thalene, N-vinylpyrrolidone, vinyl chloride or vinyl-
idene chloride; allyl compounds, such as diallyl phthala-te,
diallyl maleate, triallyl isocyanurate, triallyl phosphate or
ethylene glycol diallyl ether and the
- 10 -
mix-tures of such unsaturated monomers.
Photopolymerisable compounds are in addition un-
saturated oligomers or polymers and the mixtures tnereof
with unsaturated monomers. These include thermoplastic
resins which contain unsaturated groups, such as fumaric
acid ester groups, allyl groups or acrylate or methacrylate
groups. These unsaturated groups are usually bound through
functional groups to the main chain of these linear poly-
mers. Mixtures of oligomers with simply and poly-unsaturated
monomers are very important. Examples of such oligomers are
unsaturated polyesters, unsaturated acrylic resins and iso-
cyanate or epoxide modified acrylate oligomers as well as
polyether acrylate oligomers. Examples of poly-unsaturated
compounds are in particular the acrylates of diols and poly-
ols, for example hexamethylene diacrylate or pentaerythri-
tol tetracrylate. Acrylates are also preferred as simply
unsaturated monomers, for example butyl acrylate, phenyl
acrylate, benzyl acrylate, 2-ethylhexyl acrylate or 2-
hydroxypropyl acrylate. By choosing from the differen-t
representatives of the three components, the opportunity
is afforded to vary the consistency of the unpolymerised
mixture as well as the plasticity of the polymerised resin.
In addition to these three-component mixtures,
two-component mixtures especially are of great importance
among the polyester resins. These usually consist of an un-
saturated polyester and a vinyl compound. The unsaturated
polyesters are oligomer esterification products of at least
one unsaturated dicarboxylic acid, for example maleic,-
fumaric or citraconic acid, and usually of at least one
saturated dicarboxylic acid, for example phthalic acid,
succinic acid, sebacic acid or isophthalic acid, with
glycols, for example ethylene glycol, propanediol-1,2,
di- or triethylene glycol or tetramethylene glycol, whiist
monocarboxylic acids and znonoalcohols are generally also
used concurrently for the modification. These unsaturated
polyesters are normally dissolved in a vinyl or allyl com-
pound, styrene being preferably used for this purpose.
Photopolymerisable systems which are used for
the different purposes usually contain, in addition to the
photopolymerisable compounds and the photosensitizer, a
number of other ingredients. It is therefore often customary
to add heat inhibitors in order to prevent a premature poly-
merisation, especially during the preparation of the systems
by mixing the components. Hydroquinone, hydroquinone deriva-
tives, p-methoxyphenyl, ~-naphthylamine or ~-naphthols are
used for example for this purpose. Furthermore, small
amounts of W absorbers can be added, for example those of
the benztriazole or benzophenone type.
To increase the storage life in the dark, it is
possible to add copper compounds, such as copper naphthenate,
copper stearate or copper octoate, phosphorus compounds,
such as triphenylphosphine, tributylphosphine, triethyl
phosphite, triphenyl phosphite or tribenzyl phosphate,
quaternary ammonium compounds, such as tetramethylammonium
chloride or, trimethylbenzylammonium chloride, or hydroxyl-
amine derivatives, for example N-diethylhydroxylamine. In
addition, the photopolymerisable systems can contain chain
transfer agents, for example N-methyl-diethanolamine, tri--
ethanolamine or cyclohexene.
In order to exclude the inhibiting action of
atmospheric oxygen, paraffin or similar wax-like substances
are requently added to photohardening systems. On accounL
of their poor solubility in the po].ymer, these substances
float at the beginning of the polymerisation and form a
transparent surface layer which prevents the entry of air.
-- 1~ --
32~
The atmospheric oxygen can also be deactivated by introduc-
ing autoxidisable groups, for example allyl groups, into
the resin to be hardened.
Depending on the end-use, photopolymerisable
systems also contain fillers, such as silicic acid, talc or
gypsum, pigments, dyes, fibres, thixotropic agents or level-
ling agents.
Combinations with known photosensitizers, such as
benzoin ethers, dialkoxy acetophenones or benzyl ketals,
can also be used. Combinations of the photosensitizers of
the invention with amines and/or aromatic ketones can be
used especially for the photopolymerisation of thin layers
and printing inks. Examples of amines are triethylamine,
N-methyldiethanolamine, N-dimethylethanolamine or p-di-
methylaminobenzoate. Examples of ketones are benzophenone,
substituted benzophenone derivatives, Michler's ketone,
anthraquinone and anthraquinone derivatlves, as well as
thioxanthone and the derivatives thereof.
Photohardening is of great importance for print-
ing inks, since the drying time of the binder is a decisi-ve
factor in the production speed of printing products and
should be in the order of fractions of seconds. The sensi-
tizers of the invention are also very suitable for photo-
- hardening systems for the manufacture of printing plates;
~ixtures of soluble linear polyamides with photopolymeris-
able monomers, for example acrylamides, and a photosensi-
tizer, are usually employed for this purpose. Films or-
plates prepared 'rom these systems are exposed via the
negative (or positive) of the original and the unhardened
portions are subsequently eluted with a solvent.
- 13 -
A further field of use of UV hardeniny is meta~ coating,
for example in the varnish coating of metal sheetiny for tubes,
cans or bottle caps, as well as the UV hardening of plastic
coatings, for example of floor or wall coverings based on PVC.
~ xemplary of the UV hardening of paper coatings is the
colourless varnish coating of labels, gramophone record sleeves or
book jackets.
According to the invention, the compou~ds of the
formula I can also be used as sensitizers for the photochemical
crosslinking of polyolefins, for example polypropylene, poly-
butene, polyisobutylene and also copolymers, for example ethylene/
propylene copolymers, but preferably polyethylene of low, medium
or high density.
The photosensitizers are advantageously used for the
above fields of use in amounts of 0.1 to 20% by weight, preferably
about 0.5 to 5% by weight, based on the photopolymerisable or
crosslinkable system. The term "system" is to be understood as
meaning the mixture of the photopolymerisable or crosslinkable
compound, the photosensitizer and the other fillers and additives,
as it is used in the respective application.
The addition of the photosensitizers to the photo-
polymerisable systems is accomplished in general by simple stirring,
since most of these systems are fluid or readily soluble. Usually
the sensitizers of the invention dissolve in the system, thereby
ensuriny theix uniform distribution and the transparency of the
polymers.
The pol~rnerisation is carried out by the known methods
of polyr~risation by irradiation with light which
-- 1~ --
is rich in shortwave radiation. Suitable light sources ars
for example mercury medium pressure, high pressure and low
pressure lamps, as well as superactinic fluorescent tubes,
the emission peaks of which are in the range between 250
and 400 nm.
The following Examples describe the manufacture
and use of compounds of the formula I in more detail. Parts
and percentages are by weight.
- 15 -
3.~ V~
Manufacture and properties of -the compounds used in Examples 1
to 6.
The compounds listed in Table 1 were obtained by one or
more of the methods A, B, C, D, G, H and I.
Method A Chlorination of aromatic-aliphatic ketones
Ar_co_cRlR2H + n C12 ~ Ar-CO-CR R Cl + n HCl
The ketone is dissolved in an inert solvent, preferably in tetra-
chloromethane, and the calculated amount of chlorine is introduced
into the solution at 40-80C. Nitrogen is -then introduced to
remove dissolved HCl. Finally, the solvent is distilled off.
Purification of the chloroketone is usually not necessary and the
product can subsequently be .eacted by me-thod D, or H.
Method B Bromination of aromatic-aliphatic ketones
Ar_co_cRlR2H + n Br2 ~ Ar-CO-CRlR2Br -~ n ~Br
The calculated amount of bromine is added dropwise at room
temperature to a solution of the ketone, for example in CC14.
Working up and further processing are effected as in Method A.
Method C Chlorination with sulfuryl chloride
Ar_co_cRlR2H 2 2 ~Ar-CO-CR R -Cl
+ n SO2 + n HCl
The sulfuryl chloride is added dropwise at 40C to a solution
of the ketone in CC14. Working up and further processing as
in Method A.
- 16 -
Method D Preparation of the epoxide intermediate
Ar-CO-CR R Hal + n NaOCH3 -~Ar-f - cRlR + n NaHal
OCH3
Hal = Cl or Br
The haloketone is dissolved in methanol and a solutlon of the
stoichiometric amount of sodium methoxide in me-thanol is added
dropwise at reflux temperature. The methanol is then distilled
off and the residue is poured into ice-water and extracted with
ether. The ethereal solution is washed with water, dried over
Na2SO4, dried and concentrated. The residue is purified by
recrystallisation or vacuum distillation. The epoxide can sub-
sequently be reacted by Method E or G.
Method G ~-Aminoketones from the epoxides
Ar-C \ CRlR2 + R4R5NH ~Ar-co-cRlR2-NR4R5 + CH OH
OCH3
The epoxide is treated with the stoichiometric amount of the amine,
either without a solvent or with the addition of a small amount of
toluene or xylene, and reacted for about 10 to 20 hours at 100-
200C. ~hen using low boiling amines, for example dimethylamine
or diethylamine, the reaction is carried out in an autoclave. The
reaction mixture is diluted with benzene and extracted with dilute
hydrochloric acid. The aqueous acid solution is made alkaline with
NaOH and extracted with ether. The ethereal solution is washed
rr7ith water, dried over Na2SO4 and concentrated. The crude product
is purified b~ distillation or crystallisation. The ~-amine-
ketones are listed in Table 1.
~ 17 -
Method H ~-Aminoketones from the ~.-haloketones
Ar-CO-CR R Hal f R4R5NII - ~Ar-CO-CRlR2-NR4R5
+ R R NH2Hal
The ~-ha]oketone, undiluted or dlluted with toluene, is mixed
with 2 molar equivalents of the amine and the mixture is heated
for 10 to 20 hours to 100-200C. When using low boiling amines,
for example dimethylamine or diethylamine, the reaction is carried
out in an autoclave. Isolation and purification are effected as
in Method G.
Method I Introduction of a carbalkoxyethyl group
C~l2CH2COOAlk
Ar-CO-CHR -X + CH2 = CH-COOAlk Ar-CO-CR -X
The ketone is dissolved in dimethyl sulfoxide. To the solution
are then added l.l molar equivalents of NaOH in -the form of 4N
sodium hydroxide solution and, with cooling, l.l molar equivalents
of acrylate are added dropwise at room temperature. The reaction
mixture is diluted with ice-water and extracted with toluene. The
toluene solution is washed neutral with water, dried over Na2SO4
and concentrated. The crude product is purified by column
chro~tography or crystallisation.
- 18 -
Com- Formula ~lethod of Purification Physical
pound manufacture properties
0 CE13
~ I I
_8 \S~ C -N\ /0 B+D+G dist. bp-o 1 150 *)
CE13
o Cl~3
~9 l~ C~ -C ~ N 0 B+D+G cryst. m.p. 110-112
3 \ ~ I \ / (diisopro-
3C/ CE13 pyl ether)
O CH
31 Cl ~ C t N~ ~ B+H dist. b-p-o 1 150 )
CH3
Com- Formula rlethod of Puriflcation Physical
poul~d manufacture properties( C)
0 CH
32 113C \ / t `: : B+D+G dist. Po~l )
0 CH3
33 1I C-0-~-C t N~ \- B+H do. b.po 2 180 *)
I CH3
o 0 CIJ3
34 \ ~o-o-o\ ~o-C+N\ \- CfEl do. b.po 1 200
=0 ~ --0
C113
0 CH
113C-S-o~~--ctN\ \ B+D+G do. m.p. 68-71
b-po l 210 *)
Cl~
.
*) temperature of the air bath in bulb tube distillation.
Example 1
A resin mixture consisting of 90 parts of Laromer*
LR 8496 (acrylate resin available from BASF, West Germany), 10
parts of hexanediol diacrylate, O.5 part of ByK 300 (levelling
assistant available from ByK-Mallinckrodt, West Germany) and 3
parts of photosensitizer for hardening in the air or 0.5 part of
photosensitizer for hardening under nitrogen, is applied electro-
motively to cardboard boxes with a 15~ helix. After brief expos-
ure to air, hardening is effected with a UV device (model PPG-QC-
processer) with a UV lamp of 80 wa-tts/cm. The maximum transporta-
tion speed at which non-tacky films were obtained in air or under
nitrogen for compound No. 29 was 10 m/min under air and 90 m/min
under nitrogen.
Example 2
A resin mixture consisting of 70 parts of Ebercyl* 593
(polyester acrylate available from UCB, Belgium), 30 parts of
trimethylolpropane trisacrylate, 0.5 part of ByK 300 (levelling
assistant available from ByK-Mallinckrodt, West Germany) and 3
parts of photosensitizer, is applied to glass plates in a layer of
30-40 ~. After brief exposure to air, hardening is effected with
a UV laboratory device (model PPG/QC-processer) with a UV lamp of
80 watts/cm. After the UV hardening, -the plates are stored for
1/2 hour under normal climatic conditions and then the hardness
of the layers is determined using the pendulum device of Konig.
The hardness values as a function of the transportation speed
under the lamp are reported in the following Table.
* Trademarks
21 -
3~
. . Pendulum hardness in sec.
Photosensltlzer 10 m/min. 25 m/min.
32 146 129
134 10
41 164 152
- 22 -
