Note: Descriptions are shown in the official language in which they were submitted.
- ` ` flLE. F~N THIS Ah~c~FJrD
TEXT TRANSLATION
1328~
April 9, 1992/fe
PAT 92 348
FECY88
BASF Lack- I Farb-n Aktleng~ chaft, M~t-r
Add~tiou product~, radiation-curable ~urfac- coat~ng
compo~tion~ ba~ed on the addition product~ and th-ir
u~e for woodcoatlng and papercoatlng
The pre~ent inventlon relates to addition
products of
A) oligomerR having at least two acrylic ester and/or
methacrylic ester groups per molecule and
B) polyamines
Furthermore, the present invention relates to
radiation-curable surface coating compositions ba~ed on
the addition products and to the u~e of the radiation-
curable surface coating compositions for the coating of
wood, woodbase materials and paper
Curing of compositions based on acrylic ester~
by radiation, in particular W radiation, is known
However, the problem with this method is that the
presence of air interferes with surface-hardening
Photopolymerizable surface costing compositions
containing amines as reducing agent~ or chain-
transferring compound~ are disclosed in German Patent
Specification 2,625,538 The disadvantage of using such
a free amine is that it can act as plasticizer and
leads to an undesirable deposit on the ~urface and to
~1328~ :
. .
- 2 -
odor nuisance.
By incorporating the amino group in a molecule
which atditionally contains polymerizable groups it i9
possible, on curing-, to obtain an amine which is
present as copolymerized unit and doe~ not show the
abovementioned disadvantages. A known method of
incorporation is the addition of ~m; nes to molecules
- which are high in double bonds, which addition proceeds
analogously to a Michael addition and i8 described, for
example, in P. Moller, ~ouben-Weyl, Vol. 11/1 l1957),
pp. 277-280. US Patent Specification 2,759,913 teaches
the addition reaction of amines with activated,
olefinically unsaturated compounds, such as acrylates,
in equimolar amounts, which results in complete
conversion of the activated ethylenic double bonds.
Systematic investigations on the addition reaction of
amino alcohol~ with acrylates have been carried out by
N. Ogata and T. A~ahara, Bull. Chem. Soc. Jap. 39,
pages 1486-1490, 1966.
German Patent Specification 2,346,424 describes
the preparation of radiation-curable compositions,
starting from acrylic esters of polyhydric alcohols and
secondary, aliphatic monofunctional amines. These com-
positions have the disadvantage of reduced shelf life.
Moreover, the addition reaction of a secondary ~mine
leads to a reduction in acrylic ester functionality of
the molecule and thus also to a reduction in
crosslinking possibilities for the radiation-induced
polymerization.
" ' ' ~,-., ':
2 1 3 2 8 ~ ~ ~
- 3 -
Addition products of esters of acrylic or
methacrylic acid and polyhydric alcohol~ with pr;~ry
monoamines, in which the molar ratio of monoamine to
(meth)acrylic double -bond of the e ter i8 0.05:1 to
0.4:1, are disclosed in EP-A-280,222.
The addition products according to EP-A-280,222 are
used in radiation-curable compositions which harden in
air. However, the shelf life of the products disclosed
in EP-A-280,222 i~ insufficient. Thus, upon storage ~f
., - ., ~
the addition products, a significant increase in
vi~cosity is observed. Furthermore, addition products
of tetrahydric polyols with primary monoamines give
ri~e to compatibility problems. Product~ of this type
have a cloudy or milky-white appearance. A further ;
disadvantage of the amine-modified compositions des-
cribed in the European application is that a relatively
large amount of monoamine is necessary for ensuring
that the nitrogen contents in the addition products
obtained are sufficiently high for, for example,
systems initiated by benzophenone. Sufficiently high
nitrogen contents are necessary to ensure that in
practice the photopolymerization is sufficient and goes
to completion at the customary radiation dosage. ;~
EP-A-2,457 describes plastics for molded
articles, the plastics curing under elevated
temperatures. The plastics are Michael addition
product~ of acrylic e~ter monomers with amine~ having
an amine hydrogen functionality of at least 3. The
components are reacted at an eguivalent acrylate/ amine ~ ~
', ~'.:
21328~
. . .
hydrogen ratio of 0.5 to 2Ø
Radiation-~iurable solvent-free composition~
based on polyacrylates and mono-, di- or polyamine~ are
disclosed in US Patent Specifications Nos. 4,547,562
and 4,675,374. Species having more than one primary
amino group are mentioned as suitable di- and poly-
amines. The use of these polyamines gives highly
crosslinked surface coating compositions of higher
molecular weight and thus higher viscosity which,
without addition of reac ive thinners and solvents,
have an application vicGosity which is too high or even
lead to solid products.
Finally, US Patent Specification 4,045,416 and
US Patent Specification 3,845,056 relate to radiation-
curable surface coating compositions based onaminoacrylates which are obtained by reaction of
polyacrylates with amines having at least one amine
hydrogen. Primary and ~econdary monoamines and poly-
amines are mentioned a~ suitable amines. The polyamine
components mentioned in the US Patents are polyamine~
having more than one primary amino group, polyamines
having exclusively secondary amino groups or polyamines
having secondary and tertiary amino group~. When
polyamines having more than one primary ~m; no group are ;~
used, tha addition products obtained are inhomogeneous
and have a short shelf life, while the use of
polyamines having exclusively secondary amino groups,
such as, for example, piperazine, leads to
inhomogeneous mixture~ due to insufficient reactivities --~ ~ ~
.,., ~,~ ..~.
, '. .
21328.~
5 -
or incompatibilities. The use of polyamines having
secondary and tertiary amino groups only results in a
reduction of the acrylic or methacrylic ester
functionality of the molecule.
Accordingly, the object of the present
invention was to eliminate the disadvantage~ described
above, i.e. to provide radiation-curable binders which
have a sufficiently long shelf life and a clear
appearance, i.e. are homogeneous, even when
tetrafunctional ~meth)acrylic esters are used as
precursors. The binders should be radiation-curable
without using external synergists, for example amines.
The binders according to the invention should be low-
viscosity oligomers having comparatively good
radiation-curability and comparatively good resulting
film properties, in particular hardness. The binters
should have a low viscosity, 80 that the use of
reactive thinners and organic solvents can be omitted.
The object of the present invention is achieved
by addition products of
A) oligomers having at least two acrylic ester and/or
methacrylic ester groups per molecule and
B) polyamines,
wherein polyamines B) are diamines having a primary and
a tertiary amino group and the ratio of primary amino
groups of B) to (meth)acrylic double bonds of A) is
0.01:1 to 0.2:1, preferably 0.03:1 to 0.1:1.
Examples of suitable acrylic and methacrylic
esters (A) are esters of acrylic acid or methacrylic
~1~28~
-- 6 --
acid with dihydric aliphatic alcohols, such as ethylene
glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol,
1,2-pentanediol, neopentylglycol, 1,6-hexanediol,
2-methyl-1,5-pentanediol, 2~ethyl-1,4-butanediol, di-
methylolcyclohexane and diethylene glycol, with tri-
hydric alcohols, such as glycerol, trimethylolethane,
trimethylolpropane and trimethylolbutane, with tetra-
hydric alcohols, such as pentaerythritol, and with
alcohols containing more than 4 hydroxyl group~, ~uch
as di(trimethylolpropane), di(pentaerythritol) and
sorbitol .
Also suitable are cycloaliphatic alcohols, such
as cyclohexanols and 1,4-bis~hydroxymethyl)cyclohexane,
araliphatic alcohols, such as 1,3-xylylenediol, and
phenols, such as 2,2-bis(4-hydroxyphenyl)propane
(bisphenol A).
Esters of acrylic acid and/or methacrylic acid
with tri- or tetrahydric alcohols are preferably used
as component A).
Before being esterified with acrylic acid or
methacrylic acid, the polyhydric alcohols listed above
can have been converted into ether alcohols of higher
molecular weight by alkoxylation with, for example,
ethylene oxide or propylene oxide. This reaults in
polyether acrylates or polyether methacrylate~. Poly-
ether (meth)acrylates of this type are particularly
preferably used in the addition products according to
the invention as component (A).
The hydroxyl-containing polyethers which are
- 21328.~ -
- 7 -
e~terified with acrylic acid and/or methacrylic acid
are obtained by reaction of &i- and/or polyhydric
alcohols with different amounts of ethylene oxide
and/or propylene oxide by well-known methods (see, for
example, Houben-Weyl, Volume XIV, 2, Makromolekulare
Stoffe II tMacromolecular Substances II], (1963).
Polymerization products of tetrahydrofuran or butylene
oxide can al~o be u~ed.
Suitable components A) are also polyester
acrylates and/or polye~ter methacrylates. The polyester
(meth)acrylates are prepared by using hydroxyl-
containing poiyester~ (polye~ter polyols) as the poly-
hydric alcohols. These can be prepared by
esterification of dicarboxylic acids with diols and
triols by well-known methods (see, for example,
P.J. Flory, J. Am. Chem. Soc. 58, 1877 (1936) and J.
Am. Chem. Soc. 63, 3083 (1953).
In some ca~es, it is particularly advantageous
to react an epoxy resin with acrylic acid or
methacrylic acid in a stoichiometric amount, relative
to the epoxy functionality. Polyglycidyl ethers of
bisphenol A are particularly suitable in this respect.
Before the reaction, they may also contain a few
hydroxyl groups. The reaction with acrylic acid or
methacrylic acid leads to furth~r hydroxyl groups. Such
polyhydric acrylic esters or methacrylic esters are
designated as epoxyacrylates or -methacrylates. The
addition of hydroxyl-containing acrylic esters or
methacrylic esters, ~uch as hydroxyethyl acrylate or
- 21 3~855
- 8 -
hydroxybutyl acrylate, to isocyanato-containing mono-
or oligomerY gives the polyurethane acrylate~ or
methAcrylate~ which, like the epoxy(meth)acrylates, can
be u~ed a~ e~ter component A).
The preparation of polyether acrylate~ and
polyester acrylate~ i~ described, for example, in
DE-A-3,836,370.
Suitable diamines having a primary and a
tertiary amino group (component B)) are N,N-dialkyl-
diaminoalkanes, ~uch as, for example, N,N-dimethyl-
1,3-diaminopropane, which i8 obtainable by catalytic
.
hydrogenation of timethylaminopropionitrile. ~he pre~
~ ....
paration of thi3 polyamine is described, for example,
in ~ouben Weyl, Vol. 11/1, 1957, p. 565, in
EP-A-316,761 or in P. Lappe, H. Springer and J. Weber,
Chem.-Ztg. 111 (4), pp. 117-125 (1987).
Further suitable dialkylaminopropanes are N,N-diethyl-
. : .., -: :: ~
1,3-diaminopropane, N,N-di-n-propyl-1,3-diaminopropane,
- ~ :: : .
4-morpholinopropylam;ne, 3-(N-piperidino)propylamine,
N,N-diphenyl-1,3-diaminopropane.
. .
Other 3uitable components ~) of the addition
products according to the invention are: N,N-dialkyl-
~ ,, .,, ;
1,2-diaminoethanes, such a~ dimethylaminoethylamine, ~;
. . .
diethylaminoethylAm;ne, N-~-aminoethylmorpholine (for ~ -
preparation, see, for example, Houben Weyl, Vol. 11/1,
1957, p. 563), N,N-dialkyl-1,5-diam;nopentanes, which
. :. :
can be prepared by 1,4-addition of secondary amines to
1-cyano-1,3-butadiene to give nitrile~, followed by
catalytic hydrogenation (for preparation, see ~ouben
~ A ~ . . i, i .
.~ 213~8~5
- 9 -
Weyl, Vol. 11/1, 1957, p. 276). Examples of suitable
N,N-dialky1-1,5-diaminopentane~ are dimethylamino-
pentylamine, diethylaminopentylamine, 4-morpholino-
pentylamine.
Particularly good results are obtained by using
N,N-dimethyl-1,3-diaminopropane as d ne component B).
The ratio of A) to B) i9 selected in such a
manner that the ratio of primary amino groups of B) to
the acrylic or methacrylic double bonds of A) is 0.01:1
",~-
to 0.2:1. This ratio is preferably 0.03:1 to 0.1~
The addition products according to the inven-
tion are liquid at room temperature. They are prepared
by adding diamines B) in a Michael reaction to an
acrylic ester or methacrylic ester A) or to a mixture
of these esters. The amine-modified oligomers obtained
still contain unreacted acrylic ester and/or
methacrylic ester groups and tertiary amino groups.
The addition reaction i~ exothermic and is
carried out in liquid phase at a moderate temperature
in the ab~ence of a catalyst. The appropriate amount of
diamine (B) i8 added to ester (A) at room temperature
with stirring. The temperature rise~ to ~bout 40C.
When the reaction is complete, the evolution of heat
stops, and the temperature drops. The reaction can be
accelerated by increasing the temperature 80 that at
60C it will have subsided after about 12 hours. The
visco~ity of the mixture obtained is then constant with
time.
For reasons of reproducibility, the reaction
. 2~ 3~8.~
. . .-
- 10 -
should go as far to completion as possible, which is
~chieved at reaction temperature~ above 50C.
In general, the reaction is carried out without
solvents, but it is al o possible to u~e solvents,
especially in order to meter in solid amine~ ~) as a
solution. After Michael addition ha~ taken place, the
solvent is removed.
~ o ensure that no undesirable polymerization
takes place during the addition reaction,
10 polymerization inhibitors are usually added to the ¦
reaction mixture. Suitable polymerization inhibitors
include known product~, such as substituted phenQls,
such as 2,6-di-tert.-butyl-p-cresol, hydroquinones,
such as methylhydroquinones, and thio ethers, such as
15 thiodiglycol or phenothiazine. ;
Accordingly, the present invention also relates
- :
to a proces~ for the preparation of the addition
products according to the invention, which compri~es ~;-
reacting e3ter component A) and diamine component B)
with one another, if appropriate in an organic solvent,
with the uqe of polymerization inhibitors. ;
The amine-modified addition products according
to the invention obtained from components A) and B) are
used a~ film-forming components in radiation-curable
~urface coating composition~. Depending on the vis-
cosity of the e~ters, these radiation-curable surface
coating compositions can contain, apart from the amino-
modified oligomers according to the invention, further
copolymerizable compounds known for being used in
~S '~L : i ' ~. ,~ .': i .; ~ : ~ s .~ ,,,,,; ,
21328~
`~`
radiation-curable surface coating compositions, for
example (meth)acrylic ester~, in particular methyl
(meth)acrylate, ethyl (meth)acrylate, propyl (meth)-
acrylate, butyl (meth)acrylate, ii~opropyl (meth)-
acrylate, isobutyl (meth)acrylate, pentyl (meth~acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate,
cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
octyl (meth)acrylate, 3,5,S-trimethylhexyl (meth)-
acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate,
hexadecyl (meth)acrylate, octadecyl (meth)acrylate,
octadecenyl (meth)acrylate and the corresponding esters
of malein, fumaric, tetrahydrophthalic, crotonic, i~o~
crotonic, vinylac0tic and itaconic acids. Preference i~
given to the use of monomer3 having more than 1 double
lS bond per molecule, for example ethylene glycol diacry-
late, diethylene glycol diacrylate, propylene glycol
diacrylate, trimethylene glycol diacrylate, neopentyl
glycol diacrylate, 1,3-butylene glycol diacrylate,
1,4-~utylene glycol diacrylate, 1,6-hexamethylene
glycol diacrylate, l,10-decamethylene glycol diacry-
late, trimethylolpropane triacrylate, pentaerythritol
tetraacrylate and pentaerythritol triacrylate and the
corresponding methacrylates. Very particular preference
is given to the use of trimethylolpropane triacrylate
and acrylic esters of propoxylated trimethylolpropane.
~ owever, addition of these monomeric, copoly-
merizable compound~ ~often also called reactive
thinner~ in general not neces~ary, ~ince the amine-
modified esters according to the invention have low
~ 1328~,5
- 12 -
Vi8CoBity -
Depending on the viscosity of the addition
products according to the invention, the radiation~
curable surface coating compositions can contain water,
although addition of water is in general not necegsary
due to the low viYcogity of the film-forming
components. The advantage of the addition products
described must in particular al~o be attributed to the
fact that they are dispersible in water, i.e. the use
of organic solvent can be entirely omitted.
The addition products obtained from A) and B) contained
in the radiation-curable surface coatins compositionY
are water-Yoluble or water-dispersible by virtue of the
tertiary amino group~ contained therein. These groups
can be converted to the charged group~ by reacting at
least Yome of them with acids. Examples of acids which
are suitable for neutralizing the basic groups are
lactic acid, acetic acid, formic acid and phosphoric
acid.
The radiation-curable surface coating compo-
sitionY additionally contain photoinitiators commonly
used in radiation-curable surface coating compositions,
for example benzophenones, benzoins or benzoin ethers.
The u8e of synergists can be omitted, ~ince the esters
contained in the surface coating compositions are
ne-modified and thus exhibit a synergistic action.
The radiation-curable compositions according to
the invention can contain, apart from the m;ne-
modified reaction products obtained from esterY A) and
r ~
~` 21328~
- 13 -
diamines B), further photopolymerizable binders, which
may also be amine-modified. Examples which are suitable
as such further ~mine-modified binders are the
radiation-curable binder~ di~closed in EP-A-280,222 and
in US Patent Specifications Nos. 4,045,416, 4,547,562
and 4,675,374. Suitable non-amine-modifiet further
binder~ are the polyether acrylate~, polyether
methacrylates, polyester acrylates, polyester
methacrylates, urethane acrylate3, urethane
methacrylates, epoxy acrylates and epoxy methacrylates
described above as example for component A).
If desired, the radiation-curable surface
coating compositions according to the invention contain
customary auxiliaries and additives, for example
extenders, such as talc, heavy spar, aluminum
silicates, dolomite, antifoams, flow-improving agents
and film-forming aids, for example cellulose
derivatives, and flatting agents in the usual amounts.
The ~urface coaSing compo~itions can be applied
to the sub~trate, preferably to wood, woodbase
material~ or paper, by spray-coating, roller-coating,
flow-coating, dip-coating, knife-coating, brush-
coating, pouring or by Vakumat application.
Curing of the coating film~ takes place
immediately after application or after evaporation of
any water present by means of W or electron beams. The
equipment and conditions for these curing methods are
known from the literature (~ee, for example, R. ~olmes,
U.V. and ~.~. Curing Formulation~ for Printing Ink~,
7~
213~855
- 14 -
Coatings and Paints, SITA-Technology, Academic Press,
London, United Ringtom 1984, pages 79-111) and need no
further description.
The surface coating compositions according to
the invention are also suitable as printing inks.
The radiation-curable surface coating compo-
sitions according to the invention or the amine-
modified esters obtained from components A) and B) have
an excellent shelf life. The amine-modified ester3 are
homogeneous, have a clear appearance, good radiation
curability, and the film~ obtained therefrom after
radiation curing posse~s excellent properties. While
having a comparable nitrogen content and comparable
reactivity towards radiation, the amine-modified esters
according to the invention have lower viscosity than
the amine-modified esters according to ~P-A-280,222.
The films obtained are distinguished by excellent
tranaparency.
Below, the invention is illustrated in more
detail by way of exemplary embodiments. Parts are by
weight, unless stated otherwise:
~xa~pl--
To prepare ester component A), polyether
acrylates are prepared from acrylic acid and tri-
methylolpropane alkoxylated with propylene oxide andfrom pentaerythritol alkoxylated with ethylene oxide in
the presence of acrylic acid (polyether acrylats pre-
cursor). Preparation takes place in a reactor of batch
size 3 to 10 kg which is equipped with stirrer, air
'` - ~ ' i;': i' 'i '
~ 32855 '`
- 15 -
feed, temperature sensor and oil jacket heating.
~sterification takes place at 130C with acid catalysis
(0.5% of methanesulfonic acid, relative to the starting
materials) using 2% of cyclohexane as entrainer and
hydroquinone and hypophosphorous acid as stabilizers
(0.2% by weight of hydroquinone and 0.05% by weight of
hypophosphorous acid, relative to the starting
materials) until an 0~ group conversion of at least 85%
is reached. Residual acrylic acid and residual
entrainer are then removed in vacuo until the acid
number has reached a value of s 4 mg of ROH/g and the
solids content (1 h, 130C) is at least 98%.
Adduct formation with amine component B) is carried out
at 60C in a nitrogen ~tmosphere using 0.1% of 2,6-di-
lS tert.-butyl-p-cresol as stabilizer (polymerization
inhibitor) until a viscosity is reached which remains
constant over a period of 2 hours.
In this reaction, amine component ~) is metered into
the initially introduced ester component A) over a
period of 0.5 to 1.0 h. If piperazine is used, it is
added as a powder which ~lowly dissolves. (Comparative
Examples C1-2 and C2-3).
The table below lists th~ composition and
properties of addition products according to the inven-
tion obtained from A) and B) (~1 to E3) and those ofknown addition products obtained from A) and primary
and secondary monoamines and disecondary diamine~ as
comparison (Cl-C3).
328 '
~5
- 16 ~
: -:
~, ", o ,~ ~ .~
L~ o o~
~Q ~o ~o
u~
~0 1~ 0 0 N ~ ` E`:
~ O O ~ I~ ~ ''' ~ -~, `"' ,''' '.',
~) 0 0 4
: -: :: ~
O æ 0 4 -.`~
N CU
g ~ 8
O _ ~ N ~
. :, .
~ g æ O ~
1~1 _ ~t N ~t
_ ~,: `- '''':: :.`,':
N O 0 0 N
~1 _ ~ -I , ' " ' `, ` ~ ~
o 5.0 0 N ~ ;
1~1 g
. ` ~
~1 O ~ o ~ E ,~ o
E E ~ _
~ E o ~ Z ~ c ~ ~
o o CL o ~ o W W ~9 ~ ~ . `,`; ,
_ e _ 5 X L _ _ _ ~ ,~
~ O ~ o e o e ~ ~ e ~ ::
U ~ ~ L e ~,~ ~ ~ E 1~9
E ~ It E ~ E~ ,~ ~ ~, O 5
X ~ ~ L ~ L 11~ ~ SU IJ -- -- O -- `:
-- O ~ ~ 111 ~ ~
'' ~.' ".'"'''
~: '. : ".
-- 17 --
C~
U~
_l 0 . '~
N _
~7 ~
_ '''~'` . ' :
I~
O
~ ' ", .
--
N
al
U~ _
C~ t O
~ O
_ I~
~'J ~ ~
~ ~ C
O _. E
o o
. ~
.~ .
~
,~
~ ; ' ~' '.
s
~ ,. . .
~e U '; ` ''
~ E 4_ :.
~ O
_E O
~ ~ ~ 3
E ~ E .~1 q~
' ,.^.. , ~1328~5 : ~;
-- 1 8
, . ::~' . .
~o ~ C ~ ~ . . . .. : -~
~ ,~ 3 ~ o O
_~ O `D U _I C ~ O :
~ r~ O Y
~ ~3 ~ ~ :
_
3 ~ ~ ~ .: . .
O
-~ ~ ? ~ 0' ~o O
C o~ C ~ t ~
l ~ 5 o ql ~ 8 ~ ~:
U ~i ~ U ~ _i o ~ U .
o ~ P o ~ P ~ o : ~: :,: .: ~ .
c ~
:
* U o C ~ `
C~l ~ C ~
~ C~ ~ ~ ,., ~1, ," ,_, o ~ '
* IJ 3 ~ o
U~ UO~ ~o.
C~ o '~ :~
-
r~
c~ o o _~ c ~ o~8 o
~ J, ~ C ,~ ~, o a :
U ~ o~Ul O
o ~ ~ ~1 o ~ ~ -
P~ c ~ P~ -u~ ~ ~:
o .~ c c 0 0 "~ ~
o . .
~1 ~
.: : :
~J O 0 C O d~ ~ '
~ ~ ~ ~ . 3
o
~ U y O P ~ ....
" ~, ~o ~ ~
" ~ ,11~ O U ~ ' -
^ ~ ~ B ~: -
C o~ oo ,. ~ o~ o C o ~ o ~4., , .~. .. .
U ~ ~ _, ~ o, _, ~ ~ ,t C U o ~ . . -. ;..... .
~ ~ 3 ~ 3 ~ ~ o ~
-- ~U U C . ~ u ~ ~ ~ .J C U ;~ . .: ': .
~ ... .. ~ , C ~ o ~ o ~ .- .,
4 U~ `3 P C ~ ~0 ~ ~ P 1~
~1 U O U~ o ~S~ o ~ ~ ~ " ~ .-
P ql u tO u o ~ o ~I C ~ o ~ o C o
1!1 ~ Z'~ P O 1~~ .C P ~ ~
0 Z
: ;'
-.:
21328~,5
...... ..
-- 19 --
T-~tlng of th- addttion product~
1. Pendulum damping (X8nig, [8]) of the examples and
comparative examples a~ a function of relative
radiation dosage
A 40 ~m thick (wet film thickness) coating on
gla88 i8 prepared from 91.6 parts of the addition
products or precursors, 3.4 parts of a conventional
flatting agent and S parts of benzophenone by drawing
down. The glass plates are cured under a mercury
medium-pressure lamp (80 watt/cm, distance: 20 cm) at
variable ~peed~ of 10-40 m/min (relative doses ~ 1.0 -
a feed of 10 m/min; relative do~e~ ~ 1.0 ~ a feed of
4 x 40 m/min; relative doses ~ 4 - 4 x 10 m/min and
relative doses ~ 0.25 ^ 1 x 40 m/min). The pendulum
hardnesses of the tack-free films are determined by the
method of R8nig.
' " "
:.
. .... ...
2 1 3 2 8 5 ~
, . . . ~ ~
- 20
:,",~
1.1 ~111 1 1 1 1 rl I I I ;, ~
_ __ _ _ _ _ ~I a _
~ e~ ~ ~ I ,1 ~ o ~ I o .
_ _ ~ ~ ~ _ _ _ , _ _ _ , ' ~'"''''': ~'"'' :. '
~ ~ o r ~o el e~
_ t~ ~ ~ r _ C ~ r _ _ r ; ~ :
_ _ _ _ _ _ _ _ _ _ '~
_l ~ ~ ~o ~o u~ e~ :
_ 7c _ _ e e _ _ u ~r
_ c _ u~ _ _ _ _ _ _ _ _ _ , '~
I
~1~ ~ ~
_ __ r r r _ ~ ~1 e
r_ ~ _ _ _ _ _ _ _
c a ~ c c _ c _ ~ .
l 1, 1 ~1 ~ ~
X ~ P~ ~ ~
r~ 32855
- 21 -
2. Shelf life
The shelf life of the addition products at 50C
i8 determined.
Oven ~pecimen~ ~50C): change in viscosity with
5 time (orig.) DIN 4 t8] :
, ' ~
5 day-10 day- 30 day-120 day~ Note
. _
~1 73 74 73 75
l _470 470 4~5 570 .:~
~3 123 123 125
.~.'- ,.. .. '~.
C3-1 136 lSo 170 20 day-s 2 pha~e-
C3-2 49 52 54 ;
'~
' .., ' ~:
