U.S. patent application number 15/789548 was filed with the patent office on 2018-04-19 for photo-latent titanium oxo-chelate catalysts.
The applicant listed for this patent is BASF SE. Invention is credited to Didier Bauer, Antoine Carroy, Marc Faller, Tobias Hintermann, Caroline Lordelot, Rachel Kohli Steck.
Application Number | 20180105719 15/789548 |
Document ID | / |
Family ID | 44681463 |
Filed Date | 2018-04-19 |
United States Patent
Application |
20180105719 |
Kind Code |
A1 |
Hintermann; Tobias ; et
al. |
April 19, 2018 |
PHOTO-LATENT TITANIUM OXO-CHELATE CATALYSTS
Abstract
A titanium-oxo-chelate catalyst formulation, comprising: (i) at
least one compound of the formula (I), wherein R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9,
R.sub.10, R.sub.11 and R.sub.12 independently of each other are for
example hydrogen, halogen, C.sub.1-C.sub.20alkyl,
C.sub.6-C.sub.14aryl which is unsubstituted or substituted; or
R.sub.1, R.sub.2 and R.sub.3 and/or R.sub.4, R.sub.5 and R.sub.6
and/or R.sub.7, R.sub.8 and R.sub.9 and/or R.sub.10, R.sub.11 and
R.sub.12 together with the C-atom to which they are attached each
form a C.sub.6-C.sub.14aryl group which is unsubstituted or
substituted; or R.sub.1 and R.sub.2 and/or R.sub.4 and R.sub.5
and/or R.sub.7 and R.sub.8 and/or R.sub.10 and R.sub.11 together
with the C-atom to which they are attached form a 5- to 7-membered
carbocyclic ring; at least one chelate ligand compound of the
formula (IIa), (IIb) or (IIc), wherein R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5 and R.sub.6 are defined as above for formula (I),
is suitable as a photolatent catalyst formulation for polymerizing
compounds, which are capable to crosslink in the presence of a
Lewis acid. ##STR00001##
Inventors: |
Hintermann; Tobias;
(Therwil, CH) ; Carroy; Antoine; (Limburgerhof,
DE) ; Lordelot; Caroline; (Mannheim, DE) ;
Bauer; Didier; (Kembs, FR) ; Steck; Rachel Kohli;
(Basel, CH) ; Faller; Marc; (Hegenheim,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Family ID: |
44681463 |
Appl. No.: |
15/789548 |
Filed: |
October 20, 2017 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14007688 |
Sep 26, 2013 |
9809727 |
|
|
PCT/EP2012/055920 |
Apr 2, 2012 |
|
|
|
15789548 |
|
|
|
|
61471704 |
Apr 5, 2011 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 31/2234 20130101;
C08G 18/6229 20130101; C08G 18/68 20130101; B01J 2231/48 20130101;
C08G 18/222 20130101; B01J 31/0208 20130101; C09J 175/04 20130101;
C08G 18/792 20130101; B01J 2231/14 20130101; Y02P 20/52 20151101;
B01J 2531/46 20130101; C09D 175/16 20130101 |
International
Class: |
C09D 175/16 20060101
C09D175/16; B01J 31/22 20060101 B01J031/22; C08G 18/22 20060101
C08G018/22; C08G 18/62 20060101 C08G018/62; C09J 175/04 20060101
C09J175/04; C08G 18/68 20060101 C08G018/68; B01J 31/02 20060101
B01J031/02; C08G 18/79 20060101 C08G018/79 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 5, 2011 |
EP |
11161087.9 |
Claims
1-16. (canceled)
17. A titanium-oxo-chelate catalyst compound of the formula (IA) or
(IB) ##STR00043## wherein R.sub.20, R'.sub.20, R''.sub.20,
R.sub.21, R'.sub.21 and R''.sub.21 independently of each other are
hydrogen, halogen, C.sub.1-C.sub.20alkyl, which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.13, or are
C.sub.6-C.sub.14aryl which is unsubstituted or is substituted by
one or more C.sub.1-C.sub.8alkyl, halogen, OR.sub.13 or
NR.sub.13R.sub.14; provided that only one of R.sub.20, R'.sub.20
and R''.sub.20 in the group ##STR00044## and only one of R.sub.21,
R'.sub.21 and R''.sub.21 in the group ##STR00045## can be hydrogen;
or R.sub.20 and R'.sub.20 and/or R.sub.21 and R'.sub.21 together
with the C-atom to which they are attached form a 5- to 7-membered
carbocyclic ring, R.sub.22, R.sub.23, R.sub.24 independently of
each other are hydrogen, halogen, C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkoxy, C.sub.6-C.sub.14aryl,
C.sub.1-C.sub.8alkanoyl, C.sub.1-C.sub.8alkanoyloxy,
C.sub.7-C.sub.15aroyl, C.sub.7-C.sub.15aroyloxy, nitrile, nitro,
C.sub.1-C.sub.8alkylthio, C.sub.6-C.sub.14arylthio or
NR.sub.37R.sub.38; R.sub.25, R.sub.26, R.sub.27, R.sub.28,
R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35 and R.sub.36 independently of each other are hydrogen,
C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.14, or are C.sub.6-C.sub.14aryl which
is unsubstituted or is substituted by one or more
C.sub.1-C.sub.8alkyl, OR.sub.13 or NR.sub.13R.sub.14; or two
radicals R.sub.25 and R.sub.26 and/or two radicals R.sub.28 and
R.sub.29 and/or two radicals R.sub.31 and R.sub.32 and/or two
radicals R.sub.34 and R.sub.35 together with the C-atom to which
they are attached form a 5- to 7-membered carbocyclic ring;
provided that only one of R.sub.25, R.sub.26, R.sub.27 in the group
##STR00046## and only one of R.sub.28, R.sub.29, R.sub.30 in the
group ##STR00047## and only one of R.sub.31, R.sub.32, R.sub.33 in
the group ##STR00048## and only one of R.sub.34, R.sub.35, R.sub.36
in the group ##STR00049## can be hydrogen; and provided that
R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30,
R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35 and R.sub.36 are
not simultaneously methyl; R.sub.13 and R.sub.14 independently of
each other are C.sub.1-C.sub.8alkyl; R.sub.37 and R.sub.38
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl or
C.sub.6-C.sub.14aryl, or R.sub.37 and R.sub.38 together with the
N-atom to which they are attached form a 5- or 6-form a 5- or
6-membered saturated or unsaturated ring, which ring optionally in
addition to the N-atom comprises a further N-atom or O-atom.
18. The titanium-oxo-chelate catalyst compound of claim 17, wherein
two radicals R.sub.25 and R.sub.26 and/or two radicals R.sub.28 and
R.sub.29 and/or two radicals R.sub.31 and R.sub.32 and/or two
radicals R.sub.34 and R.sub.35 together with the C-atom to which
they are attached form a 5- to 7-membered carbocyclic ring.
19. The titanium-oxo-chelate catalyst compound of claim 18, wherein
the 5- to 7-membered carbocyclic ring(s) is/are selected from
##STR00050## wherein R.sub.x2 is R.sub.27, R.sub.36, R.sub.30
and/or R.sub.33, R.sub.y2 is C.sub.1-C.sub.20alkyl, n is an integer
1-5 and m is an integer 1-4.
20. The titanium-oxo-chelate catalyst compound of claim 17, wherein
in formula (IA) R.sub.20, R'.sub.20, R''.sub.20 independently of
each other are hydrogen, halogen or C.sub.1-C.sub.20 alkyl, which
is unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.13; R.sub.21, R'.sub.21, R''.sub.21 independently of each
other are hydrogen, halogen or C.sub.1-C.sub.20 alkyl, which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.13; R.sub.22, R.sub.23, R.sub.24 independently of each
other are hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy,
C.sub.1-C.sub.8 alkanoyl, C.sub.1-C.sub.8 alkanoyloxy, chloro,
nitrile, nitro, C.sub.1-C.sub.8 alkylthio, C.sub.6-C.sub.14
arylthio or NR.sub.37R.sub.38; and in formula (IB) R.sub.25,
R.sub.26, R.sub.27 independently of each other are hydrogen,
C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.25 and
R.sub.26 together with the C-atom to which they are attached form a
cyclopentyl or cyclohexyl ring; R.sub.31, R.sub.32, R.sub.33
independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl
which is unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14, or two radicals R.sub.31 and R.sub.32 together with
the C-atom to which they are attached form a cyclopentyl or
cyclohexyl ring; R.sub.28, R.sub.29, R.sub.30 independently of each
other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14, or two
radicals R.sub.28 and R.sub.29 together with the C-atom to which
they are attached form a cyclopentyl or cyclohexyl ring; R.sub.34,
R.sub.35, R.sub.36 independently of each other are hydrogen,
C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.34 and
R.sub.35 together with the C-atom to which they are attached form a
cyclopentyl or cyclohexyl ring.
21. The titanium-oxo-chelate catalyst compound of claim 20, wherein
in formula (IA) R.sub.20, R'.sub.20, R''.sub.20 independently of
each other are hydrogen, halogen or C.sub.1-C.sub.8 alkyl;
R.sub.21, R'.sub.21, R''.sub.21 independently of each other are
hydrogen, halogen or C.sub.1-C.sub.8 alkyl; R.sub.22, R.sub.23,
R.sub.24 independently of each other are hydrogen, C.sub.1-C.sub.8
alkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkanoyl,
C.sub.1-C.sub.8 alkanoyloxy or NR.sub.37R.sub.38; and in formula
(IB) R.sub.25, R.sub.26, R.sub.27 independently of each other are
hydrogen, C.sub.1-C.sub.8 alkyl, or two radicals R.sub.25 and
R.sub.26 together with the C-atom to which they are attached form a
cyclopentyl or cyclohexyl ring; R.sub.31, R.sub.32, R.sub.33
independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, or
two radicals R.sub.31 and R.sub.32 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring;
R.sub.28, R.sub.29, R.sub.30 independently of each other are
hydrogen, C.sub.1-C.sub.8 alkyl, or two radicals R.sub.28 and
R.sub.29 together with the C-atom to which they are attached form a
cyclopentyl or cyclohexyl ring; R.sub.34, R.sub.35, R.sub.36
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or
two radicals R.sub.34 and R.sub.35 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring;
22. The titanium-oxo-chelate catalyst compound of claim 21, wherein
in formula (IA) R.sub.20, R'.sub.20, R''.sub.20 independently of
each other are hydrogen, fluoro or C.sub.1-C.sub.8 alkyl; R.sub.21,
R'.sub.21, R''.sub.21 independently of each other are hydrogen,
fluoro or C.sub.1-C.sub.8 alkyl, R.sub.22, R.sub.23, R.sub.24
independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 alkoxy, or NR.sub.37R.sub.38; and in formula (IB)
R.sub.25, R.sub.26, R.sub.27 independently of each other are
hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14; R.sub.31,
R.sub.32, R.sub.33 independently of each other are hydrogen,
C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.14; R.sub.28, R.sub.29, R.sub.30
independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl
which is unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14; R.sub.34, R.sub.35, R.sub.36 independently of each
other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14.
23. The titanium-oxo-chelate catalyst compound of claim 22, wherein
in formula (IA) R.sub.20, R'.sub.20, R''.sub.20 are hydrogen,
fluoro or methyl. R.sub.21, R'.sub.21, R''.sub.21 are hydrogen,
fluoro or methyl. R.sub.22, R.sub.23, R.sub.24 independently of
each other are hydrogen, methyl, methoxy or dimethylamino and in
formula (IB) R.sub.25, R.sub.26, R.sub.27 independently of each
other are hydrogen or C.sub.1-C.sub.8 alkyl; R.sub.31, R.sub.32,
R.sub.33 independently of each other are hydrogen or
C.sub.1-C.sub.8 alkyl; R.sub.28, R.sub.29, R.sub.30 independently
of each other are hydrogen or C.sub.1-C.sub.8 alkyl; R.sub.34,
R.sub.35, R.sub.36 independently of each other are hydrogen or
C.sub.1-C.sub.8 alkyl.
24. The titanium-oxo-chelate catalyst compound of claim 23, wherein
in formula (IA) the groups R.sub.20, R'.sub.20R''.sub.20C-- and
R.sub.21R'.sub.21R''.sub.21C-- are identical; and in formula (IB)
the groups R.sub.25R.sub.26R.sub.27C-- and
R.sub.31R.sub.32R.sub.33C-- are identical and/or the groups
R.sub.28R.sub.29R.sub.30C-- and R.sub.34R.sub.35R.sub.36C-- are
identical.
25. A polymerizable composition comprising: (a) at least one
component which is capable of a polyaddition or polycondensation
reaction in the presence of a Lewis-acid type reactant; and (b) a
Titanium-oxo-chelate catalyst compound of claim 17.
26. A polymerizable composition of claim 25 comprising as component
(a) (a1) at least one blocked or unblocked isocyanate or
isothiocyanate component, and (a2) at least one polyol.
27. A polymerizable composition of claim 25, which comprises 0.001
to 15% by weight, preferably 0.01 to 5% by weight, of the
titanium-oxo-chelate catalyst compound, based on the total
composition.
28. A coated substrate coated on at least one surface with the
composition of claim 25.
29. A polymerized or crosslinked composition of claim 25.
30. A process for polymerizing compounds, which are capable to
crosslink in the presence of a Lewis acid, characterized in that a
titanium-oxo-chelate catalyst compound as defined in claim 17 is
added to the compounds which are capable to crosslink in the
presence of a Lewis acid and the resulting mixture is irradiated
with electromagnetic radiation of a wavelength range of 200-800
nm.
31. A process of claim 30, characterized in that instead of
irradiating with electromagnetic radiation the mixture is subjected
to a heat treatment, or the mixture is irradiated with
electromagnetic radiation and simultaneously with or after the
irradiation subjected to a heat treatment.
32. A process of claim 30 for the preparation of adhesives,
sealings, coatings, potting components, printing inks, printing
plates, foams, moulding compounds, or photostructured layers.
33. The titanium-oxo-chelate catalyst compound of claim 17 being a
compound of the formula IB' ##STR00051## wherein R'.sub.25,
R'.sub.26, R'.sub.27 and R'.sub.28 independently of each other are
hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14, or are
C.sub.6-C.sub.14aryl which is unsubstituted or is substituted by
one or more C.sub.1-C.sub.8alkyl, OR.sub.13 or NR.sub.13R.sub.14;
or two radicals R'.sub.25 and R'.sub.26 together with the C-atom to
which they are attached and/or or two radicals R'.sub.27 and
R'.sub.28 together with the C-atom to which they are attached form
a 5- to 7-membered carbocyclic ring.
Description
[0001] The present invention pertains to compositions comprising
photolatent titanium oxo-chelate catalyst compounds and their
application as catalysts in particular for crosslinking 2 pot
polyurethane and novel photolatent titanium oxo-chlate catalyst
compounds.
[0002] It is known in the art to prepare for example polyurethanes
(PU) by crosslinking isocyanate components with polyols, including
any hydroxyl-functional compounds and also polythiols, in the
presence of an organometallic, in particular a tin, catalyst.
Corresponding catalysts are known from many publications, for
example U.S. Pat. No. 5,545,600. The same type of organometallic
catalyst can also be used in order to catalyze the crosslinking via
other condensation or addition reactions, such as for example
siloxane modified binders as they are used in silane crosslinking
adhesives or sealings, as reported for example in
WO2006/136211.
[0003] The standard catalysts used today are based on Sn compounds.
These catalysts are not latent and thus the reaction between the
polyol and the poly-isocyanates is accelerated as soon as the
catalyst is added. After a short reaction time (around 0.5 h to 2
h, depending on the concentrations and the conditions), the
reaction is completed. This reaction time limits the working window
with the resin system after the mixture has been produced. Thus it
is highly desirable to be able to trigger the reaction only on
demand through an external activation such as heat or light. This
would allow extending the working window with the resins mixture
ideally until the external trigger is turned on. A further problem
underlying the invention resides in the legislative pressure on tin
catalysts due to the environmental issues raised by these products.
A general trend seen in this industry is the replacement of tin
catalysts by alternative metals, less or not detrimental to the
environment.
[0004] Photo-latent catalysts for PU crosslinking have been
reported in prior art (e.g. WO2007/147851, WO2009/0501 15. These
catalysts can be activated by irradiation with UV light.
[0005] The prior art describes mostly photo-latent tin-catalysts,
but also Bi, Zr, Al, and Ti catalysts. Photo-latent Ti catalysts
are of very high interest because they perform as good as
photo-latent Sn catalysts, but do not have the environmental issues
associated with Sn. These Ti catalysts do show a nice photo-latent
behavior, but PU formulations containing them do have a pot-life
that is not sufficient for a practical industrial application.
WO2011/032875 describes the use of specific combinations of
Ti-chelate complexes Ti(chelate).sub.2(OR).sub.2 with an excess of
specific chelate ligands which leads to an improvement of pot-life
of the formulation while maintaining a good photo-latency of the
catalyst. The addition of only a small amount of specific
1,3-diketones to the photolatent Ti complexes leads to a longer
pot-life, but equivalent photo-latency compared with the state of
the art. These catalysts are however extremely sensitive towards
hydrolysis and therefore have to be handled with special care and
under strict exclusion of humidity. Storage of the catalysts is
thus often accompanied by a loss in activity.
[0006] Metal-oxo chelate catalysts and the combination with
1,3-diketones are mentioned in JP2006/206781 as crosslinking
catalysts for polyurethane resins as well as for hardening of
silicon compositions in JP2008/280434. However, the two references
do not disclose photo-latent catalysts or latent catalysts
concepts.
[0007] This invention pertains to the use of Ti-oxo chelate complex
compounds which can be prepared under controlled hydrolysis
conditions from Ti-alkoxo chelate compounds and have high stability
towards water and thus can be easily stored even in the presence of
humidity. The Ti-oxo chelate catalyst compounds (and
catalyst/1,3-diketone combinations) which are the object of the
present invention were surprisingly found to be as reactive and
photo-latent as the Ti-alkoxo chelate compounds (and
catalyst/1,3-diketone combinations) as crosslinking catalyst for
polyurethane.
[0008] Subject of the invention is a titanium-oxo-chelate catalyst
formulation, comprising [0009] (i) at least one compound of the
formula I
[0009] ##STR00002## wherein [0010] R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10,
R.sub.11 and R.sub.12 independently of each other are hydrogen,
halogen, C.sub.1-C.sub.20alkyl, C.sub.6-C.sub.14aryl which is
unsubstituted or substituted by one or more C.sub.1-C.sub.8alkyl,
halogen, OR.sub.13 or NR.sub.13R.sub.14; provided that only one of
R.sub.1, R.sub.2 and R.sub.3 in the group
[0010] ##STR00003## and only one of R.sub.4, R.sub.5 and R.sub.6 in
the group
##STR00004## and only one of R.sub.7, R.sub.8 and R.sub.9 in the
group
##STR00005## and only one of R.sub.10, R.sub.11 and R.sub.12 in the
group
##STR00006## can be hydrogen; [0011] or R.sub.1, R.sub.2 and
R.sub.3 and/or R.sub.4, R.sub.5 and R.sub.6 and/or R.sub.7, R.sub.8
and R.sub.9 and/or R.sub.10, R.sub.11 and R.sub.12 together with
the C-atom to which they are attached each form a
C.sub.6-C.sub.14aryl group which is unsubstituted or substituted by
one or more C.sub.1-C.sub.8alkyl, halogen, OR.sub.13 or
NR.sub.13R.sub.14; [0012] or R.sub.1 and R.sub.2 and/or R.sub.4 and
R.sub.5 and/or R.sub.7 and R.sub.8 and/or R.sub.10 and R.sub.11
together with the C-atom to which they are attached form a 5- to
7-membered carbocyclic ring; [0013] R.sub.13 and R.sub.14
independently of each other are C.sub.1-C.sub.8alkyl; and [0014]
(ii) at least one chelate ligand compound of the formula IIa, IIb
or IIc
##STR00007##
[0014] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and
R.sub.6 are defined as above for formula I.
[0015] Subject of the invention further are titanium-oxo-chelate
catalyst compounds of the formula (IA) or (IB)
##STR00008##
wherein R.sub.20, R'.sub.20, R''.sub.20, R.sub.21, R.sub.21 and
R''.sub.21 independently of each other are hydrogen, halogen,
C.sub.1-C.sub.20alkyl, which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.13, or are C.sub.6-C.sub.14aryl which
is unsubstituted or is substituted by one or more
C.sub.1-C.sub.8alkyl, halogen, OR.sub.13, or NR.sub.13R.sub.14;
provided that only one of R.sub.20, R'.sub.20 and R''.sub.20 in the
group
##STR00009##
and only one of R.sub.21, R'.sub.21 and R''.sub.21 in the group
##STR00010##
can be hydrogen; or R.sub.20 and R'.sub.20 and/or R.sub.21 and
R'.sub.21 together with the C-atom to which they are attached form
a 5- to 7-membered carbocyclic ring, R.sub.22, R.sub.23, R.sub.24
independently of each other are hydrogen, halogen,
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, C.sub.6-C.sub.14aryl,
C.sub.1-C.sub.8alkanoyl, C.sub.1-C.sub.8alkanoyloxy,
C.sub.7-C.sub.15aroyl, C.sub.7-C.sub.15aroyloxy, nitrile, nitro,
C.sub.1-C.sub.8alkylthio, C.sub.6-C.sub.14arylthio or
NR.sub.37R.sub.38; R.sub.25, R.sub.26, R.sub.27, R.sub.28,
R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35 and R.sub.36 independently of each other are hydrogen,
C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one
or more OR.sub.13 or COOR.sub.14, or are C.sub.6-C.sub.14aryl which
is unsubstituted or is substituted by one or more
C.sub.1-C.sub.8alkyl, OR.sub.13 or NR.sub.13R.sub.14; or two
radicals R.sub.25 and R.sub.26 and/or two radicals R.sub.28 and
R.sub.29 and/or two radicals R.sub.31 and R.sub.32 and/or two
radicals R.sub.34 and R.sub.35 together with the C-atom to which
they are attached form a 5- to 7-membered carbocyclic ring;
provided that only one of R.sub.25, R.sub.26, R.sub.27 in the
group
##STR00011##
and only one of R.sub.28, R.sub.29, R.sub.30 in the group
##STR00012##
and only one of R.sub.31, R.sub.32, R.sub.33 in the group
##STR00013##
and only one of R.sub.34, R.sub.35, R.sub.36 in the group
##STR00014##
can be hydrogen; and provided that R.sub.25, R.sub.26, R.sub.27,
R.sub.28, R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33,
R.sub.34, R.sub.35 and R.sub.36 are not simultaneously methyl;
R.sub.13 and R.sub.14 independently of each other are
C.sub.1-C.sub.8alkyl; R.sub.37 and R.sub.38 independently of each
other are hydrogen, C.sub.1-C.sub.8alkyl or C.sub.6-C.sub.14aryl,
or R.sub.37 and R.sub.38 together with the N-atom to which they are
attached form a 5- or 6-form a 5- or 6-membered saturated or
unsaturated ring, which ring optionally in addition to the N-atom
comprises a further N-atom or O-atom.
[0016] The compounds of the formula IIa, IIb and IIe are tautomeric
forms of the same compound. Hereinafter referred to as compound of
the formula II.
[0017] C.sub.1-C.sub.20alkyl is linear or branched or cyclic and
is, for example, C.sub.1-C.sub.18-, C.sub.1-C.sub.14-,
C.sub.1-C.sub.12-, C.sub.1-C.sub.8-, C.sub.1-C.sub.6- or
C.sub.1-C.sub.4alkyl. Examples are methyl, ethyl, propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, e.g.
cyclopentyl, hexyl, e.g. cyclohexyl, heptyl, 2,4,4-tri methyl
pentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl,
pentadecyl, hexa-decyl, octadecyl and icosyl, preferably methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,
tert-butyl.
[0018] C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.6alkyl and
C.sub.1-C.sub.4alkyl have the same meanings as given above for
C.sub.1-C.sub.20alkyl up to the corresponding number of
C-atoms.
[0019] C.sub.1-C.sub.8alkyl which is unsubstituted or substituted
by one or more radicals is for example substituted 1-5 times, e.g.
1-4 times or once, twice or three times,
[0020] C.sub.1-C.sub.8alkoxy is linear or branched and is for
example C.sub.1-C.sub.6- or C.sub.1-C.sub.4-alkoxy. Examples are
methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,
iso-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy,
2,4,4-trimethylpentyloxy, 2-ethylhexyloxy or octyloxy, in
particular methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy,
sec-butyloxy, iso-butyloxy, tert-butyloxy, especially methoxy.
[0021] C.sub.1-C.sub.8alkanoyl is linear or branched and is, for
example C.sub.1-C.sub.6- or C.sub.1-C.sub.4alkanoyl or
C.sub.4-C.sub.8alkanoyl. Examples are formyl, acetyl, propionyl,
butanoyl, isobutanoyl, pentanoyl, hexanoyl, heptanoyl or octanoyl,
preferably acetyl.
[0022] C.sub.1-C.sub.8alkanoyloxy is linear or branched, and is for
example C.sub.2-C.sub.8-, C.sub.2-C.sub.6-,
C.sub.2-C.sub.4-alkanoyloxy. Examples are acetyloxy, propionyloxy,
butanoyloxy, isobutanoyloxy, preferably acetyloxy.
[0023] C.sub.1-C.sub.8alkylthio is C.sub.1-C.sub.8alkyl, which at
the "yl" moiety bears a S-atom. C.sub.1-C.sub.8alkyl has the same
meanings as given above for C.sub.1-C.sub.20alkyl up to the
corresponding number of C-atoms. C.sub.1-C.sub.8alkylthio is linear
or branched or cyclic, for example, methylthio ethylthio,
propylthio, isopropylthio, n-butylthio, sec-butylthio,
isobutylthio, tert-butylthio, in particular methylthio.
[0024] C.sub.6-C.sub.14aryl is for example phenyl, naphthyl,
anthryl or phenanthryl, in particular phenyl or naphthyl,
preferably phenyl.
[0025] C.sub.6-C.sub.14aryl which is substituted by one or more
radicals is for example substituted 1-5 times, e.g. 1-4 times or
once, twice or three times. The substituents are for example bound
in the 2,4,6-, 2,6-, 2,4-, 2,5-, 2,3,4-, 2-, 4- or 5-position of
the phenyl ring.
[0026] C.sub.7-C.sub.15aroyl is C.sub.6-C.sub.14aryl, as defined
above, which at the "yl" moiety bears a --CO-- group. Examples are
benzoyl, naphthoyl, phenanthroyl and anthroyl, especially benzoyl
and naphthoyl, in particular benzoyl.
[0027] C.sub.7-C.sub.15aroyloxy is C.sub.6-C.sub.14aryl, as defined
above, which at the "yl" moiety bears a --(CO)O-- group. Examples
are benzoyloxy, naphthoyloxy, phenanthroyloxy and anthroyloxy,
especially benzoyloxy and naphthoyloxy, in particular
benzoyloxy.
[0028] C.sub.6-C.sub.14arylthio is C.sub.6-C.sub.14aryl, which at
the "yl" moiety bears a S-atom. C.sub.6-C.sub.14aryl has the same
meanings as given above for C.sub.6-C.sub.14aryl. Examples are
phenylthio, naphthylthio, anthrylthio, phenanthrylthio, in
particular phenylthio.
[0029] Halogen is Cl, F, Br or I, for example Cl, F, Br, in
particular Cl or F, especially F.
[0030] If R.sub.1, R.sub.2 and R.sub.3 and/or R.sub.4, R.sub.5 and
R.sub.6 and/or R.sub.7, R.sub.8 and R.sub.9 and/or R.sub.10,
R.sub.11 and R.sub.12 together with the C-atom to which they are
attached each form a C.sub.6-C.sub.14aryl group for example groups
such as
##STR00015##
et. Are formed, wherein these groups are unsubstituted or
substituted with the radicals as defined above.
[0031] If R.sub.1, R.sub.2 and R.sub.3 and/or R.sub.4, R.sub.5 and
R.sub.6 and/or R.sub.7, R.sub.8 and R.sub.9 and/or R.sub.10,
R.sub.11 and R.sub.12 together with the C-atom to which they are
attached each form a C.sub.6-C.sub.14aryl group for example groups
such as etc. are formed,
##STR00016##
wherein these groups are unsubstituted or substituted with the
radicals as defined above.
[0032] If R.sub.1 and R.sub.2 and/or R.sub.4 and R.sub.5 and/or
R.sub.7 and R.sub.8 and/or R.sub.0 and R.sub.11 together with the
C-atom to which they are attached form a 5- to 7-membered
carbocyclic ring for example groups such as
##STR00017##
wherein R.sub.x is R.sub.3, R.sub.6, and/or R.sub.12, R.sub.y is
C.sub.1-C.sub.20alkyl, n is an integer 1-5 and m is an integer 1-4,
etc. are formed. As the examples show, the 5-7-membered carbocyclic
ring is defined to optionally include one or more alkyl
substituents.
[0033] If R.sub.20 and R'.sub.20 and/or R.sub.21 and R'.sub.21
together with the C-atom to which they are attached form a 5- to
7-membered carbocyclic ring for example groups such as
##STR00018##
wherein R.sub.x1 is R''.sub.20, and/or R''.sub.21, R.sub.yl is
C.sub.1-C.sub.20alkyl, n is an integer 1-5 and m is an integer 1-4,
etc. are formed. As the examples show, the 5-7-membered carbocyclic
ring is defined to optionally include one or more alkyl
substituents.
[0034] If two radicals R.sub.25 and R.sub.26 and/or two radicals
R.sub.28 and R.sub.29 and/or two radicals R.sub.31 and R.sub.32
and/or two radicals R.sub.34 and R.sub.35 together with the C-atom
to which they are attached form a 5- to 7-membered carbocyclic ring
for example groups such as
##STR00019##
wherein R.sub.x2 is R.sub.27, R.sub.36, R.sub.30 and/or R.sub.33,
R.sub.y2 is C.sub.1-C.sub.20alkyl, n is an integer 1-5 and m is an
integer 1-4, etc. are formed. As the examples show, the
5-7-membered carbocyclic ring is defined to optionally include one
or more alkyl substituents.
[0035] If R.sub.37 and R.sub.38 together with the N-atom to which
they are attached form a 5- or 6-membered saturated or unsaturated
ring, which ring optionally in addition to the N-atom comprises a
further N-atom or O-atom, for example pyrrole, pyrrolidine,
oxazole, pyri-dine, 1,3-diazine, 1,2-diazine, piperidine or
morpholine rings, in particular morpholine rings, are formed.
[0036] The provisos "provided that only one of R.sub.1, R.sub.2 and
R.sub.3 in the group R.sub.1R.sub.2R.sub.3C-- and only one of
R.sub.4, R.sub.5 and R.sub.6 in the group R.sub.4R.sub.5R.sub.6C--
and only one of R.sub.7, R.sub.8 and R.sub.9 in the group
R.sub.7R.sub.8R.sub.9C-- and only one of R.sub.10, R.sub.11 and
R.sub.12 in the group R.sub.10R.sub.11R.sub.12C-- can be hydrogen;
provided that only one of R.sub.20, R'.sub.20 and R''.sub.20 in the
group R.sub.20R'.sub.20R''.sub.20C-- and only one of R.sub.21,
R'.sub.21 and R''.sub.21 in the group
R.sub.21R'.sub.21R''.sub.21C-- can be hydrogen;
provided that only one of R.sub.25, R.sub.26, R.sub.27 in the group
R.sub.25R.sub.26R.sub.27C-- and only one of R.sub.28, R.sub.29,
R.sub.30 in the group R.sub.28R.sub.29R.sub.30C-- and only one of
R.sub.31, R.sub.32, R.sub.33 in the group
R.sub.31R.sub.32R.sub.33C-- and only one of R.sub.34, R.sub.35,
R.sub.36 in the group R.sub.34R.sub.35R.sub.36C-- can be hydrogen"
are meant to exclude compounds wherein R.sub.1R.sub.2R.sub.3C--,
R.sub.4R.sub.5R.sub.6C--, R.sub.7R.sub.8R.sub.9C--,
R.sub.10R.sub.11R.sub.12C--, R.sub.20R.sub.20R''.sub.20C--,
R.sub.21R'.sub.21R''.sub.21C--, R.sub.25R.sub.26R.sub.27C--,
R.sub.28R.sub.29R.sub.30C--, R.sub.31R.sub.32R.sub.33C-- and
R.sub.34R.sub.35R.sub.36C-- are --CH.sub.3 or --CH.sub.2R.sub.z,
wherein R.sub.z is the remaining radical R.sub.25, R.sub.26,
R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.31, R.sub.32,
R.sub.33, R.sub.34, R.sub.35 or R.sub.36.
[0037] "photolatent catalyst" refers to a compound, which upon
irradiation with light, in particular with light of the wavelengths
150-800 nm, e.g. 200-800 or 200-600 nm, provides an active
catalyst.
[0038] The terms "and/or" or "or/and" in the present context are
meant to express that not only one of the defined alternatives
(substituents) may be present, but also several of the defined
alternatives (substituents) together, namely mixtures of different
alternatives (substituents).
[0039] The term "at least" is meant to define one or more than one,
for example one or two or three, preferably one or two.
[0040] The term "optionally substituted" means, that the radical to
which it refers is either unsubstituted or substituted.
[0041] Throughout this specification and the claims which follow,
unless the context requires otherwise, the word "comprise", or
variations such as "comprises" or "comprising", will be understood
to imply the inclusion of a stated integer or step or group of
integers or steps but not the exclusion of any other integer or
step or group of integers or steps.
[0042] The term "(meth)acrylate" in the context of the present
application is meant to refer to the acrylate as well as to the
corresponding methacrylate.
[0043] The preferences indicated in the text for the compounds (I),
(IA), (IB) according to the present invention in the context of
this invention are intended to refer to all categories of the
claims, that is to the formulation, compositions, use, process
claims as well.
[0044] The compounds of the formula I, IA and I B of this invention
can be prepared by hydrolysis of corresponding Ti-dialkoxo chelate
compounds as for example described in JP10-072475A, or by
hydrolysis of corresponding Ti-dichloro chelate compounds as
described for example in U.S. Pat. No. 5,767,302 (see col. 4, line
33ff).
##STR00020##
(similar with corresponding intermediates of compounds IA or
IB)
[0045] The person skilled in the art is well aware of suitable
methods to carry out a corresponding hydrolysis reaction. For
example the hydrolysis is suitably carried out in an organic
solvent such as for example an aromatic hydrocarbon, e.g. toluene
etc., or an aliphatic hydrocarbon, e.g. pentane, hexane etc. As
alkali chemical for example aqueous ammonia can be used.
[0046] The hydrolysis also can be performed by just adding water to
a solution of the precursor compound in an organic solvent and
stirring the reaction mixture, for example at moderately elevated
temperatures, e.g. 50.degree. C.
[0047] The compounds of formula II (IIa, IIb, lie) of this
invention are commercially available or can be prepared by Claisen
condensation of the respective esters and methylketones, a reaction
well known to those skilled in the art.
[0048] The catalyst combination (that is the titanium-oxo-chelate
catalyst formulation) can be for example formed using different
approaches: i) dissolving a photo-latent catalyst compound of the
formula I, IA or IB in a solvent or part of the formulation and
adding the 1,3-diketone of the formula II to either this solution
or to another part of the formulation (or in inverse order); ii)
preparing the catalyst combination in advance as a physical mixture
of a photo-latent catalyst compound of the formula I, IA or IB and
the 1,3-diketone of the formula II which can be stored. The mixture
may be prepared by mixing of the two components or by addition of
the 1,3-diketone of formula II during the preparation of the
chelate complex of the formula I, IA or IB.
[0049] It is clear to the person skilled in the art, that the
formula I (and formula IA and IB) is a schematic drawing of the
structure of a titanium-oxo chelate complex compound. Because
organometallic Ti(IV) compounds have a preferred coordination
number of six, such compounds are known to often exist as dimers,
but they have also been found as trimers, tetramers, or even
polymeric structures, all of which are meant to be included by
formula I (IA and IB) of the present invention.
[0050] Structure examples (based on formula I) are:
##STR00021##
[0051] The titanium-oxo-chelate catalyst formulation as defined
above for example comprises [0052] (i) 50-99% by weight of at least
one compound of the formula I as defined above, and [0053] (ii)
1-50% by weight of at least one chelate ligand compound of the
formula IIa, IIb or IIc as defined above.
[0054] Of particular interest are titanium-oxo-chelate catalyst
formulations as defined above, comprising [0055] (i) at least one
compound of the formula I, wherein [0056] R.sub.1 and R.sub.2 and
R.sub.3 together with the C-atom to which they are attached form a
phenyl group which is unsubstituted or substituted by one, two or
three C.sub.1-C.sub.4alkyl, OR.sub.13 or NR.sub.13R.sub.14; [0057]
R.sub.10 and R.sub.11 and R.sub.12 together with the C-atom to
which they are attached form a phenyl group which is unsubstituted
or substituted by one, two or three C.sub.1-C.sub.4alkyl, OR.sub.13
or NR.sub.13R.sub.14; [0058] R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, independently of each other are hydrogen, halogen
or C.sub.1-C.sub.4alkyl; [0059] provided that only one of R.sub.4,
R.sub.5 and R.sub.6 in the group
[0059] ##STR00022## and only one of R.sub.7, R.sub.8 and R.sub.9 in
the group
##STR00023## can be hydrogen; [0060] or R.sub.4, R.sub.5 and
R.sub.6 and R.sub.7, R.sub.8 and R.sub.9 together with the C-atom
to which they are attached form a phenyl group: [0061] or R.sub.4
and R.sub.5 and R.sub.7 and R.sub.8 together with the C-atom to
which they are attached form a cyclohexyl ring; [0062] R.sub.13 and
R.sub.14 independently of each other are C.sub.1-C.sub.4alkyl;
[0063] (ii) at least one chelate ligand compound of the formula
IIa, IIb or IIc
##STR00024##
[0063] wherein R.sub.1, R.sub.2 and R.sub.3 independently of each
other are hydrogen, halogen, C.sub.1-C.sub.4alkyl; or R.sub.1 and
R.sub.2 and R.sub.3 together with the C-atom to which they are
attached form a phenyl group; R.sub.4, R.sub.5 and R.sub.6
independently of each other are hydrogen, halogen,
C.sub.1-C.sub.4alkyl; or R.sub.4 and R.sub.5 and R.sub.6 together
with the C-atom to which they are attached form a phenyl group.
[0064] Interesting are compounds wherein R.sub.2 and R.sub.3
together with the C-atom to which they are attached form a
C.sub.6-C.sub.14aryl group which is unsubstituted or substituted as
defined above and wherein R.sub.10, R.sub.11 and R.sub.12 together
with the C-atom to which they are attached each form a
C.sub.6-C.sub.14aryl group which is unsubstituted or substituted as
defined above.
[0065] Further of interest are compounds wherein R.sub.7, R.sub.8,
and R.sub.9, are identical; and compounds wherein R.sub.4, R.sub.5
and R.sub.6 are identical; in particular compounds, wherein
R.sub.7, R.sub.8, R.sub.9, R.sub.4, R.sub.5 and R.sub.6 are
identical.
[0066] R.sub.1, R.sub.2 and R.sub.3 as well as R.sub.10, R.sub.11
and R.sub.12 together with the corresponding C-atom to which they
are attached forming a C.sub.6-C.sub.14aryl group, for example form
a phenyl or naphthyl group which is unsubstituted or substituted as
defined above. In particular a phenyl group is formed, which is
unsubstituted or substituted by C.sub.1-C.sub.8alkyl, halogen,
OR.sub.13 or NR.sub.13R.sub.14. Substituents on the
C.sub.6-C.sub.14aryl group, in particular the phenyl group, are for
example C.sub.1-C.sub.4alkyl, especially methyl, OR.sub.13, where
R.sub.13 denotes C.sub.1-C.sub.4alkyl, especially methyl,
NR.sub.12R.sub.13, wherein R.sub.12 and R.sub.13 are
C.sub.1-C.sub.4alkyl, in particular methyl.
[0067] Preferred are compounds of the formula IA.
[0068] In preferred compounds the groups R.sub.1R.sub.2R.sub.3C--
and R.sub.10R.sub.11R.sub.12C-- are identical and/or the groups
R.sub.4R.sub.5R.sub.6C-- and R.sub.7R.sub.8R.sub.9C-- are
identical.
[0069] R.sub.20, R'.sub.20, R'.sub.20 for example independently of
each other are hydrogen, halogen or C.sub.1-C.sub.20alkyl, which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.13; or R.sub.20, R'.sub.20, R''.sub.20 for example
independently of each other are hydrogen, halogen or
C.sub.1-C.sub.8alkyl; or R.sub.20, R'.sub.20, R''.sub.20 for
example independently of each other are hydrogen, fluoro or
C.sub.1-C.sub.8alkyl, in particular R.sub.20, R'.sub.20, R'.sub.20
are hydrogen, fluoro or methyl.
[0070] R.sub.21, R'.sub.21, R'.sub.21 for example independently of
each other hydrogen, halogen or C.sub.1-C.sub.20alkyl, which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.13; or R.sub.21, R'.sub.21, R'.sub.21 for example
independently of each other are hydrogen, halogen or
C.sub.1-C.sub.8alkyl; or R.sub.21, R'.sub.21, R''.sub.21 for
example independently of each other are hydrogen, fluoro or
C.sub.1-C.sub.8alkyl, in particular R.sub.21, R'.sub.21, R''.sub.21
are hydrogen, fluoro or methyl.
[0071] Preferably the groups R.sub.20, R'.sub.20R''.sub.20C-- and
R.sub.21R'.sub.21R''.sub.21C-- are identical.
[0072] R.sub.22, R.sub.23, R.sub.24 for example independently of
each other are hydrogen, C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkanoyl,
C.sub.1-C.sub.8alkanoyloxy, chloro, nitrile, nitro,
C.sub.1-C.sub.8alkylthio, C.sub.6-C.sub.14arylthio or
NR.sub.37R.sub.38; or R.sub.22, R.sub.23, R.sub.24 for example
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkanoyl,
C.sub.1-C.sub.8alkanoyloxy or NR.sub.37R.sub.38; or R.sub.22,
R.sub.23, R.sub.24 for example independently of each other are
hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, or
NR.sub.37R.sub.38; in particular R.sub.22, R.sub.23, R.sub.24 for
example independently of each other are hydrogen, methyl, methoxy
or dimethylamino.
[0073] R.sub.25, R.sub.26, R.sub.27 for example independently of
each other are hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.11, or two radicals R.sub.25 and R.sub.26 together with
the C-atom to which they are attached form a cyclopentyl or
cyclohexyl ring; or R.sub.25, R.sub.26, R.sub.27 for example
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or
two radicals R.sub.25 and R.sub.26 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring; or
R.sub.25, R.sub.26, R.sub.27 for example independently of each
other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COO R.sub.14; or R.sub.25,
R.sub.26, R.sub.27 for example independently of each other are
hydrogen or C.sub.1-C.sub.8alkyl.
[0074] R.sub.31, R.sub.32, R.sub.33 for example independently of
each other are hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14, or two radicals R.sub.31 and R.sub.32 together with
the C-atom to which they are attached form a cyclopentyl or
cyclohexyl ring; or R.sub.31, R.sub.32, R.sub.33 for example
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or
two radicals R.sub.31 and R.sub.32 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring; or
R.sub.31, R.sub.32, R.sub.33 for example independently of each
other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14; or R.sub.31,
R.sub.32, R.sub.33 for example independently of each other are
hydrogen or C.sub.1-C.sub.8alkyl.
[0075] R.sub.28, R.sub.29, R.sub.30 for example independently of
each other are hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14, or two radicals R.sub.28 and R.sub.29 together with
the C-atom to which they are attached form a cyclopentyl or
cyclohexyl ring; or R.sub.28, R.sub.29, R.sub.30 for example
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or
two radicals R.sub.28 and R.sub.29 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring; or
R.sub.28, R.sub.29, R.sub.30 for example independently of each
other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14; or R.sub.28,
R.sub.29, R.sub.30 for example independently of each other are
hydrogen or C.sub.1-C.sub.8alkyl.
[0076] R.sub.34, R.sub.35, R.sub.36 for example independently of
each other are hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14, or two radicals R.sub.34 and R.sub.35 together with
the C-atom to which they are attached form a cyclopentyl or
cyclohexyl ring; or R.sub.34, R.sub.35, R.sub.36 for example
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or
two radicals R.sub.34 and R.sub.35 together with the C-atom to
which they are attached form a cyclopentyl or cyclohexyl ring; or
R.sub.34, R.sub.35, R.sub.36 for example independently of each
other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by one or more OR.sub.13 or COOR.sub.14; or R.sub.34,
R.sub.35, R.sub.36 for example independently of each other are
hydrogen or C.sub.1-C.sub.8alkyl.
[0077] In preferred compounds the groups
R.sub.25R.sub.26R.sub.27C-- and R.sub.31R.sub.32R.sub.33C-- are
identical and/or the groups R.sub.28R.sub.29R.sub.30C-- and
R.sub.34R.sub.35R.sub.36C-- are identical.
[0078] Interesting further are compounds of the following formula
IB'
##STR00025##
wherein R'.sub.25, R'.sub.26, R'.sub.27 and R''.sub.28
independently of each other are hydrogen, C.sub.1-C.sub.8alkyl
which is unsubstituted or substituted by one or more OR.sub.13 or
COOR.sub.14, or are C.sub.6-C.sub.14aryl which is unsubstituted or
is substituted by one or more C.sub.1-C.sub.8alkyl, OR.sub.13 or
NR.sub.13R.sub.14; or two radicals R'.sub.25 and R'.sub.26 together
with the C-atom to which they are attached and/or or two radicals
R'.sub.27 and R'.sub.28 together with the C-atom to which they are
attached form a 5- to 7-membered carbocyclic ring.
[0079] In particular preferred are the compounds as given
hereinafter in the examples.
[0080] This invention provides (photo)latent compounds as catalysts
for polyaddition or polycondensation reactions, that are catalysed
by Lewis-acid type reactants. Especially preferred is the reaction
of polyols with isocyanates.
[0081] The compounds of the formula (I) as defined above, as well
as the catalyst formulation as defined above can be used as
photolatent compounds, e.g. in processes which are initialized by
exposing the formulation to be crosslinked to electromagnetic
radiation of wavelengths in the range of 200-800 nm, in particular
the compounds of the formula (I) can be used as photolatent
compounds.
[0082] Especially suitable as photolatent compound is catalyst 12
(see examples).
[0083] Accordingly, subject of the invention also is the use the
Ti-oxo-chelate catalyst formulation as described above as a
catalyst for polyaddition or polycondensation reactions, that are
catalysed by Lewis-acid type reactants, in particular for the
crosslinking of a blocked or unblocked isocyanate or isothiocyanate
component with a polyol to form a polyurethane (PU).
[0084] Another subject is the use of a Ti-oxo-chelate catalyst
compound of the formula (I) as defined above as a catalyst for
polyaddition or polycondensation reactions, that are catalysed by
Lewis-acid type reactants, in particular for the crosslinking of a
blocked or unblocked isocyanate or isothiocyanate component with a
polyol to form a polyurethane (PU).
[0085] Subject of the invention also is the use of a Ti-oxo-chelate
catalyst compound of the formula (I) as defined above, wherein at
least one of R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
Rs, R.sub.9, R.sub.10, R.sub.11 or R.sub.12 is not methyl, as a
catalyst for polyaddition or polycondensation reactions, that are
catalysed by Lewis-acid type reactants, in particular for the
crosslinking of a blocked or unblocked isocyanate or isothiocyanate
component with a polyol to form a polyurethane (PU).
[0086] Preferred is the use of the Ti-oxo-chelate catalyst
formulation as described above.
[0087] Subject of the invention further is a polymerizable
composition comprising
(a) at least one component which is capable of a polyaddition or
polycondensation reaction in the presence of a Lewis-acid type
reactant; and (b) a Ti-oxo-chelate catalyst formulation as
described above; as well as a polymerizable composition comprising
as component (a) (a1) at least one blocked or unblocked isocyanate
or isothiocyanate component, and (a2) at least one polyol.
[0088] Another subject of the invention further is a polymerizable
composition comprising (a) at least one component which is capable
of a polyaddition or polycondensation reaction in the presence of a
Lewis-acid type reactant; and
(b) at least one Ti-oxo-chelate catalyst compound of the formula
(I) as described above; as well as a polymerizable composition
comprising as component (a) (a1) at least one blocked or unblocked
isocyanate or isothiocyanate component, and (a2) at least one
polyol.
[0089] Further subject of the invention is a polymerizable
composition comprising
(a) at least one component which is capable of a polyaddition or
polycondensation reaction in the presence of a Lewis-acid type
reactant; and (b) at least one Ti-oxo-chelate catalyst compound of
the formula (I) as described above wherein at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, R.sub.11 or R.sub.12 is not methyl; as well as a
polymerizable composition comprising as component (a) (a1) at least
one blocked or unblocked isocyanate or isothiocyanate component,
and (a2) at least one polyol.
[0090] Said polymerizable composition in addition to components (a)
and (b) can comprise further additives (d), in particular a
photosensitizer compound.
[0091] The photopolymerizable compositions generally comprise 0.001
to 15% by weight, e.g. 0.05 to 15% by weight, preferably 0.01 to 5%
by weight, most preferably 0.05 to 2.5%, of the Ti-oxo-chelate
catalyst compound of the formula I, based on the total composition.
In other words, the amount as defined above refers to the active
catalyst compound, excluding the compounds of the formula IIa, IIb
and IIc which are present in the Ti-oxo-chelate catalyst
formulation as defined above. The amounts are based on the total
weight of the composition.
[0092] The catalyst compounds and formulations of the invention can
for example be used for crosslinking of moisture curing silicone
elastomers. The use of a Ti chelate catalyst compound for
crosslinking of moisture curing silicone elastomers is e.g.
described by J.-M. Pujol and C. Prebet in J. Adhesion Sci. Technol.
2003, 17, 261. Curing by crosslinking of silicone compositions is
used in many applications such as waterproofing seals in
construction (G. M. Lucas in WO02/062893 or T. Detemmerman et al in
WO2008/045395), adhesives in structural glazing, gaskets in car
engines, adhesives for electronic devices, and antifouling or
moisture repellent coatings (H. Kobayashi et al in WO02/098983). Ti
chelates can also be used for room-temperature curable
organopolysiloxane compositions used e.g. as sealants or coating
agents for electric circuits and electrodes (A. Nabeta et al in
WO2009/054279), for curing of pressure sensitive adhesives as
described by K. Fujimoto and K. Ueda in EP1715015, or for curing of
an adhesive composition based on silane and phenolic resin (S. Sano
et al in EP1842889). They can also be used for curing of non
silicone rubber compositions as described e.g. by T. W. Wilson in
WO02/100937. Ti chelate catalysts can also be used for curing of
epoxy resins (W. J. Blank et al in Journal of Coatings Technology
2002, 74, 33), e.g. for anhydride epoxy resins as described by J.
D. B. Smith in J. Applied Polym. Sci. 1981, 26, 979, or carboxyl
epoxy resins used for heat activatable adhesive tapes (T. Krawinkel
in WO2008/043660).
[0093] Other examples of metal catalyzed crosslinking reactions are
for example the reaction of siloxane-terminated oligomers with
epoxides used in the fabrication of abrasion and weather resistant
coatings (M. Priesch in DE19935471), the reaction of epoxy resins
with hydroxyl-terminated poly(dimethyloxysilanes) and an
aminopropyltriethoxysilane crosslinker (M. Alagar et al. Eur.
Polym. J. 2000, 36, 2449), or the reaction of polyethers terminated
by hydrolysable silyl groups with epoxy silanes and ketimines (Y.
Murayama, J P06049346) or oximo-ethoxy functional sealants as
described by H. M. Haugs--by et al in EP399682. The use of room
temperature vulcanizing (RTV) siloxane rubbers for biofouling
protection is reported by J. M. Delehanty et al, GB2444255. Sol-gel
reactions catalysed by a metal catalyst are for example described
by J. Mendez-Vivar, J. of Sol-Gel Sci. Technol. 2006, 38(2),
159.
[0094] Another subject of the invention is a process for
polymerizing compounds, which are capable to crosslink in the
presence of a Lewis acid, characterized in that a catalyst
formulation according to the invention is added to said compounds
and the resulting mixture is irradiated with electromagnetic
radiation of a wavelength range of 200-800 nm; in particular a
process wherein the component which is capable to crosslink in the
presence of a Lewis acid is a mixture of (a) a blocked or unblocked
isocyanate or isothiocyanate component and (b) a polyol.
[0095] Interesting further is a process as described above,
characterized in that instead of irradiating with electromagnetic
radiation the mixture is subjected to a heat treatment, or the
mixture is irradiated with electromagnetic radiation and
simultaneously with or after the irradiation subjected to a heat
treatment.
[0096] Further subjects of the invention are a process as described
above for the preparation of adhesives, coatings, sealings, potting
components, printing inks, printing plates, foams, moulding
compounds, or photostructured layers, as well as the use of the
polymerizable composition as described above for the preparation of
adhesives, coatings, sealings, potting components, printing inks,
printing plates, foams, moulding compounds, or photostructured
layers.
[0097] Another subject is a coated substrate coated on at least one
surface with a composition as described above and a polymerized or
crosslinked composition as described above.
[0098] Polyols (component (a2)) are generally defined as polymeric
or oligomeric organic species with at least two hydroxy
functionalities.
[0099] Examples of suitable polyols include trimethylol propane,
trimethylol ethane, glycerol, 1, 2, 6-hexanetriol, ethylene glycol,
1,2-propylene glycol, 1, 3-propylene glycol, 2-methylpropane-1,
3-diol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propane diol,
cyclohexane-1, 4-dimethylol, the monoester of neopentyl glycol and
hydroxypivalic acid, hydrogenated Bisphenol A, 1,5-pentane diol,
3-methyl-pentane diol, 1,6-hexane diol, 2,2,4-trimethyl pentane-1,
3-diol, dimethylol propionic acid, pentaerythritol, di-trimethylol
propane, dipentaerythritol, etc., and mixtures thereof. Suitable
polyols also include the more recently developed hyperbranched
OH-polymers.
[0100] The hydroxyl-functional compound comprising at least two
hydroxyl-functional groups may for example also be selected from
polyester polyols, polyether polyols, e.g. poly-THF-poylol,
polyacrylate polyols, polyurethane polyols, cellulose
acetobutyrate, hydroxyl-functional epoxy resins, alkyds, and
dendrimeric polyols such as described in WO 93/17060. Also,
hydroxyl-functional oligomers and monomers, e.g. HO-functional
vinyl oligomers, such as castor oil and trimethylol propane, may be
included. Interesting polyols are acrylic and polyester polyols,
e.g. the Joncryl.RTM. acrylic polyols available from BASF (e.g.
Joncryl.RTM. 512 or 922), or Setalux.RTM. and Setal.RTM. products
available from Nuplex Resins (e.g. Setalux.RTM. 1187 XX-60,
Setal.RTM. 1606 BA-80), or Desmophen.RTM. products from Bayer
Material Science (e.g. Desmophen.RTM. A HS 1 170 BA).
[0101] In the context of the present invention also polyol
components which are suitable in water-borne system such as e.g.
waterborne 2K polyurethane, can be employed. Such polyol components
are commercially available, for example from BASF under the
trademark Joncryl.RTM., e.g. Joncryl.RTM.8311 and also the
trademark Luhydran.RTM., e.g. Luhydran.RTM. 5938T as well as from
Bayer Material Science under the trademark BAYHYDROL.RTM., eg.
BAYHYDROL.RTM. XP2470.
[0102] Suitable isocyanate components (a1) are for example
isocyanates--with functional groups capable of reacting with
hydroxyl- and are structured as follows:
##STR00026##
wherein R.sub.70 is a hydrocarbyl structure.
[0103] The organic (poly)isocyanate includes for example
polyfunctional, preferably free poly-isocyanates, with, for
instance, an average NCO functionality of 2.5 to 5, and may be
aliphatic, cycloaliphatic, araliphatic or aromatic in nature.
Examples are di-, tri- or tetra-isocyanates. The polyisocyanate may
include biuret, urethane, uretdione, and isocyanurate derivatives.
Suitable polyisocyanates include polyisocyanates having
isocyanurate structural units, such as, the isocyanurate of
hexamethylene diisocyanate and isocyanurate of isophorone
diisocyanate; the adduct of 2 molecules of a diisocyanate, such as,
hexamethylene diisocyanate and a diol such as, ethylene glycol;
uretidiones of hexamethylene diisocyanate; uretidiones of
isophorone diisocyanate or isophorone diisocyanate; the adduct of
trimethylol propane and meta-tetramethylxylene diisocyanates,
etc.
[0104] Examples of these organic polyisocyanates include
1,6-diisocyanatohexane, isophorone diisocyanate, 2,4-toluene
diisocyanate, 2,6-toluene diisocyanate, diphenyl
methane-diisocyanate, 4,4'-bis(isocyanato-cyclohexyl) methane,
1,4-diisocyanato-butane, 1,5-diisocyanato-2,2-dimethyl pentane,
2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane,
4,4-diisocyanato-cyclohexane, 2,4-hexahydrotoluene diisocyanate,
2,6-hexahydrotoluene diisocyanate, norbornane diisocyanate,
1,3-xylylen diisocyanate, 1,4-xylylen diisocyanate,
1-isocyanato-3-(isocyanato methyl)-1-methyl cyclohexane,
m-a,a-a',a'-tetramethyl xylylene diisocyanate, 1,2-propylene
diisocyanate, trimethylene diisocyanate, tetramethylene
diisocyanate, 2,3-butylene diisocyanate, hexamethylene
diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyl
hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene
diisocyanate, dodecamethylene diisocyanate, omega, omega-dipropyl
ether diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane
diisocyanate, 1,4-cyclohexane diisocyanate, isophorone
diisocyanate, 4-methyl-1,3-diisocyanatocyclohexane,
trans-vinylidene diisocyanate,
dicyclohexylmethane-4,4'-diisocyanate,
3,3'-dimethyl-dicyclohexylmethane4,4'-diisocyanate, a toluene
diisocyanate, 1,3-bis(1-isocyanato-methylethyl)benzene,
1,4-bis(1-isocyanato-1-methylethyl)benzene,
1,3-bis(isocyanatomethyl)benzene, xylene diisocyanate,
1,5-dimethyl-2,4-bis(isocyanatomethyl)benzene,
1,5-dimethyl-2,4-bis(2-isocyanatoethyl)benzene,
1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene,
4,4'-diisocyanato-diphenyl, 3,
3'-dichloro-4,4'-diisocyanatodiphenyl,
3,3'-diphenyl-4,4'-diisocyanatodiphenyl,
3,3'-dimethoxy-4,4'-diisocyanatodiphenyl,
4,4'-diisocyanatodiphenylmethane,
3,3'-dimethyl-4,4'-diisocyanatodiphenyl methane, a
diisocyanatonaphthalene, the above-mentioned derivatives thereof,
and mixtures thereof. Further examples are polyisocyanates having
isocyanurate structural units, the adduct of 2 molecules of a
diisocyanate, such as, hexamethylene diisocyanate or isophorone
diisocyanate, and a diol such as ethylene glycol, the adduct of 3
molecules of hexamethylene diisocyanate and 1 molecule of water
(e.g. as available under the trademark Desmodur.RTM. N from Bayer
Corporation), the adduct of 1 molecule of trimethylol propane and 3
molecules of toluene diisocyanate (available under the trademark
Desmodur.RTM. L from Bayer Corporation), the adduct of 1 molecule
of trimethylol propane and 3 molecules of isophorone diisocyanate,
compounds such as 1,3,5-triisocyanatobenzene and
2,4,6-triisocyanatotoluene, and the adduct of 1 molecule of
pentaerythritol and 4 molecules of toluene diisocyanate.
[0105] A specific example of an isocyanate capable of reacting with
hydroxyl groups is the HDI trimer, e.g. Desmodur.RTM. 3300
available from Bayer, or Basonat.RTM. HI 100 available from BASF.
The idealized structure of the latter is given as follows (also,
pentamer, heptamer and higher molecular weight species can be
present):
##STR00027##
[0106] Normally, these products are liquid at ambient temperature
and commercially available in a wide range. Particularly preferred
isocyanate curing agents are triisocyanates and adducts. Examples
thereof are 1,8-diisocyanato-4-(isocyanatomethyl) octane, the
adduct of 3 moles of toluene diisocyanate to 1 mole of trimethylol
propane, the iso-cyanurate trimer of 1,6-diisocyanatohexane, the
isocyanurate trimer of isophorone diisocyanate, the uretdione dimer
of 1,6-diisocyanatohexane, the biuret trimer of
1,6-diisocyanatohexane, the adduct of 3 moles of
m-.alpha.,.alpha.-.alpha.',a'-tetramethyl xylene diisocyanate to 1
mole of trimethylol propane, and mixtures thereof.
[0107] In particular interesting are cyclic trimers (isocyanurates)
and uretdiones of 1,6-hexane diisocyanate and isophorone
diisocyanate. Usually these compounds contain small quantities of
their higher homologues.
[0108] Optionally, in case the present composition is used as a
water borne coating composition, it may also comprise an organic
hydrophilic polyisocyanate compound substituted with non-ionic
groups, such as C.sub.1-C.sub.4alkoxy polyalkylene oxide groups.
For example 30 wt. % of non-ionic groups will be present on the
total solid polyisocyanate compound, e.g. 20 wt. %, preferably 15
wt. %. Ionically stabilized polyisocyanates may also be used.
[0109] In any of the compositions herein, the polymeric materials
may range from relatively low to relatively high molecular weight.
It is preferred that they be of relatively low molecular weight so
as to keep the viscosity of the compositions before crosslinking
low, so as to avoid or minimize the need for solvent(s).
[0110] As the isocyanate to be crosslinked with the latent catalyst
formulation of the present invention also blocked isocyanates may
be used. Said compounds are for example "deblocked" prior to the
use in the composition, or may be deblocked during the reaction, or
may take part in the reaction in the blocked form, e.g. in the
course of the "activation" of the latent catalyst by heat or
irradiation.
[0111] Blocked isocyanates are known in the art and for example
described in a review article by D. A. Wicks, Z. W. Wicks in
Progress in Organic Coatings, 41 (2001), 1-83, as well as by C.
Gurtler, M. Homann, M. Mager, M. Schelhaas, T. Stingl, Farbe+Lack
2004, 110(12), 34; both documents incorporated herein by
reference.
[0112] Suitable isocyanate components are for example as given
above.
[0113] Suitable blocking agents for the isocyanates are the ones
known in the art, for example alcohols, phenols, amines, imides,
amides, guanidines, amidines, triazoles, pyrazoles, active
methylene compounds, ketoximes, oximes, malonesters,
alkylacetoacetates, formiates, lactams, imidazoles, triazoles,
pyrazoles, CH-acidic cyclic ketones and mercaptans.
[0114] Examples are aliphatic, cycloaliphatic, aromatic, or alkyl
monoalcohol or phenolic compounds such as, for example, lower
aliphatic alcohols including methyl, ethyl, chloro-ethyl, propyl,
butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and lauryl
alcohols, 3,3,5-trimethylhexanol and the like. The aromatic-alkyl
alcohols include for example phenyl-carbinol and
ethylphenylcarbinol. Glycol ethers may be employed such as ethyl
glycol monoethyl ether, ethyl glycol monobutyl ether and
equivalents thereof. Examples of phenolic compounds which may be
employed comprise phenol, substituted phenols such as cresol,
xylenol, nitrophenol, chlorophenol, ethyl phenol, t-butyl phenol
and 2,5-di-t-butyl-4-hydroxy toluene.
[0115] Examples of other blocking agents that may be employed
include tertiary hydroxyl amines such as diethylethanolamin,
lactams such as caprolactam and oximes such as methyl ethyl ketone
oxime, acetone oxime and cyclohexanone oxime.
[0116] Specific examples are butanonoxime, diisoproylamine,
1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, ethylates of
malonic and acetic acid, acetoneoxime, 3,5-dimethylpyrazole,
epsilon-caprolactame, N-methyl-, N-ethyl, N-(iso)propyl, N-n-butyl,
N-isobutyl-, N-tert.-butylbenzylamine or, 1, 1-dimethylbenzylamine,
N-alkyl-N-1, 1-dimethylmethylphenylamine; adducts of benzylamine
and compounds with activated double bonds, such as malonic acid
esters, N,N-dimethylaminopropylbenzylamine and other compounds
comprising tertiary amine groups, where appropriate substituted
benylamines and/or dibenzylamine.
[0117] Use of the oximes and phenols in some instances is desirable
because some specific polyisocyanates blocked with these oximes or
phenols uncap at relatively low temperatures.
[0118] Examples of suitable CH-acidic ketones are given in WO
04/058849 and incorporated herein by reference. Preferred are
cyclopentanon-2-carboxymethylester,
cyclopentanon-2-carboxyethylester, cyclopentanon-2-carboxynitrile,
cyclohexanon-2-carboxymethylester,
cyclohexanon-2-carboxyethylester, cyclopentanon-2-carbonylmethane,
especially cyclopentanon-2-carboxymethylester,
cyclopentanon-2-carboxyethylester,
cyclohexanon-2-carboxymethylester and
cyclohexanon-2-carboxyethylester, in particular
cyclopentanon-2-carboxyethylester and
cyclohexanon-2-carboxyethylester.
[0119] It is evident that also mixtures of different blocking
agents may be used and a blocked isocyanate which may be employed
in the presently claimed composition may have different blocking
groups.
[0120] The compositions contain the blocked isocyanate in an
amount, for example, of from 5 to 95% by weight, preferably from 20
to 80% by weight, based on the total composition. The ratio
isocyanate to polyol for example varies from about 2:1 to 1:2,
preferably from 1.2:1 to 1:1.2. The molecular weight MW of the
blocked isocyanate for example ranges from about 100 to 50000,
especially from 200 to 20000.
[0121] Other additives (d), which may optionally be present in the
compositions include one or more solvents (and are meant to act
only as solvents). These preferably do not contain groups such as
hydroxyl or primary or secondary amino.
[0122] Depending on use, the compositions may contain other
materials (d). Examples of ingredients, additives or auxiliaries
(d), are pigments, dyes, emulsifiers (surfactants), pigment
dispersion aids, levelling agents, anti-cratering agents,
antifoaming agents, wetting agents, antisagging agents, heat
stabilisers, UV absorbers, antioxidants, desiccants and
fillers.
[0123] For example, especially when used as encapsulants and
sealants, the compositions may contain fillers, pigments, and/or
antioxidants.
[0124] When used as coatings, the present compositions optionally
contain typically added ingredients known in the art, which are
described below. For example there may be other polymers (e)
(especially of low molecular weight, "functionalized oligomers")
which are either inert or have a functional group other than
hydroxyl or isocyanate and also react with other reactive materials
in the coating composition.
[0125] Representative examples of such functionalized oligomers
that can be employed as components or potential crosslinking agents
of the coatings are the following: [0126] Hydroxyl oligomers: for
example the reaction product of multifunctional alcohols such as
pentaerythritol, hexanediol, trimethylol propane, and the like,
with cyclic monomeric anhydrides such as hexahydrophthalic
anhydride, methylhexahydrophthalic anhydride, and the like produce
acid oligomers. These acid oligomers are further reacted with
monofunctional epoxies such as butylene oxide, propylene oxide, and
the like to form hydroxyl oligomers. [0127] Silane oligomers: for
example the above hydroxyl oligomers further reacted with
isocyanato propyltrimethoxy silane. [0128] Epoxy oligomers: for
example the diglycidyl ester of cyclohexane dicarboxylic acid, such
as for example Araldite.RTM. CY-184 from Huntsman, and
cycloaliphatic epoxies, such as for example Celloxide 2021 and the
like from Daicel, or for example hydroxyl-terminated epoxidized
polybutadiene, e.g. Poly bd 600 and 605 from Sartomer. Also
suitable as reactive materials are for example oxetane derivatives,
e.g. OXT 101 and 121 from Toagosei or TMPO from Perstorp. [0129]
Aldimine oligomers: for example the reaction product of
isobutyraldehyde with diamines such as isophorone diamine, and the
like. [0130] Ketimine oligomers: for example the reaction product
of methyl isobutyl ketone with diamines such as isophorone diamine.
[0131] Melamine oligomers: for example the commercially available
melamines such as CYMEL.RTM. 1168 from Cytec Industries, and the
like. [0132] AB-functionalized oligomers: for example acid/hydroxyl
functional oligomers made by further reacting the above acid
oligomers with 50%, based on equivalents, of monofunctional epoxy
such as butylene oxide or blends of the hydroxyl and acid oligomers
mentioned above or any other blend depicted above. [0133]
CD-functionalized crosslinkers: for example epoxy/hydroxyl
functional crosslinkers such as the polyglycidyl ether of Sorbitol
DCE-358.RTM. from Dixie Chemical or blends of the hydroxyl
oligomers and epoxy crosslinkers mentioned above or any other blend
as depicted above.
[0134] Preferred functionalized oligomers have for example a weight
average molecular weight not exceeding about 3,000 with a
polydispersity not exceeding about 1.5; more preferred oligomers
have molecular weight not exceeding about 2,500 and polydispersity
not exceeding about 1.4; most preferred oligomers have molecular
weight not exceeding about 2,200, and polydispersity not exceeding
about 1.25.
[0135] Other additives for example also include polyaspartic
esters, which are the reaction product of diamines, such as,
isophorone diamine with dialkyl maleates, such as, diethyl
maleate.
[0136] Optionally, a hydroxyl-functional compound comprising at
least two hydroxyl-functional groups may be present in the curable
material. The hydroxyl-functional compound comprising at least two
hydroxyl-functional groups may for example be selected from
polyester polyols, polyether polyols, polyacrylate polyols,
polyurethane polyols, cellulose acetobutyrate, hydroxyl-functional
epoxy resins, alkyds, and dendrimeric polyols such as described in
WO 93/17060. Also, hydroxyl-functional oligomers and monomers, such
as castor oil and trimethylol propane, may be included. Interesting
polyols are acrylate polyols, e.g. the acrylate polyol
Setalux.RTM.1187 available from Nuplex Resins.
[0137] Coating compositions may be formulated into high solids
coating systems dissolved in at least one solvent. The solvent is
usually organic. Preferred solvents include aromatic hydrocarbons
such as petroleum naphtha or xylenes; ketones such as methyl amyl
ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone;
esters such as butyl acetate or hexyl acetate; and glycol ether
esters such as propylene glycol monomethyl ether acetate and the
like.
[0138] The compositions of this invention may additionally contain
a binder (f) of a noncyclic oligomer, i.e., one that is linear or
aromatic. Such noncyclic oligomers can include, for instance,
succinic anhydride- or phthalic anhydride-derived moieties in
hydroxyl oligomers and the like.
[0139] The compositions of the invention as coating compositions
can for example also contain as a binder an acrylic polymer of a
weight average molecular weight greater than 3,000, or a
conventional polyester such as SCD.RTM.-1040 from Etna Product Inc.
for improved appearance, sag resistance, flow and leveling and the
like. The acrylic polymer is for example composed of typical
monomers such as acrylates, methacrylates, styrene and the like and
functional monomers such as hydroxy ethyl acrylate, glycidyl
methacrylate, or gamma-methacrylylpropyl trimethoxysilane and the
like.
[0140] The coating compositions for example can also contain a
binder (f) of a dispersed acrylic component which is a polymer
particle dispersed in an organic media, which particle is
stabilized by what is known as steric stabilization. Hereafter, the
dispersed phase or particle, sheathed by a steric barrier, will be
referred to as the "macromolecular polymer" or "core". The
stabilizer forming the steric barrier, attached to this core, will
be referred to as the "macromonomer chains" or "arms".
[0141] The dispersed polymer contains about 10 to 90%, preferably
50 to 80%, by weight, based on the weight of the dispersed polymer,
of a high molecular weight core having a weight average molecular
weight of about 50,000 to 500,000. The preferred average particle
size is 0.1 to 0.5 .mu.m. The arms, attached to the core, make up
about 10 to 90%, preferably 10 to 59%, by weight of the dispersed
polymer, and have a weight average molecular weight of about 1,000
to 30,000, preferably 1,000 to 10,000. The macromolecular core of
the dispersed polymer is for example comprised of polymerized
acrylic monomer(s) optionally copolymerized with ethylenically
unsaturated monomer(s). Suitable monomers include styrene, alkyl
acrylate or methacrylate, ethylenically unsaturated monocarboxylic
acid, and/or silane-containing monomers. Such monomers as methyl
methacrylate contribute to a high Tg (glass transition temperature)
dispersed polymer, whereas such "softening" monomers as butyl
acrylate or 2-ethylhexylacrylate contribute to a low Tg dispersed
polymer. Other optional monomers are hydroxyalkyl acrylates or
methacrylates or acrylonitrile. Optionally, the macromolecular core
can be crosslinked through the use of diacrylates or
dimethacrylates such as allyl methacrylate or post reaction of
hydroxyl moieties with polyfunctional isocyanates. The macromonomer
arms attached to the core can contain polymerized monomers of alkyl
methacrylate, alkyl acrylate, each having 1 to 12 carbon atoms in
the alkyl group, as well as glycidyl acrylate or glycidyl
methacrylate or ethylenically unsaturated monocarboxylic acid for
anchoring and/or crosslinking. Typically useful hydroxy-containing
monomers are hydroxy alkyl acrylates or methacrylates as described
above.
[0142] Optionally, for example a ketone based chelating agent (as
further additive (d)) may be added to the coating composition.
Examples of these chelating agents include alpha-hydroxyl ketones,
fused aromatic beta-hydroxy ketones, dialkyi malonates, aceto
acetic esters, alkyl lactates, and alkyl pyruvates. The ketone
based chelating agent for example is used in an amount up to 10 wt.
% on solids, preferably up to 5 wt. %.
[0143] In one embodiment the coating composition additionally
comprises a pot life extending agent. A pot life extending agent is
particularly beneficial when the photolatent catalyst exhibits a
certain degree of catalytic activity also in the latent form. It
may also be the case that the photolatent catalyst contains
catalytically active impurities which deteriorate the pot life of
the composition. Pot life extending agents increase the pot life of
the coating composition, i.e. the time between the mixing of all
components and the moment when the viscosity becomes too high for
the composition to be applied. Pot life extending agents can
suitably be present in similar amounts as the photolatent catalysts
mentioned above. Preferred pot life extending agents have only a
limited or no negative impact on the drying speed of the coating
composition, in particular when curing the applied coating at
elevated temperature, such as 40 to 60.degree. C. Thus, these pot
life extending agents improve the balance of pot life and drying
speed. The pot life extending agent can also have a beneficial
effect on the appearance of the coating. Examples of suitable pot
life extending agents are carboxylic acid group-containing
compounds, such as acetic acid, propionic acid or pentanoic acid.
Aromatic carboxylic acid group-containing compounds are preferred,
in particular benzoic acid. Other suitable pot life extending
agents are phenolic compounds, tertiary alcohols such as tertiary
butanol and tertiary amyl alcohol, and thiol group-containing
compounds. It is also possible to use a combination of the
above-mentioned pot life extending agents, such as a combination of
an aromatic carboxylic acid group-containing compound and a thiol
group-containing compound or a mercapto carboxylic acid.
[0144] The composition according to the present invention may be a
water-borne composition, a solvent borne composition or a
solvent-free composition. Since the composition may be composed of
liquid oligomers, it is especially suitable for use as a high
solids composition or a solvent-free composition. Alternatively,
the coating composition of the present invention is an aqueous
powder coating dispersion wherein the isocyanate reactive compound
has a Tg above 20.degree. C. The coating composition may as well be
used in powder coating compositions and hot melt coatings
compositions. For example the theoretical volatile organic content
(VOC) in the composition is less than about 450 g/l, e.g. less than
about 350 g/l, or less than about 250 g/l.
[0145] The compositions of the invention, in particular as coating
compositions, can for example also contain conventional additives
(d) such as pigments, stabilizers, rheology control agents, flow
agents, toughening agents and fillers. Such additional additives
will, of course, depend on the intended use of the (coating)
composition.
[0146] The compositions according to the invention are typically
applied to a substrate by conventional techniques such as spraying,
electrostatic spraying, roller coating, curtain coating, dipping or
brushing. The present formulations are for example useful as a
clear coating for outdoor articles, such as automobile and other
vehicle body parts. The substrate optionally is for example
prepared with a primer and or a color coat or other surface
preparation prior to coating with the present compositions.
[0147] A layer of a coating composition is for example cured under
ambient conditions in the range of a few minutes to 24 hours, for
example 5 minutes to 3 h, preferably in the range of 30 minutes to
8 hours (depending on the type of radiation source), after
activating the latent catalyst e.g. by exposure to radiation, to
form a coating on the substrate having the desired coating
properties. One of skill in the art appreciates that the actual
curing time depends upon several parameters, including thickness,
latent catalyst concentration, ingredients in the formulation; and
it depends also upon any additional mechanical aids, such as, for
example fans that assist in continuously flowing air over the
coated substrate to accelerate the cure rate. If desired, the cure
rate may be further accelerated by heating the coated substrate at
temperatures generally in the range of from about 60.degree. C. to
150.degree. C. for a period of for example about 15 to 90 minutes.
The heating is for example performed by heating in an oven, by
subjecting the samples to hot air, by IR-exposure, by microwaves or
any other suitable means known in the art. The foregoing heating
step is particularly useful under OEM (Original Equipment
Manufacture) conditions. The cure time may also depend on other
parameters such as for example the humidity of the atmosphere.
[0148] The latent catalyst compounds and formulations of this
invention can for example be used for coating applications and
generally in areas where curing of polyurethane is required. For
example, the compositions are suitable as clear or pigmented
coatings in industrial and maintenance coating applications.
[0149] Additives (d) are for example additional coinitiators or
sensitizers which shift or broaden the spectral sensitivity. In
general these are aromatic carbonyl compounds, for example
benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin
derivatives or dyes such as eosine, rhodamine and erythrosine dyes
which improve the overall quantum yield by means, for example, of
energy transfer or electron transfer. Examples of suitable dyes
which can be added as coinitiators are triarylmethanes, for example
malachite green, indolines, thiazines, for example methylene blue,
xanthones, thioxanthones, oxazines, acridines or phenazines, for
example safranine, and rhodamines of the formula
##STR00028##
in which R is alkyl or aryl and R' is hydrogen or analkyl or aryl
radical, for example Rhodamine B, Rhodamine 6G or Violamine R, and
also Sulforhodamine B or Sulforhodamine G. Likewise suitable are
fluorones such as, for example, 5,7-diiodo-3-butoxy-6-fluorone.
[0150] Further specific examples of photosensitizers suitable as
component (d) are 3-(aroylmethylene)-thiazoline and
3-(aroylmethylene)-thiazoline derivatives and rhodanine
derivatives.
[0151] Specific examples of suitable sensitizers are known to the
person skilled in the art and are for example published in WO
06/008251, page 36, line 30 to page 38, line 8, the disclosure of
which is hereby incorporated by reference.
[0152] Particular preference is given to unsubstituted and
substituted benzophenones or thioxanthones. Examples of suitable
benzophenones are benzophenone,
4,4'-bis(dimethylamino)benzophenone,
4,4'-bis(diethylamino)benzophenone,
4,4'-bis(ethylmethyl-amino)benzophenone, 4,
4'-diphenylbenzophenone, 4,4'-diphenoxybenzophenone,
4,4'-bis(p-isopropylphenoxy)benzophenone, 4-methylbenzophenone,
2,4,6-trimethylbenzophenone, 4-phenylbenzophenone,
2-methoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide,
4-methoxy-3,3'-methylbenzophenone, isopropylthioxanthone,
chlorothioxanthone, 1-chloro-4-propoxythioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
1,3-dimethyl-2-(2-ethylhexyloxy)thioxanthone.
[0153] Likewise preferred are mixtures of benzophenones and/or
thioxanthones such as, for example, a mixture of benzophenone and
4-methylbenzophenone or of 4-methylbenzophenone and
2,4,6-trimethylbenzophenone.
[0154] Within the scope of the present invention also
radical-generating photoinitiators, such as hydroxyl ketones, amino
ketones, monacyl phosphine oxides, bisacylphosphine oxides and
oxime esters can be employed as sensitizers.
[0155] Further customary additives (d), depending on the intended
use, are optical brighteners, fillers, pigments, dyes, wetting
agents, levelling assistants, antistatics, flow improvers and
adhesion promoters, antioxidants, desiccants, light stabilizers,
e.g. UV-absorbers, for exam pie those of the hydroxybenzotriazole,
hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine
type. These compounds can be used individually or in mixtures, with
or without sterically hindered amines (HALS).
[0156] The compositions may also comprise dyes and/or white and
colored pigments. Depending on the kind of application organic as
well as anorganic pigments are used. Such additives are known to
the person skilled in the art, some examples are titan dioxide
pigments, e.g. of the rutile type or anatas type, carbon black,
zinc oxide, such as zink white, iron oxide, such as iron oxide
yellow, iron oxide red, chromium yellow, chromium green, nickel
titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate,
cadmiumyellow or cadmium red. Examples of organic pigments are
mono- or bisazo pigments, as well as metal complexes thereof,
phthalocyanine pigments, poly-cyclic pigments, such as perylene-,
anthraquinone-, thioindigo-, chinacridone- or triphenylmethane
pigments, as well as diketo-pyrrolo-pyrole-, isoindolinone-, e.g.
tetra-chlorisoindolinone-, isoindoline-, dioxazin-,
benzimidazolone- and chinophthalone pigments.
[0157] The pigments are employed alone or in combination in the
compositions according to the invention.
[0158] Depending on the intended use the pigments are used in
amount customary in the art, for example in an amount of 1-60% by
weight, or 10-30% by weight, based on the whole formulation.
[0159] The compositions may also comprise organic dyes of different
classes. Examples are azo dyes, methin dyes, anthraquinone dyes or
metal complex dyes. Customary concentrations are for example
0.1-20%, in particular 1-5%, based on the whole formulation.
[0160] The choice of additive is made depending on the field of
application and on properties required for this field. The
additives described above are customary in the art and accordingly
are added in amounts which are usual in the respective
application.
[0161] In some cases it may be advantageous to carry out heating
during or after exposure to light. In this way it is possible in
many cases to accelerate the crosslinking reaction. In the above
described processes according to the invention, instead of
irradiating with electromagnetic radiation the mixture comprising
the latent catalyst of the invention can be subjected to a heat
treatment. Another possibility, as mentioned above, is to irradiate
the reaction mixture with electromagnetic radiation and
simultaneously with irradiating or after the irradiation subject it
to a heat treatment.
[0162] Subject of the invention therefore also is a process as
described above, characterized in that instead of irradiating with
electromagnetic radiation the mixture is subjected to a heat
treatment, or the mixture is irradiated with electromagnetic
radiation and simultaneously with or after the irradiation
subjected to a heat treatment.
[0163] The compositions of the invention can be employed for
various purposes, for example as printing inks, as clearcoats, as
white paints, for example for wood, plastics or metal, as coatings,
inter alia for paper, wood, metal or plastic, as powder coatings,
as daylight-curable exterior coatings for marking buildings and
roads, for photographic reproduction processes, for holographic
recording materials, for image recording processes or for the
production of printing plates which can be developed using organic
solvents or aqueous-alkaline media, for the production of masks for
screen printing, as dental filling materials, as adhesives,
including pressure-sensitive adhesives and moisture curing silane
modified adhesives, for sealings, as laminating resins, as etch
resists or permanent resists and as solder masks for electronic
circuits, for potting components, for mouldings, for the production
of three-dimensional articles by mass curing (UV curing in
transparent moulds) or by the stereolithography process, as is
described, for example, in U.S. Pat. No. 4,575,330, for the
preparation of composite materials (for example styrenic
polyesters, which may contain glass fibres and/or other fibres and
other assistants) and other thick-layer compositions, for the
coating or encapsulation of electronic components, or as coatings
for optical fibres.
[0164] In surface coatings, it is common to use mixtures of a
prepolymer with polyunsaturated monomers which also contain a
monounsaturated monomer. The prepolymer here is primarily
responsible for the properties of the coating film, and varying it
allows the skilled worker to influence the properties of the cured
film. The polyunsaturated monomer functions as a crosslinker, which
renders the coating film insoluble. The monounsaturated monomer
functions as a reactive diluent, by means of which the viscosity is
reduced without the need to use a solvent.
[0165] The compositions according to the invention are also
suitable for use in uv-curing adhesives, e.g. in the preparation of
pressure-sensitive adhesives, laminating adhesives, hot-melt
adhesives, moisture-cure adhesives, silane reactive adhesives or
silane reactive sealants and the like, and related
applications.
[0166] Said adhesives can be hot melt adhesives as well waterborne
or solvent borne adhesives, liquid solventless adhesives or 2-part
reactive adhesives. In particular suitable are pressure-sensitive
adhesives (PSA), for example uv-curable hot melt pressure sensitive
adhesives. Said adhesives for example comprise at least one rubber
component, at least one resin component as tackyfier and at least
one oil component, for example in the weight ratio 30:50:20.
Suitable tackyfiers are natural or synthetic resins. The person
skilled in the art is aware of suitable corresponding compounds as
well as of suitable oil components or rubbers.
[0167] The pre-polymerized adhesives containing the isocyanates,
for example in blocked form, can for example be processed at high
temperature and coated onto the substrate following the hotmelt
process, afterwards full cure is achieved by an additional curing
step involving the blocked isocyanates, which is realized by
photoactivation of the photolatent catalyst.
[0168] Hotmelt adhesives are interesting as pressure sensitive
adhesives and suitable to re-place the use of solvent base
compositions, which from an environmental point of view are
unwanted. The hotmelt extrusion process in order to achieve the
high flow viscosity necessitates high application temperatures. The
compositions of the present invention comprising isocyanates are
suitable as crosslinkers in the preparation of a hotmelt coating,
where the crosslinkers enter into a chemical reaction with the
functional comonomers of the (meth)acrylate PSA. After the coating
operation, the PSAs are first crosslinked thermally, or
implementing the dual crosslinking mechanism, the PSA is
subsequently crosslinked with UV light. UV crosslinking irradiation
takes place by means of shortwave ultraviolet radiation in a
wavelength range from 200 to 400 nm, even expanding in the visible
range, e.g. up to 650 nm, depending on the source of the UV
radiation equipment, as well as on the photolatent metal catalyst.
Such systems and processes are for example described in US
2006/0052472, the disclosure of which hereby is incorporated by
reference.
[0169] The composition of the present invention is suitable for
application on a variety of substrates, e.g. it is especially
suitable for providing clear coatings in automotive OEM (Original
Equipment Manufacture) or refinish applications typically used in
coating car bodies. The coating composition of the present
invention can for example be formulated in the form of a clear
coating composition, pigmented composition, metallized coating
composition, basecoat composition, monocoat composition or a
primer. The substrate is for example prepared with a primer and or
a color coat or other surface preparation prior to coating with the
present compositions.
[0170] Suitable substrates for applying the coating composition of
the present invention include automobile bodies (or vehicle bodies
in general), any and all items manufactured and painted by
automobile sub-suppliers, frame rails, commercial trucks and truck
bodies, including but not limited to for example beverage bodies,
utility bodies, vehicle bodies, e.g. ready mix concrete delivery
vehicle bodies, waste hauling vehicle bodies, and fire and
emergency vehicle bodies, as well as any potential attachments or
components to such truck bodies, buses, farm and construction
equipment, truck caps and covers, commercial trailers, consumer
trailers, recreational vehicles, including but not limited to,
motor homes, campers, conversion vans, vans, pleasure vehicles,
pleasure craft snow mobiles, all terrain vehicles, personal
watercraft, motorcycles, bicycles, boats, and air-craft, etc.
[0171] The substrate further includes industrial and commercial new
construction and maintenance thereof; cement and wood floors; walls
of commercial and residential structures, such as for example
office buildings and homes; amusement park equipment; concrete
surfaces, such as parking lots and drive ways; asphalt and concrete
road surface, wood substrates, marine surfaces; outdoor structures,
such as bridges, towers; coil coating; railroad cars; printed
circuit boards; machinery; OEM tools; signage; fiberglass
structures; sporting goods and sporting equipment, e.g. golf balls,
ski, snowboards; etc. However, the composition of the present
invention may also generally be applied on substrates like for
example plastics, metals, glass, ceramics, etc. e.g. in it's
function as an adhesive (but not limited thereto).
[0172] The compositions of the present invention are also suitable
for "dual-cure" applications. Dual-cure is meant to be a system
which comprises heat-crosslinking components and UV-crosslinking
components as well, such as for example a 2K polyurethane (as
heat-curable component) and an acrylate component (as the
UV-curable component).
[0173] Said "dual-cure" compositions are cured by a combination of
exposure to radiation and heating, wherein the irradiation and
heating are either performed simultaneously or first the
irradiation step is performed, followed by heating, or, the
composition first is heated, followed by exposure to radiation.
[0174] The "dual-cure" compositions generally comprise an initiator
compound for the heat-curing component and a photoactive compound
according to the present invention for the photocuring step.
However, the compounds of the invention alone can function as
initiator for both systems heat-crosslinking components and
UV-crosslinking components as well.
[0175] The compositions of the invention are suitable, for example,
as coating materials for substrates of all kinds, examples being
wood, textiles, paper, ceramic, glass, plastics such as polyesters,
polycarbonates, polyethylene terephthalate, polyamides, polyolefins
or cellulose acetate, especially in the form of films, and also
metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or
SiO.sub.2, on which it is the intention to apply a protective
coating or, by imagewise exposure, an image.
[0176] The substrates can be coated by applying a liquid
composition, a solution, dispersion, emulsion or suspension to the
substrate. The choice of solvent and the concentration depend
predominantly on the type of composition and the coating process.
The solvent should be inert: in other words, it should not undergo
any chemical reaction with the components and should be capable of
being removed again after the coating operation, in the drying
process. Examples of suitable solvents are ketones, ethers and
esters, such as methyl ethyl ketone, isobutyl methyl ketone,
cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane,
tetrahydrofuran, 2-methoxyethanol, 2-ethoxy-ethanol,
1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl
acetate and ethyl 3-ethoxypropionate.
[0177] Using known coating processes, the solution is applied
uniformly to a substrate, for example by spin coating, dip coating,
knife coating, curtain coating, brushing, spraying--especially
electrostatic spraying--and reverse roll coating and by
electrophoretic deposition. It is also possible to apply the layer
to a temporary, flexible support and then to coat the final
substrate, for example a copper-clad circuit board, by means of
layer transfer via lamination.
[0178] The amount applied (layer thickness) and the nature of the
substrate (layer support) are functions of the desired field of
application. The range of layer thicknesses generally comprises
values from about 0.1 .mu.m to several mm, for example 1-2000
.mu.m, preferably 5 to 200 .mu.m, in particular 5-60 .mu.m (after
evaporation of the solvent).
[0179] The compositions according to the invention are also
suitable for use in electrodeposition paint or primer: an
electrodeposition paint generally consists of a resin containing
hydroxyl groups as a base resin and a polyisocyanate compound,
optionally blocked with a blocking agent, as a curing agent. The
electrodeposition step can be conducted, for example, under the
condition of load voltage of 50-400 kV by adjusting usually to
15-35.degree. C. the temperature of the electrodeposition bath
comprising the resin composition for electrodeposition paint which
has been diluted with deionized water etc. to a solid content
concentration of about 5-40% by weight and adjusted pH of the
system in the range of 4-9.
[0180] The film thickness of the electrodeposition coatings film
formable by using the resin composition for electrodeposition paint
is not particularly restricted. Preferably it generally is in the
range of 10-40 .mu.m based upon a cured film thickness. UV
crosslinking irradiation takes place by means of shortwave
ultraviolet radiation in a wavelength range from 200 to 650 nm,
depending on the UV photoactive moiety in the catalyst according to
the present invention and of the used photosensitizer. It is also
possible to simultaneously or afterwards submit the
electrodeposited paint to a thermal curing step. Examples of such
paints are described in US 2005/0131193 and US 2001/0053828, both
hereby are incorporated by reference.
[0181] The compositions of the present invention are also used to
prepare "powder coating compositions" or "powder coatings", either
thermal curing or radiation-curable curing ones. By "powder coating
compositions" or "powder coatings" is meant the definition as
described in "Ullmann's Encyclopedia of Industrial Chemistry, 5th,
Completely Revised Edition, Vol. A 18", pages 438 to 444 (1991) in
Section 3.4. That is powder coatings are formed by thermoplastic or
bakable, crosslinkable polymers, which are applied in powder form
to, predominantly metallic, substrates. The way in which the powder
is brought into contact with the workpiece that is to be coated
typifies the various application techniques, such as electrostatic
powder spraying, electrostatic fluidized-bed sintering, fixed bed
sintering, fluidized-bed sintering, rotational sintering or
centrifugal sintering. Preferred organic film-forming binders for
the powder coating compositions are stoving systems based, for
example, on epoxy resins, polyester-hydroxyalkylamides,
polyester-glycolurils, epoxy-polyester resins,
polyester-triglycidyl isocyanurates, hydroxy-functional
polyester-blocked polyisocyanates, hydroxy-functional
polyester-uretdiones, acrylate resins with hardener, or mixtures of
such resins.
[0182] Radiation-curable powder coatings are for example based on
solid resins and mono-mers containing reactive double bonds, for
example maleates, vinyl ethers, acrylates, acrylamides and mixtures
thereof. A UV-curable powder coating--in admixture with the
composition of the present invention--can for example be formulated
by mixing unsaturated polyester resins with solid acrylamides (for
example methyl methylacrylamidoglycolate), acrylates, methacrylates
or vinyl ethers and a free-radical photoinitiator, such
formulations being as described, for example, in the paper
"Radiation Curing of Powder Coating", Conference Proceedings,
Radtech Europe 1993 by M. Wittig and Th. Gohmann. The powder
coatings may also comprise binders as are described, for example,
in DE 4228514 and in EP 636669.
[0183] The powder coatings may additionally comprise white or
coloured pigments. For example, preferably rutile titanium dioxide
can be employed in concentrations of up to 50% by weight in order
to give a cured powder coating of good hiding power. The procedure
normally comprises electrostatic or tribostatic spraying of the
powder onto the substrate, for example metal or wood, melting of
the powder by heating, and, after a smooth film has formed,
radiation-curing of the coating with ultraviolet and/or visible
light.
[0184] The composition of the present invention for example further
may be employed for the preparation of printing inks. Printing inks
in general are known to the person skilled in the art, are used
widely in the art and are described in the literature. They are,
for example, pigmented printing inks and printing inks coloured
with dyes.
[0185] The radiation-sensitive compositions of the invention can
also be subjected to imagewise exposure. In this case they are used
as negative resists. They are suitable for electronics
(galvanoresists, etch resists and solder resists), for the
production of printing plates, such as offset printing plates,
flexographic and relief printing plates or screen printing plates,
for the production of marking stamps, and can be used for chemical
milling or as microresists in the production of integrated
circuits. There is a correspondingly wide range of variation in the
possible layer supports and in the processing conditions of the
coated substrates.
[0186] The term "imagewise" exposure relates both to exposure
through a photomask containing a predetermined pattern, for example
a slide, exposure by a laser beam which is moved under computer
control, for example, over the surface of the coated substrate and
so generates an image, and irradiation with computer-controlled
electron beams. Following the imagewise exposure of the material
and prior to developing, it may be advantageous to carry out a
brief thermal treatment, in which only the exposed parts are
thermally cured. The temperatures employed are generally
50-150.degree. C. and preferably 80-130.degree. C.; the duration of
the thermal treatment is generally between 0.25 and 10 minutes. A
further field of use for photocuring is that of metal coating, for
example the surface-coating of metal panels and tubes, cans or
bottle tops, and photocuring on polymer coatings, for example of
floor or wall coverings based on PVC.
[0187] Examples of the photocuring of paper coatings are the
colourless varnishing of labels, record sleeves or book covers.
[0188] The use of the compositions of the invention for preparing
shaped articles made from composite compositions is likewise of
interest. The composite composition is made up of a self-supporting
matrix material, for example a glass-fibre fabric, or else, for
example, of plant fibres [cf. K.-P. Mieck, T. Reussmann in
Kunststoffe 85 (1995), 366-370], which is impregnated with the
photocuring formulation. Shaped articles which are produced from
compositions according to the invention are of high mechanical
stability and resistance. The compositions of the invention can
also be used in moulding, impregnating and coating compositions, as
are described, for example, in EP 007086. Examples of such
compositions are fine coating resins on which stringent
requirements are placed with respect to their curing activity and
resistance to yellowing, or fibre-reinforced mouldings such as
planar or longitudinally or transversely corrugated light diffusing
panels.
[0189] The sensitivity of the novel compositions to radiation
generally extends from about 190 nm through the UV region and into
the infrared region (about 20,000 nm, in particular 1200 nm),
especially from 190 nm to 650 nm (depending on the photoinititator
moiety, optionally in combination with a sensitizer as described
hereinbefore) and therefore spans a very broad range. Suitable
radiation is present, for example, in sunlight or light from
artificial light sources. Consequently, a large number of very
different types of light sources are employed. Both point sources
and arrays ("lamp carpets") are suitable. Examples are carbon arc
lamps, xenon arc lamps, medium-, super high-, high- and
low-pressure mercury lamps, possibly with metal halide dopes
(metal-halogen lamps), microwave-stimulated metal vapour lamps,
excimer lamps, super-actinic fluorescent tubes, fluorescent lamps,
argon incandescent lamps, electronic flashlights, photographic
flood lamps, electron beams and X-rays. The distance between the
lamp and the substrate to be exposed in accordance with the
invention may vary depending on the intended application and the
type and output of lamp, and may be, for example, from 2 cm to 150
cm. Laser light sources, for example excimer lasers, such as
krypton F lasers for exposure at 248 nm are also suitable. Lasers
in the visible region can also be employed.
[0190] Alternatively, the actinic radiation is provided by light
emitting diodes (LED) or organic light emitting diodes (OLED), e.g.
UV light emitting diodes (UV-LED). Said LEDs allow instant on and
off switching of the radiation source. Further, UV-LEDs generally
have a narrow wavelength distribution and offer the possibility to
customize the peak wavelength and also provide an efficient
conversion of electric energy to UV radiation. As mentioned above,
depending on the light source used it is advantageous in many cases
to employ a sensitizer, as described above, whose absorption
spectrum coincides as closely as possible to the emission spectrum
of the radiation source.
[0191] The Ti-oxo-chelate compounds (and formulations) of the
present invention are stable against hydrolysis, provide a good
pot-life and a good photolatency in the compositions containing
these catalysts.
[0192] The examples which follow illustrate the invention in more
detail, without restricting the scope of the invention to said
examples only. Parts and percentages are, as in the remainder of
the description and in the claims, by weight, unless stated
otherwise. Where alkyl radicals having more than three carbon atoms
are referred to in the examples without any mention of specific
isomers, the n-isomers are meant in each case.
[0193] Preparation of the Catalysts:
[0194] The starting diisopropoxy-1,3-dionato titanium complexes are
prepared as described in WO2009/0501 15 and WO2011/032875.
Example 1.fwdarw.Catalyst 1
Preparation of
oxo-bis(4,4-dimethyl-1-(2,4,6-trimethylphenyl)-1,3-pentanedionato)-titani-
um
##STR00029##
[0196] In a 50 ml dry three-neck-flask 2.63 g (4 mmol) of
diisopropoxy-bis(4,4-dimethyl-1-(2,4,6-trimethylphenyl)-1,3-pentanedionat-
o)-titanium are dissolved in 10 ml hexane. 0.22 g (12 mmol) of
H.sub.2O are added and the reaction mixture is stirred at
50.degree. C. for 3 h. The reaction mixture is then evaporated and
dried under reduced pressure to give a solid residue which is
re-crystallized from diethyl ether to afford 0.98 g of the title
compound as a yellowish solid. M.p. 250-251.degree. C.
Example 2.fwdarw.Catalyst 2
Preparation of
oxo-bis(4,4-dimethyl-1-(3,4-dimethoxylphenyl)-1,3-pentanedionato)-titaniu-
m
##STR00030##
[0198] In a 50 ml dry three-neck-flask 0.78 g (1.13 mmol) of
diisopropoxy-bis(4,4-dimethyl-1-(3,4-dimethoxylphenyl)-1,3-pentanedionato-
)-titanium are dissolved in 5 ml acetone. 0.04 g (2.26 mmol) of
H.sub.2O are added and the reaction mixture is stirred at 500 for 6
h. The resulting suspension is then filtered and the filter cake is
dried under reduced pressure to yield 0.49 g of the title compound
as a yellowish solid. M.p. 237-240.degree. C.
Example 3.fwdarw.Catalysts 3-13
[0199] The catalysts 3-13 are prepared according to the method as
given in examples 1 and 2 for catalysts 1 and 2 using the
appropriate diisopropoxy-1,3-dionato titanium starting material.
The compounds and physical data are listed in table 1 below.
TABLE-US-00001 TABLE 1 starting material/prep- physical catalyst
aration method structure data 3 diisopropoxy-bis(4,4-di-
methyl-1-(4-dimethyl- aminophenyl)-1,3- pentanedionato)-titanium/
method of example 1 ##STR00031## orange solid; M.p. 279-281.degree.
C. 4 diisopropoxy-bis(4,4-di- methyl-1-(2,5-dimeth-
oxyphenyl)-1,3-pentane- dionato)-titanium/ method of example 1
##STR00032## yellow solid; M.p. 199-201.degree. C. 5
diisopropoxy-bis(4,4-di- methyl-1-(2,6-dimeth-
oxyphenyl)-1,3-pentane- dionato)-titanium/ method of example 2
##STR00033## yellow solid M.p. 296-298.degree. C. 6
diisopropoxy-bis(4,4-di- methyl-1-(3,5-dimeth-
oxyphenyl)-1,3-pentane- dionato)-Titanium/ method of example 1
##STR00034## yellow solid M.p. 251-253.degree. C. 7
dibutoxy-bis(4,4-dimeth- yl-1-(4-methoxyphenyl)-
1,3-pentanedionato)- titanium/ method of example 1 ##STR00035##
yellowish solid; M.p. 308-310.degree. C. 8 diisopropoxy-bis(4-
methyl-1-phenyl-1,3- pentanedionato)-titanium/ method of example 1
##STR00036## yellow solid M.p. 183-184.degree. C. 9
diisopropoxy-bis(1,1,1- trifluoro-4-phenyl-2,4-
butanedionato)-titanium/ method of example 1 ##STR00037## yellow
solid M.p. 296-297.degree. C. 10 diisopropoxy-bis(1,3-di-
phenyl-1,3-propane- dionato)-titanium/ method of example 2
##STR00038## yellow solid M.p. 335-337.degree. C. 11
diisopropoxy-bis(3-(1- methyl)cyclohexyl-1- phenyl)-1,3-propane-
dionato)-titanium/ method of example 1 ##STR00039## yellowish solid
M.p. 282-283.degree. C. 13 diisopropoxy-bis(4,4-
dimethyl-1-phenyl-1,3- pentanedionato)-titanium/ method of example
1 ##STR00040## yellowish solid M.p. 313.degree. C.
Catalyst 12
##STR00041##
[0200] is a commercially available compound.
APPLICATION EXAMPLES
[0201] The following commercially available 1, 3-diketones are used
in the application examples:
##STR00042##
[0202] Curing and Pot-Life of a Two Packs Polyurethane System Based
on a Polyacrylic Polyol and an Aliphatic Polyisocyanate:
[0203] The polyurethane is the reaction product of two basic
components: a polyol (Component A) and a polyisocyanate (Component
B). An organometallic photolatent catalyst is added to the total
composition of A and B in order to speed up the reaction of A with
B.
[0204] In the following examples A1 to A4, Component A includes all
ingredients other than the polyisocyanate. The photolatent catalyst
and the 1,3 diketone are dissolved carefully into Component A prior
to the addition of Component B.
Component A
TABLE-US-00002 [0205] 73.1 parts of a polyacrylate polyol (70% in
butyl acetate; Desmophen A HS 1 170 BA, provided by Bayer Material
Science) 2.3 parts of an additive blend (consisting of 0.9 parts of
a solution of polyacrylates as flow improvers, 0.7 parts of a
silicon defoamer and 0.7 parts of a polyether modified
dimethylpolysiloxane as silicon surface additive) 24.6 parts of
xylene/methoxypropylacetate/butylacetate (1/1/1)
Component B
[0206] Aliphatic polyisocyanate [(Hexamethylenediisocyanate-Trimer)
90% in solvent blend; Desmodur N 3390, provided by Bayer Material
Science]
[0207] The basic testing formulations are composed of:
TABLE-US-00003 7.52 parts of component A 2.00 parts of component
B
Example A1: Catalyst Efficiency Before and after Activation by UV
Light
[0208] The testing samples are prepared by adding the photolatent
Ti catalysts ("Catalyst") to 7.52 g of component A of the basic
testing formulation as described above.
[0209] After completing the mixing of component A with 2 g of
component B, the mixtures are applied with a 76.mu..eta. split
coater on two glass plates of 30 cm length. One plate is irradiated
using an UV processor from 1ST Metz (2 mercury lamps operated at
100 W/cm) at a belt speed of 5 m/min, whereas the second glass
plate is not irradiated. The reactivity of the mixtures is
determined by measuring the "tack free time" of the applied
formulation (coated glass plate) by means of a drying recorder from
Byk Gardner, where a nee-die is moving with a constant speed over
the coated substrate for 24 hrs. The recording is carried out in
the dark, at room temperature. The "tack free time" is the period
of time needed for the sample to cure in such a manner that no tack
is left on the surface upon touch of the needle from the
recorder.
[0210] The lower the value of the "tack free time", the faster is
the addition reaction of the polyol to the polyisocyanate.
[0211] The higher the difference between the value of the "tack
free time" of the irradiated sample and the non-irradiated sample
(with a tack free value of the irradiated sample, which is lower
than the one of the non-irradiated one), the more "photolatent" is
the catalyst. The catalysts which are used in the test as well as
the results are collected in the following table 1.
TABLE-US-00004 TABLE 1 Tack free time (stage 3/4) in hrs.
Catalyst/(g) No UV irradiation 2 .times. 100 W/cm @ 5 m/min
Catalyst 1/(0.0174) 13 7 Catalyst 2/(0.0185) 11 6.75 Catalyst
3/(0.0174) 10 6.25 Catalyst 4/(0.0185) 9.25 4.75 Catalyst
7/(0.0166) 9 5.5 Catalyst 8/(0.0139) 11 6 Catalyst 9/(0.0155) 10.5
7
Example A2: Formulation Stability (Pot-Life)
[0212] The testing samples are prepared by adding the Ti catalyst
("Catalyst") and 1,3-diketone free ligand ("Additive") to 7.52 g of
component A of the basic testing formulation of example A1. After
mixing component A with 2.0 g of component B, the visual pot-life
of the formulation (time where no change in viscosity is visible)
is observed: the gelled time, the time to considerable viscosity,
and the time to high viscosity are determined, while storing the
samples in dark flasks.
[0213] The catalysts and additives which are used in the test as
well as the results of the tests are collected in the following
table 2.
TABLE-US-00005 TABLE 2 Gelled Considerably Highly Time viscous
viscous Catalyst/(g) Additive/(g) (min.) (min.) (min.) -- --
>600 >3000 Catalyst 13/ -- 65 115 140 (0.059) Catalyst 13/
CAS 13988- 65 165 200 (0.059) 67-5/(0.007) Catalyst 13/ CAS 13988-
180 285 305 (0.059 67-5/(0.015) Catalyst 13/ CAS 13988- 510 < t
< 510 < t < 510 < t < (0.059) 67-5/(0.059) 960 960
960 Catalyst 13/ CAS 326-06- 270 390 460 (0.059) 7/(0.015) Catalyst
13/ CAS 120-46- 120 210 280 (0.059) 7/0.015 Catalyst 13/ CAS 18362-
210 330 390 (0.059) 64-6/(0.015) Catalyst 13/ CAS 1522-22- 120 240
280 (0.059) 1/(0.015) Catalyst 13/ CAS 22767- 240 390 510 (0.059)
90-4/(0.015) Catalyst 13/ CAS 1118- 180 300 390 (0.059)
71-4/(0.015) Catalyst 8/ -- 120 210 255 (0.055) Catalyst 8/ CAS
13988- 180 300 390 (0.055) 67-5/(0.014) Catalyst 12/ -- 300 510 540
< t < (0.054) 990 Catalyst 12/ CAS 1118- 540 < t < 540
< t < 540 < t < (0.054) 71-4/(0.013) 990 990 990
Catalyst 12/ CAS 13988- 540 < t < 540 < t < 540 < t
< (0.054) 67-5/(0.013) 990 990 990
Example A 3: Formulation Stability--Shelf-Life (Viscosity
Evolution)
[0214] The testing samples are prepared by adding photolatent Ti
catalyst ("Catalyst"), and 1, 3-diketone free ligand (CAS
13988-67-5) to 7.52 g of component A of the basic testing
formulation of example A1. The amount of ligand is adjusted to have
the following weight ratios between the organometallic photolatent
catalyst and the ligand: 70/30, 80/20.
[0215] After admixing component A with 2 g of component B, the
mixtures are stored in the dark at room temperature. The shelflife
of each formulation is monitored by measuring the viscosity at
25.degree. C. by means of a viscometer from Epprecht
Instruments+Control AG. The measurements are done after the
preparation of the formulation and each hour for 7 h. The viscosity
increases with the time. The lower the increase of the viscosity,
the longer is the shelflife of the formulation and consequently the
larger is the working window. The catalyst and ligand which are
used in the experiment as well as results are presented in the
following table 3.
TABLE-US-00006 TABLE 3 Catalyst (g)/ Viscosity at 25.degree. C.
(poises) Ligand CAS (g) Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h
Catalyst 2 (0.0185) -- 1.4 2.7 4.3 7.8 16.6 35.2 ## ## Catalyst 2
(0.0185)/ 80/20 1.2 1.5 1.9 2.4 3.1 3.6 5 58 13988-67-5 (0.0046)
Catalyst 2 (0.0185)/ 70/30 1.2 1.5 1.8 2 2.5 2.9 3.5 4 13988-67-5
(0.0079) Catalyst 3 (0.0174) -- 1.6 3.5 7.4 16 52 ## ## ## Catalyst
3 (0.0174)/ 80/20 1.1 2 3 4.2 6 9 12.8 17.6 13988-67-5 (0.0044)
Catalyst 3 (0.0174)/ 70/30 1.1 1.8 3 3.8 5 7 10 12.4 13988-67-5
(0.0075) Catalyst 4 (0.0185) -- 1.8 3.8 6.5 28 ## ## ## ## Catalyst
4 (0.0185)/ 80/20 1.1 2.1 2.8 4 6.1 9.3 12 16 13988-67-5 (0.0046)
Catalyst 4 (0.0185)/ 70/30 1.1 1.7 2.5 3.5 4.2 5.8 7.1 8.8
13988-67-5 (0.0079) Catalyst 7 (0.0166) -- 1.6 3.3 6 13 34.4 ## ##
## Catalyst 7 (0.0166)/ 80/20 1.1 1.7 2.4 3.5 4.2 5.8 8 10.8
13988-67-5 (0.0042) Catalyst 7 (0.0166)/ 70/30 1.2 1.5 2.1 2.8 3.6
5.6 7 7.8 13988-67-5 (0.0071) ## Gelled
Example A 4: Ratio "Catalyst/Ligand" Efficiency Before and after
Activation by UV-Light
[0216] The testing samples are prepared by adding photolatent Ti
catalysts and 1,3-diketone free ligand (CAS 13988-67-5) to 7.52 g
of component A of the basic testing formulation of example A1. The
amount of ligand is adjusted to have the following weight ratios
between the organometallic photolatent catalyst and ligand: 70/30,
80/20.
[0217] After mixing component A with 2 g of component B, the
mixtures are applied with a 76 .mu.m split coater on two glass
plates of 30 cm length. One plate is irradiated using a UV
processor from 1ST Metz (2 mercury lamps operated at 100 W/cm) at a
belt speed of 5 m/min, whereas the second one is not irradiated.
The reactivity of the mixtures is determined by measuring the "tack
free time". Therefore the samples are set up on a drying recorder
from ByK Gardner, where a needle is moving with a constant speed
for 24 h over the coated substrate. The recording is carried out in
the dark, at room temperature. The "tack free time" is the period
of time needed for the sample to cure in such a manner that no tack
is left on the surface upon touch of the needle in the
recorder.
[0218] The lower the value of the "tack free time", the faster is
the reaction of the polyol with the isocyanate.
[0219] The higher the difference between the value of the "tack
free time" of the irradiated sample and the non-irradiated sample
(with a tack free value of the irradiated sample, which is lower
than the one of the non-irradiated one), the more "photolatent" is
the catalyst. The catalysts and ligand which are used in the test
as well as the results are collected in the following table 4.
TABLE-US-00007 TABLE 4 Catalyst (g) Tack free time (stage 3/4) h
ligand (g) Ratio No irradiation 2 .times. 100 W 5 m/min Catalyst 2
(0.0185)/ 80/20 16 13 CAS 13988-67-5 (0.0046) Catalyst 2 (0.0185)/
70/30 17 11.5 CAS 13988-67-5 (0.0079) Catalyst 3 (0.0174)/ 80/20
14.5 11 CAS 13988-67-5 (0.0044) Catalyst 3 (0.0174)/ 70/30 13.5 9.5
CAS 13988-67-5 (0.0075) Catalyst 4 (0.0185)/ 80/20 14 8 CAS
13988-67-5 (0.0046) Catalyst 4 (0.0185)/ 70/30 14.5 6.5 CAS
13988-67-5 (0.0079) Catalyst7 (0.0166)/ 80/20 12.5 9.75 CAS
13988-67-5 (0.0042) Catalyst7 (0.0166)/ 70/30 14.5 9.75 CAS
13988-67-5 (0.0071)
[0220] In the following Example A5 Component A' includes all
ingredients other than the polyisocyanate. The photolatent catalyst
(Catalyst 12) alone or in combination with 1,3 diketone (CAS11
18-71-4) is added into Component A' prior to the addition of
Component B'.
Component A'
TABLE-US-00008 [0221] 104 parts of a polyacrylate polyol (80% in
butylacetate; Joncryl .RTM.507, provided by BASF SE) 1.2 parts of
an organically modified polysiloxane, EFKA .RTM. 3030, used as
levelling agent 51.2 parts of Butylacetate (BuAc)
Component B'
[0222] Aliphatic polyisocyanate
[(Hexamethylenediisocyanate-Trimer), 100% solid; Basonat.RTM. HI
100, provided by BASF SE]
[0223] The basic testing formulations are composed of:
TABLE-US-00009 40 parts of component A' 10.24 parts of component
B'
[0224] Prior to their addition in the Component A', the following
catalytic solutions containing the catalyst and the ligand are
prepared:
TABLE-US-00010 Catalyst 12/CAS Catalyst 12 1118-71-4 (70/30) (10%
in BuAc) (50% in BuAc) Catalyst 12 10 35 CAS 1118-71-4 -- 15
butylacetate (BuAc) 90 50 % metal 1.10% 3.90%
Example A5: Reactivity after UV-Exposure of Catalyst 12 with and
without Addition of Ligand CAS 1 118-71-4
[0225] The testing samples are prepared by adding the catalytic
solutions, described above to component A' of the basic testing
formulation.
[0226] After completing the mixing of component A' with 10.24 of
component B', the mixtures are applied with a 76 .mu.m split coater
on three glass plates of 30 cm length. One plate is three times in
a row, irradiated using an UV processor from 1ST Metz, type
BLK-U-30-2.times.1-SS-tr-N2 (1 mercury lamp operated at 100 W/cm)
at a belt speed of 10 m/min, the second plate is irradiated during
6 minutes under Dr. Hoenle Lamp-Type UVA spot 400T (distance is 20
cm), whereas the third glass plate is not irradiated. The
reactivity of the mixtures is determined by measuring the "tack
free time" of the applied formulation (coated glass plate) by means
of a drying recorder from Byk Gardner, where a needle is moving
with a constant speed over the coated substrate for 24 hrs. The
recording is carried out in the dark, at room temperature. The
"tack free time" is the period of time needed for the sample to
cure in such a manner that no tack is left on the surface upon
touch of the needle from the recorder.
[0227] The lower the value of the "tack free time", the faster is
the addition reaction of the polyol to the polyisocyanate.
[0228] The higher the difference between the value of the "tack
free time" of the irradiated sample and the non-irradiated sample
(with a tack free value of the irradiated sample, which is lower
than the one of the non-irradiated one), the more "photolatent" is
the catalyst. The catalysts which are used in the test as well as
the results are collected in the following table 5.
TABLE-US-00011 TABLE 5 Tack free time (stage 3/4) in hrs. No UV 3
passes under 6 min under Catalyst (g) irradiation 1 .times. 100
W/cm @ 10 m/min UVA spot Catalyst 12 21 14.5 4.75 (10% in BuAc)
0.716 g Catalyst 12 18.5 16 6.75 (10% in BuAc) 0.358 g Catalyst
12/CAS 16.25 9 3.25 1118-71-4 (70/30) (50% in BuAc) 0.2 g
Example A6: Adhesive Formulation for Film to Film Lamination
[0229] The solventless reactive polyurethane test adhesive is a
common system for film to film lamination in the flexible packaging
industry. Prior to the application 14 parts of the isocyanate
component of the solventless adhesive are dissolved in 7 parts
ethylacetate and then 4 parts of the hydroxy component are added
and mixed. The photolatent catalyst 12 is mixed into the hydroxy
component.
[0230] The adhesive is knife-coated in a dry layer thickness of 2.5
g/m.sup.2 (solids) onto various commercially available polymer
films. After being coated the samples are dried with a stream of
hot air and then treated with UV light by a standard mercury medium
pressure vapour lamp. The coated polymer films are laminated to a
second polymer film in a calander at 23.degree. C. and under a
pressure of 6.5 bar. The prepared film-to-film laminates are well
adhering.
* * * * *