U.S. patent application number 09/007681 was filed with the patent office on 2001-10-04 for photoactivatable nitrogen-containing bases based on alpha-amino ketones.
Invention is credited to HALL-GOULLE, VERONIQUE, TURNER, SEAN COLM.
Application Number | 20010027253 09/007681 |
Document ID | / |
Family ID | 4180006 |
Filed Date | 2001-10-04 |
United States Patent
Application |
20010027253 |
Kind Code |
A1 |
HALL-GOULLE, VERONIQUE ; et
al. |
October 4, 2001 |
PHOTOACTIVATABLE NITROGEN-CONTAINING BASES BASED ON ALPHA-AMINO
KETONES
Abstract
The invention relates to organic compounds having a molecular
weight of less than 1000 comprising at least one structural unit of
the formula (I) 1 in which R.sub.1 is an aromatic or heteroaromatic
radical which is capable of absorbing light in the wavelength range
from 200 to 650 nm and in doing so brings about cleavage of the
adjacent carbon-nitrogen bond. The compounds represent
photoinitiators for base-catalyzable reactions. Other subjects of
the invention are base-polymerizable or crosslinkable compositions
comprising compounds having a structural unit of the formula 1, a
method of implementing photochemically induced, base-catalyzed
reactions, and the use of the compounds as photoinitiators for
base-catalyzed reactions.
Inventors: |
HALL-GOULLE, VERONIQUE;
(BERN, CH) ; TURNER, SEAN COLM; (BERKLEY,
CA) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
JOANN L VILLAMIZAR
540 WHITE PLAINS ROAD
TARRYTOWN
NY
10591
|
Family ID: |
4180006 |
Appl. No.: |
09/007681 |
Filed: |
January 15, 1998 |
Current U.S.
Class: |
544/235 ;
427/558; 544/237; 544/238; 544/282; 544/405 |
Current CPC
Class: |
C08K 5/17 20130101; C07D
487/04 20130101; B33Y 70/00 20141201; C08L 91/06 20130101 |
Class at
Publication: |
544/279 ;
544/282 |
International
Class: |
C07D 471/00; C07D
239/70 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 22, 1997 |
CH |
133/97 |
Claims
What is claimed is:
1. An organic compound having a molecular weight of less than 1000
comprising at least one structural unit of the formula (II) 54in
which R.sub.1 is an aromatic or heteroaromatic radical capable of
absorbing light in the wavelength range from 200 to 650 nm and in
so doing brings about cleavage of the adjacent carbon-nitrogen
bond.
2. An organic compound according to claim 1, wherein the structural
unit of the formula (I) comprises compounds of the formula (II)
55R.sub.1 is an aromatic or heteroaromatic radical which is capable
of absorbing light in the wavelength range from 200 to 650 nm and
in doing so brings about cleavage of the adjacent carbon-nitrogen
bond; R.sub.2 and R.sub.3 independently of one another are
hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.3-C.sub.18alkynyl or phenyl and, if R.sub.2 is hydrogen or
C.sub.1-C.sub.18alkyl, R.sub.3 is additionally a group
--CO--R.sub.14 in which R.sub.14 is C.sub.1-C.sub.18alkyl or
phenyl; or R.sub.1 and R.sub.3, together with the carbonyl group
and the C atom to which R.sub.3 is attached, form a
benzocyclopentanone radical; R.sub.5 is C.sub.1-C.sub.18 alkyl or
NR.sub.15R.sub.16; R.sub.4, R.sub.6, R.sub.7, R.sub.15 and R.sub.16
independently of one another are hydrogen or C.sub.1-C.sub.18alkyl;
or R.sub.4 and R.sub.6-together form a C.sub.2-C.sub.12alkylene
bridge or R.sub.5 and R.sub.7 together, independently of R.sub.4
and R.sub.6, form a C.sub.2-C.sub.12alkylene bridge or, if R.sub.5
is NR.sub.15R.sub.16, R.sub.16 and R.sub.7 together form a
C.sub.2-C.sub.12alkylene bridge.
3. An organic compound according to claim 1, wherein R.sub.1 is an
aromatic radical which is unsubstituted or substituted one or more
times by C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.3-C.sub.18alkynyl, C.sub.1-C.sub.18haloalkyl, NO.sub.2,
NR.sub.8R.sub.9, N.sub.3, OH, CN, OR.sub.10, SR.sub.10,
C(O)R.sub.11, C(O)OR.sub.12 or halogen which is selected from the
group consisting of phenyl, naphthyl, phenanthryl, anthracyl,
pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl,
5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl,
naphtho[2,3-b]thienyl, thiathrenyl, dibenzofuryl, chromenyl,
xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl,
pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl,
isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyi,
quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,
cinnolinyl, pteridinyl, carbazolyl, .beta.-carbolinyl,
phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl,
phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl,
terphenyl, stilbenyl, fluorenyl or phenoxazinyl, or R.sub.1 is a
radical of the formulae A, B or C 5657in which R.sub.13 is
C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18haloalkyl, NO.sub.2,
NR.sub.8R.sub.9, OH, CH, OR.sub.10, SR.sub.10, C(O)R.sub.11,
C(O)OR.sub.12 or halogen; R.sub.8, R.sub.9, R.sub.10, R.sub.11 and
R.sub.12 are hydrogen or C.sub.1-C.sub.18alkyl; and n is 0 or a
number 1, 2 or 3.
4. An organic compound according to claim 1, wherein R.sub.1 is
phenyl, naphthyl, anthracyl, thioxanthyl, dibenzofuryl or pyrenyl,
the radicals phenyl, naphthyl, anthracyl, thioxanthyl and pyrenyl
being unsubstituted or being substituted one or more times by CN,
N.sub.3, NR.sub.8R.sub.9, halogen, NO.sub.2, CF.sub.3, SR.sub.10 or
OR.sub.10, or R.sub.1 is a radical of the formulae A, B or C 58in
which n is 0 and the radicals R.sub.8, R.sub.9, R.sub.10 and
R.sub.13 are as defined in claim 3.
5. An organic compound according to claim 2, wherein R.sub.2 and
R.sub.3 independently of one another are hydrogen,
C.sub.1-C.sub.6alkyl or phenyl.
6. A compound according to claim 2, wherein R.sub.4 and R.sub.6
together form a C.sub.2-C.sub.6alkylene bridge.
7. A compound according to claim 2, wherein R.sub.5 and R.sub.7
form a C.sub.2-C.sub.6alkylene bridge or, if R.sub.5 is
NR.sub.15R.sub.16, R.sub.16 and R.sub.7 together form a
C.sub.2-C.sub.6alkylene bridge.
8. A compound of the formula (II) according to claim 2, wherein
R.sub.1 is phenyl, naphthyl, anthracyl, thioxanthyl, dibenzofuranyl
or pyrenyl, the phenyl radical being unsubstituted or being
substituted one or more times by CN, NR.sub.8R.sub.9, N.sub.3,
NO.sub.2, CF.sub.3, halogen, SR.sub.10 or OR.sub.10, or R.sub.1 is
a radical of the formulae A, B or C 59n is 0 and the radicals,
R.sub.8, R.sub.9, R.sub.10 and R.sub.13 are hydrogen or
C.sub.1-C.sub.14alkyl; R.sub.2 and R.sub.3 are hydrogen or
C.sub.1-C.sub.6alkyl or phenyl; or R.sub.1 and R.sub.3, together
with the carbonyl group and the C atom to which R.sub.3 is
attached, form a benzocyclopentanone radical; R.sub.4, R.sub.6 and
R.sub.7 independently of one another are hydrogen or
C.sub.1-C.sub.6alkyl; R.sub.5 is C.sub.1-C.sub.6alkyl or
NR.sub.15R.sub.16, where R.sub.15 and R.sub.16 are hydrogen or
C.sub.1-C.sub.6alkyl; or R.sub.4 and R.sub.6 together form a
C.sub.2-C.sub.6alkylene bridge; or, independently of R.sub.4 and
R.sub.6, R.sub.5 and R.sub.7 together form a
C.sub.2-C.sub.6alkylene bridge or, if R.sub.5 is NR.sub.15R.sub.16,
R.sub.16 and R.sub.7 together form a C.sub.2-C.sub.6alkylene
bridge.
9. A process for preparing a compound having the structural unit of
the formula I according to claim 1, which comprises reacting a
compound comprising a structural unit of the formula III 60with a
compound comprising a structural unit of the formula IV 61in which
R.sub.1 is as defined in claim 1 and Halogen is F, Cl, Br or I.
10. A process for preparing a compound of the formula II according
to claim 2, which comprises reacting a compound of the formula V
62with a compound of the formula VI 63in which R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are as defined in
claim 2 and Halogen is F, Cl, Br or I.
11. A process for preparing a compound of the formula VII, 64which
comprises exposing a compound of the formula II according to claim
2 to light having a wavelength from 200 nm to 650 nm.
12. A composition comprising A) at least one compound having a
structural unit of the formula II according to claim 1 and B) at
least one organic compound capable of a base-catalysed addition or
substitution reaction.
13. A composition according to claim 12, wherein component B) is an
anionically polymerizable or crosslinkable organic material.
14. A composition according to claim 12, wherein component B) is
one of the following systems: b) a two-component system comprising
hydroxyl-containing polyacrylates, polyesters and/or polyethers and
aliphatic or aromatic polyisocyanates; c) a two-component system
comprising functional polyacrylates and a polyepoxide, where the
polyacrylate contains carboxyl or anhydride groups; i) a
two-component system comprising epoxy-containing polyacrylates and
carboxyl-containing polyacrylates; m) a two-component system
comprising a (poly)alcohol and a (poly)isocyanate, n) a
two-component system comprising an .alpha.,.beta.-ethylenically
unsaturated carbonyl compound and a compound having activated
CH.sub.2 groups.
15. A composition according to claim 12, wherein component B) is an
epoxy system.
16. A composition according to claim 12, wherein component A) is
present in an amount of from 0.01 to 10% by weight based on
component B).
17. A composition according to claim 12, which additionally
comprises a sensitizer selected from the group consisting of
thioxanthones, oxazines, acridines, phenazines and rhodamines.
18. A method of implementing base-catalysed reactions, which
comprises subjecting A) at least one compound comprising a
structural unit of the formula (I) 65according to claim 1, in which
R, is an aromatic or heteroaromatic radical which is capable of
absorbing light in the wavelength range from 200 to 650 nm and in
doing so brings about cleavage of the adjacent carbon-nitrogen
bond; and B) at least one organic compound which is capable of a
base-catalysed reaction to irradiation with light having a
wavelength of from 200 nm to 650 nm.
19. A method according to claim 18, wherein heating is carried out
during or after exposure to light.
20. A coated substrate which has been coated on at least one
surface with a composition according to claim 12.
21. A polymerized or crosslinked composition according to claim 13.
Description
[0001] The invention relates to .alpha.-amino ketones which can be
converted photochemically into amidine derivatives, to a process
for their preparation and to a process for the photochemical
preparation of the amidine derivatives. Further subjects of the
invention are base-polymerizable or crosslinkable compositions
comprising these .alpha.-amino ketones, a method of implementing
photochemically induced, base-catalysed reactions, and the use of
the .alpha.-amino ketones as photoinitiators for base-catalysed
reactions.
[0002] The photolytic cleavage of specific .alpha.-amino ketones
into free radicals and the photopolymerization of olefinically
unsaturated monomers or oligomers which this initiates have long
been known and are described, for example, in U.S. Pat. No.
5,077,402.
[0003] In addition to free-radically polymerizable oligomers or
monomers, base-catalysable systems have been disclosed in
particular for photolithographic processes. These systems require a
photoinitiator which on exposure to light releases a base. D. R.
MacKean et al., Polym. Mater. Sci. Eng. (1992), 66, 237-238 report,
for example, on the photostructuring of polyimide using specific
carbamates as photoinitiators.
[0004] It has now surprisingly been found that certain
.alpha.-amino ketones which comprise a structural unit of the
formula (I) 2
[0005] release an amidine group on exposure to visible or UV light.
This amidine group is sufficiently basic to initiate a large number
of base-catalysable reactions, especially polymerization reactions.
The compounds are of high sensitivity and through the choice of the
substituent R.sub.1 the absorption spectrum can be varied within a
wide range.
[0006] The compounds make it possible to prepare so-called one-pot
systems with base-catalysable oligomers or monomers having an
extremely long storage life. A polymerization reaction, for
example, is initiated only after exposure to light. The systems can
be formulated with little or no solvent, since the compounds can be
dissolved in the monomers or oligomers without being affected. The
active catalyst is formed only after exposure to light. These
systems can be employed for numerous purposes, such as for
finishes, coatings, moulding compounds or photolithographic
reproductions.
[0007] The invention provides organic compounds having a molecular
weight of less than 1000, comprising at least one structural unit
of the formula (I) 3
[0008] in which R.sub.1 is an aromatic or heteroaromatic radical
capable of absorbing light in the wavelength range from 200 to 650
nm and in doing so brings about cleavage of the adjacent
carbon-nitrogen bond. The structural unit of the formula (I)
features a divalent and monovalent nitrogen atom and a divalent and
monovalent carbon atom, the nitrogen atoms being in .beta. position
relative to one another.
[0009] By aromatic or heteroaromatic radicals R.sub.1 are meant
those which conform to the Huckel 4n+2 rule.
[0010] The absorption maximum can be varied within a wide range
through the choice of the aromatic or heteroaromatic radical
R.sub.1, and so the photosensitivity of the compounds can be
shifted from the UV into the daylight region.
[0011] Preference is given to organic compounds in which the
structural unit of the formula (I) comprises compounds of the
formula (II) 4
[0012] in which
[0013] R.sub.1 is an aromatic or heteroaromatic radical which is
capable of absorbing light in the wavelength range from 200 to 650
nm and in doing so brings about cleavage of the adjacent
carbon-nitrogen bond;
[0014] R.sub.2 and R.sub.3 independently of one another are
hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.3-C.sub.18alkynyl or phenyl and, if R.sub.2 is hydrogen or
C.sub.1-C.sub.18alkyl, R.sub.3 is additionally a group
--CO--R.sub.14 in which R.sub.14 is C.sub.1-C.sub.18alkyl or
phenyl; or R.sub.1 and R.sub.3, together with the carbonyl group
and the C atom to which R.sub.3 is attached, form a
benzocyclopentanone radical;
[0015] R.sub.5 is C.sub.1-C.sub.18alkyl or NR.sub.15R.sub.16;
[0016] R.sub.4, R.sub.6, R.sub.7, R.sub.15 and R.sub.16
independently of one another are hydrogen or C.sub.1-C.sub.18alkyl;
or
[0017] R.sub.4 and R.sub.6 together form a C.sub.2-C.sub.12alkylene
bridge or
[0018] R.sub.5 and R.sub.7 together, independently of R.sub.4 and
R.sub.6, form a C.sub.2-C.sub.12alkylene bridge or, if R.sub.5 is
NR.sub.15R.sub.16, R.sub.16 and R.sub.7 together form a
C.sub.2-C.sub.12alkylene bridge.
[0019] Alkyl in the various radicals having up to 18 carbon atoms
is a branched or unbranched radical such as methyl, ethyl, propyl,
isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl,
n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl.
Preference is given to alkyl having 1 to 12, especially 1 to 6
carbon atoms.
[0020] Alkenyl having 3 to 18 carbon atoms is a branched or
unbranched radical such as propenyl, 2-butenyl, 3-butenyl,
isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl,
n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or
n-4-octadecenyl. Preference is given to alkenyl having 3 to 12,
especially 3 to 6 carbon atoms.
[0021] Alkynyl having 3 to 18 carbon atoms is a branched or
unbranched radical such as propynyl --CH.sub.2--C.ident.CH),
2-butynyl, 3-butynyl, n-2-octynyl, or n-2-octadecynyl. Preference
is given to alkynyl having 3 to 12, especially 3 to 6 carbon
atoms.
[0022] The C.sub.2-C.sub.12alkylene bridge is ethylene, propylene,
butylene, pentylene, hexylene, heptylene, octylene, nonylene,
decylene, undecylene or dodecylene.
[0023] R.sub.1 is preferably an aromatic radical which is
unsubstituted or substituted one or more times by
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.3-C.sub.18alkynyl, C.sub.1-C.sub.18haloalk- yl, NO.sub.2,
NR.sub.8R.sub.9, N.sub.3, OH, CN, OR.sub.10, SR.sub.10,
C(O)R.sub.11, C(O)OR.sub.12 or halogen and is selected from the
group consisting of phenyl, naphthyl, phenanthryl, anthracyl,
pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl,
5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl,
naphtho[2,3-b]thienyl, thiathrenyl, dibenzofuryl, chromenyl,
xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl,
pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl,
isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyi,
quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,
cinnolinyl, pteridinyl, carbazolyl, .beta.-carbolinyl,
phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl,
phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl,
terphenyl, stilbenyl, fluorenyl or phenoxazinyl, or R.sub.1 is a
radical of the formulae A, B or C 5 6
[0024] in which
[0025] R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 are
hydrogen or C.sub.1-C.sub.18alkyl;
[0026] R.sub.13 is C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18haloalkyl, N0.sub.2,
NR.sub.8R.sub.9, OH, CN, OR.sub.10, SR.sub.10, C(O)R.sub.11,
C(O)OR.sub.12 or halogen; and n is 0 or a number 1, 2 or 3.
[0027] Examples of C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl
and C.sub.3-C.sub.18alkynyl have already been indicated above.
[0028] Halogen is fluorine, chlorine, bromine or iodine.
[0029] Examples of C.sub.1-C.sub.18haloalkyl are fully or partly
halogenated C.sub.1-C.sub.18alkyl. The halogen (halo) here is F,
Cl, Br, or I. Examples are the positional isomers of mono- to
decafluoropentyl, mono- to octafluorobutyl, mono- to
hexafluoropropyl, mono- to tetrafluoroethyl and mono- and
difluoromethyl and also the corresponding chloro, bromo and iodo
compounds. Preference is given to the perfluorinated alkyl
radicals. Examples of these are perfluoropentyl, perfluorobutyl,
perfluoropropyl, perfluoroethyl and, in particular,
trifluoromethyl.
[0030] Examples of the NR.sub.8R.sub.9 amino group are the
respective monoalkyl or dialkylamino groups such as methylamino,
ethylamino, propylamino, butylamino, pentylamino, hexylamino,
octadecylamino, dimethylamino, diethylamino, dipropylamino,
diisopropylamino, di-n-butylamino, di-isobutylamino, dipentylamino,
dihexylamino or dioctadecylamino. Further dialkylamino groups are
those in which the two radicals independently of one another are
branched or unbranched, for example methylethylamino,
methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino,
methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino,
ethylisobutylamino, ethyl-tert-butylamino, isopropyl-n-butylamino
or isopropylisobutylamino.
[0031] The alkoxy group OR.sub.10 having up to 18 carbon atoms is a
branched or unbranched radical such as methoxy, ethoxy, propoxy,
isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,
heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or
octadecyloxy. Preference is given to alkoxy having 1 to 12,
especially 1 to 8, for example 1 to 6 carbon atoms.
[0032] Examples of the thioalkyl group SR.sub.10 are thiomethyl,
thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl,
thioheptyl, thiooctyl or thiooctadecyl, it being possible for the
alkyl radicals to be linear or branched.
[0033] Examples of the radical R.sub.1 are phenyl, naphthyl,
phenanthryl, anthracyl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl,
5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl,
naphtho[2,3-b]thienyl, thiathrenyl, dibenzofuryl, chromenyl,
xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl,
pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl,
indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl,
phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,
cinnolinyl, pteridinyl, carbazolyl, .beta.-carbolinyl,
phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl,
phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl,
biphenyl, stilbenyl, terphenyl, fluorenyl, phenoxazinyl,
methoxyphenyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl,
bromophenyl, tolyl, xylyl, mesityl, nitrophenyl,
dimethylaminophenyl, diethylaminophenyl, aminophenyl,
diaminophenyl, 1-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl,
1-methylnaphthyl, 2-methyinaphthyl, 1-methoxy-2-naphthyl,
2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl,
1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl,
1,2-dimethyl-7-naphthyl- , 1,3-dimethyl-6-naphthyl,
1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl,
1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl,
2-hydroxy-1-naphthyl, 1,4-dihydroxy-2-naphthyl, 7-phenanthryl,
1-anthryl, 2-anthryl, 9-anthryl, 3-benzo[b]thienyl,
5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl,
4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl,
8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiinyl,
2,7-phenoxathiinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl,
2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl,
2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 3-pyrazolyl,
1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl,
5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl,
2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl,
1,5dimethyl-2-indolyl, 1-methyl-3-indazolyl,
2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl,
2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl,
isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl,
7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl,
6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl,
1,4-dimethoxy-6-phthalazinyl, 1,8naphthyridinyl-2-yl,
2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl,
2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl,
2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl,
7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl,
7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl,
3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl,
.beta.-carbolin-3-yl, 1-methyl-.beta.-carbolin-3-yl,
1-methyl-.beta.-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl,
3-acridinyl, 2-perimidinyl, 1-methyl-5-perimidinyl,
5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl,
3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl,
3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl,
4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl or
10-methyl-2-phenoxazinyl.
[0034] Radicals substituted one or more times are, for example,
substituted 1 to 5 times, 1 to 4 times or 3 times, 2 times or
once.
[0035] Where R.sub.1 and R.sub.3, together with the carbonyl group
and the C atom to which R.sub.3 is attached, form a
benzocyclopentanone radical, this means structures as follows 7
[0036] With particular preference R.sub.1 is phenyl, naphthyl,
pyrenyl, thioxanthyl or phenothiazinyl each of which is
unsubstituted or substituted one or more times by
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18haloalkyl, NR.sub.8R.sub.9,
CN, NO.sub.2, N.sub.3, SR.sub.10 or OR.sub.10, or R.sub.1 is a
radical of the formulae A, B or C 8
[0037] in which n is 0 and the radicals R.sub.8, R.sub.9, R.sub.10
and R.sub.13 are as defined above.
[0038] Further particularly preferred compounds are those in which
R.sub.1 is phenyl, naphthyl, anthracyl, thioxanthyl, dibenzofuranyl
or pyrenyl, the radicals phenyl, naphthyl, anthracyl, thioxanthyl
and pyrenyl being unsubstituted or being substituted one or more
times by CN, NR.sub.8R.sub.9, NO.sub.2, halogen, N.sub.3, CF.sub.3,
SR.sub.10 or OR.sub.10, or R.sub.1 is a radical of the formulae A,
B or C. 9
[0039] in which n is 0 and the radicals R.sub.8, R.sub.9, R.sub.10
and R13 are as defined above.
[0040] With very particular preference R.sub.1 is phenyl,
4-aminophenyl, 4-methylthiophenyl, 4-trifluoromethylphenyl,
4-nitrophenyl, 2,4,6-trimethoxyphenyl, 2,4-dimethoxyphenyl,
naphthyl, anthracyl or pyrenyl or a radical of the formula A or B
10
[0041] in which n is 0.
[0042] R.sub.2 and R.sub.3 independently of one another are
preferably hydrogen or C.sub.1-C.sub.6alkyl. It is likewise
preferred for R.sub.4 and R.sub.6 together to be a
C.sub.2-C.sub.6alkylene bridge.
[0043] Preferably, R.sub.5 and R.sub.7 are a
C.sub.2-C.sub.6alkylene bridge or, if R.sub.5 is NR.sub.15R.sub.16,
R.sub.16 and R.sub.7 together are a C.sub.2-C.sub.6alkylene
bridge.
[0044] R.sub.7 is preferably a C.sub.2-C.sub.6alkylene bridge
together with R.sub.5 or R.sub.7 is C.sub.1-C.sub.18alkyl which is
branched in the .alpha.-position of the N-atom.
[0045] A particularly preferred group of compounds of the formula
(II) are those in which R.sub.1 is phenyl, naphthyl, anthracyl,
thioxanthyl, dibenzofuranyl or pyrenyl, the phenyl radical being
unsubstituted or being substituted one or more times by CN,
NR.sub.8R.sub.9, NO.sub.2, N.sub.3, halogen, CF.sub.3, SR.sub.10 or
OR.sub.10, or R.sub.1 is a radical of the formulae A, B or C 11
[0046] n is 0 and the radicals R.sub.8, R.sub.9, R.sub.10 and
R.sub.13 are hydrogen or C.sub.1-C.sub.14alkyl;
[0047] R.sub.2 and R.sub.3 are hydrogen or C.sub.1-C.sub.6alkyl; or
R.sub.1 and R.sub.3, together with the carbonyl group and the C
atom to which R.sub.3 is attached, form a benzocyclopentanone
radical;
[0048] R.sub.4, R.sub.6 and R.sub.7 independently of one another
are hydrogen or C.sub.1-C.sub.6alkyl;
[0049] R.sub.5 is C.sub.1-C.sub.6alkyl or NR.sub.15R.sub.16, where
R.sub.15 and R.sub.16 are hydrogen or C.sub.1-C.sub.6alkyl; or
[0050] R.sub.4 and R.sub.6 together form a C.sub.2-C.sub.6alkylene
bridge; or, independently of R.sub.4 and R.sub.6,
[0051] R.sub.5 and R.sub.7 together form a C.sub.2-C.sub.6alkylene
bridge or, if R.sub.5 is NR.sub.15R.sub.16, R.sub.16 and R.sub.7
together form a C.sub.2-C.sub.6alkylene bridge.
[0052] The invention additionally provides a process for preparing
compounds having the structural unit of the formula (I), which
comprises reacting a compound comprising a structural unit of the
formula (III) 12
[0053] with a compound comprising a structural unit of the formula
(IV) 13
[0054] in which R.sub.1 is as defined above, including the
preferred meanings, and
[0055] Halogen is F, Cl, Br or I, preferably Br.
[0056] Preference is given to a process for preparing compounds of
the formula (II) which comprises reacting a compound of the formula
(V) 14
[0057] with a compound of the formula (VI) 15
[0058] in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6 and R.sub.7 are as defined above, including the preferred
meanings, and Halogen is F, Cl, Br or I.
[0059] The reaction can be carried out in a conventional manner. It
is advantageous to use a solvent or solvent mixture, for example
hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons
(methylene chloride, chloroform, carbon tetrachloride,
chlorobenzene), alkanols (methanol, ethanol, ethylene glycol
monomethyl ether) and ethers (diethyl ether, dibutyl ether,
ethylene glycol dimethyl ether) or mixtures thereof.
[0060] The reaction can be carried out within a temperature range
from -10.degree. C. to +100.degree. C. It is preferably carried out
at from 10.degree. C. to 50.degree. C.
[0061] The invention likewise provides a process for preparing a
compound of the formula (VII) 16
[0062] which comprises exposing a compound of the formula (II)
17
[0063] to light having a wavelength from 200 nm to 650 nm. The
reaction is advantageously carried out in a solvent or solvent
mixture. The concentration of the compounds of the formula (II) is
advantageously adjusted so that virtually all of the light is
absorbed in the reaction vessel.
[0064] The reaction solution is preferably stirred and, if desired,
cooled in the course of the exposure.
[0065] Suitable solvents have been listed above.
[0066] The invention additionally provides a composition
comprising
[0067] A) at least one compound having a structural unit of the
formula (I) and
[0068] B) at least one organic compound capable of a base-catalysed
addition or substitution reaction.
[0069] Preference is given to compositions comprising as component
A) organic components in which the structural unit of the formula
(I) comprises compounds of the formula (II) 18
[0070] in which the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6 and R.sub.7 are as defined above, including their
preferred meanings.
[0071] The base-catalysed addition or substitution reaction can be
carried out with low molecular mass compounds (monomers), with
oligomers, with polymeric compounds or with a mixture of these
compounds. Examples of reactions which can be carried out both with
monomers and with oligomers/polymers using the novel
photoinitiators are the Knoevenagel reaction or the Michael
addition reaction.
[0072] Of particular importance are compositions in which component
B) is an anionically polymerizable or crosslinkable organic
material.
[0073] The organic material can be in the form of mono- or
polyfunctional monomers, oligomers or polymers.
[0074] Particularly preferred oligomeric/polymeric systems are
binders or coating systems as are customary in the coatings
industry.
[0075] Examples of such base-catalysable binders or coating systems
are:
[0076] a) Acrylate copolymers having alkoxysilane or alkoxysiloxane
side groups, for example the polymers described in U.S. Pat. No.
4,772,672 or U.S. Pat. No. 4,444,974;
[0077] b) Two-component systems comprising hydroxyl-containing
polyacrylates, polyesters and/or polyethers and aliphatic or
aromatic polyisocyanates;
[0078] c) Two-component systems comprising functional polyacrylates
and a polyepoxide, where the polyacrylate contains carboxyl or
anhydride groups;
[0079] d) Two-component systems comprising fluorine-modified or
silicone-modified hydroxyl-containing polyacrylates, polyesters
and/or polyethers and aliphatic or aromatic polyisocyanates;
[0080] e) Two-component systems comprising (poly)ketimines and
aliphatic or aromatic polyisocyanates;
[0081] f) Two-component systems comprising (poly)ketimines and
unsaturated acrylate resins or acetoacetate resins or methyl
.alpha.-acrylamidomethyl- glycolate;
[0082] g) Two-component systems comprising polyamines and
polyacrylates containing anhydride groups;
[0083] h) Two-component systems comprising (poly)oxazolidines and
polyacrylates containing anhydride groups, or unsaturated acrylate
resins or polyisocyanates;
[0084] i) Two-component systems comprising epoxy-containing
polyacrylates and carboxyl-containing polyacrylates;
[0085] l) Polymers based on allyl glycidyl ether;
[0086] m) Two-component systems comprising a (poly)alcohol and a
(poly)isocyanate;
[0087] n) Two-component systems comprising an
.alpha.,.beta.-ethylenically unsaturated carbonyl compound and a
polymer which contains activated CH.sub.2 groups, it being possible
for the activated CH.sub.2 groups to be present either in the main
chain or in the side chain or in both, as is described, for
example, in EP-B-0 161 697 for (poly)malonate groups. Other
compounds having activated CH.sub.2 groups are (poly)acetoacetates
and (poly)cyanoacetates.
[0088] Among these base-catalysable binders particular preference
is given to the following:
[0089] b) Two-component systems comprising hydroxyl-containing
polyacrylates, polyesters and/or polyethers and aliphatic or
aromatic polyisocyanates;
[0090] c) Two-component systems comprising functional polyacrylates
and a polyepoxide, where the polyacrylate contains carboxyl or
anhydride groups;
[0091] i) Two-component systems comprising epoxy-containing
polyacrylates and carboxyl-containing polyacrylates;
[0092] m) two-component systems comprising a (poly)alcohol and a
(poly)isocyanate, and
[0093] n) two-component systems comprising an
.alpha.,.beta.-ethylenically unsaturated carbonyl compound and a
polymer which contains activated CH.sub.2 groups, it being possible
for the activated CH.sub.2 groups to be present either in the main
chain or in the side chain or in both, as is described, for
example, in EP-B-0 161 697 for (poly)malonate groups. Other
compounds having activated CH.sub.2 groups are (poly)acetoacetates
and (poly)cyanoacetates.
[0094] Two-component systems comprising an
.alpha.,.beta.-ethylenically unsaturated carbonyl compound and a
(poly)malonate, and their preparation, are described in EP-B-0 161
687. The malonate group here can be attached in a polyurethane,
polyester, polyacrylate, epoxy resin, polyamide or polyvinyl
polymer either in the main chain or in a side chain. The
.alpha.,.beta.-ethylenically unsaturated carbonyl compound employed
can be any double bond activated by a carbonyl group. Examples are
esters or amides of acrylic acid or methacrylic acid. In the ester
groups it is also possible for additional hydroxyl groups to be
present. Diesters and triesters are also possible.
[0095] Typical examples are hexanediol diacrylate or
trimethylolpropane triacrylate. Instead of the acrylic acid it is
also possible to use other acids and their esters or amides, such
as crotonic or cinnamic acid.
[0096] Under base catalysis, the components of the system react
with one another at room temperature to form a crosslinked coating
system which is suitable for numerous applications. Owing to its
good inherent weathering resistance it is suitable, for example,
for exterior applications as well and can, if required, be
additionally stabilized by UV absorbers and other light
stabilizers.
[0097] Other systems suitable as component B) in the novel
compositions are epoxy systems.
[0098] Epoxy resins are suitable for preparing novel, curable
mixtures comprising epoxy resins as component B) are those which
are customary in epoxy resin technology, examples of such epoxy
resins being:
[0099] I) Polyglycidyl and poly(.beta.-methylglycidyl) esters,
obtainable by reacting a compound, having at least two carboxyl
groups in the molecule with epichlorohydrin or
.beta.-methyl-epichlorohydrin. The reaction is judiciously carried
out in the presence of bases. As the compound having at least two
carboxyl groups in the molecule it is possible to use aliphatic
polycarboxylic acids. Examples of such polycarboxylic acids are
oxalic, succinic, glutaric, adipic, pimelic, suberic, azelaic or
dimerized or trimerized linoleic acid. It is also possible,
however, to employ cycloaliphatic polycarboxylic acids, such as
tetrahydrophthalic, 4-methyltetrahydrophthalic, hexahydrophthalic
or 4-methylhexahydrophthalic acid, for example. Aromatic
polycarboxylic acids, furthermore, can be used, such as phthalic,
isophthalic or terephthalic acid, for example.
[0100] II) Polyglycidyl or poly(.beta.-methylglycidyl) ethers,
obtainable by reacting a compound having at least two free
alcoholic hydroxyl groups and/or phenolic hydroxyl groups with
epichlorohydrin or .beta.-methylepichlorohydrin under alkaline
conditions or in the presence of an acidic catalyst with subsequent
alkali treatment.
[0101] The glycidyl ethers of this type are derived, for example,
from acyclic alcohols, such as ethylene glycol, diethylene glycol
and higher poly(oxyethylene) glycols, propane-1,2-diol or
poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol,
poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol,
hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane,
pentaerythritol, sorbitol, and from polyepichlorohydrins. They also
derive, however, for example, from cycloaliphatic alcohols, such as
1,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane or
2,2-bis(4-hydroxycyclohexyl)propane, or possess aromatic nuclei,
such as N,N-bis(2-hydroxyethyl)aniline or
p,p'-bis(2-hydroxyethylamino)diphenylmethane. The glycidyl ethers
can also be derived from mononuclear phenols, such as resorcinol or
hydroquinone, for example, or are based on polynuclear phenols,
such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl,
bis(4-hydroxyphenyl) sulfone,
1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl-
)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and from
novolaks, obtainable by condensing aldehydes, such as formaldehyde,
acetaldehyde, chloral or furfuraldehyde, with phenols, such as
phenol, or with phenols whose nucleus is substituted by chlorine
atoms or C.sub.1-C.sub.9alkyl groups, examples being
4-chlorophenol, 2-methylphenol, or 4-tert-butylphenol, or by
condensation with bisphenols, those of the type specified
above.
[0102] III) Poly(N-glycidyl) compounds, obtainable by
dehydrochlorination of the reaction products of epichlorohydrin
with amines containing at least two amine hydrogen atoms. These
amines are, for example, aniline, n-butylamine,
bis(4-aminophenyl)methane, m-xylylenediamine or
bis(4-methylaminophenyl)methane.
[0103] The poly(N-glycidyl) compounds also, however, include
triglycidyl isocyanurate, N,N'-diglycidyl derivatives of
cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and
diglycidyl derivatives of hydantoins, such as of
5,5-dimethylhydantoin.
[0104] IV) Poly(S-glycidyl) compounds, for example di-S-glycidyl
derivatives derived from dithiols such as ethane-1,2-dithiol or
bis(4-mercaptomethylphenyl) ether.
[0105] V) Cycloaliphatic epoxy resins, for example
bis(2,3-epoxycyclopenty- l) ether, 2,3-epoxycyclopentyl glycidyl
ether, 1,2-bis(2,3-epoxycyclopenty- loxy)ethane or
3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate- .
[0106] Alternatively it is possible to use epoxy resins in which
the 1,2-epoxide groups are attached to different heteroatoms and/or
functional groups; these compounds include, for example, the
N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether
glycidyl ester of salicylic acid,
N-glycidyl-N'-(2-glycidyloxypropyl)-5,5- -dimethylhydantoin or
2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydanto-
in-3-yl)propane.
[0107] Mixtures of epoxy resins can also be used as component
B).
[0108] The compositions comprise the photoinitiator, component A),
preferably in an amount of from 0.01 to 10% by weight, based on the
component B).
[0109] In addition to the photoinitiator, component A), the
photopolymerizable mixtures may include various additives. Examples
of these are thermal inhibitors which are intended to prevent
premature polymerization, such as hydroquinone, hydroquinone
derivatives, p-methoxyphenol, .beta.-naphthol or sterically
hindered phenols such as 2,6-di(tert-butyl)-p-cresol, for example.
To increase the dark storage stability it is possible, for example,
to use copper compounds, such as copper naphthenate, stearate or
octoate, phosphorus compounds, such as triphenylphosphine,
tributylphosphine, triethyl phosphite, triphenyl phosphite or
tribenzyl phosphite, quaternary ammonium compounds, such as
tetramethylammonium chloride or trimethylbenzylammonium chloride,
or hydroxylamine derivatives, such as N-diethyl-hydroxylamine. To
exclude atmospheric oxygen during polymerization it is possible to
add paraffin or similar waxlike substances, which owing to their
lack of solubility in the polymer migrate to the surface at the
beginning of polymerization where they form a transparent surface
layer which prevents the ingress of air. It is likewise possible to
apply an oxygen-impermeable layer. Light stabilizers which can be
added, in a small amount, are UV absorbers such as those, for
example, of the hydroxyphenylbenzotriazole,
hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine
type. Individual compounds or mixtures of these compounds can be
used, with or without the deployment of sterically hindered amines
(HALS).
[0110] Examples of such UV absorbers and light stabilizers are
given below.
[0111] 1,2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hy- droxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole- ,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hyd- roxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'--
hydroxyphenyl)benzotriazole, mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2--
octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylet-
hyl)phenyl)-5-chiorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-metho-
xycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-oc-
tyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylh-
exyloxy)carbonylethyk]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylp-
henol]; transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbo-
nylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol
300; [R--CH.sub.2CH.sub.2--COO(CH.sub.2).sub.3].sub.2-- where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
[0112] 2.2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivative.
[0113] 3. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butylphenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxyben- zoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate and
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0114] 4. Acrylates, for example ethyl or isooctyl
.alpha.-cyano-.beta.,.b- eta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl and butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.- -cyanovinyl)-2-methylindoline.
[0115] 5. Sterically hindered amines,, such as
bis(2,2,6,6-tetramethylpipe- ridyl) sebacate,
bis(2,2,6,6-tetramethylpiperidyl) succinate,
bis(1,2,2,6,6-pentamethylpiperidyl) sebacate,
bis(1,2,2,6,6-pentamethylpi- peridyl)
n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation
product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine
and succinic acid, condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-pip- eridyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-s-tri- azine,
tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethyl- piperidine,
bis(1,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2-(2-hydroxy-3,5-
-di-tert-butylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazas-
piro-[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate,
condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexameth- ylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of
2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)--
1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, condensation
product of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5--
triazine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-
-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione.
[0116] 6. Oxalamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,
2,2'-di-dodecyloxy-5,5'di-tert-butyloxanilide,
2-ethoxy-2'-ethyloxanilide- ,
N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyl- oxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanili- de, mixtures of o- and
p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.
[0117] 7.2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1
,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dime-
thylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy
-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-[4-dodecyl/tridecyloxy-(2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine.
[0118] 8. Phosphites and phosphonites, for example, triphenyl
phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearyl pentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol
diphosphite, bis-isodecyloxy pentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,
bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite,
tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene- diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,-
3,2-dioxaphosphocin,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d-
,g]-1,3,2-dioxaphosphocin, bis-(2,4-di-tert-butyl-6-methylphenyl)
methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl
phosphite.
[0119] Examples of further additives are:
[0120] Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass beads, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibres of other natural
products, synthetic fibres.
[0121] Other additives, for example plasticizers, lubricants,
emulsifiers, pigments, Theological additives, catalysts, levelling
assistants, optical brighteners, flameproofing agents, antistatics,
blowing agents.
[0122] In addition to the additives indicated above it is also
possible for additional coinitiators to be present. In general
these are 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 19
[0123] which R is alkyl or aryl and R' is hydrogen, an alkyl or
aryl radical, for example Rhodamine B, Rhodamine 6G or Violamine R,
and also Sulforhodamine B or Sulforhodamine G.
[0124] Preference is given to thioxanthones, oxazines, acridines,
phenazines and rhodamines.
[0125] In addition to the above-described base-catalysable
(curable) binders, component B), the composition may also include
other binders as well. Further olefinically unsaturated compounds,
for example, are possible. The unsaturated compounds may include
one or more olefinically double bonds. They may be of low molecular
mass (monomeric) or higher molecular mass (oligomeric). Examples of
monomers having a double bond are alkyl or hydroxyalkyl acrylates
or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl or
2-hydroxyethyl acrylate, isbornyl acrylate, methyl methacrylate or
ethyl methacrylate. Silicone acrylates are also of interest.
Further examples are acrylonitrile, acrylamide, methacrylamide,
N-substituted (meth)acrylamides, vinyl esters such as vinyl
acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl-
and halostyrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene
chloride.
[0126] Examples of monomers having two or more double bonds are the
diacrylates of ethylene glycol, propylene glycol, neopentyl glycol,
hexamethylene glycol or bisphenol A,
4,4'-bis(2-acryloyloxyethoxy)dipheny- lpropane, trimethylolpropane
triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl
acrylate, divinyl benzene, divinyl succinate, diallyl- phthalate,
triallyl phosphate, triallyl isocyanurate or
tris(2-acryloylethyl)isocyanurate.
[0127] Examples of polyunsaturated compounds of relatively high
molecular mass (oligomers) are acrylicized epoxy resins,
acrylicized polyesters or polyesters containing vinyl ether groups
or epoxy groups, polyurethanes and polyethers. Further examples of
unsaturated oligomers are unsaturated polyester resins which are
mostly prepared from maleic acid, phthalic acid and one or more
diols and have molecular weights of from about 500 to 3000. In
addition it is also possible to employ vinyl ether monomers and
oligomers, and also maleate-terminated oligomers with polyester,
polyurethane, polyether, polyvinyl ether and epoxy main chains. In
particular, combinations of vinyl ether-functional oligomers and
polymers as are described in WO 90/01512 are very suitable. Also
suitable, however, are copolymers of vinyl ether and maleic
acid-functionalized monomers. Unsaturated oligomers of this kind
can also be referred to as prepolymers.
[0128] Particularly suitable examples are esters of ethylenically
unsaturated carboxylic acids and polyols or polyepoxides, and
polymers having ethylenically unsaturated groups in the chain or in
side groups, such as unsaturated polyesters, polyamides and
polyurethanes and copolymers thereof, alkyd resins, polybutadiene
and butadiene copolymers, polyisoprene and isoprene copolymers,
polymers and copolymers having (meth)acrylic groups in side chains,
and mixtures of one or more such polymers.
[0129] If, in addition, use is made of such free-radically curable
monomers, oligomers/polymers then it is judicious to add a further
photoinitiator which dissociates into free radicals. Such
photoinitiators are known and are produced industrially. Examples
are benzophenone, benzophenone derivatives, acetophenone,
acetophenone derivatives, for example .alpha.-hydroxycycloalkyl
phenyl ketones, dialkoxyacetophenones, .alpha.-hydroxy- or
.alpha.-aminoacetophenones, 4-aroyl-1,3-dioxolanes, benzoin alkyl
ethers and benzil ketals, monoacyl phosphine oxides,
bisacylphosphine oxides, ferrocenium compounds or titanocenes.
[0130] Examples are specified in U.S. Pat. No. 5,077,402. Polymer
systems of this kind, in which curing/crosslinking takes place by
different mechanisms, are also referred to as hybrid systems.
[0131] The novel compositions can also have added to them
non-reactive binders, which is particularly judicious if the
photopolymerizable compounds are liquid or viscous substances. The
amount of the non-reactive binder can be, for example, 5-95%,
preferably 10-90% and, in particular, 40-90% by weight, based on
the overall solids content. The choice of non-reactive binder is
made in accordance with the field of use and with the properties
required for this use, such as the possibility for development in
aqueous and organic solvent systems, adhesion to substrates, and
sensitivity to oxygen.
[0132] Examples of suitable binders are polymers having a molecular
weight of around 5000-2,000,000, preferably 10,000-1,000,000.
Examples are: homo- and copolymeric acrylates and methacrylates,
for example copolymers of methyl methacrylate/ethyl
acrylate/methacrylic acid, poly(alkyl methacrylates), poly(alkyl
acrylates); cellulose esters and ethers, such as cellulose acetate,
cellulose acetate butyrate, methylcellulose, ethylcellulose;
polyvinylbutyral, polyvinylformal, cyclized rubber, polyethers such
as polyethylene oxide, polypropylene oxide, polytetrahydrofuran;
polystyrene, polycarbonate, polyurethane, chlorinated polyolefins,
polyvinyl chloride, copolymers of vinyl chloride/vinylidene
chloride, copolymers of vinylidene chloride with acrylonitrile,
methyl methacrylate and vinyl acetate, polyvinyl acetate,
copoly(ethylene/vinyl acetate), polymers such as polycaprolactam
and poly(hexamethylene adipamide) and polyesters such as
poly(ethylene glycol terephtalate) and poly(hexamethylene glycol
succinate).
[0133] The invention additionally provides a method of implementing
base-catalysed reactions which comprises subjecting
[0134] A) at least one compound comprising a structural unit of the
formula (I) 20
[0135] in which R.sub.1 is an aromatic or heteroaromatic radical
which is capable of absorbing light in the wavelength range from
200 to 650 nm and in doing so brings about cleavage of the adjacent
carbon-nitrogen bond; and
[0136] B) at least one organic compound which is capable of a
base-catalysed reaction to irradiation with light having a
wavelength of from 200 nm to 650 nm.
[0137] Component A) is preferably an organic compound in which the
structural unit of the formula (I) comprises compounds of the
formula (II) 21
[0138] in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6 and R.sub.7 are as defined above, including their preferred
meanings.
[0139] Examples and preferred meanings for base-catalysed reactions
have already been given above.
[0140] With particular preference, component B) is an anionically
polymerizable or crosslinkable organic material.
[0141] 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.
[0142] The sensitivity of the novel compositions to light generally
extends from about 200 nm through the UV region and into the
infrared region (about 20,000 nm, in particular 1200 nm) and
therefore spans a very broad range. Suitable radiation comprises,
for example, sunlight or light from artificial light sources.
Therefore, a large number of very different types of light source
can be used. Both point sources and flat radiators (lamp carpets)
are suitable. Examples are carbon arc lamps, xenon arc lamps,
medium-pressure, high-pressure and low-pressure mercury lamps,
doped if desired with metal halides (metal halogen lamps),
microwave-stimulated metal vapour lamps, excimer lamps,
superactinic fluorescent tubes, fluorescent lamps, incandescent
argon lamps, electronic flashlights, photographic flood lamps,
electron beams and X-rays, produced by means of synchrotrons or
laser plasma. The distance between the lamp and the substrate
according to the invention which is to be exposed can vary
depending on the application and on the type and/or power of the
lamp, for example between 2 cm and 150 cm. Also especially suitable
are laser light sources, for example excimer lasers. Lasers in the
visible region or in the IR region can also be employed. Very
advantageous here is the high sensitivity of the novel materials
and the possibility of adapting a dye as coinitiator to the laser
line. By this method it is possible to produce printed circuits in
the electronics industry, lithographic offset printing plates or
relief printing plates, and also photographic image recording
materials.
[0143] The novel compositions can be employed for various purposes,
for example as printing inks, as clearcoats, as white paints, for
example for wood or metal, as coating materials, inter alia for
paper, wood, metal or plastic, as powder coatings, as
daylight-curable 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, as laminating resins, as etch resists
or permanent resists and as solder masks for electronic circuits,
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.
[0144] 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.
[0145] Unsaturated polyester resins are mostly used in
two-component systems in conjunction with a monounsaturated
monomer, preferably styrene. For photoresists, specific
one-component systems are frequently employed, for example
polymaleinimides, polychalcones or polyimides, as described in
DE-A-2 308 830.
[0146] The novel photocurable compositions are suitable, for
example, as coating materials for substrates of all kinds, examples
being wood, textiles, paper, ceramic, glass, plastics such as
polyesters, polyethylene terephthalate, 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.
[0147] The substrates can be coated by applying a liquid
composition, a solution 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-ethoxyethanol, 1-methoxy-2-propanol,
1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl
3-ethoxypropionate.
[0148] 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
photosensitive 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.
[0149] 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 more than 100 .mu.m.
[0150] The novel radiation-sensitive compositions 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 micro resists 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.
[0151] 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.
[0152] 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.
[0153] 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.
[0154] Examples of the photocuring of paper coatings are the
colourless varnishing of labels, record sleeves or book covers.
[0155] The use of the novel compounds for curing 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 composite
compositions using the compounds according to the invention are of
high mechanical stability and resistance. The compounds of the
invention can also be used as photocuring agents in moulding,
impregnating and coating compositions, as are described, for
example, in EP-A-7086. 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.
[0156] The invention additionally provides for the use of an
organic compound comprising at least one structural unit of the
formula (I) 22
[0157] in which R.sub.1 is an aromatic or heteroaromatic radical
which is capable of absorbing light in the wavelength range from
200 to 650 nm and on doing so brings about cleavage of the adjacent
carbon-nitrogen bond, as a photoinitiator for photochemically
induced, base-catalysed addition or substitution reactions.
[0158] Preference is given to an organic compound in which the
structural unit of the formula (I) comprises compounds of the
formula (II) 23
[0159] , in which the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6 and R.sub.7 are as defined above, including their
preferred meanings.
[0160] Examples and preferences for base-catalysed addition or
substitution reactions have been given above.
[0161] The invention provides, furthermore, a coated substrate
which has been coated on at least one surface with a composition as
described above, and a process for the photographic production of
relief images, in which a coated substrate is subjected to
imagewise exposure and then the unexposed areas are removed with a
solvent. Of particular interest in this context is the
abovementioned exposure by means of a laser beam.
[0162] The examples which follow illustrate the invention. As in
the remainder of the description and in the claims, parts and
percentages are by weight unless stated otherwise. If alkyl or
alkoxy radicals having more than three C atoms are indicated
without reference to their isomeric form, then the respective
n-isomers are meant.
A-EXAMPLES
Preparing the photoinitiators
Example A1
[0163] 24
[0164] [R.sub.1=phenyl, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).su- b.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3--]
[0165] A solution of .alpha.-bromoacetophenone in toluene is added
with stirring to a solution of 1,5-diazabicyclo[4.3.0]nonane in
toluene. The mixture is stirred overnight at room temperature. The
reaction mixture is filtered, washed with demineralized water and
dried over MgSO.sub.4. It is subsequently dried further in vacuo to
give yields of about 85%.
[0166] U.V. (CHCl.sub.3) max. at 246 nm (.epsilon. 10400 l/mol
cm).
[0167] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.04 (2H, d, ArH), 7.48 (1H,
t, ArH), 7.34 (2H, t, ArH), 4.04 (1H, d, NCH.sub.2CO), 3.46 (1H, d,
NCH.sub.2CO), 3.02 (2H, m, NCH.sub.2), 2.87 (1H, m, NCH), 2.59 (1H,
m, NCH) and 2.3-1.3 (9H, m, CH.sub.2).
[0168] .sup.13C-NMR (CDCl.sub.3) [ppm]: 197.98, 136.16, 133.14,
128.73, 128.50, 84.04, 61.04, 53.08, 52.14, 51.18, 29.10, 24.24 and
19.37.
[0169] The examples below are prepared similarly to Example A1. The
corresponding product is obtained in all cases with a yield of
about 85%.
Example A2
[0170] [R.sub.1=diphenyl, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).- sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3--] 25
[0171] U.V. (CHCl.sub.3) max. at 287 nm (.epsilon. 19600 l/mol
cm).
[0172] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.18 (2H, d, ArH), 7.65-7.15
(7H, m, ArH), 4.05 (1H, d, NCH.sub.2CO), 3.50 (1H, d, NCH.sub.2CO),
3.09 (2H, m, NCH.sub.2), 2.61 (1H, m, NCH) and 2.3-1.4 (9H, m,
CH.sub.2).
[0173] .sup.13C-NMR (CDCl.sub.3) [ppm]: 197.68, 145.82, 140.05,
134.84, 129.40, 128.98, 128.22, 127.32, 127.18, 84.16, 61.30,
53.14, 52.17, 51.20, 29.14, 24.29 and 19.38.
Example A3
[0174] [R.sub.1=naphthyl, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).- sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3--] 26
[0175] Elemental analysis calculated for C.sub.18H.sub.22N.sub.2O:
C, 76.56; H, 7.85; N, 9.92; found: C, 76.83; H, 7.52; N, 9.42,
[0176] U.V. (CHCl.sub.3) max. at 251 nm (.epsilon. 39100 l/mol cm),
286 nm (.epsilon. 8200 l/mol cm) and 345 nm (.epsilon. 1700 l/mol
cm).
[0177] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.62 (1H, s, ArH), 8.09 (1H,
dd, ArH), 7.94 (1H, d, ArH), 7.83 (2H, m, ArH), 7.54 (2H, m, ArH),
4.15 (1H, d, NCH.sub.2CO), 3.65 (1H, d, NCH.sub.2CO), 3.07 (3H, m,
NCH.sub.2), 2.70 (1H, m, NCH) and 2.4-1.4 (9H, m, CH.sub.2).
[0178] .sup.13C-NMR (CDCl.sub.3) [ppm]: 197.92, 135.69, 132.52,
130.38, 129.80, 128.47, 128.31, 127.77, 126.65, 124.38, 84.02,
60.74, 53.14, 52.10, 51.22, 29.09, 24.06 and 19.46.
Example A4
[0179] [R.sub.1=pyrene, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).su- b.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3--] 27
[0180] Elemental analysis calculated for C.sub.25H.sub.24N.sub.2O:
C, 81.49; H, 6.57; found: C, 81.70; H, 6.74.
[0181] U.V. (CHCl.sub.3) max. at 245 nm (.epsilon. 29800 l/mol cm),
285 nm (.epsilon. 20900 l/mol cm) and 360 nm (.epsilon. 18100 l/mol
cm).
[0182] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.84 (1H, d, ArH), 8.44 (1H,
d, ArH), 8.24-7.93 (7H, m, ArH), 4.18 (1H, d, NCH.sub.2CO), 3.66
(1H, d, NCH.sub.2CO), 3.01 (3H, m, NCH.sub.2), 2.64 (1H, t, NCH)
and 2.4-1.3 (9H, m, CH.sub.2).
[0183] .sup.13C-NMR (CDCl.sub.3) [ppm]: 202.83, 133.90, 131.09,
130.56, 129.9, 129.55, 129.08, 128.27, 127.20, 126.37, 126.30,
126.03, 125.05, 124.70, 124.04, 83.86, 63.26, 53.23, 52.05, 51.12,
29.13, 24.19 and 19.42.
Example A5
[0184] [R.sub.1=4-azidophenyl, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.su- b.2).sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3--] 28
[0185] .sup.1H -NMR (CDCl.sub.3) [ppm]: 8.10 (2H, d, ArH), 6.99
(2H, d, ArH), 3.93 (1H, d, NCH.sub.2CO), 3.35 (1H, d, NCH.sub.2CO),
3.02 (2H, m, NCH.sub.2), 2.84 (1H, m, NCH), 2.49 (1H, m, NCH) and
2.3-1.3 (9H, m, CH.sub.2).
Examples A6-A36; Table 1:
[0186]
1 29 Example R.sub.1 R.sub.2 R.sub.3 R.sub.5/R.sub.7
R.sub.4/R.sub.6 A6 Phenyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A7 Phenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- A8 Naphthyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A9 Naphthyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- Al0 4-Aminophenyl H H --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- All 4-Aminophenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- Al2 4-Aminophenyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- Al3 4-Cyanophenyl H H --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A14 4-Cyanophenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- Al5 4-Cyanophenyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A16 4-Nitrophenyl H H --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A17 4-Nitrophenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- Al8 4-Nitrophenyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A19 4-Trifluoromethylphenyl H H
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A20
4-Trifluoromethyiphenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- A21 4-Trifluoromethylphenyl H H
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.3-- A22 4-Dimethylaminophenyl
H H --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A23
4-Dimethylaminophenyl H H --(CH.sub.2).sub.3--NH-- A24
4-Dimethylaminophenyl H H --(CH.sub.2).sub.5-- --(CH.sub.2).sub.3--
A25 2,4,6-Trimethoxyphenyl H H --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A26 2,4,6-Trimethoxyphenyl H H
--(CH.sub.2).sub.3--NH-- --(CH.sub.2).sub.3-- A27
2,4,6-Trimethoxyphenyl H H --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A28 4-(C.sub.14H.sub.29--O)phenyl H H
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A29
4-(C.sub.14H.sub.29--O)phenyl H H --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- A30 4-(C.sub.14H.sub.29--O)phenyl H H
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.3-- A31 30 H H
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A32 31 H H
--(CH.sub.2).sub.3--NH-- --(CH.sub.2).sub.3-- A33 32 H H
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.3-- A34 33 H H
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A35 34 H H
--(CH.sub.2).sub.3--NH-- --(CH.sub.2).sub.3-- A36 35 H H
--(CH.sub.2).sub.5-- --(CH.sub.2).sub.3--
Examples A37-A39; Table 2:
[0187]
2 36 Exam- ple R.sub.2 R.sub.1/R.sub.3 R.sub.4/R.sub.6
R.sub.5/R.sub.7 A37 H 37 --(CH.sub.2).sub.3--NH--
--(CH.sub.2).sub.3-- A38 H 38 --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A39 H 39 --(CH.sub.2).sub.3----
--(CH.sub.2).sub.3--
Examples A40-A59; Table 3:
[0188]
3 40 Example R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6
R.sub.7 A40 Phenyl H H H NH.sub.2 H H A41 Phenyl H H H
NH(C.sub.2H.sub.5) C.sub.2H.sub.5 H A42 Phenyl H H H
N(CH.sub.3).sub.2 H H A43 Phenyl H H H N(CH.sub.3).sub.2 H CH.sub.3
A44 Phenyl H H H N(CH.sub.3).sub.2 H H A45 Phenyl H H CH.sub.3
N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 A46 Phenyl H H H
N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 A47 Phenyl H H CH.sub.3
N(CH.sub.3).sub.2 H CH.sub.3 A48 Phenyl H H H N(CH.sub.3).sub.2 H
CH.sub.3 A49 Phenyl H H CH.sub.3 N(CH.sub.3).sub.2 H CH.sub.3 A50
Naphthyl H H H NH.sub.2 H H A51 Naphthyl H H H NH(C.sub.2H.sub.5)
C.sub.2H.sub.5 H A52 Naphthyl H H H N(CH.sub.3).sub.2 H H A53
Naphthyl H H H N(CH.sub.3).sub.2 H CH.sub.3 A54 Naphthyl H H H
N(CH.sub.3).sub.2 H H A55 Naphthyl H H CH.sub.3 N(CH.sub.3).sub.2
CH.sub.3 CH.sub.3 A56 Naphthyl H H H N(CH.sub.3).sub.2 CH.sub.3
CH.sub.3 A57 Naphthyl H H CH.sub.3 N(CH.sub.3).sub.2 H CH.sub.3 A58
Naphthyl H H H N(CH.sub.3).sub.2 H CH.sub.3 A59 Naphthyl H H
CH.sub.3 N(CH.sub.3).sub.2 H CH.sub.3
Example A60
[0189] [R.sub.1= 41
Example A61
[0190] [R.sub.1=4-Diethylaminophenyl, R.sub.2=R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3-- -] 42
[0191] Yellow solid (yield 87%);
[0192] Elemental analysis calculated for C.sub.19H.sub.29N.sub.3O:
C 72.34, H 9.27, N 13.32; found: C 72.06, H 9.16, N 13.20.
[0193] U.V. (CHCl.sub.3) max. at 247 nm (.epsilon. 4700), 313 nm
(.epsilon. 17300) and 364 nm (.epsilon. 5800).
[0194] I.R. (KBr) 1684 cm.sup.-1 (C.dbd.O).
[0195] .sup.1H NMR (CDCl.sub.3) [ppm]: 7.99 (2H, d, ArH), 6.52 (2H,
d, ArH), 3.92 (1H, d, NCH.sub.2CO), 3.34 (4H, q, CH.sub.2CH.sub.3),
3.31 (1H, d, NCH.sub.2CO), 3.02 (2H, m, NCH.sub.2), 2.89 (1H, m,
NCH), 2.52 (1H, m, NCH), 2.2-1.3 (9H, m, CH.sub.2) and 1.10 (6H, t,
CH.sub.2CH.sub.3).
[0196] .sup.13C-NMR (CDCl.sub.3) [ppm]: 195.61, 151.21, 131.40,
123.59, 110.06, 84.25, 61.07, 52.87, 52.21, 51.23, 44.55, 29.10,
24.46, 19.41 and 12.58.
Example A62:
[0197] 43
[0198] Red rubberlike solid (yield 72%)
[0199] U.V. (CHCl.sub.3) max. at 245 nm (.epsilon. 6700) and 330 nm
(.epsilon. 23100).
[0200] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.20 (2H, d, ArH), 7.89-7.43
(7H, m, ArH), 4.03 (1H, d, NCH.sub.2CO), 3.49 (1H, d, NCH.sub.2CO),
3.05 (2H, m, NCH.sub.2), 2.91 (1H, m, NCH), 2.60 (1H, m, NCH) and
2.3-1.4 (8H, m, CH.sub.2).
Example A63:
[0201] 44
[0202] Orange-colored oil (yield 78%)
[0203] U.V. (CHCl.sub.3) max. at 287 nm (.epsilon. 20500).
[0204] I.R. (KBr) 1690 cm.sup.-1 (C.dbd.O).
[0205] .sup.13C-NMR (CDCl.sub.3) [ppm]: 1989.14, 145.64, 139.79,
134.85, 128.97, 128.82, 128.22, 127.29, 127.16, 125.33, 82.15,
56.34, 55.51, 53.57, 52.10, 32.90, 29.07, 24.42, 24.61 and
21.48.
Example A64:
[0206] [R.sub.1=phenyl, R.sub.2=CH.sub.3, R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3-- -] 45
[0207] Orange-coloured oil (yield 86%)
[0208] I.R. (KBr) 1695 cm.sup.-1 (C.dbd.O).
[0209] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.17 (2H, d, J=7.0 Hz, ArH),
7.50-7.35 (3H, m, ArH), 4.50 /1H, q, J=6.6 Hz, NHCHCH.sub.3), 3.05
(2H, m, NCH.sub.2), 2.69 (2H, m, NCH.sub.2), 2.49 (1H, m, NCH),
2.3-1.3 (8H, m, CH.sub.3) and 1.16 (3H, d, J=6.6 Hz, CH.sub.3).
[0210] .sup.13C-NMR (CDCl.sub.3) [ppm]: 200.72, 136.61, 132.65,
129.31, 128.37, 81.83, 60.09, 52.31, 51.40, 45.50, 28.76, 25.01,
19.21 and 6.55.
Example A65:
[0211] 46
[0212] Orange-coloured oil (yield 89%).
[0213] U.V. (CHCl.sub.3) max. at 268 nm (.epsilon. 10100) and 302
(.epsilon. 7300)
[0214] I.R. (KBr) 1670 and 1600 cm.sup.-1 (C.dbd.O).
[0215] .sup.1H-NMR (CDCl.sub.3) [ppm]: 7.75 (2H, d, ArH), 6.48 (2H,
d, ArH), 6.40 (1H, s, ArH), 3.96 (1H, d, NCH.sub.2CO), 3.85 (3H, s,
OCH.sub.3), 3.80 (3H, s, OCH.sub.3), 3.65 (1H, d, NCH.sub.2CO),
3.03 (3H, m, NCH.sub.2), 2.77 (1H, m, NCH), 2.35 (1H, m, NCH) and
2.2-1.3 (8H, m, CH.sub.2).
[0216] .sup.13C-NMR (CDCl.sub.3) [ppm]: 198.70, 164.35, 160.51,
132.66, 105.24, 98.28, 83.23, 63.65, 55.54, 55.45, 52.89, 52.04,
51.33, 28.85, 24.39 and 19.44.
Example A66:
[0217] 47
[0218] Orange crystals (yield 94%).
[0219] U.V. (CHCl.sub.3) max. at 244 nm (.epsilon. 5400) and 306
(.epsilon. 17300)
[0220] I.R. (KBr) 1670 and 1590 cm.sup.-1 (C.dbd.O).
[0221] .sup.1H-NMR (CDCl.sub.3) [ppm]: 7.96 (2H, d, J=8.8 Hz, ArH),
7.14 (2H, d, J=8.8 Hz, ArH), 3.91 (1H, d, J=15.0 Hz, NCH.sub.2CO),
3.34 (1H, d, J=15.0 Hz, NCH.sub.2CO), 3.00 (2H, m, NCH.sub.2), 2.84
(1H, m, NCH), 2.49 (1H, m, NCH), 2.47 (3H, s, SCH.sub.3) and
2.2-1.3 (9H, m, CH.sub.2).
[0222] .sup.13C-NMR (CDCl.sub.3) [ppm]: 196.99, 145.90, 132.39,
129.22, 129.03, 128.23, 125.30, 124.86, 84.12, 61.28, 53.05, 52.12,
51.11, 29.10, 24.28, 19.34 and 14.75.
Example A67:
[0223] 48
[0224] U.V. (CHCl.sub.3) max. at 245 nm (.epsilon. 44800), 345 nm
(.epsilon. 3400), 370 nm (.epsilon. 3800) and 395 nm (.epsilon.
3700).
[0225] I.R. (KBr) 1670 cm.sup.-1 (C.dbd.O).
[0226] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.85 (1H, s, ArH), 8.54 (1H,
s, ArH), 8.49 (1H, s, ArH), 8.45 (1H, s, ArH), 8.12 (1H, dd, ArH),
7.99 (2H, m, ArH), 7.66-7.46 (2H, m, ArH), 4.18 (1H, d, J=15.2 Hz,
NCH.sub.2CO), 3.64 (1H, d, J=15.2 Hz, NCH.sub.2CO), 3.08 (3H, m,
NCH.sub.2), 2.70 (1H, m, NCH), and 2.4-1.4 (9H, m, CH.sub.2).
Example A68:
[0227] 49
[0228] U.V. (CHCl.sub.3) max. at 258 nm (.epsilon. 14100).
[0229] I.R. (KBr) 1685 and 1585 cm.sup.-1 (C.dbd.O).
[0230] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.00 (2H, d, J.sub.1=4.1 Hz,
J.sub.2=2.3 Hz, ArH), 7.98 (2H, dd, J.sub.1=4.1 Hz, J.sub.2=2.3 Hz,
ArH), 3.95 (1H, d, J=15.0 Hz, NCH.sub.2CO), 3.40 (1H, d, J=15.0 Hz,
NCH.sub.2CO), 3.06 (2H, m, NCH.sub.2), 2.87 (1H, m, NCH), 2.55 (1H,
m, NCH) and 2.2-1.3 (9H, m, CH.sub.2).
[0231] .sup.13C-NMR (CDCl.sub.3) [ppm]: 197.12, 134.77, 131.80,
130.45, 129.06, 128.35, 125.32, 84.18, 61.54, 53.17, 52.13, 51.09,
29.14, 24.26 and 19.32.
Example A69:
[0232] 50
[0233] .sup.1H-NMR (CDCl.sub.3) [ppm]: 8.27 (2H, d, J=8.8 Hz, ArH),
8.09 (2H, d, J=8.8 Hz, ArH), 3.92 (1H, d, J=15.1 Hz, NCH.sub.2CO),
3.31 (1H, d, J=15.1 Hz, NCH.sub.2CO), 3.07 (2H, m, NCH.sub.2), 2.89
(1H, m, NCH), 2.55 (1H, m, NCH) and 2.2-1.3 (9H, m, CH.sub.2).
Examples A70-A82; Table 4:
[0234]
4 51 Example R.sub.1 R.sub.2 R.sub.3 R.sub.5/R.sub.7
R.sub.4/R.sub.6 A70 Phenyl H CH.sub.3 --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A71 Phenyl H CH.sub.3 --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A72 Phenyl H Phenyl --(CH.sub.2).sub.5--
--(CH.sub.2).sub.3-- A73 Phenyl H Phenyl --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A74 Phenyl CH.sub.3 CH.sub.3
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A75 Phenyl CH.sub.3
CH.sub.3 --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A76*
2-Thioxanthyl H H --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A77
2-Thioxanthyl H H --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A78
2-Thioxanthyi CH.sub.3 CH.sub.3 --(CH.sub.2).sub.3--
--(CH.sub.2).sub.3-- A79 2-Thioxanthyl CH.sub.3 CH.sub.3
--(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A80 2-Thioxanthyl H
CH.sub.3 --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3-- A81
2-Thioxanthyl H CH.sub.3 --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3--
A82 2-Thioxanthyl H H --(CH.sub.2).sub.3-- --(CH.sub.2).sub.3--
[0235] The compound of Example 76 is obtained as follows: a
base-catalysed coupling reaction of thiosalicylic acid and
p-bromoacetophenone in the presence of copper is used to obtain the
keto acid which, following dehydrogenation with polyphosphoric
acid, gives the 2-acetylthioxanthone, which is brominated in the
.alpha. position. Finally, the reaction of the ketone with
1,5-diazabicyclo[4.3.0]nonane gives the compound A76.
Example A83
[0236] [R.sub.1=2-naphthyl, R.sub.2=CH.sub.3, R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3-- -] 52
[0237] .sup.1H NMR (CDCl.sub.3) [ppm]: 8.85 (0.65H, s), 8.68
(0.35H, s), 8.44-7.44 (6H, m, ArH), 4.63 (0.65H, q, J=6.5 Hz,
NCHCH.sub.3), 4.61 (0.35H, q, J=6.9 Hz, NCHCH.sub.3), 3.14-2.53
(4H, m), 2.28-1.38 (9H, m), 1.39 (1.05H, d, J=6.9 Hz, CH.sub.3) and
1.22 (1.95H, d, J=6.5 Hz, CH.sub.3).
Example A84
[0238] [R.sub.1=diphenyl, R.sub.2=CH.sub.3, R.sub.3=H,
R.sub.4/R.sub.6=--(CH.sub.2).sub.3--,
R.sub.5/R.sub.7=--(CH.sub.2).sub.3-- -] 53
[0239] .sup.1H NMR (CDCl.sub.3): 8.25 (1.5H, m, ArH), 8.01 (0.5H,
m, ArH), 7.60 (3H, m, ArH), 7.40 (4H, m, ArH), 4.53 (0.75H, q,
J=6.6 Hz, NCHCH.sub.3), 4.45 (0.25H, q, J=7.0 Hz, NCHCH.sub.3),
3.08 (2H, m), 2.73-1.46 (11 H, m), 1.36 (0.75H, d, J=7.0 Hz,
CH.sub.3), 1.19 (2.25H, d, J=6.5 Hz, CH.sub.3).
B-EXAMPLES
Use: Base catalysis with monomeric compounds
Examples B1-B4 UV-initiated Michael addition
[0240] 7.4.multidot.10.sup.-5 mol of photoinitiator (latent amidine
base) are dissolved in a mixture of dimethyl malonate and n-butyl
acrylate (1:1, 200 mg corresponding to 7.4.multidot.10.sup.-4 mol)
in a quartz vessel. The mixture is irradiated with a high-pressure
mercury lamp (200 W) from a distance of 30 cm. The conversion is
monitored as a function of time.
[0241] The results are set out in Table 5.
Example B5
Michael addition initiated with visible light.
[0242] 7.4.multidot.10.sup.-5 mol of photoinitiator A2 (latent
amidine base) and 7.4.multidot.10.sup.-5 mol of
isopropylthioxanthone are dissolved in a mixture of dimethyl
malonate and n-butyl acrylate (1:1, 200 mg corresponding to
7.4.multidot.10.sup.-4 mol) in a glass vessel. The mixture is
irradiated with a halogen lamp (500 watts) from a distance of 30
cm. The conversion is monitored as a function of time.
[0243] The following result is obtained:
[0244] Exposure time in minutes 0 30 120 300
[0245] Conversion in % 0 18 53 88
Examples B6-B9
[0246] The procedure followed is analogous to the method described
in Examples B1-B4. The initiators used and the test results are
reproduced in Table 6.
C-EXAMPLES
Use: Base catalysis with oligomeric/polymeric compounds
Examples C1-C6
[0247] Preparation of a urethane acrylate based on isophorone
diisocyanate and 4-hydroxybutyl acrylate.
[0248] The reaction is carried out under a nitrogen atmosphere and
all commercial chemicals used are employed without further
purification.
[0249] 1566.8 g (13.78 mol of NCO) of isophorone diisocyanate, 2.3
g of dibutyltin dilaurate, 2.3 g of 2,5-di-t-butyl-p-cresol and
802.8 g of butyl acetate are charged to a three-necked flask with
condenser and dropping device. Dry nitrogen is bubbled through the
reaction mixture and the temperature is slowly raised to 60.degree.
C. 1987 g (13.78 mol) of 4-hydroxybutyl acrylate are added, during
which the reaction solution warms slowly to 80.degree. C. The
temperature is held at 80.degree. C. and the dropping device is
flushed with butyl acetate (86.6 g). The reaction is monitored by
titration of the remaining amount of isocyanate, and is over when
the isocyanate content is below 0.2% based on the solids content.
The reaction product obtained has the following physical
properties:
[0250] Residual 4-hydroxybutyl acrylate: <0.002% based on solids
(HPLC analysis),
[0251] Colour: <<Gardner 1,
[0252] Viscosity: 43 cPa s (20.degree. C.),
[0253] Solids content: 79,3% (1 hour at 140.degree. C.),
[0254] GPC data (polystyrene standard): M.sub.n 778, M.sub.w 796,
d=1.02.
[0255] Preparation of a malonate polyester
[0256] The reaction is carried out under a nitrogen atmosphere and
all commercial chemicals used are employed without further
purification.
[0257] In a reaction vessel with stirrer and condenser 1045 g of
1,5-pentanediol, 1377.4 g of diethyl malonate and 242.1 g of xylene
are carefully refluxed. The maximum temperature of the reaction
mixture is 196.degree. C. while the temperature at the head of the
condenser is held at 79.degree. C. In this way 862 g of ethanol,
corresponding to a conversion of 97.7%, are distilled off. Then
xylene is stripped off in vacuo at a temperature of 200.degree. C.
The resulting polymer has a solids content of 98.6%, a viscosity of
2710 mPa s and an acid number of 0.3 mg of KOH/g based on the
solids content. M.sub.n is 1838, M.sub.w is 3186, the colour is 175
on the APHA (American Public Health Association) scale (Hazen
colour number; ISO 6271).
Example C1
Curing with UV light
[0258] 20.5 mg (6.4.times.10.sup.-5 mol) of the photoinitiator from
Example A2 are dissolved in 400 mg of a 1.3:1 mixture of the
above-described urethane acrylate and the malonate polyester. The
mixture is exposed to light in a quartz vessel using a
high-pressure mercury lamp (200 W) at a distance of 30 cm. The
polymer is tack-free after 45 minutes.
Example C2
Curing with UV light
[0259] 18.8 mg (6.4.times.10.sup.-5 mol) of the photoinitiator from
Example A3 are dissolved in 400 mg of a 1.3:1 mixture of the
above-described urethane acrylate and the malonate polyester. A
film 50 .mu.m thick is drawn out onto a glass plate and is exposed
using a high-pressure mercury lamp (200 W) at a distance of 30 cm.
The polymer film is tack-free after 30 minutes.
Example C3
Curing with visible light
[0260] 20.5 mg (6.4.times.10.sup.-5 mol) of the photoinitiator from
Example A2 and 10 mg of isopropyl-9H-thioxanthone
(6.4.times.10.sup.-5 mol) are dissolved in 400 mg of a 1.3:1
mixture of the above-described urethane acrylate and the malonate
polyester. The mixture is exposed to light in a quartz vessel using
a halogen lamp (500 W) at a distance of 30 cm. The polymer is
tack-free after 120 minutes.
Example C4
Curing with visible light
[0261] 20.5 mg (6.4.times.10.sup.5 mol) of the photoinitiator from
Example A2 and 10 mg of isopropyl-9H-thioxanthone
(6.4.times.10.sup.-5 mol) are dissolved in 400 mg of a 1.3:1
mixture of the above-described urethane acrylate and the malonate
polyester. A film 50 .mu.m thick is drawn out onto a glass plate
and is exposed using a halogen lamp (500 W) at a distance of 30 cm.
The polymer film is tack-free after 120 minutes.
Example C5
Curing with visible light
[0262] 18.8 mg (6.4.times.10.sup.-5 mol) of the photoinitiator from
Example A3 and 10 mg of isopropyl-9H-thioxanthone
(6.4.times.10.sup.-5 mol) are dissolved in 400 mg of a 1.3:1
mixture of the above-described urethane acrylate and the malonate
polyester. A film 50 .mu.m thick is drawn out onto a glass plate
and is exposed using a halogen lamp (500 W) at a distance of 30 cm.
The polymer film is tack-free after 120 minutes.
Example C6
Curing with visible light
[0263] 18.8 mg (6.4.times.10.sup.-5 mol) of the photoinitiator from
Example Al and 10 mg of isopropyl-9H-thioxanthone
(6.4.times.10.sup.-5 mol) are dissolved in 400 mg of a 1.3:1
mixture of the above-described urethane acrylate and the malonate
polyester. A film 50 .mu.m thick is drawn out onto a glass plate
and is exposed using a halogen lamp (500 W) at a distance of 30 cm.
The polymer film is tack-free after 120 minutes.
Examples C7-C8
[0264] The amounts of photoinitiator from Example A3 and
isopropyl-9H-thioxanthone (ITX) stated in Table 6 are dissolved in
400 mg of a 1.3:1 mixture of the above-described urethane acrylate
and the malonate polyester. A film 50 .mu.m thick is drawn out onto
a glass plate and is exposed using a TL03/40 W lamp at a distance
of 30 cm. After 4, 6 and 24 hours the Konig pendulum hardness (DIN
53157) and the Yellowness Index in accordance with ASTMD 1925-88
are determined in each case. The results are reproduced in Table
7.
5 TABLE 7 Pendulum hardness Example Initiator 4 h 6 h 24 h C7 25.0
parts of A3 48 71 154 12.5 parts of ITX C8 25.0 parts of A3 52 92
130 5.0 parts of ITX
* * * * *