Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
2000-09-07
2003-04-22
Hamilton, Cynthia (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C522S031000, C522S039000, C540S500000, C544S229000, C544S263000, C544S349000, C564S183000, C564S194000, C430S914000, C430S919000, C430S920000, C430S923000, C430S280100, C430S281100
Reexamination Certificate
active
06551761
ABSTRACT:
The present invention relates to &agr;-ammonium ketones, iminium ketones or amidinium ketones in the form of their tetraaryl- or triarylalkylborate salts which can be photochemically converted into amines, imines or amidines as well as to a process for their preparation. This invention also relates to base-polymerisable or crosslinkable compositions comprising these &agr;-ammonium ketones, iminium ketones or amidinium ketones in the form of their tetra- or triarylalkylborate salts, to a process for carrying out photochemically induced, base-catalysed reactions as well as to their use as photoinitiators for base-catalysed reactions.
The photolytic cleavage of specific &agr;-amino ketones into radicals and the photopolymerisation of olefinically unsaturated monomers or oligomers which this initiates have long been known and are described, for example, in EP-A-284 561.
In addition to radically polymerisable oligomers or monomers, base-catalysable systems have been disclosed in particular for photolithographic processes. These systems require a photoinitiator which releases a base on exposure to light. D. R. MacKean et al., Polym. Mater. Sci. Eng. (1992), 66, 237-238, for example, report on the photostructuring of polyimide using specific carbamates as photoinitiators.
In J. of Polymer Science: Polym. Chem. Ed., Vol. 12, 2943-2951 (1974), Ko et al. report on BF
4
−
salts containing &agr;-ammonium ketones which on exposure to light decompose into radicals with &agr;- cleavage but which do not form any free amine and which are therefore unsuitable as latent bases.
J. Chem. Soc. (C), 1971, 1863-1869 describes bromine salts of &agr;-ammonium ketones which on exposure to light result in protonated amines and which are therefore also unsuitable as latent bases.
In Chem. Mater. 1996, 8, 1360-1362, Neckers et al. recently reported on novel systems for photostructuring based on polymeric ammonium phenylborates containing mobile benzophenone groups at the polymer structure.
Surprisingly, it has now been found that certain &agr;-ammonium ketones, iminium ketones or amidinium ketones in the form of their tetraaryl- or triarylalkylborate salts release an amine, imine or amidine group on exposure to visible light or UV light. These groups are sufficiently basic to initiate a large number of base-catalysable reactions, in particular polymerisation reactions. These compounds are of high sensitivity and through the choice of the substitution pattern the absorption spectrum can be varied within a wide range.
These compounds make it possible to prepare so-called one-pot systems with base-catalysable oligomers or monomers having an extremely long storage life. A polymerisation 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.
This invention provides compounds of formula (I)
m is 1 or 2 and corresponds to the number of positive charges of the cation;
R
1
is 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, thianthrenyl dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyi, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, &bgr;-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl, fluorenyl or phenoxazinyl, these radicals being unsubstituted or mono- or polysubstituted by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
6
R
7
, N
3
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or halogen, or R
1
is a radical of formula A or B
R
2
, R
3
and R
4
are each independently of one another hydrogen, C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl or phenyl, or R
2
and R
3
and/or R
4
and R
3
form each independently of one another a C
2
-C
12
alkylene bridge; or R
2
, R
3
, R
4
, together with the linking nitrogen atom, are a phosphazene base of the P
1
, P
2
, P <t/4> type or a group of the structural formula (a), (b), (c), (d), (e), (f) or (g)
k and I are each independently of the other a number from 2 to 12;
R
5
, R
6
, R
7
, R
8
, R
9
and R
10
are hydrogen or C
1
-C
18
alkyl; or R
5
and R
1
, together with the linking carbon atoms, are a benzocyclopentanone radical;
R
11
is C
1
-C
18
alkyl, C
2
-C
18
alkenyl, C
2
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, NR
6
R
7
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or halogen; and
n is 0 or 1, 2 or 3;
R
12
, R
13
and R
14
is phenyl or another aromatic hydrocarbon, these radicals being unsubstituted or mono- or polysubstituted by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or halogen;
R
15
is C
1
-C
18
alkyl, phenyl or another aromatic hydrocarbon, the radicals phenyl and aromatic hydrocarbon being unsubstituted or mono- or polysubstituted by C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
1
-C
18
haloalkyl, NO
2
, OH, CN, OR
8
, SR
8
, C(O)R
9
, C(O)OR
10
or halogen, R
15
is a radical
X is C
1
-C
20
alkylene, C
2
-C
20
alkylene which is interrupted by —O—, —S— or NR
8
, or X is
The absorption maximum can be varied within a wide range through the choice of the aromatic or heteroaromatic R
1
and of the respective borate anion, and so the photosensitivity of the compounds can be shifted from the UV into the daylight region.
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, secbutyl, 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.
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.
Alkynyl having 3 to 18 carbon atoms is a branched or unbranched radical such as propynyl (—CH
2
—C≡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.
The C
2
-C
12
alkylene bridge is ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene.
Halogen is fluoro, chloro, bromo or iodo.
Typical examples of C
1
-C
18
haloalkyl are fully or partly halogenated C
1
-C
18
alkyl. Illustrative example thereof 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.
Examples of the NR
8
R
9
amino group are the respective monoalkyl or dialkylamino groups such as methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, octadecy
Cunningham Allan Francis
Hall-Goulle Veronique
Turner Sean Colm
Ciba Specialty Chemical Corporation
Crichton David R.
Hamilton Cynthia
Stevenson Tyler A.
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