DETAILED DESCRIPTION AND SPECIFICATION OF THE INVENTION This invention teaches the photopolymerization of free radically polymerizable compositions by a photoinitiator comprising a triarylsulfonium salt, at least one of a sensitizer and an electron donor, wherein at least one of the electron donor (embodiment 1) and the sensitizer (embodiment 2) is tethered to the triarylsulfonium salt.
When a donor is tethered to the sulfonium salt it is preferred that a sensitizer be present also.
When a sensitizer is tethered to the sulfonium salt, it is preferred that a donor be present also.
In some cases, the donor, sensitizer, and sulfonium salt will all be part of the same molecule.
In such cases, a tether can be to the donor group or to the sensitizer group or tethers can be to both donor and sensitizer groups.
Tethered sulfonium salt photoinitiators of this invention can be represented by two general formulae: General formula (1) is represented by: S.
sup.
+ (A.
sup.
1).
sub.
m (A.
sup.
2 --T--Q).
sub.
n X.
sup.
- ( 1) wherein S.
sup.
+ is a positively charged sulfur atom, A.
sup.
1 is an aryl group having 6 to 50 carbon atoms which can be substituted by 1 to 5 substituents chosen from alkyl, haloalkyl, haloaryl, alkoxy, aralkyl, alkaryl, aryloxy, thioalkyl, thioaryl groups of 1-18 carbon atoms; carboxyl, carboxaldehyde, carboxylic acid esters of alcohols of 1-18 carbons, and carboxylic acid amides of amines of 1-18 carbons.
A.
sup.
2 is an arylene group having 6 to 50 carbon atoms which can be substituted by 1 to 4 substituents chosen from alkyl, haloalkyl, haloaryl, alkoxy, aralkyl, alkaryl, aryloxy, thioalkyl, thioaryl groups of 1-18 carbon atoms; carboxyl, carboxaldehyde, carboxylic acid esters of alcohols of 1-18 carbons, and carboxylic acid amides of amines of 1-8 carbons, which is connected to Q through the tether T, m=0, 1, or 2, n=1, 2, or 3 with the proviso that n+m=3 T represents the tether which joins the triaryl sulfonium salt moiety to Q and contains at least one tetracoordinate carbon atom.
Preferably, T is chosen from divalent groups such as alkylene, aminoalkylene, aralkylene, alkarylene, haloalkylene, thioalkylene, oxyalkylene, wherein the divalent group contains 1 to 40 C atoms, and none or 1 to 10 N, 0, S, P, Si, and Se heteroatoms, and may contain amide, ester, ether, or ketone functionality along the backbone, with the proviso that every path from A
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