Ciba Specialty Chemicals Corporation

Other

Allan Francis Cunningham

Martin Kunz

Hisatoshi Kura

Christopher Curtis Dudman

Borate coinitiators for photopolymerization

Dye compounds of the formula ##STR1## wherein X is for example CH, C--CH.sub.3 or .sup.+ NOR L.sup.- ; R is inter alia C.sub.1 -C.sub.6 alkyl; R.sub.1 is for example C.sub.1 -C.sub.8 alkoxy or C.sub.1 -C.sub.12 alkyl; s is 0 to 4; R.sub.2 is for example hydrogen; Ar is for example a group ##STR2## Y inter alia is C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy; r in the formula (A) is 0 to 5, in the formulae (B) and (E) is 0 to 9 and in the formula (D) is 0 to 7; and L is an anion; in combination with an electron donor compound, especially a borate compound, are suitable as photoinitiators for the photopolymerization of radically polymerizable compositions.

Quinolinium dyes and borates in photopolymerizable compositions

Polymerizable composition

Compounds of the formula I and II ##STR1## in which R.sub.1, R.sub.2 and R.sub.3 are, for example, unsubstituted or substituted phenyl, where none of the radicals R.sub.1 -R.sub.3 is a phenyl radical which is substituted ortho to the bond to the borate atom;

Polyborate coinitiators for photopolymerization

Compounds of the formula I ##STR1## in which n and o are a number from 0 to 50, m is a number from 1 to 50, u and v are 0 or 1, and at least one of the indices u and v is 1, R.sub.1, R.sub.2, R.sub.2a, R.sub.3 and R.sub.4 independently of one another are, for example, aromatic hydrocarbons, R.sub.5, if n and o are 0, is for example C.sub.1 -C.sub.12 alkyl and, if n and/or o are greater than 0, or if n and o are 0 and at the same time only one index u or v is 1, R.sub.5 may additionally, for example, be an aromatic hydrocarbon, at least one of the radicals R.sub.1, R.sub.2, R.sub.2a, R.sub.3, R.sub.4 and R.sub.5 being an aromatic hydrocarbon radical which is sterically hindered ortho to the boron atom, X is, for example, C.sub.1 -C.sub.20 alkylene, phenylene, biphenylene, etc., and Z is a radical which is able to form positive ions, are suitable as photoinitiators, both the compounds per se and their combination with dyes or other electron acceptors. Furthermore, the polyborane precursors of these borates possess, together with borate salts, photoinitiating properties.

Polyborane photoinitiators and borate photoinitiators from polyboranes

The invention relates to photopolymerizable compositions comprising as photoinitiator a borate of the formula I or I' ##STR1## R.sub.1, R.sub.2 and R.sub.3 are, for example and independently of one another, phenyl or another aromatic hydrocarbon, with or without any heteroatoms, which radicals are unsubstituted or are substituted, or the radicals R.sub.1 and R.sub.2 form bridges to produce structures of the formula II, IIa or IIb ##STR2## with the provisos that not more than two of the radicals R.sub.1, R.sub.2 and R.sub.3 are identical and either at least two of the radicals R.sub.1, R.sub.2 and R.sub.3 are aromatic hydrocarbon radicals or phenyl radicals which are substituted in both ortho-positions or at least one radical R.sub.1, R.sub.2 or R.sub.3 is a sterically bulky aryl radical and the remaining radicals of R.sub.1, R.sub.2 and R.sub.3 are aromatic hydrocarbon radicals or are phenyl radicals which are substituted in at least one ortho-position; R.sub.4 is, for example, phenyl or C.sub.1 -C.sub.20 alkyl and G is a radical which is able to form positive ions.

Borate photoinitiators from monoboranes

Compounds of the formula I ##STR1## in which R.sub.1 is, for example, C.sub.1 -C.sub.20 alkyl or phenyl-C.sub.1 -C.sub.6 alkyl which radicals are unsubstitutedor substituted; R.sub.2, R.sub.3 and R.sub.4 independently of one another are phenyl or biphenyl, which radicals are unsubstituted or substituted; wherein the sum of the Hammett .sigma. constants (.SIGMA..sub..sigma.) of the substitutents on the aromatic radicals R.sub.2, R.sub.3 and R.sub.4 is between +0.36 and +2.58; R.sub.8, R.sub.9, R.sub.14, R.sub.15 and R.sub.16 are, for example, C.sub.1 -C.sub.12 alkyl, phenyl-C.sub.1 -C.sub.6 alkyl or phenyl, and G is a radical which is able to form positive ions. These compounds are suitable as photoinitiators for photopolymerizable compositions which contain acid groups, in the presence of a coinitiator if desired.

Acid-stable borates for photopolymerization

Compounds of the formula I or I' ##STR1## in which R.sub.1 and R.sub.2 independently of one another, for example, are an aromatic hydrocarbon, with the proviso that the aromatic hydrocarbon radical is substituted in at least one o-position, or R.sub.1 and R.sub.2, for example, independently of one another are C.sub.1 -C.sub.20 alkyl, which is substituted by R.sub.9 R.sub.10 R.sub.11 Si; R.sub.2a is, for example, a divalent aromatic hydrocarbon radical; R.sub.3 is C.sub.1 -C.sub.20 alkyl which is substituted by R.sub.9 R.sub.10 R.sub.11 Si or is an aromatic hydrocarbon; R.sub.4 is, for example, C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.12 cycloalkyl or phenyl-C.sub.1 -C.sub.6 alkyl; E is R.sub.14 R.sub.15 R.sub.16 P or R.sub.8 R.sub.8a R.sub.7 N; R.sub.7, R.sub.8 and R.sub.8a and R.sub.9, R.sub.10 and R.sub.11 independently of one another are, for example, C.sub.1 -C.sub.12 alkyl; R.sub.14, R.sub.15 and R.sub.16 independently of one another are substituted phenyl and G is a radical which is able to form positive ions, with the proviso that, if R.sub.1, R.sub.2 and R.sub.3 are 2,4,6-trimethylphenyl, R.sub.4 is not C.sub.2 -C.sub.20 alkyl or C.sub.2 -C.sub.8 alkenyl, are suitable for use as particularly reactive photoinitiators.

The invention relates to photopolymerizable compositions comprising as photoinitiator a borate of the formula I or I' ##STR1## in which R.sub.1, R.sub.2 and R.sub.3 are, for example and independently of one another, phenyl or another aromatic hydrocarbon, with or without any heteroatoms, which radicals are unsubstituted or are substituted, or the radicals R.sub.1 and R.sub.2 form bridges to produce structures of the formulae II, IIa or IIb ##STR2## with the provisos that not more than two of the radicals R.sub.1, R.sub.2 and R.sub.3 are identical and either at least two of the radicals R.sub.1, R.sub.2 and R.sub.3 are aromatic hydrocarbon radicals or phenyl radicals which are substituted in both ortho-positions or at least one radical R.sub.1, R.sub.2 or R.sub.3 is a sterically bulky aryl radical and the remaining radicals of R.sub.1, R.sub.2 and R.sub.3 are aromatic hydrocarbon radicals or are phenyl radicals which are substituted in at least one ortho-position; R.sub.4 is, for example, phenyl or C.sub.1 -C.sub.20 alkyl and G is a radical which is able to form positive ions. Additionally, the proviso is not all radicals R.sub.1, R.sub.2, R.sub.3 and R.sub.4 simultaneously are aromatic radicals.

Growing community of inventors

Marly, Switzerland

Allan Francis Cunningham