Ciba-Geigy Corporation

Ciba-Geigy Ag

Rudolf Kirchmayr

Werner Rutsch

Rinaldo Husler

Louis Felder

Godwin Berner

Andreas Schmidt

Hugo Illy

Kurt Dietliker

Helmut Zondler

Manfred Rembold

Emil Saladin

Abul Iqbal

Zhimin Hao

Kurt Weber

Daniel Bellus

Donald Richard Randell

Andre Schmitter

Henri Dubas

Werner Fussenegger

Joachim Dazzi

Henri Dietrich

Jean Brunisholz

Rinaldo Kusler

Husler

Louis Felder-Schraner, Deceased

Urs Frei

The invention relates to pyrrolo 3,4-c!pyrroles of formula ##STR1## wherein A and B are each independently of the other a group of formula ##STR2## or Q, wherein Q is a 5- or 6-membered heterocyclic aromatic amine oxide radical which is unsubstituted or substituted by one, two or three C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 alkoxy or ##STR3## and which may contain one or two fused benzene rings, R.sub.1 and R.sub.2 are each independently of the other hydrogen, halogen, C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 alkoxy, C.sub.1 -C.sub.18 alkylmercapto, --CN, --NO.sub.2 or trifiuoromethyl, D and E are each independently of the other hydrogen, C.sub.1 -C.sub.18 alkyl, C.sub.2 -C.sub.4 alkenyl, C.sub.7 -C.sub.10 aralkyl, unsubstituted phenyl or phenyl which is substituted by chloro, bromo, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 alkoxy, trifiuoromethyl or nitro, with the proviso that at least one of the sustituents A and B is an amine oxide radical Q. These novel diketopyrrolo 3,4-c!pyrroles are suitable for use as pigments, but especially as photoconductive substances in electrophotographic photoreceptors.

Pyrrolo 3,4-c!pyrroles containing amine oxide groups

Propiophenones of the formula I ##STR1## in which R.sup.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, --Si(CH.sub.3).sub.3, allyl or benzyl, R.sup.2 is hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.4 -alkyl which is substituted by C.sub.1 -C.sub.4 -alkoxy or --OH, --(CH.sub.2 --CH.sub.2 --O).sub.n --R.sup.5 where n is 2 to 20 and R.sup.5 is H or C.sub.1 -C.sub.4 -alkyl, --Si(CH.sub.3).sub.3, benzyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.4 -alkynyl or 2-tetrahydrofuranyl, or R.sup.1 and R.sup.2 together are a C.sub.1 -C.sub.6 -alkylidene radical or a C.sub.2 -C.sub.6 -alkylidene radical which is substituted by hydroxyl, C.sub.1 -C.sub.4 -alkoxy or phenyl, a linear or branched C.sub.2 -C.sub.6 -alkanediyl radical, a benzylidene, cyclopentylidene or cyclohexylidene radical or a 2,2,2-trichloroethylidene, 2-furylmethylidene or dimethylsilylidene radical, R.sup.3 is phenyl which is unsubstituted or substituted by one or more --Cl, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkylthio radicals, and is also benzoylphenyl, phenoxyphenol or phenylthiophenyl, R.sup.4 is C.sub.1 -C.sub.4 -alkyl, or phenyl which is unsubstituted or substituted by one or more --Cl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy radicals, and R.sup.5 is hydrogen or C.sub.1 -C.sub.4 -alkyl, or R.sup.4 and R.sup.5 together are a trimethylene or tetramethylene radical, and R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, --CCl.sub.3 or phenyl, subject to the condition that, if R.sup.2, R.sup.5 and R.sup.6 at the same time are hydrogen and R.sup.3 and R.sup.4 are at the same time phenyl, R.sup.1 must not be hydrogen or C.sub.1 -C.sub.4 -alkyl, also, if R.sup.3 and R.sup.4 at the same time are phenyl and R.sup.5 and R.sup.6 are at the same time hydrogen, R.sup.1 and R.sup.2 together must not be alkylidene or benzylidene, and also, if R.sup.3 and R.sup.4 at the same time are p-methoxyphenyl and R.sup.2, R.sup.5 and R.sup.6 are at the same time hydrogen, R.sup.1 must not be hydrogen, and, finally, if R.sup.2 and R.sup.6 at the same time are hydrogen and R.sup.3, R.sup.4 and R.sup.5 are at the same time phenyl, R.sup.1 must not be hydrogen, are valuable initiators for the photopolymerization of ethylenically unsaturated compounds.

Propionphenone derivatives as photoinitiators for photopolymerization

Compounds of the formula I ##STR1## in which n is 1-30 and X, Y, R, Ar.sup.1 and Ar.sup.2 are as defined in claim 1 can be prepared by reaction of a benzil dialkyl ketal with a diol. Depending on the molar ratio of the two reaction components, products having a different polycondensation degree n are obtained. the compounds can be used as photoinitiators.

Oligomeric benzil ketals and their use as photoinitiators

Compounds of the formula I ##STR1## in which n is 1-30 and X, Y, R, Ar.sup.1 and Ar.sup.2 are as defined in claim 1 can be prepared by reaction of a benzil dialkyl ketal with a diol. Depending on the molar ratio of the two reaction components, products having a different polycondensation degree n are obtained. The compounds can be used as photoinitiators.

Process for the preparation of tert-alkyl esters of the formula I ##STR1## in which m is 1 or 2, R is C.sub.4 -C.sub.12 tert-alkyl and X, if m=1, is unsubstituted or halogen-substituted alkyl, cycloalkyl, unsubstituted or substituted aryl or aralkyl, or an aromatic heterocyclic radical and, if m=2, is a direct bond, --CH.sub.2).sub.n, in which n can be an integer from 1 to 8, or 1,2-, 1,3- or 1,4-phenylene, by reaction of an ester of the formula II ##STR2## in which R.sub.1 is methyl or ethyl, with an alcohol ROH in the presence of a catalyst customary for transesterifications.

Process for the preparation of tert-alkyl esters

Compounds of the formula I, II or III ##STR1## in which Ar and Ar' are an oxygen-containing aromatic radical, R.sup.1 and R.sup.2 are a monovalent hydrocarbon radical which is substituted or unsubstituted, or R.sup.1 and R.sup.2 together form alkylene, oxaalkylene or azaalkylene, R.sup.3 is a direct bond or a divalent hydrocarbon radical, X and X' are a monovalent amino group and Y is a divalent amino or diamino group, are excellent photoinitiators for the photocuring of colored, especially pigmented, compositions containing an olefinically unsaturated, photopolymerizable binder.

Phenyl ketone derivatives

Compounds of formula X ##STR1## in which R.sub.6 is aryl, R.sub.7 is hydrogen, --OH or alkyl, R.sub.8 is alkyl, R.sub.9 is hydrogen, alkyl, alkenyl, aryl, furyl or --CCl.sub.3, when n is 1, R.sub.10 is alkyl, aryl, camphoryl, --CF.sub.3 or fluoro, or when n is 2, R.sub.10 is alkylene or arylene are latent curing catalysts for acid-curable stoving varnishes. On irradiation, the active curing catalysts which lead to acid-catalysed curing of the resins are formed from the compounds of the formula x.

Acid-curable composition containing a masked curing catalyst, and a

Propiophenones of the formula I ##STR1## in which R.sup.1 is hydrogen or C.sub.1 -C.sub.4 -alkyl, --Si(CH.sub.3).sub.3, allyl or benzyl, R.sup.2 is hydrogen, C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.4 -alkyl which is substituted by C.sub.1 -C.sub.4 -alkoxy or --OH, --(CH.sub.2 --CH.sub.2 --O).sub.n --R.sup.5 where n is 2 to 20 and R.sup.5 is H or C.sub.1 -C.sub.4 -alkyl, --Si(CH.sub.3).sub.3, benzyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.4 -alkynyl or 2-tetrahydrofuranyl, or R.sup.1 and R.sup.2 together are a C.sub.1 -C.sub.6 -alkylidene radical or a C.sub.2 -C.sub.6 -alkylidene radical which is substituted by hydroxyl, C.sub.1 -C.sub.4 -alkoxy or phenyl, a linear or branched C.sub.2 -C.sub.6 -alkanediyl radical, a benzylidene, cyclopentylidene or cyclohexylidene radical or a 2,2,2-trichloroethylidene, 2-furylimethylidene or dimethylsilylidene radical, R.sup.3 is phenyl which is unsubstituted or substituted by one or more --Cl, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkylthio radicals, and is also benzoylphenyl, phenoxyphenyl or phenylthiophenyl, R.sup.4 is C.sub.1 -C.sub.4 -alkyl, or phenyl which is unsubstituted or substituted by one or more --Cl, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy radicals, and R.sup.5 is hydrogen or C.sub.1 -C.sub.4 -alkyl, or R.sup.4 and R.sup.5 together are a trimethylene or tetramethylene radical, and R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, --CCl.sub.3 or phenyl, subject to the condition that, if R.sup.2, R.sup.5 and R.sup.6 at the same time are hydrogen and R.sup.3 and R.sup.4 ar at the same time phenyl, R.sup.1 must not be hydrogen or C.sub.1 -C.sub.4 -alkyl, also, if R.sup.3 and R.sup.4 at the same time are phenyl and R.sup.5 and R.sup.6 are at the same time hydrogen, R.sup.1 and R.sup.2 together must not be alkylidene or benzylidene, and also, if R.sup.3 and R.sup.4 at the same time are p-methoxyphenyl and R.sup.2, R.sup.5 and R.sup.6 are at the same time hydrogen, R.sup.1 must not be hydrogen, and, finally, if R.sup.2 and R.sup.5 at the same time are hydrogen and R.sup.3, R.sup.4 and R.sup.6 are at the same time phenyl, R.sup.1 must not be hydrogen, are valuable initiators for the photopolymerization of ethylenically unsaturated compounds.

Propiophenone derivatives as photoinitiators for photopolymerization

Compounds of the formula I and II ##STR1## in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, X, Y and n are as defined in claim 1, are latent curing catalysts for preparing relief images with acid-curable resins. They are distinguished by satisfactory solubility in the acid-curable resin systems, can be stored virtually indefinitely in the dark and, when exposed to shortwave light, make it possible to cure the resins by acid catalysis at a relatively low temperature.

Process for preparing relief images using acid-curable resins and masked

Compounds of formula II and X ##STR1## wherein X is O, S, SO.sub.2, methylene, isopropylidene or NCOR.sub.7 where R.sub.7 is alkyl or phenyl, Y is a direct bond or methylene, n is 1 or 2, R.sub.4 is alkyl, phenyl, naphthyl, cycloalkyl, aralkyl, camphoryl, CF.sub.3, CCl.sub.3, F or NH.sub.2 ; or is alkylene, phenylene or naphthylene, R.sub.5 is hydrogen or halogen, R.sub.6 is hydrogen, alkyl, phenyl or cyano, R.sub.8 is substituted phenyl, substituted naphthyl, anthryl or phenanthryl, R.sub.9 is alkyl R.sub.10 is alkyl or substituted phenyl, and R.sub.11 is alkyl, substituted phenyl, naphthyl, camphoryl, alkylene, phenylene or naphthylene, are latent curing catalysts for acid-curable stoving lacquers. They are distinguished by satisfactory solubility in the acid-curable resin systems, can be stored virtually indefinitely in the dark and, when exposed to shortwave light, make it possible to cure the resins by acid catalysts at a relatively low temperature.

Masked curing catalyst for acid-curable compositions

Compounds of the formula I, II or III ##STR1## in which Ar is a sulfur-containing aromatic radical, R.sup.1 and R.sup.2 are a monovalent hydrocarbon radical which is substituted or unsubstituted or R.sup.1 and R.sup.2 together form alkylene, oxaalkylene or azaalkylene, R.sup.3 is a direct bond or a divalent hydrocarbon radical, X is a monovalent amino group and X' is a divalent amino or diamino group, are excellent photoinitiators for the photocuring of colored, in particular pigmented, compositions containing an olefinically unsaturated, photopolymerizable binder.

Ketone with morpholino and s-phenyl groups as photoinitiator in

Cationically polymerizable compounds, for example epoxide compounds, can be polymerized photochemically using a catalyst combination consisting of an aromatic iodonium salt and a ketone of the formula I, II or III ##STR1## in which n is 1 or 2 and Ar, X, X', R.sup.1, R.sup.2 and R.sup.3 are as defined in claim 1. In this combination, the ketones act as a co-catalyst and drastically accelerate the photopolymerization, although they are not able to initiate a cationic photopolymerization on their own.

Photopolymerizable mixtures and processes for the photopolymerization of

Photocurable colored compositions employing alpha-amino phenone initiator

Compounds of the formula I and II ##STR1## in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6, X, Y and n are as defined in claim 1, are latent curing catalysts for acid-curable stoving lacquers. They are distinguished by satisfactory solubility in the acid-curable resin systems, can be stored virtually indefinitely in the dark and, when exposed to shortwave light, make it possible to cure the resins by acid catalysis at a relatively low temperature.

Growing community of inventors

Aesch, Switzerland

Rudolf Kirchmayr