Ciba-geigy Corporation

Martin Riediker

Eginhard Steiner

Harry Beyeler

Martin Roth

Niklaus Buhler

Manfred Rembold

Joseph Berger

Rinaldo Husler

Franciszek Sitek

Guido Bold

Peter Herold

Kurt Dietliker

Kurt Meier

Rudolf Duthaler

Robert W Lang

Konrad Oertle

Vincent Desobry

Ottmar Rohde

Hans Zweifel

Armin Schaffner

Francissek Sitek

Titanocenes of the formula I ##STR1## in which R.sup.1 are cyclopentadienyl.sup..crclbar. groups and R.sup.2 and R.sup.3 are aromatic radicals which are substituted in both ortho-positions by fluorine and, in addition, are substituted by an acyloxy group are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.

Oxygen-containing titanocenes, and the use thereof

Titanocenes with, for example, .pi.-cyclopentadienyl ligands in which one or two carbo- or heterocyclic aromatic rings are bonded to the titanium, the aromatic rings being substituted by fluorine in at least one of the two ortho-positions relative to the metal-carbon bond and being substituted by at least one free or etherified or esterified polyoxaalkylene radical, are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated substrates.

Process for the photographic production of relief images using selected

Titanocenes containing two 5-membered cyclodienyl gropus, for example cyclopentadienyl, and one or two 6-membered carbocyclic or 5- or 6-membered heterocyclic aromatic rings which are substituted by a fluorine atom in at least one of the two ortho-positions to the titanium-carbon bond and contain, as further substituents, a substituted amino radical, are suitable as photoinitiators for radiation-induced polymerization of ethylenically unsaturated compounds.

Titanocenes, the use thereof, and n-substituted fluoroanilines

The present invention relates to compositions comprising

Photoinitiator mixtures containing a titanocene and a 3-ketocoumarin

Titanocenes with, for example, .pi.-cyclopentadienyl ligands in which one or two carbo- or heterocyclic aromatic rings are bonded to the titanium, the aromatic rings being substituted by fluorine in at least one of the two ortho-positions relative to the matal-carbon bond and being substituted by at least one free or etherified or esterified polyoxaalkylene radical, are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated substrates.

Titanocenes and their use

Titanocenes containing .pi.-cyclopentadienyl ligands, in which one or two carbocyclic or heterocyclic aromatic rings are attached to the metal atom, said aromatic rings being substituted by fluorine in at least one of the two ortho-positions relative to the metal-carbon bonds, are suitable photoinitiators for the photopolymerization of ethylenically unsaturated substrates. They are distinguished by high sensitivity, stability to air and heat, and are very effective in the range from UV light to visible light.

Process for producing photographic relief images using

Compounds of the formulae I and Ia ##STR1## in which R.sup.1 is a group which can be transferred to carbonyl or imine compounds, for example alkyl, allyl, vinyl or the radical of an enol or enamine, R.sup.2 is, for example, cyclopentadienyl, R.sup.3 is the radical of an optically active sugar or sugar derivative, Me is Ti, Zr or Hf, x is 0, 1 or 2 and y is 0, 1, 2 or 3, M.sup..sym. is Li.sup..sym., Na.sup..sym., K.sup..sym., MgY.sup..sym., ZnY.sup..sym., CdY.sup..sym., HgY, CuY.sup..sym. or quaternary ammonium, Y being halogen, are suitable for use as chiral reactants for compounds containing aldehyde, keto and/or N-substituted imine groups.

Complexes containing optically active sugar ligands, a process for their

Photopolymerizable composition containing metallocenes

Titanocenes with .pi.-cyclopentadienyl ligands, in which one or two carbocyclic or heterocyclic aromatic rings are bonded to the metal, the aromatic rings being substituted in at least one of the two ortho-positions relative to the metal-carbon bonds by CF.sub.2 Z (Z=F or substituted or unsubstituted alkyl), are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated compounds. They are distinguished by a high radiation sensitivity, stability to air and thermal effects, and high effectiveness in the range from UV light to visible light.

Titanocenes and a radiation-polymerizable composition containing these

Compounds of the forulae I and Ia ##STR1## in which R.sup.1 is a group which can be transferred to carbonyl or imine compounds, for example alkyl, allyl, vinyl or the radical of an enol or enamine, R.sup.2 is, for example, cyclopentadienyl, R.sup.3 is the radical of an optically active sugar or sugar derivative, Me is Ti, Zr or Hf, x is 0, 1 or 2 and y is 0, 1, 2 or 3, M.sym. is Li.sym., Na.sym., K.sym., MgY.sym., ZnY.sym., CdY.sym., HgY, CuY.sym. or quaternary ammonium, Y being halogen, are suitable for use as chiral reactants for compounds containing aldehyde, keto and/or N-substituted imine groups.

Metal complexes containing optically active sugar ligands, a process for

Fluorinated titanocenes and photopolymerizable composition containing

The invention relates to photopolymerizable compositions comprising (a) a prepolymer containing photopolymerizable olefinic double bonds, (b) photoinitiator of the formula ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 are as defined in claim 1, and optionally (c) an ester of acrylic or methacrylic acid or an allyl ether or allyl ester of a polyol. Owing to their excellent light sensitivity, these compositions are suitable for the economic production of high temperature resistant protective layers and relief structures having excellent resolution and good contours.

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Riehen, Switzerland

Martin Riediker