Ciba Specialty Chemicals Corporation

Ciba-geigy Corporation

Basf Se Corporation

Ciba-geigy Ag

Igm Malta Limited

Jean-Pierre Wolf

Adrian Schulthess

Bettina Steinmann

Max Hunziker

Gebhard Hug

Ramanathan Ravichandran

Mervin Gale Wood

Joseph Suhadolnik

Raymond R Seltzer

Robert E Detlefsen

Revathi Iyengar

Valerio Borzatta

Andreas Kramer

James Peter Galbo

Glen T Cunkle

Anthony DeBellis

Nicola Lelli

Piero Piccinelli

Randall B Nelson

Cyril Heitner

Michael Ackerman

Peter F McGarry

John A Schmidt

Jean-Luc Birbaum

Kurt Dietliker

Adalbert Braig

Markus Frey

Manfred K&ouml;hler

Beat Michael Aebli

Peter Murer

Ivan Orban

Frans Setiabudi

Stephan Burkhardt

Thomas Bolle

Reinhard Sommerlade

Stephan Ilg

Rinaldo Hüsler

Hansjörg Grützmacher

Souâd Boulmaâz

Nils Hoeck

Daniel Stein

Andr&eacute; Litzler

Guido Tolotti

Peter Nesvadba

Pascal Hayoz

Hitoshi Yamato

Toshikage Asakura

Reinhard Schulz

David Devore

Wolfgang Peter

André Fuchs

Martin Holer

David Bramer

Eugene Valentine Sitzmann

Ernst Eckstein

Anthony David Debellis

Ljubomir Misev

Rudolf Brunner

Sevgi Zeren

Jens Geier

Markus Scherer

Hartmut Schönberg

Thomas Ulrich

Greg Losapio

Attila Latika

Rinaldo HÜSLER

Compounds of the formula (I), (II), (III), (IV) and wherein, R is hydrogen, C-Calkyl; C-Calkyl interrupted by one or more O; is -L-X&#x2014;Ror -L-R; Rhas for example one of the meanings as given for R; Ris a monovalent sensitizer or photoinitiator moiety; Arand Arfor example independently of one another are phenyl substituted by C-Calkyl, halogen or OR; or are unsubstituted naphthyl, anthryl, phenanthryl or biphenylyl; or are naphthyl, anthryl, phenanthryl or biphenylyl substituted by C-Calkyl, OH or OR; or are &#x2014;Ar-A-Ar; Aris unsubstituted phenyl naphthyl, anthryl, phenanthryl or biphenylyl; or is phenyl, naphthyl, anthryl, phenanthryl or biphenylyl substituted by C-Calkyl, ORor benzoyl; Aris phenylene, naphthylene, anthrylene or phenanthrylene; A is a direct bond, S, O or C-Calkylene; X is CO, C(O)O, OC(O), O, S or NR; L is C-Calkylene or C-Calkylene interrupted by one or more O; Ris C-Calkyl or C-Chydroxyalkyl; and Y is an anion, are suitable as photolatent acid generators. 

Sulphonium salt initiators

The invention relates to a dual thermal and ultraviolet radiation curable coating composition, comprising a) at least an ethylenically unsaturated compound; b) a hydroxylamine ester effective to enable IR-curing or NIR-curing of the ethylenically unsaturated compound; c) a photoinitiator effective to enable UV-curing of the ethylenically unsaturated compound; wherein the thermal initiator is a hydroxylamine ester which has a structural element of formula (1) or formula (1) or a polymeric hydroxylamine ester which has a repetitive structural unit of formula (11) or (I[') of formula (11) Furthermore, the invention relates to a process for curing a thermal curable coating composition composing hydroxylamine esters as thermal initiators using NIR-curing. 

Coating composition comprising hydroxylamine esters

The invention relates to novel photoinitiators of formula (I) wherein each of the substituents is given the definition as set forth in the Specification and the claims. The photoinitiators can be used to prepare multifunctional photoinitiators. 

Functionalized photoinitiators

The invention relates to a process for the preparation of (bis)acylphosphanes of formula I, wherein n and m are each independently of the other 1 or 2; R1 if n=1, is e.g. unsubstituted or substituted C-Calkyl or C-Calkenyl, or phenyl, R1 if n=2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C-Calkyl, C-Ccycloalkyl, C-Calkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under R; the process comprises the steps a) contacting e.g. elemental phosphorous [P]&#x221e;, P(Hal)with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides MeP or Me'P, wherein Me is an alkali metal and Me&#x2032; is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m=1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa, wherein R is the residue of an alcohol and Ris as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent RHal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides, which are used as photoinitiators. 

Process for preparing acylphosphanes and derivatives thereof

Incorporable photoinitiator

The present invention relates to a new, selective process for the preparation of mono- and bisacylphosphanes of formula (I) n and m are each independently of the other 1 or 2; R, if n=1, is e.g. phenyl R, if n=2, is e.g. C-Calkylene or phenylene; Ris e. g. C-Calkyl, phenyl or substituted phenyl; Ris e. g. C-Calkyl, by (1) reacting a phosphorous halide of formula IIa or a phosphorous halide oxide of formula (IIb) or a phosphorous halide sulfide of formula (IIc) with an alkali metal in a solvent in the presence of a proton source; (2) subsequent reaction with m acid halides of formula (III) An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides. 

Compounds of formula (I), wherein Ris hydrogen or alkyl; Ris C-Calkoxy or a morpholino radical; and Ris hydrogen or C-Calkoxy, are suitable for improving the solubility of specific photoinitiators in formulations and accordingly enhance the storage stability of formulations comprising a photoinitiator and compounds of formula (I) 

Storage stability of photoinitiators

The invention relates to dimer and multimer form of BAPO compounds of the formula (I) dimer and multimer forms of MAPO compounds of the formula (II) wherein R, R, and Rindependently of one another are unsubstituted or substituted C&#x2013;Calkyl, benzyl, C&#x2013;Calkoxy, C&#x2013;Ccycloalkyl or C&#x2013;Caryl; Q is a di- tri or tetravalent arylene residue; n is 1&#x2013;4, m is 0&#x2013;2, n+m is 2, 3 or 4, with the proviso, that Rand Rare different from each other. The invention further relates to a process for the preparation of dimer or multimer forms of BAPO compounds of the formula (I) and of dimer or multimer forms of MAPO compounds of the formula (II), characterized in the (n+m) equivalents of a dimetalated-phosphine RP(M)is reacted with one equivalent of a di- or polycarboxylic acid halogenide to form an intermediate of the formula III the intermediate is then reacted either with (n+m) equivalents of a further carboxylic acid halogenide (R&#x2014;CO-Hal) or with a halogenide R-Hal, the reaction products are then oxidized to form phosphine oxides of the formula I or II 

Multimer forms of mono-and bis-acylphosphine oxides

Optical fiber coating compositions which comprise at least one ethylenically unsaturated polymerizable compound and a photoinitiator blend, wherein the blend comprises (a) bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (b) 2,4,6,-trimethylbenzoylethoxyphenylphosphine oxide in an (a):(b) weight:weight ratio of between about 1:10 and about 1:8; or (c) bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (d) 2,4,6,-trimethylbenzoylethoxyphenylphosphine oxide and (e) 2-hydroxy-2-methyl-1-phenyl-1-propanone in a (c):(d):(e) weight:weight:weight ratio between about 3:1:14 and about 4:1:16; or (f) bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (g) 2-hydroxy-2-methyl-1-phenyl-1-propanone in a (f):(g) weight:weight ratio of between about 1:3 and about 1:5 exhibit fast photospeed, very low color and fast photobleaching. The photoinitiator blends have low volatility, high shelf life stability and high compatibility with resins and monomers. The photoinitiator blends are for example liquid and easy to use.

Optical fiber coatings

Compounds of formula (I), wherein A is S or O; x is 0 or 1; a is SRor N(R)(R); Rand Rare C&#x2013;Calkyl, OR, CFor halogen; R, Rand Rare hydrogen, C&#x2013;Calkyl, ORor halogen; or two of the radicals RRRRand/or Rtogether form C&#x2013;Coalkylene uninterrupted or interrupted by O, S or NR; R, RRand Rare hydrogen, C&#x2013;Calkyl; C&#x2013;Calkyl which is interrupted one or more times by non-consecutive O atoms and unsubstituted or substituted by OH and/or SH, or R, R, Rand Rg are OR; halogen; or phenyl unsubstituted or substituted one or more times by C-Calkyl; R, Rand Rare e.g. hydrogen; X is e.g. (II), and R; have one of the meanings given for Rand R; and R', R&#x2032; and Rs&#x2032; have one of the meanings given for R, Rand R; are suitable as photoinitiators, especially for irradiation with light of relatively long wavelengths 

Bathochromic mono- and bis-acylphosphine oxides and sulfides and their use as photoinitiators

Compounds of the formula (I), in which E is O or S; and x is 0 or 1, A is cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the mentioned radicals are unsubstituted or substituted by halogen, C&#x2013;Calkyl or C&#x2013;Calkoxy; or A is a group formula (II) R is C&#x2013;Calkyl, unsubstituted or substituted, C&#x2013;Calkyl which is interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted, C&#x2013;Calkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted, C&#x2013;Ccycloalkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted; C&#x2013;Carylalkyl which is unsubstituted or substituted on the aryl group. C&#x2013;Ccycloalkyl which is uninterrupted or interrupted once or more then once by O, S or NRand which is unsubstituted or substituted, C&#x2013;Carylcycloalkyl or C&#x2013;Carylcycloalkenyl; or, R is a group of the formula (III) W is a bond, &#x2014;CO&#x2014;O&#x2014; or &#x2014;CO&#x2014;N(R)&#x2014;; L a di-tri-or tetravalent linking group, n is a number of 2,3 or 4; 

Multimer forms of acylphosphines and their derivatives

Compounds of the formula Iin which or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; Rand Rare C-Calkyl, OR, CFor halogen; R, Rand Rare hydrogen, C-Calkyl, ORor halogen; Ris unsubstituted or substituted C-Calkyl, C-Calkyl, which is interrupted by O, S or NRand is unsubstituted or substituted; C-Calkenyl, uninterrupted or interrupted by O, S or NRand unsubstituted or substituted; unsubstituted or substituted C-Carylalkyl; C-Ccycloalkyl, uninterrupted or interrupted by O, S and/or NR; or C-Carylcycloalkyl; Ris C-Calkyl, C-Ccycloalkyl, phenyl, benzyl or C-Calkyl, interrupted by O or S and unsubstituted or substituted; Rand Rare hydrogen, C-Calkyl, C-Ccycloalkyl, phenyl, benzyl or C-Calkyl, interrupted by O atoms and unsubstituted or substituted; or Rand Rtogether are C-Calkylene, uninterrupted or interrupted by O, S or NR; Ris hydrogen, phenyl, C-Calkyl or C-Calkyl, interrupted by O or S and unsubstituted or substituted; and M is hydrogen, Li, Na or K; are valuable intermediates for the preparation of unsymmetrical bisacylphosphine oxides and monoacylphosphine oxides.

Organometallic monoacylalkylphosphines

Aqueous storage-stable, non-sedimenting photoinitiator suspensions comprising (a) a mono- or bis-acylphosphine oxide of formula (I), wherein R is C -C alkyl; C -C alkyl interrupted by one or more O atoms; C -C alkoxy; phenyl-C -C alkyl; or phenyl that is unsubstituted or substituted by C C alkyl, C -C alkoxy, halogen, cyclopentyl, cyclohexyl, C -C alkenyl, C -C alkyl interrupted by one or more O atoms, and/or by phenyl-C -C alkyl; or R is biphenylyl; R is an aromatic radical or has one of the meanings give for R ; R and R are each independently of the other C -C alkyl, C -C alkoxy or halogen; and R is hydrogen, C -C alkyl, C -C alkoxy or halogen; (b) a dispersant; and (c) water are suitable especially in the photopolymerisation of aqueous formulations comprising ethylenically unsaturated monomers.

Photoinitiator formulations

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Maisprach, Switzerland

Jean-Pierre Wolf