Patent DE-19850139-A1 (DE)
Title: Photoinitiator system for photopolymerizable compositions containing a new styryl-substituted o-alkylated quinolium dye compound as electron acceptor, preferably with a borate compound as electron donor
Inventor: CUNNINGHAM ALLAN FRANCIS
IPC: G03F7/029
Filed: 1998-10-30
Abstract: New styryl-substituted, o-alkylated aromatic nitrogen-heterocyclic amine oxides used as electron acceptors in photostarter systems for photopolymerizable compositions, optionally in combination with electron donors, especially new borate compounds. Compound(s) of formula (I) are new: in which: X  = CH, CCH3, C-Cl, CO-(1-8C alkyl) or <+>NOR L<->;  R  = 1-6C alkyl, benzyl, CH2COOR3, -Ar' or -CH2COAr';  Ar'  = phenyl substituted with r groups Y1;  R1 = 1-8C alkoxy, 1-12C alkyl, halogen, NO2, benzyloxy or phenoxy (both optionally ring-substituted with 1-12C alkyl, 1-6C alkoxy, halogen or CF3);  s  = 0-4;  R2  = H, 1-8C alkoxy, 1-12C alkyl, benzyloxy or phenoxy (optionally substituted as above);  R3  = H, 1-12C alkyl or benzyl;  Ar  = phenyl (A), biphenyl (B), -phenylene-CH=CH-phenyl (C), naphthyl (D), anthryl (E), pyrenyl (F), phenanthryl (G), a group of formula (H), (J) or (K), or -phenylene-N(phenyl)2 (L) (all except L optionally substituted with r groups Y); Y = 1-6C alkyl (optionally substituted with 1-6C alkoxy), or 1-6C alkoxy, halogen, CF3, NO2, CF3O, benxyloxy or phenoxy (both optionally ring-substituted as above), or if r = 2 or more and two Y groups are alkoxy, these alkoxy groups may form a condensed dioxolan or dioxan ring;  Y1  = as for Y (excepting condensed-ring dioxolan and dioxan systems);  W  = O, S or CH2;  W1  = O, S, C(R4)2 or CO; R4 = as for R2 (optionally ring-substituted with 1-12C alkyl or 1-6C alkoxy); r  = 0-5 in formula (A) and in the groups -CH2COAr' and -Ar', r = 0-9 in formulae (B), (C), (E), (F), (G), r = 0-7 in (D), 0-3 in (H), 0-5 in (J) and 0-7 in (K), provided that if Ar = group (A), then R = 1-6C alkyl, benzyl, -CH2COOR3 or  -CH2COAr', X is not <+>NOR L<->, r = 2-5 and L is an anion. Independent claims are also included for (a) a photo-starter system containing compound(s) (I) and optionally electron-donor compound(s); (b) compositions containing (A) polymerizable ethylenic compound(s) and (B) photo-starter system(s) as above; (c) a process for the photopolymerization of monomeric, oligomeric or polymeric compounds with at least one ethylenic double bond by adding this photo-starter system and irradiating with electromagnetic radiation; (d) substrates coated with composition (b) on at least one surface; (e) a process for the photographic production of relief images by irradiating a coated substrate (d) either through a mask or with a moving laser beam and then removing unexposed areas with a solvent; (f) a process for the production of compounds (I) comprising (i) preparation of an aromatic nitrogen-heterocycle with a CH2 group in one or more of the 2-, 4- and 6-positions relative to a ring N, (ii) oxidation of the relevant ring N atom to amine oxide, (iii) alkali-catalyzed reaction of the amine oxide with benzaldehyde (optionally substituted with (Y)r) and (iv) alkylation with a reagent such as methyl toluene-4-sulfonate to the oxide cation as a salt of the anion of the alkylating agent; (g) new borate compounds of formula (X): in which: R40  = phenyl (optionally substituted with 1-5 halogen, 1-4C alkoxy, 1-20C alkyl or 1-20C haloalkyl groups);  R41  = 3-12C cycloalkyl (optionally condensed with 1 or more aromatic rings);  G  = a residue which can form positive ions, preferably a dyestuff compound of formula (I), with the proviso that R40 is not phenyl or mono-para-substituted phenyl if R41 is 3-6C cycloalkyl and R41 is not substituted 1-acenaphthenyl if R40 is unsubstituted phenyl.