Patent CH-691775-A5 (CH)
Title: Photopolymerisable composition
Inventor: KUNZ MARTIN
IPC: C08F2/50
Filed: 1996-11-14
Abstract: A composition comprises: (a) polymerisable ethylenically unsaturated compound(s); and (b) compound(s) of formula (I) or (I') as unimolecular photoinitiator. - In the formulae, R1, R2 and R3 = phenyl or other aromatic hydrocarbon (optionally with heteroatom) optionally substituted 1-5 times by 1-20C alkyl (optionally substituted by OR6 or R7R8N), 2-20C alkyl which is interrupted by O, S(O)p or NR5, or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P(O)q, CN and/or a group of formula (i)-(iv), or the R2 and R3 form bridges to produce structures of formula (II), (IIa) or (IIb) in which the aromatic rings are optionally substituted by 1-20C alkyl, 2-20C alkyl which is interrupted by O, S(O)p or NR5, or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, halogen, R9R10P(O)q and/or R9R10R11Sn, provided that not more than two of R1, R2 and R3 are identical and either at least two of them are aromatic hydrocarbon radicals or phenyl radicals which are substituted in both ortho-positions or at least one of them is a sterically bulky aryl radical and the remainder are aromatic hydrocarbon radicals or phenyl radicals which are substituted in ortho-position(s); R1a = divalent aromatic hydrocarbon radical (optionally substituted by 1-6C alkyl, OR6, S(O)pR6, OS(O)2R6, NR8R7, C(O)OR6, C(O)NR8R7, C(O)R9, SiR9R10R11 or halogen) or phenyl-1-6C alkylene; R4 = phenyl or other aromatic hydrocarbon (optionally with heteroatom) optionally substituted 1-5 times by 1-20C alkyl (optionally substituted by OR6 or R7R8N), 2-20C alkyl which is interrupted by O, S(O)p or NR5,  or are substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, halogen, R9R10P(O)q, CN and/or a group of formula (i)-(iv), or R4 = 1-20C alkyl, 2-20C alkyl which is interrupted by O, S(O)p or NR5, or is 2-20C alkyl which is interrupted by O, S(O)p and/or NR5 or is phenyl, other aromatic hydrocarbon, 1-20C alkyl, 3-12C cycloalkyl, 2-8C alkenyl, phenyl-1-6C alkyl or naphthyl-1-3C alkyl optionally substituted by OR6, R6S(O)p, R6S(O)2O, R7R8N, R6OC(O), R7R8NC(O), R9C(O), R9R10R11Si, R9R10R11Sn, R12R13B, halogen, R9R10P(O)q and/or CN; Y = (CH2)n, CH=CH, C(O), NR5, O, S(O)p or a group of formula (v); n = 0, 1 or 2, m = 2 or 3; p = 0, 1 or 2; q = 0 or 1; E = R21R22R23P, R7R7aR8N or R6R6aS; R5 = H, 1-12C alkyl or phenyl-1-6C alkyl or phenyl which are optionally substituted 1-5 times by 1-6C alkyl, 1-12C alkoxy and/or halogen; R6 and R6a = as R5 except H; R7, R7a and R8 = 1-12C alkyl (optionally substituted with 1-12C alkoxy, halogen, OH, COOR6 or CN) or 3-12C cycloalkyl or phenyl-1-6C alkyl or phenyl (optionally substituted 1-5 times with 1-6C alkyl, 1-12C alkoxy and/or halogen) or R7 and R8, together with the N to which they are attached, form a 5- or 6-membered ring which may additionally contain O or S atoms;  R9, R10 and R11 = 1-12C alkyl, 3-12C cycloalkyl or phenyl-1-6C alkyl or phenyl which are optionally substituted 1-5 times by 1-6C alkyl, 1-12C alkoxy and/or halogen; R12-R15 = H, 1-12C alkyl (optionally substituted by 1-12C alkoxy), phenyl-1-6C alkyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen) or phenyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen), or R12-R15 together form an aromatic ring to which further aromatic rings may be fused; R16-R20 and R18a = H, 1-12C alkyl (optionally substituted by 1-12C alkoxy, OH or halogen) or phenyl (optionally substituted by 1-12C alkoxy, OH or halogen); R21, R22 and R23 = 1-12C alkyl, 2-12C alkenyl or 3-12C cycloalkyl (optionally substituted by R6OCO or CN) or they are phenyl-1-6C alkyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen) or phenyl (optionally substituted by mono- to penta-1-6C alkyl, -1-12C alkoxy or -halogen); X = N, S or O; and G = a radical which is able to form positive ions. - Also claimed are: (i) a compound of formula (I) or (I'); (ii) a process for the photopolymerisation of non-volatile monomeric, oligomeric or polymeric compounds containing ethylenically unsaturated double bond(s); (iii) a substrate which is coated on its surface(s) with a composition as above; (iv) a process for the photographic production of relief images which comprises subjecting a coated substrate as in (iii) to imagewise exposure and removing the unexposed areas with a solvent; (v) a process for producing relief images which comprises exposing a coated substrate as in (iii) by means of a movable laser beam (without mask) and subsequently removing the unexposed areas with a solvent; and (vi) a process for the thermal polymerisation of compounds containing ethylenically unsaturated double bonds, which comprises using (I) or (I')  as an initiator.