Patent EP-0138754-B1 (EP)
IPC: C07C225/20
Filed: 1984-08-09
Granted: 1988-05-25
Abstract: 1. Photopolymerisable mixture containing A) at least one ethylenically unsaturated photopolymerisable compound, B) at least one photoinitiator of the formula I or II   see diagramm : EP0138754,P23,F1     see diagramm : EP0138754,P23,F2   in which Ar is a phenyl, biphenylyl or benzoylphenyl group which is unsubstituted or substituted by one or more of the radicals halogen, C1 -C12 alkyl, C3 -C12 alkenyl, C5 -C6 cycloalkyl, C7 -C9 phenylalkyl, -COOH, -COO(C1 -C4 alkyl), -OR**5 methylenedioxy, -SH, -SR**6 , -SO-R**6 , -SO2 -R**6 , -CN, -SO2 NH2 , -SO2 NH(C1 -C4 alkyl), -SO2 -N(C1 -C4 alkyl)2 , -N(R**7 )(R**8 ) -NHCO-R**9 or by a group of the formula   see diagramm : EP0138754,P23,F3   or is a group of the formula III, IV or V   see diagramm : EP0138754,P23,F4     see diagramm : EP0138754,P23,F5     see diagramm : EP0138754,P24,F1   in which U is unbranched or branched C1 -C7 -alkylene, V is a direct bond, -O-, -S- or -N(R**10 )-, W is a direct bond, -O-, -S- or -N(R**10 )-, X is a divalent radical of the formulae   see diagramm : EP0138754,P24,F2   -N(R**11 )- or -N(R**11 )-(CH2 )m -N(R**11 )- where m = 1-8, Y is a direct bond, -CH2 -, -CH2 CH2 -, -O-, -S-, -CO- or -N(R**10 )-, Z is a direct bond, provided Y is not a direct bond at the same time, or is -CH2 -, -CH2 CH2 -, -O-, -S-, -CO- or -N(R**10 )-, R**1 and R**2 , independently of each other, are each C1 -C8 alkyl, OH-, C1 -C4 alkoxy-, -CN-, -COO(C1 -C8 alkyl)-, (C1 -C4 alkyl)-COO- or -N(R**3 ) (R**4 )-substituted C1 -C4 alkyl, C3 -C6 alkenyl, phenyl, chlorophenyl, R**5 -O-phenyl, R**6 -S-phenyl or C7 -C9 phenylalkyl, or R**1 and R**2 together are unbranched or branched C2 -C9 alkylene or C3 -C9 oxaalkylene or -azaalkylene, R**3 and R**4 , independently of each other, are each hydrogen, C1 -C12 alkyl, OH-, C1 -C4 alkoxy-, -CN- or -COO(C1 -C4 alkyl) monosubstituted or -polysubstituted C2 -C4 alkyl, C3 -C5 alkenyl, cyclohexyl, C7 -C9 phenylalkyl, phenyl or Cl-, OH-, C1 -C12 alkyl-, C1 -C4 alkoxy- or -COO(C1 -C4 alkyl)- substituted phenyl, or R**3 and R**4 together are C3 -C7 alkylene which can be interrupted by -O-, -S- or -N(R**12 )-, or R**4 , together with R**2 , is C1 -C7 alkylene, C7 -C10 phenylalkylene, o-xylylene or C1 -C3 oxaalkylene or -azaalkylene, R**5 is hydrogen, C1 -C12 alkyl, C3 -C12 alkenyl, cyclohexyl, hydroxycyclohexyl, Cl-, Br-, CN-, SH-, -N(C1 -C4 alkyl)2 -, piperidino-, morpholino-, OH-, -O(C1 -C4 alkyl)-, -OCH2 CH2 CN-, -OCH2 CH2 COO(C1 -C4 alkyl)-, -OOC-R**9 -, -COOH-, -COO(C1 -C8 alkyl)-, -CONH(C1 -C4 alkyl)-, -CON(C1 -C4 alkyl)2 -,   see diagramm : EP0138754,P24,F3   -CO-(C1 -C4 alkyl)- or -CO-phenyl-monosubstituted or -polysubstituted C1 -C4 alkyl, 2,3-epoxypropyl, -(CH2 CH2 O)n -H where n = 2-20, phenyl, C7 -C9 phenylalkyl, halogen-, C1 -C4 alkyl-, C1 -C4 alkoxy- or -COO(C1 -C4 alkyl)-substituted phenyl, tetrahydropyranyl, tetrahydrofuranyl, a group of the formula -CO-R**9 , -COO(C1 -C8 alkyl), -CONH(C1 -C4 alkyl), -CON(C1 -C4 alkyl)2 , -Si(R**13 )(R**14 )2 or -SO2 -R**15 , R**6 is C1 -C12 alkyl, C3 -C12 alkenyl, cyclohexyl, hydroxycyclohexyl, Cl-, Br-, CN-, SH-, -N(C1 -C4 alkyl)2 -, piperidino-, morpholino-, -OH-, -O(C1 -C4 alkyl)-, -OCH2 CH2 -CN-, OCH2 CH2 COO(C1 -C4 alkyl)-, -OOC-R**9 -, -COOH-, -COO(C1 -C8 alkyl)-, -CON(C1 -C8 alkyl)2 -,   see diagramm : EP0138754,P24,F4   -CO-(C1 -C4 alkyl)- or -CO-phenyl-monosubstituted or -polysubstituted C1 -C4 alkyl, 2,3-epoxypropyl, phenyl, C7 -C9 phenylalkyl, C7 -C9 phenylhydroxyalkyl, halogen-, C1 -C4 alkyl-, C1 -C4 alkoxy- or -COO(C1 -C4 alkyl)-substituted phenyl, 2-benzothiazolyl, 2-benzimidazolyl, -CH2 CH2 -O-CH2 CH2 -SH or -CH2 CH2 -S-CH2 CH2 -SH, R**7 and R**8 , independently of each other, are each hydrogen, C1 -C12 alkyl, -OH-, C1 -C4 alkoxy-, -CN- or -COO(C1 -C4 alkyl)- monosubstituted C2 -C4 alkyl, C3 -C5 alkenyl, cyclohexyl, C7 -C9 phenylalkyl, phenyl or C1 -C12 alkyl- or halogen-monosubstituted or -polysubstituted phenyl, or R**7 and R**8 together are C2 -C7 alkylene which can be interrupted by -O-, -S- or -N(R**12 )-, R**9 is C1 -C4 alkyl, C2 -C4 alkenyl or phenyl, R**10 is hydrogen, C1 -C4 alkyl, allyl, benzyl or C1 -C4 hydroxyalkyl, R**11 and R**11' are each hydrogen, C1 -C9 alkyl, C1 -C4 hydroxyalkyl, cyclohexyl or benzyl, R**12 is hydrogen, C1 -C4 alkyl, allyl, benzyl, C1 -C4 hydroxyalkyl, -CH2 CH2 CN or -CH2 CH2 -COO(C1 -C4 alkyl), R**13 and R**14 are each C1 -C4 alkyl or phenyl and R**15 is C1 -C18 alkyl, phenyl or C7 -C20 alkylphenyl, and C) a photosensitiser from the group of aromatic carbonyl compounds having a triplet energy of 225-310 kJ/mol, where, if B is a compound of the formula I or II in which Ar is a sulfur- or oxygen-containing radical, C is not a thioxanthone derivative.