Patent ZA-872663-B (ZA)
Title: Liquid photoinitiator mixtures
IPC: G03F7/029
Filed: 1987-04-14
Abstract: 1. A liquid photoinitiator mixture consisting of A) 70-99.9% by weight of at least one liquid acetal or ketal photoinitiator selected from A1 ) a compound of the formula I  see diagramm : EP0242330,P27,F2  in which Ar**1 and Ar**2 are independently of each other phenyl or C1 -C4 alkyl- or halogen-substituted phenyl, R**1 is C4 -C20 alkyl, C3 -C18 alkenyl, C7 -C10 phenylalkyl, a group -CH(R**3 )-COOR**4 , -R**5 -X, [CH(R**3 )-CH(R**10 )-O]m R**6 or tetrahydrofurfuryl, in which R**3 and R**10 are independently of each other hydrogen or methyl, R**4 is C1 -C20 alkyl, C3 -C5 alkenyl or C3 -C8 alkoxyalkyl, R**5 is C2 -C10 alkylene, X is halogen, -COOR**4 , -OR**4 or -NR**7 R**8 , where R**7 is C1 -C12 alkyl, allyl, benzyl, cyclohexyl, C2 -C4 hydroxyalkyl or C3 -C8 alkoxyalkyl, R**8 is hydrogen or has one of the meanings given for R**7 , or R**7 and R**8 together are C3 -C7 -alkylene which can be interrupted by O, S or NR**9 and R**9 is C1 -C4 alkyl, C2 -C4 hydroxyalkyl or 2-cyanoethyl, m is from 1 to 30 and R**6 is C1 -C20 alkyl, C3 -C5 alkenyl, C3 -C8 alkoxyalkyl, C7 -C22 alkylphenyl or C2 -C20 alkanoyl, and R**2 is C1 -C3 alkyl or has one of the meanings given for R**1 or A2 ) a compound of the formula II  see diagramm : EP0242330,P28,F1  in which R**11 is hydrogen, unsubstituted- or hydroxyl- or C1 -C4 alkoxy-substituted C1 -C10 alkyl or C7 -C10 phenylalkyl, R**12 is phenyl, 2-furyl or trichloromethyl or has one of the meanings given for R**11 , or R**11 and R**12 together with the C atom to which they are bonded form a cyclopentane or cyclohexane ring, R**13 is C1 -C4 alkyl, phenyl or Cl-, C1 -C4 alkyl or C1 -C4 alkoxy-monosubstituted or -polysubstituted phenyl, R**14 is hydrogen or C1 -C4 alkyl, R**15 is hydrogen, C1 -C4 alkyl, phenyl or trichloromethyl, R**16 is hydrogen, chlorine, C1 -C4 alkyl or C1 -C4 alkoxy, or A3 ) a compound of the formula III,  see diagramm : EP0242330,P28,F2  in which Ar**3 is phenyl or C1 -C4 alkyl- or halogen-substituted phenyl, R**17 is hydrogen, C1 -C8 -alkyl or C5 -C8 cycloalkyl, R**18 is C1 -C8 alkyl or C3 -C8 alkoxyalkyl and R**19 has one of the meanings given for R**18 , and B) 0.1-30% by weight of a titanocene photoinitiator selected from B1 ) a compound of the formula IV  see diagramm : EP0242330,P28,F3  in which R**21 and R**22 are independently of each other an unsubstituted or C1 -C4 alkyl-, chlorine-, phenyl- or cyclohexyl-substituted cyclopentadienyl or indenyl anion or R**21 and R**22 together are a divalent biscyclopentadienyl anion of the formula V,  see diagramm : EP0242330,P28,F4  in which Z is methylene, dimethylene, trimethylene, C2 -C12 alkylidene, C5 -C7 cycloalkylidene, -Si(R**25 )(R**26 )- or -Sn(R**25 )2 - and R**25 and R**26 are C1 -C12 alkyl, phenyl or benzyl, R**23 is the monovalent radical of a 6-membered carbocyclic or 5- or 6-membered heterocyclic aromatic ring which is substituted in at least one ortho-position relative to the bond to the Ti atom by fluorine and also by one or more of the groups halogen, C1 -C12 alkyl, C1 -C14 alkoxy, C2 -C10 -alkoxycarbonyl, amino-carbonyl of up to 12 carbon atoms or by a primary, secondary or tertiary amino or aminoalkyl group having up to 20 carbon atoms or a quaternary ammonium or ammoniumalkyl group having up to 30 C atoms, R**24 has one of the meanings given for R**23 or is C2 -C12 alkynyl, phenylalkynyl having 2-5 C atoms in the alkynyl radical and is unsubstituted or substituted in the phenyl radical by halogen or C1 -C4 alkyl, C1 -C14 alkoxy, di-(C2 -C4 alkyl)-amino or a quaternary ammonium group, or is a group -N3 -, -CN, -Si(R**25 )3 , -Si(R**25 )2 (R**26 ) or -Sn(R**25 )3 , or R**23 and R**24 together are a radical of the formula VI -Q-Y-Q- in which Q is a carbocyclic or 5- or 6-membered heterocyclic aromatic ring which in the 2-position relative to the Y group is bonded to the titanium atom and in the 3-position is substituted by fluorine and can contain as further substituents C1 -C4 alkyl, halogen, C1 -C4 alkoxy, di-(C1 -C4 alkyl)amino or a quaternary C3 -C20 ammonium group, Y is methylene, C2 -C12 alkylidene, C5 -C7 cycloalkylidene, a direct bond or a group -NR**27 -, -O-, -S-, -SO-, -SO2 , -CO-, -Si(R**25 )(R**26 )- or -Sn(R**25 )2 - and R**27 is hydrogen, C1 -C12 alkyl, cyclohexyl, phenyl, tolyl or benzyl, or B2 ) a compound of the formula VII  see diagramm : EP0242330,P29,F1  in which R**21 and R**22 are as defined above, R**28 is the monovalent radical of a 6-membered carbocyclic or 5- or 6-membered heterocyclic aromatic ring which is substituted in at least one ortho-position relative to the bond to the Ti atom by -CF3 and can additionally be substituted by one or more of the groups halogen, C1 -C12 alkyl, C1 -C14 alkoxy, C2 -C10 alkoxycarbonyl or aminocarbonyl or by a primary, secondary or tertiary amino or aminoalkyl group having up to 20 C atoms or a quaternary ammonium or ammoniumalkyl group having up to 30 C atoms and R**29 has one of the meanings given for R**28 or is C2 -C12 alkynyl, phenylalkynyl having 2-5 C atoms in the alkynyl radical which is unsubstituted or substituted in the phenyl radical by halogen or C1 -C4 alkyl, or is halogen or a group -Si(R**25 )3 , -Si(R**25 )2 (R**26 ), -Sn(R**25 )3 , -OH, C1 -C10 alkoxy, C6 -C10 aryloxy, unsubstituted or halogen-substituted C1 -C6 acyloxy, -N3 , -CN, -NCO or -NCS.