Titanocenes and their use

Claim 1

A composition which can be polymerized by radiation which comprises (a) at least one non-volatile monomeric, oligomeric or polymeric compound with at least one polymerizable ethylenically unsaturated double bond, and (b) an effective photoinitiating amount of at least one titanocene of formula I ##STR11## in which the two radicals R 1 independently of one another are cyclopentadienyl⊖, indenyl⊖ or 4,5,6,7-tetrahydroindenyl⊖ or said cyclopentadienyl, said indenyl or said 4,5,6,7-tetrahydroindenyl mono- or polysubstituted by C 1 -C 18 -alkyl, by C 1 -C 18 -alkoxy, by C 2 -C 18 -alkenyl, by C 5 --C 8 -cycloalkyl, by C 6 -Cl 16 -aryl, by C 7 -C 6 -aralkyl, by cyano or by halogen, or the two radicals R 1 together are a radical of formula II ##STR12## in which X is (--CH 2 --) n where n is 1, 2 or 3, alkylidene of 2 to 12 carbon atoms, or said alkylidene substituted by phenyl, cycloalkylidene of 5 to 7 ring carbon atoms, SiR 4 2 or SnR 4 2 where R 4 is C 1 -C 12 -alkyl, C 5 -C 12 -cycloalkyl, C 6 -Cl 6 -aryl or C 7 -C 6 -aralkyl; or said radical of formula II monosubstituted or polysubstituted by C 1 -C 8 -aryl, by C 1 -C 18 -alkoxy, by C 2 -C 18 -alkenyl, by C 5 -C 8 -cycloalkyl, by C 6 -C 16 -aryl, by C 7 -C 16 -aralkyl, by cyano or by halogen; R 2 is a 6-membered carbocyclic aromatic ring or a 5- or 6-membered hetrocyclic aromatic ring which is substituted by fluorine atoms in at least one of the two ortho-positions relative to the metal-carbon bond, or R 2 and R 3 together are a radical of formula III --Q--Y--Q-- (III) in which Q is a carbocyclic aromatic ring, the two bonds in each case being in the ortho-position relative to the Y group, and the meta-position relative to the Y group in each case being substituted by a fluorine atom, or R 2 or Q is further substituted by alkyl of 1 to 18 carbon atoms, by alkoxy of 1 to 18 carbon atoms, by cycloalkyl of 5 to 6 ring carbon atoms, by aralkyl of 7 to 16 carbon atoms, by aryl of 6 to 16 carbon atoms, by hydroxyl, by carboxyl, by cyano, by halogen, by teritiary or quaternary amino, by alkoxycarbonyl of 1 to 18 carbon atoms in the alkoxy group, or by mono- or dialkylaminocarbonyl of 1 to 12 carbon atoms in the alkyl group, Y is CH 2 , alkylidene of 2 to 12 carbon atoms cycloalkylidene of 5 to 7 ring carbon atoms, a direct bond, NR 4 , O, S, SO, SO 2 , CO, SiR 4 2 or SnR 4 2 where R 4 is defined above, R 3 has the same meaning as R 2 , or R 3 is alkynyl of 2 to 6 carbon atoms, phenylethynyl or said phenylethynyl substituted by halogen, by tertiary amino with 1 to 6 carbon atoms, by alkoxy of 1 to 6 carbon atoms, by carboxyl, by alkoxy or by cyano; N 3 , CN, SiR 4 3 or SnR 4 3 : in which titanocenes R 2 contains at least one polyoxaalkylene radical of the formula (--C.sub.z H.sub.2z O).sub.o --R.sup.9 in which z is a number from 2 to 6, o is a number from 1 to 20 and R 9 is H or C 1 -C 18 -alkyl, wherein said polyoxaalkylene radical is attached to the aromatic radical R 2 or Q by a direct bond or through a bridging group which is --S--, --O--, --OSO 2 --, ##STR13## where the valence bond on the left of the bridging group is attached to the aromatic ring R 2 or Q and the other valences bonds in the bridging group are attached to the polyoxaalkylene radical.