Claims
- 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.sup.1 independently of one another are cyclopentadienyl.crclbar., indenyl.crclbar. or 4,5,6,7-tetrahydroindenyl.crclbar. or said cyclopentadienyl, said indenyl or said 4,5,6,7-tetrahydroindenyl mono- or polysubstituted by C.sub.1 -C.sub.18 -alkyl, by C.sub.1 -C.sub.18 -alkoxy, by C.sub.2 -C.sub.18 -alkenyl, by C.sub.5 --C.sub.8 -cycloalkyl, by C.sub.6 -Cl.sub.16 -aryl, by C.sub.7 -C.sub.6 -aralkyl, by cyano or by halogen, or the two radicals R.sup.1 together are a radical of formula II ##STR12## in which X is (--CH.sub.2 --).sub.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.sup.4.sub.2 or SnR.sup.4.sub.2 where R.sup.4 is C.sub.1 -C.sub.12 -alkyl, C.sub.5 -C.sub.12 -cycloalkyl, C.sub.6 -Cl.sub.6 -aryl or C.sub.7 -C.sub.6 -aralkyl; or said radical of formula II monosubstituted or polysubstituted by C.sub.1 -C.sub.8 -aryl, by C.sub.1 -C.sub.18 -alkoxy, by C.sub.2 -C.sub.18 -alkenyl, by C.sub.5 -C.sub.8 -cycloalkyl, by C.sub.6 -C.sub.16 -aryl, by C.sub.7 -C.sub.16 -aralkyl, by cyano or by halogen;
- R.sup.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.sup.2 and R.sup.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.sup.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.sub.2, alkylidene of 2 to 12 carbon atoms cycloalkylidene of 5 to 7 ring carbon atoms, a direct bond, NR.sup.4, O, S, SO, SO.sub.2, CO, SiR.sup.4.sub.2 or SnR.sup.4.sub.2 where R.sup.4 is defined above,
- R.sup.3 has the same meaning as R.sup.2, or
- R.sup.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.sub.3, CN, SiR.sup.4.sub.3 or SnR.sup.4.sub.3 :
- in which titanocenes R.sup.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.sup.9 is H or C.sub.1 -C.sub.18 -alkyl, wherein said polyoxaalkylene radical is attached to the aromatic radical R.sup.2 or Q by a direct bond or through a bridging group which is --S--, --O--, --OSO.sub.2 --, ##STR13## where the valence bond on the left of the bridging group is attached to the aromatic ring R.sup.2 or Q and the other valences bonds in the bridging group are attached to the polyoxaalkylene radical.
- 2. A composition according to claim 1 which additionally contains (c) a photoinitiator or mixture thereof selected from the group consisting of the benzil ketals, the 4-aroyl-l,3-dioxolanes, the dialkoxyacetophenones, the alpha-hydroxyacetophenones and the alpha-aminoacetophenones.
- 3. A composition according to claim 1 where in the titanocene of formula I, R.sup.1 is cyclopentadienyl.crclbar. or methyl-cyclopentadienyl.crclbar.. 30
- 4. A composition according to claim 1 where in the titanocene of formula I, R.sup.2 and R.sup.3 have the same meaning.
- 5. A composition according to claim 1 where in the titanocene of formula I, R.sup.2 and R.sup.3 are 2,6-difluorophen-1-yl to which at least one polyoxaalkylene radical where R.sup.9 is hydrogen or alkyl is bonded directly or through a bridging group, and which 2,6-difluorophen-1-yl group contains additionally one or two further identical or different substituents.
- 6. A composition according to claim 1 where in the titanocene of formula I the two radicals R.sup.1 are cyclopentadienyl.crclbar. or cyclopentadienyl.crclbar. which is substituted by C.sub.1 -C.sub.4 -alkyl, and R.sup.2 and R.sup.3 are radicals of the formula ##STR14## in which R.sup.5 and R.sup.6 independently of one another are H, F, Cl or Br, and R.sup.7 is a poloxaalkylene radical which is bonded to the phenyl ring directly or through a bridging group.
- 7. A composition according to claim 1 where in the titanocene of formula I in the polyoxaalkylene radical R.sup.9 is C.sub.1 -C.sub.18 -alkyl.
- 8. A composition according to claim 1 where in the titanocene of formula I wherein the alkylene in the polyoxaalkylene radical is ethylene or 1,2-propylene.
- 9. A composition according to claim 1, where in the titanocene of formula I, R.sup.9 is C.sub.1 -C.sub.12 -alkyl, R.sup.10 is H or C.sub.1 -C.sub.12 -alkyl and R.sup.11 is C.sub.1 -C.sub.6 -alkyl, z is a number from 2 to 4, and o is a number from 2 to 6.
- 10. A composition according to claim 1 where in the titanocene of formula I the polyoxaalkylene radical together with the bridging group corresponds to one of the formulae ##STR15## in which R.sup.9 is C.sub.1 -C.sub.12 -alkyl, R.sup.10 is H or C.sub.1 -C.sub.6 -alkyl and o is a number from 2 to 6.
- 11. A composition according to claim 1 where in the titanocene of formula I,
- R.sup.1 is cyclopentadienyl.crclbar. or methylcyclopentadienyl.crclbar. and R.sup.2 and R.sup.3 are radicals of the formula ##STR16## in which R.sup.5 and R.sup.6 are hydrogen or fluorine, o is a number from 2 to 6 and R.sup.9 is C.sub.1 -C.sub.12 -alkyl.
- 12. A composition according to claim 11 wherein R.sup.5 and R.sup.6 are fluorine.
- 13. A composition according to claim 1 wherein the titanocene of component (b) is bis-(cyclopentadienyl)-bis-[4-(1,4,7-trioxa-n-undec--yl)-2,3,5,6-tetrafluorophenyl]-titanocene.
- 14. A substrate coated on at least one surface with a composition according to claim 1.
- 15. A substrate coated on at least one surface with a composition according to claim 2.
Priority Claims (1)
Number |
Date |
Country |
Kind |
3101/86 |
Aug 1986 |
CHX |
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Parent Case Info
This is a divisional application of application Ser. No. 077,261 filed on Jul. 24, 1987, now U.S. Pat. No. 4,857,654, issued on Aug. 5, 1989.
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Foreign Referenced Citations (1)
Number |
Date |
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0207893 |
Jan 1987 |
EPX |
Divisions (1)
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Number |
Date |
Country |
Parent |
77261 |
Jul 1987 |
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