Photopolymerizable compositions containing prepolymers with olefin double bonds and titanium metallocene photoinitiators
AssigneeCiba-Geigy Corporation
InventorsMartin Riediker, Ottmar Rohde, Martin Roth, Niklaus Buhler
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Abstract
The invention relates to photopolymerizable compositions comprising (a) a prepolymer containing photopolymerizable olefinic double bonds, (b) photoinitiator of the formula ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 are as defined in claim 1, and optionally (c) an ester of acrylic or methacrylic acid or an allyl ether or allyl ester of a polyol. Owing to their excellent light sensitivity, these compositions are suitable for the economic production of high temperature resistant protective layers and relief structures having excellent resolution and good contours.
Claims21
A photopolymerizable composition which comprises,
- (a) a prepolymer which contains identical or different recurring structural units of the formula I ##STR51## and which reacts, when heated, to form a thermostable ring structure, and (b) a photoinitiator,
- wherein the photoinitiator (b) is a metallocene of the formula II ##STR52## wherein R.sup.1 is each independently unsubstituted or substituted cyclopentadienyl.sup..crclbar., indenyl.sup..crclbar., or both symbols R.sup.1 together are an unsubstituted or substituted radical of the formula III ##STR53## R.sup.2 is a carbocyclic or 5- or 6-membered heterocyclic aromatic ring which is substituted in at least one of the two ortho-positions relative to the metal-carbon bond by a fluorine atom,
- R.sup.3 is C.sub.3 -C.sub.5 alkynyl, substituted or unsubstituted phenylalkynyl containing 3 to 5 carbon atoms in the alkynyl moiety, N.sub.3, CN, Si(R.sup.7).sub.3 or Sn(R.sup.7).sub.3, or has the meaning of R.sup.2, or R.sup.2 and R.sup.3 together are a radical of the formula IV
- --Q--Y--Q-- (IV),
- R.sup.4 is a tetravalent aromatic radical after removal of four functional groups, with any two functional groups being adjacent and.fwdarw.denoting structural isomers,
- R.sup.5 is a divalent aliphatic, cycloaliphatic or monocyclic or polycyclic aromatic radical, or aromatic radicals which contain a --CONH.sub.2 or --COOH group in the ortho-position to the bond to Z',
- R.sup.6 is a radical containing a photopolymerisable olefinic double bond,
- R.sup.7 is C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.6 -C.sub.16 aryl or C.sub.7 -C.sub.16 aralkyl,
- Z is --COO--, --CONH--, --O--, --NH--, --COOH/NR.sup.14 R.sup.15 -- or ##STR54## wherein/between amine and carboxyl groups denotes as ionic bond, Z' is --CONH--, --NHCO--, --NH--CO--NH-- or --O--CO--NH--, and each of R.sup.14 and R.sup.15 is independently alkyl or alkenyl each having up to 6 carbon atoms,
- with the proviso that, on heating the photopolymerisable composition to remove the radical R.sup.6, either Z and Z', or Z and Z' together with --CONH.sub.2 or --COOH groups contained in R.sup.5, form a thermostable ring system,
- X is (CH.sub.2).sub.n, in which n is 1, 2 or 3, C.sub.2 -C.sub.12 alkylidene, cycloalkylidene containing 5 to 7 ring carbon atoms, Si(R.sup.7).sub.2 or Sn(R.sup.7).sub.2,
- Q is a carbocyclic or heterocyclic 5- or 6-membered aromatic ring, each of the two bonds being in the ortho-position to the group Y and each meta-position to the group Y being substituted by a fluorine atom, and Q may contain further substituents, and Y is CH.sub.2, C.sub.2 -C.sub.12 alkylidene, cycloalkylidene containing 5 to 7 ring carbon atoms, a direct bond, NR.sup.7, O, S, SO, SO.sub.2, CO, Si(R.sup.7).sub.2 or Sn(R.sup.7).sub.2.
Dependencies are inferred from the claim text.