Photopolymerizable compositions containing cyclic cis-α-dicarbonyl compounds and selected sensitizers

Abstract

Photopolymerizable compositions comprising an ethylenically unsaturated monomer and an initiating combination of a cyclic cis-α-dicarbonyl compound and certain radiation-absorbing sensitizers are disclosed. Compositions of the invention have improved photospeed and may be chosen to provide a wide range of spectral sensitivity.

I claim: 
     
       1. A photopolymerizable composition comprising (a) at least one non-gaseous ethylenically unsaturated compound having a boiling point above 100° C. at normal atomspheric pressure and being capable of forming a high polymer by photoinitiated, addition polymerization;   (b) a cyclic cis-α-dicarbonyl compound, the excited state of which cannot react intramolecularly .Iadd., the atoms adjacent to the two vicinyl carbonyl groups being saturated when they are carbon atoms.Iaddend.; and   (c) an actinic radiation absorbing compound capable of sensitizing the polymerization initiating action of said cyclic cis-α-dicarbonyl compound, said actinic radiation absorbing compound being a nitrogen-containing aromatic or heterocyclic compound, having maximum absorption below 520 nm., selected from the class consisting of bis(p-aminophenyl-α,β-unsaturated) ketones; bis(alkylamino) acridine dyes; cyanine dyes containing two heterocyclic rings joined by a single methine group; styryl dye bases; 7-diloweralkylamino-4 lower alkyl coumarins; p-aminophenyl ketones; p-dialkylaminophenyl unsaturated compounds; and 6-dialkylaminoquinaldines.   
     
     
       2. A composition according to claim 1 wherein said cyclic cis-α-dicarbonyl compound is selected from the group consisting of 2,3-bornanedione; 2,2,5,5-tetramethyltetrahydro-3,4-furandione; imidazoletrione; indole-2,3-dione; 1,1,4,4-tetramethyl-tetralin-2,3-dione; 3-methyl-1,2-cyclopentanedione; 2,3-dioxo-5,6-diethoxy-5,6-dicyanopyrazine; and 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazine dicarboximide. 
     
     
       3. A composition according to claim 1 additionally containing a macromolecular organic polymer binder, said ethylenically unsaturated compound and said binder being present in relative amounts of from 3-95 and 5-97 parts by weight, respectively. 
     
     
       4. A composition according to claim 1 wherein said cyclic cis-α-dicarbonyl compound and said actinic radiation absorbing compound are each present in amounts of 0.001 to 10 parts by weight per 100 parts of the combined weight of said ethylenically unsaturated compound and any binder. 
     
     
       5. A composition according to claim 4 additionally containing up to 10 parts by weight of a free-radical producing hydrogen or electron donor compound per 100 parts of the combined weight of said ethylenically unsaturated compound and any binder. 
     
     
       6. A composition according to claim 1 wherein said cis-α-dicarbonyl compound is 2,3-bornanedione. 
     
     
       7. A composition according to claim 6 wherein said actinic radiation absorbing compound is selected from the group consisting of Michler's ketone; 4,4'-bis(diethylamino)benzophenone; 3,3'-diethylthiacyanine p-toluenesulfonate; 2-(p-dimethylaminostyryl)benzothiazole; [3-ethyl-naphthoxazole] [3'-ethyl-naphthiazole] monomethinecyanine p-toluenesulfonate; Diethyl Orange; 7-diethylamino-4-methyl-coumarin; and 2,5-bis(p-diethylaminobenzilidene) cyclopentanone. 
     
     
       8. A composition according to claim 1 additionally containing a thermal addition polymerization inhibitor. 
     
     
       9. A composition according to claim 1 dispersed in a hydrophilic colloid. 
     
     
       10. A photographic element comprising a support coated with a composition of claim 1. 
     
     
       11. A photographic element according to claim 10 wherein said support is a polymeric film or metallic surface. 
     
     
       12. A photographic element according to claim 11 wherein the photpolymerizable composition is dispersed in a hydrophilic colloid.