Photopolymerization co-initiator compositions comprising amine-substituted ketocoumarins and certain acetic acid derivative activators

Claim 2

In a photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is an amine-substituted ketocoumarin having an adsorption maximum between about 350 and 550 nm and a ##STR35## substituent in the 3-position wherein R 1 is alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and wherein said activator has the structure ##STR36## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy, or thioalkyl containing from 1 to 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or aromatic ring containing from 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to 5 carbon atoms.

Claim 3

A composition as defined in claim 1, wherein said addition-polymerizable compound is an acrylate.

Claim 4

In a photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is an amine-substituted coumarin having an adsorption maximum between about 350 and 550 nm and the structure ##STR37## wherein R 1 is selected from the group consisting of alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and, R 2 , R 3 , and R 4 are the same or different and are each hydrogen, dialkylamino containing from 1 to 5 carbon atoms in the alkyl portion, N-pyrrolidinyl, piperdinyl, morpholino, or when taken together R 2 -R 4 comprise the nonmetallic atoms that form, as a fused substituent on the coumarin ring, the ring ##STR38## provided that at least one of R 2 , R 3 , and R 4 is other than hydrogen; and, wherein said activator has the structure ##STR39## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necesary atoms to complete a fused heterocyclic or aromatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 5

In a photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is an amine-substituted coumarin having an adsorption maximum between about 350 and 550 nm and the structure ##STR37## wherein R 1 is selected from the group consisting of alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and, R 2 , R 3 , and R 4 are the same or different and are each hydrogen, dialkylamino containing from 1 to 5 carbon atoms in the alkyl portion, N-pyrrolidinyl, piperdinyl, morpholino, or when taken together R 2 -R 4 comprise the nonmetallic atoms that form, as a fused substituent on the coumarin ring, the ring ##STR38## provided that at least one of R 2 , R 3 , and R 4 is other than hydrogen; and, wherein said activator has the structure ##STR39## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necesary atoms to complete a fused heterocyclic or aromatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 6

In a photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is a coumarin selected from the group consisting of 3-(2-benzofuroyl)-7-diethylaminocoumarin; 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin; 7-dimethylamino-3-thenoylcoumarin; 3-benzoyl-7-diethylaminocoumarin; 3-(o-methoxybenzoyl)-7-diethylaminocoumarin; 3-(p-dimethylaminobenzoyl)-7-diethylaminocoumarin; 3,3'-carbonylbis(7-diethylaminocoumarin); 7-diethylamino-3-[3-(2-thienyl)acryloyl]coumarin; 3-(2-furoyl)-7-diethylaminocoumarin; 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin; 3-(4-morpholinocinnamoyl)-7-diethylaminocoumarin; 9-(7-diethylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 9-(7-di-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 9-(4-diethylaminocinnamoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin; 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]-benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-diethylamino-3-(4-dimethylaminocinnamylideneacetyl)coumarin; 9-[3-(9-julolidyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]-benzopyrano[9,9a,1-gh]quinolazine-10-one; 3-cinnamoyl-7-diethylaminocoumarin; 7-diethylamino-3-(4-morpholinocinnamoyl)coumarin; 7-diethylamino-3-(4-ethoxycinnamoyl)coumarin; 3-(4-bromocinnamoyl)-7-diethylaminocoumarin; 7-diethylamino-3-[3-(4-methoxy-1-naphthyl)acryloyl]coumarin; 7-diethylamino-3-cinnamylideneacetylcoumarin; 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H-[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-diethylamino-3-(3-fluorosulfonylbenzoyl)coumarin; 3-(4-cyanobenzoyl)-7-diethylaminocoumarin; 3-benzoyl-7-dimethylaminocoumarin; 3-benzoyl-7-diethylaminocoumarin; 3-benzoyl-7-pyrrolidinylcoumarin; 3-(4-iodobenzoyl)-7-dimethylaminocoumarin; 3-(4-iodobenzoyl)-7-diethylaminocoumarin; 7-dimethylamino-3-(4-dimethylaminobenzoyl)coumarin; 7-diethylamino-3-(4-nitrobenzoyl)coumarin; 7-diethylamino-3-(2-thenoyl)coumarin; 7-pyrrolidinyl-3-(2-thenoyl)coumarin; 7-diethylamino-3-(2-furoyl)coumarin; and 7-diethylamino-3-(2-methoxybenzoyl)coumarin; and wherein said activator is selected from the group consisting of N-phenylglycine, indole-3-ylacetic acid, and N-methylindole-3-ylacetic acid.

Claim 7

In a photopolymerizable composition comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is a coumarin selected from the group consisting of 3-(2-benzofuroyl)-7-diethylaminocoumarin; 3-(2-benzofuroyl)-7-(1-pyrrolidinyl)coumarin; 7-dimethylamino-3-thenoylcoumarin; 3-benzoyl-7-diethylaminocoumarin; 3-(o-methoxybenzoyl)-7-diethylaminocoumarin; 3-(p-dimethylaminobenzoyl)-7-diethylaminocoumarin; 3,3'-carbonylbis(7-diethylaminocoumarin); 7-diethylamino-3-[3-(2-thienyl)acryloyl]coumarin; 3-(2-furoyl)-7-diethylaminocoumarin; 3-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin; 3-(4-morpholinocinnamoyl)-7-diethylaminocoumarin; 9-(7-diethylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 9-(7-di-n-propylamino-3-coumarinoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 9-(4-diethylaminocinnamoyl)-1,2,4,5-tetrahydro-3H,6H,10H[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-dimethylamino-3-[3-(2-thienyl)acryloyl]coumarin; 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]-benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-diethylamino-3-(4-dimethylaminocinnamylideneacetyl)coumarin; 9-[3-(9-julolidyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H[1]-benzopyrano[9,9a,1-gh]quinolazine-10-one; 3-cinnamoyl-7-diethylaminocoumarin; 7-diethylamino-3-(4-morpholinocinnamoyl)coumarin; 7-diethylamino-3-(4-ethoxycinnamoyl)coumarin; 3-(4-bromocinnamoyl)-7-diethylaminocoumarin; 7-diethylamino-3-[3-(4-methoxy-1-naphthyl)acryloyl]coumarin; 7-diethylamino-3-cinnamylideneacetylcoumarin; 9-[3-(2-thienyl)acryloyl]-1,2,4,5-tetrahydro-3H,6H,10H-[1]benzopyrano[9,9a,1-gh]quinolazine-10-one; 7-diethylamino-3-(3-fluorosulfonylbenzoyl)coumarin; 3-(4-cyanobenzoyl)-7-diethylaminocoumarin; 3-benzoyl-7-dimethylaminocoumarin; 3-benzoyl-7-diethylaminocoumarin; 3-benzoyl-7-pyrrolidinylcoumarin; 3-(4-iodobenzoyl)-7-dimethylaminocoumarin; 3-(4-iodobenzoyl)-7-diethylaminocoumarin; 7-dimethylamino-3-(4-dimethylaminobenzoyl)coumarin; 7-diethylamino-3-(4-nitrobenzoyl)coumarin; 7-diethylamino-3-(2-thenoyl)coumarin; 7-pyrrolidinyl-3-(2-thenoyl)coumarin; 7-diethylamino-3-(2-furoyl)coumarin; and 7-diethylamino-3-(2-methoxybenzoyl)coumarin; and wherein said activator is selected from the group consisting of N-phenylglycine, indole-3-ylacetic acid, and N-methylindole-3-ylacetic acid.

Claim 8

In a radiation-responsive element including a support bearing a photopolymerizable layer comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is an amine-substituted ketocoumarin having an adsorption maximum between about 350 and 550 nm and a ##STR40## substituent in the 3-position wherein R 1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 carbon and hetero ring atoms; and, wherein said activator has the structure ##STR41## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or aromatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 9

In a radiation-responsive element including a support bearing a photopolymerizable layer comprising an addition-polymerizable compound and a co-initiator composition comprising a carbonyl sensitizer and a photopolymerization activator; the improvement wherein said sensitizer is an amine-substituted ketocoumarin having an adsorption maximum between about 350 and 550 nm and a ##STR40## substituent in the 3-position wherein R 1 is alkyl or alkenyl having 1 to about 12 carbon atoms, or a carbocyclic or heterocyclic group having about 5 to about 20 carbon and hetero ring atoms; and, wherein said activator has the structure ##STR41## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or aromatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 10

An element as defined in claim 5, wherein said polymerizable compound is an acrylate.

Claim 13

A co-initiator composition for photo-initiating addition polymerization, said composition comprising (a) an amine-substituted ketocoumarin sensitizer having an adsorption maximum between about 350 and 550 nm, and a ##STR44## substituent in the 3-position wherein R 1 is alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and (b) an activator having the structure ##STR45## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or aromatic ring containing from about 5 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 14

A co-initiator composition for photo-initiating addition polymerization, said composition comprising (a) an amine-substituted ketocoumarin sensitizer having an adsorption maximum between about 350 and 550 nm, and a ##STR44## substituent in the 3-position wherein R 1 is alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and (b) an activator having the structure ##STR45## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or aromatic ring containing from about 5 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 15

A co-initiator composition for photoinitiating addition polymerization, said composition comprising an amine-substituted coumarin sensitizer having an adsorption maximum between about 350 l and 550 nm, and the structure ##STR46## wherein R 1 is selected from the group consisting of alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and R 2 , R 3 , and R 4 are the same or different and are each hydrogen, dialkylamino containing from 1 to 5 carbon atoms in the alkyl portion, N-pyrrolidinyl, piperidinyl, morpholino, or when taken together R 2 -R 4 comprise the non-metallic atoms that form, as a fused substituent on the coumarin ring, the ring ##STR47## provided that at least one of R 2 , R 3 , and R 4 is other than hydrogen; and an activator having the structure ##STR48## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or atomatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.

Claim 16

A co-initiator composition for photoinitiating addition polymerization, said composition comprising an amine-substituted coumarin sensitizer having an adsorption maximum between about 350 l and 550 nm, and the structure ##STR46## wherein R 1 is selected from the group consisting of alkyl or alkenyl having 1 to 12 carbon atoms, or a carbocyclic or heterocyclic group having 5 to 20 carbon and hetero ring atoms; and R 2 , R 3 , and R 4 are the same or different and are each hydrogen, dialkylamino containing from 1 to 5 carbon atoms in the alkyl portion, N-pyrrolidinyl, piperidinyl, morpholino, or when taken together R 2 -R 4 comprise the non-metallic atoms that form, as a fused substituent on the coumarin ring, the ring ##STR47## provided that at least one of R 2 , R 3 , and R 4 is other than hydrogen; and an activator having the structure ##STR48## wherein Q 1 and Q 2 are each independently hydrogen; alkyl, alkoxy or thioalkyl containing from 1 to about 5 carbon atoms; aryl, aryloxy, or benzoyloxy containing from about 6 to 10 carbon atoms; hydroxy; or halogen; or together Q 1 and Q 2 are the necessary atoms to complete a fused heterocyclic or atomatic ring containing from about 4 to 6 ring atoms; and Q 3 is hydrogen or alkyl containing from 1 to about 5 carbon atoms.