Methods of developing photopolymerizable compositions containing an 0-nitroaromatic compound as photoinhibitor

Claim 1

Method of making a positive polymeric image on a substrate which comprises (1) coating the substrate with the photopolymerizable coating composition in which the photopolymerizable and photosensitive components consist essentially of (a) normally nongaseous, ethylenically unsaturated compound selected from the group consisting of unsaturated esters of polyols, unsaturated amides, vinyl esters and unsaturated aldehydes capable of addition polymerization by free-radical initiated chain propagation, (b) 0.004 to 0.7 part by weight, per part of component (a), of nitroaromatic compound of the formula ##STR22## wherein R 1 , R 2 , R 3 and R 4 , alike or different, are H, OH, halogen, NO 2 , CN, alkyl of 1 to 18 carbons, alkoxy in which the alkyl is of 1 to 18 carbons, acyloxy of 2-7 carbons, aryl of 6 to 18 carbons, benzyl, halogen-substituted phenyl, polyether of 2 to 18 carbons and 2 to 10 oxygens, dialkylamino in which each alkyl is of 1 to 18 carbons, thioalkyl in which the alkyl is of 1 to 18 carbons, or thioaryl in which the aryl is of 6 to 18 carbons, R 2 and R 3 , taken together, are --OCH 2 O-- or --O--CH 2 CH 2 O-- q in which q is an integer from 1 to 5, or any two of R 1 , R 2 , R 3 and R 4 , taken together, are the residue of a second benzene ring fused onto the benzene nucleus, with the proviso that not more than one of R 1 , R 2 , R 3 and R 4 is OH or NO 2 , R 5 is H, alkyl of 1 to 18 carbons, halogen, phenyl, or alkoxy in which the alkyl is of 1 to 18 carbons, R 6 is H, OH, alkyl of 1 to 18 carbons, phenyl, alkoxy in which the alkyl is of 1 to 18 carbons, or aryloxy of 6 to 18 carbons unsubstituted or substituted with halogen, alkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons, with the proviso that only one of R 5 and R 6 is H, or R 5 and R 6 taken together are ═O, ═CH 2 , --O--CH 2 --, ═NC 6 H 5 , ═NC 6 H 4 N(alkyl) 2 in which each alkyl is of 1 to 18 carbons, --O--C 2 H 4 --O--, ═N(alkyl) in which the alkyl is of 1 to 6 carbons, ##STR23## in which the hydrocarbylene group is of 1 to 18 carbons, or ##STR24## in which R 8 and R 9 , alike or different, are H or alkyl of 1 to 4 carbons, and R 7 and R 10 , alike or different, are --CN, --COR 11 in which R 11 is alkyl of 1 to 5 carbons, or --COOR 12 in which R 12 is alkyl of 1 to 6 carbons which may be interrupted by an oxygen atom, alkenyl of 2 to 5 carbons, or alkynyl of 2 to 5 carbons, or R 7 and R 8 together, or R 9 and R 10 together, complete a 6-membered carbocyclic ring containing a keto group, and (c) 0.001 to 10 parts by weight, per part of component (a), of an organic, radiation-sensitive, free-radical generating system, activatable by actinic radiation that does not significantly rearrange the nitroaromatic compound to an inhibitor of free-radical polymerization, (2) imagewise exposing a portion of the photopolymerizable coating through an image-bearing transparency to radiation at least 20% of which has a wavelength of 200 to 380 nm, thereby rearranging at least some of the nitroaromatic compound to polymerization inhibiting nitroso-aromatic compound, and (3) subjecting the coating to a second exposure whereby a greater portion of the coating, including the portion exposed during the imagewise exposure, is exposed to radiation substantially limited to wavelengths greater than 380 nm, whereby a positive polymeric image is formed in the areas exposed during the second exposure but not exposed during the imagewise exposure.

Claim 18

The method of making a negative polymeric image on a substrate which comprises (1) coating the substrate with the photopolymerizable coating composition in which the photopolymerizable and photosensitive components consist essentially of (a) normally nongaseous, ethylenically unsaturated compound selected from the group consisting of unsaturated esters of polyols, unsaturated amides, vinyl esters and unsaturated aldehydes capable of addition polymerization by free-radical initiated chain propagation, (b) 0.004 to 0.7 part by weight, per part of component (a), of nitroaromatic compound of the formula ##STR27## wherein R 1 , R 2 , R 3 and R 4 , alike or different, are H, OH, halogen, NO 2 , CN, alkyl of 1 to 18 carbons, alkoxy in which the alkyl is of 1 to 18 carbons, acyloxy of 2-7 carbons, aryl of 6 to 18 carbons, benzyl, halogen-substituted phenyl, polyether of 2 to 18 carbons and 2 to 10 oxygens, dialkylamino in which each alkyl is of 1 to 18 carbons, thioalkyl in which the alkyl is of 1 to 18 carbons, or thioaryl in which the aryl is of 6 to 18 carbons, R 2 and R 3 , taken together, are --OCH 2 O-- or --O--CH 2 CH 2 O-- q in which q is an integer from 1 to 5, or any two of R 1 , R 2 , R 3 and R 4 , taken together, are the residue of a second benzene ring fused onto the benzene nucleus, with the proviso that not more than one of R 1 , R 2 , R 3 and R 4 is OH or NO 2 , R 5 is H, alkyl of 1 to 18 carbons, halogen, phenyl, or alkoxy in which the alkyl is of 1 to 18 carbons, R 6 is H, OH, alkyl of 1 to 18 carbons, phenyl, alkoxy in which the alkyl is of 1 to 18 carbons, or aryloxy of 6 to 18 carbons unsubstituted or substituted with halogen, alkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons, with the proviso that only one of R 5 and R 6 is H, or R 5 and R 6 taken together are ═O, ═CH 2 , --O--CH 2 --, ═NC 6 H 5 , ═NC 6 H 4 N(alkyl) 2 in which each alkyl is of 1 to 18 carbons, --O--C 2 H 4 --O--, ═N(alkyl) in which the alkyl is of 1 to 6 carbons, ##STR28## in which the hydrocarbylene group is of 1 to 18 carbons, or ##STR29## in which R 8 and R 9 , alike or different, are H or alkyl of 1 to 4 carbons, and R 7 and R 10 , alike or different, are --CN, --COR 11 in which R 11 is alkyl of 1 to 5 carbons, or --COOR 12 in which R 12 is alkyl of 1 to 6 carbons which may be interrupted by an oxygen atom, alkenyl of 2 to 5 carbons, or alkynyl of 2 to 5 carbons, or R 7 and R 8 together, or R 9 and R 10 together, complete a 6-membered carbocyclic ring containing a keto group, and (c) 0.001 to 10 parts by weight, per part of component (a), of an organic, radiation-sensitive, free-radical generating system, activatable by actinic radiation that does not significantly rearrange the nitroaromatic compound to an inhibitor of free-radical polymerization, and (2) imagewise exposing a portion of the photopolymerizable coating through an image-bearing transparency to radiation substantially limited to wavelengths greater than 380 nm, whereby a negative polymeric image is formed in the areas exposed to the radiation.

Claim 19

The method of making a negative polymeric image on a substrate which comprises (1) coating the substrate with the photopolymerizable coating composition in which the photopolymerizable and photosensitive components consist essentially of (a) normally nongaseous, ethylenically unsaturated compound selected from the group consisting of unsaturated esters of polyols, unsaturated amides, vinyl esters and unsaturated aldehydes capable of addition polymerization by free-radical initiated chain propagation, (b) 0.004 to 0.7 part by weight, per part of component (a), of nitroaromatic compound of the formula ##STR27## wherein R 1 , R 2 , R 3 and R 4 , alike or different, are H, OH, halogen, NO 2 , CN, alkyl of 1 to 18 carbons, alkoxy in which the alkyl is of 1 to 18 carbons, acyloxy of 2-7 carbons, aryl of 6 to 18 carbons, benzyl, halogen-substituted phenyl, polyether of 2 to 18 carbons and 2 to 10 oxygens, dialkylamino in which each alkyl is of 1 to 18 carbons, thioalkyl in which the alkyl is of 1 to 18 carbons, or thioaryl in which the aryl is of 6 to 18 carbons, R 2 and R 3 , taken together, are --OCH 2 O-- or --O--CH 2 CH 2 O-- q in which q is an integer from 1 to 5, or any two of R 1 , R 2 , R 3 and R 4 , taken together, are the residue of a second benzene ring fused onto the benzene nucleus, with the proviso that not more than one of R 1 , R 2 , R 3 and R 4 is OH or NO 2 , R 5 is H, alkyl of 1 to 18 carbons, halogen, phenyl, or alkoxy in which the alkyl is of 1 to 18 carbons, R 6 is H, OH, alkyl of 1 to 18 carbons, phenyl, alkoxy in which the alkyl is of 1 to 18 carbons, or aryloxy of 6 to 18 carbons unsubstituted or substituted with halogen, alkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons, with the proviso that only one of R 5 and R 6 is H, or R 5 and R 6 taken together are ═O, ═CH 2 , --O--CH 2 --, ═NC 6 H 5 , ═NC 6 H 4 N(alkyl) 2 in which each alkyl is of 1 to 18 carbons, --O--C 2 H 4 --O--, ═N(alkyl) in which the alkyl is of 1 to 6 carbons, ##STR28## in which the hydrocarbylene group is of 1 to 18 carbons, or ##STR29## in which R 8 and R 9 , alike or different, are H or alkyl of 1 to 4 carbons, and R 7 and R 10 , alike or different, are --CN, --COR 11 in which R 11 is alkyl of 1 to 5 carbons, or --COOR 12 in which R 12 is alkyl of 1 to 6 carbons which may be interrupted by an oxygen atom, alkenyl of 2 to 5 carbons, or alkynyl of 2 to 5 carbons, or R 7 and R 8 together, or R 9 and R 10 together, complete a 6-membered carbocyclic ring containing a keto group, and (c) 0.001 to 10 parts by weight, per part of component (a), of an organic, radiation-sensitive, free-radical generating system, activatable by actinic radiation that does not significantly rearrange the nitroaromatic compound to an inhibitor of free-radical polymerization, and (2) imagewise exposing a portion of the photopolymerizable coating through an image-bearing transparency to radiation substantially limited to wavelengths greater than 380 nm, whereby a negative polymeric image is formed in the areas exposed to the radiation.