Inhibition of image formation utilizing cobalt(III) complexes

Claim 2

In an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 3

An element as defined in claim 1, wherein said photoinhibitor composition includes a heterocyclic compound.

Claim 4

An element as defined in claim 1, wherein said photoinhibitor composition is a compound having the formula: ##STR41## wherein: R is hydrogen, halide, nitro or alkyl, dialkylamino, or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 1 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 2 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, or together with R 3 comprises the necessary nonmetallic atoms to complete an aromatic ring; R 3 is hydrogen, or together with R 2 comprises the necessary nonmetallic atoms to complete an aromatic ring; Z 1 is from about 3 to about 7 ring atoms necessary to complete one or more aromatic rings; E is H, CH 3 or CX 3 ; n is 0, 1 or 2; and X is halide.

Claim 5

An element as defined in claim 1, wherein said complex becomes thermally unstable at an instability temperature greater than about 100° C. so that said ligands are releasable in response to a thermal exposure sufficient to heat said element to a temperature in excess of said instability temperature.

Claim 6

An element as defined in claim 1, wherein said complex is thermally stable at a temperature at least as high as about 130° C.

Claim 7

An element as defined in claim 1, wherein said image precursor composition includes a reducing agent for said complex and said ligands are releasable in response to a thermal exposure.

Claim 8

An element as defined in claim 1, wherein said image precursor composition includes a reducing agent precursor capable of forming, in the presence of an amine, a reducing agent for said complex, and an amine precursor capable of forming an amine in response to a thermal exposure.

Claim 9

An element as defined in claim 7, wherein said reducing agent precursor is phthalaldehyde.

Claim 10

An element as defined in claim 1, wherein said image precursor composition includes a base precursor capable of forming a base in response to a thermal exposure.

Claim 11

An element as defined in claim 1, wherein said image-forming material is capable of forming a dye in response to said release of ligands.

Claim 12

An element as defined in claim 10, wherein said material includes phthalaldehyde.

Claim 13

In an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable liqands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, an image-forming material capable of generating an image in response to the release of said ligands, and a reducing agent precursor capable of producing a reducing agent for said complex in response to a thermal exposure; the improvement comprising, in reactable association with said composition, a photoinhibitor composition capable of inhibiting said liqand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 14

In an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable liqands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, an image-forming material capable of generating an image in response to the release of said ligands, and a reducing agent precursor capable of producing a reducing agent for said complex in response to a thermal exposure; the improvement comprising, in reactable association with said composition, a photoinhibitor composition capable of inhibiting said liqand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 15

An element as defined in claim 12, wherein said reducing agent precursor is a quinone photoreductant and said exposure of said image precursor composition comprises a light exposure.

Claim 16

An element as defined in claim 1, wherein said image precursor composition includes a thiolate precursor; and said exposure of said image precursor composition comprises a thermal exposure.

Claim 17

In a radiation-sensitive element comprising in one or more operatively associated layers, a heat-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 18

In a radiation-sensitive element comprising in one or more operatively associated layers, a heat-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 19

An element as defined in claim 15, wherein said photoinhibitor composition includes a hetrocyclic compound.

Claim 20

An element as defined in claim 15, wherein said photoinhibitor composition is a compound having the formula: ##STR42## wherein: R is hydrogen, halide, nitro or alkyl, dialkylamino, or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 1 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 2 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, or together with R 3 comprises the necessary nonmetallic atoms to complete an aromatic ring; R 3 is hydrogen, or together with R 2 comprises the necessary nonmetallic atoms to complete an aromatic ring; Z 1 is from about 3 to about 7 ring atoms necessary to complete one or more aromatic rings; E is H, CH 3 or CX 3 ; n is 0, 1 or 2; and X is halide.

Claim 21

An element as defined in claim 15, wherein said complex becomes thermally unstable at an instability temperature greater than about 100° C. so that said ligands are releasable in response to a thermal exposure sufficient to heat said element to a temperature in excess of said instability temperature.

Claim 22

An element as defined in claim 15, wherein said complex is thermally stable at a temperature at least as high as about 130° C.

Claim 23

An element as defined in claim 15, wherein said image precursor composition includes a reducing agent.

Claim 24

An element as defined in claim 15, wherein said image precursor composition includes a reducing agent precursor capable of forming a reducing agent for said cobalt complex in response to a thermal exposure.

Claim 25

An element as defined in claim 15, wherein said image precursor composition includes a reducing agent precursor capable of forming, in the presence of an amine, a reducing agent for said complex, and an amine precursor capable of forming an amine in response to a thermal exposure.

Claim 26

An element as defined in claim 22, wherein said reducing agent precursor is phthalaldehyde.

Claim 27

An element as defined in claim 15, wherein said image precursor composition includes a base precursor capable of forming a base in response to a thermal exposure.

Claim 28

In an imaging element comprising, in one or more operatively associated layers, a reducible cobalt(III) complex containing amine ligands, o-phthalaldehyde, and a quinone photoreductant capable of reducing said complex upon exposure to activating radiation; the improvement wherein said element further includes an S-triazine having the formula: ##STR43## wherein: R is hydrogen, halide, nitro or alkyl, dialkylamino, or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 1 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 2 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, or together with R 3 comprises the necessary nonmetallic atoms to complete an aromatic ring; R 3 is hydrogen, or together with R 2 comprises the necessary nonmetallic atoms to complete an aromatic ring; X and Y are the same or different, and are each selected from the group consisting of halide and hydrogen, at least one of X and Y being halide.

Claim 29

In an imaging element comprising, in one or more operatively associated layers, a reducible cobalt(III) complex containing amine ligands, o-phthalaldehyde, and a quinone photoreductant capable of reducing said complex upon exposure to activating radiation; the improvement wherein said element further includes an S-triazine having the formula: ##STR43## wherein: R is hydrogen, halide, nitro or alkyl, dialkylamino, or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 1 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 2 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, or together with R 3 comprises the necessary nonmetallic atoms to complete an aromatic ring; R 3 is hydrogen, or together with R 2 comprises the necessary nonmetallic atoms to complete an aromatic ring; X and Y are the same or different, and are each selected from the group consisting of halide and hydrogen, at least one of X and Y being halide.

Claim 30

An element as defined in claim 25, wherein said complex is cobalt(III) hexa-ammine trifluoroacetate; said photoreductant is 2-isopropoxy-3-chloro-1,4-naphthoquinone; and said triazine is 2,4-bis(trichloromethyl)-6-[p-anisyl]-S-triazine.

Claim 31

In an energy-activatible image precursor composition comprising at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 32

In an energy-activatible image precursor composition comprising at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 33

A composition as defined in claim 27, wherein said photoinhibitor composition includes a heterocyclic compound containing a chromophore substituent.

Claim 34

A composition as defined in claim 28, wherein said photoinhibitor composition is a compound having the formula ##STR44## wherein: R is hydrogen, halide, nitro or alkyl, dialkylamino, or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 1 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, R 2 is hydrogen or alkoxy containing from 1 to 5 carbon atoms in the alkyl portion, or together with R 3 comprises the necessary nonmetallic atoms to complete an aromatic ring; R 3 is hydrogen, or together with R 2 comprises the necessary nonmetallic atoms to complete an aromatic ring; Z 1 is from about 3 to about 7 ring atoms necessary to complete one or more aromatic rings; E is H, CH 3 or CX 3 ; n is 0, 1 or 2; and X is halide.

Claim 35

A composition as defined in claim 27, wherein said complex becomes thermally unstable at an instability temperature greater than about 100° C., so that said ligands are releasable in response to a thermal exposure sufficient to heat said element to a temperature in excess of said instability temperature.

Claim 36

A composition as defined in claim 27, wherein said complex is thermally stable at a temperature at least as high as about 130° C.

Claim 37

A composition as defined in claim 27, and further including a reducing agent, said ligands being releasable in response to a thermal exposure.

Claim 38

A composition as defined in claim 27, and further including a reducing agent precursor capable of forming, in the presence of an amine, a reducing agent for said complex, and an amine precursor capable of forming an amine in response to a thermal exposure.

Claim 39

A composition as defined in claim 33, wherein said reducing agent precursor is phthalaldehyde.

Claim 40

A composition as defined in claim 33, wherein said image-forming material includes a material capable of forming a dye in response to said production of amines.

Claim 41

A composition as defined in claim 35, wherein both said reducing agent precursor and said material are phthalaldehyde.

Claim 42

A composition as defined in claim 27, and further including a base precursor capable of forming a base in the presence of heat.

Claim 43

A composition as defined in claim 27, in dried form, and a support to which said composition is applied to form an imaging element.

Claim 44

A composition as defined in claim 27, and further including a reducing agent precursor capable upon exposure of forming a reducing agent for said complex.

Claim 45

A composition as defined in claim 39, wherein said precursor is a quinone photoreductant.

Claim 46

A composition as defined in claim 39, wherein said precursor comprises a thiolate precursor.

Claim 47

In an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition which, upon exposure to activating radiation of a wavelength longer than about 300 nm, inhibits said ligand release, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 48

In an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands; the improvement comprising, in reactable association with said precursor composition, a photoinhibitor composition which, upon exposure to activating radiation of a wavelength longer than about 300 nm, inhibits said ligand release, said photoinhibitor composition containing a photolytic acid-generating compound.

Claim 49

A process for forming a negative or positive image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise activating by selective exposure, one of said image precursor composition and said photoinhibitor composition, whereby either ligands are released or are inhibited from release; and (b) overall activating by exposure the other of said compositions, whereby a negative image or a positive image is produced, respectively.

Claim 50

A process for forming a negative or positive image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise activating by selective exposure, one of said image precursor composition and said photoinhibitor composition, whereby either ligands are released or are inhibited from release; and (b) overall activating by exposure the other of said compositions, whereby a negative image or a positive image is produced, respectively.

Claim 51

A process for forming a positive image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise exposing said element to said activating radiation to inhibit release of said ligands; and (b) overall activating, by exposure to electromagnetic energy, said precursor composition to release said ligands in the portions of said element not exposed to said activating radiation.

Claim 52

A process for forming a positive image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise exposing said element to said activating radiation to inhibit release of said ligands; and (b) overall activating, by exposure to electromagnetic energy, said precursor composition to release said ligands in the portions of said element not exposed to said activating radiation.

Claim 53

A process as defined in claim 44, wherein said image precursor composition is thermally activatible, and the step of overall activating said precursor composition to release ligands is achieved by heating said element to a temperature effective to release said ligands.

Claim 54

A process for forming a negative image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise selectively activating by exposure to electromagnetic energy, said image precursor composition, to release said ligands imagewise; and (b) overall exposing said element to said activating exposure to inhibit release of ligands in the areas not exposed by the previous step.

Claim 55

A process for forming a negative image in an imaging element comprising, in one or more operatively associated layers, an energy-activatible image precursor composition including at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material capable of generating an image in response to the release of said ligands, and in reactable association with said precursor composition, a photoinhibitor composition capable of inhibiting said ligand release upon exposure to activating radiation of a wavelength longer than about 300 nm, said photoinhibitor composition containing a photolytic acid-generating compound; the process comprising the steps of: (a) imagewise selectively activating by exposure to electromagnetic energy, said image precursor composition, to release said ligands imagewise; and (b) overall exposing said element to said activating exposure to inhibit release of ligands in the areas not exposed by the previous step.

Claim 56

A process as defined in claim 46, wherein said image precursor composition is thermally activatible and said imagewise activating step is achieved by heating said element to a temperature effective to release said ligands.

Claim 57

A process for forming a negative or positive image in an imaging element, comprising first imagewise activating by selective exposure either (a) an image precursor composition in one or more layers, which includes at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material which generates an image in response to release of said ligands, or (b) a layer of a photoinhibitor composition associated with said precursor composition, said photoinhibitor composition being activatible by radiation of a wavelength longer than about 300 nm to inhibit said ligand release and containing a photolytic acid-generating compound. and then overall activating by exposure the other of said compositions not imagewise activated.

Claim 58

A process for forming a negative or positive image in an imaging element, comprising first imagewise activating by selective exposure either (a) an image precursor composition in one or more layers, which includes at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material which generates an image in response to release of said ligands, or (b) a layer of a photoinhibitor composition associated with said precursor composition, said photoinhibitor composition being activatible by radiation of a wavelength longer than about 300 nm to inhibit said ligand release and containing a photolytic acid-generating compound. and then overall activating by exposure the other of said compositions not imagewise activated.

Claim 59

A process for forming a negative image in an imaging element, comprising (a) imagewise activating by selective exposure an image precursor composition in one or more layers, which includes at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material which generates an image in response to release of said ligands, and (b) activating by overall exposure to radiation of a wavelength longer than 300 nm, a layer of a photoinhibitor composition associated with said precursor composition and containing a photolytic acid-generating compound that inhibits said ligand release upon said overall exposure.

Claim 60

A process for forming a negative image in an imaging element, comprising (a) imagewise activating by selective exposure an image precursor composition in one or more layers, which includes at least a cobalt(III) complex containing releasable ligands selected from amines, dimethylglyoxime, ethyl, aquo, chloro, bromo, acetylacetonato, nitro, and superoxo, and an image-forming material which generates an image in response to release of said ligands, and (b) activating by overall exposure to radiation of a wavelength longer than 300 nm, a layer of a photoinhibitor composition associated with said precursor composition and containing a photolytic acid-generating compound that inhibits said ligand release upon said overall exposure.

Claim 61

An element as defined in claim 1, wherein said photoinhibitor composition includes a halogenated compound.