# US 5,348,836 A · Silver halide photographic material > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,348,836 A - Document ID: US5348836A - Status: Granted - Kind: A - Application number: 08/050,672 - Filed: 1993-04-22 - Granted: 1994-09-20 - Earliest claimed: 1992-05-13 - Assignees: Agfa-Gevaert - Inventors: Ludo Van Rompuy; Jean-Marie Dewanckele - Web page: https://patentgrep.com/patent/US5348836A ## CPC - G03C 8/06: Silver salt diffusion transfer - C07C 323/16: the carbon skeleton containing six-membered aromatic rings - C07C 323/22: containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton - C07C 327/28: having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms - C07D 333/72: Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes - C07D 333/74: Naphthothiophenes - G03C 1/09: Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising (G03C1/34, G03C1/35 take precedence) - G03C 1/485: Direct positive emulsions - G03F 7/07: used for diffusion transfer {(G03F7/063 takes precedence)} - G03C 2001/03517: {Chloride content} - G03C 2001/03564: {Mixed grains or mixture of emulsions} - G03C 2007/3032: {Non-sensitive AgX or layer containing it} - G03C 2200/38: Lippmann (fine grain) emulsion - Y10S 430/156: Precursor compound - G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract The present invention provides a photographic material comprising on a support photosensitive silver halide particles, and substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles and a releasing compound of formula (I) or (II) as specified in the claims capable of image-wise releasing sulphide or a sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver. The present invention further provides a method for obtaining an image and a lithographic printing plate with said photographic material. ## Claims ### Claim 1 A photographic material comprising on a support photosensitive silver halide particles, and substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles and a releasing compound of formula (I) or (II) capable of image-wise releasing a sulphide or sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver: ##STR5## wherein CARRIER represents a carrier moiety that upon reaction with either the reduced or oxidized form of a developing agent or upon reaction with silver ions is capable of releasing under the conditions of development of said photosensitive silver halide the moiety -(TIME).sub.n -S-A, -S-A or sulphide, TIME represents a timing group which releases -S-A or sulphide subsequent to the release of -(TIME).sub.n -S-A from CARRIER, A represents an organic group that renders the bond between S and A readily splittable under the development conditions of said photosensitive silver halide and n represents 0 or 1. ### Claim 2 (depends on 1) A photographic material according to claim 1 wherein said substantially light insensitive silver salt particles are silver halide particles. ### Claim 3 (depends on 1) A photographic material according to claim 1 wherein said releasing compound corresponds to one of the following formulas (III) to (VI): ##STR6## wherein R.sup.1, R.sup.2 each independently represents hydrogen or an alkyl containing 1 to 5 carbon atoms; Z represents the necessary atoms for completing an aromatic ring and that may be substituted with one or more substituents; X represents --OR.sup.3 with R.sup.3 hydrogen or a hydrolizable group yielding hydroxy, --NHR.sup.4 with R.sup.4 an alkyl, aryl, aralkyl each of which may be substituted, --N.dbd.O or --NO.sub.2 ; Y represents independently from X represents one of the significances given for X or --NHSO.sub.2 --R.sup.4 ; and A, TIME and n are as defined in claim 1. ### Claim 4 (depends on 1) A photographic material according to claim 1 wherein A is hydrogen, an acyl, para-hydroxy benzyl, ortho-hydroxy benzyl each of which may be substituted, --CH.sub.2 --NHCOR, --CH.sub.2 --O--COR with R a hydrogen, alkyl, aryl or aralkyl each of which may be substituted. ### Claim 5 (depends on 1) A photographic material according to claim 1 wherein said photosensitive silver halide particles and said substantially light insensitive silver salt particles are present in the same layer. ### Claim 6 (depends on 1) A photographic material according to claim 1 further comprising a silver halide solvent or silver halide solvent precursor. ### Claim 7 (depends on 6) A photographic material according to claim 6 wherein said silver halide solvent is a cyclic imide, a 2-mercaptobenzoic acid, an alkanolamine or a mixture thereof. ### Claim 8 (depends on 1) A photographic material according to claim 1 additionally comprising a layer of physical development nuclei. ### Claim 9 A method for obtaining an image comprising the steps of: information-wise exposing a photographic material comprising on a support photosensitive silver halide particles, and substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles and a releasing compound of formula (I) or (II) capable of image-wise releasing a sulphide or sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver: ##STR7## wherein CARRIER represents a carrier moiety that upon reaction with either the reduced or oxidized form of a developing agent or upon reaction with silver ions is capable of releasing under the conditions of development of said photosensitive silver halide the moiety -(TIME).sub.n -S-A, -S-A or sulphide, TIME represents a timing group which releases -S-A or sulphide subsequent to the release of -(TIME).sub.n -S-A from CARRIER, A represents an organic group that renders the bond between S and A readily splittable under the development conditions of said photosensitive silver halide and n represents 0 or 1, developing said information-wise exposed photographic material in an alkaline processing solution in the presence of (a) developing agent(s). ### Claim 10 (depends on 9) A method according to claim 9 wherein said substantially light insensitive silver salt particles are silver halide particles. ### Claim 11 (depends on 9) A method according to claim 9, wherein said releasing compound corresponds to one of the following formulas (III) to (VI): ##STR8## wherein R.sup.1 R.sup.2 each independently represents hydrogen or an alkyl containing 1 to 5 carbon atoms; Z represents the necessary atoms for completing an aromatic ring and that may be substituted with one or more substituents; X represents --OR.sup.3 with R.sup.3 hydrogen or a hydrolizable group yielding hydroxy, --NHR.sup.4 with R.sup.4 an alkyl, aryl, aralkyl each of which may be substituted, --N.dbd.O or --NO.sub.2 ; Y represents independently from X represents one of the significances given for X or --NHSO.sub.2 --R.sup.4 ; and A, TIME and n are as defined in claim 9. ### Claim 12 (depends on 9) A method according to claim 9 wherein said developing is carried out in the presence of a silver halide solvent. ### Claim 13 (depends on 12) A method according to claim 12 wherein said silver halide solvent is a thiocyanate, a thiosulphate, a cyclic imide, a 2-mercaptobenzoic acid, an alkanolamine or a mixture thereof. ### Claim 14 A method for obtaining an image according to the DTR-process comprising the steps of: information-wise exposing a photographic material comprising on a support photosensitive silver halide particles, and substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles and a releasing compound of formula (I) or (II) capable of image-wise releasing a sulphide or sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver: ##STR9## wherein CARRIER represents a carrier moiety that upon reaction with either the reduced or oxidized form of a developing agent or upon reaction with silver ions is capable of releasing under the conditions of development of said photosensitive silver halide the moiety -(TIME).sub.n -S-A, -S-A or sulphide, TIME represents a timing group which releases -S-A or sulphide subsequent to the release of -(TIME).sub.n -S-A from CARRIER, A represents an organic group that renders the bond between S and A readily splittable under the development conditions of said photosensitive silver halide and n represents 0 or 1, contacting said information-wise exposed photographic material with an image-receiving material comprising on a support a layer containing physical development nuclei, developing said information-wise exposed photographic material whilst in contact with said image-receiving material in an alkaline processing solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s), separating said image-receiving material from said photographic material. ### Claim 15 (depends on 14) A method according to claim 14 wherein said substantially light insensitive silver salt particles are silver halide particles. ### Claim 16 (depends on 14) A method according to claim 14 wherein said releasing compound corresponds to one of the following formulas (III) to (VI): ##STR10## wherein R.sup.1, R.sup.2 each independently represents hydrogen or an alkyl containing 1 to 5 carbon atoms; Z represents the necessary atoms for completing an aromatic ring and that may be substituted with one or more substituents; X represents --OR.sup.3 with R.sup.3 hydrogen or a hydrolizable group yielding hydroxy, --NHR.sup.4 with R.sup.4 an alkyl, aryl, aralkyl each of which may be substituted, --N.dbd.O or --NO.sub.2 ; Y represents independently from X represents one of the significances given for X or --NHSO.sub.2 --R.sup.4 ; and A, TIME and n are as defined in claim 14. ### Claim 17 A method for obtaining an image according to the DTR-process comprising the steps of: information-wise exposing a photographic material comprising on a support (i) photosensitive silver halide particles, (ii) substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles, (iii) an image receiving layer containing physical development nuclei and (iv) a releasing compound of formula (I) or (II) capable of image-wise releasing a sulphide or sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver: ##STR11## wherein CARRIER represents a carrier moiety that upon reaction with either the reduced or oxidized form of a developing agent or upon reaction with silver ions is capable of releasing under the conditions of development of said photosensitive silver halide the moiety -(TIME).sub.n -S-A, -S-A or sulphide, TIME represents a timing group which releases -S-A or sulphide subsequent to the release of -(TIME).sub.n -S-A from CARRIER, A represents an organic group that renders the bond between S and A readily splittable under the development conditions of said photosensitive silver halide and n represents 0 or 1, and developing said information-wise exposed photographic material in an alkaline processing solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s). ### Claim 18 A method for preparing a lithographic printing plate according to the DTR-process comprising the steps of: information-wise exposing a photographic material comprising on a support photosensitive silver halide particles, and substantially light insensitive silver salt particles having a speed at least a factor 10 less under the same conditions of exposure and development of said photosensitive silver halide particles than said photosensitive silver halide particles and a releasing compound of formula (I) or (II) capable of image-wise releasing a sulphide or sulphide under conditions for image-wise development of said photosensitive silver halide particles to silver: ##STR12## wherein CARRIER represents a carrier moiety that upon reaction with either the reduced or oxidized form of a developing agent or upon reaction with silver ions is capable of releasing under the conditions of development of said photosensitive silver halide the moiety -(TIME).sub.n -S-A, -S-A or sulphide, TIME represents a timing group which releases -S-A or sulphide subsequent to the release of -(TIME).sub.n -S-A from CARRIER, A represents an organic group that renders the bond between S and A readily splittable under the development conditions of said photosensitive silver halide and n represents 0 or 1, contacting said information-wise exposed photographic material with an image-receiving material comprising on a support a layer containing physical development nuclei and having a hydrophilic surface, developing said information-wise exposed photographic material whilst in contact with said image-receiving material in an alkaline processing solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s), separating said image-receiving material from said photographic material. ### Claim 19 (depends on 18) A method according to claim 18 wherein said substantially light insensitive silver salt particles are silver halide particles. ### Claim 20 (depends on 18) A method according to claim 18 wherein said releasing compound corresponds to one of the following formulas (III) to (VI): ##STR13## wherein R.sup.1, R.sup.2 each independently represents hydrogen or an alkyl containing 1 to 5 carbon atoms; Z represents the necessary atoms for completing an aromatic ring and that may be substituted with one or more substituents; X represents --OR.sup.3 with R.sup.3 hydrogen or a hydrolizable group yielding hydroxy, --NHR.sup.4 with R.sup.4 an alkyl, aryl, aralkyl each of which may be substituted, --N.dbd.O or --NO.sub.2 ; Y represents independently from X represents one of the significances given for X or --NHSO.sub.2 --R.sup.4 ; and A, TIME and n are as defined in claim 18. ### Claim 21 (depends on 1, 3, 4) A method for preparing a lithographic printing plate according to the DTR-process comprising the steps of: information-wise exposing a lithographic printing plate precursor comprising on a support (i) a photosensitive silver halide, (ii) a substantially light insensitive silver salt having a speed at least a factor 10 less than said photosensitive silver halide particles under the same conditions of exposure and development of said photosensitive silver halide particles and (iii) a releasing compound as defined in any of claims 1, 3 or 4 capable of image-wise releasing under the conditions for image-wise development of said photosensitive silver halide to silver a sulphide and (iv) a layer of physical development nuclei as an outermost layer on the photosensitive side of said support, and developing said information-wise exposed photographic material in an alkaline processing solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s). ### Claim 22 (depends on 21) A method for preparing a lithographic printing plate according to claim 21 wherein the support of said photographic material is paper or a polyester film support. ### Claim 23 (depends on 1, 3, 4) A method for preparing a lithographic printing plate according to the DTR-process comprising the steps of: information-wise exposing a lithographic printing plate precursor comprising on a hydrophilic support provided with an image receiving surface or image receiving layer containing physical developement nuclei (i) a photosensitive silver halide, (ii) a substantially light insensitive silver salt having a speed at least a factor 10 less than said photosensitive silver halide particles under the same conditions of exposure and development of said photosensitive silver halide particles and (iii) a releasing compound as defined in any of claims 1, 3 or 4 capable of image-wise releasing under the conditions for image-wise development of said photosensitive silver halide to silver sulphide, developing said information-wise exposed photographic material in an alkaline processing solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s) to obtain a silver image on said image receiving surface or in said image receiving layer, and removing all layers above said silver image to expose said silver image by means of rinsing with water. ### Claim 24 (depends on 23) A method according to claim 23 wherein said hydrophilic support is an aluminium support. ### Claim 25 (depends on 3) A photographic material according to claim 3 wherein said aromatic ring is a benzene ring. ### Claim 26 (depends on 3) A photographic material according to claim 3 wherein said aromatic ring is a naphthalene ring. ### Claim 27 (depends on 11) A photographic material according to claim 11 wherein said aromatic ring is a benzene ring. ### Claim 28 (depends on 11) A photographic material according to claim 11 wherein said aromatic ring is a naphthalene ring. ### Claim 29 (depends on 16) A photographic material according to claim 16 wherein said aromatic ring is a benzene ring. ### Claim 30 (depends on 16) A photographic material according to claim 16 wherein said aromatic ring is a naphthalene ring. ### Claim 31 (depends on 20) A photographic material according to claim 20 wherein said aromatic ring is a benzene ring. ### Claim 32 (depends on 20) A photographic material according to claim 20 wherein said aromatic ring is a naphthalene ring.