Silver halide photographic material

Claim 1

A silver halide negative photographic material comprising a support having thereon at least one silver halide emulsion layer, at least one hydrophilic colloidal layer thereof comprising: (1) a hydrazine derivative; (2) a compound having no substantial absorption maximum in the visible light region represented by formula (I): ##STR26## wherein Z 11 and Z 12 , which may be the same or different, each represents a non-metallic atomic group necessary for forming a substituted or unsubstituted heterocyclic ring selected from benzoxazole, benzothiazole, benzoselenazole, naphthoxazole, naphthothiazole, naphthoselenazole, thiazole, thiazoline, oxazole, selenazole, selenazoline, pyridine, benzimidazole and quinoline; R 11 and R 12 , which may be the same or different, each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group, provided that at least one of R 11 and R 12 is substituted with an acid group; X represents a counter ion necessary for charge balance; and n is 0 or 1; and (3) at least one compound represented by formula (II) or (III): ##STR27## wherein R 1 and R 2 , which may be the same or different, each represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or an amino group; R 3 represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and Q represents a single bond or a divalent group selected from sulfur, selenium, oxygen, a disulfide group, ##STR28## wherein R 4 has the same definition as R 3 ; provided that R 1 and R 2 , R 1 and R 3 , or R 3 and R 4 may be linked to form a substituted or unsubstituted 5-membered or 6-membered heterocyclic ring; further provided at least one of R 2 and R 4 represents a group other than hydrogen when R 1 and R 3 are linked to form a heterocyclic ring, and said heterocyclic ring formed by R 1 and R 3 is a ring other than a rhodanine ring; and ##STR29## wherein R 21 , R 22 , R 23 , and R 24 , which may be the same or different, each represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a primary amino group, a secondary amino group, a tertiary amino group, a carbonamido group, a sulfonamido group, an alkyl group, an aryl group, a 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, a formyl group, a keto group, a sulfo group, a carboxyl group, an alkylsulfonyl group or an arylsulfonyl group; provided that at least one of R 21 , R 22 , R 23 , and R 24 represents a group other than hydrogen when the compound represented by formula (III) is 1,4-dihydroxybenzene, said at least one compound of the formula (II) and the formula (III) being incorporated in said layer containing said hydrazine compound.

Claim 21

A method for forming an image comprising the steps of: (a) imagewise exposing a silver halide negative photographic material comprising a support having thereon at least one silver halide emulsion layer, at least one hydrophilic colloidal layer thereof comprising: (1) a hydrazine derivative; (2) a compound substantially having no absorption maximum in the visible light region represented by formula (I): ##STR33## wherein Z 11 and Z 12 , which may be the same or different, each represents a non-metallic atomic group necessary for forming a substituted or unsubstituted heterocyclic ring selected from benzoxazole, benzothiazole, benzoselenazole, naphthoxazole, naphthothiazole, naphthoselenazole, thiazole, thiazoline, oxazole, selenazole, selenazoline, pyridine, benzimidazole and quinoline; R 11 and R 12 , which may be the same or different, each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group, provided that at least one of R 11 and R 12 is substituted with an acid group; X represents a counter ion necessary for charge balance; and n is 0 or 1; and (3) at least one compound represented by formula (II) or (III): ##STR34## wherein R 1 and R 2 , which may be the same or different, each represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or an amino group; R 3 represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and Q represents a single bond or a divalent group selected from sulfur, selenium, oxygen, a disulfide group, ##STR35## wherein R 4 has the same meaning as R 3 ; provided that R 1 and R 2 , R 1 and R 3 , or R 3 and R 4 may be linked to form a substituted or unsubstituted 5-membered or 6-membered heterocyclic ring; further provided at least one of R 2 and R 4 represents a group other than hydrogen when R 1 and R 3 are linked to form a heterocyclic ring, and said heterocyclic ring formed by R 1 and R 3 is a ring other than a rhodanine ring, and ##STR36## wherein R 21 , R 22 , R 23 , and R 24 , which may be the same or different, each represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a primary amino group, a secondary amino group, a tertiary amino group, a carbonamido group, a sulfonamido group, an alkyl group, an aryl group, a 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, a formyl group, a keto group, a sulfo group, a carboxyl group, an alkylsulfonyl group or an arylsulfonyl group; provided that at least one of R 21 , R 22 , R 23 , and R 24 represents a group other than hydrogen when the compound represented by formula (III) is 1,4-dihydroxybenzene, said at least one compound of the formula (II) and the formula (III) being incorporated in said layer containing said hydrazine compound; and (b) developing said exposed material with a developer solution having a pH of from 10.5 to 12.3 and containing a sulfite ion concentration of at least 0.15 mol/liter, to form a negative image.

Claim 22

A method for forming an image comprising the steps of: (a) imagewise exposing a silver halide negative photographic material comprising a support having thereon at least one silver halide emulsion layer, at least one hydrophilic colloidal layer thereof comprising: (1) a hydrazine derivative; (2) a compound substantially having no absorption maximum in the visible light region represented by formula (I): ##STR33## wherein Z 11 and Z 12 , which may be the same or different, each represents a non-metallic atomic group necessary for forming a substituted or unsubstituted heterocyclic ring selected from benzoxazole, benzothiazole, benzoselenazole, naphthoxazole, naphthothiazole, naphthoselenazole, thiazole, thiazoline, oxazole, selenazole, selenazoline, pyridine, benzimidazole and quinoline; R 11 and R 12 , which may be the same or different, each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aralkyl group, provided that at least one of R 11 and R 12 is substituted with an acid group; X represents a counter ion necessary for charge balance; and n is 0 or 1; and (3) at least one compound represented by formula (II) or (III): ##STR34## wherein R 1 and R 2 , which may be the same or different, each represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or an amino group; R 3 represents hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and Q represents a single bond or a divalent group selected from sulfur, selenium, oxygen, a disulfide group, ##STR35## wherein R 4 has the same meaning as R 3 ; provided that R 1 and R 2 , R 1 and R 3 , or R 3 and R 4 may be linked to form a substituted or unsubstituted 5-membered or 6-membered heterocyclic ring; further provided at least one of R 2 and R 4 represents a group other than hydrogen when R 1 and R 3 are linked to form a heterocyclic ring, and said heterocyclic ring formed by R 1 and R 3 is a ring other than a rhodanine ring, and ##STR36## wherein R 21 , R 22 , R 23 , and R 24 , which may be the same or different, each represents hydrogen, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a primary amino group, a secondary amino group, a tertiary amino group, a carbonamido group, a sulfonamido group, an alkyl group, an aryl group, a 5-membered or 6-membered heterocyclic group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, a formyl group, a keto group, a sulfo group, a carboxyl group, an alkylsulfonyl group or an arylsulfonyl group; provided that at least one of R 21 , R 22 , R 23 , and R 24 represents a group other than hydrogen when the compound represented by formula (III) is 1,4-dihydroxybenzene, said at least one compound of the formula (II) and the formula (III) being incorporated in said layer containing said hydrazine compound; and (b) developing said exposed material with a developer solution having a pH of from 10.5 to 12.3 and containing a sulfite ion concentration of at least 0.15 mol/liter, to form a negative image.