Silver halide photographic photosensitive materials and a method of image formation in which they are used

Claim 1

A method for forming an image comprising, the step of processing a photographic photosensitive material with a developer having a pH of 9.6 to 11.0, wherein the photographic photosensitive material comprises a support, having thereon at least one silver halide emulsion layer and at least one protective layer over said emulsion layer, wherein said silver halide emulsion layer is comprised of silver halide grains having a silver chloride content of at least 50 mol % which contain from 1×10 -8 to 5×10 -6 mol of a rhodium compound per mol of silver, at least one hydrazine derivative selected from among those of general formula (1) or (2) indicated below is included in at least one of said emulsion layer or another hydrophilic colloid layer, at least one compound selected from among colloidal silica and polyacrylamide derivatives is included in at least one of said silver halide layer and another hydrophilic colloid layer, and the dynamic friction coefficient of the outermost layer of said protective layer is not more than 0.35: ##STR26## wherein R 1 represents an aliphatic group or an aromatic group which includes either a partial structure of --O--(CH 2 CH 2 O) n --, --O--(CH 2 CH(CH 3 )O) n -- or --O--(CH 2 CH(OH)CH 2 O) n -- (where n is an integer of 3 or more), or which contains a quaternary ammonium cation; G 1 represents --CO--, --COCO--, --CS--, --C(═NG 2 R 2 )--, --SO--, --SO 2 -- or --P(O)(G 2 R 2 )--; G 2 represents a single bond, --O--, --S-- or --N(R 2 )--, R 2 represents an aliphatic group, an aromatic group or a hydrogen atom, and in those cases where a plurality of R 2 groups is present within the hydrazine derivative of formula (1), these groups may be the same or different; one of A 1 and A 2 is a hydrogen atom, and the other represents a hydrogen atom or an acyl group, or an alkyl or aryl sulfonyl group; R.sub.1 --NHNH--G--R.sub.2 General Formula ( 2) wherein R 1 represents an aliphatic group, an aromatic group or a heterocyclic group; G represents --CO--, --SO 2 --, --SO--, --COCO--, a thiocarbonyl group, an iminomethylene group or --P(O)(R 3 )--, and R 2 represents an alkyl group in which the carbon atom of the alkyl group bonded to G is also bonded to at least one electron attractive group; R 3 represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group; R 1 and R 2 of formula (2) do not contain a silver halide adsorptive group; wherein said silver halide emulsion has been spectrally sensitized by means of at least one dye selected from among those of general formula (4), (5) or (6): ##STR27## wherein W 1 and W 4 represent hydrogen atoms; W 3 and W 6 represent hydrogen atoms, methyl groups or methoxy groups; W 2 is an alkyl group which may be branched of a total carbon number not more than 6, an alkoxy group which has a total carbon number of not more than 5, a bromine atom, an iodine atom, an aryl group of a total carbon number not more than 9 or a chlorine atom when W 3 represents a methyl group or a methoxy group, or it may be joined with W 1 or W 3 to form a benzene ring; W 5 represents an alkyl group which may be branched of a total carbon number not more than 6, an alkoxy group of a total carbon number not more than 5, a halogen atom, a hydroxy group, an aryl group of a total carbon number not more than 9, an aryloxy group of a total carbon number not more than 9, an arylthio group of a total carbon number not more than 8, an alkylthio group of a total carbon number not more than 4 or an acylamino group of a total carbon number not more than 4, or W 5 may be joined with W 4 or W 6 to form a benzene ring; R 1 and R 2 may be the same or different, representing alkenyl groups or alkyl groups having a total carbon number not more than 10, and at least one of R 1 and R 2 is a group which contains a sulfo group or a carboxyl group; R 3 represents a lower alkyl group; X 1 represents a counter ion which is required to neutralize the charge; n 1 represents 0 or 1, and is 0 when an intramolecular salt is formed; ##STR28## wherein V 1 represents a hydrogen atom; V 2 represents a hydrogen atom, a halogen atom, a hydroxy group, a lower alkyl group which may be branched, a lower alkoxy group, an aryl group of a total carbon number not more than 9, an aryloxy group of a total carbon number not more than 9, an arylthio group of a total carbon number not more than 8, a lower alkylthio group or an acylamino group of total carbon number not more than 4, or it may be joined with V 1 or V 3 to form a benzene ring; V 3 represents a hydrogen atom, a methyl group or a methoxy group; V 4 represents an electron attractive group; V 5 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom; R 21 , R 22 and R 23 may be the same or different, representing alkenyl groups or alkyl groups having a total carbon number not more than 10, and at least one of R 21 , R 22 and R 23 is a group which has a sulfo group or a carboxyl group; X 21 represents a counter ion which is required to neutralize the charge; and n 21 represents 0 or 1, and n 21 is 0 when an intramolecular salt is formed; ##STR29## wherein V 31 and V 33 represent a hydrogen atom or an electron attractive group and V 32 and V 34 represent an electron attractive group; R 31 , R 32 , R 33 and R 34 may be the same or different, represent an alkyl group having a total carbon number of 10 or less or an alkenyl group having a total carbon number of 10 or less, and at least one of R 31 , R 32 , R 33 and R 34 have a sulfo group or carboxyl group; X 31 represents a counter ion which is required to neutralize the charge; n 31 represents 0 or 1, and it is 0 when an intramolecular salt is formed.

Claim 2

A method for forming an image comprising, the step of processing a photographic photosensitive material with a developer having a pH of 9.6 to 11.0, wherein the photographic photosensitive material comprises a support, having thereon at least one silver halide emulsion layer and at least one protective layer over said emulsion layer, wherein said silver halide emulsion layer is comprised of silver halide grains having a silver chloride content of at least 50 mol % which contain from 1×10 -8 to 5×10 -6 mol of a rhodium compound per mol of silver, at least one hydrazine derivative selected from among those of general formula (1) or (2) indicated below is included in at least one of said emulsion layer or another hydrophilic colloid layer, at least one compound selected from among colloidal silica and polyacrylamide derivatives is included in at least one of said silver halide layer and another hydrophilic colloid layer, and the dynamic friction coefficient of the outermost layer of said protective layer is not more than 0.35: ##STR26## wherein R 1 represents an aliphatic group or an aromatic group which includes either a partial structure of --O--(CH 2 CH 2 O) n --, --O--(CH 2 CH(CH 3 )O) n -- or --O--(CH 2 CH(OH)CH 2 O) n -- (where n is an integer of 3 or more), or which contains a quaternary ammonium cation; G 1 represents --CO--, --COCO--, --CS--, --C(═NG 2 R 2 )--, --SO--, --SO 2 -- or --P(O)(G 2 R 2 )--; G 2 represents a single bond, --O--, --S-- or --N(R 2 )--, R 2 represents an aliphatic group, an aromatic group or a hydrogen atom, and in those cases where a plurality of R 2 groups is present within the hydrazine derivative of formula (1), these groups may be the same or different; one of A 1 and A 2 is a hydrogen atom, and the other represents a hydrogen atom or an acyl group, or an alkyl or aryl sulfonyl group; R.sub.1 --NHNH--G--R.sub.2 General Formula ( 2) wherein R 1 represents an aliphatic group, an aromatic group or a heterocyclic group; G represents --CO--, --SO 2 --, --SO--, --COCO--, a thiocarbonyl group, an iminomethylene group or --P(O)(R 3 )--, and R 2 represents an alkyl group in which the carbon atom of the alkyl group bonded to G is also bonded to at least one electron attractive group; R 3 represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group; R 1 and R 2 of formula (2) do not contain a silver halide adsorptive group; wherein said silver halide emulsion has been spectrally sensitized by means of at least one dye selected from among those of general formula (4), (5) or (6): ##STR27## wherein W 1 and W 4 represent hydrogen atoms; W 3 and W 6 represent hydrogen atoms, methyl groups or methoxy groups; W 2 is an alkyl group which may be branched of a total carbon number not more than 6, an alkoxy group which has a total carbon number of not more than 5, a bromine atom, an iodine atom, an aryl group of a total carbon number not more than 9 or a chlorine atom when W 3 represents a methyl group or a methoxy group, or it may be joined with W 1 or W 3 to form a benzene ring; W 5 represents an alkyl group which may be branched of a total carbon number not more than 6, an alkoxy group of a total carbon number not more than 5, a halogen atom, a hydroxy group, an aryl group of a total carbon number not more than 9, an aryloxy group of a total carbon number not more than 9, an arylthio group of a total carbon number not more than 8, an alkylthio group of a total carbon number not more than 4 or an acylamino group of a total carbon number not more than 4, or W 5 may be joined with W 4 or W 6 to form a benzene ring; R 1 and R 2 may be the same or different, representing alkenyl groups or alkyl groups having a total carbon number not more than 10, and at least one of R 1 and R 2 is a group which contains a sulfo group or a carboxyl group; R 3 represents a lower alkyl group; X 1 represents a counter ion which is required to neutralize the charge; n 1 represents 0 or 1, and is 0 when an intramolecular salt is formed; ##STR28## wherein V 1 represents a hydrogen atom; V 2 represents a hydrogen atom, a halogen atom, a hydroxy group, a lower alkyl group which may be branched, a lower alkoxy group, an aryl group of a total carbon number not more than 9, an aryloxy group of a total carbon number not more than 9, an arylthio group of a total carbon number not more than 8, a lower alkylthio group or an acylamino group of total carbon number not more than 4, or it may be joined with V 1 or V 3 to form a benzene ring; V 3 represents a hydrogen atom, a methyl group or a methoxy group; V 4 represents an electron attractive group; V 5 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom; R 21 , R 22 and R 23 may be the same or different, representing alkenyl groups or alkyl groups having a total carbon number not more than 10, and at least one of R 21 , R 22 and R 23 is a group which has a sulfo group or a carboxyl group; X 21 represents a counter ion which is required to neutralize the charge; and n 21 represents 0 or 1, and n 21 is 0 when an intramolecular salt is formed; ##STR29## wherein V 31 and V 33 represent a hydrogen atom or an electron attractive group and V 32 and V 34 represent an electron attractive group; R 31 , R 32 , R 33 and R 34 may be the same or different, represent an alkyl group having a total carbon number of 10 or less or an alkenyl group having a total carbon number of 10 or less, and at least one of R 31 , R 32 , R 33 and R 34 have a sulfo group or carboxyl group; X 31 represents a counter ion which is required to neutralize the charge; n 31 represents 0 or 1, and it is 0 when an intramolecular salt is formed.