Silver halide photographic material

Claim 2

A negative-type silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, said silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto containing (a) a compound represented by the following general formula (I): R.sub.1 --NHNH--G--R.sub.2 (I) wherein R 1 is an aliphatic or aromatic group, R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, and G is a carbonyl group, a sulfonyl group a sulfoxy group, a phosphoryl group, or an N-substituted or unsubstituted imino group, and (b) a compound represented by the following general formulae (III) or (IV) ##STR12## wherein T is an atomic group necessary for forming a 5-membered hetero ring composed of 3 or 4 hetero atoms selected from nitrogen, oxygen and sulfur; J is a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, an alkylthio group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or a substituted ammonium group, an alkylamido group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or a substituted ammonium group, an alkylcarbamoyl group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or a substituted ammonium group, an alkyl group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or a substituted ammonium group, or an aromatic group having about 6 to 31 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or a substituted ammonium group, wherein M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion; and Z 1 is a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group, a hydrohalogenic acid salt or a sulfonic acid salt thereof, or --S--Z O wherein Z O is an alkyl group, an aromatic group, or a heteroaromatic group, said group Z O being substituted with at least one group selected from the group consisting of a hydroxy group, a --SO 3 M 1 group, or a --COOM 1 group wherein M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion, a substituted or unsubstituted amino group or a substituted or unsubstituted ammonium group, or with a substituent having at least one group selected from the above groups: A--ALK--SM.sup.2 (IV) wherein A is a hydroxy gorup, a --SO 3 M 1 group, a --COOM 1 group or a --N(R 3 ) 2 group, where M 1 is as defined above, R 3 is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms and the two R 3 groups may combine to form a ring; ALK is a substituted or unsubstituted aklylene group having 2 to 12 carbon atoms; and M 2 is a hydrogen atom, a --S--ALK--A group or a ##STR13## group wherein R 4 is a hydrogen atom, a substituted or unsubstituted alkyl group having about 1 to 5 carbon atoms or a substituted or unsubstituted phenyl group having about 1 to 10 carbon atoms, and X - is a halide ion or a sulfonic acid ion.

Claim 3

The negative-type silver halide photographic material as claimed in claim 1, wherein the light-sensitive silver halide emulsion layer is composed of a silver halide emulsion containing at least about 0.5 mol% of silver iodide.

Claim 4

The negative-type silver halide photographic material as claimed in claim 1, wherein said aliphatic group represented by R 1 is a straight, branched or cyclic alkyl group having about 1 to 20 carbon atoms, said aromatic group represented by R 1 is a monocyclic aryl group, a dicyclic aryl group or an unsaturated heterocyclic group, said alkyl group represented by R 2 is an alkyl group having 1 to 4 carbon atoms, said aryl group represented by R 2 is a monocyclic or dicyclic aryl group, said alkoxy group represented by R 2 contains 1 to 8 carbon atoms and said aryloxy group represented by R 2 is monocyclic.

Claim 5

The negative-type silver halide photographic material as claimed in claim 3, wherein G is a carbonyl group and R 2 is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group or a substituted or unsubstituted phenyl group.

Claim 6

The negative-type silver halide photographic material as claimed in claim 3, wherein G is a sulfonyl group, and R 2 is a methyl group, an ethyl group, a phenyl group or a 4-methylphenyl group.

Claim 7

The negative-type silver halide photographic material as claimed in claim 3, wherein G is a phosphoryl group, and R 2 is methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group.

Claim 8

The negative-type silver halide photographic material as claimed in claim 3, wherein G is a sulfoxy group and R 2 is a cyanobenzyl group or a methylthiobenzyl group.

Claim 9

The negative-type silver halide photographic material as claimed in claim 3, wherein G is an N-substituted or unsubstituted imino group and R 2 is methyl group, an ethyl group or a substituted or unsubstituted phenyl group.

Claim 10

The negative-type silver halide photographic material as claimed in claim 4, wherein R 2 is a hydrogen atom.

Claim 11

The negative-type silver halide photographic material as claimed in claim 1, wherein said compound represented by general formula (III) is represented by the following general formula (V): ##STR14## wherein: M 3 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion; R 5 is a hydrogen atom or a substituted or unsubstituted alkyl group having about 1 to 19 carbon atoms; R 6 is a group --SO 3 M 1 , a group --COOM 1 , wherein M 1 has the same definition as M 1 in the general formula (II), or --OH; Q is S, NH, or CONH linked to the thiadiazole ring through N; and p is an integer of 1 to 6.

Claim 12

The negative-type silver halide photographic material as claimed in claim 1, wherein said compound of general formula (I) is present in an amount of about 1×10 -6 to 5×10 -2 mol per mol of silver halide, and said compound of general formula (III) is present in an amount of from about 1×10 -5 to 1×10 -2 mol per mol of silver halide.

Claim 13

A process comprising imagewise exposing a negative-type silver halide photographic material, developing said negative-type silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, said silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto containing (a) a compound represented by the following general formula (I): R.sub.1 --NHNH--G--R.sub.2 (I) wherein R 1 is an aliphatic or aromatic group, R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, and G is a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an N-substituted or unsubstituted imino group, and (b) a compound represented by the following general formulae (III) or (IV) ##STR15## wherein T is an atomic group necessary for forming a 5-membered hetero ring composed of 3 or 4 hetero atoms selected from nitrogen, oxygen and sulfur; J is a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, an alkylthio group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkylamido group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkylcarbamoyl group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkyl group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, or an aromatic group having about 6 to 31 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group; M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion; and Z 1 is a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group, a hydrohalogenic acid salt or a sulfonic acid salt thereof, or --S--Z O wherein Z O is an alkyl group, an aromatic group, or a heteroaromatic group, said group Z O being substituted with at least one group selected from the group consisting of a hydroxy group, a --SO 3 M 1 group, or a --COOM 1 group wherein M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion, a substituted or unsubstituted amino group or a substituted or unsubstituted ammonium group, or with a substituent having at least one group selected from the above groups; A--ALK--SM.sup.2 (IV) wherein A is a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group or a --N(R 3 ) 2 group, where M 1 is as defined above, R 3 is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and the two R 3 groups may combine to form a ring; ALK is a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms; and M 2 is a hydrogen atom, a group --S--ALK--A or a group ##STR16## wherein R 4 is a hydrogen atom, a substituted or unsubstituted alkyl group having about 1 to 5 carbon atoms or a substituted or unsubstituted phenyl group having about 1 to 10 carbon atoms, and X -- is a halide ion or a sulfonic acid ion.

Claim 14

A process comprising imagewise exposing a negative-type silver halide photographic material, developing said negative-type silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, said silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto containing (a) a compound represented by the following general formula (I): R.sub.1 --NHNH--G--R.sub.2 (I) wherein R 1 is an aliphatic or aromatic group, R 2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, and G is a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an N-substituted or unsubstituted imino group, and (b) a compound represented by the following general formulae (III) or (IV) ##STR15## wherein T is an atomic group necessary for forming a 5-membered hetero ring composed of 3 or 4 hetero atoms selected from nitrogen, oxygen and sulfur; J is a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, an alkylthio group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkylamido group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkylcarbamoyl group having about 2 to 18 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, an alkyl group having about 1 to 19 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group, or an aromatic group having about 6 to 31 carbon atoms which is substituted with a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group, a substituted amino or ammonium group; M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion; and Z 1 is a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group, a hydrohalogenic acid salt or a sulfonic acid salt thereof, or --S--Z O wherein Z O is an alkyl group, an aromatic group, or a heteroaromatic group, said group Z O being substituted with at least one group selected from the group consisting of a hydroxy group, a --SO 3 M 1 group, or a --COOM 1 group wherein M 1 is a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion, a substituted or unsubstituted amino group or a substituted or unsubstituted ammonium group, or with a substituent having at least one group selected from the above groups; A--ALK--SM.sup.2 (IV) wherein A is a hydroxy group, a --SO 3 M 1 group, a --COOM 1 group or a --N(R 3 ) 2 group, where M 1 is as defined above, R 3 is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and the two R 3 groups may combine to form a ring; ALK is a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms; and M 2 is a hydrogen atom, a group --S--ALK--A or a group ##STR16## wherein R 4 is a hydrogen atom, a substituted or unsubstituted alkyl group having about 1 to 5 carbon atoms or a substituted or unsubstituted phenyl group having about 1 to 10 carbon atoms, and X -- is a halide ion or a sulfonic acid ion.

Claim 15

The process as claimed in claim 12, wherein said compound of general formula (I) is present in an amount of about 1×10 -6 to 5×10 -2 mol per mol of silver halide, and said compound of general formula (II) is present in an amount of from about 1×10 -5 to 1×10 -2 mol per mol of silver halide.

Claim 16

The process as claimed in claim 12, wherein said reducing solution contains a cerium (IV) salt.

Claim 17

The process as claimed in claim 12, wherein in the negative-type silver halide photographic material said aliphatic group represented by R 1 is a straight, branched or cyclic alkyl group having about 1 to 20 carbon atoms, said aromatic group represented by R 1 is a monocyclic aryl group, a dicyclic aryl group or an unsaturated heterocyclic group, said alkyl group represented by R 2 is an alkyl group having 1 to 4 carbon atoms, said aryl group represented by R 2 is an a monocyclic or dicyclic aryl group, said alkoxy group represented by R 2 contains 1 to 8 carbon atoms and said aryloxy group represented by R 2 is monocyclic.

Claim 18

The process as claimed in claim 13, wherein G is a carbonyl group and R 2 is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group or a substituted or unsubstituted phenyl group.

Claim 19

The process as claimed in claim 13, wherein G is a sulfonyl group, and R 2 is a methyl group, an ethyl group, a phenyl group or a 4-methylphenyl group.

Claim 20

The process as claimed in claim 13, wherein G is a phosphoryl group, and R 2 is methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group.

Claim 21

The process as claimed in claim 13, wherein G is a phosphoryl group, and R 2 is a cyanobenzyl group or a methylthiobenzyl group.

Claim 22

The process as claimed in claim 13, wherein G is an N-substituted or unsubstituted imino group and R 2 is a methyl group, an ethyl group or a substituted or unsubstituted phenyl group.

Claim 23

The process as claimed in claim 14, wherein R 2 is a hydrogen atom.