Radiographic silver halide photographic material having a good developing speed, an excellent image tone and low residual color after processing
View Patent ↗A green-sensitized black-and-white silver halide negative working photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing tabular silver halide grains, further comprising in said emulsion layer or in a layer adjacent thereto, a heteroatomic sulfinic acid compound, a disulfide compound or a combination thereof, wherein each of said compounds has a solubilizing group having a pK a -value of 10 or less.
1. A black-and-white silver halide negative working photographic material comprising a subbed transparent support, and, in order, at one or both sides thereof, at least one light-sensitive silver halide emulsion layer, and a protective layer, wherein said material is spectrally sensitized in the wavelength range from 540–570 nm, wherein at least one light-sensitive emulsion layer thereof comprises tabular grains having a thickness in the range from 0.04 μm up to 0.20 μm, wherein said grains having an aspect ratio in the range from 5:1 up to 50:1 represent a projective surface area of at least 70% of the total projected surface of all grains present in the emulsion and wherein said material comprises at least one compound according to general formula (I):
wherein:
X represents a functional group containing sulfur, apart from a thiol group or a thiolate;
Y is selected from the group consisting of an oxygen atom, a sulfur atom, NR 2 ,
R 1 is selected from the group consisting of hydrogen, a heteroatomic group, an aryl or heteroaryl group, S—R 7 and NR 8 R 9 ;
R 2 , R 5 , R 6 and R 7 are selected from the group consisting of hydrogen, an aliphatic or heteroatomic group, an aryl or heteroaryl group provided that R2 is not —NR 3 R 4 or —N═CR 5 R 6 ;
R 3 , R 4 , R 8 and R 9 are selected from the group consisting of hydrogen, an aliphatic or heteroatomic group; an aryl or heteroaryl group, an acyl group, a sulphonyl group and a phosphoryl group;
wherein any of R 3 and R 4 , R 5 and R 6 , R 8 and R 9 may represent atoms necessary to form a five to eight membered, and wherein R 1 and Y may form a five to eight membered ring, further characterized in that at least one of Y and R 1 is substituted by a solubilizing group having a pK a of 10 or less.
2. A silver halide material according to claim 1 , wherein in said compound according to general formula (I), X— is represented by a group according to formula (II),
wherein M represents a hydrogen atom or a counterion.
3. A silver halide material according to claim 1 , wherein in said compound according to general formula (I), X— is represented by a group according to formula (III),
wherein Y and R 1 are defined in formula (III) as in claim 1 .
4. A silver halide photographic material according to claim 1 , wherein said material further comprises a compound according to general formula (IV),
wherein Y and R1 are defined as in claim 1 and M represents a hydrogen atom or a counterion.
5. A silver halide photographic material according to claim 2 , wherein said material further comprises a compound according to general formula (IV),
wherein Y and R1 are defined as in claim 1 and M represents a hydrogen atom or a counterion.
6. A silver halide photographic material according to claim 3 , wherein said material further comprises a compound according to general formula (IV),
wherein Y and R1 are defined as in claim 1 and M represents a hydrogen atom or a counterion.
7. A silver halide photographic material according to claim 1 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
8. A silver halide photographic material according to claim 2 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
9. A silver halide photographic material according to claim 3 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
10. A silver halide photographic material according to claim 4 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
11. A silver halide photographic material according to claim 5 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
12. A silver halide photographic material according to claim 6 , wherein said solubilizing group is selected from the group consisting of a carboxylic acid or salt thereof, a sulfonic acid or salt thereof, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or salt thereof.
13. A silver halide photographic material according to claim 1 , wherein Y is a sulfur atom.
14. A silver halide photographic material according to claim 2 , wherein Y is a sulfur atom.
15. A silver halide photographic material according to claim 3 , wherein Y is a sulfur atom.
16. A silver halide photographic material according to claim 4 , wherein Y is a sulfur atom.
17. A silver halide photographic material according to claim 5 , wherein Y is a sulfur atom.
18. A silver halide photographic material according to claim 6 , wherein Y is a sulfur atom.
19. A silver halide photographic material according to claim 1 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
20. A silver halide photographic material according to claim 2 , wherein R 1 — is represented by formula (V) wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
21. A silver halide photographic material according to claim 3 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
22. A silver halide photographic material according to claim 4 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
23. A silver halide photographic material according to claim 5 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
24. A silver halide photographic material according to claim 6 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
25. A silver halide photographic material according to claim 13 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
26. A silver halide photographic material according to claim 14 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
27. A silver halide photographic material according to claim 15 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
28. A silver halide photographic material according to claim 16 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
29. A silver halide photographic material according to claim 17 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
30. A silver halide photographic material according to claim 18 , wherein R 1 — is represented by formula (V), wherein
wherein:
A is a solubilizing group selected from the group consisting of a carboxylic acid, a sulfonic acid, a phosphonate, a phosphate, a sulfate and an acylsulfonamide or a corresponding salt thereof, and
L represents an aliphatic divalent linking group.
31. A black-and-white silver halide negative working photographic material comprising a subbed transparent support, and, in order, at one or both sides thereof, at least one light-sensitive silver halide emulsion layer, and a protective layer, wherein said material is spectrally sensitized in the wavelength range from 540–570 nm, wherein at least one light-sensitive emulsion layer thereof comprises tabular grains having a thickness in the range from 0.04 μm up to 0.20 μm, wherein said grains having an aspect ratio in the range from 5:1 up to 50:1 represent a projective surface area of at least 70% of the total projected surface of all grains present in the emulsion and wherein said material comprises at least one compound selected from:
32. A black-and-white silver halide negative working photographic material comprising a subbed transparent support, and, in order, at one or both sides thereof, at least one light-sensitive silver halide emulsion layer, and a protective layer, wherein said material is spectrally sensitized in the wavelength range from 540–570 nm, wherein at least one light-sensitive emulsion layer thereof comprises tabular grains having a thickness in the range from 0.04 μm up to 0.20 μm, wherein said grains having an aspect ratio in the range from 5:1 up to 50:1 represent a projective surface area of at least 70% of the total projected surface of all grains present in the emulsion and wherein said material comprises at least one compound selected from:
33. A silver halide photographic material according to claim 1 , wherein at least one of the compounds according to formula (I) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 10 −6 to 10 −1 mol per mol of silver halide.
34. A silver halide photographic material according to claim 2 , wherein at least one of the compounds according to formula (II) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 10 −6 to 10 −1 mol per mol of silver halide.
35. A silver halide photographic material according to claim 3 , wherein at least one of the compounds according to formula (III) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 10 −6 to 10 −1 mol per mol of silver halide.
36. A silver halide photographic material according to claim 1 , wherein at least one of the compounds according to the formula (I) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 0.4 mmol to 0.1 mol per mol of silver halide.
37. A silver halide photographic material according to claim 2 , wherein at least one of the compounds according to the formula (II) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 0.4 mmol to 0.1 mol per mol of silver halide.
38. A silver halide photographic material according to claim 3 , wherein at least one of the compounds according to the formula (III) is present in the light-sensitive silver halide emulsion layer or in a layer adjacent thereto, in an amount from 0.4 mmol to 0.1 mol per mol of silver halide.
39. A silver halide photographic material according to claim 1 , wherein the coating amount of the tabular silver halide grains, expressed as an equivalent amount of silver nitrate, is in a range of from 0.1 to 6 g/m 2 .
40. A silver halide photographic material according to claim 2 , wherein the coating amount of the tabular silver halide grains, expressed as an equivalent amount of silver nitrate, is in a range of from 0.1 to 6 g/m 2 .
41. A silver halide photographic material according to claim 3 , wherein the coating amount of the tabular silver halide grains, expressed as an equivalent amount of silver nitrate, is in a range of from 0.1 to 6 g/m 2 .
42. A silver halide photographic material according to claim 1 , wherein inbetween said light-sensitive silver halide emulsion layer and said protective layer, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
43. A silver halide photographic material according to claim 2 , wherein inbetween said light-sensitive silver halide emulsion layer and said protective layer, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
44. A silver halide photographic material according to claim 3 , wherein inbetween said light-sensitive silver halide emulsion layer and said protective layer, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
45. A silver halide photographic material according to claim 4 , wherein inbetween said light-sensitive silver halide emulsion layer and said protective layer, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
46. A silver halide photographic material according to claim 1 , wherein inbetween said light-sensitive silver halide emulsion layer and said subbed transparent support, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
47. A silver halide photographic material according to claim 2 , wherein inbetween said light-sensitive silver halide emulsion layer and said subbed transparent support, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
48. A silver halide photographic material according to claim 3 , wherein inbetween said light-sensitive silver halide emulsion layer and said subbed transparent support, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
49. A silver halide photographic material according to claim 4 , wherein inbetween said light-sensitive silver halide emulsion layer and said subbed transparent support, an intermediate non-light sensitive hydrophilic layer is present, coated with fine silver halide grains rich in silver iodide.
50. A silver halide photographic material according to claim 1 , wherein in said protective layer fine silver halide grains rich in silver iodide are present.
51. A silver halide photographic material according to claim 2 , wherein in said protective layer fine silver halide grains rich in silver iodide are present.
52. A silver halide photographic material according to claim 3 , wherein in said protective layer fine silver halide grains rich in silver iodide are present.
53. A silver halide photographic material according to claim 4 , wherein in said protective layer fine silver halide grains rich in silver iodide are present.
54. A silver halide photographic material according to claim 42 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
55. A silver halide photographic material according to claim 43 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
56. A silver halide photographic material according to claim 44 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
57. A silver halide photographic material according to claim 45 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
58. A silver halide photographic material according to claim 46 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
59. A silver halide photographic material according to claim 47 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
60. A silver halide photographic material according to claim 48 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
61. A silver halide photographic material according to claim 49 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
62. A silver halide photographic material according to claim 50 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
63. A silver halide photographic material according to claim 51 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
64. A silver halide photographic material according to claim 52 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
65. A silver halide photographic material according to claim 53 , wherein said fine grains rich in silver iodide having a grain diameter of not more than 100 nm, are coated in amounts in the range from 0.3 to 0.6 g/m 2 , wherein said amounts are expressed as equivalent amounts of silver nitrate.
66. A silver halide photographic material according to claim 1 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
67. A silver halide photographic material according to claim 2 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
68. A silver halide photographic material according to claim 3 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
69. A silver halide photographic material according to claim 4 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
70. A silver halide photographic material according to claim 46 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
71. A silver halide photographic material according to claim 47 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
72. A silver halide photographic material according to claim 48 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
73. A silver halide photographic material according to claim 49 , wherein said material is a single-side or double side coated radiographic material, wherein average thicknesses of the tabular grains present in a light-sensitive layer thereof are in the range from 0.06 to 0.15 μm and wherein average aspect ratios of said tabular grains are in the range from 10:1 to 25:1.
74. A black-and-white silver halide negative working photographic material comprising a subbed transparent support, and, in order, at one or both sides thereof, at least one light-sensitive silver halide emulsion layer, and a protective layer, wherein said material is spectrally sensitized in the wavelength range from 540–570 nm, wherein at least one light-sensitive emulsion layer thereof comprises tabular grains having a thickness in the range from 0.04 μm up to 0.20 μm, wherein said grains having an aspect ratio in the range from 5:1 up to 50:1 represent a projective surface area of at least 70% of the total projected surface of all grains present in the emulsion and wherein said material comprises at least one compound according to general formula (I):
wherein:
X represents a functional group containing sulfur, apart from a thiol group or a thiolate;
Y is selected from the group consisting of an oxygen atom, a sulfur atom, NR 2 ,
R 1 is selected from the group consisting of hydrogen, a heteroatomic group, an aryl or heteroaryl group, S—R 7 and NR 8 R 9 ;
R 2 is selected from the group consisting of hydrogen, an aliphatic and an aryl group;
R 5 , R 6 and R 7 are selected from the group consisting of hydrogen, an aliphatic or heteroatomic group, an aryl or heteroaryl group;
R 3 , R 4 , R 8 and R 9 are selected from the group consisting of hydrogen, an aliphatic or heteroatomic group; an aryl or heteroaryl group, an acyl group, a sulphonyl group and a phosphoryl group;
wherein any of R 3 and R 4 , R 5 and R 6 , R 8 and R 9 may represent atoms necessary to form a five to eight membered, and wherein R 1 and Y may form a five to eight membered ring, further characterized in that at least one of Y and R 1 is substituted by a solubilizing group having a pK a of 10 or less.