Title:
SILVER HALIDE PHOTOGRAPHIC MATERIAL.
Kind Code:
A4


Abstract:
Abstract of EP0572662
A silver halide photographic material having at least one silver halide emulsion layer formed on a support, wherein at least one silver halide emulsion is a tellurium-sensitized monodisperse silver halide emulsion.



Inventors:
Nozawa, Yasushi (JP)
Mifune, Hiroyuki (JP)
Sasaki, Hirotomo (JP)
Application Number:
EP19920901446
Publication Date:
11/02/1994
Filing Date:
12/18/1991
Assignee:
FUJI PHOTO FILM CO LTD (JP)
International Classes:
G03C1/09; G03C1/16; G03C1/18; (IPC1-7): G03C1/09; G03C1/035
European Classes:
G03C1/09
View Patent Images:



Claims:
1. A silver halide photographic light-sensitive material comprising a support and at least one silver halide emulsion layer formed on the support, said emulsion layer containing at least one silver halide emulsion which is a tellurium-sensitized monodispersed emulsion.

2. The light-sensitive material according to claim 1, wherein said monodispersed silver halide emulsion has a variation coefficient of 22% or less in terms of grain-size distribution.

3. The light-sensitive material according to claim 1, wherein said monodispersed silver halide emulsion has a variation coefficient of 18% or less in terms of grain-size distribution.

4. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been tellurium-sensitized in the presence of at least one compound represented by the following formula (I): EMI87.1 where R1, R2 and R3 are aliphatic groups, aromatic groups, heterocyclic groups, OR4, NR5(R6), SR7, OSiR8(R9)(R10), X or hydrogen atoms, R4 and R7 are aliphatic groups, aromatic groups, heterocyclic group, hydrogen atoms or cations, R5 and R6 are aliphatic groups, aromatic groups, heterocyclic groups or hydrogen atoms, R8, R9 and R10 are aliphatic groups, and X is a halogen atom.

5. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been tellurium-sensitlzed in the presence of at least one compound represented by the following formula (I): EMI88.1 where R11 is aliphatic group, aromatic group, heterocyclic group or -NR13(R14), R12 is -NR15(R16), -N(R17)N(R18)R19 or -OR20, R13, R14, R15, R16, R17, R19 and R10 are hydrogen atoms, aliphatic groups, aromatic groups, heterocyclic groups or acyl groups, R11 and R15. R11 and R17, R11 and R18, R11 and R20, R13 and R15, R13 and R17, R13 and R18, and R13 and R20 can combine, forming a ring.

6. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been tellurium-sensitized in the presence of at least one tellurium sensitizer of such type that silver telluride is formed at a pseudo-first-order reaction rate constant K of 1 x 10<-><8> to 1 min<-><1>.

7. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been tellurium-sensitized in the presence of at least one tellurium sensitizer of such type that silver telluride is formed at a pseudo-first-order reaction rate constant K of 1 x 10<-><7> to 1 x 10<-><1> min<-><1>.

8. The light-sensitive material according to claim 1, wherein said monodispersed silver halide emulsion has been subjected to tellurium sensitization and sulfur sensitization.

9. The light-sensitive material according to claim 6, wherein said tellurium sensitization has been achieved by a tellurium sensitizer which is a compound which reacts with a silver halide emulsion at a temperature of 40 DEG C to 95 DEG C, at pH of 3 to 10, and pAg of 6 to 11, forming silver telluride.

10. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been further gold-sensitized.

11. The light-sensitive material according to claim 1, wherein said silver halide emulsion has been reacted with thiocyanate.

Description:

The present invention will be described in more detail below by way of its examples, but the present invention is not limited to these examples. Mode of Carrying Out the Invention Example 1

First, a monodispersed emulsion was prepared which contained double-structured octahedral grains slightly rounded and having an average iodine content of 12 mol%. an average size of 1.1 mu m, and a variation coefficient of 15% in terms of size distribution. The cores of the grains had an iodine content of 24 mol%, and the shells covering up the cores had an iodine content of 0 mol%. The emulsion was desilvered by means or the ordinary flocculation, thereby obtaining emulsion A.

Three emulsions B, C, and D were prepared which were identical to emulsion A, except that their variation coefficients were 20%, 24% and 32%, respectively.

These emulsions, which is not chemically sensitized, A, B, C, an D were chemically sensitized at 61 DEG C with auric chloride, potassium thio cyanate, and the sulfur sensitizers and/or tellurium sensitizers shown in Table 1 (later presented), so that they might have optimum sensitivities when exposed for 1/100 second.

Emulsions A, B, C, and D, thus chemically sensitized were coated on film supports, thereby preparing Samples 1 to 16.

More specifically. each sample comprised an undercoated triacetylcellulose film support, an emulsion layer, and a protective layer, both layers having been formed on the support simultaneously. The emulsion layer contained any one of emulsions A to D (silver content: 1.5 x 10<-><2> mol/m<2>), the coupler represented by the following formula, used in an amount of 1.5 x 10<-><3> mol/m<2>, a stabilizing agent, a coating aid, and gelatin. The protective layer contained gelatin, a film hardener, a coating aid, and a matting agent. EMI57.1 Samples 1 to 16 were exposed to light for sensitometry and then color-developed. Their densities were measured by means of a green filter. Samples 1 to 16 exhibited the photographic properties, which are shown in Table 1.

The development process was performed at 38 DEG C under the following conditions:

Columns=2 1. Color developing:1 min. 45 sec. 2. Bleaching:6 min. 30 sec. 3. Water-washing:3 min. 15 sec. 4. Fixing:6 min. 30 sec. 5. Water-washing:3 min. 15 sec. 6. Stabilizing:3 min. 15 sec.

The solutions used in the processing steps specified above had the following compositions:

Columns=2 Title: Color developing solution Sodium nitrilotetraacetate1.4 g Sodium sulfite4.0 g Sodium carbonate30.0 g Potassium bromide1.4 g Hydroxyamine sulfate2.4 g 4-(N-ethyl-N- beta -hydroxyethylamino)-2-methylaniline sulfate4.5 g Water to make1 liter
Columns=2 Title: Bleaching Solution Ammonium bromide160.0 g Ammonia water (28%)25.0 ml Sodium ethylenediamine tetraacetoferrate (III)130 g Glacial acetic acid14 ml Water to make1 litter
Columns=2 Title:

Fixing Solution Sodium tetrapolyphosphate2.0 g Sodium sulfite4.0 g Ammonium thiosulfate (70%)175.0 ml Sodium bisulfate4.6 g Water to make1 litter

Columns=2 Title: Stabilizing Solution Formalin (37 wt%)8.0 ml Water to make1 litter

Samples 1 to 16 were subjected to wedge exposure for 1/100 second. The light source used in the wedge exposure was a filter adjusted to a color temperature of 4800 DEG K. The sensitivities of the samples were compared at an optical density of 0.2, using that, i.e., 100, of Sample 1 as reference.

The gradations of Samples 1 to 16 were compared, with that, i.e., 1.0, of Sample 1 used as reference. The gradation of each sample was evaluated in terms of sample was evaluated in terms of the inclination of the straight line connected two points on the fog-characteristic curve, which indicated optical densities of 0.2 and 1.0, respectively.

Further, to evaluate the fog occurring during the storage of each sample, the sample was left to stand for 7 days in atmosphere at temperature of 50 DEG C and relative humidity of 60%, and thereafter was processed under the same conditions as specified above. The fog of the sample was measured and compared with the fog the sample had immediately after it had been prepared. The difference in fog, thus obtained, was recorded as change occurring during the storage.

The results of this test were as is shown in the following Table 1. EMI60.1 EMI61.1

As is evident from Table 1, the usefulness of the present invention is obvious, as will be discussed.

Samples 14 to 16, which contained a tellurium-sensitized polydispersed emulsion, was more sensitive than Sample 13 which contained a sulfur-sensitized emulsion. However, they had much fog and a great change in fog, and their gradations were not so high. Further, Samples 14 to 16 demonstrated no advantage which might resulted from the combination of sulfur sensitization and tellurium sensitization.

By contrast, Samples 2 to 4, 6 to 8, and 10 to 12, which fall within the scope of the invention, had not only a relatively small fog and a small change in fog, but also a high sensitivity and a great gradation.

Comparison of Samples 2, 6, and 10 with Samples 3, 7, and 11, respectively, reveals that a monodispersed emulsion having a variation coefficient of 22% or less is preferred, and that a monodispersed emulsion having a variation coefficient of 18% is more preferred.

Comparison of Sample 11 with 12 shows that the tellurium sensitizer represented by the formula (I) is superior to those disclosed in Canadian Patent 800, 958 and British Patent 1,295,462. (Similarly, comparison of Samples 7, 8, 11, and 12 proves that the compound of the formula (II) is also excellent.)

Also, as is clearly seen from the photographic properties of Samples 2 with 3, 6 with 7, and 10 with 11, the combined application of a sulfur sensitizer and a tellurium sensitizer helped to increase gradation and decrease fog, though it decreased sensitivity a little. Example 2

A monodispersed emulsion was prepared which contained triple-structured octahedral grains slightly rounded and having an average iodine content of 4 mol% and an average size of 0.6 mu m. The cores of the grains had an iodine content of 1 mol%, the inner shells covering up the cores had an iodine content of 38 mol%, the outer shells had an iodine content of 1 mol%. The emulsion was subjected to the same experiment as in Example 1, except that it was chemically sensitized in the presence of appropriate amounts of the three sensitizing dyes specified below.

The use of this emulsion was found to achieve the same advantage as accomplished in Example 1. EMI63.1 Example 3

A monodispersed emulsion was prepared which contained triple-structured octahedral grains slightly rounded and having an average iodine content of 5 mol% and an average size of 0.35 mu m. The cores of the grains were formed of silver bromide, the inner shells covering up the cores were made of silver iodobromide and having an iodine content of 38 mol%, and the outer shells were made of silver iodide. The emulsion was subjected to the same experiment as in Example 1, except that it was chemically sensitized in the presence of an appropriate amount of 4 hydroxy-6-methyl-1,3,3a,7-tetraazaindene. The emulsion also established the usefulness of the present invention. Example 4

An emulsion was prepared which contained tabular grains having an average iodine content of 8.8 mol%, an average aspect ratio of 7.2 and an equivalent-sphere diameter of 0.65 mu m and having dislocation lines. The emulsion was put to the same experiment as in Example 1, and established the usefulness of the present invention. Example 5

The following experiment was conducted in accordance with the instructions disclosed in JP-A-61-67845.

An emulsion was prepared by means of double-jet method, which contained tetradecahedral silver halide grains having an average size of 1.5 mu m, and an average variation coefficient of 12%. The cores of the grains had a silver iodide content of 2 mol%, and the shells thereof had a thickness of 0.3 mu m and a silver iodide of 0.5 mol%. The emulsion was divided into two portions. The first portion was chemically sensitized and spectrally sensitized with dimethylselenourea as emulsion D used in Example 1 disclosed in JP-A-61-67845 and was coated on a support, thereby preparing Sample 51. The second portion of the emulsion was processed in the same way as the first portion, except that compound 10 was used in place of dimethylselenourea, thereby preparing Sample 52.

Samples 51 and 52 were put to sensitometry test, the results of which were as is represented in the following Table 2. The sensitivity and gradation of each sample, shown in Table 2, are of relative values, with those of Sample 51, i.e., 100 and 1.0, respectively, used as reference.

Id=Table 2 Columns=4 Head Col 1: Sample No. Head Col 2: Fog Head Col 3: Sensitivity Head Col 4: Gradation 510.071001.0 520.091151.30

As is obvious from Table 2, the present invention is useful. Example 6

Various layers were coated on an undercoated triacetylcellulose film support, forming a multilayered color light-sensitive material (hereinafter referred to as "Sample 101"). (Compositions of light-sensitive layers)

Numerals corresponding to each component indicates a coating amount represented in units of g/m<2>. The coating amount of a silver halide is represented by the coating amount of silver. The coating amount of a sensitizing dye is represented in units of moles per mole of a silver halide in the same layer. (Sample 101)

Columns=2 Title: Layer 1: Antihalation layer Black colloidal silversilver 0.18 Gelatin0.40
Columns=2 Title: Layer 2: Interlayer 2,5-di-t-pentadecylhydorquinone0.18 EX-10.18 EX-30.020 EX-122.0 x 10<-><3> U-10.060 U-20.080 U-30.10 HBS-10.10 HBS-20.020 Gelatin0.04
Columns=2 Title: Layer 3:

First red-sensitive emulsion layer Emulsion Asilver 0.25 Emulsion Bsilver 0.25 Sensitizing dye I6.9 x 10<-><5> Sensitizing dye II1.8 x 10<-><5> Sensitizing dye III3.1 x 10<-><4> EX-20.17 EX-100.020 EX-140.17 U-10.070 U-20.050 U-30.070 HBS-10.060 Gelatin0.87

Columns=2 Title: Layer 4: Second red-sensitive emulsion layer Emulsion Gsilver 1.00 Sensitizing dye I5.1 x 10<-><5> Sensitizing dye II1.4 x 10<-><5> Sensitizing dye III2.3 x 10<-><4> EX-20.20 EX-30.050 EX-100.015 EX-140.20 EX-150.050 U-10.070 U-20.050 U-30.070 Gelatin1.30
Columns=2 Title: Layer 5:

Third red-sensitive emulsion layer Emulsion Dsilver 1.60 Sensitizing dye I5.4 x 10<-><5> Sensitizing dye II1.4 x 10<-><5> Sensitizing dye III2.4 x 10<-><4> EX-20.097 EX-30.010 EX-40.080 HBS-10.22 HBS-20.10 Gelatin1.63

Columns=2 Title: Layer 6: Interlayer EX-50.040 HBS-10.020 Gelatin0.80
Columns=2 Title: Layer 7:

First green-sensitive emulsion layer Emulsion Asilver 0.15 Emulsion Bsilver 0.15 Sensitizing dye IV3.0 x 10<-><5> Sensitizing dye V1.0 x 10<-><4> Sensitizing dye VI3.8 x 10<-><4> EX-10.021 EX-60.26 EX-70.030 EX-80.025 HBS-10.10 HBS-30.010 Gelatin0.63

Columns=2 Title: Layer 8: Second green-sensitive emulsion layer Emulsion Csilver 0.45 Sensitizing dye IV2.1 x 10<-><5> Sensitizing dye V7.0 x 10<-><5> Sensitizing dye VI2.6 x 10<-><4> EX-60.094 EX-70.026 EX-80.018 HBS-10.16 HBS-38.0 x 10<-><3> Gelatin0.50
Columns=2 Title: Layer 9:

Third green-sensitive emulsion layer Emulsion Esilver 1.20 Sensitizing dye IV3.5 x 10<-><5> Sensitizing dye V8.0 x 10<-><5> Sensitizing dye VI3.0 x 10<-><4> EX-10.013 EX-110.065 EX-130.019 HBS-10.25 HBS-20.10 Gelatin1.54

Columns=2 Title: Layer 10: Yellow filter layer Yellow colloid silversilver 0.050 EX-50.080 HBS-10.030 Gelatin0.95
Columns=2 Title: Layer 11: First blue-sensitive emulsion laver Emulsion Asilver 0.080 Emulsion Bsilver 0.070 Emulsion Fsilver 0.070 Sensitizing dye VII3.5 x 10<-><4> EX-80.042 EX-90.72 HBS-10.28 Gelatin1.10
Columns=2 Title: Layer 12:

Second blue-sensitive emulsion layer Emulsion Gsilver 0.45 Sensitizing dye VII2.1 x 10<-><4> EX-90.15 EX-107.0 x 10<-><3> HBS-10.050 Gelatin0.78

Columns=2 Layer 13: Third blue-sensitive emulsion layer Emulsion Hsilver 0.77 Sensitizing dye VII2.2 x 10<-><4> EX-90.20 HBS-10.070 Gelatin0.69
Columns=2 Title: Layer 14: First protective layer Emulsion Isilver 0.20 U-40.11 U-50.17 HBS-15.0 x 10<-><2> Gelatin1.00
Columns=2 Title: Layer 15: Second protective layer H-10.40 B-1 (diameter: 1.7 mu m)5.0 x 10<-><2> B-2 (diameter: 1.7 mu m)0.10 B-30.10 S-10.20 Gelatin1.20

Further, all layers of Sample 101 contained W-1, W-2, W-3, B-4, B-5, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rohdium salt, so that they may have improved storage stability, may be more readily processed, may be more resistant to pressure, more antibacterial and more anti fungal, may be better protected against electrical charging, and may be more readily coated. Emulsions A to I, used in preparing Sample 101, will be specified in Table 3, and the structures of the compounds used in Sample 101 will be shown below.

Emulsions D, B, and G for use in Sample 101 were replaced with others, as in Examples 1, 2, and 4, and the same test as described above was performed (except that the color developing time was changed to 3 min. 15 sec.).

The same advantages were achieved in Examples 1, 2, and 4 were attained in a multilayered color light-sensitive material. EMI70.1 EMI71.1 EMI72.1 EMI73.1 EMI74.1 EMI75.1 EMI76.1 EMI77.1 EMI78.1 EMI79.1 EMI80.1 HBS-1 Tricresylphosflate HBS-2 Di-n-bulylphthalate EMI80.2 EMI81.1 EMI82.1 EMI83.1 EMI84.1 EMI85.1 EMI86.1