Field of the Invention
[0001] This invention relates to a silver halide emulsion that allows production of photographic
films that have less pressure sensitivity.
Background of the Invention
[0002] Pressure applied to photographic emulsion coatings can produce both reversible and
irreversible effects on the sensitometry of the photographic product. Sufficient pressure
can cause irreversible distortion of the emulsion grains or cause the formation of
physical defects that alter the sensitivity for latent image formation. It has been
generally recognized that effect of pressure on the sensitivity of photographic products
increases with the magnitude of the applied pressure.
[0003] Various types of pressure effects on silver halide photographic systems have been
known for long periods of time. In general, pressure sensitivity can be described
as an effect which causes the photographic sensitometry of film products to change
after the application of some kind of a mechanical stress to a coated photographic
film.
[0004] In photographic systems, pressure sensitivity, as described, in this general term
produces considerable quality defects of products that manifest as increased or decreased
density marks on them after development. Such stress may be received from transport
mechanism in cameras or other exposing devices or possibly during processing operations.
In general, the pressure sensitivity problem increases with the physical size of the
emulsion crystals. There is, therefore, a need to produce photographic coatings that
are less sensitive to mechanical stress in order to improve the quality of many of
the current photographic products.
[0005] Dry gelatin is hard and can thus easily transmit applied stress to the silver halide
crystals in a coated photographic system. Prior arts describe the inclusion of low
glass transition temperature, Tg, soft polymer latexes into coated photographic films.
It is known to include polymers in the emulsion containing layers, and to incorporate
of such polymers into overcoat layers. Inclusion of polymers tends to reduce pressure
sensitivity of photographic film products. Present day photographic products have
higher and higher photographic speeds and consequently are larger and larger in dimension
and exhibit more severe pressure sensitivity problems. It is known to use organic
solvent dispersions in photographic layer to reduce the pressure sensitivities of
film products. However, in order to reduce the pressure sensitivity of present day
high speed and high pressure sensitivity photographic products, the solvent loads
of the films have to be so high that such films show signs of delamination in the
layers containing the solvent dispersion when pressure is applied for testing. Therefore,
it would be desirable to reduce pressure sensitivity of photographic products without
inhibiting developability or diminishing the integrity of film product.
[0006] It has also been proposed to use gelatin grafted and case hardened gelatin grafted
polymer particles and photographic film products to decrease their pressure sensitivity.
Such techniques are disclosed in U.S. Patents 5,066,572 - O'Connor et al and 5,026,632
- Bagchi et al.
[0007] U.S. Patent 4,853,322 - Makino et al discloses a silver halide emulsion wherein the
tabular grains have a diameter of at least 0.15 micrometer, an aspect ratio of not
more than 8, and a ratio of the thickness (b) of the tabular grain to the longest
spacing between two or more parallel twin planes (a) of at least 5. These grains are
imbedded to produce an improvement in sharpness and granularity.
[0008] JP-A-1 142 627 suggests that an improved sensitivity, graininess and sharpness, but
also good pressure resistance can be obtained with tabular twinned grain emulsions
having an aspect ratio of less than 8 and a T/S ratio (thickness (T) divided by twin
planes separation (S)) of more than 5.
Problem to Be Solved by the Invention
[0009] There remains a need for silver halide emulsions that are not pressure sensitive
and have good speed and granularity performance.
Summary of the Invention
[0010] An object of this invention is to overcome disadvantages of prior silver halide emulsions.
[0011] A further object is to reduce pressure sensitivity of photographic film.
[0012] Another further object is to provide a method of forming color negative film that
has reduced pressure sensitivity and good speed/grain performance.
[0013] These and other objects of the invention are generally accomplished by providing
a silver halide emulsion wherein said grains comprise tabular silver halide grains
of an aspect ratio of less than 4, and wherein greater than 50 percent of said grains
have a thickness (T) divided by twin plane separation (S) of greater than 20 and up
to 30. It is preferred that such grains have an aspect ratio of 3, comprise greater
than 80 percent of said emulsion and that said grains are greater than 0.1 micron
equivalent circular diameter. It is further preferred that such emulsion be used in
at least one of the yellow layers of a color negative film.
Advantageous Effect of the Invention
[0014] The invention has many advantages over prior practices. It allows the formation of
photographic products having lower fog but without an increase in granularity in comparison
with photographic emulsions having a greater aspect ratio and lower thickness. These
emulsions have good resistance to pressure fog but maintain a good granularity position.
Also, they exhibit a lower tendency to pressure fog than grains of greater aspect
ratio.
Brief Description of Drawings
[0015] Fig. 1 illustrates the relationship between aspect ratio and pressure fog in films
of the invention.
[0016] Fig. 2 illustrates the relationship between granularity and ratio thickness and twin
plane separation.
Detailed Description of the Invention
[0017] There has been found to be a relationship between pressure fog propensity and aspect
ratio. As illustrated in Fig.1, the slope of the pressure fog sensitivity increases
drastically after an aspect ratio of greater than 4 is reached. Therefore, it would
be desirable to utilize grains of an aspect ratio of less than 4 in photographic uses
where pressure fog may be a problem. Pressure fog particularly affects the upper layers
of emulsion in a color negative film. These typically are the blue sensitive layers
that contain yellow dye-forming couplers. However, normally if a grain of less than
4 in an aspect ratio is utilized, it will have less sensitivity to light than a grain
of greater aspect ratio. In accordance with the invention, however, it has been discovered
that silver halide grains having a size greater than 0.1 micron in equivalent circular
diameter, and wherein at least 50 percent of these tabular grains possess a thickness
(T) to twin plane separation (S) ratio greater than 20 and up to 30 that the speed
will be maintained even for less (lower aspect ratio) tabular grains.
[0018] As is illustrated in Fig. 2, there has been found to exist a relationship between
granularity position and the thickness for twin plane separation ratio (T/S) for emulsions
of the invention. As illustrated in Fig. 2, granularity decreases as the T/S ratio
increases. A preferred ratio of T/S is greater than 15 with a most preferred embodiment
being greater than 20. S is defined as the longest spacing between adjacent twin planes
in a twin crystal. It is also preferred that at least 80 percent of the total projected
area be comprised of grains of greater than 0.1 micron.
[0019] The emulsions of the invention as above stated find their preferred use in the upper
layer or layers of a color negative film. Such films are generally formed with the
upper layers being blue sensitive and, therefore, containing yellow dye-forming couplers.
The upper layers being nearer the surface of the film are most subject to pressure
sensitivity deterioration. Generally, the effect of pressure on the film is to increase
the fog level in the yellow layers.
[0020] While the preferred use is in the blue layer, the emulsions of the invention also
may be utilized in the cyan dye-forming layer or in the magenta dye-forming layer.
They also are suitable for use in color paper or in black-and-white films.
[0021] The thick tabular grain emulsions of the invention generally are produced by adjustment
of the conditions disclosed in U.S. Patent 4,853,322 - Makino et al, U.S. Patent 4,434,226
- Wilgus et al, U.S. Patent 4,414,310 - Daubendiek et al, U.S. Patent - Wey, U.S.
Patent 4,433,048 - Solberg et al, U.S. Patent 4,386,156 - Mignot, U.S. Patent 4,504,570
- Evans et al, U.S. Patent 4,400,463 - Maskasky, U.S. Patent 4,414,306 - Wey et al,
U.S. Patents 4,435,501 and 4,643,966 - Maskasky, and U.S. Patents 4,672,027 and 4,693,964
- Daubendiek et al. Also specifically contemplated are those silver bromoiodide grains
with a higher molar proportion of iodide in the core of the grain than in the periphery
of the grain, such as those described in G.B. Patent 1,027,146; Japanese 54/48521;
U.S. Patent 4,379,837; U.S. Patent 4,444,877; U.S. Patent 4,665,012; U.S. Patent 4,686,178;
U.S. Patent 4,565,778; U.S. Patent 4,728,602; U.S. Patent 4,668,614; U.S. Patent 4,636,461;
E.P 264,954. The silver halide emulsions can be either monodisperse or somewhat polydisperse
as precipitated. The grain size distribution of the emulsions can be controlled by
silver halide grain separation techniques or by blending silver halide emulsions of
differing grain sizes.
[0022] Sensitizing compounds, such as compounds of copper, thallium, lead, bismuth, cadmium,
and Group VIII noble metals can be present during precipitation of the silver halide
emulsion, as illustrated by U.S. Patents 1,195,432; 1,951,933; 2,448,060; 2,628,167;
2,950,972; 3,448,709; and 3,737,313.
[0023] The silver halide emulsions can be either monodispersed or polydispersed as precipitated.
The grain size distribution of the emulsions can be controlled by silver halide grain
separation techniques or by blending silver halide emulsions of differing grain sizes.
The emulsions can include Lippmann emulsions and ammoniacal emulsions, as illustrated
by Glafkides, Photographic Chemistry, Vol 1. Fountain Press, London, 1958, pp. 365-368
and pp. 301-304; excess halide ion ripened emulsions as described by G.F. Duffin,
Photographic Emulsion Chemistry, Focal Press Ltd., London, 1966, pp. 60-72; thiocyanate
ripened emulsions, as illustrated by U.S. Patent 3,320,069; thioether ripened emulsions,
as illustrated by U.S. Patents 3,271,157; 3,574,628; and 3,737,313 or emulsions containing
weak silver halide solvents, such as ammonium salts, as illustrated by U.S. Patent
3,784,381 and
Research Disclosure, December 1978, No. 134, June 1975, Item 13452.
[0024] The silver halide emulsions can be surface sensitized. Noble metal (e.g., gold),
middle chalcogen (e.g., sulfur, selenium, or tellurium), and reduction sensitizers,
employed individually or in combination, are specifically contemplated. A preferred
method of sensitization is sulfur and gold.
[0025] Typical chemical sensitizers are listed in
Research Disclosure, December 1978, Item 17643, Section III.
[0026] The silver halide emulsions can be spectrally sensitized with dyes from a variety
of classes, including the polymethine dye class, which included the cyanines, merocyanines,
complex cyanines and merocyanines (i.e., tri-, tetra-, and polynuclear cyanines and
merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines. Illustrative
spectral sensitizing dyes are disclosed in
Research Disclosure, Item 17643, cited above, Section IV. The preferred sensitizing compound has been
found to be the dye given in the examples below for good speed/grain performance.
[0027] The silver halide emulsions, as well as other layers of the photographic recording
materials, of this invention can contain as vehicles hydrophilic colloids, employed
alone or in combination with other polymeric materials (e.g., lattices). Suitable
hydrophilic materials include both naturally occurring substances such as proteins,
protein derivatives, cellulose derivatives - e.g., cellulose esters, gelatin - e.g.,
alkali treated gelatin (cattle, bone, or hide gelatin) or acid treated gelatin (pigskin
gelatin), gelatin derivatives - e.g., acetylated gelatin, phthalated gelatin and the
like, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen
derivatives, collodion, agar-agar, arrowroot, and albumin. The vehicles can be hardened
by conventional procedures. Further details of the vehicles and hardeners are provided
in
Research Disclosure, Item 17643, cited above, Sections IX and X.
[0028] The following examples are illustrative and not exhaustive of the embodiments of
the invention. The invention is intended to be only limited by the claims. Parts and
percentages are by weight unless otherwise indicated.
Examples 1-8
[0029] The description below is representative of the general process of forming silver
halide grains of the invention.
(a) 94.0 cc of 1.5N AgNO3 was added in two minutes to 4.5 liters of 0.1N NaBr solution containing 4 g/l gelatin
@ 35°C. The pBr starts at 1.11 and finishes at 1.25.
(b) To the above solution was added 4.5 liters of 37.8 g/l gelatin solution @ 85°C.
This was allowed to stir 16.7 minutes. The resulting solution equilibrated at 77°C
with a pBr of 1.56.
(c) 1.5N AgNO3 and 1.5N NaBr were then run 8.0 to 42.0 cc/min. over 10.5 min. at constant pBr.
(d) 250cc of 1.0N KI solution was added in two minutes.
(e) 3.0N AgNO3 and 3.0N NaBr were then run from 21 to 51 cc/min. over 10 minutes. Initially only
AgNO3 is added until original pBr is reached than pBr is held constant. Then 3.0N solution
from 51 to 103 cc/min. for 9 minutes. A solution of potassium hexachloroiridate (4.0
X 10-7 mole/mol Ag) was added during the last 2.5 minutes of the last run.
(f) To this solution 0.5 liters of 3.8N NaBr was added, then 0.15 mole AgI lippman.
The resulting pBr was 0.84.
(g) 3.0N AgNO3 was then added @ 47.0 cc/min. until a pBr of 2.35 was reached. Any remaining AgNO3 (total 10.0 moles AgX made) was added @ 47.0 cc/min. and constant VAg using 3.0N
NaBr.
(h) The emulsion was then washed via ultrafiltration and spectrally and chemically
sensitized in a conventional manner.
[0030] Example 1 modifies the above general procedure in that AgI lippman was used in step
D in place of the KI.
[0031] Example 2 differs from the representative process by decreasing the amount of AgNO
3 added in Step A to 47 cc delivered in one minute.
[0032] Example 3 differs from the representative process by adding the iodide solution from
Step D concurrently with the first 10 minutes of Step E.
[0033] Example 4 is like Example 2 except Step A equals 2 minutes.
[0034] Example 5 differs from the representative process by Step A equaling 70.5 cc over
90 seconds and Step C is extended from 8 to 72 cc/min. over 20 minutes. An equal amount
of silver was removed from the beginning of Step E, thereby keeping the total silver
added in Steps C and E constant.
[0035] Example 6 is like Example 2 except Step A equals 70.5 cc for 1.5 minutes.
[0036] Example 7 is like Example 5 except Step C is 8.0 to 57 cc/min. over 15 min. keeping
the total silver added in Steps C and E constant.
[0037] Example 8 is the representative process as described above.
[0038] Example 9 uses the known fast yellow emulsion of the Kodak Ektar 125 film.
[0039] Example 10 uses the known mid-yellow emulsion from the Gold 100 film.
[0040] Each emulsion was separately optimized with NaSCN, dye, KAuCl
4, Na
2S
2O
3 · SH
2O and 3-methyl benzothiazolium iodide. All emulsions independently arrived at approximately
the same degree of dye per surface area. Chemical sensitizers were also at about the
same amount of sensitizer per surface area for each grain. The sensitized dye used
is given below.

As the spectral sensitizing dyes and degree of chemical sensitization are the same,
any beneficial behavior is therefore characteristic of the grain. Those optimized
finishes were then tested in a variety of formats for several characteristics.
[0041] The benefits of this invention may be realized when this emulsion is used as a mid-component
in a three (or more) emulsion blue sensitive layer(s) of a color negative system.
[0042] The emulsions were specifically tested in the multilayer structure illustrated below.

[0043] It would, however, be obvious to one skilled in the art that these benefits could
be derived in virtually any structure and also not unique to a negative format or
tested.
[0044] Since these candidates are intended to be mid-components of a multilayer system,
it is impractical to measure their light sensitivity as they are practically used.
Therefore, the speeds quoted in Table I were generated in a single layer format given
below.
TABLE I
| Example ID |
mm ECD |
mm THICK |
T/S |
A.R. |
SPEED |
Speed Gamma Normal Grain |
Rough Roller |
| 1 |
0.89 |
0.48 |
24 |
1.85 |
304 |
-0.3 |
18 |
| 2 |
1.06 |
0.58 |
29 |
1.83 |
315 |
+1.0 |
19 |
| 3 control |
1.12 |
0.17 |
8 |
6.60 |
305 |
+3.5 |
28 |
| 4 |
1.11 |
0.59 |
30 |
1.88 |
318 |
+2.0 |
25 |
| 5 |
1.00 |
0.38 |
19 |
2.63 |
305 |
+2.0 |
23 |
| 6 |
0.93 |
0.55 |
28 |
1.69 |
309 |
+1.5 |
19 |
| 7 |
0.95 |
0.50 |
25 |
1.90 |
313 |
+2.0 |
19 |
| 8 |
0.84 |
0.53 |
26 |
1.58 |
294 |
0.0 |
20 |
| 9 control |
1.40 |
0.13 |
7 |
10.76 |
300 |
+6.0 |
47 |
| 10 control |
0.90 |
0.41 |
- |
2.20 |
295 |
+4.0 |
18 |
Emulsions 9 and 10 are comparative examples - one with high A.R. and one with low
A.R.
ECD = equivalent circular diameter
A.R. = aspect ratio |

[0045] The cyan coupler at 1076 m/m
2, silver bromide iodide at 1076 mg/m
2, gel at 5167 mg/m
2 and DOX SCAVENGER at 19.4 mg/m
2 and antifoggant at 49.5 mg/m
2 were coated on an acetate support in a gelatin matrix and cross-linked with 1.5%
BVSM. Said coatings were exposed with a 5500 K light source using DLV filter. These
were then developed in a C41 process. Densities were measured as a function of exposure,
speed was defined as 0.15 above D
min normalized for contrast.
[0047] The laydown of the common slow component was 161 mg/m
2 of silver bromide grains that are 0.5µ ECD, 0.17µ thick, and 1.3 molar percent iodide.
The level of the invention and control emulsion is always 323 mg/m
2 silver bromoiodide. Yellow coupler (R
1) was coated at 377 mg/m
2 yellow coupler (R
2) at 805 mg/m
2, antifoggant (1) at 8 mg/m
2, antifoggant (2) 0.15 mg/m
2. Latent image addenda at 0.03 mg/m
2 and the diar coupler at 64.6 mg/m
2. All materials are in a 538 mg/m
2 gel matrix hardened with 1.5% BVSM.
[0048] The pressure sensitivity responses were created by the use of a rough roller on the
multilayer coatings. Half of a film specimen are subjected to a pressure of 40 psi
by a roller which is not smooth. This hardened stainless steel roller has been roughened
to a specified peaks/area. The rollers peaks count is 50 peaks/sq. cm. This leads
to very high local pressures which are intended to mimic the pressures associated
with a practical scratch. The film is then exposed and processed in a normal fashion.
The delta densities quoted in the rough roller column are simply the density difference
in a non-exposed region between a subjected to the pressure roller area and a non-subjected
area. A decrease in this difference implies a decreased sensitivity to scratches.
[0049] Granularity (Speed Gamma Normal Grain) was also measured in a multilayer format.
The numbers quoted in Table I are an average of three points, normalized for contrast
taken from the region where the candidate is known to be imaging. They are quoted
relative to Example 8 and speed is normalized by assuming one stop equals 7 grain
units.
[0050] The grain sizes quoted are obtained by actually measuring and summing each grain
as photographed on scanning electron microscope. This technique was also used to obtain
grain thicknesses. The twin plane separations were individually measured concurrently
with thickness on a transmission electron microscope. In order to accomplish this,
grains were cross-sectioned at very low temperatures to obtain workable specimens.
The thicknesses obtained with the TEM was very much in agreement with those from the
SEM.
[0051] The following Examples 11 and 12 illustrate the emulsions of the invention utilized
in preferred film structures. The emulsions in the invention are used in the slow
blue layer in the 3 percent iodide emulsion.
Example 11
[0052] A three color photographic film was prepared as follows using conventional surfactants,
and antifoggants and the materials indicated. After providing a developable image
and then processing in accordance with the Kodak C-41 process (British Journal of
Photography, pp. 196-198(1988)) excellent results were obtained.
| Support |
mg/dm2 |
| Layer 1 |
|
| Antihalation layer |
1.4 Black filamentary silver |
| 1.6 Oxidized developer (D-Ox) scavanging coupler (1) |
| 0.5 Magenta filter dye (1) |
| 0.1 Cyan filter dye (2) |
| 0.5 Magenta dye forming coupler (2) |
| 0.75 UV absorbing dye (8) |
| 24 Gelatin. |
| Layer 2 |
|
| First red layer |
6.1 Slow Ag Br/I emulsion containing 1.3 mole% iodide and 55 mg of sensitizing dye
(1) and 693 mg of sensitizing dye (2) per mole of silver halide. |
| 6.6 Slow Ag Br/I Tabular grain("T-grain") emulsion containing 3 mole% iodide and 57
mg of sensitizing dye (1) and 689 mg of sensitizing dye (2) per mole of silver halide. |
| 4.5 Cyan dye forming coupler (3) |
| |
0.5 Cyan dye forming development inhibitor releasing coupler ("DIR") (4). |
| 0.5 Cyan dye forming couplers (5) |
| 0.05 Cyan filter dye (4) |
| 26.9 Gelatin |
| Layer 3 |
|
| Second Red Layer |
8.6 Fast Ag Br/I T-Grain emulsion containing 3 mole% iodide and 55 mg of sensitizing
dye (1) and 691 mg of sensitizing dye (2) per mole of silver halide. |
| 1.2 Cyan dye forming coupler (3) |
| 0.4 Cyan dye forming coupler (6) |
| 0.3 Cyan dye forming DIR coupler (4) |
| 17.2 Gelatin |
| Layer 4 |
|
| Color Corr. Layer |
2.7 Fast Ag Br/I T-grain emulsion containing 3 mole% iodide and 510 mg of sensitizing
dye (3) and 145 mg of sensitizing dye (4) per mole of silver halide. |
| 0.3 Magenta dye forming DIR coupler (7) |
| 0.14 Orange filter dye (5) |
| 7.5 Gelatin |
| Layer 5 |
|
| Interlayer |
6.5 Gelatin |
| Layer 6 |
|
| First Green Layer |
5.6 Slow Ag Br/I emulsion containing 1.3 mole% iodide and 510 mg of sensitizing dye
(3) and 145 mg of sensitizing dye (4) per mole of silver halide |
| 5.6 Slow Ag Br/I T-grain emulsion containing 1.5 mole% iodide and 510 mg of sensitizing
dye (3) and 145 mg of sensitizing dye (4) per mole of silver halide |
| 4.4 Fast Ag Br/I T-grain emulsion containing 3 mole% iodide and 575 mg of sensitizing
dye (3) and 160 mg of sensitizing dye (4) per mole of silver halide |
| 2.3 Magenta dye forming coupler (8) |
| 1.8 Magenta dye forming coupler (9) |
| 0.2 Magenta dye forming DIR coupler (7) |
| 0.03 Cyan dye forming coupler (5) |
| 0.1 Magenta filter dye (6) |
| 21.2 Gelatin |
| Layer 7 |
|
| Second Green Layer |
7.5 Fast Ag Br/I T-grain emulsion containing 3 mole% iodide and 575 mg of sensitizing
dye (3) and 160 mg of sensitizing dye (4) per mole of silver halide |
| 0.8 Magenta dye forming coupler (8) |
| 0.3 Magenta dye forming (DIR)coupler (7) |
| 0.03 Cyan dye forming coupler (5) |
| 14.0 Gelatin |
| Layer 8 |
|
| Yellow Coll. Silver Filter Layer |
0.5 D-Ox scavanging coupler (1) |
| 8.6 Gelatin |
| Layer 9 |
|
| First Blue Layer |
1.2 Slow Ag Br/I emulsion containing 1.3 mole% iodide and 808 mg of sensitizing dye
(5) per mole of silver halide |
| 5.1 Slow Ag Br/I emulsion containing 3 mole% iodide of 383 mg of sensitizing dye (5)
per mole of silver halide. |
| 3.8 Yellow dye forming coupler (10) |
| 9.1 Yellow dye forming coupler (11) |
| 0.6 Yellow dye forming DIR coupler (12) |
| 21.5 Gelatin |
| Layer 10 |
|
| Second Blue Layer |
6.5 Fast Ag Br/I emulsion containing 7.5 mole% of iodide and 383 mg of sensitizing
dye (5) per mole of silver halide. |
| 1.4 Yellow dye forming coupler (11) |
| 0.8 Yellow dye forming (DIR) coupler (12) |
| 0.05 Cyan dye forming coupler (5) |
| 0.8 Yellow filter dye (7) |
| 9.7 Gelatin |
| Layer 11 |
|
| |
2.1 Lippman Ag Br emulsion |
| 1.1 UV absorbing dye (3) |
| 1.1 UV absorbing dye (8) |
| 7.0 Gelatin |
| Layer 12 |
|
| Protective Gel Overcoat |
8.8 Gelatin |
Example 12
Dyes
Sensitizing Dyes