Field of the Invention
[0001] The present invention relates to a silver halide photographic light-sensitive material,
particularly to a silver halide photographic light-sensitive material capable of being
super-rapidly processed and, more particularly, to a super-rapidly processable silver
halide photographic light-sensitive material which causes little or no trouble in
coating, which is highly sensitive, and which is excellent in the graininess as well
as in the pressure resistance.
Background of the Invention
[0002] In recent years, the consumption of silver halide photographic light-sensitive materials
has been and is increasing steadily. Accordingly, the processing number of silver
halide photographic light-sensitive materials increases, leading to the demand for
even more rapid processing, i.e., for the increase in the processing number of light-sensitive
materials per unit time.
[0003] The above-mentioned tendency is seen also in the field of light-sensitive materials
for X-ray use, for example, medical radiographic films. That is, the significant increase
in the number of diagnoses due to the strict observation of periodical medical checks.,
etc., and the increase in the medical inspection items for the purpose of making the
diagnosis even more correct leads to the increase in the number of radiographing films.
[0004] On the other hand, there is also the necessity to inform medical examinees of diagnostic
results as soon as possible; that is, there are strong demands for more rapid processing
than ever before to immediately provide the processed results for the diagnosis. Particularly
the angiography, the radiographing carried out in the midst of a surgical operation,
and the like, essentially need the viewing of the finished radiographic image in no
time.
[0005] In order to meet the above wishes of the medical field, it is necessary to further
speed up the processing of X-ray films as well as to promote the automation of the
diagnostic procedure (including radiographing and transportation).
[0006] However, if a rapid processing of a film takes place, it tends to bring about the
problems that the film (a) shows an inadequate image density (the sensitivity, contrast
and maximum density are deteriorated), (b) is not completely fixed, (c) is not sufficiently
washed, and, (d) is not completely dried. And the incomplete fixation and washing
of a film cause the film to be discolored during the storage thereof, thus deteriorating
the image quality.
[0007] One way to solve these problems is to reduce the amount of gelatin. However, the
reduction of the amount of gelatin gives rise to various other problems: For example,
(1) such troubles as coating marks, coating streaks, etc., tend to appear in the coating
of a silver halide photographic light-sensitive material, (2) where the film is rubbed
with each other or with other materials, the rubbed part, after being developed, tends
to have a higher density than that of the other parts; the so-called scratch darkening,
(3) when the film, after being bent, is imagewise exposed and then developed, the
bent part tends to have a lower density than that of the other parts; the so-called
pressure desensitization, and (4) since a developer solution can permeate and diffuse
fast into the layer, the development becomes active, causing the developed silver
to become coarse, so that the graininess looks roughened.
[0008] It has been so difficult to solve these problems to date that it was unable to reduce
the amount of gelatin in conventional films.
[0009] The advent of a super-rapid processing system is desired as has been described above.
The super-rapid processing
* herein means a processing by an automatic processor of which the total time required
for the overall processing from the point of time when the leading end of a film is
inserted into the processor and transported through the developer bath, first cross-over
rack, fixer bath, second cross-over rack, wash water bath, third cross-over rack,
and drying rack up to the time when the trailing end of the film gets out of the drying
section [in other words, the quotient (sec.) obtained after dividing the whole length
of the processing line (m) by the line transport speed (m/sec.)] is from 20 seconds
to 60 seconds.
[0010] The reason why the cross-over time is to be included in the processing time, although
well-known to those in the art, is because it is considered that, even in the cross-over
passage, the preceding process liquid is present in the gelatin layer to have the
processing action substantially go on.
[0011] Japanese Patent Examined Publication No. 47045/1976 describes the importance of an
amount of gelatin used in rapid processing, wherein the total processing time including
the cross-over time is described to be from 60 to 120 seconds. This processing time,
however, is unable to satisfy the recent demand for super-rapid processing.
[0012] Also, particularly as the medical X-ray checks increase in recent years, the international
opinion as well as the medical world demands strongly the reduction of exposure dose.
In order to meet this demand, fluorescent intensifying screens, intensifying screens,
devices or means such as fluorescent screens, X-ray image intensifiers, etc., are
used. The improvement of these devices or means and the increase in the sensitivity
of photographic light-sensitive materials for X-ray use in recent years are remarkable.
On the other hand, high-precision radiographic technology is demanded for more precise
medical checks. Since the larger the amount of X-ray irradiation the higher the precision,
a radiographing technique for irradiating a large dose has been developed and a large-capacity
X-ray generator has also been developed therefor. However, such the radiographing
technique requiring a large dose is unacceptable because it runs rather counter to
the foregoing demand for the reduction of exposure dose. Accordingly, the radiographic
field requires a high-precision photographing technique which uses a small exposure
dose, and therefore longs for the development of a photographic light-sensitive material
capable of giving precise images with a small X-ray dose; i.e., a still higher-speed
photographic light-sensitive material.
[0013] There are a large variety of techniques to increase the speed of a photographic light-sensitive
material with its silver halide grain size remaining intact; that is, sensitizing
methods. If a proper sensitizing technique is used, a light-sensitive material may
be expected to have its speed increased with its grain size remaining as it is; i.e.,
with its covering power kept on. Many are reported as the technique, including, e.g.,
methods of adding to an emulsion a development accelerator such as a thioether, methods
for the supersensitization of a spectrally sensitized silver halide emulsion by use
of an appropriate combination of sensitizing dyes, techniques of improving optical
sensitizers, and the like.
[0014] These methods, however, are not always widely usable in high-speed silver halide
photographic light-sensitive materials. That is, the silver halide emulsion for high-speed
silver halide photographic light-sensitive materials is chemically sensitized to an
utmost possible extent, so that, if any of the above methods is applied, a light-sensitive
material tends to be fogged during the storage thereof. In addition, in the medical
radiographic field, those conventionally used regular type which were sensitive to
wavelengths around 450nm are out-of-date, and are now replaced by orthochromatic-type
light-sensitive materials' sensitive to wavelengths of from 540 to 550nm. Those thus
sensitized are sensitive to a wider wavelength region and also have a higher speed
than conventional ones so as to allow the reduction of an exposure dose, thus making
smaller the influence upon the human body. Thus, the dye sensitization is a very useful
sensitizing means, but has lots of problems yet to be solved; for example, there still
remain problems that no adequate sensitivity can be obtained depending on the type
of the photographic emulsion used, and so forth.
[0015] Also, there are cases where various mechanical pressure applied prior to exposure
causes a pressure sensitization trouble (desensitization marks found on a light-sensitive
material at the time of its development, caused by mechanical pressure applied before
exposure). For example, a medical X-ray film sheet, since its size is large, sometimes
bends from its supported portion due to its own weight to cause a pressure desensitization
trouble which tends to appear in the form of so-called knick marks.
[0016] Also, nowadays medical X-ray photographic systems such as automatic exposure and
processing apparatus provided with mechanical transport systems are widely used. In
these apparatus, mechanical force is applied to the film in transit, and tends to
cause both the foregoing pressure-darkening and pressure desensitization troubles
especially in the winter season or in a dry place. Such phenomena will probably constitute
a serious hindrance to diagnoses. Particularly it is well-known that the larger the
grain size of and the higher the speed of a silver halide photographic light-sensitive
material the more easily does the pressure desensitization trouble occur.
[0017] There are those methods using, e.g., thalium or dyes for the purpose of improving
so as not to cause the pressure desensitization as described in U.S. Patent Nos. 2,628,167,
2,759,822, 3,455,235, 2,296,204, French Patent No. 2,296,204, and Japanese Patent
Publication Open to Public Inspection (hereinafter referred to as Japanese Patent
O.P.I. Publication) Nos. 107129/1976 and 11602/1975, and the like, but some of them
are not adequate in the degree of the improvement, some produce a conspicuous dye
stain, and some others can not necessarily be considered to derive adequately the
nature of a high-speed silver halide photographic light-sensitive material utilizing
chiefly the ordinary surface high sensitivity of a large average grain size.
[0018] On the other hand, many attempts have hitherto been made to improve silver halide
photographic light-sensitive materials so as not to cause the pressure desensitization
by changing the physical property of the binder thereof. Such attempts are found in,
e.g., U.S. Patent Nos. 3,536,491, 3,775,128, 3,003,878, 2,759,821 and 3,772,032, Japanese
Patent O.P.I. Publication Nos. 3325/1978, 56227/1975, 147324/1975 and 141625/1976,
and the like. However, these techniques, although improving light-sensitive materials
in respect of the pressure desensitization, deteriorates conspicuously the physical
properties of the binder such as dryability, scratch resistance, etc., and thus cannot
improve light-sensitive materials fundamentally.
Summary of the Invention
[0019] It is an object of the present invention to provide a silver halide photographic
light-sensitive material which, when subjected to a super-rapid processing whose total
processing time is from 20 to 60 seconds, is solved in respect of the above problems
of conventional techniques and excellent in the sensitivity, contrast, maximum density,
fixability, dryability, and the like.
[0020] Another object of the present invention is to provide a silver halide photographic
light-sensitive material which causes little or no trouble in the coating thereof
even though it uses a small amount of gelatin.
[0021] Still other objects of the present invention will be apparent from what will be described
hereinafter.
[0022] The above objects of the present invention are accomplished by a silver halide photographic
light-sensitive material comprising a support having thereon at least one hydrophilic
colloid layer comprising at least one silver halide emulsion layer, wherein the hydrophilic
colloid layers are formed by one or more times of coating provided that wet thickness
of the layer coated in each coating is within the range of from 35 to 80 µm, and a
total gelatin content of the whole hydrophilic colloid layer is in an amount of from
2.20 to 3.10 g/m
2. and a method for processing in which the above-mentioned silver halide photographic
light-sensitive material is processed by an automatic processor for the time within
the range of from 20 to 60 seconds.
[0023] When an amount of gelatin used is exceeds 3.10 g/m
2, the applicability to super-rapid processes will be insufficient, because the developing
time and drying time are prolonged; and when a gelatin amount is not more than 2.20
g/m
2, a uniform coated layer is liable to hardly be formed and the graininess of images
will also be deteriorated.
[0024] When a gelatin amount exceeds 3.10 g/m
2, a wet layer thickness will cause a few coating trouble, and when it is not more
than 3.1 g/m
2, such a wet layer thickness will seriously affect a layer coating.
Detailed Description of the Invention
[0025] The wet layer thickness herein, where one or two or more coating liquids are coated
superposedly simultaneously on a support, implies the total of the thicknesses (µm)
of the wet layers immediately after the coating of the liquids (in other words, immediately
before the beginning of drying). (If one single layer alone is coated, it is the thickness
of the layer in the wet condition immediately after the coating of this layer.) The
wet layer thickness can be found by the following formula:
Wet layer thickness (µm) = [A total of supply amounts of coating liquids (liter/min.)
x 10001 / [coating speed (m/min.) x coating width (m)]
[0026] Also, the wet layer thickness herein, where coatings are made serially, i.e., where
after one layer is coated and dried another layer is superposed thereon, also implies
the thickness of each coated liquid.
[0027] In this invention, the wet layer thickness is in the range of from 35 to 75µm, and
most preferably from 45 to 70pm. If the wet layer is too thick, the load at the time
of drying becomes so large as to increase the amount of heat for drying and to lower
the coating speed, thus leading to the increase in the production cost, the deterioration
of the productivity, and the like. If the wet layer thickness is too thin to the contrary,
it is difficult to carry out a uniform coating with no trouble.
[0028] In the silver halide photographic light-sensitive material of this invention, the
gelatin content of the hydrophilic colloid layer (including the silver halide emulsion
layer) on the light-sensitive silver halide emulsion layer side on the support thereof
is in the range of from 2.20 to 3.10g/
m2.
[0029] If the amount of gelatin is smaller than the lower limit of the range, it increases
coating troubles, while the amount of gelatin exceeds the upper limit, it deteriorates
the dryability of the light-sensitive material. The amount of gelatin is more preferably
from 2.40 to 2.90g/m
2, and most preferably from 2.50 to 2.80g/m
2.
[0030] Another preferred embodiment of this invention is such that, where the hydrophilic
colloid layer on the silver halide emulsion side consists of two or more layers, the
layers are coated under the condition that the surface tension of the liquid constituting
the topmost layer thereof is 6 dyne/cm smaller than that of the coating liquid forming
the hydrophilic colloid layer adjacent to the said topmost layer. The difference in
the surface tension between the two layers is more preferably not less than 8 dyne/cm,
and most preferably not less than 10 dyne/cm.
[0031] In order to obtain such the difference in the surface tension, at least one surface
active agent should be used. The surface active agent may or may not be used in the
adjacent layer to the topmost layer. If the agent should be used, it may be either
the same as or different from that used in the topmost layer.
[0032] Materials usable as the surface active agent include nonionic surface active agents
such as, e.g., saponins (steroid type), alkylene-oxide derivatives such as, e.g.,
polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene
glycol-alkyl ethers or polyethylene glycol-alkylaryl ethers, polyethylene glycol esters,
polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene
oxide adducts of silicone; glycidol derivatives such as an alkenyl-succinic acid polyglycerides,
alkyl-phenol polyglycerides; fatty acid esters of polyhydric alcohols, alkyl esters
of sugar, and the like; anionic surface active agents containing an acid group such
as a carboxyl, sulfo, phospho, sulfate or phosphate group, such as, e.g., alkyl-carboxylates,
alkyl-sulfonates, alkylbenzenesulfonates, alkylnaphthalene-sulfonates, alkyl-sulfates,
alkyl-phosphates, N-acyl-N-alkyl-taurines, sulfosuccinates, sulfoalkyl-polyoxyethylenealkylphenyl
ethers, polyoxyethylenealkyl phosphates, and the like; amphoteric surface active agents
such as amino acids, aminoalkylsulfonic acids, aminoalkyl-sulfates or phosphates,
alkyl-betaines, amine oxides, and the like; cationic surface active agents such as
alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary
ammonium salts such as pyridinium, imidazolium, etc., aliphatic or heterocyclic ring-containing
sulfoniums or sulfonium salts, and the like; fluorine-containing surface active agents,
polyoxyethylene- having fluorine-containing suface active agents, and the like.
[0033] The above-described alkylene-oxide-type surface active agents include those as described
in Japanese Patent Examined Publication No. 9610/1976, West German Patent No. 2,648,746,
Japanese Patent O.P.I. Publication Nos. 129623/1978, 896524/1979, 98235/19790, 203435/1983,
208743/1983, 80848/1985 and 94126/1985, and the like. Examples of the combined use
of the alkylene-oxide-type surface active agents and other compounds are found in
Japanese Patent O.P.I. Publication Nos. 89626/1979, 70837/1980, 11341/1982, 109947/1982,
74554/1984, 76741/1985, 76742/1985, 76743/1985, 80839/1985, 80846/1985, 80847/1985,
131293/1975 and 29715/1978, and the like. Examples of the anionic surface active agents
include those described in Japanese Patent O.P.I. Publication No. 21922/1978, British
Patent No. 1,503,218, and Japanese Patent Examined Publication No. 1617/1981, and
higher alcohols' sulfates, higher alkylsulfonates, alkylbenzenesulfonates, dialkylsulfosuccinates,
acylmethyltaurides, N-acylsarco- sinates, fatty acid monoglyceride sulfates, α-sulfonic
acids, and the like..
[0034] Examples of the above fluorine-containing surface active agent include those compounds
disclosed in, e.g., Japanese Patent Examined Publication Nos. 9393/1972, 43130/1973,
25087/1977 and 1230/1982, Japanese Patent O.P.I. Publication Nos. 46733/1974, 16525/1975,
34233/1975, 32322/1976, 14224/1979, 111330/1979, 557762/1980, 19042/1981, 41093/1981,
34856/1981, 11341/1982, 29691/1982, 64228/1982, 146248/1982, 114944/1981, 114945/1981,
196544/1983, 200235/1983, 109548/19
85 and 136534/1982, U.S. Patent Nos. 3,589,906, 3,775,126 and 4,292,402, and Research
Disclosure 16630, and the like, and those compounds exemplified in Japanese Patent
O.P.I. Publication No. 164738/1985.
[0037] Commercially available fluorine-containing surface active agents include those available
in the trade name of Unidyne from Daikin Industry Co., Ltd., those in the trade name
of Fluorad from 3M (Sumitomo 3M).
[0038] As described above, the preferable embodiments in which the hydrophilic colloidal,
layers of the invention each comprise two or more layers include, for example, an
embodiment in which the topmost layer comprises a hydrophilic colloidal layer and
the layer adjacent to the topmost layer comprises a silver halide emulsion layer.
[0039] In this case, the wet-coated layer thickness ratio of the above-mentioned emulsion
layer to a hydrophilic colloidal layer at the time of coating is, preferably, from
6 : 4 to 9 : 1 and, more preferably, from 7 : 3 to 9 : 1. If the wet-coated layer
thickness ratio of the emulsion layer is less than 6 and the wet-coated layer thickness
ratio of the hydrophilic colloidal layer is increased accordingly, it is liable to
cause such a trouble as streaks, blotches and so forth at the time of coating. If
the wet-coated layer
rthickness ratio of the emulsion layer exceeds 9, it is liable to cause scratches and
blackening.
[0040] Subsequently, the silver halide grains to be used in the light-sensitive silver halide
emulsion layer of the light-sensitive material of this invention will be described
below:
One preferred embodiment of this invention is such that the average grain size of
the silver halide grains used in the silver halide emulsion layer is from 0.30 to
1.20wm, more preferably from 0.40 to 1.00µm, and most preferably from 0.40 to 0.80µm.
[0041] In this specification, the silver halide grain size implies the length of an edge
of a cube equivalent in the volume to the grain, and the average grain size is the
arithmetical average of the grain sizes.
[0042] The grain size distribution of the grains used may be either wider or narrower.
[0043] The grain size distribution of the silver halide grains in the emulsion layer is
discretional, but the grains may also be monodisperse. The term "monodisperse" used
herein means a disperse system that 95% of grains are within the size range of the
average grain size ± 60%, and preferably within the range of + 40%, wherein the average
grain size is the average of the diameters of the projected areas of silver halide
grains.
[0044] The silver halide grains in the emulsion layer may be each in the form of a regular
crystal such as a cubic, octahedral, tetradecahedral or dodecahedral crystal, or in
the form of an irregular crystal such as a spherical or tabular crystal, or in the
complex form of these crystals. Also, the silver halide grains may also be a mixture
of various crystal-line forms-having grains. The grain may also be a composite-type
silver halide crystal formed by combining an oxidized product crystal such as of PbO
with a silver halide crystal such as of silver chloride, epitaxially grown silver
halide crystal (such as one formed by epitaxially growing silver iodobromide, silver
iodide, etc. on silver bromide), or a crystal wherein a regular hexahedral silver
chloride crystal is orientedly superposed on a hexagonal-system or regular octahedral
silver iodide crystal.
[0045] Also, the emulsion layer may be of an emulsion containing super-tabular silver halide
grains each of which has a diameter that is not less than five times the thickness
thereof and the total projected area of the super-tabular grains accounts for not
less than 50% of the grand total projected area of the whole grains contained in the
emulsion. This matter is described in detail in Japanese Patent O.P.I. Publication
Nos. 127921/1983 and 113927/1983.
[0046] The silver halide grains contained in the light-sensitive silver halide emulsion
in this invention is desirable to comprise regular-structure or regular-form grains
accounting for at least 80% by weight or by number.
[0047] The regular-structure or regular-form grain herein implies a grain containing no
anisotropic growth such as the twinning plane but growing isotropically; e.g., in
the cubic, tetradecahedral, regular octahedral, dodecahedral or spherical form. Methods
for the preparation of such regular silver halide grains are described in, e.g., the
Journal of Photographic Science (J. Phot. Sci.), 5, 332 (1961); Ber. Bunsenges. Phys.
Chem., 67, 949 (1963), and International Congress of Photographic Science of Tokyo
(1967), and the like. Such regular silver halide grains may be obtained by controlling
the reaction condition under which silver halide grains are grown by use of the simultaneous
mixing process. In the simultaneous mixing process, the silver halide grains are prepared
by pouring equivalent amounts of both a silver nitrate solution and a halide solution
into an aqueous protective colloid solution with vigorously stirring.
[0048] In the practice of this invention, where, for example, the above regular silver halide
grains should be incorporated, irregular silver halide grains may also be incorporated.
However, where such irregular grains should be present, they should be not more than
about 50% by weight or by number. In the preferred embodiment, regular silver halide
grains account for at least 60 to 70% by weight.
[0049] In preparing an emulsion having monodisperse and/or regular silver halide grains,
it is desirable that the supply of silver and halide ions be made so as to have the
growth rate of the grains increase gradually continuously or by stages in the critical
growth rate or in the allowable range to supply silver halide necessary and sufficient
for the growth of the existing grains alone without dissolving the existing crystalline
grains as they grow and without allowing the production and growth of new grains.
Examples of the gradual growth of silver halide grains are described in Japanese Patent
Examined Publication Nos. 36890/1973, 16364/1977, and Japanese Patent O.P.I. Publication
No. 142329/1980.
[0050] In other words, it is effective to supply the silver and halide ions so that the
growth rate of silver halide grains is 30 to 100% of the critical growth rate.
[0051] The critical growth rate varies according to temperature, pH, pAg, the degree of
stirring, the composition of silver halide grains, solubility, grain sizes, inter-grain
intervals, crystal habits, or the type and concentration of protective colloid, and
it is easily experimentally found by the microscopic observation or the measurement
of the turbidity of a liquid phase suspending emulsion grains.
[0052] In practicing this invention, the silver halide grains to be used in the light-sensitive
silver halide emulsion layer may be prepared by the application of those neutral process,
acidic process, ammoniacal process, orderly mixing process, inversely mixing process,
double-jet process, controlled double-jet process, conversion process, core/shell
process or the like, as described in, e.g., T. H. James, 'the Theory of the Photographic
Process," 4th ed., (Macmillan, 1977); P. Glfkides, "Chimie et Physique Photographique,"
(Paul Montel, 1967); G. F. Duffin, 'Photographic Emulsion Chemistry," (The Focal Press,
1966); V.L. Zelikman et al, "Making and Coating Photographic Emulsion. (The Focal
Press, 1964), and the like.
[0053] As a different type of the double-jet process, the tripple-jet process may also be
used in which soluble halides different in the composition (e.g., a soluble silver
salt, soluble bromide, and soluble iodide) are separately added.
[0054] A method for growing grains in the presence of an excessive amount of silver ions
(the so-called inversely mixing process) may also be used.
[0055] As one type of the simultaneously mixing process, a method for keeping constant the
pAg of the liquid phase where silver halide is formed; i.e., the so-called controlled
double-jet process, may also be used.
[0056] According to this process, a silver halide emulsion having regular-crystalline-form
grains of nearly uniform sizes can be obtained.
[0057] In the formation of silver halide grains, in order to control the growth of the grains,
a silver halide solvent may be used, examples of which include ammonia, potassium
thiocyanide, ammonium thiocyanide, thioether compounds (such as those described in
U.S. Patent Nos. 3,271,157, 3,574,628,
3,704,130, 4,297,439, 4,276,374), thione compounds (such as those described in Japanese
Patent O.P.I. Publication Nos. 144319/1978, 82408/1978, 77737/1980), amine compounds
(such as those described in Japanese Patent O.P.I. Publication No. 100717/1979), and
the like. Among these, ammonia is preferred.
[0058] Separately formed two or more different silver halide emulsions may be used in a
mixture.
[0059] It is desirable that these silver halide grains or emulsion contain at least one
salt from the group consisting of those salts (soluble salts) of iridium, thalium,
palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten and
platinum. The salt content of the emulsion is preferably from 10
6 to 10
1 moles per mole of pAg, and particularly preferably at least one salt out of the thalium,
palladium and iridium salts should be contained in the emulsion. These salts may be
used alone or in a mixture, and their adding position (time) is discretional. By doing
this, improvement on the flash exposure characteristic, prevention of the pressure
desensitization, prevention of the fading of latent images, sensitization, and other
effects can be expected.
[0060] In practicing this invention, that the pAg in the mother liquid containing a protective
colloid is at least 10.5 in the midst of the growth of silver halide grains prior
to chemical sensitization can be adopted as a preferred embodiment. Particularly preferably
the silver halide grains should pass through even once an atmosphere having a pAg
of not less than 11.5. By rounding each of the grains with the (111) face thereof
increased in thus manner, the effect of this invention can be raised farther. Such
the (111) face of the grain is desirable to account for not less than 5% of the entire
area thereof.
[0061] In this instance, the increasing rate of the (111) face (the rate of the increased
face to the same face before passing through the pAg atmoshere of not less than 10.5)
is preferably not less than 10%, and more preferably from 10 to 20%.
[0062] Description of the judgement as to which of the (111) face and the (100) face covers
the external surface of the silver halide grain or of the method of measuring the
proportion of the faces can be found in the report by Akira Hirata in the 'Bulletin
of the Society of Scientific Photography of Japan' No. 13, pp. 5-15 (1963).
[0063] Whether the (111) face has increased by 5% or above or not can be easily ascertained
by the Hirata's measurement after passing the grain once through the atmosphere of
the protective colloid-containing mother liquid having a pAg of at least 10.5.
[0064] In this instance, the point of time when the above pAg is to be settled is desirable
to be after completion of the addition of 2/3 of the whole amount of silver to be
added and before the desalting process usually taking place prior to chemical sensitization.
It is because this manner facilitates the obtaining of a monodisperse emulsion having
a narrow grain size distribution.
[0065] In addition, the ripening in the atmosphere of a pAg of not less than 10.5 is desirable
to take place for more than two minutes.
[0066] Under such the pAg control, the (111) face increases by not less than 5% to thereby
make the grain form round, whereby the grain whose (111) face accounts for not less
than 5% of the entire surface area thereof can be obtained.
[0067] Still another preferred embodiment of this invention is a light-sensitive silver
halide emulsion layer comprised substantially of silver iodide and comprising silver
halide grains of a multistrata structure, the said grains each being comprised of
strata of which arbitrary two adjacent strata having their own uniform iodide distributions,
wherein the difference in the iodide content between the two strata (between the coats
or between the internal core and the coat) is not less than 10 mole% and the average
silver iodide content of the outmost stratum is not more than 10 mole%, the said silver
halide grains being chemically sensitized.
[0068] The multistrata structure-having grain herein is one comprising an internal core
having thereon arbitrary silver halide compositions-having coat which may be either
a single stratum or two more more strata such as, for example, those superposed in
the form of three, four...strata, and preferably not more than five strata.
[0069] Silver halide for use in the formation of the internal core and coat may be silver
bromide, silver iodobromide or silver iodide, but may be a mixture of a small amount
of silver chloride therewith.
[0070] To be concrete, the amount of silver chloride is not more than about 10 mole%, and
more preferably not more than about 5 mole%.
[0071] And the outmost stratum is substantially silver bromide or silver iodobromide (iodide
content is not more than 10 mole%), and may also contain less than several mole% chlorine
atoms.
[0072] In the light-sensitive material of this invention, the average silver iodide content
of the whole silver halide grains is preferably not more than 10 mole%, and more preferably
not more than 6 mole%.
[0073] For example, in the light-sensitive material for use in radiography or the like,
since silver iodide may aggravate the problem of development restraining or of infectious
development, in practice the silver iodide content is desirable to be held down to
a given limit.
[0074] The silver iodide content should be not more than 10 mole% of the whole grains, preferably
not more than 7 mole%, and most preferably not more than 3 mole%.
[0075] Where the internal core is comprised of silver iodobromide, it is desirable to be
a homogeneous solid solution phase, wherein the "homogeneous" will be described in
detail below:
That is, it implies that, where powdery silver halide grains are subjected to an X-ray
diffraction analysis, the half-value width of the peak of the face index of [200]
of silver iodobromide obtained by using Cu-Ks X rays is not more than A2 = 0.30(deg).
In addition, the using condition of the diffractometer used herein, where the scanning
speed of the goniometer is regarded as ω (deg/min.), time constant as y(sec.), and
receiving slit width as γ(mm), is expressed as ωγ being equal to or less than 10.
[0076] In the silver halide composition of the internal core, the average iodine content
thereof is preferably not more than 40 mole%, and more preferably from zero up to
20 mole%.
[0077] The difference in the silver iodide content between adjacent two strata (between
arbitrary two strata of the coat or between the coat and the internal core) is preferably
not less than 10 mole%, more preferably not less than 20 mole%, and most preferably
not less than 25 mole%.
[0078] The silver iodide content of the coat other than the outmost coat is preferably from
10 mole% to 100 mole%.
[0079] Where the silver halide grain is comprised of not less than three strata of which
the coat strata are of silver iodobromide, they need not always be all homogeneous,
but it is more desirable that all the strata be homogeneous silver iodobromide.
[0080] Such the high silver iodide content-having coat (or internal core), in the case of
a negative-type silver halide emulsion layer, is desirable to be present below the
outmost surface coat, while on the other hand, in the case of a positive-type silver
halide emulsion, it may be present either in the internal or in the external.
[0081] The silver iodide content of the outmost coat is preferably not more than 10 mole%,
and more preferably from zero up to 5 mole%.
[0082] The silver iodide content of the internal core and the coat of the silver halide
grains used in the light-sensitive silver halide emulsion layer of this invention
may be found by any of those methods as described in, e.g., J. I. Goldstein and D.
B. Williams,
*X-Ray Analysis in TEM/ATEM, Scanning Electron Microscopy (1977), Vol. 1, (IIT Research
Institute), p. 651 (March 1977).
[0083] Where the silver halide grain of the silver halide emulsion layer of this invention
is comprised of, e.g., two strata, it is desirable that the internal core be of a
higher iodide content than the outmost stratum, while in the case of three strata,
it is desirable that the stratum underneath the outmost coat or the internal core
be of a higher iodide content than the outmost coat.
[0084] In order to remove the soluble salts from the emulsion after the formation of the
precipitate or after the physical ripening, the noodle washing method which is carried
out by gelling gelatin may be used or the flocculation method utilizing inorganic
salts, anionic surfactants, anionic polymers (such as polystyrenesulfonic acid) or
gelatin derivatives (such as acylated gelatin, carbamoylated gelatin) may also be
used. The process of removing the soluble salts is allowed to be omitted.
[0085] The present invention are applicable suitably to chemically sensitized silver halide
grains; for, if the grains are unsensitized ones, the sensitivity thereof in itself
is so low that both scratch trouble and pressure desensitization must hardly occur.
[0086] The silver halide grains of the light-sensitive silver halide emulsion layer of this
invention may be of either the positive type or negative type.
[0087] Where it is of the negative type, the chemical sensitization thereof is desirable
to be made so that the sensitivit, when taken at the point of [fog + 0.1] in optical
density, is not less than 60% of the optimum sensitivity.
[0088] Where it is of the positive type, the chemical sensitization thereof is desirable
to be made to the inside of the grain so that the sensitivity, when taken at the point
of [maximum density -0.1] in optical density, is not less than 60% of the maximum
sensitivity.
[0089] For the chemical sensitization any of those methods as described in, e.g., 'Die Grundlagen
der Photographischen Prozesse mit Silberhalogeniden,
l edited by H. Frieser, (Akademische Veragaesellschaft, 1968), pp. 675-734, may be
used.
[0090] That is, the sulfur sensitization method which uses active gelatins; sulfur-containing
compounds capable of reacting with silver, such as thiosulfates, thioureas, mercapto
compounds, rhodanines; the reduction sensitization method which uses reductive materials
such as stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid and
silane compounds; the noble-metal sensitization method which uses noble-metallic compounds
such as gold complex salts, complex salts of the metals belonging to Group VIII of
the periodic table of elements, such as Pt, Ir, Pd, etc.; and the like, may be used
alone or in combination.
[0091] Concrete examples of these methods are described in U.S. Patent Nos. 1,574,944, 3,410,689,
2,278,947, 2,728,668, and 3,656,955 for the sulfur sensitization; U.S. Patent Nos.
2,983,609, 2,419,974 and 4,054,458 for the reduction sensitization; and U.S. Patent
Nos. 2,599,083 and 2,448,060, and British Patent No. 618,061 for the noble-metal sensitization.
[0092] Still another preferred embodiment of this invention is the light-sensitive silver
halide emulsion layer of this invention containing at least one sensitizing dye selected
from the group consisting of those compounds having the following Formulas [I], [II]
and [III].
[0093] If an embodiment using any of those compounds of Formulas [I], [II] and [III] is
adopted, the light-sensitive emulsion is orthochromatically sensitized, so that the
emulsion is improved farther in respect of the pressure desensitization and scratch-darkening
troubles. Namely, regular-type emulsions, since they use highly sensitive large-size
grains for forming the toe portion of characteristic curves, have been poor in the
characteristic against the pressure desensitization and scratch-darkening troubles,
while the orthochromatic type as in this embodiment, since highly sensitized by the
dye sensitization, allows to make the grain size of the silver halide used smaller.
As a result, the light-sensitive silver halide emulsion can be improved further on
the characteristic thereof against the pressure desensitization and scratch-darkening
troubles.
[0094] Formulas [I], [II] and [III] are as follows:
Formula [I]

wherein R1, R2 and R3 each is a substituted or unsubstituted alkyl, alkenyl or aryl group, provided that
at least one of the R1 and R3 is a sulfoalkyl or carboxyalkyl group; X

is an anion; Z1 and Z2 each is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted
carbocyclic ring; and n is 1 or 2, provided that n is 1 when an intramolecular salt
is formed.
Formula [II]

wherein R4 and R5 each is a substituted or unsubstituted alkyl, alkenyl or aryl group, provided that
at least any one of the R4 and R5 is a sulfoalkyl or carboxyalkyl group; R6 is a hydrogen atom or a lower alkyl or aryl group; X

is an anion; Z1 and Z2 each is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted
carbocyclic ring; and n is 1 or 2, provided that n is 1 when an intramolecular salt
is formed.
Formula [III]

wherein R7 and R9 each is a substituted or unsubstituted lower alkyl group; R8 and R10 each is a lower alkyl, hydroxyalkyl, sulfoalkyl or carboxyalkyl group; X

is an anion; Z1 and Z2 each is a group of nonmetallic atoms necessary to complete a substituted or unsubstituted
carbocyclic ring; and n is 1 or 2, provided that n is 1 when an intramolecular salt
is formed.
[0095] In these formulas, the carbocyclic ring completed by Z
1 or Z
2 is desirable to be an aromatic ring such as a substituted or unsubstituted benzene
ring or naphthalene ring.
[0096] The alkyl group represented by the R
1, R
2 or R
3 may be a branched one, and more preferably is an alkyl group having not more than
10 carbon atoms, and may have a substituent. Examples of the substituent include sulfo,
aryl, carboxyl, amine (primary, secondary and tertiary) residues, alkoxy, aryloxy,
hydroxy, alkoxycarbonyl, acyloxy, acyl, aminocarbonyl, cyano and the like groups,
and halogen atoms. Examples of the alkyl group include methyl, ethyl, sulfoethyl,
sulfopropyl, sulfobutyl, benzyl, phenethyl, carboxyethyl, carboxymethyl, dimethylaminopropyl,
methoxyethyl, phenoxypropyl, methylsulfonylethyl, p-tert-butylphenoxyethyl, cyclohexyl,
octyl, decyl, carbamoylethyl, sulfophenethyl, sulfobenzyl, 2-hydroxy-3-sulfopropyl,
ethoxycarbonylethyl, 2,3-disulfopropoxypropyl, sulfopropoxyethoxyethyl, trifluoroethyl,
carboxybenzyl, cyanopropyl, p-carboxyphenethyl, ethoxycarbonylmethyl, pivaloylpropyl,
propionylethyl, anisyl, acetoxyethyl, benzoyloxypropyl, chloroethyl, morpholinoethyl,
acetylaminoethyl, N-ethylaminocarbonylpropyl, cyanoethyl, and the like groups.
[0097] The alkenyl group represented by the R
1, R
2, R
3 or R
4 is preferably an alkenyl group having not more than 10 carbon atoms, such as an allyl,
2-butenyl, 2-propinyl or the like group.
[0098] The aryl group represented by the R
1, R
2. R
3 or R
4 is, for example, a phenyl, carboxyphenyl, sulfophenyl or the like group.
[0099] The anion represented by the X

of Formula [I] is, for example, chlorine ion, bromine ion, iodine ion, thiocyanic
acid ion, sulfuric acid ion, perchloric acid ion, p-toluenesulfonic acid ion, ethylsulfuric
acid ion, or the like.
[0100] The following are examples representative of the compound having Formula [I]:
[0102] In Formula [II], the R
6 is a hydrogen atom, a lower alkyl group or an aryl group. The lower alkyl groups
inclide, for example, a methyl, ethyl, propyl, butyl or the like group. The aryl groups
include, for example, a phenyl group. The R
4 and R
5 represent those each denoted by the R
2 and R
3, respectively, in the foregoing Formula [I].
[0103] The anion represented by the X2 also represents those each denoted by the X

of Formula [I].
[0104] The following compounds are the typical examples of the. compounds each having Formula
[II]:
[0106] Subsequently, in Formula [III], the lower alkyl group represented by the R
7 or R
9 include, for example, a methyl, ethyl, propyl, butyl or the like group. The substituted
lower alkyl group represents ones, whose alkyl portion has from 1 to 4 carbon atoms,
out of those denoted by the R
1 through R
3 of Formula [I]. The lower alkyl group denoted by the R
8 or R
10 represents the same ones each denoted by the R
7 or R
9. The hydroxyalkyl group, sulfoalkyl group, and carboxyalkyl group denoted by the
R
8 or R
10 represent those each denoted by the R
1 through R3 of Formula [I].
[0107] The anions denoted by the X

also represent those each denoted by the X

.
[0108] The following compounds are the typical examples of the compounds each having Formula
[III]:
[0110] In the present invention, a total amount of these compounds having Formulas [I],
[II] and [III] is to be within the range of from 10 mg to 900 mg per mole of silver
halide, and particularly preferably from 60 mg to 600 mg.
[0111] Any of these compounds of Formulas [I], [II] and [III] may be added to any discretional
positions in the course of preparing the light-sensitive material, such as at a point
of time before, in the midst of, or after completion of the chemical ripening, or
before coating the emulsion.
[0112] The photographic emulsion to be used in the light-sensitive silver halide emulsion
layer of the light-sensitive material of this invention may contain various compounds
for the purpose of preventing the light-sensitive material from being fogged or of
stabilizing the photographic characteristics of the light-sensitive material during
the preparring process, the storage or the processing thereof, examples of which compounds
to be incorporated include azoles such as benzothiazolium salts, nitroimidazoles,
nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles
and, preferably, 1-phenyl-5-mercaptotetrazole and the like; mercapto- pyrimidines;
mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as
triazaindenes, tetra- zaindenes and, preferably, 4-hydroxy-substituted(1,3,3a,7)-tetrazaindenes,
pentazaindenes and the like; benzenethio- sulfonic acid, benzenesulfinic acid, benzenesulfonic
acid amide and the like; they are known as antifoggants or stabilizers.
[0113] For more details, a reference can be made to E. J. Birr, 'Stabilization of Photographic
Silver Halide Emulsions', Focal Press 1974.
[0114] Examples of the usable compounds include those thiazolium salts described in, for
example, U.S. Patent Nos. 2,131,038, 2,694,716, etc.; those azaindenes described in
U.S. Patent Nos. 2,886,437, 2,444,605, etc.; those urazoles described in U.S. Patent
No. 3,287,135; those sulfocatechols described in U.S. Patent No. 3,236,632; those
oximes described in British Patent No. 623,448; those mercaptotetrazoles described
in U.S. Patent Nos. 2,403,927, 3,266,897, 3,397,987, etc.; nitron; nitroindazoles;
those polyvalent metal salts described in U.S. Patent No. 2,839,403; those thuronium
salts described in U.S. Patent No. 3,220,839; and those salts of palladium, platinum
and gold described in U.S. Patent Nos. 2,566,263, 2,597,715, etc.; and the like.
[0115] The light-sensitive material of this invention may contain in the hydrophilic colloid
layer thereof a water-soluble dye as a filter dye, antiirradiation dye or antihalation
dye or for various other purposes. Examples of such dyes include oxonol dyes, hemioxonol
dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these dyes,
the useful ones include, for example, oxonol dyes, hemioxonol dyes and merocyanine
dyes.
[0116] In the light-sensitive material of this invention, where the hydrophilic colloid
layer thereof contains a dye or ultraviolet absorbing agent, it may be mordanted by
a cationic polymer or the like therefor.
[0117] As for such dyes, "Absorbing and Filter Dyes
* described in Research Disclosure vol. 176, pp. 23-26, may also be used.
[0118] For the purpose of increasing sensitivity and/or contrast or accelerating development,
the photographic emulsion layers of a photographic light-sensitive material of this
invention, may contain, for example, polyalkylene oxides or the derivatives thereof
such as the ethers, esters or amines thereof, thioether compounds, thiomorpholines,
quaternary ammonium salt compounds, urethane drivatives, urea derivatives, imidazole
derivatives, 3-pyrazolidones, or the like.
[0119] Gelatin may be advantageously used as the binder or protective colloid for the hydrophilic
colloid layers such as the emulsion layers, intermediate layers, protective layers
and the like of the light-sensitive materials of this invention, but different hydrophilic
colloid materials other than gelatin may also be used alone or in combination with
gelatin.
[0120] Where gelatin is used in practicing this invention, the gelatin may be either limed
or acid-treated one. Details of the manufacture of gelatin are found in Arthur Vise,
the "Macromolecular Chemistry of Gelatin' (Academic Press, 1964). Usable examples
of the foregoing hydrophilic colloids include proteins such as, e.g., gelatin derivatives,
graft polymers of gelatin with other macromolecular materials, albumin, casein, etc.;
cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose
sulfates, etc., and sugar derivatives such as sodium alginate, starch derivatives,
etc.; and various synthetic hydrophilic macromolecular materials including homo- or
co-polymers such as polyvinyl alcohols, partially acetalated polyvinyl alcohols, poly-N-vinyl-
pyrolidones, polyacrylic acids, polymethacrylic acids, polyacrylamides, polyimidazoles,
polyvinylpyrazoles, etc.; and the like.
[0121] The photographic light-sensitive materials of this invention may contain in the photographic
emulsion layer and other hydrophilic colloid layers thereof an inorganic or organic
hardening agent, examples of which include, e.g., chromium salts such as chrome alum,
chromium acetate; aldehydes such as formaldehyde, glyoxal, glutaraldehyde; N-methylol
compounds such as dimethylol urea, methyloldi- methyl-hydantoin; dioxane derivatives
such as 2,3-dihydroxydioxane; active vinyl compounds such as 1,3,5- triacryloyl-hexahydro-2-triazine,
1,3-vinylsulfonyl-2-propanol; active halogen compounds such as (2,4-dichloro-6-hydroxy-3-triazine),
mucohalogenic acids such as mucochloric acid, mucophenoxychloric acid; and the like.
These may be used independently or in combination.
[0122] The photographic light-sensitive material of this invention may contain in the photographic
emulsion layer or other hydrophilic colloid layers thereof water-insoluble or less-soluble
synthetic polymer-dispersed products for the purpose of improving dimensional stability
or the like, examples of which products include, e.g., alkyl (meth)acrylates, alkoxyalkyl
(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters such as
vinyl acetate; acryl nitrile, olefins, styrenes., and the like, which may be used
alone or in combination, and also include polymers comprised of those monomers constituting
the combination of any of these materials with acrylic acid, methacrylic acid, α,s-unsaturated
dicarboxylic acid, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrenesulfonic
acid, and the like.
[0123] In the silver halide photographic light-sensitive material of this invention, a protective
layer may be suitably provided. The protective layer is a hydrophilic colloid layer,
for which hydrophilic colloid may be used those exemplified previously. The protective
layer may be either a single layer or superposed layers.
[0124] The silver halide photographic light-sensitive material of this invention may contain
in the emulsion layer or protective layer, preferably in the protective layer, a matting
agent and/or smoothing agent. Suitably usable examples of the matting agent are those
organic compounds like water-dispersible vinyl polymers such as polymethylmethacrylate
having appropriate grain sizes (of from 0.3 to 5 µm, or of not less than twice the
thickness of the protective layer, particularly preferably not less than four times
the thickness) or inorganic compounds such as silver halide, strontium-barium sulfate,
and the like. The smoothing agent not only is useful for and has similar effects to
the matting agent in preventing sticking trouble but also is effective in improving
the friction property in connection with the adaptability of movie film to movie cameras
or projectors. Useful examples of the smoothing agent include waxes such as liquid
paraffin, higher fatty acids, etc.,
polyfluorinated hydrocarbons or derivatives thereof, polyalkyl-polysiloxanes, polyaryl-polysiloxanes,
polyalkylaryl-polysiloxanes, silicones such as alkylene-oxide-addition derivatives
of these compounds, and the like.
[0125] The photographic light-sensitive material of this invention may, if necessary, use
various other additives, such as dyes, developme.: accelerators, brightening agents,
anticolor-stain agents, ultraviolet absorbing agents, and the like. To be concrete,
those as described in Research Disclosure, vol. 176, pp. 22-31 (RD-17643, 1978) may
be used.
[0126] The silver halide photographic light-sensitive materials of this invention may further
be provided, if necessary, with the layers such as an antihalation layer, intermediate
layer, filter layer, and the like.
[0127] The photographic light-sensitive materials of this invention may be completed by
having the photographic emulsion layers and other layers thereof coated on one side
of or both sides of an erastic support material commonly used in ordinary photographic
light-sensitive materials. Useful materials for the elastic support include films
comprised of semisynthetic or synthetic high polymers such as cellulose nitrate, cellulose
acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
etc., or papers on which is coated or laminated a baryta layer or a-olefin polymer
(such as polyethylene, polypropylene, ethylene/butene copolymer), or the like. The
support may be colored with a dye or a pigment. The surface of the support is generally
subbed in order to improve the adherence thereof to the photographic emulsion layer.
The surface of the support may be subjected to corona discharge treatment, ultraviolet
ray irratiation, flame treatment or the like, before or after the subbing treatment.
To be concrete, those as disclosed in Research Disclosure vol. 176, p. 25, Item "Supports"
may be used.
[0128] In the photographic light-sensitive material of this invention, the photographic
emulsion layer or other hydrophilic colloid layers may be coated on a support or on
other layers by any of various coating methods, such as the dipping coating method,
roller coating method, curtain coating method, extrusion coating method, and the like.
To be more concrete, those methods such as described in Research Disclosure vol. 176,
pp. 27-28, Item 'Casting Procedures' may be used.
[0129] The silver halide photographic light-sensitive material may apply, to be concrete,
to light-sensitive materials for X-ray use, lithographic light-sensitive materials,
black-and-white photographic light-sensitive materials, color negative light-sensitive
materials, color reversal light-sensitive materials, color photographic papers, colloid
transfer process, silver salt diffusion transfer process, dye transfer process, silver-dye
bleaching process, print-out light-sensitive materials, thermal-development-type light-sensitive
materials, and the like.
[0130] Exposure to be made for obtaining photographic images may be made in usual manner;
by using any of various light sources including, e.g., natural light such as sunlight,
tungsten light, fluorescent lamp light, mercury vapor lamp light, xenon arc light,
carbon arc light, xenon flash light, cathode-ray-tube flying spot, light-emitting
diode, laser beams such as those of gas laser, YAG laser, dye laser, semiconductor
laser, etc. Exposure may also be made to the light emitted from a phosphor excited
by electron beams, X rays, y rays, a rays, and the like. Exposure time may be much
shorter than 1/1000 second such as 11104 to 1/10
6 second by using, e.g., a xenon flash or cathode-ray tube or much longer than one
second, not to speak of one second to 1/1000 second usually used in ordinary type
cameras. The spectral composition of the light to be used in exposure may be adjusted
by using at need a proper color filter. The photographic processing of the light-sensitive
material of this invention may be carried out by the application of any of those various
methods and various processing solutions such as described in, e.g., Research Disclosure,
vol. 176, pp. 25-30 (RD-17643). The silver halide photographic light-sensitive materials
of the invention may be photographically processed, according to purposes, in any
one of the photographic processes for reproducing silver images, i.e., a black-and-white
photographic process or a photographic process for reproducing dye images, i.e., a
color photographic process.
[0131] In particular, the photographic processes suitable for the silver halide photographic
light-sensitive materials of the invention include a black-and-white photographic
process in which the whole processing time is from 20 to 60 seconds in the case of
using an automatic processor.
[0132] In such a black-and-white process as metioned above, a developing step, a fixing
step and a washing step are carried out. There may be some instances where a washing
step may be omitted if a stabilizing step is to be applied after the completion of
a developing.step or both of a stopping step and a fixing step. It is also allowed
to carry out a developing step with an independent alkaline solution, provided that
a color developing agent or the precursors thereof are incorporated into a light-sensitive
material to be processed, and it is further allowed to carry out a developing step
in which a lith developer is used as the developer.
[0133] The black-and-white developers which may be used in a black-and-white process include,
for example, those so-called a primary black-and-white developer which may usually
be used in the well-known processes applicable to color photographic light-sensitive
materials, and those which may be used in the processes applicable to black-and-white
photographic light-sensitive materials. They are also allowed to contain a variety
of additives which may generally be added to black-and-white developers.
[0134] The typical examples of the additives include developing agents such as 1-phenyl-3-pyrazolidone,
Metol and hydroquinone; preservatives such as a sulfite; processing accelerator comprising
an alkali substance such as those of sodium hydroxide, sodium carbonate, potassium
carbonate and so forth; inorganic or organic inhibitors such as potassium bromide,
2-methylbenzimidazole, methylbenzthiazole and so forth; hard-water softeners such
as a polyphosphate; such an excessive surface-development inhibitor comprising a small
amount of an iodide or a mercapto compound; and so forth.
[0135] The above-mentioned developers are of the aqueous alkaline solutions each containing,
independently or in combination, ordinary type black-and-white photographic developing
agents including, for example, hydroquinone; an alkyl hydroquinone such as t-butyl
hydroquinone, methyl hydroquinone and dimethyl hydroquinone; a catechol; a pyrazole;
a chlorohydroquinone; Dichlorohydroquinone; an alkoxy hydroquinone such as a methoxy
or ethoxy hydroquinone; an aminophenol developing agent such as an N-methyl-p-aminophenol
and a 2,4-diaminophenol; an ascorbic acid developing agent; an N-methyl-p-aminophenol
sulfate; a pyrazolone such as 4-aminopyrazolone; a 3-pyrazolidone developing agent
such as l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-phenyl-4-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone,
1-phenyl-2-acetyl -4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone,
1-(2-benzothiazolyl)-3-pyrazolidone and 3-acetoxy-i-phenyl-3-pyrazolidone; and so
forth.
[0136] Among the above, a combination of hydroquinone and a 3-pyrazolidone or an aminophenol
is particularly useful for a rapid process at a high-temperature.
[0137] The developers which may be used preferably in the invention are also allowed to
contain a hardening agents.
[0138] As for such hardening-agents, a dialdehyde type hardening agents may preferably be
used therein. They include, for example, a β-methyl glutaraldehyde, a glutaraldehyde,
an a-methyl glutaraldehyde, a maleic glutaraldehyde, a succinic dialdehyde, a methoxysuccinic
dialdehyde, an a.a-dimethyl glutaraldehyde, a methylmaleic dialdehyde, a methylsuccinic
dialdehyde, an α-methyl-β-ethoxy glutaraldehyde, an a-n-butoxy glutaraldehyde, an
α-ethyl-β-ethoxy glutaraldehyde, a β--n-butoxy glutaraldehyde, an α,α-dimethoxysuccinic
dialdehyde, a β-isopropoxysuccinic dialdehyde, an α,α-diethylsuccinic dialdehyde,
and butylmaleic aldehyde.
[0139] The above-mentioned dialdehyde type hardening agents may ordinarily be used in an
amount of from 1 to 20 g per liter of a processing liquid used and, more preferably,
from 3 to 5 g.
[0140] If required, such developers are also allowed to contain perservatives including,
for example, alkali-metal sulfites such as sodium sulfite, a potassium sulfite, potassium
metahydrogensulfite and so forth; buffers such as a carbonate, boric acid, a borate
and an alkanolamine; an alkalizing agent such as a hydroxide and carbonate; dissolution
assistants such as a polyethylene glucol and the esters thereof; pH adjusting agents
including organic acids such as acetic acid; sensitizers such as a quaternary ammonium
salt; development accelerators; surface active agents; and so forth.
[0141] The above-mentioned developers are further allowed to contain antifogging agents
including, for example, benzotriazoles such as 5-nitroindazole, 5-nitro-benzimidazole,
5-methyl-benzotriazole and 5-nitrobenzotriazole; tetrazoles or thiazoles such as benzothiazole
or 1-phenyl-5-mercapto- tetraazole, or the compounds such as described in British
Patent No. 1,269,268; and chelating agents such as ethylenediaminetetraacetic acid,
the alkali-metal salts thereof, a polyphosphate and a nitriloacetate.
[0142] A pH value of the developer prepared as mentioned above may be so selected as to
satisfactorily render the desired density and contrast and such a pH value is so adjusted
as to be within the range of from about 8 to 12 and, particularly, from about 9.0
to 10.5.
[0143] The temperature and time applied to a development process are correlated to each
other and will be determined in relation to a total processing period of time. In
the invention, they are preferably, for example, at a temperature of from 30 to 40°C
for a time of from 10 to 20 seconds.
[0144] The fixers are the aquous solutions each containing a water-soluble aluminium compound
having a pH value of about 3.8 to 5.0 at 20°C. In the methods of the invention, a
stopping step may be inserted after the developing step. However, such a stopping
step is generally omitted from the processes using a roller-transport type automatic
processor, in which, therefore, a developer is brought into a fixer, so that the pH
value of the fixer will be raised. Accordingly, it is, desired to adjust the pH value
of a fixer between about 3.8 and 4.6 at 20°C.
[0145] The fixers are those of a thiosulfate such as ammonium thiosulfate, a sodium thiosulfate
or the like and, in particular, ammonium thiosulfate is preferable from the viewpoint
of a fixing rate. The amount of the fixers used may suitably be varied and, generally,
within the range of from about 0.1 to 5 mol per liter.
[0146] In such a fixer, the aqueous aluminium-salt solutions which mainly serve as a hardening
agent are the compounds which are popularly known as the hardening agents of an acid
fixer with hardener, including, for example, aluminium chloride, aluminium sulfate,
potassium alum and so forth. In the invention, the preferable temperature and time
in a fixing step are, for example, at a temperature of from 20 to 35°C and for a time
of from 4 to 15 seconds.
[0147] According to the methods of the invention, a photographic material having been developed
and fixed will then be washed and dried. Such a washing step is to be carried out
for almost completely removing silver salts dissolved by the prior fixing step. The
preferable washing temperature and time are at a temperature of about 20 to 50°C and
for a time of from 5 to 12 seconds.
[0148] Such a drying step may be carried out at a temperature of from about 40 to 100°C
and the drying time may suitably be varied according to the conditions of atmosphere,
however, the drying step may be allowed to carry out, normally, for a time of from
about 5 to 15 seconds. r
[0149] There is no special limitation to the types of automatic processors which may preferably
be used to embodying the invention and capable of processing within a time of from
20 to 60 seconds, but any automatic processors of a roller-transport type, a belt-transport
type and so forth and, more preferably, those of the roller-transport type may preferably
be used.
[0150] The silver halide photographic light-sensitive material of this invention has effects
as shown in the following (1) through (6):
(1) The light-sensitive material can be subjected to a super-rapid processing whose
total processing time is from 20 seconds to 60 seconds, and, where processed by the
super-rapid processing method, is excellent in the sensitivity, contrast, maximum
density, fixability and dryability, and causes no problems of changes in the quality
even by lack of washing as well as of fixation.
(2) The light-sensitive material, even when the gelatin content of the hydrophilic
colloid layer on the light-sensitive silver halide emulsion layer side is small, causes
little or no coating troubles such as coating marks, coating streaks, etc.
(3) The coating speed can be increased under the condition wherein the drying water
content is equal per unit time, so that the productivity is improved.
(4) The light-sensitive material, where the light-sensitive silver halide thereof
is sensitized by the sensitizing dye having the foregoing Formula [I]. [II] or [III],
is improved on the antiscratch-darkening effect, pressure-desensitization resistance,
graininess and antidye- staining effect in addition to the above-mentioned effects.
(5) The light-sensitive silver halide emulsion layer, when containing silver iodobromide
grains of the foregoing multistrata structure, shows effects further excellent in
the sensitivity as well as in the antiscratch-darkening effect.
(6) Where the hydrophilic colloid layer on the light-sensitive silver halide emulsion
side is comprised of two or more layers and when the surface tension of the coating
liquid thereof meets the foregoing conditions, the coating trouble mentioned in the
above (2) can be reduced further.
Examples
[0151] The present invention will be illustrated further in .detail by the following examples:
Example-1
[0152] A silver iodobromide emulsion containing 3.0 mole% silver iodide was first prepared
by the full ammoniacal normal precipitation. The obtained emulsion was of an average
grain size of 1.00 µm and was regarded herein as E-1. To Emulsion E-1 were added chloroaurate,
sodium thiosulfate, and ammonium thiocyanate to therey effect the optimum gold-sulfur
sensitization of the emulsion. The emulsion was then stabilized by using 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene,
and subsequently the gelatin consentration thereof was adjusted so as to be of the
gelatin quantities as given in Table 1.
[0153] The emulsion was coated along with a hardening agent- added protective layer prepared
as given in Table 1 simultaneously superposedly by the slide hopper coating method
on both sides of a subbed polyester film support in the order of the silver halide
emulsion layer and then protective layer from the support side, whereby Samples No.1
through No.19 were obtaind. The amount of silver was 55mg/m
Z.
[0154] The amount of the hardening agent in each of these samples was adjusted so that the
melting time is about 30 minutes when measured by the following method:
That is, the time interval of from the beginning of the immersion of a sample cut
into 1cm x 2cm size in an aqueous 1.5% sodium hydroxide solution up to the time when
the emulsion begins to dissolve out was regarded as melting time.
[0155] The coating speed, in order to equalize the drying amount of water per unit time,
was varied according to the wet thickness. The faster the coating speed the better
from the stand-point of productivity.
[0156] The thus obtained samples each was measured with respect to coating troubles thereof,
such as coating streaks, coating marks and so forth, and the number and degrees thereof
were measured to be rated into 5 grades of from 1 (inferior) to 5 (superior). Those
rated 3 to 5 have no problem, but those of 1 and 2 are ones unacceptable for practical
use.
[0157] The sensitivity measurement was made as follows: Each sample was placed between a
pair of optical wedges with their density inclinations placed face-to-face mirror-symmetrically,
and it was exposed through the wedges simultaneously for 1/12.5 second to light having
a color temperature of 5,400°K in the same amount from light sources illuminating
it from both directions.
[0158] Each sample was processed in the following steps with a roller-transport type automatic
processor and the whole processing period of time of which was 45 seconds.

[0159] The developer used was XD-90, and the fixer was XF (both are products of Konishiroku
Photo Industry Co., Ltd.).
[0160] From the obtained characteristic curve of each sample the exposure at the point of
base density + fog density + 1.0 was found, and the relative speed of each sample
was obtained on the basis thereof.
[0161] The dryability of each sample was rated as follows:
Namely, the sample that was subjected to the 45-second processing and has come out
of the drying section was collectively rated with respect to the touch and the degree
of scratches, etc., in comparison with other samples into 5 grades of from 1 (inferior)
to 5 (superior). Those of from 3 to 5 have no problem, but those of 1 and 2 are unacceptalble
for practical use.
[0162] Some of the samples were also processed in the above 45-second automatic processor
with its line speed down to half (1/2) to thereby obtain the sensitivity thereof in
the conventional 90-second processing. The results obtained in above are given in
Table 2.
[0163] As is apparent from Table 2, the samples for the present invention have satisfactory
coatability and collectively excellent in the sensitivity, productivity (i.e., a coating
speed to equalize the drying amount of water per unit time) and dryability, and thus
they are found to be highly adaptable to the super-rapid processing.
Example-2
[0165] The preparation of multistrata structure-having silver halide grains-containing emulsions
E2 to E6 will be described as follows: An ammoniacal silver nitrate solution and a
solution containing potassium bromide and 2.0 mole% potassium iodide, with the temperature,
pAg and pH thereof being kept at 45°C, 11.0 and 9.0, respectively, were added by the
double-jet method to an aqueous gelatin solution. The addition was gradually accelerated
with the growth of the grains.
[0166] The obtained emulsion was a monodisperse emulsion of octahedral silver halide grains
with an average grain size of 0.65gm. To this emulsion, serving as a core, were further
added by the double-jet method ammoniacal silver nitrate and potassium bromide solutions
under the conditions of pAg=11.0 and pH=9.0 to thereby form pure silver bromide shells.
It was an emulsion of octahedral monodisperse grains with an average grain size of
0.70µm. This emulsion was regarded as E-2.
[0167] Subsequently, emulsions of octahedral silver iodobromide grains containing 5 mole%,
10 mole%, 25 mole% and 40 mole% silver iodide, respectively, were prepared in nearly
the same manner as in E-2 except that the proportion of the potassium bromide to the
potassium iodide was varied, the core grain size was varied so as to make the average
silver iodide content after the formation of the shell uniform, and the adding speed
in the initial stage of the mixing was controlled so as to equalize the grain sizes.
The following process took place in quite the same manner as in E-2 to thereby prepare
octahedral grains-having emulsions of an average grain size of 0.70gm, which were
regarded as E-3, E-4, E-5 and E-6, respectively. E-1 and E-2 through E-6 were chemically
sensitized and coated in the same manner as in Example-1 except that the sensitizing
dye given in Table 3 was added to the emulsions before the chemical sensitization,
whereby Samples No..20 to No.41 were obtained, provided that the emulsions each was
prepared with an amount of silver of 42mg/dm
2 and with gelatin in the same amount as in Example-1 as shown in Table 3. The obtained
samples are as given in Table 3.
[0168] These samples were evaluated in the same manner as in Example-1. And the RMS granularity
was measured in the following manner: The sample containing no sensitizing dye was
sandwiched in sheets of Intensifying Screen NS for regular film use (manufactured
by Konishiroku Photo Industry Co., Ltd.) and each of those samples containing the
sensitizing dye was sandwiched in sheets of Intensifying Screen KO-250 for orthochromatic
film use (manufactured by Konishiroku Photo Industry Co., Ltd.), and each sandwiched
sample was exposed through an aluminum wedge for 0.10 second to X rays under the conditions
of a tube voltage of 90KVP and a tube current of 100mA, and then subjected to the
foregoing 45-second processing. Subsequently, the portion of a density of 1.0 of the
emulsion layer on the side facing toward the X-ray generator was peeled apart, while
the emulsion layer on the other side was measured by means of a one-touch-type RMS
Measuring Instrument (manufactured by Konishiroku Photo Industry Co., Ltd.) with its
aperture size of 50x200µm. The smaller the obtained value the more excellent.
[0169] Measurements of the pressure desensitization and scratch darkening were made by the
following methods:
As for the pressure desensitization, each sample was conditioned for 5 hours at 23°C
with 35%RH, and then, under the condition, was bent about 280° with a radius of curvature
of 2cm. Three minutes after the bending, each sample was exposed through an optical
wedge for 1/10 second to the light from a tungsten lamp as a light source, and then
developed.
[0170] And the pressure desensitization was expressed as the density difference AD between
the density of the desensitized portion in the initial density of 1.0 and the not-bent
portion having the density of 1.0. Namely, the smaller the value the smaller the pressure
desensitization.
[0171] On the other hand, as for the scratch darkening, each sample, after being conditioned
at 23°C with 55%RH for 4 hours, was scratched continuously by a 0.3-mil-radius-point-
having sapphire needle with its load being varied, and then developed. The scratch
darkening was expressed as the load (g) applied at the point where darkening began.
That is, the smaller the value (g) the weaker the scratch darkening.
[0172] As is apparent from Table 4, these samples for this invention and havining a silver
halide emulsion layer containing the silver iodobromide grains of the foregoing specific
multistrata structure and optically sensitized by the sensitizing dye having the foregoing
general formula are excellent in the coatability, high in the productivity, and also
collectively excellent in the sensitivity, dryability, granularity, pressure resistance,
and the like, and therefore they are highly suitable for the super-rapid processing.
Example-3
[0174] Emulsions of octahedral silver iodobromide grains comprising core grains prepared
in the same manner as in E-3 to E-6 and containing 5 mole %, 10 mole%, 25 mole% and
40 mole% silver iodide, respectively, were prepared. On each of the grains was formed
a shell in the same manner as in E-2 except that the shell contains 1.0 mole% silver
iodide, whereby octahedral monodisperse emulsions having an average grain size of
0.70gm were prepared. The emulsions were regarded as E-7, E-8, E-9 and E-10, respectively.
[0175] These emulsions were chemically sensitized, spectrally sensitized and then coated
in the same manner as in Example-2, whereby Samples No.42 through No.
49 were obtained.
[0176] These samples were evaluated in the same manner as in Example-2. The results are
given in
'Table 5.
[0177] As is apparent from Table 5, these samples for this invention and having a light-sensitive
silver halide emulsion layer containing silver iodobromide grains of the foregoing
specific multistrata structure are collectively excellent in the coatability, productivity,
sensitivity, granularity, pressure-desensitization resistance, antiscratch-darkening
effect, and the like, and also high in the sensitivity particularly when spectrally
sensitized by the sensitizing dye having the foregoing general formula. And in comparison
with the conventional 90-second processing, despite of the sensitivity equal to or
more than that of the conventional system (Sample No.42) the processing time can be
reduced to half, and therefore the processability is doubled.
Comparative Dye (1)

Comparative Dye (2)

Comparative Dye (3)




Example-4
[0178] Under the controlled conditions of 60°C, pAg=8.0 and pH=2.0, a 2.0 mole% silver iodide-containing
silver iodobromide cubic grains-having emulsion of an average grain size of 0.20 µm
was obtained by the double-jet method. Part of this emulsion was used as the core
to be grown as follows: That is, to the solution containing the core grains and gelatin
were added by the double-jet method an ammoniacal silver nitrate solution and a solution
containing potassium iodide and potassium bromide under the conditions of 40°C, pAg=8.0
and pH=9.5, whereby a first coat containing 5 mole%, 10 mole%, 25 mole% or 40 mole%
silver iodide was formed over the core. Each of the respective emulsions was then
subjected to the same treatment as in E-2 except that pAg was adjusted to 9.0 to thereby
form a pure silver bromide second coat over the above first coat-formed grain, whereby
cubic monodisperse grains-having silver iodobromide emulsions of an average grain
size of 0.60µm were prepared, which were regarded as E-11, E-12, E-13 and E-14, respectively.
The average silver iodide content of these emulsions was all 3.0 mole%.
[0179] These emulsions each was chemically sensitized, optically sensitized and coated in
the same manner as in Example-2, whereby Samples No.50 to No.54 were obtained.
[0180] The contents of these samples are given in Table 7.
[0181] These samples were evaluated in the same manner as in Example-2, and the results
are shown in Table 8.
[0182] As is apparent from Table 8, these samples for this invention and having a light-sensitive
silver halide emulsion layer containing silver iodobromide grains of the foregoing
specific multistrata structure and sensitized by the sensitizing dye having the foregoing
general formula are collectively excellent in the coatability, productivity, sensitivity,
granularity, pressure-desensitiation resistance, antiscratch-darkening effect, and
the like. In comparson with the conventional 90-second processing, despite the sensity
equal to or more than that of the conventional system (Samples No.50 and No.43) the
processing time can be shortened to half, and, therefore, the processability is understood
to be doubled.

Example-5
[0183] Each of these samples obtained in Example-4 was subjected to 30-second processing
by making faster the line speed of the automatic processor. The results are shown
in Table 9.
[0184] As is apparent from Table 9, these samples for this invention, even in the 30-second
processing, each shows a sensitivity equal to or more than that of the conventional
system (Sample No.50 processed for 90 seconds), has no problem in the dryability and
is suitably usable in the 30-second process, and it is understood that the use of
such the light-sensitive material allows reducing the processing time in the conventional
system to 1/3, and therefore the processability is tripled.
