FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide color photographic material. More
particularly, the present invention relates to a multilayer silver halide color photographic
material comprising a diffusive development inhibitor-releasing compound.
BACKGROUND OF THE INVENTION
[0002] In recent years, the photographic properties of color photographic light-sensitive
materials have shown a remarkable progress toward higher sensitivity and picture quality.
The demand of further improvement in these photographic properties has grown. The
industry has made efforts to provide light-sensitive materials having further improved
photographic properties. In order to improve the picture quality, efforts have been
made to improve the graininess, sharpness and color reproducibility of light-sensitive
materials.
[0003] In connection with the improvement in the sharpness and color reproducibility of
light-sensitive materials, it has heretofore been known to previously incorporate
in a silver halide color photographic material a compound which releases a development
inhibitor in correspondence to the image density upon development.
[0004] As such a compound there has been known a so-called DIR compound as described in
British Patent No- 953,454, and U.S. Patents 3,227,554, and 4,095,984 which undergoes
coupling reaction with an oxidation product of an aromatic primary amine color developing
agent to form a coupling product and release a development inhibitor. There has also
been known a so-called DIR hydroquinone which undergoes alternating oxidation reaction
with an oxidation product of a developing agent to release a development inhibitor.
(These compounds will be hereinafter referred to as "DIR compounds".)
[0005] Such a DIR compound releases a development inhibitor which serves to exhibit an edge
effect which leads to an improvement in the sharpness, prevent the developed silver
from increasing its size, thus improving the graininess, and exhibit an interlayer
effect which leads to an improvement in the color reproducibility. However, the DIR
compound has an inherent disadvantage that when used in a large amount, it causes
a deterioration in the sensitivity of the silver halide emulsion incorporated in the
same layer. Therefore, in a color-sensitive layer consisting of a plurality of emulsion
layers having different sensitiv ities, the deterioration in the sensitivity of the
layer having the highest sensitivity is minimized and a DIR compound is incorporated
more in layers having a lower sensitivity. In order to further solve such a disadvantage,
a DIR compound as described in JP-A-59-131934 (The term "JP-A" as used herein means
an "unexamined published Japanese patent application") has been developed which releases
a highly diffusive development inhibitor upon development (hereinafter referred to
as "diffusive DIR coupler"). However, this DIR coupler is disadvantageous in that
it deteriorates the graininess of the layer in which it is incorporated. In order
to eliminate this disadvantage, an approach as described in JP-A-60-93435 has been
worked out which comprises the combined use of a diffusive DIR coupler and a nondiffusive
DIR coupler wherein the proportion of the diffusive DIR coupler to the nondiffusive
DIR coupler is low in the high sensitivity layer but high in the low sensitivity layer
so that the reduction in the sensitivity is minimized without deteriorating the graininess.
However, even this approach leaves to be desired in that it causes an essential deterioration
in the sensitivity. Furthermore, if such a DIR compound is incorporated in the low
sensitivity layers, the reduction in the gradation (so-called low contrast) caused
by the deterioration in the color density cannot be avoided due to an interlayer effect.
Particularly, if an emulsion of finely divided particles is incorporated in low sensitivity
layers to improve the graininess thereof, and a DIR coupler is incorporated in some
of said low sensitivity layers, the gradation therein is reduced while the interlayer
effect between said layer and other layers is lowered. This can be believed because
that the increase in the total surface area due to the incorporation of finely divided
particles emulsion causes an increase in the amount of a development inhibitor consumed
in the layer comprising such an emulsion.
[0006] Thus, it has been impossible to provide a high contrast portion with an emulsion
of finely divided silver halide particles while improving the sharpness and color
reproducibility of a light-sensitive material comprising a diffusive DIR coupler.
SUMMARY OF THE INVENTION
[0007] It is therefore an object of the present invention to provide a silver halide color
photographic material which exhibits an excellent sharpness and color reproducibility.
[0008] It is another object of the present invention to provide a color photographic light-sensitive
material which exhibits an excellent sharpness and color reproducibility and enables
a proper control of the gradation when finished into prints.
[0009] These and other objects of the present invention will become more apparent from the
following description and examples.
[0010] These objects of the present invention are accomplished with a silver halide color
photographic material comprising on a support light-sensitive layers consisting of
a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, at least
one of these color-sensitive layers being composed of a plurality of silver halide
emulsion layers having substantially the same color sensitivity and different light
sensitivities, characterized in that all of said color-sensitive layers contains a
compound which reacts with an oxidation product of an aromatic primary amine color
developing agent to release a diffusive development inhibitor or a precursor thereof
and/or a compound which cleaves after the reaction with an oxidation product of an
aromatic primary amine color developing agent a compound which reacts with another
molecule of the oxidation product of an aromatic primary amine color developing agent
to cleave a development inhibitor (hereinafter referred to as "diffusive development
inhibitor-releasing compound"), that at least one of said color-sensitive layers consists
of at least two light-sensitive layers having different sensitivities, and that the
content of said diffusive development inhibitor-releasing compound shows the highest
value except in the layer having the lowest sensitivity in each of said color-sensitive
layers.
[0011] In a preferred embodiment, at least one of the silver halide emulsion layers having
the lowest sensitivity with regard to the corresponding color-sensitive layer substantially
comprises particulate silver halide having a diameter of 0.5 u.m or less as calculated
in terms of circle. Preferably the ratio of the gradation (-).1) of said lowest sensitivity
layer to the gradation (y2) of the layer having the next lowest sensitivity (y1/y2)
in the same color-sensitive layer is 1 or more.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] By way of example and to make the description more clear, reference is made to the
accompanying drawings in which:
Fig. 1 is the characteristics curve of a light-sensitive material of the present invention
which has been exposed to white light and then color-developed in which the optical
density (D) is plotted on the ordinates and the logarithm of the exposure (E) is plotted
on the abscissa (shown. at 1, 2 and 3 are the curve for yellow density (blue-sensitive
layer), magenta density (green-sensitive layer, and cyan density (red-sensitive layer),
respectively);
Fig. 2 is the characteristics curve of a specimen which has been exposed to light
through a blue separation filter and then color-developed (shown at 4, 5 and 6 are
the curve for yellow density, magenta density and cyan density, respectively.).
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention will be further described with reference to the diffusive development
inhibitor-releasing compounds of the present invention. The diffusive development
inhibitor-releasing compounds of the present invention can advantageously be represented
by the general formulas [I] to [IV]:

wherein A represents a coupling component which can react with an oxidation product
of a color developing agent to release -TIME-Z
2 group or -P-Z
2 group; B represents a redox portion which undergoes reduction-oxidation reaction
with an oxidation product of a color developing agent and then undergoes hydrolysis
with alkali to release Zi; TIME represents a timing group; Z
1 represents a diffusive development inhibitor; -P-represents a group which undergoes
reaction with an oxidation product of a developing agent after cleavage from A or
B to release a development inhibitor; and Z
2 may be a diffusive development inhibitor or a development inhibitor having a small
diffusivity, with the proviso that if -TIME-Z
2 or -P-Z
2 exhibits diffusivity, A-TIME-Z
2 and A (or B)-P-Z
2 are diffusive DIR compounds.
[0014] Examples of the development inhibitor represented by Z
1 or Z
2 include those described in Research Disclosure No. 17643 (Dec., 1978). Preferred
examples of such a development inhibitor include mercaptotetrazole, selenotetrazole,
mercaptobenzothiazole, selenobenzothiazole, mercaptobenzooxazole, selenobenzooxazole,
mercaptobenzimidazole, selenobenzimidazole, benzotriazole, mercaptotriazole, mer-
captooxadiazole, mercaptothiadiazole, and derivatives thereof.
[0016] In the general formulas [Z-1 and [Z-2], R
11 and R
12 each represents an alkyl group, alkoxy group, acylamino group, halogen atom, alkoxycarbonyl
group, thiazolideneamino group, aryloxycarbonyl group, acyloxy group, carbamoyl group,
N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy
group, sulfamoyl group, sulfonamide group, N-alkylcarbamoyloxy group, ureide group,
hydroxy group, alkoxycarbonylamino group, aryloxy group, alkylthio group, arylthio
group, anilino group, aryl group, imide group, hetero group, cyano group, alkylsulfonyl
group, or aryloxycarbonylamino group.
[0017] The sulffix n represents an integer 1 or 2. When n represents 2, R
11 and R
2 may be the same or different, and the total number of carbon atoms contained in n
number of R
11 and R
12's is 0 to 20.
[0018] In the general formulas [Z-3], [Z-4], [Z-5], and [Z-6], R
13, R
14, R
15, R
16, and R
17 each represents an alkyl group, aryl group or heterocyclic group.
[0019] When R
11 to R
17 each represents an alkyl group, they may be substituted or unsubstituted, chain or
cyclic. If they are substituted, the substituents may be halogen atom, nitro group,
cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl
group, sulfamoyl group, carbamoyl group, hydroxyl group, alkanesulfonyl group, arylsulfonyl
group, alkylthio group, or arylthio group.
[0020] When R
11 to R
17 each represents an aryl group, they may be substituted. In this case, the substituents
may be alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom,
nitro group, amino group, sulfamoyl group, hydroxyl group, carbamoyl group, aryloxycarbonylamino
group, alkoxycarbonylamino group, acylamino group, cyano group, or ureide group.
[0021] When R
11 to R
17 each represents a heterocyclic group, they may be five- or six-membered monocyclic
or condensed ring groups containing nitrogen atom, oxygen atom or sulfur atom as hetero
atom. Examples of such groups include pyridyl group, quinolyl group, furyl group,
benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl
group, benzotriazolyl group, imide group, and oxazine group. These groups may be further
substituted by the substituents described with reference to the above described aryl
group.
[0022] In the general formulas [Z-1 ] and [Z-2], the number of carbon atoms contained in
R
11 and R
12 is 0 to 20, preferably 7 to 20.
[0023] In the general formulas [Z-3], [Z-4], [Z-5] and [Z-6], the total number of carbon
atoms contained in R
13 to R
17 is 0 to 20, preferably 4 to 20.
[0024] A preferred development inhibitor of the present invention is a compound which reacts
with an oxidation product of a developing agent to release a development inhititor
diffuses from the layer in which it has been incorporated to another layer upon development
to exhibit a development inhibiting effect.
[0025] The coupler component represented by A may be a dye-forming coupler such as acylacetanilides,
malondiesters, malondiamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles,
indazolones, phenols, and naphthols, or a coupler component which substantially doesn't
form a dye, such as acetophenones, indanones, and oxazolones.
[0027] In these general formulas, R
30 represents an aliphatic group, aromatic group, alkoxy group or heterocyclic group;
and R
31 and R
32 each represents an aromatic group or heterocyclic group.
[0028] The aliphatic group represented by R
30 may be preferably a C
1 -
20 substituted or unsubstituted chain or cyclic group. Examples of the substituent for
the aliphatic group include alkoxy, aryloxy and acylamino group.
[0029] When Rao, R
31 or R
32 represents an aromatic group, they may be phenyl or naphthyl groups, preferably phenyl
groups. These phenyl groups may contain substituents such as alkyl group, alkenyl
group, alkoxy group, alkoxycarbonyl group and alkylamide group having 30 carbon atoms
or less. These phenyl groups represented by R
30, R
31 and R
32 may be substituted by alkyl group, alkoxy group, cyano group or halogen atom.
[0030] R
33 represents a hydrogen atom, alkyl group, halogen atom, carbonamide group or sulfonamide
group. The suffix t represents an integer 1 to 5. R
34 and R
35 each represents a hydrogen atom, alkyl group or aryl group. Preferred examples of
such an aryl group include phenyl group. Such an alkyl group or aryl group may contain
substituents such as halogen atom, alkoxy group, aryloxy group, and carboxyl group.
R
34 and R
35 may be the same or different.
[0031] The general formula [III] represents a compound which undergoes reduction-oxidation
reaction with an oxidation product of an aromatic primary amine developing agent and
then hydrolysis with alkali to release a development inhibitor or its precursor (hereinafter
referred to as "DIR redox compound"). In the general formula [III] B represents a
redox portion. More particularly, such a DIR redox compound is represented by the
general formula [IX]:

[0032] In the general formula [IX], G and G' each represents a hydrogen atom or a phenolic
hydroxyl protective group capable of deblocking a protective group during a photographic
processing. Typical examples of such a protective group include hydrogen atom, acyl
group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, and oxazolyl group.
[0033] R
18, R
19 and R
20 may be the same or different and each represents a hydrogen atom, halogen atom, alkyl
group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, cyano
group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group, sulfo
group, sulfonyl group, acyl group, carbonamide group, sulfonamide group or heterocyclic
group.
[0034] R
18 and R
19, R
18 and G, R
19 and G', and R
20 and G may be connected to each other to form an aromatic or nonaromatic ring. At
least one of R
18, R
19 and R
20 contains a C
10-20 nondiffusive group.
[0035] Z is a development inhibitor as defined above.
[0036] In the present invention, P is preferably a group which becomes a redox group or
coupler after the cleavage from A or B.
[0037] As described above, a compound which reacts with an oxidation product of a developing
agent to release a development inhibitor which diffuses to the layer in which it has
been incorporated to another layer upon development to exhibit a development inhibiting
effect can be used in the present invention.
[0038] The preparation of these compounds of the present invention can be easily accomplished
by any suitable method as described in U.S. Patents 3,227,554, 3,617,291, 3,933,500,
3,958,993, 4,149,886, 4,234,678, and 4,248,962, JP-A-51-13239, JP-A-57-56837, JP-A-52-90932,
JP-A-56-114946, JP-A-57-154234, JP-A-58-98728, JP-A-58-209736, JP-A-58-209737, JP-A-58-209738,
JP-A-58-209740, JP-A-61-255342, JP-A-62-24252, and JP-A-61-156043 British Patent Nos.
2,070,266, and 2,072,363, Research Disclosure No. 21228 (December, 1981), JP-B-58-9942
and JP-B-51-16141 (the term "JP-B" as used herein means an "examined Japanese patent
publication") and EP-A-255,085.
[0039] Specific examples of suitable diffusive development inhibitors which can be used
in the present invention will be shown hereinafter, but the present invention should
not be construed as being limited thereto.
[0041] The present light-sensitive material may comprise at least one silver halide emulsion
layer made of at least a blue-sensitive layer, a green-sensitive layer and a red-sensitive
layer on a support. The number and order of these silver halide emulsion layers and
light-insensitive layers are not specifically limited. A typical example of such a
layer structure is a silver halide photographic material comprising on a support at
least one light-sensitive layer comprising a plurality of silver halide emulsion layers
having substantially the same color sensitivity and different light sensitivities.
The light-sensitive layer is a unit light-sensitive layer having a sensitivity to
any of blue light, green light and red light. In a multilayer silver halide color
photographic material, the arrangement of such unit light-sensitive layers is such
that a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer are
arranged in this order from the support side. However, this order may be reversed
depending on the purpose of application. Alternatively, the layer arrangement is such
that layers having the same color sensitivity have a layer having a different color
sensitivity interposed therebetween.
[0042] Various light-insensitive layers such as intermediate layers may be provided interposed
between the above described silver halide light-sensitive layers and on the top and
under the bottom thereof.
[0043] These intermediate layers may comprise couplers and DIR compounds as described in
JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038. These
intermediate layers may also comprise a color stain inhibitor as commonly used.
[0044] The plurality of silver halide emulsion layers which constitute each unit light-sensitive
layer may employ a two-layer structure comprising a high sensitivity emulsion layer
and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470
and British Patent No. 923,045. In general, such a layer structure may be employed
that the light sensitivity gradually decreases toward the support. Furthermore, a
light-insensitive layer may be provided interposed between silver halide emulsion
layers. Alternatively, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541,
and JP-A-62-206543, such a layer structure may be employed that a low sensitivity
emulsion layer is provided remote from the support while a high sensitivity emulsion
layer is provided near the support. If the low sensitivity layer comprises an emulsion
of particulate silver hajide having a particle size of 0.5 u.m or less, particularly
0.2 u.m or less, as in the present invention, it may preferably be provided remote
from the support.
[0045] A specific example of suitable layer structures which can be used in the present
invention is such that a low sensitivity blue-sensitive layer (BL), a high sensitivity
blue-sensitive layer (BH), a high sensitivity green-sensitive layer (GH),, a low sensitivity
green-sensitive layer (GL), a high sensitivity red-sensitive layer (RH), and a low
sensitivity red-sensitive layer (RL) are arranged in this order from the support or
that BH, BL, GL, GH, RH, and RL or BH, BL, GH, GL, RL, and RH are arranged in this
order remote from the support.
[0046] Alternatively, a blue-sensitive layer, GH, RH, GL, and RL may be arranged in this
order remote from the support as described in JP-B-55-34932. A blue-sensitive layer,
GL, RL, GH, and RH may be arranged in this order remote from the support as described
in JP-A-56-25738 and JP-A-62-63936.
[0047] Alternatively, such a three-layer structure as described in JP-B-49-15495 may be
used in which the upper layer is a silver halide emulsion layer having the highest
sensitivity, the middle layer is a silver halide emulsion layer having a sensitivity
lower than that of the upper layer, and the lower layer is a silver halide emulsion
layer having a sensitivity lower than that of the middle layer. In such a layer structure,
the sensitivity decreases toward the support. In such a structure comprising three
layers having different sensitivities, a middle sensitivity emulsion layer, a high
sensitivity emulsion layer and a low sensitivity emulsion layer may be arranged in
this order remote from the support in each color-sensitive layer as described in JP-A-59-202464.
[0048] As described above, various layer structures and arrangements may be selected depending
on the purpose of application of the light-sensitive material.
[0049] The present diffusive DIR compound may be incorporated in at least one layer of the
different sensitivity layers in each color-sensitive layer. If the diffusive DIR compound
is incorporated in one layer other than the lowest sensitivity layer, it may not be
incorporated in the lowest sensitivity layer. For example, when each color-sensitive
layer consists of a high sensitivity layer and a low sensitivity layer, such an embodiment
may be employed that the high sensitivity layer in each color-sensitive layer contains
the present diffusive DIR compound or that at least one color-sensitive layer contains
the present diffusive DIR compound in both the high sensitivity layer and the low
sensitivity layer.
[0050] When a color-sensitivity layer is composed of a single light-sensitive emulsion layer,
the diffusive DIR compound is incorporated into the same layer.
[0051] Alternatively, when one color-sensitive layer is composed of a high sensitivity layer,
a middle sensitivity layer and a low sensitivity layer, at least the high sensitivity
layer or the middle sensitivity layer may contain the diffusive DIR compound while
the low sensitivity layer may or may not.
[0052] Besides the above diffusive DIR compound, a nondiffusive DIR compound may be used
singly or in admixture therewith. The nondiffusive DIR compound is a compound having
a relatively higher intralayer development inhibiting effect/intertayer development
inhibiting effect ratio than the present diffusive DIR compound.
[0053] The amount of the diffusive DIR compound to be incorporated is in the range of 0.01
to 20 mol%, preferably 0.05 to 10 mol%, particularly 0.1 to 5 mol% with regard to
the moles of silver halide incorporated in the same layer.
[0054] The amount of the nondiffusive DIR compound to be incorporated is as specified above.
If the nondiffusive DIR compound and the diffusive DIR compound are used in combination,
the proportion of the two components is not specifically limited.
[0055] The amount of the diffusive DIR compound to be incorporated is in the range of 1
to 60 mol%, preferably 5 to 50 mol% with regard to the moles of uncolored color coupler
which mainly forms color images in the same layer.
[0056] The gradation (y) according to the present invention will be described hereinafter.
The gradation (y) to be used in the present invention can be determined by the slope
of the linear portion of D-log E curve made by plotting the exposure (E) on the abscissa
and the optical density (D) on the ordinates in the process commonly used in this
art.
[0057] The term "gradation of the lowest sensitivity layer" as used herein means the slope
of the linear portion of D-log E curve in the high exposure range (namely high density
portion). The high exposure portion of D-log E curve varies with the exposure. Therefore,
in the present method, the high exposure portion of D-log E curve ranges from the
exposure point (E
o) at which the optical density on D-log E curve begins to change from the fog density
(density of unexposed portion after development) to Δlog E (=log E-log Eo) of -0.5
to + 4.5. In this case, the high exposure range is Δlog E of about 2.5 to 4.5.
[0058] Explaining more particularly with reference to density, the gradation of the lowest
sensitivity layer in the blue-sensitive layer may be normally represented by the highest
value in the gradation of the yellow density range of about 1.5 to 3.0 obtained when
color-developed after exposed to while light. The gradation of the lowest sensitivity
layer in the green-sensitive layer may be normally represented by the highest value
in the gradation of the magenta density range of about 1.2 to 2.5 obtained when color-developed
after exposed to white light. the gradation of the red-sensitive layer may be normally
represented by the highest value in the gradation of the cyan density range of about
1:0 to 2.0 obtained when color-developed after exposed to white light.
[0059] The gradation of the next lowest sensitivity layer according to the present invention
is the gradation of the Δlog E range of 0.5 to 2.5. Explaining more particularly with
reference to density, the gradation of the next lowest sensitivity layer in the blue-sensitive
layer may be represented by the gradation of the linear portion in the yellow density
range of about 0.6 to 1.6 as described above. Similarly, the gradation of the next
lowest sensitivity layer in the green-sensitive layer may be represented by the gradation
of the linear portion in the magenta density range of about 0.4 to 1.3, and the gradation
of the next lowest sensitivity layer in the red-sensitive layer may be represented
by the gradation of the linear portion in the cyan density range of about 0.1 to 1.2.
In this range, if two or more lines can be drawn above A log E of 0.5, the gradation
of the next lowest sensitivity layer may be represented by the gradation of the linear
portion nearest to the high exposure range.
[0060] The gradation (G) according to the present invention (slope of the linear portion
of H-D curve (= D - log E curve) wherein D represents optical density and E represents
exposure) will be described hereinafter. If the gradation of the lowest sensitivity
layer (namely high exposure portion) is represented by γ
1, and the gradation of the next lowest sensitivity layer is represented by -
12, the value of γ
1/γ
2 ratio according to the present invention is in the range of 1.00 to 5.00, preferably
1.25 to 3.50, more preferably 1.50 to 3.00.
[0061] The lowest sensitivity layer of the present invention may comprise an emulsion of
finely divided particles of silver halide having a diameter of about 0.5 µm or less,
preferably about 0.35 u.m or less, and more preferably about 0.2 u.m or less as calculated
in terms of diameter of circle having the same area as the projected area of particle.
[0062] The embodiments of the present invention can be applied to general silver halide
color photographic materials as well as intermediate photographic materials.
[0063] The current color negative photographic materials are imagewise exposed, color-developed,
and then used as original picture through which color print materials are exposed
to light. Ideally speaking, these photographic materials preferably have a constant
gradation from the low exposure range to the high exposure range. However, this makes
it difficult to adjust the gradation during printing. On the other hand, if the exposed
portion has a high contrast and a low contrast, it is made possible to adjust the
gradation during printing. This technique is widely applied and particularly effective
when an intermediate photographic material adapted to be exposed to original picture
(transparent positive picture) is used. However, there have never been commercially
available an intermediate photographic material comprising the above diffusive DIR
couplers and exhibiting a high picture quality and a varying gradation. It has been
very difficult to design a high contrast portion with an emulsion of finely divided
particles of silver halide while improving the sharpness and color reproducibility
by the use of diffusive DIR couplers. The present invention can accomplish this object.
[0064] Preferred silver halide incorporated in the photographic emulsion layer in the photographic
light-sensitive material to be used in the present invention is silver iodobromide,
silver iodochloride or silver iodochlorobromide having a silver iodide content of
about 30 mol% or less. Particularly preferred is silver iodobromide having a silver
iodide content of about 2 mol% to about 25 mol%.
[0065] The silver halide grain to be incorporated in the photographic emulsion may have
a regular crystal structure such as cube, octahedron and tetradecahedron, an irregular
crystal structure such as sphere and plate, a crystal structure having crystal defect
such as twinning plane, or a composite thereof.
[0066] The silver halide grain according to the present invention may be either finely divided
particles having a particle diameter of about 0.1 µm or less or large size particle
having a particle diameter of up to about 10 u.m as calculated in terms of projected
area. The silver halide emulsion according to the present invention may be in the
form of a monodisperse emulsion or a polydisperse emulsion. The lowest sensitivity
layer of the present invention may preferably comprise finely divided particulate
silver halide having a particle diameter of 0.2 u.m or less. The finely divided particulate
silver halide may be preferably in the form of monodisperse cubic particle. The blue-sensitive
layer and green-sensitive layer may preferably comprise tabular particulate silver
halide. More preferably, the blue-sensitive layer may comprise silver chloroiodobromide
as described in Japanese Patent Application No. 62-103808.
[0067] The preparation of s silver halide photographic emulsion which can be used in the
present invention can be accomplished by any suitable method as described in Research
Disclosure Nos. 17643 (december, 1978), pp. 22 to 23, "I. Emulsion preparation and
types", and 18716 (November, 1979), page 648, P. Glafkides, Chemie et Physique Photographique,
Paul Montel, 1967, G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966,
and V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press,
1964.
[0068] Monodisperse emulsions as described in U.S. Patents 3,574,628, and 3,655,394, and
British Patent No. 1,413,748 may be preferably used in the present invention.
[0069] Alternatively, tabular grains having an aspect ratio of about 5 or more may be used
in the present invention. The preparation of such tabular grains can be easily accomplished
by any suitable method as described in Gutoff, "Photographic Science and Engineering",
Vol. 14, pp. 248 to 257, 1970, U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520,
and British Patent No. 2,112,157.
[0070] The crystal structure of the present silver halide grain may be uniform, or such
that the halide composition varies between the inner portion and the outer portion
thereof, or may be a layer structure. Alternatively, silver halides having different
compositions may be connected to each other by an epitaxial junction or by any suitable
compound other than silver halide such as silver thiocyanate, and zinc oxide.
[0071] Alternatively, a mixture or particles having various crystal structures may be used.
[0072] The present silver halide emulsion may be normally subjected to physical ripening,
chemical ripening, and spectral sensitization before use. Examples of additives to
be used in such processes are described in Research Disclosure Nos. 17643 and 18716.
The places where, such a description is found are summarized in the table shown below.

[0073] As suitable color stain inhibitors there may be used compounds as described in U.S.
Patents 3,926,436, and 4,447,523, JP-B-61-13748, and Japanese Patent Application No.
60-165511.
[0074] The present light-insensitive finely divided particulate silver halide will be described
hereinafter.
[0075] The term "finely divided particulate silver halide" as used herein means a finely
divided particulate silver halide which is not sensitive to light during imagewise
exposure and is not substantially developed during development. Such a finely divided
particulate silver halide may have previously been fogged, but may preferably have
previously not been fogged.
[0076] Such a finely divided particulate silver halide may have a silver bromide content
of 0 to 100 mol%. The finely divided particulate silver halide may have various compositions
so long as it has such a silver bromide content. Particularly, the finely divided
particulate silver halide may contain silver chloride and/or silver iodide if desired.
Preferably, silver iodobromide containing 0.5 to 10 mol% of silver iodide may be used.
[0077] The present finely divided particulate silver halide may have an average particle
diameter of 0.01 to 0.5 u.m, preferably 0.02 to 0.2 u.m. The average particle diameter
of particulate silver halide can be determined by the average value of diameter of
particles as calculated in terms of diameter of circle having the same area as the
projected area thereof. The measurement of the average particle diameter of particulate
silver halide can be accomplished by any suitable method as described in "SHASHINKOGAKU
NO KISO-GINENSHASHINHEN", Nihon Shashin Gakkai, January 30, 1979, pp. 227 to 228.
[0078] The present finely divided particulate silver halide can be prepared by the same
method as used in the preparation of ordinary light-sensitive silver halide emulsion
or in accordance with the method. In this case, the surface of the particulate silver
halide doesn't need to be chemically sensitized or spectrally sensitized. However,
prior to being added to the coating solution, the finely divided particulate silver
halide may preferably have previously contained any known stabilizers such as thiazole
compound, azaindene compound, benzothiazolium compound, mercapto compound, and zinc
compound incorporated therein.
[0079] Such a finely divided particulate light-insensitive silver halide may be incorporated
in a protective layer, emulsion layer or intermediate layer in the present light-sensitive
layer. Preferably, the finely divided particulate light-insensitive silver halide
may be incorporated in the protective layer. The amount of the finely divided particulate
light-insensitive silver halide to be incorporated is in the range of 0.05 to 2.0
g/m
2, preferably 0.1 to 1.0 g/m2.
[0080] Various color couplers can be used in the present invention. Specific examples of
such color couplers are described in patents cited in Research Disclosure No. 17643
(VII-C-G).
[0081] Preferred examples of yellow couplers which may be used in the present invention
are described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739,
and British Patent Nos. 1,425,020, and 1,476,760.
[0082] As a magenta coupler there may be preferably used a 5-pyrazolone or pyrazoloazole
compound. Particularly preferred examples of such a compound are described in U.S.
Patents 4,310,619, 4,351,897, 3,061,432, 3,725,067, 4,500,630, and 4,540,654, European
Patent No. 73,636, JP-A-60-33552, and JP-A-60-43659, and Research Disclosure Nos.
24220 (June 1984), and 24230 (June 1984).
[0083] As a cyan coupler there may be preferably used a phenolic or naphtholic coupler.
Preferred examples of such a cyan coupler are described in U.S. Patents 4,052,212,
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002,
3,758,308, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,451,559, and 4,427,767, West
German Patent Application (OLS) No. 3,329,729, and European Patent Nos. 121,365A,
and 161,626A.
[0084] Examples of a colored coupler for correcting unnecessary absorption by color-forming
dye are described in Research Disclosure No. 17643 (VII-G), U.S. Patents 4,163,670,
4,004,929, and 4,138,258, and British Patent No. 1,146,368, and JP-B-57-39413.
[0085] Examples of a coupler which provides a color-forming dye having a proper diffusivity
are described in U.S. Patent 4,366,237, British Patent No. 2,125,570, European Patent
No. 96,570, and West German Patent Application (OLS) No. 3,234,533.
[0086] Typical examples of polymerized dye-forming couplers are described in U.S. Patent
Nos. 3,451,820, 4,080,211, and 4,367,282, and British Patent No. 2,102,173.
[0087] Couplers which release a photographically useful residual group upon coupling may
be preferably used in the present invention.
[0088] Preferred examples of couplers which imagewise release a nucleating agent or a development
accelerator upon development are described in British Patent Nos. 2,097,140, and 2,131,188,
and JP-A-59-157638, and JP-A-59-170840.
[0089] Examples of other couplers which can be used in the present light-sensitive material
include competing couplers as described in U.S. Patent 4,130,427, polyvalent couplers
as described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618, couplers which release
a dye which can be recovered after elimination as described in European Patent No.
173,302A, bleach accelerator releasing couplers as described in RD No. 11449, RD 24241,
and JP-A-61-201247, and ligand releasing couplers as described in U.S. Patent 4,553,477.
[0090] The incorporation of the present couplers in the light-sensitive material can be
accomplished by various known dispersion methods.
[0091] Examples of high boiling solvents which can be used in an oil-in-water dispersion
process are described in U.S. Patent 2,322,027.
[0092] Specific examples of process and effects of latex dispersion method and latex for
use in such dispersion method are described in U.S. Patent 4,199,363, and West German
Patent Application (OLS) Nos. 2,541,274, and 2,541,230.
[0093] Examples of suitable supports which can be used in the present invention are described
on page 28 of Research Disclosure No. 17643 and from the right column on page 647
to the left column on page 648 in Research Disclosure No. 18716.
[0094] The invention comprises a process for producing a color image characterized in that
the silver halide color photographic material described above is exposed to light
and processed by methods comprising developing bleaching, fixing, rinsing, stabilizing
and drying.
[0095] The development of a color photographic light-sensitive material according to the
present invention can be accomplished by an ordinary method as described in Research
Disclosure No. 17643 (pp. 28 to 29) and Research Disclosure No. 18716 (left column
to right column on page 651
[0096] The color developing solution to be used in the development of the present light-sensitive
material is preferably an alkaline aqueous solution containing an aromatic primary
amine color developing agent as a main component. As such a color developing agent
there may be used as aminophenol compound. Preferred examples of such a color developing
agent include p-phenylenediamine compounds. Typical examples of such p-phenylenediamine
compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-0-hydroxylethylaniline,
3-methyl-4-amino-N-ethyl-N-p-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-,8-methoxyethyl
aniline, and sulfate, hydrochloride, phosphate, and p-toluenesulfonate thereof. These
compounds may be used in combination depending on the purpose of application.
[0097] The color developing solution normally comprises pH buffers such as carbonate, borate,
and phosphate of alkaline metal, and development inhibitors or fog inhibitors such
as bromide, iodide, benzimidazoles, benzothiazoles, and mercapto compounds. Typical
examples of other additives which may be optionally incorporated in the color developing
solution include various preservatives such as hydroxylamine, diethylhydroxylamine,
sulfite, hydrazines, phenyl semicarbazides, triethanolamine, catecholsulfonic acids
and triethyienediamine(1,4-diazabicycio[2,2,2]octane), organic solvents such as ethylene
glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene
glycol, quaternary ammonium salts and amines, dye-forming couplers, competing couplers,
fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone,
thickening agents, and chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic
acid, alkylphosphonic acid and phosphonocarboxylic acid (e.g., ethylenediaminetetraacetic
acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine
tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic
acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic
acid, ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof).
[0098] In the reversal processing of the light-sensitive material, the color development
normally follows the black-and-white development. Examples of black-and-white developing
agents which can be incorporated in the black-and-white developing solution include
dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone,
aminophenols such as N-methyl-p-aminophenol, and combinations thereof.
[0099] The pH value of these color developing solutions and black-and-white developing solutions
is normally in the range of 9 to 12. The replenisher amount of these developing solutions
depends on the color photographic light-sensitive material to be processed but is
normally in the range of 3 t or less per 1 m
2 of the light-sensitive material. By using a replenisher solution having a less bromide
ion content, the replenisher amount of these developing solutions can be reduced to
500 ml or less. If the replenisher amount of these developing solutions is reduced,
the area of contact between the processing tank and air is preferably reduced to prevent
evaporation and air oxidation of the solution. Alternatively, a means of inhibiting
accumulation of bromide ion in the developing solution may be used to reduce the replenisher
amount of the developing solution.
[0100] The photographic emulsion layer which has been color-developed is normally bleached.
The bleaching may be effected simultaneously with or separately of fixing (blix).
In order to expedite the processing, the bleaching may be followed by the blix. Furthermore,
the photographic emulsion layer may be processed in two continuous blix baths. The
blix may be followed by the fixing. Alternatively, the blix may be followed by the
bleaching. These processes may be optionally selected depending on the purpose of
application. Examples of bleaching agents which can be used in the present invention
include compounds of polyvalent metal such as iron (III), cobalt (III), chromium (VI),
and copper (II), peroxide, quinones, and nitro compounds. Typical examples of such
bleaching agents include ferricyanides, dichromates, organic complex salts of iron
(III) or cobalt (III) with, e.g., aminopolycarboxylic acid such as ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic
acid, 1,3-diaminopropanetetraacetic acid and glycoletherdiaminetetraacetic acid, or
citric acid, tartaric acid, malic acid, or other organic acid, persulfate, bromate,
permanganate, and nitrobenzenes. Among these compounds, aminopolycarboxylic acid-iron
(III) complexes such as ethylenediaminetetraacetic acid-iron (III) complex and persulfate
may be preferably used in the light of rapidity in processing and prevention of environmental
pollution. Furthermore, aminopolycarboxylic acid-iron (III) complexes are particularly
useful in the bleaching solution or blix solution. The pH value of a bleaching solution
or blix solution comprising such an aminopolycarboxylic acid-iron (III) complex is
normally in the range of 5.5 to 8. In order to expedite the processing, the pH value
of the solution may be lower than this range.
[0101] The present bleaching solution, blix solution, or prebath thereof may optionally
contain a bleach accelerator. Specific examples of useful bleach accelerators include
compounds containing mercapto group or disulfide group as described in U.S. Patent
3,893,858, West German Patent Nos. 1,290,812, and Research Disclosure No. 17129 (July
1978), thiazolidine derivatives as described in JP-A-50-1.40129, thiourea derivatives
as described in U.S. Patent 3,706,561, iodides as described in JP-A-58-16235, polyoxyethylene
compounds as described in West German Patent No. 2,748,430, polyamine compounds as
described in JP-B-45-8836, and bromide ion. Among these compounds, compounds containing
mercapto group or disulfide group may be preferably used because of their high accelerating
effect. Particularly preferred are compounds as described in U.S. Patent 3,893,858,
West German Patent No. 1,290,812, and JP-A-53-95630. Furthermore, compounds as described
in U.S. Patent 4,552,834 may be preferably used. These bleach accelerators may be
incorporated in the light-sensitive material. These bleach accelerators are useful
particularly when a color light-sensitive material for use in photographing is subjected
to blix.
[0102] Examples of suitable fixing agents include thiosulfates, thiocyanates, thioether
compounds, thioureas, and iodides (in a large amount). Among these compounds, thiosulfates
are normally used. Particularly, ammonium thiosulfate can be most widely used. As
a suitable preservative for the blix solution there may be preferably used sulfite,
bisulfite or carbonyl-bisulfite addition product.
[0103] The present silver halide color photographic material which has been subjected to
desilvering process is normally subjected to rinse and stabilization. The amount of
rinsing water to be used at the rinsing step can be widely selected depending on the
characteristics of the light-sensitive material (due to materials used, e.g., couplers),
the application of the light-sensitive material, the temperature of the rinsing water,
the number of rinsing tanks (number of stages), the supply process (countercurrent
or forward current), and other various conditions. Among these conditions, the relationship
between the number of rinsing tanks and the used amount of water can be determined
by the method as described in Journal of the Society of Motion Picture and Television
Engineering, Vol. 64, p. 248 to 253, May 1955.
[0104] in the multistage countercurrent process as described in the above cited reference,
the amount of rinsing water to be used can be drastically reduced. However, this process
is disadvantageous in that the increase in the time of retention of water in the tank
causes propagation of bacteria which produce suspended matter that can be attached
to the light-sensitive material. In the processing of the present color light-sensitive
material, such a disadvantage can be extremely effectively eliminated by the method
as described in JP-A-62-288838 which comprises reduction in the calcium and magnesium
ion content. Alternatively, there may be preferably used isothiazolone compounds and
thiabendazoles as described in JP-A-57-8542, chlorinic sterilizers such as sodium
chlorinated isocyanurate, or sterilizers as described in Hiroshi Horiguchi, "Anti-bacterial
and anti-fungal Chemistry", Eisei Gijutsukai, "Technique for Sterilization and Fungicidal
Treatment of Microorganism", and Nihon Bokin Bobai Gakkai, "Dictionary of Sterilizers
and Fungicides".
[0105] The pH value of the rinsing water to be used in the processing of the present light-sensitive
material is in the range of 4 to 9, preferably 5 to 8. The temperature of the rinsing
water and the rinsing time can be widely selected depending on the characteristics
and application of the light-sensitive material to be processed but is normally in
the range of 15 to 45
. C and 20 seconds to 10 minutes, preferably 25 to 40° C and 30 seconds to 5 minutes,
respectively. Furthermore, the present light-sensitive material can be directly processed
with a stabilizing solution in stead of the above described rinsing solution. In such
a stabilization process, any known method as described in JP-A-57-8543, JP-A-58-14834,
and JP-A-60-220345 can be used.
[0106] The above described rinse may be optionally followed by another stabilization process
such as stabilizing bath for use as the final processing bath for color light-sensitive
materials for photographing use which contains formalin and a surface active agent.
This stabilizing bath may also comprise various chelating agents or fungicides.
[0107] The overflow solution produced by the replenisher of the above described rinsing
water and/or stabilizing solution may be recycled at the desilvering step or other
steps.
[0108] The present silver halide light-sensitive material may comprise a color developing
agent for the purpose of simplification and expedition of the processing. Such a color
developing agent may be preferably incorporated in the form of various precursors.
Examples of such precursors include indoaniline compounds as described in U.S. Patent
3,342,597, Schiff's base type compounds as described in U.S. Patent 3,342,599, and
Research Disclosure Nos. 14850 and 15159, aldol compounds as described in Research
Disclosure No. 13924, metal complexes as described in U.S. patent 3,719,492, and urethane
compounds as described in JP-A-53-135628.
[0109] The present silver halide color light-sensitive material may optionally comprise
various 1-phenyl-3-pyrazolidones for the purpose of promoting color development. Typical
examples of such compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
[0110] In the present invention, the various processing solutions can be used at a temperature
of 10 to 50 C. These solutions are normally used at a temperature of 33 to 38° C.
The temperature range may be raised to promote the processing and thus shorten the
processing time. On the contrary, the temperature range may be lowered to improve
the picture quality or the stability of the processing solutions. In order to save
the silver content in the tight-sensitive material, the processing utilizing cobalt
intensification or hydrogen peroxide intensification as described in West German patent
No. 2,226,770 and U.S. Patent 3,674,499 can be used.
[0111] The present invention will be further described in the following examples, but the
present invention should not be construed as being limited thereto.
EXAMPLE 1
[0112] In order to evaluate the effectiveness of the present invention, a multilayer color
light-sensitive material specimen 101 was prepared by coating various layers of the
following compositions on an undercoated cellulose triacetate film support.
Specimen 101
[0114] Besides the above described components, a surface active agent was incorporated in
each layer as a coating aid.
[0115] Thus, Specimen 101 was prepared.
[0117] After being exposed to light, the color photographic light-sensitive material thus
prepared was then processed as follows:
Processing A
[0118]

[0119] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0120]

Bleaching solution
[0121]

Fixing solution
[0122]

Stabilizing solution
Specimen 102
[0124] Specimen 102 was prepared in the same manner as in Specimen 101 except that the nondiffusive
DIR coupler EX-4 to be incorporated in the 3rd layer was replaced by the diffusive
DIR coupler T-131 of the present invention in the amount as shown in Table 1 and the
nondiffusive DIR coupler EX-4 to be incorporated in the 4th layer was replaced by
the diffusive DIR coupler T-131 of the present invention in the amount as shown in
Table 1.
Specimen 103 and 104
[0125] Specimen 103 was prepared in the same manner as in Specimen 101 except that the nondiffusive
DIR coupler EX-5 to be incorporated in the 10th layer was replaced by the diffusive
DIR coupler T-104 of the present invention in the amount as shown in Table 1 and the
nondiffusive DIR coupler EX-5 to be incorporated in the 11th layer was replaced by
the diffusive DIR coupler T-144 of the present invention in the amount as shown in
Table 1.
[0126] Specimen 104 was prepared in the same manner as in Specimen 102 except that the nondiffusive
DIR coupler to be incorporated in the 10th layer and the diffusive DIR coupler to
be incorporated in the 11th layer were replaced in the same manner as in Specimen
103.
Specimen 105
[0127] Specimen 105 was prepared in the same manner as in Specimen 101 except that the nondiffusive
DIR coupler EX-4 to be incorporated in the 3rd layer was replaced by the diffusive
DIR coupler T-131 of the present invention in the amount as shown in Table 1, the
nondiffusive DIR coupler EX-4 to be incorporated in the 4th layer was replaced by
the diffusive DIR coupler T-131 of the present invention in the amount as shown in
Table 1, the nondiffusive DIR coupler EX-5 to be incorporated was replaced by the
diffusive DIR coupler T-144 of the present invention in the amount as shown in Table
1, and the nondiffusive DIR coupler EX-5 to be incorporated in the 11th layer was
replaced by the DIR coupler T-104 of the present invention in the amount as shown
in Table 1.
Specimen 106 to 109
[0128] Specimens 106 to 109 were prepared in the same manner as in Specimen 105 except that
the diffusive DIR coupler T-131 to be incorporated in the 4th layer was replaced by
the diffusive DIR couplers T-144, T-104, T-117 and T-118 in the amounts as shown in
Table 1, respectively.
Specimen 110
[0129] Specimen 110 was prepared in the same manner as in Specimen 106 except that the diffusive
DIR coupler T-104 to be incorporated in the 10th layer was replaced by the diffusive
DIR coupler T-144 in the amount as shown in Table 1.
[0130] Specimens 101 to 110 thus prepared were then subjected to the following tests. The
results are shown in Table 1.
[0131] These specimens were measured for the MTF value at a frequency of 40 lines per 1
mm in yellow image and cyan image.
[0132] The MTF measurement method is described in T. H. James, "The Theory of the Photographic
Process", 4th Edition, Macmillan Publishing Co., 1977, pp. 604 to 607.
[0133] In order to determine the color reproducibility, particularly saturation, the ratio
of the gradation of D-log E curve obtained when exposed to light through a separation
filter to the gradation of D-log E curve obtained when exposed to white light was
calculated. The D-Iog E curve was obtained by plotting the logarithm of the exposure
(E) on the abscissa and the optical density (D) on the ordinates. The gradation is
represented by the slope of D-log E curve. The higher this ratio is, the higher is
the saturation.
[0135] Table 1 shows that the present invention provides a color negative light-sensitive
material excellent in the color reproducibility and sharpness which enables the gradation
adjustment during printing.
EXAMPLE 2
Specimen 201
[0137] Besides the above components, a surface active agent as coating aid and a film hardener
H-1 were incorporated in each layer.
[0138] Thus, Specimen 201 was prepared.
Specimen 202
[0139] Specimen 202 was prepared in the same manner as in Specimen 201 except that the nondiffusive
DIR coupler EX-20 was incorporated in the 3rd layer in the amount as shown in Table
2.
Specimen 203 to 205
[0140] Specimens 203 to 205 were prepared in the same manner as in Specimen 201 except that
the nondiffusive DIR coupler EX-20 to be incorporated in the 7th layer was replaced
by the diffusive DIR couplers T-117, T-104 and T-118 of the present invention in the
amounts as shown in Table 2, respectively.
Specimen 206
[0141] Specimen 206 was prepared in the same manner as in Specimen 203 except that the silver
halide emulsion with an average particle size of 0.20 µm to be incorporated in the
3rd layer was replaced by a silver halide emulsion with an average particle size of
0.55 µm.

[0142] Specimens 201 to 206 thus prepared were then subjected to the same tests as conducted
in Example 1. The results are shown in Table 2. Table 2 shows that the present invention
provides a color negative light-sensitive material excellent in the color reproducibility
and sharpness which enables the gradation adjustment during printing.
EXAMPLE 3
[0144] Specimens 101 to 110 and Specimens 201 to 206 were developed in accordance with the
processing methods B to and then subjected to the same tests as conducted in the preceding
examples. Almost the same results as in Examples 1 and 2 were obtained. Thus, it can
be seen that the present light-sensitive materials can accomplish the objects of the
present invention even when developed in accordance with the processing methods B
to I.
[0145] The color photographic light-sensitive material specimens thus prepared were exposed
to light, and then processed by means of an automatic developing machine in accordance
with the following method until the accumulated supply amount of the processing solution
reached 3 times the volume of the tank.
Processing method B
[0146]

[0147] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0148]

Bleaching solution
[0149]

Fixing solution
[0150]

Stabilizing solution
[0151]

Processing method C
[0152]

[0153] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0154]

Blix solution
[0155]

Rinsing solution
[0156] Tap water was passed through a mixed bed column filled with a strongly acidic H-type
cation exchange resin (Amberlite IR-120B of Rohm & Haas Co.) and an OH type anion
exchange resin (Amberlite IR-400) so that the concentration of calcium and magnesium
each reached 3 mg/ℓ or less. Sodium dichlorinated isocyanurate and sodium sulfate
were added to the solution in amounts of 20 mg/t and 1.5 g/ℓ, respectively.
[0157] The pH value of the solution thus prepared was in the range of 6.5 to 7.5.
Stabilizing solution
[0158]

Processing method D
[0159]

Color developing solution
[0160]

Blix solution
[0161] (The tank solution was used also as the replenisher.)

Rinsing solution
[0162] (The tank solution was used also as the replenisher)
[0163] Tap water was passed through a mixed bed column filled with a strongly acidic H-type
cation exchange resin (Amberlite IR-120B of Rohm & Haas Co.) and an OH-type anion
exchange resin (Amberlite IR-400) so that the concentration of calcium and magnesium
each reached 3 mg/ℓ or less. Sodium dichlorinated isocyanurate and sodium sulfate
were added to the solution in amounts of 20 mg/ℓ and 0.15 g/ℓ, respectively.
[0164] The pH value of the solution thus prepared was in the range of 6.5 to 7.5.
Stabilizing solution
[0165] (The tank solution was used also as the replenisher)

Processing method E
[0166]

[0167] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0168]

Bleaching solution
[0169]

Fixing solution
[0170]

Rinsing solution
[0171] (The tank solution was used also as the replenishe.)

Stabilizing solution
[0172] (The tank solution was used also as the replenisher.)

Processing method F
[0173]

[0174] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0175]

Bleaching solution
[0176]

Fixing solution
[0177]

Stabilizing solution
[0178] (The tank solution was used also as the replenisher.)

Processing method G
[0179]

[0180] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0181]

Bleaching solution
[0182]

Fixing solution
[0183]

Rinsing solution
[0184] (The tank solution was used also as the replenisher)
[0185] Tap water was passed through a mixed bed column filled with a strongly acidic H-type
cation exchange resin (Amberlite IR-120B of Rohm & Haas Co.) and an OH-type anion
exchange resin (Amberlite IR-400) so that the concentration of calcium and magnesium
each reached 3 mg/t or less. Sodium dichlorinated isocyanurate and sodium sulfate
were added to the solution is amounts of mg/t and 1.5 g/ℓ, respectively.
[0186] The pH value of the solution thus prepared was in the range of 6.5 to 7.5.
Stabilizing solution
[0187]

Processing method H
[0188]

[0189] The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0190]

Bleaching solution
[0191]

Blix solution
[0192]

Rinsing solution
[0193] Tap water was passed through a mixed bed column filled with a strongly acidic H-type
cation exchange resin (Amberlite IR-120B of Rohm & Haas Co.) and an OH-type anion
exchange resin (Amberlite IR-400) so that the concentration of calcium and magnesium
each reached 3 mg/ℓ or less. Sodium dichlorinated isocyanurate and sodium sulfate
were then added to the solution is amounts of 20 mg/t and 1.5 g/t, respectively.
[0194] The pH value of the solution thus prepared was in the range of 6.5 to 7.0.
Stabilizing solution
[0195]

Processing method I
[0196]

(The composition of the processing solutions used will be described hereinafter.
Color developing solution
[0197]

Bleaching solution
[0198] (The tank solution was used also as the replenisher.)
[0199]

Blix solution
[0200] (The tank solution was used also as the replenisher.)

Rinsing solution
[0201] (The tank solution was used also as the replenisher)
[0202] Tap water was passed through a mixed bed column filled with a strongly acidic H-type
cation exchange resin (Amberlite IR-120B of Rohm & Hass Co.) and an OH-type anion
exchange resin (Amberlite IR-400) so that the concentration of calcium and magnesium
each reached 3 ml/ℓ or less. Sodium dichlorinated isocyanurate and sodium sulfate
were added to the solution is amounts of mg/i and 1.5 g/ℓ, respectively.
[0203] The pH value of the solution thus prepared was in the range of 6.5 to 7.5.
Stabilizing solution
[0204] (The tank solution was used also as the replenisher.)

[0205] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.