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Description  |
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The present invention relates to a processing method applied to the
photographic silver halide material, and particularly to a color
development processing method that requires less quantity of replenisher
and provides constant stabilized photographic performances at a cheap
cost.
In case an automatic processor is used for the continuous processing of the
color photographic silver halide material (hereinafter referred to as the
"color photographic material"), a method, in which while the color
photographic material is processed the replenisher is added corresponding
to the quantity of such material to be processed has been used. In this
case, however, it is a practice at present that a very large volume of
replenisher is added, most of which overflows the tank of automatic
processor being discarded as waste. This poses a serious problem both in
the pollution control and in the cost saving.
In recent years, in the color paper processing, the replenishing volume of
color developer per 100 cm.sup.2 has been reduced by the 3HC (3-Chemical
High Concentration) process provided by Eastman Kodak Co. from the
conventional level of about 7.5 to 4.8 cc and further by the EP-2 (Ekta
Print 2) process from 4.8 to 3.2 cc. This prone toward a lower volume of
replenisher (hereinafter referred to the "lower replenishment") is
intended for the more effective pollution control and cost reduction
(i.e., reduction in the cost of chemicals for processing) by reducing the
fraction of replenisher that overflows to be discarded as the waste.
It is possible to reduce the volume of replenisher further. However, as far
as the conventional method is used, it is very difficult to achieve the
lower replenishment. The most important reason for it lies in a fact that
the color developing agent and photographic organic reagents such as the
development accelerator are less soluble in water. The bath tank is
replenished with the replenisher so the ingredients comprising the color
developer in the tank may be maintained individually at a constant
concentration. Therefore, these ingredients must be added by the
prescribed quantities regardless of the volume of replenisher used. Thus,
the smaller the volume of replenisher, the thicker individual ingredients
in the replenisher. Otherwise, the ingredients comprising the color
developing bath can not be maintained individually at a constant level.
However, since the color developing agent and photographic organic
reagents such as the development accelerator are less soluble in water as
mentioned above, it is very difficult to reduce the volume of replenisher
in the conventional method.
There is an attempt to solve this problem by adding a concentrating agent
to the color developer bath replenisher but it is not enough to solve the
essential problem of the less soluble nature of the color developing agent
and development accelerator themselves. Thus, it fails in providing a
color developing bath replenisher having desirable concentrations of
ingredients.
Another approach to this problem is to partially reuse the waste color
developer, which has overflown the tank, for the purpose of the pollution
control and cost reduction. In this case, however, it is necessary to use
a very inefficient replenishing method in which the effective ingredients
such as the color developing agent, development accelerator, and alkali
are added in a form of powder or solution to the waste color developer to
provide the color developer bath replenisher for recycling.
Further, if higher concentration is used for individual ingredients in the
replenisher, there appears a problem of a poorer performance of the
replenisher in preservation, and particularly the color developing agent
during preservation at low temperatures deposit.
Further, the lower replenishment with use of a replenisher containing
ingredients at high concentrations makes the concentrations of ingredients
in the bath to sensitively increase or decrease in response to a slight
change in the volume of replenisher. Therefore, the color photographic
material to be processed shows larger fluctuations in its photographic
performances, and particularly in its sensitivity and gamma.
It is thus highly desirable to provide a color development processing
system with lower replenishment that is cheap in the running cost and
convenient to use, requires no particular thickening of effective
ingredients in the replenisher and is still capable of providing stable
photographic performances.
We have studied color development processing system with use of a
replenisher for color developer that contains no color developing agent or
a slight quantity of such agent at most. It is possible to significantly
reduce the concentration of the color developing agent in the replenisher,
resulting in an improvement in the preservative performance of this
replenisher. Further, since a constant quantity of color developing agent
is fed from the color photographic material into the color developer bath
regardless of any increase or decrease in the volume of replenisher, the
photographic performances of the color photographic material have been
much improved in stability.
The first object of the present invention is thus to provide a color
development processing method that gives replenisher of a color developer
of superior stability in preservation and is cheap in cost.
The second object of the present invention is to provide a lower
replenishment color development processing method that is improved for
higher photographic performances and particularly for more balanced
photosensitivity and gamma in individual layers of the multi-layered color
photographic material without lowering the level of sensitivity and gamma,
and in addition capable of increasing the maximum concentration and
decreasing the stain density.
The third object of the present invention is to provide a lower
replenishment continuous color development processing method that is
improved for higher stability of photographic performances, for example,
their smaller fluctuations.
Other objects, features and advantages of the present invention will appear
more fully from the following description.
The present invention provides a new processing method to process, after an
exposure, the photographic material, which comprises at least a
photosensitive silver halide emulsion layer containing a coupler laid on a
support with a color developing agent and/or its precursor contained in
this layer or other layer or layers, for the color development while
adding replenisher for the color developer that contains 0 to 0.016 mol/1
of color developing agent.
In the present invention, it is not necessary to dissolve a large quantity
of the color developing agent into the replenisher in advance, for the
color photographic material contains the color developing agent or its
precursor as mentioned above and therefore, the color developing agent is
contained in the photosensitive material during the processing for
development and particularly during the processing of a large quantity of
photographic material.
The color developing agent or its precursor used in this invention can be
added to the photosensitive layer of silver halide emulsion that contains
a coupler, as illustrated in FIG. 1. However, it is preferable to add it
to a layer different from the silver halide emulsion layer, such as the
intermediate or protective layer, as illustrated in FIG. 2. Further, it is
more preferable to add the precursor of the color developing agent rather
than the color developing agent itself to the silver halide emulsion layer
in FIG. 1 or the intermediate or protective layer in FIG. 2 since adverse
effects, such as fogging, desensitization and staining, are thereby
reduced.
Further, another constituent layer may be provided to add the color
developing agent or its precursor. For example, the compound may be
contained in a layer provided on the backside of base as illustrated in
FIG. 3 or it may be added to a constituent layer that is provided on the
same side as the silver halide emulsion layer without overlapping it as
illustrated in FIG. 4. If the silver halide emulsion layer does not
overlap the one containing the color developing agent or its precursor as
in FIGS. 3 and 4, the objects of the present invention will be fulfiled
fully regardless of whether the color developing agent or its precursor is
used.
Namely, in the present invention, the color developing agent and/or its
precursor may be contained in one or more of the following constituent
layers:
(1) Silver halide emulsion layer itself,
(2) Layer laminated with the silver halide emulsion layer on the same side
of a support (it is not necessary that these two layers are adjacent to
each other),
(3) Layer not laminated with the silver halide emulsion layer but formed on
the same side of support as the latter layer, and
(4) Layer formed on the other side of support to the silver halide emulsion
layer.
The content of the color developing agent and/or its precursor used in the
present invention is 0.01 to 4.0 times and preferably 0.05 to 2.0 times as
much as the total silver halide content of photographic material on molar
basis per unit area. It is necessary to change the concentration of the
color developing agent in the replenisher of color developer according to
such content of the color developing agent and/or its precursor in the
color photographic material.
Further, the concentration of the color developing agent in the replenisher
of color developer used in the present invention is from 0 to 0.016 mol/1,
and preferably from 0 to 0.008 mol/1. It is preferable to lower the
concentration of the color developing agent in the above replenisher as
much as possible. Thus, the most preferable embodiment of the present
invention uses an alkali solution that does not contain the color
developing agent for replenishment. We confirmed that the replenishment
only with an alkali solution, if achieved by the method of present
invention makes the preparation and quality control of the replenisher
very easy, substantially improving the efficiency of the continuous color
development processing.
The color developing agent used in the color developer, the replenisher and
photographic material of the present invention may be one of the known
color developing agents. Preferable examples of the color developing agent
are primary aromatic amines or salts of such amines with inorganic acids,
such as hydrochloric acid, sulfuric acid and phosphoric acid, or salts of
such amines with organic sulfonic acids of low molecular weight, such as
benzenesulfonic acid and p-toluenesulfonic acid. p-phenylenediamines and
p-aminophenols can be cited as typical examples of the preferable color
developing agent.
Precursors of color developing agent contained in the photographic material
of the present invention are, for example, Shiff bases of the U.S. Pat.
No. 3,342,599 formed between primary aromatic amine developing agents and
salicylaldehydes, addition products of U.S. Pat. No. 3,719,492 formed
between primary aromatic amines and metal salts, such as lead and cadmium
salts, precursors in a form of phthalimide of British Pat. No. 1,069,061
formed by reacting primary aromatic amines and phthalic acid, precursors
of Japanese Patent Publication Open to Public Inspection No. 135,628/1978
formed by binding .beta.-(benzenesulfonyl)ethoxycarbonyl to primary
aromatic amines, precursors of Japanese Patent Publication Open to Public
Inspection No. 79,035/1979 formed by binding .beta.-cyanoethoxycarbonyl to
primary organic amines, precursors of Japanese Patent Application No.
82,175/1979 formed by adding tetraphenylboron to primary aromatic amines,
and precursors of Japanese patent application No. 92,014/1979 formed by
adding long-chained monoalkylsulfuric acid esters to primary aromatic
amines.
Further, West German Pat. Nos. 1,159,758 and 1,200,679, and U.S. Pat. No.
3,705,035 are known in this respect.
These precursors are released from the photographic material into the color
developer bath as they are dissolved by alkali or their molecules are
cleaved under the action of alkali. Among the color developing agents or
their precursors that can be used in the present invention, it is more
preferable for the objects of the invention to select those that are
released in larger quantities from the photographic material into the
color developer bath. Primary aromatic amine developing agents that are
well suited to the objects of the present invention are expressed by the
following general formula:
##STR1##
In the above formula, R.sub.1, R.sub.2 and R.sub.3 represent individually
a hydrogen atom or substituted or unsubstituted alkyl group including 1 to
4 carbon atoms.
Actual examples of the primary aromatic amine developing agent that is well
suited to the objects of the present invention are given below:
______________________________________
No. Chemical formula
______________________________________
1.
##STR2##
2.
##STR3##
3.
##STR4##
4.
##STR5##
5.
##STR6##
6.
##STR7##
7.
##STR8##
8.
##STR9##
9.
##STR10##
10.
##STR11##
##STR12##
##STR13##
##STR14##
##STR15##
##STR16##
##STR17##
##STR18##
##STR19##
##STR20##
20.
##STR21##
##STR22##
##STR23##
##STR24##
##STR25##
______________________________________
The color developing agent or its precursor used in this invention can be
dissolved in a hydrophilic organic solvent, such as methyl alcohol, ethyl
alcohol, or acetone, for direct dispersion into a hydrophilic colloid
solution or it can be dispersed in a hydrophilic colloid solution using
latex or some other polymer or by an oil/water emulsion type dispersion
method. For the oil used in the oil/water emulsion type dispersion method,
there are oils used for dissolving the coupler in the oil protect type
photographic material. They are, for example, tri-o-cresyl phosphate,
trihexyl phosphate, dioctyl butyl phosphate, dibutyl phthalate, diethyl
laurylamide, 2,4-diarylphenol, and octyl benzoate.
To disperse the oil phase in which such agent or/its precursor is dissolved
into the water phase, a usual surfactant is used. Examples of such usual
surfactant are anionic surfactants containing acidic groups, such as
carboxylate, sulfonate, phosphate, sulfate ester, and phosphate ester
groups, nonionic surfactants, cationic surfactants and amphoteric
surfactants.
For the hydrophilic colloid, gelatin and other materials that are known as
the photographic binder are used. For example, use is made of gelatin
derivatives, graft polymers made from gelatin and some other high
polymers, cellulose derivatives, such as hydroxyethyl cellulose,
carboxylmethyl cellulose, and cellulose sulfate ester, sodium alginate,
derivatives of starch, and many hydrophilic synthetic polymers and
copolymers such as partial acetal of polyvinyl alcohol,
poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. Latex, may also
be used. Examples are the compounds as described in U.S. Pat. No.
3,518,088 and Research Disclosure No. 148-14850 (1976).
Further, a known photographic antioxidant or stabilizer may be added to the
present emulsion. For example, derivatives of hydroquinone, reductones of
ascorbic acid, etc., hydroxylamines, sulfonyl compounds, and active
methylene compounds may be added.
To process the photosensitive material for color development in the present
invention, the conventional color developer is used. The pH of this
developer is set between about 7 and 14 and preferably between about 8 and
13. The temperature of developer is selected between 20.degree. C. and
70.degree. C. and preferably between 25.degree. C. and 55.degree. C. Color
developing agent is contained in the color developer in an amount of
1/500.about.3/100 mol/l.
For the buffering agent used in the color developer, sodium hydroxide,
potassium hydroxide, sodium carbonate, potassium carbonate, tertiary
sodium or potassium phosphate, potassium metaborate, borax, etc. are used
singly or in combination. Further, for addition of a buffering action,
convenience of preparation, or higher ionic strength, disodium or
dipotassium hydrogen phosphate, sodium or potassium dihydrogen phosphate,
sodium or potassium bicarbonate, boric acid, alkali nitrate, alkali
sulfate and other salts may be used.
Beside, a proper quantity of a fog restrainer may be added. Examples of
such fog restrainer are inorganic halides or known organic antifoggants.
Beside, an arbitrary development accelrator may be added in combination as
necessary.
In addition, benzyl alcohol and phenethyl alcohol as described in U.S. Pat.
No. 2,304,925, and pyridine, ammonia, hydrazine, and amines are also
effective development accelerators depending on purposes.
For the auxiliary developing agent, N-methyl-p-aminophenol hemisulfate
(common name: Metol), benzyl-p-aminophenol hydrochloride,
N,N-diethyl-p-aminophenol hydrochloride, p-aminophenol sulfate, phenidone,
N,N,N',N-tetramethyl-p-phenylenediamine hydrochloride, etc. may be used.
The preferable added quantity is usually between 0.01 and 1.0 g/l.
For the fogging agents, such as alkali metal polyhydride, aminoborane, or
ethylenediamine, particularly, those compounds as described in Japanese
Patent Publication No. 38,816/1972 may be employed in a color developer
for a direct positive photographic material.
The color developer bath replenisher of the present invention may be
formulated with use of the compounds as used in the above color developer.
The concentration of the color developing agent in the replenisher is 0 to
0.016 mol/l and preferably 0 to 0.008 mol/l, which changes depending on
the quantity of the color developing agent or its precursor contained in
the photographic material. Most preferably, the photographic material
itself contains all the necessary quantity of the color developing agent
and/or its precursor consumed in the color developing reaction. In this
case, the concentration of the color developing agent in the replenisher
may practically vanish, so the quality control of the replenisher is much
simplified.
For the pH value of the replenisher of this invention, the full pH range
may be used. In case of acidic pH, however, an additional labor of
separately replenishing with an alkali solution is necessary. Therefore,
the preferable pH range being from 8.5 to 13.0.
Replenishing amount depends on primarily color photographic material and
generally is about 0.5.about.5.0 cc/100 cm.sup.2 of color photographic
material, preferably 0.8 3.0 cc/100 cm.sup.2.
The color developing agent or its precursor used in the photosensitive
material of the present invention may be applied both to the general color
photographic material, such as the nega color film, color paper, positive
color film, and color reversal film, and to the direct positive type color
photographic material.
Further, such color developing agent or its precursor may also be applied
to the black and white photosensitive halide material together with the
coupler for the black dye formation. In this case, a reduction in the
quantity of silver halide may be achieved.
The photographic material of the present invention contains in the layer of
photosensitive emulsion a so-called coupler or a compound that reacts with
the oxidized color developing agent to form a dye. This coupler has a
molecular structure that prevents it from dispersing into other layer or
layers during the manufacturing process or processing process.
For the yellow coupler, generally, open-chained diketomethylene compounds
are widely used. Examples are given in U.S. Pat. Nos. 3,341,331, 2,875,057
and 3,551,155, West Germany OLS Pat. No. 1,547,868, U.S. Pat. Nos.
3,265,506, 3,582,322, and 3,725,072, West Germany OLS Pat. No. 2,162,899,
U.S. Pat. Nos. 3,369,895 and 3,408,194, West Germany OLS Pat. Nos.
2,057,941, 2,213,461, 2,219,917, 3,261,361, and 2,263,875.
For the magenta coupler, 5-pyrazolone compounds are primarily used through
indazolone compounds and cyanoacetyl compounds may also be used. Examples
are given in U.S. Pat. Nos. 2,439,098, 2,600,788, 3,062,653 and 3,558,319,
British Pat. No. 956,261, U.S. Pat. Nos. 3,582,322, 3,615,506, 3,519,429,
3,311,476, and 3,419,391, Japanese Patent Application Nos. 21,454/1966 and
56,050/1973, West German Pat. No. 1,810,464, Japanese Patent Publication
No. 2,016/1969, Japanese patent application No. 45,971/1973, U.S. Pat. No.
2,983,608, etc.
For the cyan coupler, derivatives of phenol or naphthol are primarily used.
Examples are given in U.S. Pat. Nos. 2,369,929, 2,474,293, 2,698,794,
2,895,826, 3,311,476, 3,458,315, 3,560,212, 3,582,322, 3,591,383,
3,386,301, 2,434,272, 2,706,684, 3,034,892, and 3,583,971, West German OLS
Patent No. 2,163,811, Japanese patent publication No. 28,836/1970,
Japanese patent publication No. 33,238/1973, etc.
In addition, a development inhibitor releasing coupler (so-called DIR
coupler) or a compound capable of releasing a development inhibitor during
the color development reaction may be added.
For the above DIR coupler or the like, two types may by used in the same
layer to satisfy the characteristic requirements for the photosensitive
material. It is a matter of course that the same compound is used in 2 or
more different layers.
Further, the photographic material of the present invention may contain a
black dye forming coupler as disclosed in West Germany OLS Pat. No.
2,644,194 and Japanese Patent Application No. 70,471/1978.
The halide emulsion used in the photographic material of the present
invention is prepared by an ordinary method, which may be formulated using
any of silver chloride, bromide, chlorobromide, iodobromide, and
chloroiodobromide. Such halide emulsion may be chemically sensitized by an
ordinary method. Further, a photosensitive dye, antifoggant, hardening
agent, plasticizer, surfactant, and other additives of common use may be
added to such emulsion.
For the base used to support layers in the photosensitive material of the
present invention, cellulose film, plastic film, as well as glass, paper,
laminated products, and further polymer-laminated paper are useful.
An antifoggant to suppress fogging of the halide may be added in the
photosensitive layer of the photosensitive material. Typical examples of
the useful antifoggant are heterocyclic organic compounds, such as
tetrazole, azaindene, and triazole, and aromatic or heterocyclic compounds
having a mercapto group or groups.
The layers of the photosensitive material of the present invention may
contain a hardening agent, plasticizer, lubricant, surfactant, brightener,
and other additives that are usually used in the technical field of
photography.
In the photographic emulsion, cyanine dyes, such as cyanine, merocyanine,
hemicyanine, may be used singly or in combination with themselves or
styryl dyes for spectral sensitization or supersensitization as necessary.
The photographic emulsion as mentioned above is coated on a plane material
that shows no remarkable changes in dimensions during processing.
The invention will now be described more fully referring to the following
examples.
EXAMPLE 1
A surface of a resin-coated paper base was coated with the following
layers, successively in the order of description, to prepare Samples I and
II.
Preparation of Sample I
Layer 1--Layer of yellow color forming blue-sensitive halide emulsion.
A coupler
.alpha.-(1-benzyl-2,4-dioxo-3-imdazolidinyl)-.alpha.-bivalyl-2-chloro-5-[.
alpha.(2,4-di-t-amylphenoxy)butylamido]acetoanilide is dissolved in
dibutylphthalate (hereinafter called "DBP") and then dispersed in an
aqueous gelatine solution. The dispersed solution was added to a
chloroiodobromide emulsion containing 1 mol% of iodide and 80 mol% of
bromide. The coating was conducted to a thickness that corresponded to a
quantity of silver and coupler of 420 mg/m.sup.2 and 562 mg/m.sup.2,
respectively.
Layer 2--Intermediate layer (gelatine layer 1.mu. thick).
Layer 3--Layer of green-sensitive halide emulsion.
A magenta coupler
1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyr
azolone is dissolved in tricresy phosphate (hereinafter called "TCP") and
then dispersed in an aqueous gelatine solution. The dispersed solution was
added to a chlorobromide emulsion containing 30 mol% of bromide. The
coating was conducted to a thickness that corresponded to a quantity of
silver and coupler of 580 mg/m.sup.2 and 684 mg/m.sup.2, respectively.
Layer 4--Intermediate layer (gelatine layer 1.mu. thick).
Layer 5--Layer of cyan color forming red-sensitive halide emulsion.
A cyan coupler
2,4-dichloro-3-methyl-6-[.alpha.(2,4-di-t-amylphenoxy)butylamido]phenol
was dissolved in TCP and then dispersed in an aqueous gelatine solution.
The dispersed solution was added to a chlorobromide emulsion containing 80
mol% of bromide. The coating was conducted to a thickness that
corresponded to a quantity of silver and coupler of 520 mg/m.sup.2 and 458
mg/m.sup.2, respectively.
Layer 6--Protective layer (gelatine layer 1.mu. thick).
Each of Layers 1, 3 and 5 contained a stabilizer sodium salt of
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, a hardening agent
bis(vinylsulfonylmethyl)ether, and a coating aid saponin.
Preparation of Sample II
A compound No. 13 was dissolved in dioctylphthalate and then dispersed in
an aqueous gelatine solution. The dispersed solution was added to the
emulsions prepared for Layers 4 and 6 of Sample I and the coating was made
with these emulsions to provide Layers 4 and 6 of Sample II in a thickness
corresponding to a quantity of the compound of 250 mg/m.sup.2. Other
layers were formed just in the same method as applied to Sample I.
Strips, each 10,000 m long and 82 mm wide, were cut from both of Samples I
and II. A camera was loaded with a color nega film for shooting at ASA
100. The film was processed for color development. Using the developed
negative, the cut s-rips were uniformly exposed to the shot image in an
automatic color printer and processed using an automatic processor as
follows:
Color developing (21/2 min)--Bleach-fixing (11/2 min)--Washing (31/2
min)--Drying.
The processing temperature was set to 33.degree. C. at individual steps
while the processing aqueous solutions were formulated as follows:
Formulation of the color developer (aqueous):
______________________________________
Concentration (g/l)
Tank Replenishing
Replenishing
Compound solution solution I solution II
______________________________________
Potassium carbonate
26 30 30
Aqueous
60% 1-hydroxy-
0.9 1.1 1.1
ethylidene-1,1-
diphosphonic acid
Potassium sulfite
20 2.5 2.5
Ethylene glycol
16 20 20
Brightening agent-
1.6 2.0 2.0
derivative of 4,4'-
diaminostilbenephos-
phonic acid
Hydroxylamine sulfate
3.2 4.0 4.0
Potassium bromide
0.64 0 0
Potassium chloride
0.50 0 0
4-amino-3-methyl-N,N-
2.7 2.7 0
diethylaniline
hydrochloride
pH (adjusted with 10.20 10.40
potassium hydroxide)
______________________________________
The replenishing solution was added 26.5 ml per 1 m of sampel strip. The
tank solution in the above table corresponded to a solution with which the
automatic processor was filled from the beginning (the same applies
hereinafter).
The replenishing solutions I and II were used for the continuous processing
of Samples I and II, respectively, for color development. It is noted that
the replenishing solution II did not contain the color developing agent
4-amino-3-methyl-N,N-diethylaniline hydrochloride at all.
Formulation of bleach-fix bath (aqueous):
______________________________________
Concentration (g/l)
in tank solution &
Compound replenishing solution
______________________________________
Ethylenediaminetetraacetic acid
65
ferric ammonium salt
Aqueous 50% ammonium sulfite
15
Aqueous 60% ammonium thiosulfate
160
Ethylenediaminetetraacetic acid
40
sodium salt
pH (adjusted with ammonia water)
7.1
______________________________________
The replenishing solution of the above formulation was added 26.5 ml per 1
m of sample strip.
Washing:
8.28 ml of water was run per 1 m of sample strip.
To see the photographic performances, the wedge exposed parts of the above
Samples I and II were processed at the start and at the end of 10,000 m
processing, respectively.
The processed samples were compared in Table 1 for fogging, relative
sensitivity and maximum development density in yellow (Y), magenta (M) and
cyan (C). The relative sensitivity was estimated by comparison to the
sample I processed at the start of processing whose sensitivity in Y, M
and C was taken 100, respectively.
It is found from Table 1 that there was more fogging in Sample I at the end
than at the start of processing. The replenishing solution I used for the
continuous processing of Sample I was nearly saturated with the color
developing agent 4-amino-3-methyl-N,N-diethylaniline hydrochloride, which
separated gradually in a oily form as the solution was left to stand at
ambient temperature several days or several weeks after it preparation.
The separated oily color developing agent was liable to air oxidation
being gradually darkened. It was found that there was more fogging in
Sample I as the above changes gradually proceeded. Further, a slight
desensitization was also detected.
TABLE 1
__________________________________________________________________________
Relative Maximum color
Processing
Fogging sensitivity
density
timing
Y M C Y M C Y M C
__________________________________________________________________________
Sample I
At start
0.06
0.07
0.06
100
100
100
2.45
2.44
2.46
(not covered
by the At end
0.17
0.19
0.14
94
96
97
2.42
2.39
2.43
invention
Sample II
At start
0.06
0.07
0.06
100
100
100
2.47
2.46
2.46
(covered by
the invention
At end
0.06
0.07
0.06
99
101
100
2.47
2.45
2.45
__________________________________________________________________________
By contrast, the replenishing solution II used for the continuous
processing of Sample II contained no color developing agent, so it did not
show such separation of dark oily color developing agent as observed with
the replenishing solution I. Thus, the replenishing solution II could
always be kept at a transparent state even during a long term storage. As
a result, the photographic performances exhibited at the start of
processing Sample II differed almost nothing from those at the end of such
processing and it was found that a practically constant level of
photographic performances were always available.
EXAMPLE 2
Successive layers were formed as in Example 1 but for Layer 4 to which the
compound No. 13 was added to a quantity of 250 mg/m.sup.2. Sample III was
thus prepared.
Strips, 10,000 m long and 82 mm wide, were cut from Sample III and exposed
just in the same way as in Example 1. The replenishing solution III used
for the continuous processing of Sample III was formulated as follows:
Formulation of the replenishing solution III:
______________________________________
Compound Concentration (g/l)
______________________________________
Potassium carbonate 30
Aqueous 60% 1-hydroxyethylidene-
1.1
1,1-diphosphonic acid
Potassium sulfite 2.5
Ethylene glycol 20
Brightening agent - derivative of
2.0
4,4'-diaminostilbenediphosphonic acid
Hydroxylamine sulfate 4.0
Potassium bromide 0
Potassium chloride 0
4-amino-3-methyl-N,N-diethylaniline
1.4
hydrochloride
pH (adjusted with potassium hydroxide)
10.40
______________________________________
The replenishing quantity was just the same as in Example 1.
The bleach-fix bath was also prepared in the same formulation as the one
used in Example 1.
The replenishing solution III contained the color developing agent at a
concentration substantially below the saturation level, so any separation
of dark oily color dveloping agent as observed in the replenishing
solution I was not identified. Therefore, like Sample II, Sample III also
gave favorable results.
EXAMPLE 3
Preparation of Sample IV:
A transparent cellulose triacetate film base was undercoated to give a
hydrophilic property. The base was then successively coated with layers A
to H of hydrophilic colloids as described below in the order of
description and dried to give a multi-layered color nega photosensitive
material:
Layer A--Antihalation layer
The base was coated with a gelatine solution in which grey colloidal silver
was dispersed to a thickness corresponding to 1.8 g/m.sup.2 of gelatine
and 250 mg/m.sup.2 of grey colloidal silver.
Layer B--Intermediate layer
An intermediate gelatine layer was formed by coating next to the
antihalation layer to a thickness corresponding to a quantity of gelatine
of 1.2 g/m.sup.2.
Layer C--Cyan color forming layer
A cyan colorless coupler
1-hydroxy-N-[.alpha.-2,4'-di-tert-amylphenoxy)butyl]-2-naphthoamide, cyan
colored coupler 1-hydroxy-4-(2'-acetyl-phenylazo)-N-[.alpha.-2",
4"-di-tert-amylphenoxy)butyl]-2-naphthamide, and DIR compound
2-(1-phenyl-5-tetraazolylthio)-4-(2,4-di-t-amylphenoxyacetamide)-1-iredano
ne were dissolved in a coupler solvent that was made red-sensitive by the
use of a panchrmoatic sensitizing dye and composed of tri-o-cresyl
phosphate. The solution was dispersed in gelatine solution using an
anionic surfactant as the dispersing aid to give a photosensitive
iodobromide gelatine emulsion. The coating was conducted to a thickness
corresponding to 4.0 g gelatin, 3.5 g silver, 1.1 g colorless coupler,
0.32 g colored coupler, and 0.11 g DIR compound per 1 m.sup.2.
Layer D--Intermediate layer
2,5-di-sec-dodecyl-hydroquinone, a compound to inhibit any interlayer
diffusion of the oxidation products of the color developing agent was
dissolved in di-n-butyl phthalate and then dispersed in gelatine solution.
The coating was made next to the cyan color forming layer to a thickness
corresponding to a quantity of gelatine of 1.2 g/m.sub.2 and diffusion
inhibitor compound of 0.15 g/m.sup.2.
Layer E--Magenta color forming layer
A magenta colorless coupler
1-(2,4,6-trichlorophenyl)-3-3-]-(2,4-di-tert-amylphenoxy-acetamido]benzami
do-5-pyrazolone, magenta colored coupler 1-(2,4,6-trichlorophenyl)-3
3-[-(2,4-di-tert-amulphenoxy)acetamido]benzamido-4-(p-methoxyphenylazo)-5-
pyrazolone and DIR compound
2-(1-phenyl-5-tetraazolylthio)-4-(2,4-di-t-amylphenoxyacetamido)-1-indanon
e were dissolved in a coupler solvent that was made green-sensitive by the
use of an orthochromic sensitizing dye and composed of tri-o-cresyl
phosphate. The solution was dispersed in gelatine solution using a
dispersing aid to give a photosensitive iodobromide emulsion. The coating
was conducted to a thickness corresponding to 4.0 g of gelatine, 3.0 g of
silver, 1.1 g of cololess coupler, 0.37 g of colored coupler and 0.11 g of
DIR compound per 1 m.sup.2.
Layer F--Yellow filter layer.
Using a gelatine emulsion, in which yellow colloidal silver and
2,5-di-sec-dodecyl-hydroquinone, a compound to prevent any interlayer
diffusion of the oxidized form of color developing agent and to inhibit
any staining due to such oxidation products, dissolved in di-n-butyl
phosphate were dispersed, the coating was made to a thickness
corresponding to 1.5 g of gelatine, 0.10 g of yellow colloidal silver and
0.2 g of hydroquinone derivative per 1 m.sup.2.
Layer G--Yellow color forming layer.
A yellow coupler
3-benzoylacetamino-4-methoxy-(2,',4'-di-tert-amylphenoxy)acetanilide was
dissolved in di-n-butyl phthalate and then dispersed in a blue-sensitive
iodobromide emulsion. The coating was conducted to a thickness
corresponding to 3.5 g of gelatine, 1.5 g of silver and 2.5 g of yellow
coupler per 1 m.sup.2.
Layer H--Protective layer.
The coating was made with gelatine solution to a thickness corresponding to
a quantity of gelatine of 1.2 g/m.sup.2.
Each of Layers A to H contained a coating aid and gelatine hardening agent.
Preparation of Sample V:
After preparation of Sample IV, the other side of the cellulose triacetate
film base that was opposite to the emulsion layers was undercoated to give
a hydrophilic property. It was then successively coated with Layers I and
J of hydrophilic colloid as described below in the order of description
and dried to give Sample V.
Layer I--Layer containing a color developing agent.
A color developing agent 3-methyl-4-amino-N-ethyl-N-(-hydroxyethyl)aniline
sulfate was dissolved in a gelatine solution and the pH was adjusted to
5.5. The coating was made to a thickness corresponding to 5.0 g of
gelatine and 4.7 g of color developing agent per 1 m.sup.2.
Layer J--Protective layer.
The coating was made with gelatine solution to a thickness corresponding to
a quantity of gelatine of 1.2 g/m.sup.2.
The above Samples IV and V were cut 35 mm wide. The image shooting was made
at an exposure condition of ASA 100. Individual sample strips 10,000 m
long were processed as specified below in the automatic processor while
making up the processing solution for development. It is noted that the
replenishing solutions IV and V were those used in the continuous color
development of Samples IV and V, respectively, the latter replenishing
solution not containing the color developing agent
4-amino-3-methyl-N-ethyl-N-(-hydroxyethyl)aniline sulfate at all.
Processing condition:
Color development (31/4 min)--Bleaching (61/2 min)--First washing (31/4
min)--Fixing (61/2 min)--Second washing (31/4 min)--Stabilization (11/2
min).
The processing temperature was set to 38.degree. C. at individual steps and
the processing solutions used were formulated as follows:
Formulation of the color developing solution (aqueous):
______________________________________
Concentration (g/l)
Tank Replenishing
Replenishing
Compound solution solution IV
solution V
______________________________________
Potassium carbonate
30 36 36
Potassium sulfite
3 5 5
Sodium bromide
1.2 0 0
Potassium iodide
0.002 0 0
Hydroxylamine sulfate
3 4.3 4.3
3-methyl-4-amino-N-
4.8 7.5 0
ethyl-N-
(-hydroxyethyl)aniline
sulfate
pH (adjusted w | | |
