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Description  |
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This invention relates to a process for forming a dye photographic image
which may be of the yellow, magenta or cyan nature. More particularly, the
invention is concerned with a process for forming such dye photographic
image, which is favorable in light absorption characteristic and excellent
in fastness, by subjecting a light-sensitive silver halide photographic
material to color development with an aromatic primary amine type
developing agent in the presence of a novel yellow, magenta or cyan
coupler.
Generally, the formation of a color photographic image according to
subtractive color photography is carried out by subjecting a
light-sensitive silver halide color photographic material to color
development by use of an aromatic primary amine type developing agent in
the presence of yellow, magenta and cyan couplers. In this case, silver
halide particles of the photographic material, which have been exposed to
light, are reduced by means of the developing agent, and the oxidation
product of the developing agent, which has been formed at the same time,
couples with the couplers to give a color photographic image composed of
yellow, magenta and cyan dyes.
Each of the above-mentioned couplers may be incorporated into either of a
silver halide photographic emulsion or a color developer. Generally, a
light-sensitive silver halide photographic material, which has been
incorporated with the couplers, is called an internal type photographic
material, while that which is to be processed with a color developer
incorporated with the couplers, is called an incorporated type
photographic material.
The yellow dye photographic image of a color photograph has absorbed a blue
light in the wavelength region of about 400-500 m.mu., the magenta dye
photographic image of a color photograph has absorbed a green light in the
wavelength region of about 500-600 m.mu., and the cyan dye photographic
image of a color photograph has absorbed a red light in the wavelength
region of about 600-700 m.mu..
For the purpose, in general, the yellow couplers used are those having an
open chain active methylene group, the magenta couplers are those having a
pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole or indazolone
nucleus, and the cyan couplers used are those having a phenolic hydroxyl
group.
The couplers to be used are preferably compounds which not only form a dye
image but also have such various characteristic properties that, for
example, they are favorable in color: developability, are high in
solubility in alkalis, water and organic solvents, are high in
dispersibility and stability in silver halide photographic emulsions, and
can form a dye which is fast to light, heat, humidity and the like, are
capable of light absorption over a desirable wavelength region and are
high in transparency and color density.
Although many investigations concerning couplers having the above-mentioned
properties have been made hitherto, the actual technical state is such
that no desirable coupler capable of satisfying all the above-mentioned
characteristic properties has been found yet.
An object of the present ivention is to provide a novel coupler which has
such desirable properties required for couplers as mentioned previously
and which is suitable for forming a color photographic image according to
substractive color photography, and to provide a process for forming a dye
image desirable for a color photograph by developing a light-sensitive
silver halide photographic material in the presence of one of said
couplers.
The above-mentioned object can be accomplished by subjecting a
light-sensitive silver halide photographic material to color development
using an aromatic primary amine type developing agent in the presence of,
as a yellow, magenta or cyan coupler, a compound having a
monohydro-polyfluoroalkyl group which is represented by the general
formula,
A -- C.sub.n F.sub.2n H
wherein A is the residue of coupler which may be of the yellow, magenta or
cyan nature and n is a positive integer of 1 to 18, provided that when A
is a cyan coupler residue and n is an even number of 2 to 10, the hydrogen
atom of --C.sub.n F.sub.2n H being at the .omega.-position, the terminal
group of the cyan coupler residue to which the --C.sub.n F.sub.2n H group
is bound should not be a --NHCO group (while the --C.sub.n F.sub.2n H
group is bound to the side of the CO radical of the cyan coupler).
The coupler of the above-mentioned general formula (hereinafter referred to
as the coupler of the present invention) is characterized by having in its
molecular structure a monohydro-polyfluoroalkyl group having a hydrogen
atom at the terminal, and can display various characteristic properties by
virtue of the presence of said group. Further, the
monohydropolyfluoroalkyl group may be introduced into any position of the
coupler structure. For instance, said group may be present in a split-off
group if a coupler has such split-off group which can be liberated during
the development.
That is, the coupler of the present invention is favorable in solubility in
water, alkalis and organic solvents, in dispersion stability in
photographic emulsions, and in color developability, and gives by color
development a yellow, magenta or cyan dye image which is high in maximum
color density, has a light absorption in a desirable wavelength region, is
favorable in transparency and is excellent in fastness to light, heat and
humidity.
On the other hand, U.S. Pat. No. 2,772,162 has taught that a coupler having
a perfluoroalkylcarbonamido group has such characteristic as being
particularly excellent in heat resistance. The coupler of the present
invention has an alkyl-group in which many fluorine atoms have substituted
for hydrogens, and hence is also excellent in heat resistance. In addition
to such advantage in heat resistance, however, a coupler of the present
invention is specifically excellent in solubility in usual solvents for
couplers, this resulting from the existence of one hydrogen atom in its
molecular structure. Further, such a coupler of the invention where a
monohydro-polyfluoroalkyl group is introduced into a position near the
dye-forming nucleus of the coupler characteristically shifts the
absorption wavelength region of the formed dye toward the longer
wavelength side. Still further, a coupler of the present invention has
better absorption characteristic and excellent in color reproduction when
it is a yellow coupler, has better color developability with higher
maximum density when it is a magenta coupler, and has particularly
excellent solubility when it is a cyan coupler, all these being derived
from the particular feature of the invention, that is the existence of a
monohydro-polyfluoroalkyl group.
The couplers of the present invention include those which are soluble in
water, alkalis or oils, and those of the internal type which are to be
incorporated into silver halide photographic emulsions and of the
incorporated type which are to be incorporated into color developers, and
the kinds thereof are decided according to the kinds of groups which are
introduced into the dye-forming nuclei.
Typical examples of the yellow couplers of the present invention are shown
below.
##STR1##
Typical examples of the magenta couplers of the present invention are shown
below.
##STR2##
Typical examples of the cyan couplers of the present invention are shown
below.
##STR3##
Procedures for synthesizing typical couplers of the present invention are
explained below with reference to synthesis examples.
SYNTHESIS EXAMPLE 1
Synthesis of Coupler (2)
1-(1) Synthesis of .omega.-monohydro-octafluoropentanoyl chloride:
74 Grams of .omega.-monohydro-octafluoropentanoic acid (synthesized
according to the method disclosed in U.S. Pat. No. 2,559,629) is gradually
added dropwise into 62.4 g. of phosphorus pentachloride, and the resulting
mixture is reacted at 90.degree. C. .+-. 10.degree. C. for one hour,
whereby a colorless transparent liquid reaction mixture is obtained. This
reaction mixture is distilled at atmospheric pressure to obtain 54 g. of
the end product which is a colorless liquid having a boiling point of
89.degree. to 93.degree. C.
1-(2) synthesis of the Coupler (2):
26 Grams of the .omega.-monohydro-octafluoropentanoyl chloride obtained in
the above-mentioned step 1-(1) is added dropwise at room temperature over
a period of 30 minutes to a solution comprising 27 g. of
.alpha.-pivalyl-2-chloro-5-amino-acetanilide and 150 ml of CH.sub.3 CN,
and the resulting mixture is stirred in a bath at the outside bath
temperature of 70.degree. to 80.degree. C. for 3 hours. Subsequently, the
liquid reaction mixture is concentrated and the residue is poured into a
ethanol-water (1:1) solvent mixture to deposit precipitates, which are
then collected by filtration and dried under reduced pressure to obtain
the end product consisting of white crystals having a melting point of
133.degree. to 135.degree. C.
SYNTHESIS EXAMPLE 2
Synthesis of Coupler (1)
Exactly the same procedure as in 1-(1) of Synthesis Example 1 is repeated,
except that 29 g. of .alpha.-benzoyl-2-chloro-5-amino-acetanilide and 26
g. of .omega.-monohydro-octafluoropentanoyl chloride are used. Finally,
the concentrated residue is poured into a ethanol-water (1:1) solvent
mixture to deposit precipitates, which are collected and dried under
reduced pressure. Thereafter, the precipitates are recrystallized from
carbon tetrachloride to obtain 38 g. of the end product consisting of
white crystals having a melting point of 104.degree. to 107.degree. C.
SYNTHESIS EXAMPLE 3
Synthesis of Coupler (14)
Exactly the same procedure as in 1-(2) of Synthesis Example 1 is repeated,
except that 21 g. of
.alpha.-(2-chloro-3-amino)-benzoyl-4-dodecyloxyacetanilide and 13 g. of
.omega.-monohydro-octafluoropentanoyl chloride. Finally, the concentrated
residue is recrystallized from methanol to obtain 17 g. of the end
product.
SYNTHESIS EXAMPLE 4
Synthesis of Coupler (25)
16.4 g of .omega.-monohydro-tetrafluoropropionyl chloride obtained
according to the procedure similar to that of 1-(1) of Synthesis Example 1
is added to a solution comprising 27.8 g. of
1-(2,4,6-trichlorophenyl)-3-amino-5-pyrazolone, 150 ml of CH.sub.3 CN and
5 ml of pyridine, and the resulting mixture is reacted by heating. The
reaction mixture is poured into water to deposit crystals, which are
recrystallized, after drying, from CH.sub.3 CN to obtain 20 g. of the end
product consisting of white crystals having a melting point of 221.degree.
to 223.degree. C.
SYNTHESIS EXAMPLE 5
Synthesis of Coupler (30)
A mixture comprising 20.2 g. of
1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-amino-anilino)-5-pyrazolone, 200
ml of CH.sub.3 CN and 13.2 g. of .omega.-monohydro-octafluoropentanoyl
chloride is reacted by heating for 3 hours. The liquid reaction mixture is
concentrated and heated to dryness. The dried residue is recrystallized
from a n-hexane-ethanol (4:1) solvent mixture to obtain 14 g. of the end
product consisting of white crystals having a melting point of 201.degree.
to 203.degree. C.
As mentioned previously, the couplers of the present invention include
those which are soluble in water, alkalis and oils. Among the water- and
alkali-soluble couplers, those which are of the type having
diffusion-preventing groups can be dispersed and incorporated according to
the so-called Fischer's dispersion method into silver halide photographic
emulsions. Examples of the couplers belonging to this type are the
aforesaid coupler (19). On the other hand, those which are of the type
having no diffusionpreventing groups are incorporated into color
developers and can be used for the processing of light-sensitive silver
halide color photographic materials of the incorporated type. Examples of
the couplers belonging to this type are the aforesaid couplers (1), (2)
and (25). Further, the oil-soluble couplers are dissolved as oil-protected
type couplers in high boiling point organic solvents and may be dispersed
and incorporated into silver halide photographic emulsions.
For incorporation into light-sensitive silver halide photographic materials
of, for example, the oil-protected type couplers among those of the
present invention, there may be adopted any of the known procedures. For
example, one or more of the couplers are dissolved in one, or if necessary
both, of a high boiling solvent having a boiling point of more than
175.degree. C. such as tricresyl phosphate or dibutyl phthalate, and a low
boiling solvent such as butyl acetate or butyl propionate. Thereafter, the
resulting solution is mixed with an aqueous gelatin solution containing a
surfactent, and then emulsified by means of a high speed rotary mixer or a
colloid mill to form an emulsion. This emulsion is incorporated directly
into a silver halide photographic emulsion, which is then coated on a
support including glass plates, synthetic resin plates, various film
bases, baryta papers and polyethylene laminate papers, and is then dried
to remove a major proportion of the low boiling solvent, whereby a
light-sensitive silver halide photographic material can be prepared.
Alternatively, the said emulsion is once set, finely cut (extruded into
the form of noddles) and subsequently freed from the low boiling solvent
by water-washing or the like means, and the thus treated emulsion is
incorporated into said photographic emulsion, which is then coated on said
support and dried, whereby a light-sensitive silver halide photographic
material can be obtained.
The above-mentioned incorporation procedure is merely an example, and it is
needless to say that the manner of incorporation of the coupler of the
present invention is not limited to the above.
In the above case, the amount of the coupler to be incorporated into the
emulsion is preferably in the range from 10 to 100 g. per mole of the
silver halide, in general. However, the amount of said coupler is not
always limited to said range, but may be properly varied according to the
application purpose of the resulting photographic material. Further, the
coupler of the present invention may be incorporated into two or more of
different emulsion layers of a multi-layered light-sensitive color
photographic material.
The silver halide emulsion used in the present invention may be prepared by
use of any silver halide salt such as silver chloride, silver iodobromide
or silver chlorobromide, and may contain a chemical sensitizer such as a
sulfur sensitizer, a natural sensitizer present in gelatin, a reduction
sensitizer or noble metal salts. Further, the emulsion may contain
ordinary photographic additives such as, for example, antifoggant,
stabilizer, anti-stain agent, anti-irradiation agent, physical
property-improving high molecular weight additive, hardener, coating aid,
etc., and may contain as an optical sensitizer any of carbocyanine and
merocyanine dyes.
The thus obtained light-sensitive color photographic material is exposed to
radiation such as .alpha.-rays or .beta.-rays, visible rays of ultraviolet
rays, developed with a color developer containing an aromatic primary
amine type compound as a developing agent, and then subjected to
bleaching, desilvering and fixing to obtain an image containing a high
density dye excellent in spectral absorption characteristic and durability
and favorable in transparency. Obviously, the processing of a
light-sensitive color photographic material containing a coupler of the
present invention may also be made by using a bleach solution or a
bleach-fix solution which contains as its oxidizing agent, iron chloride,
potassium bichromate, potassium persulfate, potassium or the like
ferricyanide, or the polyvalent cation or alkali metal complex of a
water-soluble organic acid. In such processing, bleaching and fixation may
be made successively or concurrently. According to the situation,
bleaching may be followed by treatment with a bleach-neutralizing bath and
then with a fixing bath. In all the cases, satisfactory result can be
obtained. The durability of the color image can further be enhanced when
the photographic material containing the coupler of the present invention
is incorporated with an ultraviolet absorber of the benzophenone type,
e.g. 2-hydroxy-4-dodecyloxybenzophenone, or the triazole type, e.g.
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole.
Typical examples of the aromatic primary amine type developing agent used
for development in the present invention are sulfates, sulfites and
hydrochlorides of N,N-diethyl-p-phenylenediamine,
N-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4-aminoaniline,
N-ethyl-N-hydroxyethyl-p-phenylenediamine,
N-ethyl-N-hydroxyethyl-2-methyl-p-phenylenediamine and
N,N-diethyl-2-methyl-p-phenylenediamine.
Further, the color developer may contain a development control agent, e.g.
citrazinic acid, in addition to the aforesaid developing agent.
The present invention is illustrated in further detail below with reference
to examples, but the examples are by way of illustration, and the modes of
practice of the invention are, of course, not limited to the examples.
In the examples, such known couplers as shown below were used as control
couplers for comparison.
##STR4##
EXAMPLE 1
10 Grams of each of the couplers (11), (12), (15), (36), (38), (45), (48)
and (52) and the control couplers (i), (ii), (iii) and (iv) was completely
dissolved at 60.degree. C. in a mixture comprising 20 ml. of dibutyl
phthalate and 60 ml. of ethyl acetate. This solution was mixed with 5 ml.
of a 10% aqueous solution of Alkanol B(alkylnaphthalene sulfonate,
commercially available from E. I. Du Pont de Nemours & Co.) and 20 ml. of
a 5% aqueous gelatin solution, and the resulting mixture was emulsified by
use of a colloid mill to prepare a dispersion of each coupler.
Subsequently, each coupler dispersion was added to 500 g. of a high speed
negative, gelatinous silver iodobromide emulsion (containing 6 mole% of
silver iodide), which was then coated on a cellulose triacetate film base
and dried to obtain twelve kinds of photographic materials each having a
stable coating film which were designated Sample Nos. (1) to (12).
After exposure through an optical wedge, each sample was subjected to color
development at 20.degree. C. for 10 minutes, using a color developer of
the following composition:
Composition of the color developer:
N-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate:
5.0 g.
Anhydrous sodium sulfite: 2.0 g.
Sodium carbonate (monohydrate): 50.0 g.
Potassium bromide: 1.0 g.
Sodium hydroxide: 0.55 g.
Benzyl alcohol: 4.0 g.
Water to make: 1,000 ml.
Subsequently, the developed sample was subjected to ordinary stopping (for
2 minutes), fixing (for 5 minutes) and water-washing (for 10 minutes), and
then bleached for 5 minutes with a bleaching solution of the following
composition:
Composition of the bleaching solution:
Potassium ferricyanide: 100 g.
Potassium bromide: 50 g.
Water to make: 1,000 ml.
Thereafter, the sample was subjected to water-washing for 5 minutes, and
then fixed at 20.degree. C. for 5 minutes with a fixing solution of the
following composition:
Composition of the fixing solution:
Sodium thiosulfate (pentahydrate): 250 g.
Water to make: 1,000 ml.
The sample was again subjected to water-washing for 25 minutes, and then
dried to form a yellow dye image on Samples (1), (2), (3), (9) and (10), a
magenta dye image on Samples (4), (5) and (11), and a cyan dye imate on
Samples (6), (7), (8) and (12), respectively.
The dye image formed in each sample was measured in speed, gamma, maximum
density (D.sub.max), absorption maximum wavelength (.lambda..sub.max) and
fastness to light, heat and humidity. The results obtained were as set
forth in Table 1.
In the table, the speed was represented by a relative value measured by
assuming as 100 the speed of Sample (9) for yellow couplers, that of
Sample (11) for magenta couplers and that of Sample (12) for cyan
couplers. Further, the light fastness was represented by the percentage to
the density of untreated dye of the density of residual dye after treating
the sample for 16 hours by use of a Xenon Fade-O-Meter, and the
heat-humidity fastness was represented by the percentage to the density of
untreated dye of the density of residual dye after incubating the sample
for two weeks under the conditions of 50.degree. C. and 80%RH.
Table 1
__________________________________________________________________________
Fastness
Sample .lambda..sub.max
Light
Heat-humidity
No. Coupler
Speed
Gamma
D .sub.max
(mu)
fastness
fastness
__________________________________________________________________________
1 Coupler (11)
125 1.10
2.13
448 94 96
2 Coupler (12)
150 1.30
2.51
448 95 97
3 Coupler (15)
130 1.33
2.40
453 90 95
4 Coupler (36)
132 1.36
2.48
540 95 99
5 Coupler (38)
115 1.27
2.33
558 89 85
6 Coupler (45)
160 1.20
2.70
665 96 95
7 Coupler (48)
146 1.22
2.60
670 97 93
8 Coupler (52)
135 1.21
2.56
680 95 95
Control
9 coupler (i)
100 0.98
1.80
447 90 95
Control
10 coupler (ii)
120 1.10
2.13
453 83 94
Control
11 coupler (iii)
100 1.20
2.25
555 80 73
Control
12 coupler (iv)
100 1.11
2.20
678 92 90
__________________________________________________________________________
As is clear from Table 1, Samples (1) to (8), in which had been used the
couplers of the present invention, gave dye photographic images which were
more favorable in photographic properties than other samples, in which had
been used the control couplers. Moreover, the images obtained were quite
clear and were excellent in transparency.
EXAMPLE 2
Samples (6), (7), (8) and (12) prepared in Example 1 were individually
exposed through an optical wedge, and then subjected to color development
at 38.degree. C. (for 3 minutes and 15 seconds), bleaching (for 6
minutes), water-washing (for 3 minutes), fixing (for 6 minutes and 30
seconds), water-washing (for 3 minutes) and stabilization (for 1 minute
and 30 seconds) to investigate the influence derived from the difference
in manner of development treatment. As the result, it was confirmed that
the photographic properties of the dye image formed in each sample were
the same as in Example 1.
The compositions of the color developer and bleaching solution used in this
example were as follows:
Composition of the color developer:
N-ethyl-N-(.beta.-hydroxyethyl)-3-methyl-4-aminoaniline hydrochloride: 5.0
g.
Anhydrous sodium sulfite: 2.0 g.
Sodium carbonate (monohydrate): 50.0 g.
Potassium bromide: 1.0 g.
Sodium hydroxide: 0.55 g.
Water to make: 1,000 ml.
Composition of the bleaching solution:
Iron ammonium ethylenediamine tetraacetate: 100 g.
Diammonium ethylenediamine tetraacetate: 10 g.
Ammonium bromide: 150 g.
Glacial acetic acid: 10 ml.
Water to make: 1,000 ml.
EXAMPLE 3
10 Grams of each of the couplers (8), (14), (30) and (53) and the control
coupler (ii), (iii) and (iv) was completely dissolved at 60.degree. C. in
a mixture comprising 20 ml. of tricresyl phosphate and 60 ml. of ethyl
acetate. This solution was mixed with 5 ml. of a 10% aqueous solution of
Alkanol B and 200 ml. of a 5% aqueous gelatin solution, and the resulting
mixture was emulsified by use of a colloid mill to prepare a dispersion of
each coupler.
Subsequently, each coupler dispersion was added to a high speed silver
iodobromide emulsion (containing 4 mole% of silver iodide), which was then
coated on a cellulose acetate film base and dried to obtain seven kinds of
photographic materials each having a stable coating film which were
designated Sample Nos. (13) to (19).
After exposure through an optical wedge, each sample was first developed at
21.degree. C. for 12 minutes, using a developer of the following
composition:
Composition of the developer:
Metol: 3.0 g.
Anhydrous sodium sulfite: 50.0 g.
Hydroquinone: 6.0 g.
Sodium carbonate: 40.0 g.
Potassium bromide: 3.5 g.
Potassium thiocyanate: 2.0 g.
Water to make: 1,000 ml.
Subsequently, the developed sample was subjected to stopping,
film-hardening and water-washing treatments according to ordinary
procedures, thereafter to secondary exposure by use of a white light, and
then to color development at 21.degree. C. for 13 minutes, using a color
developer of the following composition:
Composition of the color developer:
N,n-diethyl-2-methyl-p-phenylenediamine: 3.0 g.
Anhydrous sodium sulfite: 4.0 g.
Sodium carbonate: 20.0 g.
Potassium bromide: 2.0 g.
Water to make: 1,000 ml.
Thereafter, the sample was subjected to stopping, water-washing, bleaching
and fixing treatments according to ordinary procedures, washed with
running water for 20 minutes and then dried to form a yellow colored
positive image on Samples (13), (14) and (17), a magenta colored positive
image on Samples (15) and (18) and a cyan colored positive image on
Samples (16) and (19), respectively.
The dye image formed in each sample was measured in speed, D.sub.max,
.lambda..sub.max and fastnesses to light and to heat-humidity. The results
obtained were as set forth in Table 2.
In the table, the speed was represented by a relative value measured by
assuming as 100 the speed of Sample (17) for yellow couplers, that of
Sample (18) for magenta couplers and that of Sample (19) for cyan
couplers, and the fastnesses were represented by percentages measured in
the same manner as in Example 1.
Table 2
______________________________________
Fastness
Sam- Heat-
ple Light humidity
No. Coupler Speed D.sub.max
.lambda..sub.max
fastness
fastness
______________________________________
13 Coupler (8)
133 2.42 457 92 97
14 Coupler (14)
125 2.26 456 93 97
15 Coupler (30)
130 2.46 540 94 97
16 Coupler (53)
137 2.60 683 97 96
Control
17 coupler (ii)
100 2.14 455 85 95
Control
18 coupler (iii)
100 2.24 557 81 73
Control
19 coupler (iv)
100 2.30 680 93 90
______________________________________
As is clear from Table 2, the dye positive images formed in Samples (13) to
(16), in which the couplers of the present invention had been used, were
more excellent particularly in heat-humidity fastness than the image
formed in Samples (17) to (19), in which the control coupler had been
used, and the images were quite clear and were favorable in transparency.
EXAMPLE 4
A high speed silver iodobromide emulsion (containing 5 mole% of silver
iodide) was coated on a polyester film base and then dried to prepare a
light-sensitive photographic material having a single emulsion layer. This
photographic material was exposed through an optical wedge, and then
subjected to color development at 24.degree. C. for 3 minutes, using an
external type color developer of the below-mentioned composition which had
been incorporated with the coupler (1).
Composition of the color developer:
N,n-diethyl-2-methyl-p-phenylenediamine: 2.0 g.
Anhydrous sodium sulfite: 2.0 g.
Sodium carbonate (monohydrate): 20.0 g.
Potassium bromide: 1.0 g.
Coupler (1): 2.0 g.
Water to make: 1,000 ml.
Subsequently, the sample was washed with water for 4 minutes, treated with
an ordinary bleaching bath for 5 minutes, washed with water for 5 minutes,
fixed for 5 minutes, washed with water for 30 minutes and then dried to
obtain a highly transparent yellow dye image having such excellent
spectral absorption characteristic as an absorption maximum of 457 m.mu..
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