FIELD OF THE INVENTION
[0001] This invention relates to a novel cyan coupler for a raw material of a silver halide
color photographic light-sensitive material and particularly to a novel cyan couplerfor
photographic use capable of forming a dye image excellent in fastness against heat,
moisture and light.
BACKGROUND OF THE INVENTION
[0002] Generally in the case of preparing a color photograph, a silver halide color photographic
light-sensitive material is exposed to light and is then color-developed. At that
time, a dye is produced, in the areas exposed to light, by reacting an oxidized aromatic
primary amine color developing agent with a due-forming coupler and a dye-image is
formed thereby. In such a photographic process as mentioned above, a color reproduction
process is used in a subtractive color system and thereby each of yellow, magenta
and cyan color images is formed.
[0003] Heretofore, the above-mentioned couplers for photographic use generally applicable
to form a yellow color-image include, for example, an acylacetanilido type coupler,
those generally applicable to form a magenta color-image include, for example, a pyrazolone,
pyrazolobenzimidazole, pyrazolotriazole or indazolone type coupler, and those generally
applicable to form a cyan color-image include, for example, a phenol or naphthol type
coupler. The dye-images came out of these couplers have been so required as neither
to be discolored not to be faded down, even if the images are exposed to light for
a long time or they are stored at a high temperature and a high humidity.
[0004] The researches and practical application of the above-mentioned phenol type and naphthol
type couplers have been progressed so far for serving as a coupler for producing a
cyan dye. However, they have still not been satisfactory a bit to the points of the
spectral absorption characteristics, heat resistance and moisture resistance of a
cyan dye-image formed thereby. Therefore, for aiming at the improvements thereof,
various proposals, including the selections and investigation of substituents to be
put inside a coupler, have so far been made. However, none of such a coupler as satisfiable
to every requirement for these characteristics has not yet been discovered.
[0005] Japanese Patent Publication Open to Public Inspection (hereinafter referred to as
JP OPI Publication) Nos. 62-278552/1987 and 62-279340/1987 describe each of the pyrroloimidazole
type couplers. However, these couplers could not be a cyan coupler, because they have
not any electron withdrawing group in the 2nd position and have the absorption of
a dye produced thereby in a short wave.
[0006] Taking the situations such as mentioned above into consideration, the present inventors
have further progressed their studies and, resultingly, they have discovered a coupler
for photographic use that is capable of forming a dye-image having a hue invariable
against heat, moisture and light.
SUMMARY OF THE INVENTION
[0007] It is, accordingly, an object of the invention is to provide a novel cyan coupler
for photographic use that is applicable to serve as a raw material of a silver halide
color photographic light-sensitive material, and another object of the invention is
to provide a cyan coupler for color photographic use that is capable of forming a
dye-image not producing any variation of the hue thereof caused by heat, moisture
and light.
[0008] The above-mentioned objects of the invention can achieved with a coupler for photographic
use that is represented by the following Formula (I), (II) or (III).
wherein R , R
2, R
3 and Y represent each a hydrogen atom or a substituent; EWG represents an electron
withdrawing group having a Hammett's substituent constant δ
P of not less than 0.3 and X represents a hydrogen atom or a group capable of splitting
off upon reacting with an oxidized product of a color developing agent, provided that
R
3 shall not be split off by reacting with an oxidized product of the color developing
agent.
[0009] Now, the invention will be detailed below.
[0010] In Formulas (I), (II) and (III), the substituents represented by R , R
2, R
3 include each of the groups of alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio,
arylthio, alkenyl and cycloalkyl. Besides the above, the substituents also include,
for example, a halogen atom, each of the groups of cycloalkenyl, alkinyl, heterocyclic,
sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy,
heterocyclic-oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imido,
ureido, sulfamoylamino, alkoxycarbonyl amino, aryloxycarbonyl- amino, alkoxycarbonyl,
aryloxycarbonyl, heterocyclic-thio, thioureido, carboxy, mercapto, nitro and sulfo,
and a spiro compound residual group and a cross-linked hydrocarbon compound residual
group.
[0011] Among each of the groups represented by R , R
2, R
3, the alkyl groups are preferable to have 1 to 32 carbon atoms and may also be straight-chained
or branched.
[0012] The aryl group is preferable to be phenyl.
[0013] The acyl amino group include, for example, those of alkylcarbonyl amino and acylcarbonyl
amino.
[0014] The sulfonamido group include those of alkylsulfonylamino and arylsulfonyl amino.
[0015] The alkyl components and aryl components of the alkylthio groups and arylthio groups
include an alkyl group and an aryl group each represented by R , R
2, R
3.
[0016] The alkenyl group is preferable to have 2 to 32 carbon atoms. The cycloalkyl group
is preferable to have 3 to 12 carbon atoms and more preferable to have 5 to 7 carbon
atoms. The alkenyl group may also be straight-chained or branched.
[0017] The cycloalkenyl group is preferable to have 3 to 12 carbon atoms and more preferable
to have 5 to 7 carbon atoms. It is preferable that the sulfonyl groups include alkylsulfonyl
and arylsulfonyl; the sulfinyl groups, those of alkylsulfinyl and arylsulfinyl; the
phosphonyl groups, those of alkylphosphonyl, alkoxyphosphonyl, aryloxyphosphonyl and
arylphosphonyl; the acyl groups, those of alkylcarbonyl and arylcarbonyl; the carbamoyl
groups, those of alkylcarbamoyl and arylcarbamoyl, the sulfamoyl groups, those of
alkylsulfamoyl and arylsulfamoyl; the acyloxy groups, those of alkylcarbonyloxy and
arylcarbonyloxy; the sulfonyloxy groups, those of alkylsulfonyloxy and arylsulfonyloxy;
the carbamoyloxy groups, those of alkylcarbamoyloxy and arylcarbamoy- loxy; the ureido
groups, those of alkylureido and arylureido; the sulfamoylamino groups, those of alkylsulfamoylamino
and arylsulfamoylamino; the heterocyclic groups, those of the 5- to 7-membered including,
concretely, those of 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl and 1-tetrazolyl;
the heterocyclic-oxy groups include, preferably, those having a 5- to 7-membered heterocyclic
ring, such as those of those of 3,4,5,6-tetrahydropyranyI-2-oxy and 1-phenyltetrazole-5-oxy;
the heterocyclic-thio groups include, preferably, those having a 5- to 7-membered
heterocyclic ring, such as those of 2-pyridylthio, 2-benzothiazolylthio and 2,4-di-
phenoxy-1,3,5-triazole-6-thio; the siloxy groups, those of trimethylsiloxy, triethylsiloxy
and dimethylbutylsi- loxy; the imido groups, those of succin imido, 3-heptadecyl succin
imido, phthalimido and glutarimido; the spiro compound residual groups, those of spiro
[3.3] heptane-1-yl; and the cross-linked hydrocarbon compound residual groups, those
of bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1
3.7] decane-1-yl and 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl; respectively.
[0018] The above-given groups may also have a further substituent including a ballast group
such as a long- chained hydrocarbon group and a polymer residual group.
[0019] In Formulas (I), (II) and (III), the substituents represented by EWG include a substituent
having a Ham- mett's substituent constant σ
P of not less than 0.3. They include typically a cyano group, a nitro group, a sulfonyl
group (such as those of octylsulfonyl, phenylsulfonyl, trifluoromethylsulfonyl and
pentafluorophenylsulfonyl), a β-carboxyvinyl group, a sulfinyl group (such as those
of t-butylsulfinyl, tolylsulfinyl, trifluoromethylsulfinyl and pentafluorophenylsulfinyl),
a β, l3-dicyanovinyl group, a halogenated alkyl group (such as those of trifluoromethyl,
perfluorooctyl and ω-hydroperfluoro-dodecyl), a formyl group, a carboxyl group, a
carbonyl group (such as those of acetyl, pivaloyl, benzoyl and trifluoro-acetyl),
an alkyloxycarbonyl or aryloxycarbonyl group (such as those of ethoxycarbonyl and
phenoxycarbonyl), 1-tetrazolyl group, 5-chloro-1-tetrazolyl group, a carbamoyl group
(such as those of dodecylcarbamoyl and phenylcarbamoyl) and a sulfamoyl group (such
as those of trifluoromethylsulfamoyl, phenylsulfamoyl and ethylsulfamoyl).
[0020] The groups represented by X, which are capable of splitting off upon making a reaction
thereof with an oxidized product of a color developing agent, include, for example,
a halogen atom (such as those of chlorine, bromine and fluorine) and each of the groups
of alkylene, alkoxy, aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy,
aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic-thio,
alkyloxythiocarbonylthio, acylamino, sulfonamido, a nitrogen-containing heterocyclic
ring coupled by a N-atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.
Among them, a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an
alkylthio group, an arylthio group and a nitrogen-containing heterocyclic ring group
coupled by a N-atom are preferred.
[0021] Y represents a hydrogen atom or a substituent. The preferable substituents include,
for example, those capable of splitting off after making a reaction thereof with an
oxidized product of a developing agent, which include, for example, a group capable
of splitting off under the alkaline conditions, such as those described in JP OPI
Publication No. 61-228444/1986 and a substituent capable of coupling off upon making
a reaction thereof with an oxidized product of a developing agent such as those described
in JP OPI Publication No. 56-133734/1981. Among them, hydrogen atom is preferred to
be represented by Y.
[0023] In the formulas, R
1, R
2, R
3, EWG and X are each synonymous with the R
1, R
2, R
3, EWG and X denoted in Formula (I), respectively.
[0025] Compounds (I) of the invention can be synthesized in accordance with the synthesizing
process described in Journal of the American Chemical Society, Vol.90, No.140, pp.3830-3834,
(1968).
Synthesis Example (I)
[0026] Exemplified compound (12) was synthesized in the following route.
Synthesis of Intermediate (b)
[0027] (a) of 22.6 g (in 0.2 mols) and a-bromoacetophenone of 19.9 g (in 0.1 mols) are reacted
in 200 cc of ethyl acetate at room temperature for 16 hours. After completing the
reaction, the resulting crystals are taken out through a filtration and the filtrated
crystals are recrystallized with acetonitrile, so that 40 g of intermediate (b) can
be obtained (at a yield of 95%).
Synthesis of Intermediate (d)
[0028] Intermediate (b) of 21.3 g (in 0.05 mols) is dispersed in 250 cc of N,N-dimethyl
formamide and 10.0 g of potassium carbonate is then added thereto. The resulting mixture
is stirred at room temperature for 20 minutes. Then, 11.9 g of(c) (in 0.05 mols) is
gradually added and an organic phase is extracted therefrom. The extracted organic
phase is dried and condensed. The resulting residue is refined through a column chromatography.
Thereafter, the refined residue is recrystallized from methanol, so that 6.10 g of
intermediate (d) can be obtained (in a yield of 21%).
Synthesis of Exemplified Compound (12)
[0029] (d) of 5.81 g (in 0.01 mols) is dissolved in 60 cc of ethyl acetate and 0.5 g of
5% palladium carbon is added. They are reacted together at room temperature for 4
hours under one hydrogen atmospheric pressure. After completing the reaction, a catalyst
is separated through a filtration and a solvent is distilled off under reduced pressure.
The resulting residue is recrystallized from ethanol, so that 3.54 g of the subject
exemplified compound (12) can be obtained (in a yield of 72%).
[0030] The structure of the resulting compound is confirmed by H-NMR, IR and MASS spectra.
Synthesis Example (II)
[0031] Exemplified compound (11-16) was synthesized in accordance with the following scheme.
Synthesis of Intermediate (c)
[0032] (a) of 18.9 g (in 0.1 mols) (that was synthesized in accordance with the process
described in Chemical Heterocyclic Compound, Vo1.11, p.1059, 1975) and (b) of 43.1
g (in 0.1 mols) are dissolved in 200 cc of dimethyl sulfoxide. Then, 11.2 g of potassium-t-butoxide
(in 0.1 mols) is gradually added. After a reaction is made at 50°C for 2 hours, the
reactant is allowed to cool and is then poured in dilute hydrochloric acid solution,
so that an extraction is made with ethyl acetate. The resulting extracted solution
is washed with water and a solvent is then distilled off under reduced pressure. Ethyl
acetate of 200 cc is added to the resulting residue and the mixture is heatedly reacted
for 5 hours under reflux conditions. After completing the reaction, the reactant is
washed with water and dried, and the solvent is distilled of under reduced pressure.
The resulting residue is recrystallized with ethanol, so that 23.8 g of intermediate
(c) (in a yield of 42%) can be obtained.
Synthesis of Exemplified Compound (16)
[0033] Intermediate (c) of 5.66 g (in 0.01 mols) is heated and refluxed, so that a reaction
is made for 4 hours. After completing the reaction, the reactant is poured in ice
water and neutralized with sodium carbonate. The resulting crystals are taken out
through a filtration. The resulting crude crystals are recrystallized with ethanol,
so that 3.90 g of the subject exemplified compound (16) (in a yield of 72%) can be
obtained.
[0034] The structure thereof was confirmed by H-NMR, IR and MASS spectra.
[0035] Compound (III) of the invention can be synthesized in accordance with the synthesization
process described in Arch. Pharm. Vol.325, No.4, pp.225-234, 1992.
Synthesis Example (III)
[0036] Exemplified compound (14) was synthesized in the following route.
(i) Synthesis of Intermediate (14c)
[0037] (14a) of 4.40 g (in 0.01 mols) (that was synthesized in the synthesization process
described in J. Org. Chem., Vo1.29, p.3459, 1964) and (14b) of 3.24 g (in 0.02 mols)
are heated and refluxed in 30 ml of acetone for 3 hours. After completing the reaction,
a solvent is distilled off under reduced pressure and an organic layer is extracted
by adding ethyl acetate and water. Thereafter, the residue obtained by distilling
the solvent under reduced pressure is refined in a column chromatography. Thereafter,
a crystallization is further made with ethanol, so that 2.47 g of intermediate (14c)
(in a yield of 49%) can be obtained.
(ii) Synthesis of Intermediate (14d)
[0038] Intermediate (14c) of 5.04 g (in 0.01 mols) and zinc of 6.53 g (in 0.1 mols) are
dispersed in 50 ml of acetone and 10 ml of conc. sulfuric acid is dropped therein
at room temperature. After completing the dropping it, a further reaction is made
for one hour at room temperature. After completing the reaction, the resulting insoluble
matter is separated through a filtration. Then, ethyl acetate and water are added
thereto. After completing the neutralization, an organic layer is extracted out. Thereafter,
the residue obtained by distilling off a solvent under reduced pressure is refined
in a column chromatography, so that 3.53 g of intermediate (14d) (in a yield of 88%)
can be obtained.
(iii) Synthesis of Intermediate (14f)
[0039] Intermediate (14d) of 4.01 g (in 0.01 mols) and (14e) of 4.26 g (in 0.02 mols) are
reacted in 20 ml of N,N-dimethyl formamide at 110°C for 3 hours. After completing
the reaction, ethyl acetate and water are added thereto, so that an organic layer
is extracted. Thereafter, a solvent is distilled off under reduced pressure. The resulting
residue is refined in a column chromatography, so that 4.01 g of intermediate (14f)
(in a yield of 62%) can be obtained.
(iv) Synthesis of Exemplified Compound (14)
[0040] Intermediate (14f) of 6.47 g (in 0.01 mols) is dissolved in 60 ml of acetic acid
and zinc of 1.96 g (in 0.03 mols) is gradually added thereto at room temperature.
Then, a reaction is made for 3 hours at room temperature. After completing the reaction,
ethyl acetate and water are added and, after completing a neutralization, an organic
layer is extracted. Thereafter, a solvent is distilled off under reduced pressure
and the resulting residue is recrystallized with ethanol, so that 3.97 g of the subject
exemplified compound (14) (in a yield of 77%) can be obtained.
[0041] The structure thereof was confirmed by H-NMR, IR and MASS spectra.
[0042] The couplers of the invention may be ordinarily used each in an amount within the
range of 1x1 0-3 to 1 mol and, preferably, 1x10-
2 to 8x10-
1 mols per mol of silver halide.
[0043] The couplers of the invention may be used with other kinds of cyan couplers in combination.
To the couplers of the invention, the processes and techniques used in any common
dye-forming couplers may be similarly applied.
[0044] The couplers of the invention may be used as a raw material for forming a color photograph
obtained in any color development processes including, concretely, a coupler-in-developer
type color development process and a coupler-in-emulsion type color development process.
When the couplers of the invention are used in a coupler-in-developer type color development
process, the couplers of the invention can be used by dissolving them in an aqueous
alkaline solution or an organic solvent (such as alcohol) and the resulting solution
is then added in a development processing solution.
[0045] When the couplers of the invention are used as a raw material for forming a color
photograph in a coupler-in-emulsion type color development process, the couplers of
the invention are used by containing them in a photographic light-sensitive material.
Typically, the following process can preferably be used; the couplers of the invention
are compounded in a silver halide emulsion and the emulsion is coated on a support,
so that a color light-sensitive material can be formed.
[0046] The couplers of the invention are used in such a color photographic light-sensitive
material as a color negative or positive film and a color printing paper.
[0047] The above-mentioned light-sensitive materials including color printing paper, in
which the couplers of the invention are used, may be for the monochromatic and multicolor
use. In a multicolor type light-sensitive material, the couplers of the invention
may be contained in any layers. It is, however, usual to contain them in a red light-sensitive
silver halide. Amulticolortype light-sensitive material has the dye-image forming
component units sensitive to the three primary-color regions of spectra, respectively.
Each of the component units may be comprised of a single or multilayered emulsion
layer having a sensitivity to a specific region of spectra. The component layers of
a light-sensitive material, including the layers as the image-forming component units,
may be arranged in a variety of orders as well known in the art.
[0048] Atypical multicolor type light-sensitive material is comprised of a support bearing
thereon a cyan dye-image forming component unit comprising at least one red light-sensitive
silver halide emulsion layer containing at least one cyan coupler (in which at least
one cyan coupler is a cyan coupler of the invention), a magenta dye-image forming
component unit comprising at least one green light-sensitive silver halide emulsion
layer containing at least one magenta coupler and a yellow dye-image forming component
unit comprising at least one blue light-sensitive silver halide emulsion layer containing
at least one yellow coupler.
[0049] Alight-sensitive material may have an additional layer such as a filter layer, an
interlayer, a protective layer and an undercoat layer.
[0050] A coupler of the invention may be contained in an emulsion in a conventionally known
method. For example, after a coupler of the invention is dissolved independently or
combination in a high boiling organic solvent having a boiling point of not lower
than 175°C such as tricresyl phosphate and dibutyl phthalate or a low boiling solvent
such as butyl propionate independently or, if required, a mixed solution thereof,
the resulting solution is mixed with an aqueous gelatin solution containing a surfactant
and the resulting mixture is emulsified by a high-speed rotary mixer or a colloid
mill. Then, a silver halide is added thereto, so that a silver halide emulsion applicable
to the invention can be prepared.
[0051] The silver halide compositions preferably applicable to a light-sensitive material
containing a coupler of the invention include, for example, silver chloride, silver
chlorobromide or silver chloroiodobromide and, further, a mixture thereof such as
a mixture of silver chloride and silver bromide may also be applied thereto. To be
more concrete, when a silver halide emulsion is applied to a color printing paper,
a rapid developability is particularly required. It is, therefore, preferable to contain
a chlorine atom as a halogen composition of a silver halide. It is particularly preferable
to contain silver chloride, silver chlorobromide or silver chloroiodobromide each
containing at least 1% of silver chloride.
[0052] A silver halide emulsion is chemically sensitized in an ordinary method and can also
be spectrally sensitized to any desired wavelength region.
[0053] For the purposes of preventing a fog production and/orkeeping the stability of photographic
characteristics in the courses of preparing, preserving or photographic processing
a light-sensitive material, a compound having been known in the art as an antifoggant
or a stabilizer can be added to a silver halide emulsion.
[0054] An anticolor-foggant, a dye-image stabilizer, a UV absorbent, an antistatic agent,
a matting agent a surfactant and so forth, which are commonly used in a light-sensitive
material, may be used in a color light-sensitive material containing a coupler of
the invention.
[0055] The above-mentioned additives may be referred to, for example, Research Disclosure,
Voi.176, pp.22-31, (Dec., a978).
[0056] A color photographic light-sensitive material containing a coupler of the invention
is capable of forming an image in any color development processes having been known
in the art.
[0057] A color photographic light-sensitive material using a coupler relating to the invention
and containing a color developing agent as either itself or its precursor in a hydrophilic
colloidal layer thereof may also be processed in an alkali-activated bath.
[0058] After color-developing a color photographic light-sensitive material using a coupler
of the invention, it is then bleached and fixed. The bleaching and fixing treatments
may also be carried out at the same time.
[0059] After completing the fixing treatment, a washing treatment is usually carried out.
It is also allowed to carry out a stabilizing treatment in place of a washing treatment
or the both treatments may further be carried out in combination.
EXAMPLES
[0060] Now, the invention will concretely be detailed with reference to the following examples.
However, the invention shall not be limited thereto.
Example 1
[0061] Red-sensitive color photographic light-sensitive material sample 1 was prepared by
coating the following layers on a paper support laminated with polyethylene on the
both sides thereof, in the order from the support side. The amounts of the compounds
added will be indicated in terms per sq.meter unless otherwise expressly stated, (provided
that the amounts of silver halides used will be indicated in terms of a silver content
thereof.)
Layer 1: An emulsion layer
[0062] This layer was comprised of a comparative cyan coupler (a) in an amount of 9.1x1
0-4 mols dissolved with 1.3 g of gelatin, 0.21 g of a red-sensitive silver chlorobromide
emulsion (containing silver chloride of 99.5 mol%) and 0.45 g of dioctyl phosphate.
Layer 2: A protective layer
[0063] This layer was a protective layer containing 0.50 g of gelatin. To this layer, sodium
2,4-dichloro-6-hydroxy- s-triazine was also added so as to be in an amount of 0.017
g per g of gelatin.
[0064] Next, Samples 2 through 24 were each prepared in quite the same manner as in Sample
1, except that comparative coupler (a-1) was replaced by a coupler shown in Table
1 in the same amount as that of the comparative coupler (a).
[0065] The resulting Samples 1 through 8 were each exposed to light through a wedge in an
ordinary method and were then developed in the following steps.
Color developing solution
[0066] With the processed Samples 1 through 8, the densities thereof were measured through
a densitometer (Model KD-7 manufactured by Konica Corp.). Each of the processed samples
was then allowed to stand for 14 days under the atmospheric conditions of a high temperature
and a high humidity (at 60°C and 80%RH) and the heat resistance and moisture resistance
of the resulting dye-images were checked up.
[0067] Each of the samples was exposed to Xenon rays emitted from a Xenon fade-o-meter for
10 days and the resulting density thereof was measured to check up the light fastness.
The results thereof will be shown in Table 1; provided, therein the heat resistance,
moisture resistance and light fastness of each dye-images will be indicated by a dye
residual percentage obtained after testing the heat resistance, moisture resistance
and light fastness at an initial density of 1.0.
[0068] As is obvious from the results shown in Table 1, it was proved that every sample
applied with the couplers of the invention was high in dye residual percentage, excellent
in heat and moisture resistance and fast against light, as compared to the samples
applied with the comparative couplers.
Example 2
[0069] A red-sensitive color light-sensitive material (Sample 23) was prepared by coating
the following layers on a subbed triacetate film in the order from the support side.
The amounts of the additives added thereto are indicated by an amount per sq.meter,
unless otherwise expressly stated, (provided that the amounts of silver halides used
therein are indicated by an amount in terms of the silver contents.
Layer 1: An emulsion layer
[0070] This layer was a red-sensitive emulsion layer comprising comparative cyan coupler
(b) in an amount of 8.0x10-
4 mols that was dissolved with 1.4 g of gelatin, 1.5 g of a red-sensitive silver iodobromide
emulsion (containing 4 mol% of silver iodide) and 1.1 g of tricresyl phosphate.
Layer 2: A protective layer
[0071] This layer was a protective layer containing 1.5 g of gelatin. Sodium 2,4-dichloro-6-hydroxy-s-triazine
was also added thereto as a layer hardener so that the contents thereof could be 0.017
g per g of gelatin.
[0072] Samples 24 through 44 were prepared in quite the same manner as in Sample 23, except
that Comparative Coupler b-1 was replaced by the couplers shown in Table 2, (provided,
the couplers were each added in the same mols as that of Comparative coupler b-1).
[0074] Color developing solution
[0075] With the processed Samples 23 through 44, the densities thereof were measured through
a densitometer (Model KD-7 manufactured by Konica Corp.). Each of the processed samples
was then allowed to stand for 14 days under the atmospheric conditions of a high temperature
and a high humidity (at 60°C and 80%RH) and the heat resistance and moisture resistance
of the resulting dye-images were checked up.
[0076] Each of the samples was exposed to Xenon rays emitted from a Xenon fade-o-meter for
10 days and the resulting density thereof was measured to check up the light fastness.
The results thereof will be shown in Table 2; provided, therein the heat resistance,
moisture resistance and light fastness of each dye-images will be indicated by a dye
residual percentage obtained after testing the heat resistance, moisture resistance
and light fastness at an initial density of 1.0.
[0077] The color-image produced on each sample was enlarged 10 times as large as the original
on a Konica color paper, and a color paper development process (in CPK-18P) was carried
out. The resulting color reproducibility was evaluated by 5 grades with the eye. The
evaluation is indicated that the higher the evaluation value was, the more the color
reproducibility was excellent.
[0078] As is obvious from the results shown in Table 2, it was proved that every sample
applied with the couplers of the invention was high in dye residual percentage, excellent
in heat-moisture resistance, fast against light and also excellent in color reproducibility,
as compared to the samples applied with the comparative coupler b-1. It was also proved
that the samples applied with the couplers of the invention were excellent in reproducibility,
as compared to the samples applied with comparative coupler c-1, c-2 or c-3.
Example 3
[0079] Samples 45 through 60 of the red-sensitive color reversal type photographic light-sensitive
materials containing the couplers shown in Table 3 were each prepared respectively
by coating the following layers on a triacetyl cellulose film support in the order
from the support side.
Layer 1: An emulsion layer
[0080] This layer was a red-sensitive emulsion layer comprising the couplers shown in Table
3 in an amount of 9.1x10-
4 mols each dissolved with 1.4 g of gelatin, 0.5 g of a red-sensitive silver chlorobromide
emulsion (containing 96 mol% of silver chloride) and 1.5 g of dibutyl phthalate.
Layer 2: A protective layer
[0081] This layer was a protective layer containing 0.5 g of gelatin. To this layer, sodium
2,4-dichloro-6-hydroxy- s-triazine was also added so as to be in an amount of 0.017
g per g of gelatin.
[0082] The resulting Samples 1 through 8 were each exposed to light through a wedge in an
ordinary method and were then developed in the following steps.
[0083] The following compositions of the processing solutions were used.
[0085] With each of the processed samples, the heat-moisture resistance and light fastness
of the resulting dye-images were checked up in the same manner as in Example 2. The
results thereof will be shown in Table 3.
[0086] As is obvious from the results shown in Table 3, it was proved that every sample
applied with the couplers of the invention was high in dye residual percentage, excellent
in heat and moisture resistance and fast against light, as compared to the samples
applied with the comparative couplers.
Example 4
[0087] On a transparent polyethylene terephthalate film support, a heat-development type
light-sensitive layer comprising the following components in the amounts indicated
below, so that a heat-development type light-sensitive material was thereby prepared.
Silver iodobromide (converted into Ag content)
[0088] Another sample was prepared by making use of Coupler II-or 111-23 in place of Coupler
1-28.