FIELD OF THE INVENTION
[0001] This invention relates to a silver halide color photographic material, and more particularly
to a silver halide color photographic material which forms a cyan dye image whose
density is not reduced even when processed with a bleaching bath or bleach-fix bath
has been fatiqued or otherwise has a weak oxidizing capacity, and also forms an image
excellent in sharpness.
BACKGROUND OF THE INVENTION
[0002] It is well known that an aromatic primary amine color developing agent oxidized with
an exposed silver halide can be reacted with a coupler to produce a dye, such as indophenol
dyes, indoaniline dyes, indamine dyes, azomethine dyes, phenoxazine dyes, phenadine
dyes, or the like, to form a dye image.
[0003] Of such couplers, phenolic couplers or naphthoic couplers known as cyan dye image
forming couplers have been noted to have a disadvantage that the dye image produced
therefrom has low fastness to heat or light, or undergoes density reduction when processed
with a bleaching bath or bleach-fix bath having weak oxidizing capacity or a fatigued
bleaching bath or bleach-fix bath. In order to overcome this disadvantage, phenolic
cyan couplers having a phenylureido group at the 2-position and a carbonamido group
at the 5-position have been disclosed, e.g., in Japanese Patent Application (OPI)
Nos. 33249/83 and 33250/73 (the term "OPI" as used herein means "unexamined published
application") and U.S. Patent 4,444,872. Although such cyan couplers are superior
in the above-described respects to conventional phenolic or naphthoic cyan couplers,
they involve disadvantages in that the spectral absorption of the dye image produced
is liable to great variation depending on the density, in that a precipitate would
be formed or color developability would be reduced due to poor solubility unless a
sufficient amount of a high-boiling organic solvent is used, and the like, as has
pointed out in U.S. Patent 4,594,314. Therefore, use of these phenolic couplers inevitably
increases the film thickness, resulting in deterioration of image sharpness.
[0004] In an attempt to decrease color density dependence of the spectral absorption of
the above-described couplers, naphthoic cyan couplers having an amido group at the
5-position have been described in European Patent 161626A. However, the objects and
effects of the present invention are not described in European Patent 161626A.
[0005] Japanese Patent Application (OPI) No. 11452/81 discloses a light-sensitive material
containing a high-boiling point organic solvent in an amount of from 0.01 to 0.3%
by weight based on a total amount of 5-pyrazolone magenta couplers. However, this
technique aims at improvement on resistance to formaldehyde, and is, hence, entirely
different from the present invention, from the standpoint of developed hue and effects.
SUMMARY OF THE INVENTION
[0006] One object of this invention is to provide a silver halide color photographic light-sensitive
material which does not undergo reduction in cyan color density even when processed
with a bleaching bath or bleach-fix bath having been fatigued or having a weak oxidizing
capacity.
[0007] Another object of this invention is to provide a silver halide color photographic
light-sensitive material having excellent dye image preservability.
[0008] A further object of this invention is to provide a silver halide color photographic
material having excellent sharpness.
[0009] As a result of extensive investigations, the present inventors have found that combined
use of these couplers with a small amount of a high-boiling point organic solvent
is freed from deterioration of color developability or precipitation as encountered
with the combined use of phenolic couplers having a ureido group at the 2-position
and a small amount of a high-boiling organic solvent, while retaining the superiority
of such phenolic couplers. It has also been found that application of such a coupler-solvent
combination to light-sensitive materials containing 2-equivalent polymeric magenta
couplers as magenta couplers produces a further pronounced effect.
[0010] It has now been found that the above objects can be accomplished by a silver halide
color photographic material comprising a support having provided thereon at least
one silver halide emulsion layer containing a cyan coupler, at least one silver halide
emulsion layer containing a magenta coupler, and at least one silver halide emulsion
layer containing a yellow coupler, wherein said cyan coupler-containing emulsion layer
contains at least one cyan coupler represented by formula (I) shown below and a high-boiling
point organic solvent in an amount of not more than 30% by weight based on the total
amount of said cyan coupler(s).
[0011] Formula (I) is represented by

wherein R₁ represents -CONR₅R₆, -NHCOR₅, -NHCOOR₇, -NHSO₂R₇, -NHCONR₅R₆ or -NHSO₂NR₅R₆,
wherein R₅ and R₆ (which may be the same or different) each represents a hydrogen
atom, an aliphatic group, an aromatic group or a heterocyclic group, or R₅ and R₆
are taken together to form a nitrogen-containing heterocyclic ring, and R₇ represents
an aliphatic group, an aromatic group or a heterocyclic group; R₂ represents a group
capable of substituting for a hydrogen atom of a naphthalene ring, or a plurality
of R₂ (which may be the same or different) groups together form a ring; m represents
0 or an integer of from 1 to 3; R₃ represents a monovalent organic group; and X represents
a hydrogen atom or a group releasable upon coupling with an oxidation product of an
aromatic primary amine developing agent, or R₃ together with R₂ or X form a ring.
DETAILED DESCRIPTION OF THE INVENTION
[0012] In formula (I), R₆ and R₇ in groups represent ing R₁ each preferably represents
an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from
6 to 30 carbon atoms, and a heterocyclic group having from 2 to 30 carbon atoms.
[0013] Typical examples of the group (or atom, hereinafter the same) capable of substituting
for a hydrogen atom of a naphthalene ring as represented by R₂ include a halogen atom,
a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a cyano
group, an aliphatic group, an aromatic group, a heterocyclic group, a carbonamido
group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group,
an acyl group, an acyloxy group, an aliphatic oxy group, an aromatic oxy group, an
aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic
sulfonyl group, a sulfamoylamino group, a nitro group, an imido group, etc. These
groups for R₂ contain up to 30 carbon atoms in total. When m is 2, (R₂)
m represents, for example, a dioxymethylene group.
[0014] The monovalent organic group as represented by R₃ preferably includes a group represented
by formula (II)
R₈(Y)
n- (II)
wherein Y represents

NH,

CO or

SO₂;
n represents 0 or 1; and R₈ represents a hydrogen atom, an aliphatic group having
from 1 to 30 carbon atoms, an aromatic group having from 6 to 30 carbon atoms, a heterocyclic
group having from 2 to 30 carbon atoms,

wherein R₉, R₁₀, and R₁₁ each has the same meaning as R₅, R₆, and R₇ as above defined,
and R₉ and R₁₀ may be taken together to form a nitrogen-containing heterocyclic ring.
[0015] Examples of the nitrogen-containing heterocyclic ring formed by -NR₅R₆ or -NR₉R₁₀
include a morpholine ring, a piperidine ring, a pyrrolidine ring, etc.
[0016] Typical examples of the group (or atom, hereinafter the same) releasable upon coupling
as represented by X include a halogen atom,

an aromatic azo group having from 6 to 30 carbon atoms, a heterocyclic group having
from 1 to 30 carbon atoms containing a nitrogen atom at which to bond to the coupling
position of the coupler (e.g., succinimido group, a phthalimido group, a hydantoinyl
group a pyrazolyl group, a 2-benzotriazolyl group, etc.), etc., wherein R₁₂ represents
an aliphatic group having from 1 to 30 carbon atoms, an aromatic group having from
6 to 30 carbon atoms or a heterocyclic group having from 2 to 30 carbon atoms.
[0017] The expression "aliphatic group" as used herein includes saturated or unsaturated,
substituted or unsubstituted, and straight or branched chain or cyclic groups. Typical
examples of the aliphatic group are a methyl group, an ethyl group, a butyl group,
a cyclohexyl group, an allyl group, a propargyl group, a methoxyethyl group, an n-decyl
group, an n-dodecyl group, an n-hexadecyl group, a trifluoromethyl group, a heptafluoropropyl
group, a dodecyloxypropyl group, a 2,4-di-t-amylphenoxypropyl group, a 2,4-di-t-amylphenoxybutyl
group, etc.
[0018] The expression "aromatic group" as used herein includes substituted or unsubstituted
groups. Typical examples of the aromatic group are a phenyl group, a tolyl group,
a 2-tetradecyloxyphenyl group, a pentafluorophenyl group, a 2-chloro-5-dodecyloxycarbonylphenyl
group, a 4-chlorophenyl group, a 4-cyanophenyl group, a 4-hydroxyphenyl group, etc.
[0019] The expression "heterocyclic group" as used herein includes substituted or unsubstituted
groups. Typical examples of the heterocyclic groups are a 2-pyridyl group, a 4-pyridyl
group, a 2-furyl group, a 4-thienyl group, a quinolinyl group, etc.
[0020] In formula (I), R₁ preferably represents -CONR₅R₆. Specific examples of -CONR₅R₆
include a carbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group, a
dodecylcarbamoyl group, a hexadecylcarbamoyl group, a decyloxypropylcarbamoyl group,
a dodecyloxypropylcarbamoyl group, a 2,4-di-t-amylphenoxypropylcarbamoyl group, a
2,4-di-t-amylphenoxybutylcarbamoyl group, etc.
[0021] R₂ preferably represents a halogen atom, an aliphatic group, a carbonamido group,
a sulfonamido group, etc. More preferably m in (R)
m is zero.
[0022] R₃ preferably represents the group of formula (II) wherein n is 0, and R₈ represnets
-COR₉ (e.g., a formyl group, an acetyl group, a trifluoroacetyl group, a chloroacetyl
group, a benzoyl group, a pentafluorobenzoyl group, a p-chlorobenzoyl group, etc.),
-COOR₁₁ (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl
group, a decyloxycarbonyl group, a methoxyethoxycarbonyl group, a phenoxycarbonyl
group, etc.), -SO₂R₁₁ (e.g., a methane sulfonyl group, an ethanesulfonyl group, a
butanesulfonyl group, a hexadecanesulfonyl group, a benzenesulfonyl group, a toluenesulfonyl
group, a p-chlorobenzenesulfonyl group, etc.), -CONR₉R₁₀ (e.g., an N,N-dimethylcarbamoyl
group, an N,N-diethylcarbamoyl group, an N,N-dibutylcarbamoyl group, a morpholinocarbonyl
group, a piperidinocarbonyl group, a 4-cyanophenylcarbonyl group, a 3,4-dichlorophenylcarbamoyl
group, a 4-methanesulfonylphenylcarbamoyl group, etc.), -SO₂NR₉R₁₀ (e.g., an N,N-dimethylsulfamoyl
group, an N,N-diethylsulfamoyl group, an N,N-dipropylsulfamoyl group, etc.), etc.
R₃ more preferably represents -COOR₁₁, -COR₉ or -SO₂R₁₁ with -COOR₁₁ being most preferred.
[0023] X preferably represents a hydrogen atom, a chlorine atom, an aliphatic oxy group
(e.g., a 2-hydroxyethoxy group, a 2-chloroethoxy group, a carboxymethyloxy group,
a 1-carboxyethoxy group, a 2-methanesulfonylethoxy group, a 3-carboxypropyloxy group,
a 2-methoxyethoxycarbamoylmethyloxy group, a 1-carboxytridecyl group, a 2-(1-carboxytridecylthio)ethyloxy
group, a 2-carboxymethylthioethyloxy group, a 2-methanesulfonamidoethyloxy group,
etc.), an aromatic oxy group (e.g., a 4-acetamidophenoxy group, a 2-acetamidophenoxy
group, a 4-(3-carboxypropaneamido)phenoxy group, etc.) or a carbamoyloxy group (e.g.,
an ethylcarbamoyl group, a phenylcarbamoyloxy group, etc.).
[0024] The cyan coupler according to the present invention includes a polymer inclusive
of a dimer wherein two or more monomer units derived from the compound of formula
(I) are connected at any of R₁, R₂, R₃, and X via a divalent or higher valent group.
In this case, each of the above-illustrated substituents may have a total carbon atom
number out of the range respectively recited.
[0025] In cases where the compound of formula (I) is polymerized to form a polymeric coupler,
such a polymeric coupler typically includes a homo- or copolymer of an addition polymerizable
ethylenically unsaturated compound having a cyan dye forming coupler residue (cyan
forming monomer). Such a polymer comprises one or more repeating units represented
by formula (III) shown below, and, if desired, one or more non-color-forming ethylenically
unsaturated monomers as copolymerizable units.
[0026] Formula (III) is represented by

wherein R represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms
or a chlorine atom; A represents -CONH-, -COO- or a substituted or unsubstituted phenylene
group; B represents a substituted or unsubstituted alkylene, phenylene or aralkylene
group; L represents -CONRʹ-, -NRʹCONRʹ-, -NRʹCOO-, -NRʹCO-, -OCONRʹ-, -NRʹ-, -COO-,
-OCO-, -CO-, -O-, -SO₂-, -NRʹSO₂- or -SO₂NRʹ, wherein Rʹ represents a hydrogen atom
or a substituted or unsubstituted alkyl or aryl group; a, b, and c each represents
0 or 1; and Q represents a cyan coupler residual group derived from the compound represented
by formula (I) by removing any one of hydrogen atoms other than the hydrogen atom
of the 1-positioned hydroxyl group.
[0027] The polymeric coupler preferably includes a copolymer comprising the cyan forming
monomer providing the repeating unit of formula (III) and the non-color-forming ethylenically
unsaturated comonomers which do not couple with an oxidation product of an aromatic
primary amine developing agent. Specific examples of such comonomers are acrylic acid,
α-chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid), esters or amides
of these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide,
diacetonacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl
acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, β,β-hydroxymethacrylate,
etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl laurate, etc.),
acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and derivatives
thereof, e.g., vinyl toluene, divinylbenzene, vinylacetophenone, sulfostyrene, etc.),
itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers
(e.g., vinyl ethyl ether, etc.), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine,
2- or 4-vinylpyridine, and the like.
[0028] Of these comonomers, acrylic esters, methacrylic esters, and maleic esters are preferred.
These non-color-forming ethylenically unsaturated monomers may be used either individually
or in combinations of two or more thereof. For example, a combination of methyl acrylate
and butyl acrylate, a combination of butyl acrylate and styrene, a combination of
butyl methacrylate and methacrylic acid, a combination of methyl acrylate and diacetonacrylamide,
etc. can be employed.
[0029] As is well known in the art of polymeric couplers, the kind of the ethylenically
unsaturated monomers to be copolymerized with vinyl monomers corresponding to the
repeating unit of formula (III) can be selected appropriately so as to exert favorable
influences upon physical and/or chemical properties of the resulting copolymers, such
as solubility, compatibility with binders for photographic colloidal compositions,
e.g., gelatin, flexibility, heat stability, and the like.
[0030] The polymeric coupler which can be used in the present invention can be prepared
by polymerizing the vinyl monomer providing the repeating unit of formula (III), dissolving
the resulting oleophilic polymer in an organic solvent, and dispersing the organic
solution in a gelatin aqueous solution to form a latex. The process disclosed in U.S.
Patent 3,451,820 may be applied to a dispersion of the oleophilic polymer in a gelatin
aqueous solution. The polymeric coupler may also be prepared by direct emulsion polymerization
in accordance with the process as disclosed in U.S. Patents 4,080,211 and 3,370,952.
[0032] The couplers represented by formula (I) can be synthesized easily in accordance with
the process described in European Patent 161626A.
[0033] The high-boiling point organic solvents which can be used in the present invention
are those having a boiling point of 175°C or higher at normal pressure (760 mmHg).
[0034] Examples of the high-boiling point organic solvents which can be used in combination
with the couplers of formula (I) include phosphoric esters, e.g., triphenyl phosphate,
tricresyl phosphate, octyldiphenyl phosphate, tri-2-ethylhexyl phosphate, tri-n-hexyl
phosphate, tri-iso-nonyl phosphate, tricyclohexyl phosphate, tributoxyethyl phosphate,
tri-2-chloroethyl phosphate, etc.; benzoic esters, e.g., 2-ethylhexyl benzoate, 2-ethylhexyl
2,4-dichlorobenzoate, etc.; fatty acid esters, e.g., di-2-ethylhexyl succinate, 2-hexyldecyl
tetradecanoate, tributyl citrate, etc.; amides, e.g., N,N-diethyldodecanamide, N-tetradecylpyrrolidone,
etc.; dialkylanilines, e.g., 2-butoxy-5-t-octyl-N,N-dibutylaniline, etc.; chlorinated
paraffins, i.e., paraffins having a chlorine content of from 10 to 80% by weight;
phenols, e.g., 2,5-di-t-amylphenol, 2,5-di-t-hexyl-4-methoxyphenol, 2-ethylhexyl p-hydroxybenzoate,
etc.; phthalic esters, e.g., dibutyl phthalate, dicyclohexyl phthalate, diheptyl phthalate,
di-2-ethylhexyl phthalate, didodecyl phthalate, etc.; and the like. Preferred among
them are phosphoric esters and phthalic esters.
[0035] The amount of the high-boiling point organic solvent to be used in this invention
should not exceed 0.3 g per gram of the coupler of formula (I) (i.e., it should not
exceed 30 wt%). If it exceeds 0.3 g/g-coupler, sharpness is conspicuously deteriorated.
A preferred amount of the high-boiling point solvent is 0.15 g or less, more preferably
0.05 g or less, and most preferably 0.01 g or less, per gram of the coupler. The
high-boiling point organic solvent may not be used at all. In this case, the coupler
is emulsified in the hydrophilic colloid by using a low-boiling point organic solvent
(having a boiling point of from about 30°C to about 160°C, such as 2-ethoxyethyl acetate,
N,N-dimethylformamide, etc.)
[0036] The amount of the cyan coupler represented by formula (I) usually ranges from 1.0
× 10⁻⁵ to 3.0 ×10⁻³ mol/m², and preferably from 5.0 × 10⁻⁵ to 1.5 × 10⁻³ mol/m².
[0037] When the silver halide color photographic material according to the present invention
contains two or more silver halide emulsion layers being sensitive to the same color
but differing in sensitivity, the present invention is preferably applied to layers
other than the layer having the highest sensitivity.
[0038] The magenta couplers which can be used in the present invention are preferably polymeric
magenta couplers, and more preferably those obtained from a monomer represented by
formula (IV)

wherein R₂₁ represents a hydrogen atom, an alkyl group having from 1 to 4 carbon
atoms or a chlorine atom; D represents -COO-, -CONR₂₂- or a substituted or unsubstituted
phenyl group; E represents a substituted or unsubstituted alkylene, phenylene or aralkylene
group having from 1 to 10 carbon atoms; F represents -CONR₂₂-, -NR₂₂CONR₂₂-, -NR₂₂COO-,
-NR₂₂CO-, -OCONR₂₂-, -NR₂₂-, -COO-, -OCO-, -CO-, -O-, -S-, -SO₂-, -NR₂₂SO₂- or -SO₂NR₂₂-,
wherein R₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic
or aryl group, a plurality of R₂₂, if any, may be the same or different; p, q, and
r each represents 0 or 1 provided that at least one of them is 1; and T represents
a coupler residual group derived from a magenta coupler represented by formula (V)
shown below.
[0039] Formula (V) is represented by

wherein Ar represents an alkyl group, an aryl group, and a heterocyclic group; R₂₃
represents a substituted or unsubstituted anilino group, a substituted or unsubstituted
acylamino group (e.g., an alkylcarbonamido group, a phenylcarbonamido group, an alkoxycarbonamido
group, a phenyloxycarbonaido group, etc.), a substituted or unsubstituted ureido group
(e.g., an alkylureido group, a phenylureido group, etc.) or a substituted or unsubstituted
sulfonamido group; and Z represents a hydrogen atom, a halogen atom (e.g., a chlorine
atom, a bromine atom, etc.), a coupling releasable group bonded via an oxygen atom
(e.g., an acetoxy group, a propanoyloxy group, a benzoyloxy group, an ethoxyoxaloyloxy
group, a pyruvoyloxy group, a cinnamoyloxy group, a phenoxy group, a 4-cyanophenoxy
group, a 4-ethanesulfonamidophenoxy group, an α-naphthoxy group, a 4-cyanoxy group,
a 4-methanesulfonamidophenoxy group, a 3-pentadecylphenoxy group, a benzyloxycarbonyloxy
group, an ethoxy group, a 2-cyanoethoxy group, a benzyloxy group, a 2-phenethyloxy
group, a 2-phenoxyethoxy group, a 5-phenyltetrazolyloxy group, a 2-benzothiazolyloxy
group, etc.), a coupling releasable group bonded via a nitrogen atom (e.g., those
described in British Patent Application No. 2,132,783, e.g., a benzenesulfonamido
group, an N-ethyltoluenesulfonamido group, a heptafluorobutaneamido group, a 2,3,4,5,6-pentafluorobenzamido
group, an octanesulfonamido group, a p-cyanophenylureido group, an N,N-diethylsulfamoylamino
group, a 1-piperidyl group, a 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a 1-benzyl-5-ethoxy-3-hydantoinyl
group, a 2-oxo-1,2-dihydro-1-pyridinyl group, an imidazolyl group, a pyrazolyl group,
a 3,5-diethyl-1,2,4-triazol-1-yl group, a 5- or 6-bromobenzotriazol-1-yl group, a
5-methyl-1,2,3,4-triazol-1-yl group, a benzimidazolyl group, etc.) or a coupling
releasable group bonded via a sulfur atom (e.g., a phenylthio group, a 2-carboxyphenylthio
group, a 2-methoxy-5-octylphenylthio group, a 4-methanesulfonylphenylthio group,
a 4-octanesulfonamidophenylthio group, a benzylthio group, a 2-cyanoethylthio group,
a 5-phenyl-2,3,4,5-tetrazolylthio group, a 2-benzothiazolyl group, etc.).
[0040] In the monomer of the formula (IV), the coupler residual group T of formula (V) is
bonded to (D) (E) (F) at any of Ar, X, and R₂₃.
[0041] In formula (V), the group as represented by Ar includes a substituted or unsubstituted
alkyl group (the substituent includes a halogen atom, a cyano group, a benzyl group,
etc.), a substituted or unsubstituted heterocyclic group (e.g., a 4-pyridyl group,
a 2-thiazoyl group, etc.), and a substituted or unsubstituted aryl group. The substituent
for the heterocyclic group or aryl group includes an alkyl group (e.g., a methyl group,
an ethyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.),
an aryloxy group (e.g., a phenyloxy group, etc.), an alkoxycarbonyl group (e.g., a
methoxycarbonyl group, etc.), an acylamino group (e.g., an acetylamino group, etc.),
a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbamoyl group, an ethylcarbamoyl
group, etc.), a dialkylcarbamoyl group (e.g., a dimethylcarbamoyl group, etc.), an
arylcarbamoyl group (e.g., a phenylcarbamoyl group, etc.), an alkylsulfonyl group
(e.g., a methylsulfonyl group, etc.), an arylsulfonyl group (e.g., a phenylsulfonyl
group, etc.), an alkylsulfonamido group (e.g., a methanesulfonamido group, etc.),
an arylsulfonamido group (e.g., a phenylsulfonamido group, etc.), a sulfamoyl group,
an alkylsulfamoyl group (e.g., an ethylsulfamoyl group, etc.), a dialkyl sulfamoyl
group (e.g., a dimethylsulfamoyl group, etc.), an alkylthio group (e.g., a methylthio
group), an arylthio group (e.g., a phenylthio group, etc.), a cyano group, a nitro
group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.),
and the like. When two or more of these groups substitute the heterocyclic or aryl
group, they may be the same or different. Preferred among these substituents are a
halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano
group.
[0042] The substituent for the group as represented by R₂₃ includes a halogen atom (e.g.,
a fluorine atom, a chlorine atom, a bromine atom, etc.), a straight or branched chain
alkyl group (e.g., a methyl group, a t-butyl group, an octyl group, a tetradecyl group,
etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a 2-ethylhexyloxy
group, a tetradecyloxy group, etc.), an acylamino group (e.g., an acetamido group,
a benzamido group, a butanamido group, an octanamido group, a tetradecanamido group,
an α-(2,4-di-t-amylphenoxy)acetamido group, an α-(2,4-di-t-amylphenoxy)butylamido
group, an α-(3-pentadecylphenoxy)hexanamido group, an α-(4-hydroxy-3-t-butylphenoxy)tetradecanamido
group, a 2-oxo-pyrrolidin-1-yl group, a 2-oxo-5-tetradecylpyrrolidin-1-yl group,
an N-methyltetradecanamido group, etc.), a sulfonamido group (e.g., a methanesulfonamido
group, a benzenesulfonamido group, an ethylsulfonamido group, a p-toluenesulfonamido
group, an octanesulfonamido group, a p-dodecylbenzenesulfonamido group, an N-methyltetradecanesulfonamido
group, etc.), a sulfamoyl group (e.g., a sulfamoyl group, an N-methylsulfamoyl group,
an N-ethylsulfamoyl group, an N,N-dimethylsulfamoyl group, an N,N-dihexylsulfamoyl
group, an N-hexadecyluslfamoyl group, an N-[3-(dodecyloxy)propyl]sulfamoyl group,
an N-[4-(2,4-di-t-amylphenoxy)butyl]sulfamoyl group, an N-methyl-N-tetradecylsulfmaoyl
group, etc.), a carbamoyl group (e.g., an N-methylcarbamoyl group, an N-butylcarbamoyl
group, an N-octadecylcarbamoyl group, an N-[4-(2,4-di-t-amylphenoxy)butyl]carbamoyl
group, an N-methyl-N-tetradecylcarbamoyl group, etc.), a diacylamino group (e.g.,
an N-succinimido group, an N-phthalimido group, a 2,5-dioxo-1-oxazolidinyl group,
a 3-dodecyl-2,5-dioxo-1-hydantoinyl group, a 3-(N-acetyl-N-dodecylamino)succinimido
group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, a tetradecyloxycarbonyl
group, a benzyloxycarbonyl group, etc.), an alkoxysulfonyl group (e.g., a methoxysulfonyl
group, a butoxysulfonyl group, an octyloxysulfonyl group, a tetradecyloxysulfonyl
group, etc.), an aryloxysulfonyl group (e.g., a phenoxysulfonyl group, a p-methylphenoxysulfonyl
group, a 2,4-di-t-amylphenoxysulfonyl group, etc.), an alkanesulfonyl group (e.g.,
a methanesulfonyl group, an ethanesulfonyl group, an octanesulfonyl group, a 2-ethylhexylsulfonyl
group, a hexadecanesulfonyl group, etc.), an arylsulfonyl group (e.g., a benzenesulfonyl
group, a 4-nonylbezenesulfonyl group, etc.), an alkylthio group (e.g., a methylthio
group, an ethylthio group, a hexylthio group, a benzylthio group, a tetradecylthio
group, a 2-(2,4-di-t-amylphenoxy)ethylthio group, etc.), an arylthio group (e.g.,
a phenylthio group, a p-tolylthio group, etc.), an alkyloxycarbonylamino group (e.g.,
a methoxycarbonylamino group, an ethoxycarbonylamino group, a benzyloxycarbonylamino
group, a hexadecyloxycarbonylamino group, etc.), an alkylureido group (e.g., an N-methylureido
group, an N,N-dimethylureido group, an N-methyl-N-dodecylureido group, an N-hexadecylureido
group, an N,N-dioctadecylureido group, etc.), an acyl group (e.g., an acetyl group,
a benzoyl group, an octadecanoyl group, a p-dodecanamidobenzoyl group, etc.), a nitro
group, a carboxyl group, a sulfo group, a hydroxyl group, a trichloromethyl group,
and the like. The alkyl moiety and the aryl moiety of the above-enumerated substituents
have a carbon atom number of from 1 to 36 and from 6 to 38, respectively.
[0043] Z preferably represents a coupling releasable group bonded at a nitrogen atom, and
more preferably a pyrazolyl group.
[0044] The alkylene group as represented by E in formula (IV) may have either a straight
chain or a branched chain. Examples of the alkylene group are a methylene group, a
methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene
group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a decylmethylene
group, etc. Examples of the aralkylene group as represented by E are a benzylidene
group, and the phenylene group as represented by E are a p-phenylene group, an m-phenylene
group, a methylphenylene group, etc.
[0045] The substituents for these groups as E include an aryl group (e.g., a phenyl group,
etc.), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group
(e.g., a methoxy group, etc.), an aryloxy group (e.g., a phenoxy group, etc.), an
acyloxy group (e.g., an acetoxy group, etc.), an acylamino group (e.g., an acetylamino
group, etc.), a sulfonamido group (e.g., a methanesulfonamido group, etc.), a sulfamoyl
group (e.g., a methylsulfamoyl group, etc.), a halogen atom (e.g., a fluorine atom,
a chlorine atom, a bromine atom, etc.), a carboxyl group, a carbamoyl group (e.g.,
a methylcarbamoyl group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl
group, etc.), a sulfonyl group (e.g., a methylsulfonyl group, etc.), and the like.
When two or more of these substituents are present, they may be the same or different.
[0046] The polymeric magenta coupler which can be used in the present invention includes
not only a homopolymer or copolymer of the monomer represented by formula (IV), but
also a copolymer obtained from the monomer of formula (IV) and non-color-forming ethylenically
unsaturated monomers which do not couple with an oxidation product of an aromatic
primary amine developing agent.
[0047] Specific examples of the non-color-forming ethylenically unsaturated monomer to be
copolymerized with the monomer of formula (IV) are acrylic esters, e.g., methyl acrylate,
ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl
acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate,
phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2-(2-methoxyethoxy)ethyl
acrylate, etc.; methacrylic esters, e.g., methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate,
2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, etc.; crotonic esters, e.g.,
butyl crotonate, hexyl crotonate, etc.; vinyl esters, e.g., vinyl acetate, vinyl propionate,
vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, etc.; maleic diesters, e.g.,
diethyl maleate, dimethyl maleate, dibutyl maleate, etc.; fumaric esters, e.g., diethyl
fumarate, dimethyl furamate, dibutyl fumarate, etc.; itaconic esters, e.g., diethyl
itaconate, dimethyl itaconate, dibutyl itaconate, etc.; acrylamides, e.g., acrylamide,
methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, t-butylacrylamide,
cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide,
phenylacrylamide, etc.; methacrylamides, e.g., methylmethacrylamide, ethylmethacrylamide,
n-butylmethacrylamide, t-butylmethacrylamide, 2-methoxymethacrylamide, dimethylmethacrylamide,
diethylmethacrylamide, etc.; vinyl ethers, e.g., methyl vinyl ether, butyl vinyl ether,
hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.;
styrenes, e.g., styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene. butoxystyrene,
acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate,
2-methylstyrene, etc.; and the like.
[0048] Examples of other comonomers to be copolymerized with the monomer of formula (IV)
include allyl compounds (e.g., allyl acetate, etc.), vinyl ketones (e.g., methyl vinyl
ketone, etc.), vinyl heterocyclic compounds (e.g., vinylpyridine, etc.), glycidyl
esters (e.g., glycidyl acrylate, etc.), unsaturated nitriles (e.g., acrylonitrile,
etc.), acrylic acid, methacrylic acid, itaconic acid, maleic acid, itaconic acid monoalkyl
esters (e.g., monomethyl itaconate, etc.), maleic acid monoalkyl esters (e.g., monomethyl
maleate, etc.), citraconic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acids
(e.g., acryloyloxymethylsulfonic acid, etc.), acrylamidoalkylsulfonic acids (e.g.,
2-acrylamido-2-methylethanesulfonic acid, etc.), and so on. The acids of the above-enumerated
compounds may be in the form of a salt with an alkali metal (e.g., sodium, potassium,
etc.) or an ammonium ion.
[0049] Preferred among these comonomers are acrylic esters, methacrylic esters, styrenes,
maleic esters, acrylamides, and methacrylamides. These comonomers may be used either
individually or in combinations of two or more thereof. For example, a combination
of n-butyl acrylate and styrene and a combination of n-butyl acrylate and butylstyrene,
t-butylmethacrylamide and n-butyl acrylate can be employed.
[0050] The above-described polymeric magenta couplers usually contain the monomer unit derived
from the compound of formula (IV) in a proportion of from 5 to 80% by weight, and
preferably from 30 to 70% by weight in view of color reproducibility, color developability,
and stability. These polymeric magenta couplers usually have an equivalent molecular
weight (grams of polymer containing 1 mol of a monomer coupler) of about 250 to 4,000,
though not limiting.
[0051] The polymeric couplers according to the present invention are added to a silver halide
emulsion layer or layers adjacent thereto. When added to a silver halide emulsion
layer, the amount of the polymeric magenta coupler to be used ranges from 0.005 to
0.5 mol, and preferably from 0.01 to 0.10 mol, per mol of silver. When added to a
light-insensitive layer, the amount to be used ranges from 0.01 to 1.0 g, and preferably
from 0.1 to 0.5 g, per m².
[0052] The polymeric magenta couplers can be prepared in the same manner as described for
polymeric cyan couplers using the processes of U.S. Patents 3,451,820, 4,080,211,
and 3,370,952, etc. In particular, the above-described polymeric magenta couplers
can be synthesized by using polymerization initiators and solvents disclosed in Japanese
Patent Application (OPI) Nos. 5543/81, 94752/82, 176038/82, 204038/82, 28745/83, 10738/83,
42044/83, and 145944/83. The polymerization temperature should be determined in connection
with the desired molecular weight of the resulting polymer, the kind of the polymerization
initiator to be used, or like factors can be selected from a wide range of from 0°C
or less up to 100°C or more, and usually of from 30°C to 100°C.
[0054] Silver halide which can be used in the photographic emulsion layer of the photographic
material of the present invention may be any of silver bromide, silver iodobromide,
silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred are
silver iodobromide and silver iodochlorobromide having a silver iodide content of
not more than about 30 mol%, and more preferred is silver iodobromide having a silver
iodide content of from about 2 to about 25 mol%.
[0055] The silver halide grains in the photographic emulsion may have a regular crystal
form, such as cubic, octahedral and tetradecahedral forms, an irregular crystal form,
such as a spherical form, a crystal form having a defect, such as a twin, or a composite
crystal form thereof.
[0056] The silver halide may be fine grains having a grain size of about 0.1 µm or smaller
or giant grains having a projected area diameter reaching about 10 µm. The silver
halide emulsion may be a mono-dispersion having narrow size distribution or a poly-dispersion
having broad size distribution.
[0057] The silver halide emulsions to be used can be prepared by known processes as disclosed,
e.g., in
Research Disclosure, No. 17643, pp.22-23, "I. Emulsion Preparation and Types" (Dec., 1978),
ibid, No. 18716, p.648 (Nov., 1979), P. Glafkides,
Chimie et Physique Photographique, Paul Montel (1967), G.F. Duffin,
Photographic Emulsion Chemistry, Focal Press (1966); V.L. Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Press (1964), etc. In some detail, the emulsion can be prepared by any of
the acid process, the neutral process, the ammonia process, etc. The reaction between
a soluble silver salt and a soluble halogen salt can be carried out by any of a single
jet process, a double jet process, a combination thereof, and the like. A so-called
reverse mixing process in which grains are formed in the presence of excess silver
ions may be used. Further, a so-called controlled double jet process, in which a pAg
value of a liquid phase in which silver halide grains are formed is maintained constant,
may also be used. According to the controlled double jet process, a silver halide
emulsion having a regular crystal form and a substantially uniform grain size can
be obtained. Two or more silver halide emulsions separately prepared may be used
as a mixture.
[0058] The silver halide emulsion comprising grains having a regular crystal form (regular
grains) can be prepared by controlling pAg and pH values during grain formation. For
details, reference can be made to, e.g.,
Photographic Science and Engineering, Vol. 6, pp.159-165 (1962);
Journal of Photographic Science, Vol. 12, pp. 242-251 (1964), U.S. Patent 3,655,394, and British Patent 1,413,748.
[0059] The monodisperse emulsion as above referred to typically includes those containing
silver halide grains having a mean grain size of about 0.1 µm or greater, and particularly
of from about 0.25 to 2 µm, in which at least about 95% by weight or number of the
total grains fall within a size range of 40%, and particularly 20%, of the mean grain
size. Such monodisperse emulsions can be prepared by the processes described in U.S.
Patents 3,574,628 and 3,655,394, and British Patent 1,413,748. The monodisperse emulsions
described in Japanese Patent Application (OPI) Nos. 8600/73, 39027/76, 83097/76, 137133/78,
48521/79, 99419/79, 37635/83, and 49938/83, etc. can also be used to advantage in
the present invention.
[0060] Plate-like (tabular) grains having an aspect ratio of about 5 or more (i.e., 5/1
or more) can also be used. Such plate-like grains can be prepared easily by the processes
described in Gutoff,
Photographic Science and Engineering, Vol. 14, pp.248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520,
British Patent 2,112,157, etc. Use of the plate-like grains brings about improvements
on efficiency of color sensitization by sensitizing dyes, graininess, sharpness, and
the like, as suggested in U.S. Patent 4,434,226.
[0061] The individual silver halide crystals may have either a homogeneous structure or
a heterogeneous structure, such as a core-shell structure or a layered structure differing
in halogen composition. These emulsion grains are disclosed in British Patent 1,027,146,
U.S. Patents 3,505,068 and 4,444,877, Japanese Patent Application No. 248469/B3, etc.
Further, they may have a heterogeneous structure in which a silver halide grain having
a different halogen composition or a compound other than silver halides, e.g., silver
thiocyanate, lead oxide, etc., is fused by epitaxy. These emulsion grains are disclosed
in U.S. Patents 4,094,684, 4,142,900, and 4,459,353, British Patent 2,038,792, U.S.
Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962, and 3,852,067, Japanese
Patent Application (OPI) No. 162540/84, etc.
[0062] A mixture of silver halide grains having various crystal forms can also be employed.
[0063] The emulsion to be used in the present invention is usually subjected to physical
ripening, chemical ripening and spectral sensitization. Additives to be used in these
steps and other photographically useful additives which can be used in the present
invention are described in
Research Disclosure (RD), No. l7643 (Dec. l978) and
ibid, No. l87l6 (Nov. l979) as tabulated below.

[0064] In addition to the foregoing cyan and magenta couplers, other various color couplers
can be used in this invention. Specific examples of usable color couplers are described
in
Research Disclosure, No. 17643, VII-C to G. Important are dye forming couplers which produce three primary
colors according to subtractive color process, i.e., yellow, magenta, and cyan. In
this connection, anti-diffusible 4- or 2-equivalent couplers which can be used advantageously
include those described in
Research Disclosure, No. 17643, VII-C to D and, in addition, couplers hereinafter described.
[0065] Yellow couplers to be used typically include hydrophobic acylacetamide couplers having
a ballast group, whose specific examples are given in U.S. Patents 2,407,210, 2,875,057,
and 3,265,506. In the present invention, 2-equivalent yellow couplers are preferred.
Typical examples of such couplers are those of oxygen-release type as described in
U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620; and those of nitrogen-release
type as described in Japanese Patent Publication No. 10739/83, U.S. Patents 4,401,752
and 4,326,024,
Research Disclosure, No. 18053 (Apr., 1979), British Patent 1,425,020, and West German Patent Publication
Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812.
Inter alia, α-pivaloylacetanilide couplers are excellent in color fastness, and particularly
fast ness to light, and α-benzoylacetanilide couplers provide high color densities.
[0066] The magenta couplers which can be used in the present invention include indazolone
or cyanoacetyl couplers, and preferably 5-pyrazolone or pyrazoloazole couplers which
have a ballast group and are thereby hydrophobic. The 5-pyrazolone couplers preferably
have an arylamino group or an acylamino group at the 3-position from the standpoint
of hue and density of the developed color. Typical examples of such couplers are described,
e.g., in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896,
and 3,936,015. Preferred releasable groups for 2-equivalent 5-pyrazolone couplers
are nitrogen atom-release type groups as described in U.S. Patent 4,310,619 and arylthio
groups as described in U.S. Patent 4,351,897. 5-Pyrazolone couplers having the ballast
group described in European Patent 73,636 provide high color densities. The pyrazoloazole
couplers include pyrazolobenzimidazoles described in U.S. Patent 3,061,432, and preferably
pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent 3,725,067, pyrazolotetrazoles
described in
Research Disclosure, No. 24220 (June, 1984) and Japanese Patent Application (OP) No. 33552/85, and pyrazolopyrazoles
described in
Research Disclosure, No. 24230 (Jun., 1984) and Japanese Patent Application (OPI) No. 43659/85. From
the standpoint of reduced side absorption of yellow and light-fastness of the produced
dye, the imidazolo[1,2-b]pyrazoles described in U.S. Patent 4,500,630 are preferred,
and the pyrazolo[1,5-b][1,2,4]triazoles described in U.S. Patent 4,540,654 are particularly
preferred.
[0067] Cyan couplers which can be used in the present invention include hydrophobic and
anti-diffusible naphthoic and phenolic couplers. Typical examples are naphthol couplers
described in U.S. Patent 2,474,293, and preferably 2-equivalent naphthol couplers
of oxygen-release type described in U.S. Patents 4,052,212, 4,146,396, 4,228,233,
and 4,296,200. Examples of the phenolic couplers are described in U.S. Patents 2,369,929,
2,801,171, 2,772,162, and 2,895,826.
[0068] Cyan couplers which form cyan dyes fast to moisture and heat are advantageously used
in the present invention. Typical examples of such cyan couplers include phenolic
couplers having an alkyl group having at least 2 carbon atoms at the m-position as
described in U.S. Patent 3,772,002; 2,5-diacylamino-substituted phenol couplers as
described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173,
West German Patent Publication No. 3,329,729, and European Patent 121,365; phenolic
couplers having a phenylureido group at the 2-position and an acylamino group at the
5-position as described in U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767;
and the like.
[0069] In order to correct unnecessary absorptions of the developed color, it is preferable
to use a colored coupler in combination for masking in color light-senisitive materials
for photogrpahing. Typical examples of the colored couplers are yellow-colored magenta
couplers described in U.S. Patent 4,163,670 and Japanese Patent Publication No. 39413/82
and magenta-colored cyan couplers described in U.S. Patents 4,004,929 and 4,138,258
and British Patent 1,146,368. Other examples of colored couplers are described in
Research Disclosure, No. 17643, VII-G (Dec. 1978).
[0070] Graininess can be improved by using a coupler which forms a dye having moderate diffusibility.
Examples of such a coupler are described in U.S. Patent 4,366,237 and British Patent
2,125,570 for magenta couplers; and in European Patent 96,570 and West German Patent
Publication No. 3,234,533 for yellow, magenta, and cyan couplers.
[0071] The dye forming couplers and the above-described special couplers may be in the form
of a polymer including a dimer. Typical examples of polymerized dye forming couplers
are described in U.S. Patents 3,451,820 and 4,080,211. Typical examples of polymerized
magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
[0072] Couplers capable of releasing a photographically useful residue upon coupling can
also be used in this invention with advantage. Useful examples of DIR couplers which
release a developing inhibitor are described in
Research Disclosure, No.l7643, VII-F (Dec. l978).
[0073] DIR (development inhibitor releasing) couplers which are preferably combined with
the present invention include those which are inactivated in a developer as described
in Japanese Patent Application (OPI) No. 151944/82; timing type DIR couplers as described
in U.S. Patent 4,248,962 and Japanese Patent Application (OPI) No. 154234/82; and
reactive type DIR couplers as described in Japanese Patent Application (OPI) No. 39653/84.
Particularly preferred are developer-inactivated type DIR couplers described in Japanese
Patent Application (OPI) Nos. 151944/82 and 217932/83 and Japanese Patent Application
Nos. 75474/84, 82214/84, and 90438/84; and reactive type DIR couplers described in
Japanese Patent Application No. 39653/84.
[0074] The light-sensitive materials of the present invention can also use couplers which
imagewise release a nucleating agent or a development accelerator or a precursor thereof
at the time of development. Specific examples of these couplers are described in British
Patents 2,097,140 and 2,131,188. Couplers capable of releasing a nucleating agent
having adsorptivity onto silver halide, such as those described in Japanese Patent
Application (OPI) Nos. 157638/84 and 170840/84, are particularly preferred.
[0075] Supports which can be used suitably in the present invention are described, e.g.,
in
Research Disclosure, No. 17643, p.28 (Dec. l987) and
ibid, No.l87l6, p. 647, right column to p. 648, left column (Nov. l979).
[0076] The color photographic material in accordance with the present invention can be subjected
to development processing by known methods as described, e.g., in
Research Disclosure, No. 17643, pp.28-29 (Dec. l978)
ibid, No. l87l6, p. 65l, left to right columns (Nov.l979).
[0077] Color developing solutions to be used for development processing preferably include
alkaline aqueous solutions containing, as a main component, an aromatic primary amine
developing agent. Usable color developing agents include aminophenol compounds, and
preferably p-phenylenediamine compounds. Typical examples of the latter are 3-methyl-4-amino-N,N-di
ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides or
p-toluenesulfonates thereof. These diamines are more stable and thereby preferred
in the form of a salt rather than in a free form.
[0078] The color developing solutions generally contain pH buffers, such as carbonates,
borates or phosphates of alkali metals, and developing inhibitors or antifoggants,
such as bromides, iodides, benzimidazoles, benzothiazoles, mercapto compounds, etc.
If desired, the color developing solutions may further contain preservatives, e.g.,
hydroxylamines, sulfites, etc.; organic solvents, e.g., triethanolamine, diethylene
glycol, etc.; development accelerators, e.g., benzyl alcohol, polyethylene glycol,
quaternary ammonium salts, amines, etc.; competing couplers; nucleating agents, e.g.,
sodium boron hydride, etc.; auxiliary developing agents, e.g., 1-phenyl-3-pyrazolidone,
etc.; tackifiers; various chelating agents, e.g., aminopolycarboxylic acids, aminopolyphosphonic
acids, alkylphosphonic acids, phosphonocarboxylic acids, etc.; antioxidants, e.g.,
those described in West German Patent Publication No. 2,622,950; and the like.
[0079] Reversal color light-sensitive materials are usually subjected to black-and-white
development and then to color development. Black-and-white developing solutions to
be used can contain one or more of known black-and-white developing agents, such as
dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone)
and aminophenols (e.g., N-methyl-p-aminophenol).
[0080] The photographic emulsion layers after color development are usually subjected to
bleaching. Bleaching may be effected simultaneously with fixation, or these two steps
may be carried out separately. For speeding up of processing, bleaching may be followed
by bleach-fixation (blix). Bleaching agents to be used in bleaching or blix include
compounds of polyvalent metals, e.g., iron (III), cobalt (III), chromium (VI), copper
(II), etc., peracids, quinones, nitroso compounds, and the like. Examples of these
bleaching agents are ferricyanides; bichromates; organic complex salts of iron (III)
or cobalt (III), such as complex salts with aminopolycarboxylic acids, e.g., ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic
acid, etc., or organic acids, e.g., citric acid, tartaric acid, malic acid, etc.;
persulfates; manganates; nitrosophenol; and so on. Of these, (ethylenediaminetetraacetato)iron
(III) salts, (diethylenetriaminepentaacetato)iron (III) salts and persulfates are
preferred in view of speeding up of processing and conservation of the environment.
In particular, (ethylenediaminetetraacetato)iron (III) salts are useful in both of
an independent bleaching bath and a bleach-fix monobath.
[0081] The bleaching bath, bleach-fix bath or a pre-bath thereof can contain, if desired,
a bleaching accelerator. Examples of useful bleaching accelerators are compounds having
a mercapto group or a disulfide group as described in U.S. Patent 3,893,858, West
German Patents 1,290,812 and 2,059,988, Japanese Patent Application (OPI) Nos. 32736/78,
57831/78, 37418/78, 65732/78, 72623/78, 95630/78, 95631/78, 104232/78, 124424/78,
141623/78 and 28426/78,
Research Disclosure, No. 17129 (July 1978); thiazolidine derivatives as described in Japanese Patent
Application (OPI) No. 140129/75; thiourea derivatives as described in Japanese Patent
Publication No. 8506/70, Japanese Patent Application (OPI) Nos. 20832/77 and 32735/78,
and U.S. Patent 3,706,561; iodides as described in West German Patent 1,127,715 and
Japanese Patent Application (OPI) No. 16235/83; polyethylene oxides as described in
West German Patents 966,410 and 2,748,430; polyamine compounds as described in Japanese
Patent Publication No. 8836/70; the compoudns described in Japanese Patent Application
(OPI) Nos. 42434/84, 59644/74, 94927/78, 35727/79, 26506/80, and 163940/83; and iodine
or bromine ions. Preferred among them are compoudns having a mercapto group or a disulfide
group because of their great acceleratory effects. In particular, the compounds disclosed
in U.S. Patent 3,893,858, West German Patent 1,290,812 and Japanese Patent Application
(OPI) No. 95630/78 are preferred. The compounds disclosed in U.S. Patent 4,552,834
are also preferred. These bleaching accelerators may be incorporated into the light-sensitive
material. These bleaching accelerators are particularly effective for bleach-fix
of color light-sensitive materials for photography.
[0082] Fixing agents to be used for fixation include thiosulfates, thiocyanates, thioethers,
thioureas, and a large amount of iodides, with thiosulfates being commonly employed.
Sulfites, bisulfites or carbonylbisulfite addition compounds are suitably used as
preservatives of the bleach-fix bath or fixing bath.
[0083] The bleach-fix or fixation is usually followed by washing and/or stabilization. Washing
and stabilizing solutions may contain various known compounds for the purpose of preventing
precipitation or saving water. For example, additives to be used for prevention of
precipitation include water softeners, such as inorganic phosphoric acids, aminopolycarboxylic
acids, organic aminopolyphosphonic acids, organic phosphoric acids, etc.; bactericides
or fungicides; and metal salts, such as magnesium salts, aluminum salts and bismuth
salts. Surface active agents and various hardeners can also be added for the purpose
of reducing a drying load or preventing uneven drying. The compounds described in
L.E. West,
Photo. Sci. Eng., Vol. 6, pp.344-359 (1965) may also be used. In particular, addition of chelating
agents and fungicides is effective.
[0084] Washing is generally carried out by using two or more washing vessels arranged countercurrently,
by which water saving can be effected. The washing step may be replaced by a multi-stage
countercurrent stabilization step as described in Japanese Patent Application (OPI)
No. 8543/82, in which 2 to 9 vessels arranged countercurrently are required. The stabilization
baths to be used in this step contain various compounds for image stabilization in
addition to the aforesaid additives. Such compounds include various buffers for film
pH adjustment (e.g., to a pH of from 3 to 9) (e.g., borates, metaborates, borax, phosphonates,
carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic
acids, dicarboxylic acids, polycarboxylic acids and combinations thereof) and aldehydes,
e.g., formalin. If desired, the stabilization bath may further contain other additives,
such as chelating agents (e.g., inorganic phosphoric acids, aminopolycarboxylic acids,
organic phosphoric acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc.),
bactericides (e.g., benzoisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole,
halogenated phenols, sulfanilamide, benzotriazole, etc.), surface active agents,
fluorescent brightening agents, hardeners, and the like. These compounds may be added
in combinations of two or more thereof for the same or different purposes.
[0085] It is preferable to add various ammonium salts to the stabilization bath as film
pH adjusting agents after processing. Examples of such ammonium salts are ammonium
chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite,
ammonium thiosulfate, etc.
[0086] For processing of color light-sensitive materials for photographing, the (washing-stabilization)
step after fixation that is commonly adopted may be replaced by the aforesaid stabilization
step and washing step (water saving processing). In this case, if the magenta coupler
used is 2-equivalent, formalin may be excluded from the stabilization bath.
[0087] The time required for washing and stabilization varies depending on the type of the
light-sensitive material processed and the conditions for processing, and usually
ranges from 20 seconds to 10 minutes, and preferably from 20 seconds to 5 minutes.
[0088] For the purpose of simplification and speeding up of processing, a color developing
agent, preferably in the form of its precursor, can be incorporated into the silver
halide color photographic material according to the present invention. The precursors
of the color developing agent suitable for incorporation include indoaniline compounds
as described in U.S. Patent 3,342,597, Schiff base type compounds as in U.S. Patent
3,342,599,
Research Disclosure, No. l4850 (Aug. l976) and
ibid, No. l5l59 (Nov. l976), aldol compounds as in
Research Disclosure, No. 13924, metal complexes as in U.S. Patent 3,719,492, urethane compounds as in
Japanese Patent Application (OPI) No. 135628/78, as well as various salt types as
in Japanese Patent Application (OPI) Nos. 6235/81, 16133/81, 59232/81, 67842/81, 83734/81,
83735/81, 83736/81, 89735/81, 81837/81, 54430/81, 106241/81, 107236/81, 97531/82,
and 83565/82, etc.
[0089] For the purpose of accelerating color development, the color light-sensitive materials
of the present invention can further contain therein various 1-phenyl-3-pyrazolidones.
Typical examples thereof are described in Japanese Patent Application (OPI) Nos. 64339/81,
144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83, and 115438/83,
etc.
[0090] Each of the above-described processing solutions is used at a temperature between
10°C and 50°C, and usually between 33°C and 38°C. It is possible to use higher temperatures
to accelerate processing to thereby reduce the processing time or lower temperatures
required to achieve improvements on image quality or stability of processing solutions.
In order to save silver used in light-sensitive materials, intensification may be
carried out by using a cobalt or hydrogen peroxide intensifier, as described in West
German Patent 2,226,770 or U.S. Patent 3,674,499.
[0091] If necessary, each of the processing baths may be provided with a heater, a temperature
sensor, a liquid level sensor, a circulating pump, a filter, a floating lid, a squeegee,
etc.
[0092] In cases where processing is carried out in a continuous manner, a constant finish
can be assured by preventing variations of processing solution compositions by using
a replenisher for each processing solution. The amount to be replenished can be reduced
to a half or less of the standard amount to cut the cost.
[0093] The present invention is now illustrated in greater detail by way of the following
examples, but it is to be understood that the present invention is not limited thereto.
EXAMPLE 1
[0095] Each of the above layers further contained Gelatin Hardener H-1 and a surface active
agent.
[0096] In the preparation of Sample 101, the coating composition for the 3rd layer was prepared
as follows.
[0097] In 150 ml of ethyl acetate were dissolved 60 g of Coupler I-13 and 3.4 g of Coupler
C-4 under heating, and the solution was mixed with 1000 g of a 10 wt% aqueous solution
of gelatin having dissolved therein 5.0 g of sodium dodecylbenzenesulfonate, and the
mixture was dispersed in a domestic mixer for 10 minutes.
[0098] Samples 102 to 110 were prepared in the same manner as for Sample 101, except that
Couplers I-13 and C-4 as used in the 3rd and 4th layers were changed in kind and amount
as shown in Table 1 below, and that the gelatin coverage was adjusted so that the
film strength of the 3rd layer and that of the 4th layer were equal.
[0099] Each of Samples 101 to 110 was imagewise exposed to white light for sensitometry
and then subjected to color development processing according to the following procedure
at 38°C. The processed sample was determined for density through a red filter. Further,
each of the samples was exposed to light through a pattern for MTF measurement and
then subjected to the same color development processing to calculate an MTF value
at a spatial frequency of 25 c/mm. The results obtained are shown in the Table.

[0101] Note:
1) Colorless coupler of the 3rd and 4th layers other than colored couplers and DIR
compounds.
2) Weight ratio of HBS-1 (high-boiling point organic solvent) to the main cyan coupler
of the present invention.
3) Relative ratio of DIR coupler to the main coupler of the present invention, taking
that of Sample l0l as l (standard).
4) Relative logarithm of a reciprocal of an exposure providing a cyan dye density
of fog + 0.5, taking that of Sample 101 as O (standard).
5) Fine crystals were observed in the sample, and the MTF measurement was impossible.
[0102] It can be seen from Table 1 that the comparative samples, in which a cyan coupler
out of the scope of the present invention is dispersed with the aid of a high-boiling
organic solvent, undergo precipitation of the coupler as observed in Samples 106 and
107 or reduction of color developability as observed in Sample 108, while all the
samples according to the present invention (Samples 101 to 103) exhibit satisfactory
color developability. It is also apparent that Samples 101 to 103 show obviously increased
MTF values indicative of improved sharpness as compared with Sample 104 or 105 in
which the coupler within the scope of the present invention is combined with a large
amount of the high-boiling point organic solvent.
EXAMPLE 2
[0103] Sample 201 was prepared in the same manner as for Sample 101 of Example 1, except
for replacing Coupler C-4 in the 3rd and 4th layers with one-half the molar quantity
of C-14, replacing Coupler C-5 in the 5th layer with two-third the molar quantity
of Coupler I-14, and further replacing Coupler C-9 in the 9th layer with one-half
the molar quantity of Coupler C-15.
[0104] Samples 202 to 206 were prepared in the same manner as for Sample 201, except that
the main coupler in the 3rd and 4th layers, Coupler I-13, was replaced with the equimolar
amount of each of Couplers I-11, I-3, I-53, C-11, and C-13, respectively.
[0105] Sample 207 was prepared in the same manner as for Sample 201, except for replacing
the main coupler in the 7th and 8th layers, Coupler C-6, with double the molar amount
of Coupler C-16 and using an additional amount of gelatin to make the film strength
of both layers equal.
[0106] Sample 208 was prepared in the same manner as for Sample 201, except that the main
coupler of the 7th and 8th layers, Coupler C-6, was replaced with double the molar
amount of Coupler C-9 and the amount of the organic solvent was doubled to make the
color developability and preservability substantially equal to those of Sample 201.
[0107] Each of Samples 201 to 208 was exposed to light and development-processed in the
same manner as described in Example 1. The processing of Example 1 is herein designated
as Processing A. The sensitivity, gamma, and MTF values of the processed samples were
determined. In addition, the cyan density of the processed samples on the point having
been exposed at an exposure of 1 × 20⁻³ CMS was also measured. The results obtained
are shown in Table 2 below.
[0108] Further, the same procedure was repeated, except for replacing the bleaching solution
as used in Processing A with a bleaching solution prepared as follows. This processing
is designated as Processing B. The bleaching solution used in Processing B was designed
to be a model of a fatigued processing solution after use for processing a large quantity
of light-sensitive materials.
[0109] The samples having been processed according to Processing B were determined for cyan
density in the same manner as described above. The results obtained are also shown
in the Table.

[0110] Steel wool was poured into (D-2), and the preparation was sealed and left to stand
to allow Fe(III)-EDTA to be converted to Fe (II)-EDTA. A 100 ml portion of the resulting
solution was added to (D-1).

[0111] From Table 2, the following observations can be made. Sample 205 using the comparative
coupler showed an extremely low color density so that the relative sensitivity, gamma,
and MTF value were unmeasurable. Sample 206 shows considerable reduction in cyan
color density when processed with a fatigued bleaching solution.
[0112] On the other hand, Samples 201 to 204 according to the present invention sufficiently
satisfy these performance requirements, clearly demonstrating the effectiveness of
the present invention. Further, it can be seen that Samples 207 or 208, in which a
4-equivalent polymeric magenta coupler (C-16) or a 4-equivalent magenta coupler (C-9)
was used, respectively, in the 7th and 8th layers, shows a slightly reduced MTF value.
In other words, the effects of the cyan couplers of the invention to improve sharpness
can be ensured by using 2-equivalent magenta couplers in combination rather than 4-equivalent
magenta couplers.
[0114] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.