JP2866941B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial applications)   BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic light-sensitive materials, and
Silver halide color photographic light-sensitive materials with improved durability
You. (Conventional technology)   After exposing the silver halide photographic material,
Oxidized by silver halide by image processing
The aromatic primary amine developing agent reacts with the color-forming coupler,
A color image is formed.   4-equivalent coupler as yellow image forming coupler
Alternatively, JP-A-50-87650, British Patent No. 3,369,695,
No. 3,408,194, 3,415,652, 3,447,928
One hydrogen atom of the active methylene group
Oxy group, halogen element, sulfoxy group, acyloxy
Α-acyl acetanilides substituted by a group such as
As is known, these couplers have a coupling reaction activity.
Disadvantages such as insufficient image quality and poor image fastness
I was   Insufficient color developability due to fluctuations in developer components
In that the sex change is large and stable quality cannot be obtained.
This is a problem, and the improvement in image robustness depends on the storage time.
Because improvement of quality is a cause, improvement is strongly desired.
Noh. (Problems to be solved by the invention)   Overcoming these disadvantages, more active yellow coupler
Is an active methylene group described in JP-A-47-26133.
One hydrogen atom is directly linked by a heterocycle containing a nitrogen atom.
Indirectly substituted couplers are known.   However, when using these couplers
Is the light of the yellow image generated, although the color development is improved,
And its robustness under wet heat conditions has been significantly improved.
Still, it was not enough.   On the other hand, hindered yellow image stabilizers
Amines and indadophenols are UK patent 1326889
Nos. 1354313 and 1410846.   However, these compounds are certainly yellow
Although it improves the robustness of the image, its effect is small and
It was not a minute.   Therefore, an object of the present invention is to provide an excellent color developing property and a yellow color.
Silver halide color photographic exposure with improved color image fastness
It is to provide materials. (Means to solve the problem)   As a result of various studies to achieve the object of the present invention,
A small amount of the yellow coupler represented by the following general formula (I)
At least one of the compounds represented by the following general formula (A)
Silver halide color photographic photosensitive material containing at least one kind
Find that the material achieves the object of the invention
Was.   General formula (I)  Where R¹Is a substituted or unsubstituted N-phenylcarbamoy
R^TwoIs a substituted or unsubstituted alkyl group or
Represents a substituted or unsubstituted aryl group; X¹Is below
Represents a group represented by formula (a), (b) or (c).   In the formulas (a) and (b), R^Three, R^FourAre the same but different
May be hydrogen, halogen, carboxylic acid
Ter group, amino group, alkyl group, alkylthio group, al
Coxy group, alkylsulfonyl group, alkylsulfini
Group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted
Represents a substituted phenyl group or a heterocyclic ring.   In equation (c), W¹Is in the formula (c) Required to form a 4-, 5-, or 6-membered ring with
Represents a non-metallic atom.   General formula [A] (Where R^Five, R⁶, R⁷And R⁸Is a hydrogen atom or
Represents a substituent, Y₁And Y_TwoAre hydrogen atom and fat respectively
Group, aromatic group, heterocyclic group, acyl group, sulfonyl group, etc.
X represents a single bond or a divalent linking group
And n represents 1 or 2. However, the substitution position of X is
−OY₁Or -OY_TwoIn the ortho or para position with respect to
Y when it is in para position₁And Y_TwoOne of them is a hydrogen atom
And the other is not a hydrogen atom. )   The two-equivalent coupler used in the present invention has the general formula (I)
This will be described in detail below.   In the formula (I), R¹Is a substituted or unsubstituted N-phenylcar
Represents a bamoyl group, and represents an N-phenylcarbamoyl group
Substituents include well-known substitutions in yellow couplers.
Groups such as alkyl, alkenyl, alkoxy,
Alkoxycarbonyl group, halogen atom, alkoxyca
Rubamoyl group, aliphatic amide group, alkylsulfamoi
Group, alkylsulfonamide group, alkylureido
Group, alkyl-substituted succinimide group, aryloxy
Group, aryloxycarbonyl group, arylcarbamoy
Group, arylamide group, arylsulfamoyl group,
Arylsulfonamide group, arylureido group, cal
Boxoxy, sulfo, nitro, cyano, thiocyano
Represents a group or the like. There may be two or more substituents,
In this case, they may be the same or different.   R^TwoWhen represents an alkyl group,
Tertiary alkyl groups are preferred, for example, t-butyl group, t-
Amyl group, t-octyl group, 1,1-diethylpropyl
Group, 1,1-dimethylhexyl group, 1,1,5,5-tetramethyl
Hexyl groups and the like are mentioned as typical examples. R^Two
Is a substituent of the substituted alkyl group or the substituted aryl group of R¹
Are typical examples.   X¹The coupling-off group is a 2-equivalent yellow coupler.
The coupling-off group to be formed, that is, the following general formula (a),
Represents a group represented by (b) or (c).  R^Three, R^FourAre hydrogen, halogen, carboxylic acid
Stel group, amino group, alkyl group, alkylthio group,
Lucoxy group, alkylsulfonyl group, alkylsulfi
Nyl group, carboxylic acid group, sulfonic acid group, unsubstituted or
Represents a substituted phenyl group or a heterocyclic ring, and these groups are
They may be the same or different.   W¹Is in the formula Required to form a four-, five-, or six-membered ring with
Represents a non-metallic atom.   More preferred in the yellow coupler used in the present invention
Those are represented by the following general formula (I ').   General formula (I ')   Where R⁹A tertiary alkyl group having 4 to 12 carbon atoms, or
Represents a halogen atom, an alkyl group, or an alkoxy group.
Represents a substituted phenyl group or an unsubstituted phenyl group
You. R^TenRepresents a halogen atom or an alkoxy group. R
¹¹Has a hydrogen atom, a halogen atom or a substituent,
Represents a good alkoxy group. R¹²Has a substituent
Acylamino group, alkoxycarbonyl group,
Killsulfamoyl group, aryl group sulfamoyl group,
Alkylsulfonamide group, arylsulfonamide
Group, alkyl ureide group, aryl ureide group, succi
An imido group, an alkoxy group, or an aryloxy group
Express.   X^TwoIs represented by the following general formula (d), (e) or (f)
Represents the notation.   Where R¹³, R¹⁴Represents a hydrogen atom, an alkyl group,
Group, alkoxy group, aryloxy group or hydroxy group
Represents a group. R¹⁵, R¹⁶And R¹⁷Is a hydrogen atom,
A kill group, an aryl group, an aralkyl group, or an acyl group.
Express. W^TwoRepresents an oxygen or sulfur atom.   Particularly preferred in the yellow coupler used in the present invention
Those are represented by the following general formula (I ″).   General formula (I ″)   Where R¹⁸Is an alkyl group which may have a substituent.
Or a phenyl group.   These yellow couplers are described, for example, in JP-B-51-10783.
No. 51-33410, No. 51-33410, JP-A-47-26133
No. 48-73147, No. 51-102636, No. 52-82424,
No. 52-115219, UK Patent 1425020, West German Patent 1547868
Can be synthesized according to the method described in the above item.   Next, a yellow coupler component represented by the general formula (I)
Examples are shown, but the present invention is not limited to these.
No.   Next, R in the general formula [A]^Five, R⁶, R⁷, R⁸, X,
Y₁, Y_TwoAnd n will be described in detail.   In general formula [A], R^Five, R⁶, R⁷And R⁸Each
Represents a hydrogen atom or a substituent, and is preferably a substituent.
Aliphatic groups, aromatic groups (eg, phenyl,
), A heterocyclic ring (for example, 2-pyridyl, 2-tetrahydrid
Lopyranyl), a halogen atom (for example, fluorine, chlorine,
Bromine), aliphatic oxy group (for example, methoxy, butoxy)
C), acyloxy group (eg, acetoxy, benzoyl
Oxy), sulfonyloxy (eg, benzenesulfo
Nyloxy), acylamino group (eg, acetylamino
Benzoylamino), sulfonamide group (for example,
Methanesulfonamide), amino groups, aliphatic and aromatic
Group oxycarbonyl group (for example, phenoxycarboni
, Butoxycarbonyl), carbamoyl group (for example,
Dimethylcarbamoyl, phenylcarbamoyl), hydride
And a roxy group. R when n is 2_ThreeAnd R_FourIs
Each may be the same or different.   In general formula [A], Y₁And Y_TwoAre hydrogen sources
Radicals, aliphatic radicals, aromatic radicals (eg phenyl, naphthy
), A heterocyclic group (eg, 2-pyridyl, 2-tetrahi
Dropyranyl), an acyl group (eg, acetyl, benzo
Yl, 2-ethylhexyloxycarbonyl), sulfo
Nil group (for example, methanesulfonyl, benzenesulfonyl
) And silyl groups (for example, trimethylsilyl)
I, when n is 2, Y_TwoAre the same but different
Is also good.   In the general formula [A], X represents a single bond or a divalent linking group.
And an example of a preferred linking group is an alkylidene group
(Eg, methylene, isopropylidene), acyl bond
, Oxygen atom, sulfur atom, sulfonyl bond, amino
Groups, ester bonds and amino bonds.   In the general formula [A], n represents 1 or 2.   As used herein, the term "aliphatic group" refers to a linear, branched or
Represents a cyclic aliphatic hydrocarbon group, alkyl, alkenyl
And saturated and unsaturated compounds such as alkynyl groups
Meaning. Typical examples are methyl and ethyl.
Group, butyl group, dodecyl group, octadecyl group, iconose
Nil, iso-propyl, tert-butyl, tert-o
Octyl, tert-dodecyl, cyclohexyl, cyclo
Lopentyl group, allyl group, vinyl group, 2-hexadecenyl
And propargyl group.   Among the substituents described above, those that can be substituted further include
An alkyl group, an aryl group, a heterocyclic group, an alkoxy group
(E.g., methoxy group, 2-methoxyethoxy group
An aryloxy group (eg, 2,4-di-tert-a)
Milphenoxy group, 2-chlorophenoxy group, 4-sia
Nophenoxy group, etc.), alkenyloxy group (for example,
An acyl group (e.g., 2-propenyloxy group, etc.)
Cetyl group, benzoyl group, etc.), ester group (for example,
Butoxycarbonyl group, phenoxycarbonyl group, ace
Toxyl group, benzoyloxy group, butoxysulfonyl
Group, toluenesulfonyloxy group, etc.), amide group (eg
For example, acetylamino, ethylcarbamoyl,
Tylcarbamoyl group, methanesulfonamide group, butyl
Sulfamoyl group), sulfamide group (for example,
Propylsulfamoylamino group, etc.), imide group (eg
For example, succinimide group, hydantoinyl group, etc.), c
Raid group (for example, phenylureido group, dimethylureide
Group), an aliphatic or aromatic sulfonyl group (eg,
For example, methanesulfonyl group, phenylsulfonyl group
), An aliphatic or aromatic thio group (eg, ethylthio)
Group, phenylthio group, etc.), hydroxy group, cyano
Group, carboxy group, nitro group, sulfo group, halogen atom
And the like.   In the general formula [A], preferably Y₁, Y_TwoFew of
At least one is preferably not a hydrogen atom.
It is particularly preferred that the hydrogen atom is the other and the other is not a hydrogen atom
No.   In the general formula [A], X is preferably not a single bond.
No.   In formula [A], -OY₁Or -OY_TwoAnd X respectively
Is preferably an ortho or para position, and an ortho position
Is more preferred.   In general formula [A], Y₁And Y_TwoAre hydrogen sources
Preferred are aliphatic, aliphatic and acyl groups.   Specific examples of the compounds represented by the general formula [A] are shown below.
Although shown, the present invention is not limited to these.   The synthesis method of the phenol derivative used in the present invention is known.
Yes, for example G. Casiraghiet,al.,Makromol Chem,1
83, 2611 (1982), the method described in JP-A-60-8088, etc.
And a phenol derivative can be synthesized from JP-B-61-34664.
Oxygen substituent by the method described in JP-A-62-262047.
Can be guided to   The couplers represented by the general formula (I) are present in the same layer
1 × 10 per mole of silver halide^-3Mole to 1 mole ratio
Is preferably added to the emulsion layer, more preferably 5 ×
Ten^-2Mol ~ 5 x 10^-1It is a mole ratio.   The compound of the general formula (A) is represented by the general formula (I)
1 to 200 mol% of the coupler
Good, particularly preferably in the range of 2 mol% to 30 mol%.
You.   In carrying out the present invention, it is represented by the general formula (I)
The lipophilic coupler and the compound represented by the general formula (A) are
It is preferable to dissolve or impregnate the oily fine particles. This
As the substance constituting the lipophilic fine particles of
In addition, if desired, an oily solvent for additives such as couplers (wash
(Including those fixed in greenhouses such as boxes) or poly
Mer, coupler, color mixture inhibitor, ultraviolet absorber, etc.
The additive itself is a substance also serving as an oily solvent.   Here, the lipophilic fine particles are substantially equivalent to the aqueous gelatin solution.
Fine particles that do not dissolve and exist as a separate phase in the aqueous gelatin solution
Means child.   The lipophilic fine particles according to the present invention usually have the general formula (I)
The coupler and the compound of the formula (A) have a boiling point of 17 at atmospheric pressure.
High boiling point solvent (oil) alone at 0 ° C or higher or low boiling point solvent
Medium alone (if oil is not required as described above), or
It is dissolved in a mixed solvent of the oil and a low boiling point solvent,
The solution is emulsified and dispersed in an aqueous solution of hydrophilic colloid such as gelatin.
Prepared. There is no particular limitation on the particle size of the lipophilic fine particles,
0.05μ ~ 0.5μ is preferred, especially 0.1μ ~ 0.3μ is preferred
No.   The oil / coupler ratio was 0.1% by weight.
It is preferably from 00 to 2.0.   Specific examples of the oil include, for example, phthalic acid
Kill ester (dibutyl phthalate, dioctyl phthalate
, Diisodecyl phthalate, dimethoxyethyl phthalate
Rate, etc.), phosphate esters (diphenyl phosphe)
, Triphenyl phosphate, tricresyl fluor
Sulfate, dioctyl butyl phosphate, monoph
Enyl-pt-butylphenylphosphate, trio
Custyl phospate, trinonyl phospate),
Citrate esters (eg, acetyl citrate
Benzoic acid esters (eg, octyl benzoate),
Alkyl amides (eg, diethyl lauryl amide, dib
Tyl lauryl amide), fatty acid esters (eg dib
Toxiethyl succinate, diethyl azelate),
Limesic acid esters (for example, Trimesic acid
Le).   In addition, polymers such as acrylic acid, methacrylic acid, etc.
And its esters (eg, methyl acrylate, ethyl
Acrylate, butyl methacrylate, etc.), acrylic
Amides, methacrylamides, vinyl esters (eg,
Vinyl acetate, vinyl propionate, etc.)
Rilonitrile, styrene, divinylbenzene, vinyla
Alkyl ether (for example, vinyl ethyl ether), male
Formate esters (eg methyl maleate),
N-vinyl-2-pyrrolidone, N-vinylpyridine, 2
Mono- and 4-vinylpyridine, etc. alone
Or latex polymers produced using two or more
Is a water-insoluble organic solvent-soluble polymer.   In addition, the lipophilic fine particles according to the present invention are used for producing fine particles.
Low boiling point solvent, the boiling point at atmospheric pressure
150 ° C organic solvent such as ethyl acetate, isopropyl acetate
, Lower alkyl acetates such as butyl acetate,
Ethyl onate, methanol, ethanol, secondary butyl alcohol
Alcohol, cyclohexanol, fluorinated alcohol,
Tyl isobutyl ketone, β-ethoxyethyl acetate
, Methyl cellosolve acetate, acetone, methyl acetate
Seton, acetonitrile, dioxane, dimethylform
Amide, dimethyl sulfoxide, chloroform, cyclo
Hexane and the like can be mentioned.   Further, the compound of the present invention also forms a photosensitive material.
Various known materials, for example, silver halide,
And cyan couplers.   As the magenta coupler that can be used in the present invention,
Leprotected, indazolone or cyanoases
Cyl, preferably 5-pyrazolone and pyrazolot
Pyrazoloazole couplers such as lyazoles
Can be 5-pyrazolone couplers are aryl at the 3-position
Coupler substituted with amino group or acylamino group
Is preferred in terms of the hue and color density of the coloring dye,
Representative examples are U.S. Pat.Nos. 2,311,082 and 2,343,703,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and 3,936,015 etc.
Have been. Removal of 2-equivalent 5-pyrazolone coupler
As the base, the nitrogen source described in U.S. Pat.No. 4,310,619
A leaving group or as described in U.S. Pat.No. 4,351,897.
A reelthio group is preferred. Also described in European Patent 73,636.
The 5-pyrazolone couplers with ballast groups listed
High color density.   Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in 369,879, preferred
Or pyrazolo described in U.S. Pat.No. 3,725,067
[5,1-c] [1,2,4] triazoles, Research Day
Pyrazolo described in Closure 24220 (June 1984)
Tetrazoles and Research Disclosure 24
230 (June 1984) pyrazolopyrazoles
I can do it. Low yellow absorption and light of colored dye
In terms of robustness, the imidazo described in EP 119,741
[1,2-b] pyrazoles are preferred, EP 119,8
No. 60 pyrazolo [1,5-b] [1,2,4] triazolone
Is particularly preferred.   The cyan coupler that can be used in the present invention includes oil
Protected naphthol and phenolic caps
Naphtow described in U.S. Patent No. 2,474,293
Based couplers, preferably U.S. Pat.No. 4,052,212,
Nos. 4,146,396, 4,228,233 and 4,296,200
No. 2 naphthol-based oxygen atom-elimination type
Puller is a typical example. Also phenolic
Specific examples of pullers are described in U.S. Pat.Nos. 2,369,929 and 2,80
Nos. 1,171, 2,772,162, 2,895,826, etc.
It is listed. Cyan cap robust against humidity and temperature
Is preferably used in the present invention, and typical examples thereof are given below.
The phenol described in U.S. Patent No. 3,772,002
Phosphors having an alkyl group at the meta-position of the nucleus that is greater than or equal to the ethyl group
Nol based cyan coupler, U.S. Pat.No. 2,772,162,
No. 3,758,308, No. 4,126,396, No. 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and
2,5-diacylamino described in No. 58-42671
Substituted phenolic couplers and U.S. Patent 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Phenylureido group at the 2-position described in 7,767 and the like
Having an amino group and having an acylamino group at the 5-position
And system couplers.   In addition, antioxidants, color enhancers, ultraviolet absorbers,
Prevent fading of anne, magenta and / or yellow dye images
Agent, color mixture inhibitor, stain inhibitor, antifoggant, spectral
Sensitizer, dye, hardener, surfactant, antistatic agent, development
An accelerator and a desilvering accelerator can be added.   Hereinafter, the color developer of the present invention will be described.   The color developer used in the present invention contains a known fragrance.
Contains a primary amine color developer. Preferred example
Is a p-phenylenediamine derivative.
However, the present invention is not limited to these. D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-Amino-5- (N-ethyl-N-lauryl
Amino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl
Le) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-
Droxyethyl) amino] aniline D-6 4-Amino-3-methyl-N-ethyl-N-
(Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenyl
Ruethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-Amino-3-methyl-N-ethyl-N-me
Toxiethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-Amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline   Particularly preferred among the above p-phenylenediamine derivatives
4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline (exemplification
Compound D-6).   In addition, these p-phenylenediamine derivatives are made of sulfuric acid.
Salt, hydrochloride, sulfite, p-toluene sulfonate, etc.
May be used. Use of the aromatic primary amine developing agent
The dosage is preferably from about 0.1 g to about 20 g per developer, more
Preferably, the concentration is from about 0.5 g to about 10 g.   Also, sodium sulfite is used as a preservative in color developers.
, Potassium sulfite, sodium bisulfite, calcium bisulfite
Lium, sodium metasulfite, potassium metasulfite, etc.
If necessary, sulfites and carbonyl sulfite adducts
Can be added.   In addition, the color developing agent is directly used as a preservative compound.
Various hydroxylamines, Japanese Patent Application No. 61-186559
Hydrazic acids described in JP-A-61-170756.
And hydrazides, pp. 61-188742 and 61-203253.
The phenols described in JP-A-61-188741
Loxyketones and α-aminoketones and / or
It is preferable to add various sugars described in JP-A-61-180616.
Also, in combination with the above compounds, Japanese Patent Application Nos. 61-147823 and 61-147823.
-16674, 61-165621, 61-164515, 61-
No. 170789, and monoamines described in No. 61-168159
Nos. 61-173595, 61-164515, 61-186560
Diamines, etc., 61-165621, and 61-16
Polyamines described in No. 9789 and polyamines described in No. 61-188619.
Amines, nitroxy radicals described in JP-A-61-197760
Alcohol described in Nos. 61-186561 and 61-197419
Oximes described in JP-A-61-198987;
It is preferable to use tertiary amines described in No. 5149.   Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, JP-A-59-180588
Salicylic acids, alkanol alcohols described in JP-A-54-3532
Mines, polyethyleneimine described in JP-A-56-94349
, The aromatic polyhydroxyl described in U.S. Pat.
Si compounds may be contained as needed. Especially aromatic
Addition of polyhydroxy compound and triethanolamine
Is preferred.   The color developer used in the present invention is preferably pH 9
~ 12, more preferably 9 ~ 11.0, and its color development
The liquid contains other known developer component compounds.
be able to.   In order to maintain the above pH, it is necessary to use various buffers.
preferable. Specific examples of the buffer include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, dinatriphosphate
Potassium, dipotassium phosphate, sodium borate, potassium borate
Lium, sodium tetraborate (borax), potassium tetraborate
Sodium, sodium o-hydroxybenzoate (salicylic acid
Sodium), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (5-sul
Sodium fosalicylate), 5-sulfo-2-hydroxy
Potassium benzoate (potassium 5-sulfosalicylate)
And the like. However, the present invention
It is not limited to these compounds.   The amount of the buffer added to the color developer was 0.1 mol / mol.
More preferably, it is particularly 0.1 mol / ~ 0.4 mol.
/ Or more is particularly preferable.   In addition, calcium and magnesium
Stability of color developer
Various chelating agents can be used to improve
You.   Specific examples are shown below, but are not limited to these.
No.   Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethyl
Diamine tetraacetic acid, N, N, N-trimethylene phosphone
Acid, ethylenediamine-N, N, N ', N'-tetramethylene
Phosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, glycol ether di
Amine tetraacetic acid, ethylenediamine orthohydroxyphene
Nylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic
Acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
N, N'-bis (2-hydroxybenzyl) ethylenedia
Min-N, N'-diacetic acid   These chelating agents may be used in combination of two or more if necessary.
Is also good.   The amount of these chelating agents added depends on the amount of metal in the color developer.
It is sufficient if the amount is sufficient to block ions. For example, 1
It is about 0.1g to 10g per unit.   An optional development accelerator may be added to the color developer if necessary.
Can be added.   The aforementioned compound used in the present invention is substantially a benzene.
In the case of color developer containing no alcohol
Particularly remarkable effects can be obtained. The amount of benzyl alcohol is
0.5 ml / or less is preferable, and most preferable is not contained at all.
Is not the case.   Other development accelerators include JP-B-37-16088,
7-5987, 38-7826, 44-12380, 45-9919
No. 3,813,247 and the like.
Ter compounds, JP-A-52-49829 and JP-A-50-15554
The p-phenylenediamine compound represented by
No. 137726, JP-B-44-30074, JP-A-56-156826
And quaternary ammonium represented by Nos. 52-43429, etc.
Salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,23
Nos. 0,796 and 3,253,919, JP-B-41-11431, U.S.
No. 2,482,546, 2,596,926 and 3,582,346
Amine compounds described in JP-B-37-16088, 42-2
No. 5201, U.S. Pat.No. 3,128,183, JP-B-41-11431,
No. 42-23883 and U.S. Pat.No.3,532,501.
Polyalkylene oxide, other 1-phenyl-3
-Pyrazolidones, imidazoles, etc. as required
Can be added.   In the present invention, if necessary, any fog prevention
Agents can be added. As antifoggant, sodium chloride
Alkali metal such as potassium, potassium bromide, and potassium iodide
Logenides and organic antifoggants can be used. Organic mosquito
As the antifoggant, for example, benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazo
, 5-methylbenzotriazole, 5-nitrobenzo
Triazole, 5-chloro-benzotriazole, 2-
Thiazolyl-benzimidazole, 2-thiazolylmethyl
Le-benzimidazole, indazone, hydroxya
Nitrogen-containing heterocyclic compounds such as Zaindolizine and Adenine
Can be given as a representative example.   The color developer used in the present invention contains a fluorescent whitening agent.
It is preferred to contain. 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred.
New The addition amount is 0 to 5 g /, preferably 0.1 g to 4 g /.
You.   If necessary, alkyl sulfonic acid, aryl phos
Various types such as fonic acid, aliphatic carboxylic acid and aromatic carboxylic acid
A surfactant may be added.   The processing temperature of the color developing solution of the present invention is preferably from 20 to 50 ° C.
Or 30-40 ° C. Processing time is 20 seconds to 5 minutes, preferably
Is 30 seconds to 2 minutes. It is preferable that the replenishment amount is small,
Photosensitive material 1m^Two20-600ml, preferably 50-300ml
You. More preferably, it is 100 ml to 200 ml.   Next, the desilvering step in the present invention will be described.   In the desilvering step of the present invention, a bleach-fix solution is used. In the present invention
In this case, if the process time of the desilvering step is shortened, the effect of the present invention
The fruits become more pronounced. That is, less than 6 minutes, more preferred
30 seconds to 4 minutes. More preferably 30 seconds to 60 seconds
You.   Hereinafter, the bleach-fix solution used in the present invention will be described.   The bleaching solution used in the bleach-fixing solution used in the present invention.
Whitening agents include iron, cobalt, nickel, manganese,
Organic complexes of rom can be used, especially iron (II
I) organic acid complex salts (eg, ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as ethylenetriaminepentaacetic acid
, Aminopolyphosphonic acids, phosphonocarboxylic acids and
Complex salts such as organic phosphonic acids) or citric acid, tartar
Organic acids such as acid and malic acid are preferred.   Of these, amino (III) aminopolycarboxylic acid complexes
Salts are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Aminopolycarboxylic acids useful for forming organic complex salts
Are listed as ethylenediaminetetraacetic acid,
Liamine pentaacetic acid, 1,3-diaminopropanetetraacetic acid, pro
Pyrene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexa
Diaminetetraacetic acid, methyliminodiacetic acid, iminodivinegar
Acid, glycol ether diamine tetraacetic acid, etc.
be able to.   These compounds are sodium, potassium, lithium or
May be any of ammonium salts. Of these compounds
Inside, ethylenediaminetetraacetic acid, diethylenetriamine
Pentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diamine
Iron (III) complex of nopropanetetraacetic acid and methyliminodiacetic acid
Salt is preferred because of its high bleaching power.   These ferric ion complex salts may be used in the form of a complex salt.
Chairs, ferric salts such as ferric sulfate, ferric chloride, nitric acid
Ferric, ammonium ferric sulfate, ferric phosphate, etc.
In solution with a chelating agent of minopolycarboxylic acid
A ferrous ion complex salt may be formed. Also, chelating agents
May be used in excess of the ferric ion complex salt.
No. The addition amount is 0.01 to 1.0 mol /, preferably 0.05 to
~ 0.50 mol /. Bleach-fix solution and / or these
In the pre-bath, various compounds may be used as bleaching accelerators.
Can be. For example, U.S. Pat.No. 3,893,858,
German Patent No. 1,290,812, JP-A-53-95630
Bulletin, Research Disclosure No. 17129 (1978
July issue) mercapto group or disulfide bond
And JP-B-45-8506, JP-A-52-2083.
No. 2, No. 53-32735, U.S. Pat.
Thiourea-based compounds or halo such as iodine and bromine ions
Genides are preferred because of their excellent bleaching power.   In addition, the bleach-fixing solution used in the present invention includes bromide
(Eg potassium bromide, sodium bromide, ammonium bromide
) Or chlorides (eg, potassium chloride, sodium chloride)
Thorium, ammonium chloride) or iodide (eg,
Rehalogenating agents such as ammonium iodide)
Wear. Boric acid, borax, sodium metaborate, vinegar as required
Acid, sodium acetate, sodium carbonate, potassium carbonate,
Sulfurous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate
One or more of pH buffering agents such as thorium and tartaric acid
Inorganic acids, organic acids and their alkali metals or
Monium salt or ammonium nitrate, guanidine, etc.
Can be added.   The fixing agent used in the bleach-fixing solution according to the present invention is a publicly known fixing agent.
Known fixing agents: sodium thiosulfate, ammonium thiosulfate
It is preferred to use thiosulfates such asium. Ma
A fixing agent described in JP-A-55-155354 and a large amount of iodine
From combinations of halides such as potassium halide
A special bleach-fixing solution can also be used. One
The amount of the fixing agent is preferably 0.3 to 2 mol, more preferably.
Or 0.5 to 1.0 mole.   The pH of the bleach-fix solution of the present invention is 3.5 to 6.5, which is more preferable.
Or 4-6. Each of these to adjust the pH
Species, organic and inorganic acids, bases and buffers can be used
You. For example, acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid,
NaOH hydroxide as alkali such as propionic acid and phenic acid
Lium, potassium hydroxide, aqueous ammonia, various amines
And the like, but are not limited thereto. pH
Is higher than that of the present invention, the desilvering property and image stability are poor, and
If it is low, the liquid stability will deteriorate and the leuco conversion of the cyan dye will be remarkable.
Become.   In addition, the bleach-fix solution contains various fluorescent whitening agents and defoamers.
Agent or surfactant, polyvinylpyrrolidone, methano
And an organic solvent such as a polymer.   The bleach-fixing solution or fixing agent in the present invention is used as a preservative.
Sulfites (eg, sodium sulfite, potassium sulfite
, Ammonium sulfite, etc.), bisulfite (eg
For example, ammonium bisulfite, sodium bisulfite,
Potassium sulfate, etc.), metabisulfite (eg, meta
Potassium bisulfite, sodium metabisulfite, metabisulfite
Sulfite ion releasing compounds such as ammonium sulfate, etc.
It contains. These compounds are converted to sulfite ions
About 0.02 to 0.50 mol / content is preferable, and
Preferably it is 0.04 to 0.40 mol /.   As a preservative, sulfite is generally added,
In addition, ascorbic acid or carbonyl bisulfite addition
Or a carbonyl compound or the like may be added.   Furthermore, buffers, optical brighteners, chelating agents, defoamers,
A mold agent or the like may be added as necessary.   Next, the washing step used in the present invention and / or
The stabilization step will be described in detail.   The replenishment amount of the washing and / or stabilization step in the present invention is
It is preferably 3 to 50 times the amount brought in from the previous bath, more preferably
Or 5 to 30 times. Bring in from previous bath here
The measured amount is the physical properties of the photosensitive material, squeegee strength, and processing speed.
Depends on degree etc., 1m^TwoPer practically about 20ml ~ 100ml
is there. Treatment method of washing and / or stabilizing step of the present invention
In order to reduce the amount of replenishment, it is
A multistage countercurrent system having two to six stages is particularly preferable.
In this case, a particularly preferable replenishment amount is 1 m of the photosensitive material.^Two50ml per
It is about 500ml.   According to the multi-stage countercurrent method, the effect of the present invention is remarkable.
Increase the residence time of water in the tank,
Breeding and the resulting suspended matter adheres to the photosensitive material.
Problem arises. In the processing of the color light-sensitive material of the present invention,
A solution to such a problem is described in Japanese Patent Application No. 61-131632.
How to reduce the amount of calcium and magnesium
Can be used effectively. Also, JP-A-57-8542
Isothiazolone compounds and thiabendazole
Chlorinated isocyanurate described in No. 61-120145
Chlorine disinfectant such as thorium, described in Japanese Patent Application No. 60-105487
Benzotriazole, copper ions and others by Hiroshi Horiguchi
"The chemistry of fungicides", edited by the Sanitary Technology Society, "Sterilization and disinfection of microorganisms,
Antifungal Technology ", edited by the Japanese Society of Antifungals and Fungi," Encyclopedia of Antifungal Agents, "
Can be used.   In addition, the washing water may contain a surfactant or a hardener as a draining agent.
Use a chelating agent represented by EDTA as a water softener.
Can be.   Continue with the above washing process or directly without going through the washing process
It can also be treated with a stabilizing solution. Image stabilization in stabilizer
A compound having a chemical function is added, for example, to formalin
Typical aldehyde compounds and membranes suitable for dye stabilization
Buffers for adjusting the pH or ammonium compounds
I can do it. Also, after prevention of bacterial growth in the liquid or after treatment
The above-mentioned various sterilization methods are used to impart a fungicide to the photosensitive material.
Agents and fungicides can be used.   In addition, add surfactants, optical brighteners, and hardeners
Can also. In the processing of the photosensitive material of the present invention, stabilization
When directly performed without going through the washing step,
Nos. 8543, 58-14834, 60-220345, etc.
All known methods can be used.   In addition, 1-hydroxyethylidene-1,1-diphospho
Acid, ethylenediaminetetramethylenephosphonic acid, etc.
May be used, or magnesium or bismuth compounds
This is a preferred embodiment.   The pH of the washing step or the stabilizing step of the present invention is 4 to 10.
And preferably 5 to 8. The temperature depends on the application of the photosensitive material.
Various settings can be made depending on the characteristics and the like, but generally 15 to 45 ° C is preferable.
Or 20-40 ° C. Time can be set arbitrarily, but it is short
The effect of the present invention is more remarkable, preferably 30 seconds ~
4 minutes, more preferably 30 seconds to 2 minutes. Replenishment is low
Not preferred in terms of running costs and reduced emissions
No.   The method of the present invention is suitable for processing using a color developer.
It can be applied to any processing steps. For example, color
Paper, color reversal paper, color direct positive photosensitive material
Color, color positive film, color negative film, color
It can be applied to the processing of reversal films, etc.
Preferred for color paper and color reversal paper
No.   The silver halide emulsion of the light-sensitive material used in the present invention,
Any halogenation such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride
Can be used. For example, color paper
When performing rapid processing or low replenishment of
Silver chlorobromide emulsion or silver chloride emulsion containing
Furthermore, the silver chloride content is preferably 80 or more, and 90 to 90%.
The case of 100 mol% is particularly preferred. Also need high sensitivity
Fog during manufacture, storage and / or processing
If it is particularly necessary to keep
Silver bromochloride emulsion containing at least 3 mol%
May be contained), and more preferably 70 mol% or more.
preferable. Color photographic materials for photography include silver iodobromide,
Silver bromide is preferred, where the silver iodide content is 0.1 to 15 mol
% Is preferred.   The silver halide grains used in the present invention have an inside and a surface.
Multi-phase with joint structure even with different phases
Even if the structure or the whole particle consists of a uniform phase
May be. They may be mixed.   Average grain size of silver halide grains used in the present invention
The distribution may be narrow or wide, but halogenated
The standard deviation in the particle size distribution curve of the silver emulsion was
Value (variation rate) within 20%, particularly preferably 15
% Of the so-called monodispersed silver halide emulsion is used in the present invention.
It is preferred to use The target gradation of the photosensitive material
Milk having substantially the same color sensitivity to satisfy
Two or more monodisperse halos with different particle sizes in the agent layer
Silver Genide Emulsion (with monodispersity
Are mixed in the same layer or multi-layer coating in another layer
can do. Two or more polydisperse halogenations
Silver emulsion or a combination of monodisperse and polydisperse emulsions
They can be mixed or layered.   The silver halide grains used in the present invention have a cubic,
Regular, such as a tetrahedron, dodecahedron, or tetrahedron
With or without co-existing crystals
And irregular, such as spherical
It may have a crystalline form, or a combination of these crystalline forms
It may have a shape. Also, tabular grains may be used.
Tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more
But with an emulsion that accounts for more than 50% of the total projected area of the grain
Is also good. Using an emulsion composed of a mixture of these various crystal forms
You may.   These various types of emulsions mainly have a latent image formed on the surface.
Surface latent image type or internal latent image type formed inside the particle
May be.   The photographic emulsion used in the present invention is Research Disclosur
e vol. 170 Item No. 17643 (I, II, III) (1978, 12
Month).   Emulsions used in the present invention are usually physically ripened or chemically ripened.
Use those that have undergone synthesis and spectral sensitization. like this
The additives used in the process are Research Disclosure
-Volume 176, No. 17643 (December 1978) and Volume 187,
No. 18716 (1979, November)
The locations are summarized in the table below.   Known photographic additives that can be used in the present invention include the above two photographic additives.
Listed in Research Disclosure, and later
The places listed are shown in the table above. Example 1   On a paper support laminated on both sides with polyethylene,
Preparation of multilayer silver halide photosensitive material A having the following layer structure
did. The coating liquid was prepared as follows. (First layer coating solution adjustment)   Yellow coupler (ExY-1) and (ExY-2) respectively
In 10.2 g and 9.1 g, 27.2 cc of ethyl acetate and a high boiling solvent (Sol
v-1) 7.7 cc (8.0 g) was added and dissolved, and this solution was
10% zeolite containing 8cc of sodium decylbenzenesulfonate
It was emulsified and dispersed in 185 cc of a ratine aqueous solution. This emulsified dispersion
And the emulsions EM1 and EM2 are mixed and dissolved to give the following composition.
The concentration of gelatin was adjusted to prepare a coating solution for the first layer. second
The coating solution for the 7th layer to the 7th layer is prepared in the same manner as the coating solution for the first layer.
It was adjusted. 1-oxy-
Using 3,5-dichloro-S-triazine sodium salt
Was.   (Cpd-2) was used as a thickener. (Layer structure)   The composition of each layer is shown below. The numbers indicate the coating amount (g / m^Two)
You. The silver halide emulsion represents a coating amount in terms of silver. Support   Polyethylene laminated paper (A white pigment (TiO 2_Two) And blue tint
Including fees. ) First layer (blue feeling layer)   Monodisperse chlorobromide spectrally sensitized with sensitizing dye (ExS-1)
Silver emulsion (EM1) ... 0.13   Monodisperse chlorobromide spectrally sensitized with sensitizing dye (ExS-1)
Silver emulsion (EM2) ... 0.13   Gelatin …… 1.86   Yellow coupler (ExY-1) 0.44   Yellow coupler (ExY-2) …… 0.39   Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer)   Gelatin …… 0.99   Color mixture inhibitor (Cpd-3) ...... 0.08 Third layer (green layer)   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-2, 3)
Silver bromide emulsion (EM3) 0.05   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-2, 3)
Silver bromide emulsion (EM4) ... 0.11   Gelatin …… 1.80   Magenta coupler (ExM-1) 0.39   Color image stabilizer (Cpd-4) ... 0.20   Solvent (Solv-2) ... 0.12   Solvent (Solv-3) ... 0.25 4th layer (UV absorption layer)   Gelatin …… 1.60   UV absorber (Cpd-7 / Cpd-8 / Cpd-9 = 3/2/6: weight
Ratio) …… 0.70   Color mixing inhibitor (Cpd-10) ...... 0.05   Solvent (Solv-4) …… 0.27 Fifth layer (red layer)   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-4, 5)
Silver bromide emulsion (EM6) ...... 0.07   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-4, 5)
Silver bromide emulsion 0.16   Gelatin …… 0.92   Cyan coupler (ExC-1) 0.32   Color image stabilizer (Cpd-8 / Cpd-9 / Cpd-12 = 3/4/2: weight
Ratio) …… 0.17   Dispersion polymer (Cpd-11) ... 0.28   Solvent (Solv-2) ... 0.20 6th layer (UV absorbing layer)   Gelatin …… 0.54   UV absorber (Cpd-7 / Cpd-9 / Cpd-12 = 1/5/3: weight
Ratio) …… 0.21   Solvent (Solv-2) 0.08 7th layer (protective layer)   Gelatin …… 1.33   Acrylic modified copolymer of polyvinyl alcohol (modified
Degree 17%) ... 0.17   Liquid paraffin ...... 0.03   Also, at this time, as the irradiation prevention dye,
Cpd-13 and Cpd-14 were used. Furthermore, each layer contains an emulsifying dispersant
Alkanol XC (Dupont), Alkyl
Sodium rubenzenesulfonate, succinate and
And Megafac F-120 (manufactured by Dainippon Ink and Chemicals, Inc.). Halo
Using Cpd-15 and Cpd-16 as stabilizers for silver genide
Was.   The details of the emulsion used are as follows. Emulsion name Shape Particle size Br content (mol%) Coefficient of variation   EM1 cube 1.0 80 0.08   EM2 cube 0.75 80 0.07   EM3 cube 0.5 83 0.09   EM4 cube 0.4 83 0.10   EM5 cube 0.5 73 0.09   EM6 cube 0.4 73 0.10   The structural formula of the compound used is as follows.   Next, in the first layer of the photosensitive material, a yellow cap
In Table 1 of equal mol (sum of ExY-1 and ExY-2)
It can be replaced with the coupler of the present invention or the general formula of the present invention
The compound represented by (A) is further added to the coupler by 50 mol.
The same light-sensitive materials B to R were prepared except that 1% was added.   After imagewise exposure of the above photosensitive material, Fuji color paper processing
Using a PP600 machine, the color development tank
Continuous processing (running test
G).   The composition of each processing solution is as follows. Rinse liquid Ion-exchanged water (calcium and magnesium each less than 3ppm
under)   The photographic properties are the minimum density (Dmin) and the maximum density (Dmax).
Expressed by dots.   Then, as an image fastness test, 1. light fastness test and,
2. Wet heat stability test was performed. As a light resistance test,
200 hours irradiation with non-fade meter (85,000 Lux)
The test was carried out under the conditions, and the color density of 2.0 before the test was
Expressed as a percentage of the concentration reached after the experiment.   In addition, the wet heat stability test was conducted at 80 ° C-70% pH for 14 days.
After the test, the color density of 2.0 before the test is
Expressed as a percentage of the concentration reached.   The results are shown in Table 1.  As is clear from Table 1, the yellow coupler of the present invention
And a photosensitive material containing the compound of the present invention maintain high color developability.
At the same time, the image robustness has been significantly improved.
Recognize. Example 2   On a paper support laminated on both sides with polyethylene,
Preparation of multilayer silver halide photosensitive material A having the following layer structure
did. The coating liquid was prepared as follows. (First layer coating solution adjustment)   Ethyl acetate to 19.1 g of each yellow coupler (ExY-1)
27.2cc and high boiling point solvent (Solv-1) 7.7cc (8.0g)
Dissolve and add this solution to 10% dodecylbenzene sulfone
Emulsified in 185cc of 10% gelatin aqueous solution containing 8cc of sodium acid
Dispersed. This emulsified dispersion is mixed with emulsions EM7 and EM8.
Dissolve and adjust the gelatin concentration to the following composition.
A first layer coating solution was prepared. Coating solution for 2nd to 7th layer
Was prepared in the same manner as in the first layer coating solution. Zelatin in each layer
1-oxy-3,5-dichloro-S-toate
Riadin sodium salt was used.   (Cpd-2) was used as a thickener. (Layer structure)   The composition of each layer is shown below. The numbers indicate the coating amount (g / m^Two)
You. The silver halide emulsion represents a coating amount in terms of silver. Support   Polyethylene laminated paper (A white pigment (TiO 2_Two) And blue tint
Including fees. ) First layer (blue feeling layer)   Monodisperse chlorobromide spectrally sensitized with sensitizing dye (ExS-1)
Silver emulsion (EM7) ... 0.15   Monodisperse chlorobromide spectrally sensitized with sensitizing dye (ExS-1)
Silver emulsion (EM8) ... 0.15   Gelatin …… 1.86   Yellow coupler (ExY-1) 0.82   Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer)   Gelatin …… 0.99   Color mixture inhibitor (Cpd-3) ...... 0.08 Third layer (green layer)   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-2, 3)
Silver bromide emulsion (EM9) ... 0.12   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-2, 3)
Silver bromide emulsion (EM10) …… 0.24   Gelatin …… 1.24   Magenta coupler (ExM-1) 0.39   Color image stabilizer (Cpd-4) ... 0.25   Color image stabilizer (Cpd-5) ... 0.12   Solvent (Solv-2) ... 0.25 4th layer (UV absorption layer)   Gelatin …… 1.60   UV absorber (Cpd-6 / Cpd-7 / Cpd-8 = 3/2/6: weight
Ratio) …… 0.70   Anti-color mixing agent (Cpd-9) 0.05   Solvent (Solv-3) ...... 0.42 Fifth layer (red layer)   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-4, 5)
Silver bromide emulsion (EM11) ...... 0.07   Monodisperse salts spectrally sensitized with sensitizing dyes (ExS-4, 5)
Silver bromide emulsion (EM12) ... 0.16   Gelatin …… 0.92   Cyan coupler (ExC-1) ... 0.15   Cyan coupler (ExC-2) ... 0.18   Color image stabilizer (Cpd-7 / Cpd-8 / Cpd-10 = 3/4/2: weight
Ratio) …… 0.17   Dispersion polymer (Cpd-11) ... 0.14   Solvent (Solv-1) 0.20 6th layer (UV absorbing layer)   Gelatin …… 0.54   UV absorber (Cpd-6 / Cpd-8 / Cpd-10 = 1/5/3: weight
Ratio) …… 0.21   Solvent (Solv-4) ...... 0.08 7th layer (protective layer)   Gelatin …… 1.33   Acrylic modified copolymer of polyvinyl alcohol (modified
Degree 17%) ... 0.17   Liquid paraffin ...... 0.03   Also, at this time, as the irradiation prevention dye,
Cpd-12 and Cpd-13 were used. Furthermore, each layer contains an emulsifying dispersant
Alkanol XC (Dupont), Alkyl
Sodium rubenzenesulfonate, succinate and
And Magefacx F-120 (manufactured by Dainippon Ink). C
Using Cpd-14 and Cpd-15 as stabilizers of silver logenide
Was.   The details of the emulsion used are as follows. Emulsion name Shape Particle size Br content (mol%) Coefficient of variation  EM7 cube 1.0 1.0 0.10  EM8 cube 0.8 1.0 0.10  EM9 cube 0.45 1.5 0.09  EM10 cube 0.34 1.5 0.09  EM11 cube 0.45 1.5 0.09  EM12 cube 0.34 1.6 0.10   Coefficient of variation = standard deviation / average size   Then, in the first layer of the photosensitive material, a yellow cap
The couplers are replaced by the equivalent molar couplers shown in Table 2.
Or a compound represented by formula (A) of the present invention
-The same photosensitive material except that 50 mol% is further added.
Charges B to J were prepared.   After exposing the above photosensitive material through an optical wedge, the next step
Processed.             Processing steps temperature time             Color development 35 ° C 45 seconds             Bleaching and fixing 30-36 ° C 45 seconds             Stable 30-37 ° C 20 seconds             Stable 30-37 ° C 20 seconds             Stable 30-37 ° C 20 seconds             Stable 30-37 ° C 30 seconds             Drying 70-85 ° C 60 seconds (The four-tank countercurrent method was used for stable →.)   The composition of each processing solution is as follows. Color developer   800ml of water   2.0 g of ethylenediaminetetraacetic acid   8.0 g of triethanolamine   Sodium chloride 1.4g   25g potassium carbonate   N-ethyl-N- (β-methanesulfonamidoethyl
G) -3-Methyl-4-aminoaniline sulfate 5.0 g   N, N-diethylhydroxylamine 4.2g   5,6-dihydroxybenzene-1,2,4-trisulfonic acid                                               0.3g   Fluorescent brightener (4,4'-diaminostilbene) 2.0g 1000ml with water   pH (25 ° C) 10.10 Bleaching fixer   400ml of water   Ammonium thiosulfate (70%) 100ml   Sodium sulfite 18g   Ammonium iron (III) ethylenediaminetetraacetate 55g   Disodium ethylenediaminetetraacetate 3g   Glacial acetic acid 8g 1000ml with water   pH (25 ℃) 5.5 Stabilizing liquid   Formalin (37%) 0.1g   0.7 g of formalin-sulfurous acid adduct   5-chloro-2-methyl-4-isothiazoline-3-
ON 0.02g   2-methyl-4-isothiazolin-3-one 0.01 g   Copper sulfate 0.005g 1000ml with water   pH (25 ℃) 4.0   After the treatment, the same photographic properties as in Example 1 were evaluated. Conclusion
The results are shown in Table 2.   As is apparent from Table 2, the photosensitive material of the present invention has a high emission rate.
It can be seen that both color properties and image fastness are compatible. Example 3   Corona EDM treated double-sided polyethylene laminate
1st layer (lowest layer)-7th layer (top layer) applied to paper sequentially
And a light-sensitive material was prepared. The adjustment of the coating solution for each layer is as follows
It is on the street. The coupler used for the coating solution, color image stability
Details such as the structural formula of the agent and the like will be described later.   The coating liquid for the first layer was prepared as follows. You
That is, 200 g of yellow coupler, 93.3 g of anti-fading agent, high boiling
To 10 g of point solvent (p) and 5 g of solvent (q),
Heat the mixture containing 600 ml of ethyl acetate to 60 ° C
Later, alkanol B (trade name, alkyl naphthalenesul)
5% aqueous solution (Honate, manufactured by DuPont)
% Gelatin aqueous solution. Then this solution
Emulsify using a colloid mill to prepare a coupler dispersion.
Was. Ethyl acetate was distilled off from this dispersion under reduced pressure to give a blue-sensitive milk.
Dye for agent layer and 1-methyl-2-mercapto-5
-Acetylamino-1,3,4-triazole added emulsion
Added to 1,400 g (including 96.7 g of Ag and 170 g of gelatin)
And 2,600 g of a 10% aqueous gelatin solution is added to prepare a coating solution.
It was adjusted. Support Paper support laminated on both sides with polyethylene 1st layer (blue layer)   Silver chlorobromide emulsion (silver bromide 80mol%) …… 290   Yellow coupler ...... 600   Anti-fading agent (r) 280   Solvent (p) 30   Solvent (q) 15   Gelatin …… 1800 Second layer (color mixture prevention layer)   Silver bromide emulsion (unpost-heat particle size 0.05 micron) silver ...... 10   Color mixture inhibitor (s) 55   Solvent (p) 30   Solvent (q) 15   Gelatin …… 800 3rd layer (green layer)   Silver chlorobromide emulsion (silver bromide 70mol%) …… 305   Magenta coupler ...... 670   Anti-fading agent (t) 150   Anti-fading agent (u) 10   Solvent (p) 200   Solvent (q) 10   Gelatin …… 1400 4th layer (color mixture prevention layer)   Color mixing inhibitor (s) 65   UV absorber (n) ... 450   UV absorber (o) 230   Solvent (p) 50   Solvent (q) 50   Gelatin ... 1700 5th layer (red-sensitive layer)   Silver chlorobromide emulsion (70 mol% silver bromide) ...... 210   Cyan coupler ......   Anti-fading agent (r) 250   Solvent (p) 160   Solvent (q) 100   Gelatin …… 1800 6th layer (UV absorbing layer)   UV absorber (n) 260   UV absorber (o) 70   Solvent (p) 300   Solvent (q) 100   Gelatin ...... 700 7th layer (protective layer)   Gelatin ...... 620 n: 2- (2-hydroxy-3,5-di-tert-amylphenyl
Le) Benzotriazole o: 2- (2-hydroxy-3,5-di-tert-butylphenyl
Le) Benzotriazole p: di (2-ethylhexyl) phthalate q: dibutyl phthalate r: 2,5-di-tert-amylphenyl-3,5-di-tert-bu
Tyl hydroxybenzoate s: 2,5-di-tert-octylhydroquinone t: 1,4-di-tert-amyl-2,5-dioctyloxyben
Zen u: 2,2'-methylenebis- (4-methyl-6-tert-butyl
Til phenol   The following sensitizing dyes were used for the respective emulsion layers. Blue-sensitive emulsion layer: anhydro-5-methoxy-5'-methyl
-3,3'-Disulfopropyl selenocyanine hydro
Oxide Green-sensitive emulsion layer: anhydro-9-ethyl-5,5'-dif
Enyl-3,3'-disulfoethyloxacarbocyani
Hydroxide Red-sensitive emulsion layer: 3,3'-diethyl-5-methoxy-9,9 '
-(2,2-dimethyl-1,3-propano) thiazicarbocyan
Ninyoside   The following stabilizers were used as stabilizers for each emulsion layer. 1-methyl-2-mercapto-5-acetylamino-1,
3,4-triazole   In addition, the following substances are used as irradiation prevention dyes.
Using. 4- (3-carboxy-5-hydroxy-4- (3-
(3-carboxy-5-oxo-1- (4-sulfonato
Phenyl) -2-pyrazolin-4-ylidene) -1-p
Lopenyl) -1-pyrazolyl) benzenesulfonate
Dipotassium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7-
Disulfonatoanthracene-1,5-diyl) bis (amido
Methanesulfonate) -tetrasodium salt   Also, as a hardening agent, 1,2-bis (vinylsulfonyl)
Ethane was used.   The couplers used are as follows.   The compound (A-7) of the present invention is formed on the first layer of the photosensitive material.
(A-8), (A-20) and (A-43) are couplers respectively
To make 4 types of photosensitive materials with 30 mol% added to
Thereafter, the same processing and operation as in Example 1 were performed.
The same effects as in Example 1 were obtained. (The invention's effect)   Yellow couplers of the general formula (I) according to the invention and general
The color development of the coupler by combination with the compound of formula (A)
And the robustness of color images against light and wet heat have been improved.
You.

   ────────────────────────────────────────────────── ─── Continuation of front page       (56) References JP-A-62-178954 (JP, A)                 JP-A-61-6652 (JP, A)                 JP-A-54-48535 (JP, A)                 JP-A-62-262047 (JP, A)                 JP-A-61-250641 (JP, A)

Claims (1)

(57) [Claims] A silver halide color photograph comprising a layer containing at least one yellow coupler represented by the following general formula (I) and at least one compound represented by the following general formula (A). Photosensitive material. General formula (I) In the formula, R ¹ represents a substituted or unsubstituted N-phenylcarbamoyl group, R ² represents an alkyl group or an aryl group,
X ¹ represents a group represented by the following formula (a), (b) or (c). In the formulas (a) and (b), R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, a halogen atom, a carboxylic ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl. Group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl group or heterocycle. In the formula (c), W ¹ is Together with a non-metallic atom required to form a 4-, 5- or 6-membered ring. General formula [A] (Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a hydrogen atom or a substituent, and Y ₁ and Y ₂ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group , a sulfonyl group and a silyl group, X represents a single bond or a divalent linking group, n represents 1 or 2. However, the substitution position of X is the ortho-position or for -OY ₁ or -OY ₂ When it is in the para position and is in the para position, one of Y ₁ and Y ₂ is a hydrogen atom, and the other is not a hydrogen atom.