JP2581945B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic material having high sensitivity, low fog, excellent processing stability, and suitable for rapid processing. It relates to a photographic material.

(Prior Art) A silver halide color light-sensitive material comprises three kinds of silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light and red light, and comprises an aromatic primary amine. Using a so-called coupler which reacts with an oxidized form of a developing agent to form a dye, it usually develops yellow, magenta and cyan, respectively.

In this case, preferable couplers are those having good color developing properties such that the coupling speed is as high as possible and a high color density is provided within a limited time. Further, all coloring dyes are required to have little side absorption.

On the other hand, the formed color photographic image is required to have good storage stability under various conditions.

Of these, JP-A-60-229029 as a yellow coupler
The couplers which are excellent in color developing property and high in activity as disclosed in JP-A No. 2000-216, are known.

As silver halide to be used in combination with these excellent couplers, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be selected. There is a need to be. However, recently, in addition to high sensitivity, demands for shortening the development processing time and simplifying the processing system and operation have been increasing. This is due to the necessity of shortening the finish delivery time, reducing the work in the lab, improving the productivity, or miniaturizing the processing system for a small lab called a so-called mini lab and simplifying the operation. In order to simultaneously satisfy the two viewpoints of high sensitivity and rapid processing in a blue-sensitive silver halide emulsion layer, the conventional combination of a coupler and silver halide alone was not sufficient. In other words, silver halides mainly composed of silver bromide which have been mainly used in the past from the viewpoint of high sensitivity are disadvantageous in terms of speedup in principle because of the suppression of the development of bromine ions released when they are developed themselves. On the other hand, from the viewpoint of rapid processing, it is preferable to use silver halide mainly composed of silver chloride. In this case, it is known that development is fast, but fogging is easy, storage stability is poor, and sensitivity is further lowered. It also has the drawback.

(Problems to be Solved by the Invention) In particular, silver halide grains having a large size are generally used in the blue-sensitive silver halide emulsion layer in view of sensitivity and color reproduction. Was in a more disadvantageous situation. As an attempt to cope with the rapid processing using silver halide mainly composed of silver bromide, JP-A-59-48755 discloses a method in which silver bromide is 50 to 97 mol% (silver iodide is 2 mol% or less, and the balance is silver chloride). ) Describes the use of emulsions (preferably monodisperse emulsions) characterized by containing core / shell type silver halide grains in which the silver bromide content in the surface layer of the grains is higher than the inside.

However, this technique alone was not sufficient for applying to a blue-sensitive silver halide emulsion layer with high sensitivity and rapid processing. In the past, many attempts have been made in the past to overcome the above-mentioned disadvantages using silver halide mainly composed of silver chloride. As an attempt to increase the sensitivity, Japanese Patent Laid-Open No. 58-9573
No. 6, No. 58-108533, No. 60-222844, No. 60-222845
There is known a high temperature silver-containing silver chlorobromide emulsion having grains having a layered structure as described in Japanese Patent Application Laid-Open (Kokai) No. H10-26095. Fog also occurs when sensitizing formed particles, which is described in JP-A-58-125612 and JP-A-61-4794.
No. 0 shows a method of improvement. As described above, various proposals have been made for increasing the sensitivity and lowering the fog of silver halide mainly composed of silver chloride. However, as a blue-sensitive silver halide emulsion layer, it can be applied to rapid processing with high sensitivity and low fog. Neither was enough to get the system.

Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material having a blue-sensitive halide emulsion layer having high sensitivity, low fog, excellent processing stability, and suitable for rapid processing. .

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive photosensitive silver halide emulsion layer on a support, represented by the following general formula ( A dispersion of lipophilic fine particles obtained by emulsifying and dispersing a mixed solution in which at least one of the yellow couplers represented by I) and at least one of a water-insoluble and organic solvent-soluble homo- or copolymer are dissolved is a blue-sensitive halogen. This is achieved by a silver halide color photographic material which is contained in a silver halide emulsion layer and wherein the silver halide emulsion layer in the emulsion layer is a monodispersed silver chlorobromide emulsion.

General formula (I) R ₈ in the general formula (I) represents an N-phenylcarbamoyl group, and the phenyl group can have a substituent.
When there are two or more substituents, they may be the same or different. The following are examples of acceptable substituents.

Aromatic groups (for example, phenyl group, naphthyl group, etc.), heterocyclic groups (for example, 2-pyridyl group, 2-imidazolyl group,
2-furyl group, 6-quinolyl group, etc.), aliphatic oxy group (eg, methoxy group, 2-methoxyethoxy group, 2-propenyloxy group, etc.), aromatic oxy group (eg, 2,4
-Di-tert-amylphenoxy group, 4-cyanophenoxy group, 2-chlorophenoxy group, etc., acyl group (eg, acetyl group, benzoyl group, etc.), ester group (eg, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, Benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc., amide group (eg, acetylamino group, methanesulfonamide group, ethylcarbamoyl group, butylsulfamoyl group, etc.), imide group (eg, succinimide group, hydantoinyl group, etc.) ), Ureido groups (eg, phenylureido group, dimethylureide group, etc.), aliphatic or aromatic sulfonyl groups (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio groups (eg, phenylthio group, ethylthio group) A hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfone group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.).

Desirable R ₈ is represented by the following general formula (A).

General formula (A) [In the formula, G ₁ represents a halogen atom or an alkoxy group, and G ₂ represents a hydrogen atom, a halogen atom, or an optionally substituted alkoxy group. R ₉ represents an alkyl group which may have a substituent. As the substituent of G ₂ and R ₂ in the general formula (A),
For example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group, a heterocyclic group (for example, N-morpholino group, N-piperidino group, 2-
Furyl group), a halogen atom, a nitro group, a hydroxy group, a carboxyl group, a sulfo group, an alkoxycarbonyl group and the like.

Preferred leaving groups Y ₃ include groups represented by the following general formulas (B) to (E).

Of the general formulas (E), preferably (E-1) to (E-
3).

The alkyl group (residue) and the aryl group (aryl residue) in the group represented by the general formula may be further substituted with the substituents described above.

Compounds of the general formula (I) are described in JP-A-54-48541, JP-B-58
-10739, U.S. Patent 4,326,024 and Research Disclosure 18053.

Specific examples of the compound of the general formula (I) are shown below, but the present invention is not limited to these exemplified compounds.

The coupler represented by the general formula (I) is usually contained in the silver halide emulsion layer constituting the blue light-sensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per 1 mol of silver halide.

In the present invention, the water-insoluble and organic solvent-soluble polymer preferably used has a glass transition point of 60 ° C. or higher, more preferably 90 ° C. or higher.

 Preferred structures are described below.

1) The repeating unit constituting the polymer has a main chain or a side chain. A water-insoluble or organic solvent-soluble homo- or copolymer having a bond.

More preferably, 2) the repeating unit constituting the polymer has a main chain or a side chain thereof. A water-insoluble or organic solvent-soluble homo- or copolymer having a bond.

3) The repeating unit constituting the polymer has a main chain or a side chain. (However, G ₁ and G ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. However, G ₁ and G ₂
Are not simultaneously hydrogen atoms. Or a water-insoluble or organic solvent-soluble homo- or copolymer having

More preferably, in the polymer according to the above item 3),
Either G ₁ or G ₂ is a hydrogen atom, and one of the substituted or unsubstituted alkyl groups has 3 to 12 carbon atoms.
And a polymer having 6 to 12 carbon atoms constituting an aryl group.

Hereinafter, the polymer according to the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

(A) Vinyl polymer The monomers forming the vinyl polymer of the present invention include:
Acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, sec-butyl acrylate, t
ert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
Octyl acrylate, tert-octyl acrylate,
2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate,
Dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) Ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9),
1-bromo-2-methoxyethyl acrylate, 1,1-
And dichloro-2-ethoxyethyl acrylate. In addition, the following monomers can be used.

Methacrylates: Specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-methacrylate.
Butyl methacrylate, isobutyl methacrylate, se
c-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy)
Ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol mono Methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-
Propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate ( Additional mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt, and the like.

Vinyl esters: Specific examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and salicylic acid. Vinyl and the like; acrylamides: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, diclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethyl Acrylamide, diethylacrylamide, β-cyanoethylacrylamide, N -(2-acetoacetoxyethyl)
Acrylamide, diacetone acrylamide, tert-octyl acrylamide, etc .: Methacrylamides: For example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert
-Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxy methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N-
(2-acetoacetoxyethyl) methacrylamide, etc .; olefins: for example, dicyclopentaneene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene,
Bromostyrene, methyl vinyl benzoate, etc .; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl ether; and others, butyl crotonate, hexyl crotonate, dimethyl itaconate, itaconic acid Dibutyl, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone,
Examples include methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylene malononitrile, vinylidene, and the like.

As the monomer (for example, the above-mentioned monomer) used in the polymer of the present invention, two or more kinds of monomers are used as comonomers for various purposes (for example, for improving the solubility). Further, for the purpose of controlling color development and solubility, as long as the copolymer does not become water-soluble, a monomer having an acid group as exemplified below may be used as a comonomer.

Acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, and the like; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate Citraconic acid; styrene sulfonic acid; vinylbenzyl stionic acid; vinyl sulfonic acid; acryloyloxyalkyl sulfonic acid, such as acryloyloxy sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, and the like; methacryloyloxy alkyl sulfonic acid For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc .; Alkyl sulfonic acids, for example,
2-acrylamide-2-methylethanesulfonic acid, 2
-Acrylamide-2-methylpropanesulfonic acid, 2
-Acrylamide-2-methylbutanesulfonic acid and the like;
Methacrylamide alkylsulfonic acid, for example, 2-methacrylamide-2-methylethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-
Methacrylamido-2-methylbutanesulfonic acid and the like; these acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

When the hydrophilic monomers (here, those which become water-soluble when made into a homopolymer) among the above-mentioned vinyl monomers and other vinyl monomers used in the present invention are used as comonomers. As long as the copolymer does not become water-soluble, the ratio of the hydrophilic monomer in the copolymer is not particularly limited, but usually, preferably 40%
Mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less. When the hydrophilic comonomer copolymerized with the monomer of the present invention has an acid group, from the viewpoint of image preservation as described above, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol. %Less than,
Preferably, it is at most 10 mol%, most preferably when no such comonomer is present.

The monomers of the present invention in the polymer are preferably methacrylate, acrylamide and methacrylamide. Particularly preferred are acrylamide and methacrylamide.

(B) Polymers Condensed by Polycondensation and Polyaddition The polymers obtained by polycondensation generally include polyesters composed of polyhydric alcohols and polybasic acids and polyamides composed of diamines, dibasic acids and ω-amino-ω-carboxylic acids. Known as the polymer by the polyaddition reaction is polyurethane such as diisocyanate and dihydric alcohol.

As the polyhydric alcohol, HO-R ₁ -OH (R ₁ has 2 carbon atoms)
To about 12 hydrocarbon chain, especially glycols having an aliphatic hydrocarbon chain) comprising structure, or a valid polyalkylene glycols, polybasic acids, HOOC-R ₂ -COOH
Those having (R ₂ represents a simple bond or a hydrocarbon chain having 1 to about 12 carbon atoms) are effective. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol,
Isobutylene diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, glycerin, diglycerin, triglycerin,
1-methylglycerin, erythrit, mannitol, sorbit and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and fumaric acid. Acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. Can be

As the diamine, hydrazine, methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, dodecyl methylene diamine, 1,4-diaminocyclohexane, 1,4-diaminomethylcyclohexane, o-aminoaniline, p-
Examples include aminoaniline, 1,4-diaminomethylbenzene and di (4-aminophenyl) ether.

Glycidin, β as the ω-amino-ω-carboxylic acid
-Alanine, 3-aminopropanoic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 11-aminododecanoic acid,
-Aminobenzoic acid, 4- (2-aminoethyl) benzoic acid and 4- (4-aminophenyl) butanoic acid.

As the diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
p-xylene diisocyanate, 1,5-naphthyl diisocyanate and the like.

(C) Others For example, polyesters and polyamides obtained by ring-opening polymerization In the formula, X represents -0-, -NH-, and m represents an integer of 4 to 7. —CH ₂ — may be branched.

Such monomers include β-propiolactone,
ε-caprolactone, dimethylpropiolactone, α-
Examples include pyrrolidone, α-piperidone, ε-caprolactam, and α-methyl-ε-caprolactam.

Two or more of the polymers of the present invention described above may be used in combination.

The molecular weight and the degree of polymerization of the polymer of the present invention have substantially no significant effect on the effects of the present invention, but as the molecular weight increases,
It takes a long time to dissolve in an auxiliary solvent, and it is difficult to emulsify and disperse due to a high solution viscosity, resulting in coarse particles. As a result, the color developability is reduced or the coating property is poor. And other problems are likely to occur. Reducing the viscosity of the solution by using a large amount of an auxiliary solvent as a countermeasure causes a new process problem. From the above viewpoint, the viscosity of the polymer is preferably 5,000 cps or less, more preferably 2,000 cps or less, when 30 g of the polymer is dissolved in 100 cc of the auxiliary agent used. The molecular weight of the polymer usable in the present invention is preferably 150,000 or less, more preferably 100,000 or less.

The water-insoluble polymer in the present invention is a polymer in which the solubility of the polymer in 100 g of distilled water is 3 g or less, preferably 1 g or less.

The ratio of the polymer of the present invention to the auxiliary solvent varies depending on the type of the polymer used, and varies over a wide range depending on the solubility in the auxiliary solvent, the degree of polymerization, the solubility of the coupler, and the like. Usually at least a coupler,
High-boiling coupler solvent and polymer are dissolved in co-solvents. A co-solvent is used in an amount necessary to obtain a sufficiently low viscosity so that the solution is easily dispersed in water or aqueous hydrophilic colloid. Is done. The higher the degree of polymerization of the polymer, the higher the viscosity of the solution, so it is difficult to uniformly determine the ratio of the polymer to the co-solvent regardless of the type of polymer, but it is usually about 1: 1 to 1:50 ( (Polymerization ratio) is preferable. The ratio of the polymer of the present invention to the coupler (polymerization ratio) is 1:20
To 20: 1, more preferably 1:10 to 10: 1.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited thereto.

Synthesis Example (1) Synthesis of Methyl Methacrylate Polymer (P-3) 50.0 g of methyl methacrylate, 0.5 g of sodium polyacrylate, and 200 ml of distilled water were placed in a 500 ml three-necked flask.
The mixture was heated to 80 ° C. with stirring in a nitrogen stream. 500 mg of dimethyl azobisisobutyrate was added as a polymerization initiator to initiate polymerization.

After polymerization for 2 hours, the polymerization solution was cooled, and the polymer in the form of beads was filtered and washed with water to obtain P-348.7 g.

Synthesis Example (2) Synthesis of t-butylacrylamide polymer (P-57) A mixture of 50.0 g of t-butylacrylamide and 250 ml of toluene was placed in a 500 ml three-necked flask, and heated to 80 ° C. with stirring in a nitrogen stream. 10 ml of a toluene solution containing 500 mg of azobisisobutyronitrile as a polymerization initiator was added to initiate polymerization.

After polymerization for 3 hours, the polymerization solution was cooled, poured into hexane 1, the precipitated solid was filtered off, washed with hexane, and dried by heating under reduced pressure to obtain 47.9 g of P-57.

A dispersion of lipophilic fine particles containing the coupler and the polymer of the present invention is typically prepared as follows.

After completely dissolving the polymer of the present invention, which is a so-called linear polymer synthesized by a solution polymerization method, emulsion polymerization or suspension polymerization, which is a so-called linear polymer, a high boiling coupler solvent and a coupler together in an auxiliary organic solvent. This solution is dispersed in water, preferably in an aqueous hydrophilic colloid solution, more preferably in an aqueous gelatin solution, with the aid of a dispersant, in the form of fine particles by means of ultrasonic waves, a colloid mill or the like, and contained in a silver halide emulsion. . Alternatively, water or a hydrophilic colloid aqueous solution such as an aqueous gelatin solution is added to a dispersing aid such as a surfactant, the polymer of the present invention, a high-boiling coupler solvent and an auxiliary organic solvent containing a coupler, and oil-in-water droplets are added with phase inversion. It may be a dispersion. After removing the auxiliary organic solvent from the prepared dispersion by a method such as distillation, noodle washing or ultrafiltration, the dispersion may be mixed with a photographic emulsion. The auxiliary organic solvent referred to here is an organic solvent useful at the time of emulsification and dispersion, a drying step at the time of coating, and one which is substantially removed from the photosensitive material to the final droplet by the above-described method and the like, and has a low boiling point. An organic solvent or a solvent that has some solubility in water and can be removed by washing with water. As auxiliary organic solvents, lower alcohols such as ethyl acetate and butyl acetate,
Acetate, ethyl propionate, secondary butyl alcohol, notyl ethyl ketone, methyl isobutyl ketone, β
-Ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like.

Further, if necessary, an organic solvent that is completely miscible with water,
For example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, and the like can be partially used in combination.

These organic solvents can be used in combination of two or more kinds.

The average particle diameter of the lipophilic fine particles thus obtained is
It is preferably from 0.04 μ to 2 μ, more preferably from 0.06 μ to 0.4 μ. The particle size of the lipophilic fine particles can be measured by, for example, a measuring device such as Nanosizer manufactured by Coulter, UK.

The blue-sensitive silver halide emulsion according to the present invention has a coefficient of variation (a value obtained by dividing the standard deviation in statistics by the average grain size and expressed as a percentage) of 15% or less (more preferably 10% or less). Is a monodisperse emulsion.

Such a monodisperse emulsion may be a single emulsion having the above-mentioned coefficient of variation.
Coefficient of variation of more than 15% or less (preferably 10% or less)
The emulsion may be a mixture of monodisperse emulsions prepared separately. The particle size difference or mixing ratio can be arbitrarily selected, but preferably the average particle size difference is 0.2 μm or more,
The use of an emulsion within the range of μm or less.

The average grain size of the silver halide grains in the photographic emulsion (in the case of spheres or spheres, in the case of cubic grains the ridge length is taken as the grain size and expressed as an average based on the projected area) is not particularly limited. However, it is preferably 2 μm or less, particularly preferably 0.2 to 1.5 μm.

The silver halide grains in the photographic emulsion layer may be those having regular crystals such as cubic, tetradecahedral or octahedral (normal crystal emulsions) or irregular such as spherical or tabular. It may have a crystal or a composite of these crystal forms. It may consist of a mixture of particles of different crystal forms.
Among them, the use of the above-mentioned normal crystal emulsion is preferred.

Further, an emulsion may be used in which tabular silver halide grains having a diameter of 5 times or more the thickness thereof occupy 50% or more of the total projected area.

In the present invention, silver chlorobromide is used as silver halide,
Especially for rapid processing, 90 mol% of silver chloride
Silver chlorobromide containing at least (preferably at least 98 mol%) is preferred. The silver chlorobromide may contain a small amount of silver iodide, but preferably does not contain it at all.

For the definition and measurement method of the coefficient of variation, see James, "Theory of The Photographic Process, The Macmilan".
It is described on page 39 of the llan Company, 3rd edition (1966).

The silver halide grains may have different phases between the inside and the surface layer. Further, the particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle. The latter grains are particularly useful as direct positive emulsions.

Cadmium salts, zinc salts, thallium salts, lead salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts may be coexistent in the course of silver halide grain formation or physical ripening.

Silver halide emulsions are usually chemically sensitized. A conventional method can be applied to the chemical sensitization method, and details thereof are described in JP-A-62-21.
No. 5,272, page 12, lower left column, line 18 to lower right column, line 16;

Silver halide emulsions are usually spectrally sensitized. For the spectral sensitization, a usual methine dye can be used, and details thereof are described in JP-A-62-215272, page 22, line 3 to page 38 from the lower right column and on March 16, 1987. It is stated on the separate sheet of the amendment.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene), pentaazaindenes and the like Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, and the like, can be added.

Examples of magenta couplers that can be used in the green sensitive layer include oil-protected, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based and pyrazoloazole-based couplers such as pyrazolotriazoles. 5-pyrazolone couplers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof are U.S. Patent 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 No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is preferable. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazole described and Research Disclosure 24
230 (June 1984). Any of the couplers described above may be a polymer coupler.

These compounds are specifically represented by the following general formula (M-
1), (M-2), or (M-3).

Among the pyrazoloazole couplers, U.S. Pat.
The imidazole [1,2-b] pyrazoles described in 500,630 are preferred, and the pyrazolo [1,5-b] [1,2,4] triazole described in U.S. Pat. No. 4,540,654 is particularly preferred.

Other pyrazolotriazole couplers in which a branched alkyl group is directly linked to the 2,3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 226,849.

 Specific examples of these couplers are listed below.

As a cyan coupler usable in the red-sensitive layer, a phenol-based cyan coupler and a naphthol-based cyan coupler are the most typical.

U.S. Pat.
369,929, 4,518,687, 4,511,647 and 3,772,0
As described in No. 02 and the like, there are those having an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position (including polymer couplers). Typical examples thereof include:
Coupler of Example 2 described in Canadian Patent 625,822, Compound (1), 4,564,5 described in U.S. Pat. No. 3,772,002
No. 90, compounds (I-4) and (I-5),
Compounds (1), (2), (3) and (2) described in
4) and compound (C-2) described in JP-A-62-70846.

U.S. Patent
2,772,162, 2,895,826, 4,334,011, 4,50
There are 2,5-diacylaminophenol-based couplers described in U.S. Pat. No. 0,653 and JP-A-59-164555, and typical examples thereof include compound (V) described in U.S. Pat. No. 2,895,826 and 4,557,999. Described compounds (17) and 4,56
Compounds (2) and (12) described in 5,777, compound (4) described in 4,124,396, and compound (I-19) described in 4,613,564 can be exemplified.

U.S. Patent
No. 4,327,173, No. 4,564,586, No. 4,430,423, JP-A-6
No. 1,390,441 and Japanese Patent Application No. 61-100222, in which a nitrogen-containing heterocyclic ring is condensed with a phenol nucleus. Typical examples thereof include couplers (1) described in US Pat. No. 4,327,173. (3), compounds (3) and (16) described in 4,564,586, and compound (1) described in 4,430,423
And (3), and the following compounds.

As phenolic cyan couplers, other U.S. Pat.Nos. 4,333,999, 4,451,559, 4,444,872, 4,4
Uleide couplers described in, for example, 27,767, 4,579,813, and European Patent (EP) 067,689B1, and typical examples thereof include couplers (7) described in U.S. Pat. No. 4,333,999 and 4,451,559. Couplers (1), 4,4
Couplers (14) described in 44,872, couplers (3) described in 4,427,767, couplers (6) and (24) described in 4,609,619, and couplers (1) and (11) described in 4,579,813. And couplers (45) and (50) described in European Patent No. (EP) 067,689B1, and a coupler (3) described in JP-A-61-42658.

As the naphthol cyan coupler, those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, US Pat. No. 2,313,586) and those having an alkylcarbamoylyl group at the 2-position (for example, US Pat. No. 2,474,293) No. 4,282,312) having an arylcarbamoyl group at the 2-position (for example, Japanese Patent Publication No. 50-14523);
Those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60-237448, JP-A-61-145557, and JP-A-61-145557)
153640), those having an aryloxy leaving group (for example, US Pat. No. 3,476,563), those having a substituted alkoxy leaving group (for example, US Pat. No. 4,296,199, those having a glycolic acid leaving group (for example, Japanese Patent Publication No. 60-39217) and so on.

The coupler used in the present invention is oil-soluble and is generally dissolved in a high-boiling solvent, optionally using a low-boiling solvent in combination, and this solution is emulsified and dispersed in an aqueous gelatin solution, and then the dispersion is halogenated. It is preferably added to a silver emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber or a known anti-fading agent may be used in combination.

If the method of adding the coupler used in the present invention is further described in detail, the coupler and, if necessary, a hydroquinone derivative, an ultraviolet absorber or an anti-fading agent, etc. are simultaneously represented by the following general formulas (XXIII) to (XXVIII). Dissolved in a low boiling solvent such as ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, or cyclohexanetetrahydrofuran (if necessary, these high boiling solvents and low boiling solvents may be used alone). Gelatin containing an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate. Mixed with an aqueous solution containing a hydrophilic binder such as , High-speed mixer, and emulsified by a colloid mill or an ultrasonic dispersing device or the like, can be used is added to the silver halide emulsion.

General formula (XXIII) General formula (XXIV) W ₁ -COOW ₂ General formula (XXV) General formula (XXVI) Formula (XXVII) W ₁ -0-W ₂ Formula (XXVII) HO-W _{6 In the} formula, W ₁ , W ₂ and W ₃ are each a substituted or unsubstituted alkyl group, cycloalkyl group, or alkenyl group , An aryl group or a heterocyclic group, W ₄ represents W ₁ , O—W ₁ , or S—W ₁ , n is an integer of 1 to 5,
When n is 2 or more, W ₄ may be the same or different, and in formula (VII), W ₁ and W ₂ may be connected to each other to form a condensed ring.

W ₆ represents a substituted or unsubstituted alkyl group or aryl group, and the total number of carbon atoms constituting W ₆ is 12 or more.

The high-boiling coupler solvent that can be used in the present invention has a general formula (XX)
In addition to the compounds of formulas (III) to (XXVIII), compounds having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher are immiscible with water and can be used as long as they are good solvents for couplers. The melting point of the high boiling coupler solvent is preferably 80 ° C. or less. The boiling point of the high boiling coupler is
Preferably it is 160 ° C. or higher, more preferably 170 ° C. or higher.

When the melting point of the coupler solvent exceeds about 100 ° C., crystallization of the coupler tends to occur, and the effect of improving the color development tends to be poor.

The photosensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol derivative and the like as a color fogging inhibitor or a color mixture inhibitor. May be.

In the light-sensitive material of the present invention, various anti-fading agents can be used. That is, as organic discoloration inhibitors for cyan, magenta and / or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarins,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and silylation of the phenolic hydroxyl groups of these compounds, Representative examples include alkylated ether or ester derivatives. In addition, (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato)
A metal complex represented by a nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat.No. 2,735,765 , UK Patent No.
No. 2,066,975, JP-A-59-10539, JP-B-57-19764, and the like, hindered phenols are described in U.S. Pat.
No. 5, JP-A-52-72225, U.S. Pat.No. 4,225,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. No., Japanese Patent Publication No. 56-21144
No. 3,336,135 U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, and ethers and ester derivatives of phenolic hydroxyl groups are disclosed in U.S. Pat. No. 4,174,220 and 4,254,
No. 216, 4,264,720, JP-A-54-145530, 55-
No. 6321, No. 58-105147, No. 59-10539, Japanese Patent Publication No. 57-3
No. 7856, U.S. Pat.No.4,279,990, Japanese Patent Publication No. 53-3263, and the like, and metal complexes are described in U.S. Pat.Nos. 4,050,938 and 4,241,1.
55 and British Patent 2,027,731 (A). These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into both layers adjacent to the cyan coloring layer.

Among the anti-fading agents, spiroindanes and hindered amines are particularly preferred.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers, especially with the pyrazoloazole coupler.

That is, the compound (A) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (B) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized compound of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable from the viewpoint of preventing the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the remaining color developing agent or its oxidized product and the coupler.

Preferred as the compound (A) is a secondary reaction rate constant k2 with p-anisidine (in trioctyl phosphate at 80 ° C.) of from 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec. It is a compound that reacts.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (A) can be represented by the following general formula (AI) or (AII).

General formula (AI) R _1- (A) ₁ -X General formula (AII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine-based developing agent to the compound of the general formula (AII). Represents a group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (AI) and (AII) are described in JP-A-62-158342, JP-A-62-158643, and JP-A-62-158643.
-212258, 62-214681, 62-228034 and 62-
No. 279843.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (for example, US Pat. No. 3,533,794)
), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamate compounds (for example, US Patent 3,70
Nos. 5,805 and 3,707,375), butadiene compounds (for example, those described in U.S. Pat. No. 4,045,229), and benzooxide compounds (for example, U.S. Pat.
No. 455) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes,
Hemioxonol and merocyanine dyes are useful. Details of useful oxonol dyes are described in JP-A-62-215272.
On page 158, upper right column to page 163.

As a binder or protective colloid which can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

As the support used in the present invention, usually, a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, which are used for a photographic light-sensitive material, In addition, there are a laminate thereof, a thin glass film, paper and the like. Paper coated or laminated with a polymer of an α-olefin having 2 to 10 carbon atoms, such as a baryta or α-olefin polymer, especially polyethylene, polypropylene, ethylene butene copolymer, a vinyl chloride resin containing a reflective material such as TiO ₂ , A support such as a plastic film whose surface is roughened to improve the adhesion to other polymer substances as shown in JP 47-19068 also gives good results. Further, an ultraviolet curable resin can also be used.

These supports are selected from transparent and opaque ones according to the purpose of the light-sensitive material. It is also possible to add a dye or a pigment to make it transparent and colored.

The opaque support was originally opaque such as paper, or a transparent film to which a dye or a pigment such as titanium oxide was added, or surface-treated by a method shown in JP-B-47-19068. Plastic films and the like are also included.
The support is usually provided with an undercoat layer. In order to further improve the adhesiveness, the surface of the support may be subjected to a preliminary treatment such as corona discharge, ultraviolet irradiation, or flame treatment.

The color light-sensitive material applicable to the production of the color photograph of the present invention is an ordinary color light-sensitive material such as a color negative film, a color paper, a reversal color paper, a color reversal film and the like, and a color light-sensitive material for printing is particularly preferable.

In the development of the light-sensitive material of the present invention, a black-and-white developer and / or
Alternatively, a color developing solution is used. The color developing solution is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. 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. Can be These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, such as hydroxyamine, diethylhydroxyamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimidinoacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N , N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleach-fixing agent can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831, JP-A-53-37,
No. 418, No. 53-72,623, No. 53-95,630, No. 53-95, 63
No. 1, 53-10,4232, 53-124,424, 53-141,6
No. 23, No. 53-28,426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17,129 (July 1978);
No. 129 thiazolidine derivative; JP-B-45-8,506
No., JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 3,706,561; West German Patent No. 1,12
7,715; iodides described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; -42,434, 49-59,644, 53
-94,927, 54-35,727, 55-26,506, 58-
No. 163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West Patent No. 1,290,812, and
Compounds described in No. 95,630 are preferred. In addition, U.S. Pat.
The compounds described in 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely.
As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
elevi-sion Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

In the processing of the photosensitive material of the present invention, the pH of the washing water is 4-
9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally, the temperature is 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in Nos. 57-8,543, 58-14,834, and 60-220,345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various breakers of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64,339, JP-A-57-14,4547 and JP-A-58-45,047.
No. 115,438 and the like.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

(Example 1) On a paper support laminated on both sides with polyethylene,
A multilayer silver halide light-sensitive material having the following layer structure was prepared. The coating liquid was prepared as follows.

(Preparation of First Layer Coating Solution) Exemplary Compound of the Invention (Cpd-11) having an average molecular weight of about 60,000
1.9 g, shown in Table 1.

Yellow coupler 2,38 × 10 ^-2 mol to ethyl acetate 27.2cc
Further, high boiling point solvents Solv-13,85cc and Solv-23.85cc were added and dissolved, and this solution was emulsified and dispersed in 185cc of a 10% aqueous gelatin solution containing 8cc of 10% sodium dodecylbenzenesulfonate. The emulsified dispersion and the emulsions EM1 and EM2 were mixed and dissolved, and the gelatin concentration was adjusted so as to have the following composition to prepare a first layer coating solution. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-S-triazine sodium salt was used.

 (Cpd-2) was used as a thickener.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² , where only the yellow coupler is mol / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper (The polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye.) First layer (blue-sensitive layer) Single layer spectrally sensitized with sensitizing dye (ExS-1) Dispersed silver chlorobromide emulsion (EM1) Monodispersed silver chlorobromide emulsion (EM2) spectrally sensitized with 0.16 sensitizing dye (ExS-1) ... 0.16 Gelatin ... 1.86 Color image stabilizer ( Cpd-1) 0.02 Polymer of the invention (Cpd-11) 0.08 Yellow coupler (Table 1) 1.03 × 10 ^-3 solvent (solv-1 and solv-2 volume ratio 1: 1) ... 0.35 Second layer (mixing prevention layer) Gelatin …… 0.99 Color mixture prevention agent (Cpd-3) …… 0.03 Solvent (Solv-3) …… 0.06 Third layer (green sensitive layer) Sensitizing dye (ExS-2,3) ) Monodisperse silver chlorobromide emulsion (EM3) spectrally sensitized with 0.05) Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 0.05 sensitizing dye (ExS-2,3) ... 0.11 gelatin …… 1.80 Magenta (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.20 Color image stabilizer (Cpd-5) 0.05 Color image stabilizer (Cpd-6) 0.04 Solvent ( solv-3) ... 0.12 Solvent (solv-4) ... 0.25 Fourth layer (ultraviolet absorbing layer) Gelatin ... 1.60 Ultraviolet absorber (Cpd-7 / Cpd-8 / Cpd-9 = 3/2/6: Weight ratio) 0.70 Color mixture inhibitor (Cpd-3) 0.05 Solvent (solv-5) 0.27 Fifth layer (red-sensitive layer) Spectral sensitized with sensitizing dye (ExS-4,5) Monodisperse silver chlorobromide emulsion (EM5) ...... 0.07 Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with sensitizing dye (ExS-4,5) ... 0.16 Gelatin ... 0.92 Cyan coupler (ExC) -1) 0.17 Cyan coupler (ExC-2) 0.15 Polymer of the invention (Cpd-11) 0.30 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) ... 0.01 color image stabilizer (Cpd-7 / Cpd-9 / Cpd-12 = 3/4/2: weight ratio) ... 0.17 Color image stabilizer (Cpd-1) ... 0.03 Solvent (solv-2) ... 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin ... 0.54 Ultraviolet absorbing agent (Cpd-7 / Cpd-8 / Cpd-9 = 1/5/3: weight ratio) 0.21 Color mixture inhibitor (Cpd-3) 0.02 Solvent (solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modification of polyvinyl alcohol Coalescence (degree of modification 17%) ... 0.17 Liquid paraffin ... 0.03 At this time, the anti-irradiation dye is Cp
d-13 and Cpd-14 were used. Further, in each layer, alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinate and Me
gafac F-120 (Dainippon Ink) was used. Cpd-15 and Cpd-16 were used as stabilizers for silver halide.

 The details of the emulsion used are as follows.

The silver halide emulsion (EM-
1) was prepared as follows.

(Second grade) Sulfuric acid (1N) 20cc (Liquid 1) was heated to 74 ° C., and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 9 minutes. After a further 10 minutes, (Sixth solution) and (Sixth solution) were simultaneously added for 45 minutes. Five minutes after the addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.2, monodisperse cube of average particle size 0.96 μm, coefficient of variation (standard deviation divided by average particle size: s / d) 0.08, silver bromide 80 mol% A silver chlorobromide emulsion was obtained. Sodium thiosulfate was added to this emulsion to perform optimum chemical sensitization.

For the silver halide emulsion of the blue-sensitive emulsion layer of the present invention (EM2) and the silver halide emulsion of the green-sensitive and red-sensitive emulsion layers of the present invention (EM3 to EM6), the amount of chemical and the temperature were determined in the same manner as described above. And by changing the time.

 The structural formula of the compound used is as follows.

Solv-1 ((iso) C ₉ H ₁₉ O ₃ P = O Solv-3 tricresyl phosphate Sample Nos. 101 to 107 shown in Table 1 were prepared by changing the yellow coupler type in the above coated samples. As a comparative example, a sample in which the monodisperse silver chlorobromide emulsion (EM1 and EM2) used in the first layer coating solution was replaced with a polydisperse silver chlorobromide emulsion (EM7), and the polymer of the present invention was obtained from the first layer coating solution. (Cpd-1
Samples excluding 1) and samples using the yellow coupler (Y) outside the present invention were prepared (Sample Nos. 108 to 114). The details are shown in Table 1.

The silver halide emulsion for the blue-sensitive emulsion layer for comparison was prepared as follows.

(9 liquids) sulfuric acid (1N) 10cc (Liquid 8) is heated to 75 ° C. and (Liquid 9) is added. Thereafter, (solution 10) was added over a period of 40 minutes. In addition, (10
Solution) One minute after the start of addition, (solution 11) was added over 40 minutes. Five minutes after the addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust to pH 6.2, average particle size 0.82
A polydisperse silver chlorobromide emulsion having a thickness of .mu.m, a coefficient of variation of 0.27 and silver bromide of 80 mol% was obtained. Sodium thiosulfate was added to this emulsion,
Optimal chemical sensitization was applied.

Samples 101 to 114 were exposed to blue light through an optical wedge, and then subjected to continuous processing (running test) using Fuji Color Paper Processor RP-600 until the replenishment of the color development tank was doubled in the following processing steps. Then, the relative sensitivity and fog value at an optical density of 1.0 were measured and evaluated. The relative sensitivity was evaluated using the color development time as standard (10
(0 seconds), the movement when the time was changed by ± 30 seconds was also used as a measure of the suitability for rapid processing and the magnitude of processing fluctuation. For convenience, relative sensitivity refers to the difference in sensitivity between samples.
The relative sensitivity of the standard development of No. 104 was 100, and the relative sensitivity at the standard time was 100 when the development time was changed for the same sample. The fog value was a value at standard time.
The evaluation results are shown in Table 2.

The composition of each processing solution is as follows.

Rinse liquid Ion exchange water (3 ppm or less for calcium and magnesium each) As apparent from Table 2, the yellow coupler of the present invention,
Samples combining polymers and monodisperse emulsions are highly sensitive
Low fog, little change in sensitivity due to fluctuations in development time,
In addition, sufficient sensitivity is obtained in a shorter time. In other words, it is found that the material has excellent processing stability and is suitable for rapid processing.

(Example 2) On a paper support laminated on both sides with polyethylene,
A multilayer silver halide light-sensitive material having the following layer structure was prepared. The coating liquid was prepared as follows.

(Preparation of the first layer coating solution) 1.98 of the exemplified compound (Cpd-11) having an average molecular weight of about 60,000, 2.38 × 10 ^-2 mol of the yellow coupler shown in Table 3, 27.2 cc of ethyl acetate and a high boiling solvent (Solv-6) 7.7cc (8.0g)
Was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. The emulsified dispersion and the emulsion EM8 were mixed and dissolved, and the gelatin concentration was adjusted so as to have the following composition to prepare a first coating solution. Coating solutions for the second to seventh layers were prepared in the same manner as the first coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-S-triazine sodium salt was used.

 (Cpd-2) was used as a thickener.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ^2, but only the yellow coupler is mol / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper (The polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye.) First layer (blue-sensitive layer) Single sensitized with sensitizing dye (ExS-7) Dispersed silver chlorobromide emulsion (EM8) 0.27 Gelatin 1.86 Polymer of the present invention (Cpd-11) 0.08 Yellow coupler (Table 3) 1.83 × 10 ^-3 solvent (Solv-6) 0.35 Second layer (color mixture prevention layer) Gelatin… 0.99 Color mixture inhibitor (Cpd-3)… 0.06 Solvent (Solv-3)… 0.12 Third layer (green sensitive layer) Sensitizing dye (ExS-3,6) ) Monodisperse silver chlorobromide emulsion spectrally sensitized with (EM9… 0.45 Gelatin… 1.21 Magenta coupler (ExM-2)… 0.35 Color image stabilizer (Cpd-4)… 0.12 Color image stabilizer ( Cpd-10) 0.06 Color image stabilizer (Cpd-20) 0.10 Color image stabilizer (Cpd-21) 0.01 Solvent (Solv-3) 0.25 Solvent (Solv-4) 0.25 Four (Ultraviolet absorption layer) Gelatin 1.60 Ultraviolet absorber (Cpd-7 / Cpd-9 / Cpd-17 = 3/2/6: weight ratio) 0.70 Color mixing inhibitor (Cpd-3) 0.05 Solvent ( Solv-7) 0.42 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EM-10) spectrally sensitized with sensitizing dye (ExS-4,5) 0.20 Gelatin 0.92 Cyan coupler (ExC-3) 0.15 Cyan coupler (ExC-4) 0.18 Color image stabilizer (Cpd-7 / Cpd-9 / Cpd-18 = 3/4/2: weight ratio) 0.17 colors Image stabilizer (Cpd-1) 0.02 Polymer of the invention (Cpd-11) 0.14 Solvent (Solv-6) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.54 Ultraviolet absorber (Cpd-7 / Cpd-9 / Cpd-17 = 1/5/3 weight ratio ...... 0.21 Solvent (Solv-7) ...... 0.08 Seventh layer (protective layer) Acid-treated gelatin ... 1.33-Acrylic modified copolymer of polyvinyl alcohol ( Denaturation 17%) ... 0.17 Liquid paraffin ... 0.03 In addition, at this time, the anti-irradiation dye, Cp
d-13 and Cpd-19 were used. Further, in each layer, alkanol XC (Du-pont), sodium alkylbenzenesulfonate, succinate, and Megafac F-120 (manufactured by Dainippon Ink) were used as emulsifying dispersant coating aids. Cpd-14 and Cpd-15 were used as stabilizers for silver halide.

 The details of the emulsion used are as follows.

The symbols of the compounds used in this example are the same as those in Example 1. Other compounds are shown below.

Solv-6 dibutyl phthalate Solv-7 dioctyl sebacate In the above coated samples, samples Nos. 201 to 204 in Table 3 were prepared by changing the yellow coupler type. As a comparative example, the monodisperse silver chlorobromide emulsion (EM-8) used in the coating solution for the first layer was changed from a polydisperse silver chlorobromide emulsion (EM-11: particle diameter 0.86 μm, Br content 0.6% by mole). The coefficient was changed to 0.25), the sample obtained by removing the polymer (Cpd-11) of the present invention from the coating solution for the first layer, and the sample using the yellow coupler of the present invention <(Y): the one used in Example 1> (Sample N
o.205-211). The details are shown in Table 3.

After exposing the samples 201 to 211 to blue light through an optical wedge, the samples were processed in the following steps, and evaluated in the same manner as in Example 1. However, the experiment was conducted while changing the development time by ± 15 seconds with respect to the standard (45 seconds). Table 4 shows the evaluation results. Step Temperature Time Color developing 35 ° C. 30 seconds, 45 seconds, 60 seconds blix 30 to 36 ° C. 45 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 20 seconds stable 30 to 37 ° C. 30 seconds drying 70-85 ° C 60 seconds (4 tank countercurrent method to stable →) The composition of each processing solution is as follows. Color developing water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N -Diethylhydroxylamine 4.2g 5,6-Dihydroxybenzene-1,2,4 trisulfonic acid 0.3g Fluorescent whitening agent (4,4'- diaminostilbene) 2.0g Add water 1000ml pH (25 ° C) 10.10 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Iron (III) ammonium ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 3g Glacial acetic acid 8g Add water 1000ml pH (25 ℃) 5.5 Stabilizer Formalin (37% 0.1 g formalin-sulfite adduct 0.7 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-iso Thiazolin-3-one 0.01 g Copper sulfate 0.005 g Add water 1000 ml pH (25 ° C) 4.0 As is clear from Table 4, the sample obtained by combining the yellow coupler, the polymer, and the monodispersed emulsion of the present invention has high sensitivity.
It is understood that the material is excellent in processing stability and low in fog like Example 1, and is suitable for rapid processing. This effect is due to the fact that P-Pd as exemplified above in place of Cpd-11 as the polymer of the present invention.
3, P-110, P-119, P-120 and P-122 can be obtained in the same manner.

Further, even when ExM-1 used in Example 1 was used in place of ExM-2 as a magenta coupler, the above effect was not deteriorated.

(Effects of the Invention) A color photographic light-sensitive material having a blue-sensitive emulsion layer having high sensitivity, low fog, excellent processing stability, and suitable for rapid processing by combining the yellow coupler, the polymer and the monodispersed silver chlorobromide emulsion of the present invention. The material is obtained. In particular, in the embodiment in which a color photographic light-sensitive material using a silver chlorobromide emulsion containing 90 mol% or more of silver chloride is subjected to color development processing containing diethylhydroxylamine, the effects of the present invention are more remarkably exhibited. .

Claims (2)

(57) [Claims] 1. A silver halide color photographic material having a blue-sensitive, green-sensitive and red-sensitive photosensitive silver halide emulsion layer on a support, wherein at least one of yellow couplers represented by the following formula (I): And a dispersion of lipophilic fine particles obtained by emulsifying and dispersing a mixture in which at least one of a water-insoluble and organic solvent-soluble homopolymer or copolymer is dissolved is contained in the blue-sensitive silver halide emulsion layer, and A silver halide color photographic light-sensitive material, wherein the silver halide emulsion in the emulsion layer is a monodispersed silver chlorobromide emulsion. General formula (I) In the formula, R ₈ represents a substituted or unsubstituted N-phenylcarbamoyl group, and Y ₃ represents a group bonded via an oxygen atom or a nitrogen atom and capable of leaving by a coupling reaction with an oxidized developing agent. . 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion in the blue-sensitive silver halide emulsion layer is a silver chlorobromide emulsion containing 90 mol% or more of silver chloride.