JPH06273904A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness and graininess as well as color reproduction and dependence of processing by incorporating a specified magenta dye-forming coupler in an emulsion layer. CONSTITUTION:The emulsion layer contains flat single dispersion emulsion agent having an average aspect ratio of >=2.0 and a structure different in the composition of silver halide/and the emulsion layer highest in sensitivity has an average silver iodide content not above those of the emulsion layers among the emulsion layers in the same unit and, in the photosensitive emulsion layer unit nearest to the light-incident side, an average silver iodide content is <=3mol%, green-sensitive emulsion layers contain the magenta dye-forming coupler represented by formula I in which R1 is H or a substituent; Z is a nonmetallic atomic group necessary to form an optionally substituted condensed 5-membered azole ring containing 2-4 N atoms: and X is a group to be released by coupling with the oxidation product of a developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material having improved image sharpness, graininess, color reproducibility and processing dependence.

[0002]

2. Description of the Related Art Usually, in a multilayer color photographic material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, light scattering by silver halide grains tends to reduce the sharpness of an emulsion layer located below. It has been known. US Patent No. 4,
434,226 and 4,439,520,
A color photographic light-sensitive material having improved sharpness, sensitivity and graininess by using tabular silver halide emulsion grains is described. U.S. Pat. No. 4,433,048 discloses that tabular grains having an AgI distribution in the grains increasing from the center toward the surface exhibit excellent sensitivity and size ratio.

Further, in JP-A-62-18552, silver halide grains contained in all silver halide emulsion layers are composed of silver iodobromide containing 4 mol% or less of silver iodide. It is disclosed that a color photographic light-sensitive material containing tabular silver halide grains in at least one layer has excellent color reproducibility. On the other hand, JP-A-62-1855
No. 6 shows that the photosensitive material using monodisperse tabular silver halide grains has excellent image sharpness and graininess as compared with those using polydisperse tabular grains, and JP-A-63-15161.
No. 8 discloses a method for preparing the monodisperse tabular grains. Further, JP-A-2-256043 discloses that image sharpness and graininess are improved by using a monodisperse tabular emulsion having an improved AgI distribution between silver halide emulsion grains, and EP-0514743A1. In the issue,
A method of improving the sharpness by an emulsion that defines the tabularity has been proposed. Although these methods have made some progress in improving sharpness, graininess, or color reproduction, no detailed examination of the layering effect or spectral sensitivity has been made, and as a result, improvement in color reproduction is extremely insufficient. It was something.

Regarding the design of spectral sensitivity, for example, US Pat. No. 3,672,898 describes a spectral sensitivity distribution with good color rendering properties. However, there is no consideration given to the spectral absorption characteristics of each coloring dye and the layering effect, and satisfactory results cannot be obtained by this alone. Japanese Patent Application Laid-Open No. 61-34541 discloses a method for realizing spectral sensitivity that imitates the color matching spectral sensitivity of the human eye, and Japanese Patent Application Laid-Open No. 3-12.
No. 2636 discloses a method for realizing spectral sensitivity that imitates the color matching spectral sensitivity of the human eye in a color reversal film, but a simpler approximation method has been demanded. Furthermore, for example, JP-A-3-194546 and JP-A-3-19
4547 and JP-A-4-240845 disclose preferable spectral sensitivities, but preferable layering effect and sharpness
The study of graininess improvement was insufficient.

The color-forming dye-forming coupler is yellow, which is used in conventional silver halide color photographic light-sensitive materials.
Since the coloring dyes formed by the magenta and cyan couplers have unnecessary sub-absorption, the color reproducibility tends to be impaired. Therefore, as a technique for improving the color reproducibility, a coupler that forms an image dye with less side absorption has been studied. For magenta dyes, attention has been paid to the improvement of the hue of magenta color by using a pyrazoloazole-based magenta coupler instead of the conventional 5-pyrazolone type magenta coupler. The azomethine dye formed by the reaction of these couplers with the oxidation product of the color developing agent is 430
It is known that the amount of sub-absorption that is harmful for color reproduction in the vicinity of nm is small and thus the saturation is high, which is preferable for color reproduction. For these couplers, see, for example, US Pat. No. 3,725,067.
No. 60,172,982 and 60-33552.
No. 61-72238, U.S. Pat. No. 4,500,6.
No. 30, No. 4,540, 654, No. 5,021,
No. 325 and others.

In addition to these improvements in image quality, in recent years there has been a growing demand for small fluctuations in photographic properties due to composition factors of the processing liquid.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having good color reproduction and good processing dependence in addition to sharpness and graininess.

[0008]

The objects of the present invention have been achieved by the following silver halide color photographic light-sensitive materials. (1) In a photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer unit each comprising one or more emulsion layers on a support, at least one of the emulsion layers
The average of the emulsion layers having the highest sensitivity among the emulsion layers constituting the emulsion layer unit containing a tabular monodisperse emulsion having a structure due to the difference in halogen composition inside the grains having an average aspect ratio of 2 or more The silver iodide content is less than or equal to the average silver iodide content of another emulsion layer in the same unit, the average silver iodide content of the photosensitive emulsion layer unit closest to the incident light side is 3 mol% or less, and Which is less than the average silver iodide content of the emulsion layer unit, and the green-sensitive emulsion layer contains at least one magenta dye-forming coupler represented by the following general formula (M). Silver halide color photographic light-sensitive material.

[0009]

[Chemical 2] In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. (2) The silver halide color photographic light-sensitive material as described in (1) above, wherein at least one light-sensitive emulsion layer contains a polymer having a polyalkylene oxide block polymer component in its molecule. (3) A positive image is obtained by performing negative B / W development after imagewise exposure and then color-developing with residual silver halide to obtain a positive image.
The described silver halide color photographic light-sensitive material.

The present invention will be described in detail below. In the present invention, the red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layer units each mean an emulsion layer group mainly sensitive to substantially the same wavelength range of incident light, and usually at least one layer and three layers each. It is composed of the following layers, but may have three or more layers.

By tabular grains is meant having two substantially parallel surfaces, the thickness of the grains being as defined in 2 above.
It is represented by the distance between two parallel planes. The diameter of the particle is represented by the diameter of a circle having an area equal to the projected area of the particle. The aspect ratio of the particles means the ratio of the diameter and the thickness of the particles. A tabular emulsion is an emulsion mainly composed of such tabular grains, and the average aspect ratio is the average value of the aspect ratios of tabular grains accounting for 50% or more of the projected area of all emulsion grains contained in one emulsion. means. The tabular emulsion used in the present invention has an average aspect ratio of 2 or more, preferably 5 or more, and may be 8 or more. Similarly, it is preferably 30 or less.

A monodisperse emulsion is one having a variation coefficient vc of 25% or less, which is obtained by dividing the standard deviation S of the diameter of a circle equal to the projected area of all grains contained in the emulsion by the average grain size r, but not more than 25%. Is 20% or less, more preferably 15% or less. The particle size can be measured, for example, by the method described in Chapter 2 of "Theory of Photographic Process" by Mies and James, 3rd edition, published by Macmillan Co. (1966).

Monodisperse tabular emulsions are described, for example, in US Pat.
It can be prepared by the method described in 97,354. Further, US Pat. No. 5,147,771
No. 5,147,772, and No. 5,14.
No. 7,773 shows that a good monodisperse emulsion can be obtained by using a polyethylene oxide block copolymer. In that method, for example, PLURON can be used.
A compound represented by the following chemical formula 3 called IC ^™ 31R1 is used. This compound is used in the step of forming silver halide tabular grains in an amount of 100% by weight or less, preferably 30% by weight or less, based on the amount of silver used for tabular nucleation. This amount is preferably 2% by weight or more,
It is more preferably 10% by weight or more. Further, it is preferable to add the above amount before the start of grain formation, and it may be added additionally during the growth process of tabular grains. It may also be added only during the grain formation process.
Furthermore, as shown below, various polyalkylene oxide
By using a block copolymer, an emulsion composed of tabular grains having a low degree of dispersion can be prepared.

[0014]

[Chemical 3] The halogen composition of the emulsion used in the present invention is silver haloiodide, but silver iodobromide is preferred. Silver iodide content is 40 with respect to silver
Mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and similarly preferably 0.1 mol% or less.
It is at least mol%, more preferably at least 1 mol%. In order to realize the preferred multilayer effect of the present invention, the emulsion layer having the highest sensitivity among the emulsion layers constituting each emulsion layer unit has the average silver iodide content of the other emulsion layers in the same unit. Must be below the content. The average silver iodide content of the emulsion layer unit closest to the incident light side is 3 mol% or less, preferably 2.5 mol% or less, and similarly 0.1 mol% or more. ,
It is more preferably 0.5 mol% or more. The average silver iodide content of the second and third emulsion layer units from the incident light side is determined by the required interlayer effect.

The light-sensitive emulsions other than the tabular monodisperse emulsions can be composed of tabular polydisperse emulsions having an average aspect ratio of 2 or more, non-tabular twin polydisperse or monodisperse emulsions, and regular monodisperse emulsions. Regular monodisperse emulsions are cubic, octahedral, 1
It is usually composed of a dihedron, a tetrahedron, and a surface in which these crystal habits are mixed, and the corners may or may not be rounded. Further, the surface is not necessarily flat and may have irregularities or protrusions. Further, it may be bonded to a crystal part having a different halogen composition epitaxially on a face, a ridge or a vertex, or a compound other than silver halide such as silver rhodanide or lead oxide. The content of the tabular monodisperse emulsion of the present invention in the same emulsion layer is preferably 20% by weight to 100% by weight in terms of silver amount, and 30% by weight is preferable.
More preferably, it is from 100% by weight to 100% by weight.

All the emulsions used in the present invention preferably have a structure having different compositions inside the grains. The difference in composition is preferably due to the difference in AgI content.
It is preferable that the maximum value of I is inside the particle. The maximum value may be one or two or more. The high AgI
The AgI content of the phase is the average Ag in the emulsion containing the grains.
It is more than twice the I content and 100% AgI. Further, each emulsion preferably has one or more dislocation lines inside the grains, more preferably 10 or more dislocation lines.
The dislocation lines may be uniformly present in the grains, may be localized in a part or a plurality of phases forming a structure, and may be concentrated in the outermost phase or a part thereof.

The latent image forming site of the photosensitive emulsion may be mainly on the surface or inside, and may be on both the surface and inside, but it is necessary to be a negative type emulsion. Among the internal latent image types, JP-A-63-264740
The core / shell type internal latent image type emulsions described in JP-A No. 1994-242242 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion is 3-40 depending on the development process.
nm is preferred and 5-20 nm is particularly preferred.

Each photosensitive emulsion layer is formed by one or more emulsions. When a plurality of tabular emulsions are mixed, the average aspect ratio of the higher sensitive emulsion is preferably higher than that of the lower sensitive emulsion. The silver iodide content of the higher-sensitive emulsion is preferably lower than that of the lower-sensitive emulsion. A mixture of a tabular emulsion and a non-tabular twin crystal emulsion or a regular emulsion is also preferably used. It is also preferable to use a plurality of regular emulsions, especially when the average grain size is 0.4 μm or less.

A light-sensitive material having the above-mentioned emulsion constitution can remarkably exert its effect in a color reversal photographic light-sensitive material.

In the present invention, the spectral sensitivity distribution of the blue sensitive layer is such that the wavelength giving the maximum sensitivity is 410 nm to 470 nm.
And the sensitivity at 480 nm in the spectral sensitivity distribution at the minimum density +0.7 is 80% or less with respect to the maximum sensitivity, but the sensitivity at 480 nm is more preferably 50% or less with respect to the maximum sensitivity. The above relationship is the minimum concentration +
Not limited to 0.7, it is preferable to be established at each concentration at which the characteristic curve can be reproduced.

In the present invention, the spectral sensitivity distribution of the green sensitive layer is such that the wavelength giving the maximum sensitivity is from 530 nm to 590 nm.
, The sensitivity of 500 nm in the spectral sensitivity distribution at the minimum density +0.7 is 30% or less of the maximum sensitivity, but the wavelength giving the maximum sensitivity is from 530 nm to 570 n.
m, and it is more preferable that the sensitivity at 500 nm in the spectral sensitivity distribution at the minimum density +0.7 is 25% or less with respect to the maximum sensitivity.

In the present invention, the spectral sensitivity distribution of the red sensitive layer is such that the wavelength giving the maximum sensitivity is 590 nm to 660 nm.
However, it is more preferably 600 nm to 650 nm.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), page 648, ibid. Thirty
7105 (Nov. 1989), pp. 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
It can be prepared using the method described in Press, 1964).

Monodisperse emulsions are described, for example, in US Pat.
It can be prepared by the method described in 4,628, 3,655,394 and British Patent 1,413,748.

The tabular grains are described, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photographic Science).
nce and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157.

The tabular monodisperse emulsion of the present invention can be used in any color-sensitive emulsion layer, but it is particularly preferably used in the green-sensitive emulsion layer.

The polymer having the block polymer component of polyalkylene oxide of the present invention in the molecule will be described in more detail. In the photographic light-sensitive material of the present invention, particularly useful compounds for preparing a silver halide emulsion are the hydrophobic polyalkylene oxide represented by the general formula (I) represented by the following chemical formula 4 and the compound represented by the following chemical formula 5. General formula (II) shown
Is a polymer having a hydrophilic polyalkylene oxide block polymer component represented by

[0028]

[Chemical 4]

[0029]

[Chemical 5] In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (eg, methyl, chloromethyl, ethyl, n-butyl), an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl), n represents an integer of 1 to 10.
Here, when n = 1, R ¹ does not become a hydrogen atom. R ² represents a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (eg, hydroxymethyl, carboxymethyl) substituted with a hydrophilic group (eg, hydroxy, carboxyl).

X and y represent the number of repeating units (number average degree of polymerization). The preferred range of x and y varies depending on the structure of the polymer, but x is 2 to 1000, preferably 3 to 500, and y is 1 to 100.
It is 0, preferably 2 to 400. The ratio of the components of the general formula (I) and the general formula (II) in the block polymer may be variously changed depending on the hydrophilicity / hydrophobicity of each unit and the type of emulsion prepared, but roughly speaking, the weight ratio is 4: 4. It is within the range of 96 to 96: 4.

Among the hydrophobic polyalkylene oxides represented by the general formula (I), polypropylene oxide (R ¹ = methyl group, n = 1) is particularly preferable, and among the hydrophilic polyalkylene oxides represented by the general formula (II). Polyethylene oxide (R ² = hydrogen atom) and polyglycerol (R ² = CH ₂ OH) are preferable, and polyethylene oxide is particularly preferable.

With respect to the polymer having the above block copolymer component in the molecule, a compound having polypropylene oxide-polyethylene oxide, which is a typical component, as a block copolymer component will be described in more detail below. Typical examples of the polymers used in the present invention are shown below.
Can be represented by the general formulas (III) to (X) shown in Chemical formula 13.

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13] Among the above general formulas (III) to (X), x, x ′, x ″,
x ′ ″, y, y ′, y ″, y ′ ″ represents the number of repetitions of each unit, and its preferable range is x in the general formulas (I) and (II),
Same as y. R ³ represents a monovalent group, and specifically,
It represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, preferably a substituted or unsubstituted lower alkyl group (having 6 or less carbon atoms). As a specific example of R ³ ,
Methyl, ethyl, n-propyl, isopropyl, t-butyl, chloromethyl, methoxycarbonylmethyl, N-
Mention may be made of methyl-N-ethylaminoethyl and N, N-diethylaminoethyl.

L represents a trivalent or tetravalent linking group.
Specific examples of L are shown in Chemical Formulas 14 to 15 below, but are not limited to these.

[0042]

[Chemical 14]

[0043]

[Chemical 15] Specific examples of the polymer having a block polymer component in the molecule used in the present invention are shown in Tables 1 and 2 below, but the present invention is not limited thereto.

[0044]

[Table 1]

[0045]

[Table 2] For specific examples, general description of the above-mentioned polymers used in the present invention, and for specific examples of preparation of silver halide emulsions using this type of polymer, European Patent Publication Nos. 513722, 513723, 513724, 5
13725, 513742, 513743, 51806
6 etc. can be mentioned.

The polymer of the present invention contains 1 per silver atom in the emulsion.
It is preferable to add more than wt%, and 200 wt%
The following is preferable, and 100% by weight or less is more preferable. Further, the polymer of the present invention is preferably used for a monodisperse tabular emulsion, more preferably for a monodisperse tabular emulsion used for a green-sensitive emulsion layer. The polymer of the present invention is preferably added before the formation of silver halide grains.

The magenta dye-forming coupler used in the present invention will be described in detail below. Among the coupler skeletons represented by the general formula (M), a preferable skeleton is 1 H -imidazo [1,2- b ] pyrazole, 1 H -pyrazolo [1,5-
b ] [1,2,4] triazole, 1 H -pyrazolo [5,1- c ] [1,2,4] triazole, 1 H -pyrazolo [1,5- d ] tetrazole and 1 H -pyrazolo [1 , 5- a ] benzimidazole, which are represented by formulas (M-I), (M-II) and (M
-III), (M-IV) and (MV).

[0048]

[Chemical 16] Among the coupler skeletons represented by these formulas, those represented by (M-II) and (M-III) are more preferred, and those represented by (M-III) are most preferred. The substituents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , n and X in these formulas will be described in detail.

R ₁₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, Alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo A group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group, or an azolyl group, R ₁₁
May form a bis form with a divalent group.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-). Amylphenyl, 2,
4,6-Trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2 -Methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {2- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl)) Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
N- (2-dodecyloxyethyl) sulfamoyl, N
-Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi). Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned.

R ₁₂ is a group similar to the substituents exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. Or a cyano group.

R ₁₃ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or an alkoxy group. It is a carbonyl group, a carbamoyl group or an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an arylthio group.

R ₁₄ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, acylamino group, alkoxycarbonylamino group, sulfonamide group, sulfamoylamino group, or cyano It is a base.

N represents an integer of 1 to 4, preferably an integer of 1 to 3.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent, and the splitting off group is described in detail. A halogen atom, an alkoxy group, an aryloxy group, an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group A nitrogen heterocyclic group, an imide group, an arylazo group, etc., and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, X is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy). ), An aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy,
4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy Groups (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg methanesulfonamino, trifluoromethanesulfonamino, p-toluene) Sulfonylamino), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxy Ruboniruokishi group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio, 1-carboxy-dodecyl thio, phenylthio, 2-butoxy-5
-T-octylphenylthio, 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group ( For example, 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazole-1-
Iyl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-1-pyrazolyl, 1,2-dihydro-2-oxy- 1-pyridyl), imide group (for example, succinimide, hydantoinyl), arylazo group (for example, phenylazo, 4-
Methoxyphenylazo). In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, particularly preferably a halogen atom, or It is a substituted aryloxy group. Most preferable X is a chlorine atom or a substituted aryloxy group represented by -OAr.

Ar is a substituted aryl group, and more specifically,
Examples thereof include phenyl and naphthyl, and more specifically, phenyl, 4-methylphenyl, 4-methoxycarbonylphenyl, 4-methanesulfonylphenyl, 4-benzoylphenyl, 4- (4-benzyloxybenzenesulfonyl) phenyl, 2,4. -Dimethylphenyl, 2,
4,6-Trimethylphenyl, 2,4-di-methoxyphenyl, 4-t-octylphenyl, 4-n-nonylphenyl, 4-octadecyloxyphenyl, 4-methyl-3-tetradecanoylaminophenyl, 1- An aryl group such as naphthyl, 2-naphthyl, or 4-n-octanoyloxy-1-naphthyl. Examples of the substituents for substituting these aryl groups include the same substituents as those exemplified for R ₁₁ .

Preferred Ar is a substituted aryl group having 6 to 30 carbon atoms, particularly preferably a phenyl group having an alkyl group having 1 to 30 carbon atoms as a substituent at the 4-position or an alkoxy group having 1 to 20 carbon atoms. A phenyl group having an alkoxycarbonyl group at the 4-position as a substituent.

A more preferable structure of the magenta coupler represented by the formula (M) is represented by the following formula (M-VI).
Alternatively, it is represented by (M-VII).

[0061]

[Chemical 17] In the formula, R ₁₁ and X are the same groups as the substituents exemplified in the formula (M-III). Y represents a carbonyl group or a sulfonyl group. R ₂₁ is a halogen atom, an alkoxy group, an alkyl group,
It represents a monovalent organic group such as a nitro group, an alkoxycarbonyl group, and a cyano group. R ₂₂ is an alkyl group, an aryl group,
Represents a heterocyclic group, the alkyl group having 4 or more carbon atoms 3
It is preferably 2 or less, and may have a substituent. The aryl group or the heterocyclic group preferably has one or more substituents, and the substituent preferably has 4 or more and 32 or less carbon atoms. Further, the heterocyclic group may be either a 5- or 6-membered ring, and examples thereof include pyridyl, imidazolyl and benzimidazolyl. m represents an integer of 0 to 5 and n represents an integer of 0 to 4,
Is preferably 0 or 1, and more preferably 0. R ₂₃ and R ₂₄ are a hydrogen atom, an alkyl group,
Alternatively, it represents an aryl group, and R ₂₅ represents a sulfonyl group or an acyl group. p represents an integer of 0 to 5. p is preferably 0 or 1, and particularly preferably 0.

More specifically, the alkyl group and aryl group of R ₂₃ and R ₂₄ are linear or branched alkyl groups having 1 to 32 carbon atoms, and aryl groups having 6 to 30 carbon atoms. It represents a substituted or unsubstituted phenyl group or naphthyl group, which may have the same substituents as those exemplified for R ₁₁ . Preferred R
₂₃ and R ₂₄ are a hydrogen atom, an alkyl group of methyl, ethyl, isopropyl or t-butyl, or an aryl group of phenyl or naphthyl, more preferably a hydrogen atom, an alkyl group of methyl, ethyl or isopropyl, and particularly preferably Is a hydrogen atom, methyl.

R ₂₅ represents a sulfonyl group or an acyl group, and first of all, the sulfonyl group will be described in detail. It is a substituted or unsubstituted alkanesulfonyl group, or a substituted or unsubstituted arenesulfonyl group, more specifically, methanesulfonyl, Hexanesulfonyl, dodecanesulfonyl, 2-hexyldecanesulfonyl, 1
-(4-pentadecanoylaminophenyl) methanesulfonyl, 4- (2-n-butyloxy-5-t-octylbenzenesulfonyl) butanesulfonyl, or 2
An alkanesulfonyl group such as-(4-t-octylphenoxy) ethanesulfonyl, or benzenesulfonyl, 4-octadecyloxybenzenesulfonyl, 2-
Octadecyloxy-5-t-butylbenzenesulfonyl, 2-dodecyloxy-5-t-butylbenzenesulfonyl, 2-octyloxy-5-t-octylbenzenesulfonyl, 4-pentadecanoylaminobenzenesulfonyl, 2-octyloxy. An arenesulfonyl group such as -5- (2-octyloxy-5-t-octylbenzenesulfonamide) benzenesulfonyl, 1-naphthalenesulfonyl, or 4-octyloxy-1-naphthalenesulfonyl. A more preferable sulfonyl group for R ₂₅ is a substituted or unsubstituted arenesulfonyl group.

Next, the acyl group for R ₂₅ will be described in detail. These acyl groups are a substituted or unsubstituted alkanoyl group or a substituted or unsubstituted aryloyl group.

The acyl group will be described in more detail. Acetyl, hexanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, 2- (2,4-di-t-).
Octylphenoxy) butanoyl, 2- (2,4-di-
t-octylphenoxy) hexanoyl, 2- [4-
Alkanoyl group such as (4-hydroxybenzenesulfonyl) phenoxy] dodecanoyl, 4-dodecanesulfonylbutanoyl or 2- (4-methoxyphenoxy) dodecanoyl, or benzoyl, 1-naphthalenyl, 4-dodecyloxybenzoyl, 2-octadecyloxy An aryloyl group such as benzoyl, 2,5-dioctyloxybenzoyl, 4-t-octylbenzoyl, 3-tridecylaminobenzoyl, 2,6-dioctyloxybenzoyl or 1,4-dioctyloxy-2-naphthalenyl. The more preferred acyl group for R ₂₅ is a substituted or unsubstituted benzoyl group.

Among the magenta couplers represented by the formulas (M-VI) and (M-VII), a more preferable structure is shown below.
A coupler represented by the formula (M-VIII) shown in FIG.

[0067]

[Chemical 18] In the formula, R ₁₁ is the same group as the substituent exemplified in the formula (M-III), more preferably methyl, ethyl or a tertiary alkyl group having 1 to 4 carbon atoms, and t-butyl. Is most preferred. X is a group similar to the substituent exemplified in the formula (M-III).

R ₃₁ , R ₃₂ , and R ₃₃ are each a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, and more preferably methyl. Is.

R ₃₄ is a group derived from a substituted or unsubstituted amino acid. Specific examples of R ₃₄ are shown below in Chemical formulas 19 to 20, but are not limited thereto.

[0070]

[Chemical 19]

[0071]

[Chemical 20] In the compounds represented by the formulas (M-I) to (MV),
When R ₁₁ , R ₁₂ or R ₁₃ or X is a divalent group to form a bis form, R ₁₁ , R ₁₂ or R ₁₃ is a substituted or unsubstituted alkylene group (eg methylene, ethylene, 1 , 10-decylene, -CH ₂ CH ₂ -O-CH
₂ CH ₂ -), substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, 2,5
-Dimethyl-1,3-phenylene, 2,5-dichloro-
1,3-phenylene), X represents a divalent group obtained by appropriately replacing the above monovalent group.

The linking group represented by any one of R ₁₁ , R _{12 and} R _{13 in} the case where the vinyl monomer contains one of the formulas (MI) to (MV) is an alkylene group ( A substituted or unsubstituted alkylene group such as methylene,
Ethylene, 1,10-decylene, -CH ₂ CH ₂ OCH
₂ CH ₂ —), a phenylene group (a substituted or unsubstituted phenylene group, such as 1,4-phenylene, 1,3-phenylene, 2,5-dimethyl-1,3-phenylene, 2,
5-dichloro-1,3-phenylene), -NHCO-,
-CONH -, - O -, - OCO- and aralkylene group (e.g., _{-CH 2 C 6 H 4 CH 2} -, - CH 2 CH 2 C
₆ H ₄ CH ₂ CH ₂ —, —CH ₂ C ₆ H ₂ Cl ₂ —CH
_2- ) Includes groups that are established by combining those selected from.

Preferred linking groups include:

--CH ₂ CH _2- , --CH ₂ CH ₂ CH _{2
C 6 H 4 NHCO -, -} C 6 H 4 NHCO -, - CH 2
_{CH 2 NHCO -, - CH 2} CH 2 OCO -, - CH 2
_{CH 2 O-CH 2 CH 2} -NHCO -, - CH 2 CH 2
_{C 6 H 4 CH 2 CH 2} NHCO- Incidentally vinyl group of the formula (M-I) ~ (M -V) may take a substituent other than those represented by the preferred substituent is a hydrogen atom, a chlorine atom or a carbon, Represents a lower alkyl group of 1 to 4 (eg methyl, ethyl).

Monomers including those represented by the formulas (MI) to (MV) are non-color-forming, ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developing agents. Copolymers may be made.

Examples of the non-color-forming, ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent include acrylic acid, α-chloroacrylic acid and α-alkylacrylic acid (eg methacrylic acid). And esters or amides derived from these acrylic acids (eg, acrylamide, n-butyl acrylamide, t-
Butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl Methacrylate, ethylmethacrylate, n-butylmethacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl. Compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone, sulfur Styrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-
Vinyl-2-pyrrolidone, N-vinylpyridine, and 2
-And 4-vinyl pyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together. Examples are n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, and methyl acrylate and diacetone acrylamide.

As is well known in the polymer color coupler art, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical properties and / or chemistry of the copolymer formed. Properties such as solubility, compatibility with photographic colloid composition binders such as gelatin,
It can be chosen such that its flexibility, thermal stability, etc. are positively affected.

The polymer coupler used in the present invention may be either water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable.

In the silver halide color photographic light-sensitive material of the present invention, the amount of the magenta coupler used is preferably 0.003 to 5 mol, more preferably 0.01 to 2 mol, and particularly preferably 0.01 to 2 mol, based on 1 mol of the light-sensitive silver halide. Preferably 0.02
~ 0.5 mol.

Compound examples of the magenta coupler represented by the formula (M) are shown in the following chemical formulas 21 to 50, but are not limited thereto.

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

[0087]

[Chemical 27]

[0088]

[Chemical 28]

[0089]

[Chemical 29]

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

[0093]

[Chemical 33]

[0094]

[Chemical 34]

[0095]

[Chemical 35]

[0096]

[Chemical 36]

[0097]

[Chemical 37]

[0098]

[Chemical 38]

[0099]

[Chemical Formula 39]

[0100]

[Chemical 40]

[0101]

[Chemical 41]

[0102]

[Chemical 42]

[0103]

[Chemical 43]

[0104]

[Chemical 44]

[0105]

[Chemical formula 45]

[0106]

[Chemical formula 46]

[0107]

[Chemical 47]

[0108]

[Chemical 48]

[0109]

[Chemical 49]

[0110]

[Chemical 50] References which describe a method for synthesizing the coupler represented by the formula (M) are listed below.

The compound of formula (MI) is, for example, US Pat. No. 4,500,630, and the compound of formula (M-II) is, for example, US Pat. Nos. 4,540,654 and 4,705,86.
No. 3, JP-A Nos. 61-65245 and 62-20945.
No. 7, 62-249155, and the compound of the formula (M-III) are described, for example, in JP-B-47-27411, U.S. Pat.
The compounds of 725,067 and formula (M-IV) can be synthesized, for example, by the method described in JP-A-60-33552.

In the present invention, the magenta couplers in the same layer may be used alone or in combination of two or more different kinds. Further, the magenta coupler of the present invention can be used in combination with a known coupler.

In the present invention, an anionic surfactant can be used for the preparation of the emulsified dispersion of the magenta coupler. As the surfactant, for example, sodium triisopropylnaphthalenesulfonate, sodium dodecylbenzenesulfonate and sodium maleate diestersulfonate are preferable, and sodium triisopropylnaphthalenesulfonate is more preferable. The amount of these surfactants added is 0.05 g per 1 g of coupler.
10g is preferable and 0.1g-1g is more preferable.

The light-sensitive material of the present invention is not particularly limited in the number and order of layers of the silver halide emulsion layer and the non-light-sensitive layer.
In general, the unit photosensitive layers (emulsion layer units) are arranged in order from the support side in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that photosensitive layers having different color sensitivities are sandwiched between the same color sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438 and 5
9-113440, 61-20037, 61-1
Couplers as described in 20038, DI
The R compound and the like may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or HB / BL / GL / GH / RH / RL,
Alternatively, they can be installed in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, blue-sensitive layers / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-
No. 63936, the blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.
It can also be arranged in the order of. In addition, Japanese Patent Publication Sho-49-154
As described in Japanese Patent Publication No. 95, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a halide having a lower sensitivity than the middle layer. An arrangement may be mentioned in which a silver emulsion layer is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layer / High-sensitivity emulsion layer /
The low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat. Nos. 4,663,271 and 4,705,744 are used.
No. 4,707,436, JP-A-62-1604.
B, described in the specifications of No. 48 and No. 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L, GL, and RL, adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process are Research Disclosure No. 17643, the same No. 1871
6 and No. 6 No. 307105, and the corresponding portions are summarized in Table A below.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
A silver halide grain whose inside or surface is fogged is uniform (non-imagewise) regardless of the unexposed area of the light-sensitive material.
It means a silver halide grain that can be developed. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498, JP-A-59-2.
No. 14852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
Is preferred. The shape of the grains is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains are preferable.

In the present invention, a non-photosensitive unfogged fine grain silver halide emulsion can also be used. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment. The unfogged fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Further, the average grain size (average value of circle equivalent diameter of projected area) is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm, in the same manner as in the case of ordinary photosensitive silver halide. Can be prepared. in this case,
The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, before adding this to the coating solution, triazole-based,
It is preferable to add a known stabilizer such as an azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table A below.

Table A Additive Types RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention 24 to 25 pages 649 right column 868 to 870 Agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dye, ultraviolet absorber 7. Stain, page 25, right column, page 650, left column, page 872, inhibitor-right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 left column 874-875 10. Binder page 26 page 651 left column page 873-874 11. Plasticizer, page 27, page 650, right column, page 876, lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound which can be immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof to the light-sensitive material of the present invention, irrespective of the amount of developed silver. Is preferably contained. Dyes dispersed in the light-sensitive material of the present invention by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or EP317,308A, US Pat.
It is preferable to incorporate the dyes described in JP-A No. 0,555 and JP-A-1-259358.

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-C-
G, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

As the magenta coupler which can be used in combination with the magenta coupler of the present invention, 5-pyrazolone type and pyrazoloazole type compounds are preferable. For example, US Pat.
310,619, 4,351,897, EP 73,636, and US 3,061,432.
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure N.
o. 24230 (June 1984), JP-A-60-43.
No. 659, No. 61-72238, No. 60-35730.
No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,54
0,654, 4,556,630, International Publication W
Those described in O88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and examples thereof include US Pat. No. 4,052,2.
No. 12, No. 4,146, 396, No. 4,228,
No. 233, No. 4,296,200, No. 2,36
9,929, 2,801,171, 2,7
72, 162, 2, 895, 826, 3,
772,002, 3,758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patent 12
No. 1,365A, No. 249,453A, U.S. Pat. No. 3,446,622, No. 4,333,999, No. 4,775,616, No. 4,451,559,
No. 4,427,767, No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, and those described in JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-554.
Nos. 64-555 and 64-556, and pyrazoloazole-based couplers described in US Pat. No. 4,818,6.
The imidazole coupler described in No. 72 can also be used. Typical examples of polymerized dye-forming couplers are disclosed, for example, in US Pat.
080,211, 4,367,282, 4,409,320, 4,576,910, British Patent 2,102,137, European Patent 341,18.
8A. Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237.
No., British Patent No. 2,125,570, European Patent No. 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643, Item VII-G, ibid. Three
07105, Item VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Examined Patent Publication No. 57-39413, US Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are RD17 described above.
643, Item VII-F and No. 307105, VII-
Patents described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable. R. D. No. The bleaching accelerator releasing couplers described in 11149, 24241 and JP-A-61-201247 are effective in shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,0
97,140, 2,131,188, JP-A-5
Those described in 9-157638 and 59-170840 are preferable. Further, JP-A-60-107029,
Compounds which release a fogging agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687. Is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers as described in US Pat. No. 4,427, for example US Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, and multi-equivalent couplers, such as JP-A-60-185950 and JP-A-62-24252.
REDOXOXIDE COMPOSITION RELEASE COUPLERS
R coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A and 313,30
8A, a coupler that releases a dye that undergoes color recovery after release, such as a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a leuco dye-releasing coupler described in JP-A-63-75747. U.S. Pat. No. 4,77
Examples thereof include couplers that release the fluorescent dye described in No. 4,181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat.
No. 22,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-
Ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl Phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4
-Di-tert-amylphenol), aliphatic carboxylic acid esters (for example bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example N, N-dibutyl-
2-butoxy-5-tert-t-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 50
An organic solvent having a temperature of from ℃ to about 160 ℃ can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363,
It is described in West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

Suitable supports which can be used in the present invention are, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition of the coating solution. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 on the side opposite to the side having the emulsion layer.
Hydrophilic colloid layer of μm to 20 μm (referred to as back layer)
Is preferably provided. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic 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 their salts can be mentioned as representative examples.

Next, processing solutions and processing steps for the color reversal photosensitive material of the present invention other than the color developing solution will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleach-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleach-fixing-washing-stable 10) Color development-bleaching-bleach-fixing-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Coloring development-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stabilization In the processing steps from 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely the stabilizing step of the final step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black and white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-).
3-pyrazolidone), aminophenols (eg N-
Methyl-p-aminophenol), 1-phenyl-3-
Pyrazolines, ascorbic acid and US Pat. No. 4,063
A heterocyclic compound such as a 1,2,3,4-tetrahydroquinoline ring and an indole ring described in No. 7,872 can be used alone or in combination.
In the black-and-white developer used in the present invention, if necessary, a preservative (for example, sulfite, bisulfite, etc.), a buffer (for example, carbonate, boric acid, borate, alkanolamine),
Alkaline agents (eg hydroxides, carbonates), dissolution tablets (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts) ), A development accelerator, a surfactant, an antifoaming agent, a film hardener, and a viscosity imparting agent. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and a sulfite salt added as the above preservative usually serves its function. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂
It can be exemplified _{S 2 O 5, K 2 S} 2 O 3, Na 2 S 2 O 3. The pH value of the developer thus adjusted is selected to a level that provides the desired density and contrast, but is in the range of about 8.5 to about 11.5, and about 9.2.
More preferably, it is -10.0. In order to carry out the sensitizing process using such a black and white developer, it is usually up to 3 times the standard process.
You can extend the time up to about twice. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The pH of these color developing solutions is generally 9 to 12, and more preferably 11.0 to 12.0. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the light-sensitive material 1
Less than 3 liters per square meter, 500m by reducing the bromide ion concentration in the replenisher
It can be 1 or less. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used after black and white development may contain a known fogging agent. That is, for example, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,2)
82), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-aminopolycarboxylic acid complex salt (US Pat. No. 1,20).
Stannous ion complex salts (such as US Pat. No. 9,050), borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (GB Pat. No. 1,0).
11,000 specification).
The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9. Instead of the reversal bath, a light reversal process by re-exposure may be performed, and the reversal step may be omitted by adding the above-mentioned fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog and to reduce the carry-in of the color developing solution to the desilvering process. Also, in order to wash out and detoxify the sensitizing dyes, dyes and other sensitive material parts contained in the photographic light-sensitive material and the color developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

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. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts with citric acid, tartaric acid and malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927, and 54-35, 727, 5
Compounds described in JP-A Nos. 5-26,506 and 58-163,940; bromide ions can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add imidazoles such as methylimidazole in an amount of 0.1 to 10 mol / L.

The total time of the desilvering process is preferably as short as possible within the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow method is described in the Journal of the Societ.
y of Motion Picture and T
Elevision Engineers, Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by a method disclosed in JP-A-62-288,838.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, by Horiguchi Hiroshi, Chemistry "(1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Microbial and Antifungal Encyclopedia" (1986) Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used. Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

[0147]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. Example 1 Preparation of Sample 101 A multilayer color light-sensitive material consisting of layers having the following compositions was prepared on a 127 μm-thick cellulose triacetate film support having an undercoat, to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g High boiling organic Solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g High boiling point organic solvent Oil-4 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Yellow colloidal silver Silver amount 0.07 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C -0.05g Puller C-3 0.05g Coupler C-9 0.05g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.1 g High boiling point organic solvent Oil-3 0.1 g Additive P-1 0.1 g Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g Coupler C-9 0.05 g High boiling point organic solvent Oil-2 0.1 g High boiling point organic solvent Oil-3 0.1 g Additive P-1 0.1 g No. 6 layers: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g High boiling point organic solvent Oil-3 0.1 g additive P-1 0.1 7th layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.1 g UV absorber U-4 0.1 g Dye D-5 0.02 g Compound Cpd-D 5 mg Compound Cpd-L 5 mg Compound Cpd-M 5 mg Eighth layer: intermediate layer Surface and inside fogged silver iodobromide emulsion (average particle size 0.06 μm , Coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.02 g Yellow colloidal silver Silver amount 0.07 g Gelatin 1.0 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.05 g Coupler C-7 0.05g Coupler C-8 0.25g Compound Cpd-B 0.03g Compound Cpd-D 10 mg Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-J 0.02g Compound Cpd-L 0.02g Compound Cpd-M 0.2 mg High Boiling-point organic solvent Oil-1 0.1 g High-boiling-point organic solvent Oil-2 0.1 g High-boiling-point organic solvent Oil-3 0.1 g 10th layer: Medium-sensitive green sensitive emulsion layer Emulsion H Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.2 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-L 0.05 g Compound Cpd-M 0.2 mg High boiling point organic solvent Oil-2 0.01 g High boiling point organic solvent Oil-3 0.1 g Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-K 5 mg Compound Cpd-L 0.02g Compound Cpd-M 2 mg High boiling point organic solvent Oil-1 0. 02g High boiling organic solvent Oil-2 0.02g High boiling organic solvent Oil-3 0.05g 12th layer: Intermediate layer Gelatin 0.6 g Compound Cpd-L 0.02 g Dye D-1 0.1 g Dye D- 2 0.05 g Dye D-3 0.07 g High boiling point organic solvent Oil-1 0.05 g 13th layer: Yellow filter layer Yellow colloidal silver 0.07 g Gelatin 1.1 g Mixed color Inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15 layers: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g High-boiling point organic solvent Oil-1 0.02 g High-boiling point organic solvent Oil-3 0.1 g 16th layer: Medium sensitivity blue sensitive emulsion layer Emulsion L Silver amount 0.5 g Gelatin 0.9 g Coupler C -5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil-3 0.1 g 17th layer: High sensitivity blue Sensitive emulsion layer Emulsion M Silver amount 0.2 g Milk N Silver amount 0.2 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-3 0.1 g Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g High Boiling point organic solvent Oil-1 0.02 g Formalin scavenger Cpd-H 0.2 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average grain 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant Agent W-2 0.03 g In addition to the above composition, an additive F- is used for all emulsion layers.
1-F-8 were added. In addition to the above composition, a gelatin hardening agent H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents. In the emulsification of the organic composition, 20 to 50% by weight of the surfactant for emulsification was added to the total amount of the coupler, the ultraviolet absorber, the high boiling point organic solvent and the like. Surfactant: W-5 70%, W-6 20%, W-3 1
The mixture was used at a ratio of 0%. The structures of the compounds used for Sample 101 are shown in Chemical Formulas 51 to 64 below.

[0148]

[Chemical 51]

[0149]

[Chemical 52]

[0150]

[Chemical 53]

[0151]

[Chemical 54]

[0152]

[Chemical 55]

[0153]

[Chemical 56]

[0154]

[Chemical 57]

[0155]

[Chemical 58]

[0156]

[Chemical 59]

[0157]

[Chemical 60]

[0158]

[Chemical formula 61]

[0159]

[Chemical formula 62]

[0160]

[Chemical formula 63]

[0161]

[Chemical 64] The silver iodobromide emulsions used in Sample 101 are shown in Tables 3 to 5 below.

[0162]

[Table 3]

[0163]

[Table 4]

[0164]

[Table 5] Specific examples of the method for preparing the emulsion are shown below.

Preparation of Emulsions F, H and I To a 1.0 liter 1.0% by weight gelatin solution containing 0.10 M potassium bromide kept at a temperature of 60 ° C., it was stirred by the double jet method. 42 cc of 0.5 M silver nitrate solution and 0.5 M potassium bromide solution were added for 30 seconds. After that, 1.0M silver nitrate solution 10
Slowly add 0 cc, then add NH ₄ OH and p
After maintaining at H = 9.3 for 20 minutes, the pH was returned to the original value, and further, over 60 minutes, an aqueous solution of silver nitrate containing 130 g of silver nitrate and an aqueous solution of potassium bromide containing 1.7 g of potassium iodide were added at a constant flow rate. During this period, pBr was kept at 2.35. Further, an aqueous silver nitrate solution containing 20 g of silver nitrate and an aqueous potassium bromide solution were added at a constant flow rate for 10 minutes while maintaining pBr at 2.55. After that, the emulsion was desalted by a conventional flocculation method, and at 40 ° C., pH = 6.5, pAg.
After adjusting to = 8.5, optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. Thus, an emulsion having a sphere-converted diameter of 1 μm and an AgI content of 1.0 mol% was obtained. Similarly, emulsions F, H, and I were prepared by changing the temperature during grain formation, the amount of potassium iodide, and the grain formation potential. In all emulsions, tabular grains accounted for 98% or more of the projected area of all grains having a projected area equivalent to a circle of 0.2 μm or more. Spectral sensitization of the above emulsion was carried out by adding the spectral sensitizing dyes shown in Table 4 after chemical sensitization.

Preparation of Sample 102 Sample 101 was prepared in the same manner except that the green-sensitive emulsions F, H, and I of Sample 101 were replaced by emulsions O, P, and Q shown in Table 6 below so as to match the coating silver amounts. 102 was created. Emulsions O, P and Q were prepared in the same manner as Emulsions F, H and I.

Preparation of Sample 103 Sample 103 was prepared in the same manner, except that the green-sensitive emulsions F, H, and I of Sample 101 were replaced by emulsions R, S, and T shown in Table 6 so that the coated silver amounts were adjusted. It was created.

A method for preparing the emulsions R, S and T is shown below. Preparation of Emulsions R, S and T Into 1.0 liter of 1.0 wt% gelatin aqueous solution containing 0.08M potassium bromide, while stirring it, 0.5M silver nitrate solution and 0.5M were prepared by double jet method. 42 cc of potassium bromide aqueous solution was added for 25 seconds. During this time, the temperature was kept at 40 ° C. Gelatin after addition 1
4g was added and the temperature was raised to 75 ° C. afterwards,
Slowly add 100 cc of 1.0 M silver nitrate aqueous solution, further add NH ₄ OH and maintain at pH = 9.3 for 20 minutes, then return to the original pH, and in another 60 minutes, add silver nitrate aqueous solution containing 130 g of silver nitrate and iodide. An aqueous potassium bromide solution containing 1.7 g of potassium was added at an accelerated flow rate (the flow rate at the end was 19 times that at the start). During this period, pBr was kept at 2.35. Further, the flow rate of the silver nitrate aqueous solution containing 20 g of silver nitrate and the potassium bromide aqueous solution accelerated in 10 minutes while maintaining the pBr at 2.55 (the flow rate at the end is 5
Times). After that, the emulsion was desalted by a conventional flocculation method, and at 40 ° C., pH = 6.5, pAg.
After adjusting to = 8.5, optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. Thus, an emulsion having a sphere-converted diameter of 1 μm and an AgI content of 1.0 mol% was obtained. Similarly, emulsions R, S and T were prepared by changing the temperature during grain formation, the amount of potassium iodide and the grain formation potential. Spectral sensitization is Emulsion F, respectively.
It carried out similarly to H and I. In all emulsions, tabular grains accounted for 98% or more of the projected area of all grains having a projected area equivalent to a circle of 0.2 μm or more.

Preparation of Sample 104 Sample 104 was prepared in the same manner except that instead of the green-sensitive emulsions F, H and I of Sample 101, emulsions U, V and W shown in Table 6 were replaced by adjusting the coating silver amounts. It was created.

The method for preparing the emulsions U, V and W will be described below.

Preparation of Emulsions U, V and W 4 cc of PLURONI was added to 1.0 liter of 4.0% by weight aqueous gelatin solution containing 0.04 M potassium bromide.
C ^™ 31Rl was added to maintain the temperature at 45 ° C. and adjust the pH to 1.85. While stirring, a 0.5 M silver nitrate solution and a 0.5 M potassium bromide aqueous solution were added by 42 cc for 50 seconds while maintaining pAg at 9.7 respectively. After adjusting the pAg to 9.8, the temperature was raised to 60 ° C., 14 cc of 0.8N ammonium nitrate was added, and then the pH was adjusted to 10.0 with NaOH. After 10 minutes, 100 g gelatin and 0.1 cc PLURON
P with an aqueous solution containing IC ^™ 31Rl in 1 liter
Ag was adjusted to 9.2 and pH was adjusted to 5.8. 1
Aqueous silver nitrate solution containing 30 g of silver nitrate and potassium iodide 1.
An aqueous potassium bromide solution containing 7 g was added at an accelerated flow rate (the flow rate at the end was 19 times that at the start). During this period pAg
Was kept at 9.2. Further, an aqueous silver nitrate solution containing 20 g of silver nitrate and an aqueous potassium bromide solution were added over 10 minutes at an accelerated flow rate (the flow rate at the end was 5 times that at the start) while keeping pBr at 2.55. After that, the emulsion was desalted by a conventional flocculation method and pH = 6.
5, after adjusting to pAg = 8.5, it was optimally chemically sensitized with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. In this way, the diameter when converted to a sphere is 1 μm,
An emulsion having an AgI content of 1.0 mol% was obtained. Similarly, the temperature at the time of grain formation, the amount of potassium iodide and the grain formation potential were changed, and the emulsions U, V,
W was prepared. In all emulsions, tabular grains accounted for 98% or more of the projected area of all grains having a projected area equivalent to a circle of 0.2 μm or more.

[0172]

[Table 6] Here, as in Sample 101, emulsions F, H, and I were added to the green-sensitive emulsion layer.
Is referred to as emulsion constitution (i).

Similarly, as in Sample 102, emulsions O, P, and Q were used.
Is used in the emulsion constitution (ii), and when Emulsions R, S and T are used as in Sample 103, the emulsion constitution (iii) is used.
Emulsion constitution (iv) is the case where emulsions U, V, and W are used as in sample 104.

Preparation of Samples 104 to 120 Compounds of the present invention shown in Table 7 instead of couplers C-4, C-7 and C-8 added to the 9th to 11th layers of Samples 101, 102, 103 and 104. Was replaced with 1 times the moles of the total moles of the layer, Samples 101, 102,
Samples 105 to 120 were prepared in the same manner as 103 and 104.

[0175]

[Table 7] The obtained samples 101 to 120 were cut into strips and exposed through an optical wedge to measure RMS graininess. Development processing was performed through the following processing steps. The sample after the treatment was measured with a micro densitometer under the condition of an aperture diameter of 48 microns to determine RMS granularity. The measured value at a magenta density of 1.0 is shown.

These MTF values were measured in order to evaluate the sharpness of samples 101-120. For the MTF value, see T.W. H. See James, "Theory of Photographic Processing," 4th Edition, Macmillan, Inc. for more details. The MTF value of the magenta image at a spatial frequency of 25 cycles / mm is shown. Furthermore, the pH dependency of the first developing solution was examined as an evaluation of the processing factor dependency. The strips of Samples 101-120 were gradation exposed through an optical wedge. The developing treatment was carried out through the following treating steps, and the pH of the first developing solution was adjusted to 9.60 to 9.
The development processing was performed in the same manner except that 74 prepared with potassium hydroxide was separately prepared and the first developing solution in the following processing step was replaced. The sensitometry of both treatments obtained after the treatment was overlapped at a density of 1.0, and the sensitivity fluctuation width at the fog +0.1 of the magenta image was obtained, and this value was shown.
In addition, the samples 101 to 120 were processed into a 35 mm size patrone form, and practical shooting was performed. The subject was a color checker manufactured by Macbeth. The obtained practical sample was sensory-evaluated by a plurality of evaluators. The evaluation was carried out in five stages, and the average value was shown.

The results are summarized in Table 8.

Processing Step Time Temperature First development 6 minutes 38 ° C. Water washing 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Pre-bleaching 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. Fixing 4 minutes 38 ° C. Water washing 4 minutes 38 ℃ final rinse 1 minute 25 ℃ The composition of each treatment solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Sodium bicarbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Water was added. 1000 ml pH 9.60 pH was adjusted with sulfuric acid or potassium hydroxide. [Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate 12-hydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with sulfuric acid or potassium hydroxide. [Pre-bleaching] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 6.0 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water is added 1000 ml pH 6.20 pH is Adjusted with acetic acid or sodium hydroxide. [Bleach] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The .70 pH was adjusted with nitric acid or sodium hydroxide. [Fixer] Ammonium thionitrate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia. [Final rinse liquid] 1,2-benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Polymaleic acid (average molecular weight 2,000) 0.1 g Water 1000 ml pH 7.0

[0179]

[Table 8] From Table 8, graininess, sharpness and reproducibility are improved by using the tabular monodisperse emulsion of the present invention and satisfying the average silver iodide content of the green-sensitive layer and the blue-sensitive layer of the present invention. Can be seen from samples 102 and 103. Further, the effect is further enhanced by using the copolymer of the present invention (Sample 1
04). When the average silver iodide content of the green-sensitive layer or the blue-sensitive layer did not satisfy the conditions of the present invention, no particular improvement in color reproducibility exhibited in Samples 103 and 104 was observed. Further, when the magenta coupler of the present invention is used, both the graininess and the sharpness are lowered (Samples 105 to 110), which is not satisfactory, but the use of the tabular monodisperse emulsion of the present invention lowers the graininess and the sharpness. Can be reduced (Sample 111 to Sample 120). Also in this case, it can be seen that the effect of adding the copolymer of the present invention to the emulsion layer is great. Further, when the magenta coupler of the present invention is used,
In addition to the improvement in color reproducibility, the processing dependence of the first development is improved, but a better effect can be obtained by using it together with the tabular monodisperse emulsion of the present invention like Samples 111 to 120. . The processing dependence is M represented by the formula (M-VIII).
Best results are obtained with -3 and M-74. As described above, the surprising effect that all of the graininess, sharpness, color reproducibility, and processing dependence are improved is obtained only by the combination of the present invention.

Example 2 Preparation of Sample 201 A sample 201 was prepared by forming a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μm and having an undercoat. The numbers represent the added amount (g) per m ² . The effect of the added compound is not limited to the described use. First layer: Antihalation layer Gray colloidal silver 0.34 Gelatin 2.40 Second layer: Intermediate layer Gelatin 1.20 Third layer: Low-sensitivity red-sensitive emulsion layer Emulsion EMA Silver amount 0.60 Gelatin 0.90 Coupler CP-1 0.20 High boiling point organic solvent oil-1 0.10 Compound Cpd-X 0.05 Fourth layer: high-sensitivity red-sensitive emulsion layer Emulsion EMB Silver amount 0.50 Gelatin 1.50 Coupler CP-10. 90 High boiling organic solvent oil-1 0.40 Fifth layer: Intermediate layer Gelatin 0.60 Compound Cpd-X 0.16 Dye DA 0.65 Sixth layer: Intermediate layer Gelatin 0.60 Seventh layer: Low sensitivity green Sensitive emulsion layer Emulsion EMC Silver amount 0.45 Gelatin 0.90 Coupler CP-2 0.20 Coupler CP-3 0.07 High boiling point organic solvent oil-2 0.11 Eighth layer: High sensitivity green feeling Emulsion layer Emulsion EMD Silver amount 0.45 Gelatin 1.50 Coupler CP-2 0.60 Coupler CP-3 0.25 High boiling point organic solvent oil-2 0.40 Ninth layer: Intermediate layer Gelatin 0.60 Tenth layer : Intermediate layer Gelatin 0.60 Compound Cpd-X 0.11 Dye DB 0.27 11th layer: Low-sensitivity blue-sensitive emulsion layer Emulsion EME Silver amount 0.45 Gelatin 0.90 Coupler CP-4 0.18 High boiling point organic Solvent oil-1 0.06 Compound Cpd-X 0.05 12th layer: High-sensitivity blue-sensitive emulsion layer Emulsion EMF Silver amount 0.55 Gelatin 2.40 Coupler CP-4 1.55 High boiling organic solvent oil-10 .50 thirteenth layer: first protective layer ultraviolet absorber U-1 0.38 ultraviolet absorber U-2 0.13 compound Cpd-X 0.07 gelatin 1.40 14th layer: second protective layer Protective layer Gelatin 0.97 Yellow colloidal silver Silver amount 0.003 Gelatin hardening agent H-2 0.31 The emulsions used in Sample 201 are shown in Tables 9 to 10 below.

[0181]

[Table 9]

[0182]

[Table 10] The compounds used are shown in Chemical formulas 65 to 66 below.

[0183]

[Chemical 65]

[0184]

[Chemical formula 66] Preparation of Sample 202 Instead of the emulsions EMC and EMD of the seventh and eighth layers of Sample 201, the emulsions EMG and EMH shown in Table 11 were replaced by adjusting the coating silver amount, and further the couplers CP-2 and CP-3 were used. A sample 202 was prepared in the same manner except that the magenta coupler M-3 of the present invention was replaced by 1 mol per mol of the total mol of each layer instead of.

[0185]

[Table 11] The emulsions EMG and EMH were prepared according to the emulsions U, V and W of Example 1. Spectral sensitization was performed in the same manner as emulsions EMC and EMD.

The sample 202 was evaluated in the same manner as in Example 1 and good results similar to those in Example 1 were obtained. Example 3 Sample 202, 7th and 8th layer couplers CP-2 and C
A sample 301 was prepared in the same manner except that the magenta coupler M-2 of the present invention was replaced by 1 mol per mol of the total mol of each layer instead of P-3. Evaluation was performed in the same manner as in Example 1 using Sample 301, and good results similar to those in Example 1 were obtained. Example 4 Sample 202, 7th and 8th layer couplers CP-2 and C
A sample 401 was prepared in the same manner except that the magenta coupler M-36 of the present invention was replaced by 1 mol per mol of the total mol of each layer instead of P-3. Evaluation was performed in the same manner as in Example 1 using Sample 401, and good results similar to Example 1 were obtained. Example 5 7th and 8th layer couplers CP-2 and C of sample 202
A sample 501 was prepared in the same manner except that the magenta coupler M-55 of the present invention was replaced by 1 times the total number of moles of each layer instead of P-3. Evaluation was performed in the same manner as in Example 1 using Sample 501, and good results similar to Example 1 were obtained. Example 6 Emulsion R of the green sensitive layer of Samples 111-113 of Example 1,
Samples 601 to 603 were prepared in the same manner except that the emulsions X, Y, and Z shown in Table 12 were replaced in place of S and T by adjusting the coating silver amounts. The method for preparing the emulsions X, Y and Z used here is shown below.

Containing 0.08 M Potassium Bromide
To 1.0 liter of 0% by weight gelatin aqueous solution, while stirring this, 25 M of a 0.5 M silver nitrate aqueous solution and an aqueous solution of 0.005 M potassium iodide and 0.495 M potassium bromide were prepared by the double jet method. 4 for each second
2 cc was added. During this time, the temperature was kept at 40 ° C. After the addition, 14 g of gelatin was added and the temperature was raised to 75 ° C. After that, 100 cc of 1.0 M silver nitrate aqueous solution was slowly added, and NH ₄ OH was further added to adjust the pH to 9.3.
After 20 minutes, the pH was returned to the original value, and in 60 minutes, an aqueous solution of silver nitrate containing 130 g of silver nitrate and an aqueous solution of potassium bromide containing 1.6 g of potassium iodide were accelerated (the flow rate at the end was at the start). 19 times). During this period, pBr was kept at 2.35. 2 in 10 minutes
Aqueous silver nitrate solution containing 0 g of silver nitrate and potassium iodide 0.0
An aqueous KBr solution containing 7 g was added at an accelerated flow rate (the flow rate at the end was 5 times that at the start) while keeping pBr at 2.55. Thereafter, the emulsion was desalted by a conventional flocculation method, and at 40 ° C., pH = 6.5 and pAg = 8.5.
After the adjustment, the optimum chemical sensitization was performed with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate. Thus, an emulsion having a sphere-converted diameter of 1 μm and an AgI content of 1.0 mol% was obtained. Similarly, the temperature at the time of grain formation, the amount of potassium iodide, and the grain formation potential were changed, and spectral sensitization was performed in the same manner as in Emulsions F, H, and I to prepare a desired emulsion.

An experiment similar to that of Example 1 was conducted using the obtained samples 601 to 603, and the results shown in Table 13 were obtained.

[0189]

[Table 12]

[0190]

[Table 13] From Table 13, Samples 601 to 6 in which the emulsion has no internal structure
No. 03 does not sufficiently improve graininess and processing dependence, but corresponding Samples 111 to 113 show excellent effects on graininess and processing dependence as shown in Table 8 when the emulsion has an internal structure. I understand.

[0191]

According to the present invention, a silver halide color photographic light-sensitive material having good graininess, sharpness, color reproducibility and processing dependence can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/20

Claims (3)

[Claims] 1. A photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer unit each comprising one or more emulsion layers on a support, and at least one of the emulsion layers has an average aspect ratio of 2 The above-mentioned emulsion contains a tabular monodisperse emulsion having a structure depending on the difference in halogen composition, and the emulsion layer having the highest sensitivity among the emulsion layers constituting the emulsion layer unit containing the emulsion has the same average silver iodide content. The average silver iodide content of the other emulsion layers in the unit is less than the average, the average silver iodide content of the photosensitive emulsion layer unit closest to the incident light side is 3 mol% or less, and the average of the other emulsion layer units is A silver halide photographic material having a silver iodide content or less and containing at least one magenta dye-forming coupler represented by the general formula (M) shown in the following chemical formula 1 in the green-sensitive emulsion layer. Photographic material. [Chemical 1] In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 2. A silver halide color photographic light-sensitive material according to claim 1, wherein at least one light-sensitive emulsion layer contains a polymer having a polyalkylene oxide block polymer component in its molecule. 3. A positive image is obtained by performing negative B / W development after imagewise exposure, and then performing color development with the remaining silver halide.
Or the silver halide color photographic light-sensitive material described in 2.