JPH05289241A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material high in sensitivity and improved in storage stability, sharpness, and desilverability by making it contain a specified compound. CONSTITUTION:The silver halide color photographic sensitive material has at least each one of blue-, green-, and red-sensitive silver halide emulsion layers on a support and it is characterized by having the silver halide emulsion layer containing flat silver halide grains having an aspect ratio (diameter/thickness of a circle corresponding to the silver halide grains) of >=2.0 and in a hydrophilic colloidal layer the compound of formula in which each of R24 and R26 is H, an alkyl, or the like; R24 and R25 may form a 6-membered ring; Q is -O- or -NR22; each of L1-L3 is a methine group: and k is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material of the present invention, and further to a light-sensitive material having a dyed layer and a tabular silver halide emulsion layer.

The present invention also relates to a silver halide color photographic light-sensitive material having improved color reproducibility, sharpness and desilvering property.

[0003]

2. Description of the Related Art The technology of silver halide color photographic light-sensitive materials has been improved more and more in recent years, but in the world, the demand for sensitivity and the demand for image quality continue to be demanded and further progress is required. In addition, the world is accelerating the trend of simple, speedy, resource-saving, and energy-saving, and we are entering an era in which only environmentally friendly products on the earth can be accepted.

Among these, silver halide color photographic light-sensitive materials must have high image quality, have little processing dependence even when subjected to simple processing and rapid processing, and have little deterioration in image quality after processing.

Techniques for incorporating a dye into a silver halide light-sensitive material for improving the image quality or adjusting the sensitivity have been conventionally carried out in the art. For example, photographic emulsion layers and / or other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, the filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer is reflected on the interface between the emulsion layer and the support or on the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. A coloring layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer for the purpose of preventing blurring or halation of an image based on the image. When there are a plurality of photographic emulsion layers, an antihalation layer may be placed between those layers.

Coloring of the photographic emulsion layer is also carried out in order to prevent deterioration of image sharpness (usually called irradiation) due to light scattering in the photographic emulsion layer.

Recently, yellow colloidal silver (usually Carey Lea Silver) in color photographic light-sensitive materials is used.
Called r), dyes for crossover cut layer in X photographic light-sensitive materials, dyes for dyeing non-light-sensitive emulsion layers for safelight safety in printed photographic light-sensitive materials Is spreading.

The dyes used for these purposes are required to satisfy the following conditions. (1) It has an appropriate spectral absorption according to the purpose of use. (2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a reduction in sensitivity, latent image regression, or fog. (3) It should not be decolorized in the course of photographic processing or be dissolved in a processing solution or washing water to leave no harmful coloring on the photographic light-sensitive material after processing. (4) Do not diffuse from the dyed layer to other layers. (5) It has excellent stability over time in a solution or photographic material and does not discolor or fade.

With a general so-called water-soluble dye, it is not possible to dye only a layer having a certain characteristic, and it is diffused in all layers in the light-sensitive material, which reduces unnecessary sensitivity and silver halide. May have adverse effects.

In order to avoid these problems, dyes having a suppressed diffusivity for dyeing a specific layer are known. For example, US Pat. No. 4,420,555 and JP-A-61-204630 are known as diffusion-resistant dyes. No. 61-205934, No. 6
2-56958, 62-222248, 63-
No. 184749 and JP-A-3-144438.

With these diffusion-resistant dyes, it is possible to dye a specific layer and improve the above-mentioned drawbacks to some extent.
There is a problem that the decolorization and elution properties in the processing solution, which are important functions, are inferior, and the storage stability is insufficient and the photographic properties deteriorate over time. It was being done.

In a photographic light-sensitive material comprising a silver halide emulsion layer, light scattering by silver halide grains is known to reduce the sharpness of the emulsion layer.

US Pat. Nos. 4,434,226 and 4,434
Nos. 439,520 and 4,433,048 describe improvement in sharpness and the like by using a tabular silver halide emulsion and its application to a photographic light-sensitive material.

However, the tabular silver halide grains cause performance deterioration such as increased fog when the light-sensitive material containing them is stored at high temperature or high temperature and high humidity.
Further, there is a drawback that the desilvering performance deteriorates with the increase of the sensitizing dye used.

Under such circumstances, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in International Publication (WO) 88 /
No. 04794, U.S. Pat. Nos. 4,950,586, 4,857,446 and the like, and improvement of storability by combining these dyes with a tabular emulsion is disclosed in JP-A-3-100541. As described in JP-A-3-119344, these dyes have drawbacks such as broad hue, low absorbance as a dispersion, and weak wet heat stability.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and improved storability, sharpness and desilvering property.

[0019]

The object of the present invention is achieved by a light-sensitive material having the following 1, 2, and 3 constitutions. 1) In a color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, the following general formula (I) Hydrophilic colloid layer containing a compound represented by and aspect ratio (equivalent circle diameter of silver halide /
Halogenation characterized in that the silver halide grains having a grain thickness of 2.0 or more have an emulsion layer containing tabular silver halide grains in which 50% (area) or more of all silver halide grains in the emulsion are present. Silver color photographic light-sensitive material.

[0020]

[Chemical 4] In the formula, R ²¹ is a hydrogen atom, alkyl, alkenyl, aryl, heterocycle, ureido, sulfonamide, sulfamoyl, sulfonyl, sulfinyl, alkylthio, arylthio, oxycarbonyl, acyl, carbamoyl, cyano, alkoxy, aryloxy, amino, or amide. Represents a group. Q is -O- or -NR ²² - represents, R
²² represents a hydrogen atom, alkyl, aryl, or heterocycle.

R ²³ , R ²⁴ and R ²⁵ are hydrogen atom, alkyl,
Alternatively, it represents aryl and R ²⁴ and R ²⁵ may form a 6-membered ring.

R ²⁶ represents a hydrogen atom, alkyl, aryl or amino.

L ¹ , L ² and L ³ represent methine, and k is 0 or 1.

2) A silver halide color photographic light-sensitive material containing a compound represented by the following general formula (M) in at least one layer of the light-sensitive material shown in 1).

[0025]

[Chemical 5] Here, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group 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 hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

3) A silver halide color photographic light-sensitive material containing a compound represented by the following general formula (Y) in at least one layer of the light-sensitive material shown in 1).

[0027]

[Chemical 6] Here, R ₁₀₁ represents an aryl group, R ₁₀₂ and R ₁₀₃ represent a substituent, and X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. l is 0-4
When 1 is 2 or more, plural R _{103 s} may be the same or different. Can be achieved by

In the above 1), 2) and 3), the aspect ratio is preferably 2.0 to 20. Also,
The silver halide grains having an aspect ratio of 2.0 or more preferably account for 60% or more (area) of the total silver halide grains, and more preferably 70% or more.

Next, the compound of the general formula (I) used in the present invention will be explained in detail.

The alkyl group represented by R ²¹ may have a substituent, and is preferably an alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, tert-butyl, normal butyl and 1-methyl. Cyclopropyl, chloromethyl, trifluoromethyl, ethoxycarbonylmethyl and the like are preferable.

The aryl group represented by R ²¹ may have a substituent and is preferably an aryl group having 6 to 20 carbon atoms, for example, phenyl, 4-methoxyphenyl, 4-acetylaminophenyl and 4-methane. Sulfonamidophenyl, 4-benzenesulfonamidophenyl and 1-ethoxycarbonylpropanesulfonamidophenyl are preferred.

The alkyl group represented by R ²² may have a substituent and is preferably an alkyl group having 1 to 18 carbon atoms, for example, methyl, 2-cyanoethyl, 2-hydroxyethyl, 2-acetoxyethyl, cyclohexyl. , Methoxycarbonylacetoxyethyl is preferred.

The phenyl group or substituted phenyl group represented by R ²² is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 3,5-di (ethoxycarbonyl) phenyl. ,
4-di (ethoxycarbonylmethyl) aminocarbonylphenyl, 4-normaloctyloxycarbonylphenyl, 4-butanesulfonamidocarbonylphenyl,
4-methanesulfonamidocarbonylphenyl, 3-sulfamoylphenyl, 4-methanesulfonamidophenyl, 4-methanesulfonamidosulfonylphenyl,
4-Acetylsulfamoylphenyl, 4-propionylsulfamoylphenyl, 4-N-ethylcarbamoylsulfamoylphenyl and the like are preferable.

Examples of the heterocyclic group represented by R ²² include pyridyl and 4-hydroxy-6-methylpyrimidine-2-
4-hydroxy-6-tert-butylpyrimidine-2
-Yl, sulfolan-3-yne.

The alkyl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl or propyl. A methyl group is particularly preferable.

The aryl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an aryl group having 1 to 13 carbon atoms, and particularly preferably a phenyl group.

The 6-membered ring formed by R ²⁴ and R ²⁵ may be saturated, unsaturated or heterocyclic, but a benzene ring is particularly preferable.

The alkyl group represented by R ²⁶ may have a substituent, and is preferably an alkyl group having 1 to 18 carbon atoms,
For example, methyl, ethyl, ethoxycarbonylmethyl, tert-butoxycarbonylmethyl, ethoxycarbonylethyl, dimethylaminomethyl, 2-cyanoethyl, 3-acetamidopropyl, 3-propionylaminopropyl, 3-benzenesulfonamidopropyl, 3-propanesulfonamido. Propyl, tetrahydrofurfuryloxycarbonylethyl, 2-acetoxyethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl are preferred.

The phenyl group or substituted phenyl group represented by R ²⁶ is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 4-di (ethoxycarbonylmethyl) aminocarbonylphenyl. , 4-normaloctyloxycarbonylphenyl, 4-hydroxyethoxycarbonylphenyl, 4-propanesulfonamidophenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidocarbonylphenyl, 4-acetylsulfamoylphenyl are preferred.

The amino group represented by R ²⁶ is preferably a dialkylamino group, for example, dimethylamino and diethylamino.

The compound represented by the general formula (I) must be sparingly soluble in water having a pH of 6 or less and does not contain a sulfo group, a salt of a sulfo group, a carboxy group or a salt of a carboxy group as a substituent.

The compound represented by the general formula (I) preferably has a dissociative group other than the above. Examples of preferred dissociative groups include substituted sulfonylamino (eg C
_{H 3 SO 2 NH-, C 6} H 5 SO 2 CH-), acyl sulfamoyl, acylsulfamoyl, sulfonylcarbamoyl, carbamoyl sulfamoyl, there is a phenolic hydroxyl group.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0044]

[Chemical 7]

[0045]

[Chemical 8]

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

[Chemical 30]

[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36] Next, the compound represented by formula (M) will be described in detail.

[0074]

[Chemical 37] Here, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group 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 hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

The present coupler will be described in detail below. Among the coupler skeletons represented by the formula (M), a preferable skeleton is 1H-imidazo (1,2-b) pyrazole, 1H-pyrazolo (1,5-b) (1,2,4) triazole, 1H.
-Pyrazolo (5,1-c) (1,2,4) triazole, 1H-pyrazolo (1,5-d) tetrazole and 1H-pyrazolo (1,5-a) benzimidazole, each of formula (M- I), (M-II), (M-II
It is represented by I), (M-IV) and (MV).

[0076]

[Chemical 38] Substituents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and n in these formulas
And X will be described in detail.

R ₁₁ is hydrogen atom, halogen atom, alkyl, aryl, heterocycle, cyano, hydroxy, nitro, carboxy, sulfo, amino, alkoxy, aryloxy, acylamino, alkylamino, anilino,
Ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamide, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocycleoxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imide, heterocyclethio , Sulfinyl, phosphonyl, aryloxycarbonyl, acyl, or azolyl, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), alkyl (eg, straight chain or branched chain alkyl having 1 to 32 carbon atoms, aralkyl, alkenyl, alkynyl, Cycloalkyl, cycloalkenyl, 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 (eg, phenyl, 4-t-butylphenyl,
2,4-di-t-amylphenyl, 2,4,6-trimethylphenyl, 3-tridecanamido-2,4-6-trimethylphenyl, 4-tetradecanamidophenyl), heterocycle (for example, 2-furyl) , 2-thienyl,
2-pyrimidinyl, 2-benzothiazolyl), cyano,
Hydroxy, nitro, carboxy, sulfo, amino, alkoxy (for example, metoquino, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy (for example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino (e.g. acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3 -T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), Anilino (eg, phenylamino, 2-
Chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-
{2- (3-t-butyl-4-hydroxyphenoxy)
Dodecane amide} anilino), ureido (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfa). Moylamino), alkylthio (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-t-butylphenoxy) propylthio), arylthio (eg, phenylthio, 2-butoxy-5-t
-Octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide (e.g. methinesulfone) Amide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl (for example,
N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N-methyl-N-dodecylcarbamoyl, N- {3-
(2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-)
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocycleoxy (eg, 1-phenyltetrazole-
5-oxy, 2-tetrahydropyranyloxy), azo (eg, phenylazo, 4-methoxyphenylazo,
4-pivaloylaminophenylazo, 2-hydroxy-
4-propanoylphenylazo), acyloxy (eg acetoxy), carbamoyloxy (eg N-
Methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino (eg, phenoxycarbonylamino), imide (eg, N-succinimide, N-phthalimide, 3- Octadecenylsuccinimide), heterocyclic thio (eg, 2-benzothiazolylthio, 2,4
-Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl (for example, phenoxyphosphonyl) , Octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl (eg phenoxycarbonyl) acyl (eg acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl (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 includes alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino. R ₁₂ is the same as the substituents exemplified for R ₁₁ . A group, preferably a hydrogen atom, alkyl, aryl, heterocycle, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl, or cyano.

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

R ₁₄ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, alkyl, aryl, heterocycle, alkoxy, aryloxy, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfonyl, acyl, Acylamino, alkoxycarbonylamino, sulfonamide, sulfamoylamino, or cyano.

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

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described as a halogen atom, alkoxy, aryloxy, acyloxy or alkyl. Or arylsulfonyloxy, acylamino, alkyl or aryl sulfonamide, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl, aryl or heterocyclic thio, carbamoylamino, 5- or 6-membered nitrogen-containing heterocyclic ring, imide, arylazo, etc. , These groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkoxy (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy. (For example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy,
4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy (eg acetoxy, tetradecanoyloxy,
Benzoyloxy), alkyl or arylsulfonyloxy (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino (eg, dichloroacetylamino, heptafluorobutyrylamino),
Alkyl or aryl sulfonamide (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy (eg, phenoxycarbonyloxy). ), An alkyl, aryl or heterocyclic thio group (eg, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), carbamoylamino ( For example, N-methoxycarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocycle (eg, 1-imidazole). Lil, 1-pyrazolyl, 1,
2,4-triazol-1-yl, tetrazolyl, 3,
5-dimethyl-1-pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4
-Acetylamino-1-pyrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide (eg succinimide, hydantoinyl), arylazo (eg phenylazo, 4-methoxyphenylazo) and the like. 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, alkoxy, aryloxy, alkyl or arylthio, a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, particularly preferably a halogen atom, a substituted aryloxy, It is a substituted arylthio or substituted 1-pyrazolyl group.

Examples of compounds of the magenta coupler represented by the formula (M) are shown below, but the invention is not limited thereto.

[0086]

[Chemical Formula 39]

[0087]

[Chemical 40]

[0088]

[Chemical 41]

[0089]

[Chemical 42]

[0090]

[Chemical 43]

[0091]

[Chemical 44]

[0092]

[Chemical 45]

[0093]

[Chemical 46]

[0094]

[Chemical 47]

[0095]

[Chemical 48]

[0096]

[Chemical 49]

[0097]

[Chemical 50]

[0098]

[Chemical 51]

[0099]

[Chemical 52]

[0100]

[Chemical 53]

[0101]

[Chemical 54]

[0102]

[Chemical 55]

[0103]

[Chemical 56]

[0104]

[Chemical 57]

[0105]

[Chemical 58]

[0106]

[Chemical 59]

[0107]

[Chemical 60]

[0108]

[Chemical formula 61]

[0109]

[Chemical formula 62]

[0110]

[Chemical 63]

[0111]

[Chemical 64]

[0112]

[Chemical 65]

[0113]

[Chemical 66]

[0114]

[Chemical 67] References which describe a method for synthesizing the coupler represented by the formula (M) are listed below.

Compounds of formula (M-I) are described in US Pat.
Compounds of formula (M-II), such as U.S. Pat. Nos. 00,630 and 4,540,654, 4,705,863,
JP-A-61-65245, JP-A-62-209457,
The compound of the formula (M-III), such as JP-A-62-249155, is disclosed in JP-B-47-27411 and US Pat. No. 3,72.
Compounds of formula (M-IV), such as 5,067, are disclosed in
It can be synthesized by the method described in 0-33552 or the like.

The compound represented by formula (Y) used in the present invention will be described in detail.

[0117]

[Chemical 68] In the formula (Y), R ₁₀₁ is aryl, R ₁₀₂ is a hydrogen atom, a halogen atom (F, Cl, Br, I or less, the same in the description of the formula (Y)), alkoxy, aryloxy, an alkyl group or dialkyl. The amino group is replaced by R ₁₀₃
Is a substitutable group on the benzene ring, X is a hydrogen atom or a group (referred to as a leaving group) capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine developer, and 1 is 0 to 4
Represents the integers of. However, when 1 is plural, plural R ₁₀₃ may be the same or different.

Here, examples of R ₁₀₃ include, for example, halogen atom, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carbonamide, sulfonamide, carbamoyl,
There are sulfamoyl, alkylsulfonyl, arylsulfonyl, ureido, sulfamoylamino, alkoxycarbonylamino, nitro, heterocycle, cyano, acyl, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, and examples of leaving groups include, for example, a nitrogen atom. There are heterocycles, aryloxys, arylthios, acyloxys, alkylsulfonyloxys, heterocycleoxys, halogen atoms attached to the ring active position.

In formula (Y), preferably R ₁₀₁ is phenyl or a phenyl substituted with a halogen atom, alkyl or alkoxy, R ₁₀₂ is a halogen atom, alkoxy or phenoxy, R ₁₀₃ is a halogen atom, alkoxy, Alkoxycarbonyl, carbonamido, sulfonamide, carbamoyl or sulfamoyl, wherein X is aryloxy or a 5- to 7-membered ring N bonded to the coupling active position at a nitrogen atom,
It is a heterocycle which may include S, O and P, and l is an integer of 0 to 2. The coupler represented by the formula (Y) has a substituent R
₁₀₁ , X or

[0120]

[Chemical 69] At 2 is bound via a divalent or divalent group
It may be a polymer or a multimer or more, a homopolymer or a copolymer containing a non-color-forming polymer unit.

Specific examples of the coupler represented by the formula (Y) are shown below.

[0122]

[Chemical 70]

[0123]

[Chemical 71]

[0124]

[Chemical 72]

[0125]

[Chemical formula 73] Examples of compounds other than the above-mentioned yellow couplers used in the present invention and / or methods for synthesizing these yellow couplers are described in, for example, US Pat.
408,194, 3,894,875, 3,9
33,501, 3,973,968, 4,02
No. 2,620, No. 4,057,432, No. 4,11
5,121, 4,203,768, 4,24
8,961, 4,266,019, 4,31
4,023, 4,327,175, 4,40
1,752, 4,404,274, 4,42
0,556, 4,711,837, 4,72
9,944, European Patents 30,747A, 28
4,081A, 296,793A, 313,3
08A, West German Patent No. 3,107,173C, JP-A Nos. 58-42044, 59-174839 and 62.
-276547 and 63-123047.

The emulsion of the present invention preferably has an aspect ratio of 2 or more, more preferably an average aspect ratio of 3 or more 8.
Less than tabular silver halide grains. Here, tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case twin plane is (111)
This refers to the (111) plane when ions at all lattice points on both sides of the plane have a mirror image relationship. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape.The triangular shape is a triangular shape, the hexagonal shape is a hexagonal shape, and a circular shape. Have circular parallel outer surfaces.

The tabular grain aspect ratio in the present invention means a value obtained by dividing the grain diameter of each tabular grain having a grain diameter of 0.1 μm or more by the thickness. The thickness of the particles is measured by evaporating the metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can easily.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surfaces of the particles.

The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is 0.15 to 5.
It is preferably 0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

The average aspect ratio is calculated as the arithmetic mean of the aspect ratios of each grain for at least 100 silver halide grains. It can also be obtained as a ratio of the average diameter to the average thickness of the particles.

The emulsion of the present invention contains tabular silver halide grains having an aspect ratio of 2 or more, preferably tabular silver halide grains having an average aspect ratio of 3 or more and less than 8, and preferably 60% of the total projected area. % Or more is occupied by such tabular silver halide grains.

The proportion of tabular grains is preferably 60% or more and particularly preferably 80% or more of the total projected area.

Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-1516.
According to the description of No. 18, etc., but its shape is briefly described, 70% or more of the total projected area of silver halide grains is the length of the side having the maximum length with respect to the length of the side having the minimum length. The hexagonal tabular silver halide having a hexagonal ratio of 2 or less and having two parallel outer surfaces as outer surfaces is further occupied by a hexagonal tabular silver halide grain. Has a monodispersity of 20% or less (a value obtained by dividing the variation (standard deviation) of the particle size represented by the circle-converted diameter of the projected area by the average particle size).

Further, the emulsion of the present invention preferably has dislocation lines. Dislocations of tabular grains are described, for example, in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by the direct method described in (1972) using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample is placed to prevent damage (printout etc.) due to electron beam. Observe by permeability in the cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly by using a high-voltage type (200 kV or more for a particle having a thickness of 0.25 μm) electron microscope. .. From the photograph of the grain obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The average number of dislocation lines is 10 or more per grain. More preferably, the average number of particles per particle is 20 or more. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, about 10
It is possible to count on the order of 20 or 30, which is clearly distinguishable from the case where there are only a few. The average number of dislocation lines per grain is 100
The number of dislocation lines is counted for particles or more and the number average is obtained.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and the dislocation lines start from the position x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reach the outer circumference. The value of x is preferably 10 or more and 100
Less than, more preferably 30 or more and less than 99,
Most preferably, it is 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but it is not a perfect shape and may be distorted. This type of dislocation is not found in the central region of the grain. The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be substantially uniform over the entire outer circumference of the tabular grain, or may be locally located on the outer circumference. That is, taking a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only in the vicinity of the six vertices, or dislocation lines may be limited in the vicinity of one of the vertices. . On the contrary, it is possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grain.
When dislocation lines are formed over the entire main plane, the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, the dislocation lines are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The position of the dislocation may be limited to the outer periphery, the main plane, or the local position as described above.
These may be formed in combination. That is, they may exist on the outer circumference and the main plane at the same time.

Introduction of dislocation lines on the outer periphery of tabular grains can be achieved by providing a specific high silver iodide layer inside the grains. Here, the high silver iodide layer includes the case where discontinuous high silver iodide regions are provided. Specifically, it can be obtained by preparing a base grain and then providing a high silver iodide layer and covering the outside thereof with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the base tabular grains is lower than that of the high silver iodide layer, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.
Mol%.

The high silver iodide layer inside the grain means a silver halide solid solution containing silver iodide. In this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable as the silver halide, but silver iodide or silver iodobromide (silver iodide content of 10 to 40 mol%) is preferable. More preferable. In order to selectively make the high silver iodide layer inside the grain (hereinafter referred to as the inner high silver iodide layer) exist at any place on the side or the corner of the base grain, the generation condition of the base grain and the internal It can be controlled by the production conditions of the high silver iodide layer. As conditions for forming the base silver particles, pAg (logarithm of reciprocal of silver ion concentration), presence / absence of silver halide solvent, kind and amount, and temperature are important factors. By setting the pAg at the time of growth of the base grain to 8.5 or less, more preferably 8 or less, the internal high silver iodide layer can be made to selectively exist near the apex of the base grain. On the other hand, the internal high silver iodide layer can be made to exist on the sides of the base grains by setting the pAg at the time of growing the base grains to 8.5 or more, more preferably 9 or more. The threshold value of these pAg changes up and down depending on the temperature and the presence / absence, type and amount of the silver halide solvent. When thiocyanate is used as the silver halide solvent, the threshold value of pAg shifts to a higher value. Particularly important as the pAg at the time of growth is the pAg at the end of the growth of the base grains. On the other hand, even when the pAg at the time of growth does not satisfy the above value, it is possible to control the selected position of the internal high silver iodide layer by adjusting the pAg after growth of the base grain and ripening. is there. At this time, ammonia, amine compounds and thiocyanate salts are effective as silver halide solvents. The so-called conversion method can be used to form the internal high silver iodide layer. This method includes a method of adding a halogen ion having a lower solubility of a salt forming silver ion than a halogen ion forming the particle or the surface vicinity of the particle at the time of grain formation. In the present invention, it is preferable that the amount of halogen ion having a small solubility to be added to the surface area of the particle at that time is a certain value (related to the halogen composition) or more. For example, it is preferable to add a certain amount or more of KI to the surface area of AgBr particles at the time of grain formation. Specifically, it is preferable to add 8.2 × 10 ⁻⁵ mol / m ² or more of iodide salt.

A more preferable method of forming an internal high silver iodide layer is a method of adding an aqueous silver salt solution at the same time as adding an aqueous halide salt solution containing a silver iodide salt.

For example, at the same time as the addition of the KI aqueous solution, AgNO
₃ Add aqueous solution with double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may deviate from each other. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that pAg at the time of double jet addition of the halide aqueous solution containing these iodine ions and the silver salt aqueous solution is decreased with the double jet addition time. P before the start of addition
Ag is preferably 6.5 or more and 13 or less. More preferably, it is 7.0 or more and 11 or less. PAg at the end of addition
Is most preferably 6.5 or more and 10.0 or less.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system at the time of forming the high silver iodide layer is preferably 30 ° C or higher and 70 ° C or lower, more preferably 30 ° C or higher and 5 ° C or higher.
It is 0 ° C or lower.

Most preferably, the formation of the internal high silver iodide layer is fine grain silver iodide (fine silver iodide, hereinafter the same).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodobromide or fine grain silver chloroiodobromide can be added. It is particularly preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm, but fine particles having a particle size of 0.01 μm or less or 0.1 μm or less can also be used. Regarding the preparation method of these fine silver halide grains, Japanese Patent Application No. 63-7851
Nos. 63-195778, 63-7852, 63-7853, 63-194861 and 6
Reference can be made to the description regarding No. 3-194862. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides. It is also possible to use the above-described silver halide solvent when ripening to dissolve the fine particles. It is not necessary for all of the added fine particles to be dissolved and disappeared immediately, as long as they are dissolved and disappeared when the final particles are completed.

The outer layer covering the internal high silver iodide layer is lower than the silver iodide content of the high silver iodide layer, preferably the silver iodide content is 0 to 30 mol%, more preferably 0 to 20 mol%. Mol%
Most preferably, it is 0 to 10 mol%. The position of this internal high silver iodide layer is measured from the center of the projected hexagon or the like of the grain, and is not less than 5 mol% and not more than 100 mol% with respect to the silver amount of the whole grain.
It is preferably present in the range of less than 20 mol% and more preferably less than 98 mol% and more preferably more than 50 mol%
It is preferably within the range of less than 0 mol%. The amount of silver halide forming these internal high silver iodide layers is 50 mol% or less, and more preferably 20 mol% or less, based on the total silver amount of the grains. These high silver iodide layers are prescriptive values for the production of silver halide emulsions, and are not values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal high silver iodide layer often disappears in the final grain due to a recrystallization process or the like, and the above is all about the manufacturing method thereof.

Therefore, in the final grain, the dislocation line can be easily observed by the above-mentioned method, but the internal silver iodide layer introduced for introducing the dislocation line cannot be confirmed as a clear layer in many cases. For example, the entire outer peripheral region of the tabular grains may be observed as a high silver iodide layer. X-ray diffraction, EP
MA (also called XMA) method (a method of scanning silver halide grains with an electron beam to detect the silver halide composition), ESCA (also called XPS) method (irradiated with X-rays and emitted from the grain surface It can be confirmed by combining the method of separating the coming photoelectrons).

The temperature at the time of forming the outer layer covering the internal high silver iodide layer, pAg, is arbitrary, but the preferred temperature is 3.
It is 0 ° C. or higher and 80 ° C. or lower. Most preferably, it is 35 ° C or higher and 70 ° C or lower. Preferred pAg is 6.5 or more 1
It is 1.5 or less. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

To introduce dislocation lines into the main surface of tabular grains, after preparing the base grains, silver halochloride is deposited on the main surface, and the silver halochloride is subjected to conversion to obtain high silver bromide or high silver iodide. A layer may be formed and a shell may be further provided on the outside thereof. Examples of the halosilver chloride include silver chloride or silver chlorobromide or silver chloroiodobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more. Deposition of these halosilver chloride base grains on the main plane can be carried out by adding an aqueous solution of silver nitrate and an appropriate alkali metal salt (for example, potassium chloride) separately or simultaneously, or an emulsion comprising these silver salts. It is also possible to deposit by adding and aging. Deposition of these silver halochlorides is possible in all pAg regions, but is most preferably 5.0 or more and 9.5 or less. in this way,
Tabular grains are mainly grown in the thickness direction. The amount of this halosilver chloride layer is 1 mol% in terms of silver based on the base grains.
It is above 80 mol%. It is more preferably 2 mol% or more and 60 mol% or less. By converting this silver halochloride layer with an aqueous solution of a halide capable of forming a silver salt having a solubility lower than that of silver halochloride, dislocation lines can be introduced on the main planes of the tabular grains.
After conversion of this silver halochloride layer, for example with an aqueous solution of KI, it is possible to grow the shell and obtain the final grains. The halogen conversion of these halosilver chloride layers does not mean that all of them are replaced by silver salts having a lower solubility than halosilver chloride, but preferably 5% or more, more preferably 10% or more, most preferably 20% or more. , Replaces silver salts with low solubility. By controlling the halogen structure of the base grain on which the halosilver chloride layer is provided, it is possible to introduce dislocation lines at local sites on the principal plane. For example, when a base grain having an internal high silver iodide structure is used by laterally displacing the base tabular grain, dislocation lines can be introduced only in the peripheral main planes excluding the central portion of the main plane. When the base grains having an outer high silver iodide structure are used by displacing the base tabular grains in the lateral direction, dislocation lines can be introduced only in the central portion of the main plane except the peripheral portion. Further, it is also possible to deposit a halosilver chloride only on a site limited in area by using a locally dominant substance for epitaxial growth of halosilver chloride, for example, iodide, and introduce a dislocation line only to the site. The temperature during the deposition of halosilver chloride is 30 ° C or higher,
70 ° C or lower is preferable, and more preferably 30 ° C or higher and 5
It is 0 ° C or lower. It is possible to carry out conversion after depositing these halosilver chlorides and then grow the shell, but it is also possible to carry out halogen conversion while growing the shell after depositing halosilver chloride.

The position of the internal halosilver chloride layer formed substantially parallel to the principal plane may be in the range of 5 mol% or more and less than 100 mol% with respect to the total amount of silver in the grains on both sides from the center of grain thickness. It is more preferably 20 mol% or more and less than 95 mol%, and particularly preferably 50 mol% or more and less than 90 mol%.

The silver iodide content of the shell is preferably 0-3.
It is 0 mol%, more preferably 0 to 20 mol%. The temperature at the time of shell formation and pAg are arbitrary, but the preferred temperature is 30 ° C. or higher and 80 ° C. or lower. Most preferably 35
The temperature is not lower than 70 ° C and not higher than 70 ° C. A preferable pAg is 6.5 or more and 11.5 or less. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt. In the final grain, the internal halosilver chloride layer that has undergone halogen conversion may not be confirmed by the above-described method for analyzing halogen composition, depending on conditions such as the degree of halogen conversion. However, dislocation lines can be clearly observed.

The method of introducing dislocation lines at arbitrary positions on the principal plane of the tabular grain and the method of introducing dislocation lines at arbitrary positions on the outer periphery of the tabular grains described above are appropriately combined and used. It is also possible to introduce dislocation lines.

The silver halide emulsion that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography).
Theory and Practice (193
0)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Ph.
otographic Science and En
Gineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1
It can be easily prepared by the method described in No. 57, etc.

The internal sensitivity of the tabular grain of the present invention after the surface chemical sensitization can be enhanced by performing the chemical sensitization at the stage before the completion of grain formation. Preferably, the chemical sensitization is carried out at a stage before 80% of the total amount of silver in the grains.

This chemical sensitization was performed by James (T.H.
James), The Theory of Photographic Process, 4th edition, published by Macmillan, 1977.
Year, (TH James, The Theory o
f the Photographic Procedures
s, 4th ed, Macmillan, 1977).
It can be carried out using activated gelatin as described on pages 67-76, and also Research Disclosure 120, April 1974, 12008; Research.
Disclosure, Volume 34, June 1975, 134
52, U.S. Pat. Nos. 2,642,361 and 3,29.
7,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent No. 1,315,755, p.
It can be carried out using Ag, 5 to 10, pH 5 to 8 and a temperature of 30 to 80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds, and sulfur-containing compounds as described in US Pat. Nos. 3,857,711, 4,266,018 and 4,054,457. It is performed in the presence of a compound or a sulfur-containing compound such as hypo, a thiourea compound, and a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat.
1,038, 3,411,914, 3,55
No. 4,757, JP-A No. 58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143. In addition to, or as an alternative to chemical sensitization, US Pat. Nos. 3,891,446 and 3,984,24
It can be reduction sensitized with, for example, hydrogen as described in US Pat. No. 2,518,698.
No. 2,743,182 and No. 2,743,18
Reduction enhancement with stannous chloride, thiourea dioxide, polyamines and such reducing agents as described in No. 3 or by treatment with low pAg (eg less than 5) and / or high pH (eg greater than 8). You can feel it. US Pat. Nos. 3,917,485 and 3,
The chemical sensitization method described in 966,476 can also be applied.

In addition, Japanese Patent Application No. 59-112981 and 59
The sensitizing method using an oxidizing agent described in No. 122928 can also be applied.

As another method of increasing the internal sensitivity, there is a method of introducing a gap of halogen composition before the grain formation. This is also preferably 80% of the total amount of silver
It is better to introduce it at a stage before%.

The larger the gap of the halogen composition, the higher the internal sensitivity, but in the case of silver iodobromide, for example, 5 mol%
It is preferable that the above difference in silver iodide content exists, and further that there is a difference in silver iodide content of 10 mol% or more.

When the tabular grains of the present invention are produced, the addition rate, amount and concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halide solution (eg KBr aqueous solution), which are added to accelerate the grain growth, are increased. The method is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,672,900.
No. 3, 3,650,757, 4,242,445
No. 5, JP-A-55-142329 and JP-A-55-15812.
You can refer to the description of No. 4 etc.

A silver halide solvent is useful for promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging.
Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be mixed in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. It is also possible to add a halide salt, a silver salt or a deflocculant, and to introduce them into the reactor. As another variation, the ripening agent can be introduced independently at the silver halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. Alternatively, JP-A-53-
The thione compounds as disclosed in No. 82408 and No. 53-144319 can also be used.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor, or they may be added along with one or more salts according to conventional methods. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
No. and Research Disclosure, 134
Vol., June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc,
(Chalcogen compounds such as sulfur, selenium and tellurium),
The properties of silver halide can be controlled by allowing compounds such as gold and Group VII noble metal compounds to be present during the silver halide precipitation process. Japanese Patent Sho 58-
No. 1410, Moisar et al., Journal of Photographic Science, 25 volumes,
As described in 1977, pp. 19-27, the silver halide emulsion can reduce and sensitize the inside of the grain during the precipitation formation process.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. No. 4,094,68.
No. 4, No. 4,142,900, No. 4,459,353
No., British Patent No. 2,038,792, US Patent No. 4,
349,622, 4,395,478, 4,4
33,501, 4,463,087, 3,65
6,962, 3,852,067, JP-A-59-
No. 162540 and the like.

The tabular grains used in the present invention can be used in combination with ordinary chemically sensitized silver halide grains (hereinafter referred to as non-tabular grains) in the same silver halide emulsion layer.
Particularly in the case of a color photographic light-sensitive material, tabular grains and non-tabular grains can be used in different emulsion layers and / or the same emulsion layer. Here, examples of non-tabular grains include regular grains having regular crystal bodies such as cubes, octahedra, and tetradecahedrons, and grains having regular crystal shapes such as spheres and potatoes. You can As the silver halide of these grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is 2 mol% to 2
Silver iodobromide containing up to 5 mol% silver iodide.

The grain size of the non-tabular grains used here is 0.
It may be fine particles of 1 μm or less or large size grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polymonodisperse emulsion having a wide distribution.

The non-tabular grains used in the present invention are those described in Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chimie et Ph.
ysique Photographie Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
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 Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of the acidic method, the neutral method, and the ammonia method may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the above regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering (Photogr).
apic Science and Engineer
ing) Volume 6, 159-165 (1962); Journal of Photographic Science (Jou)
rnal of Photographic Scie
No.), 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,4.
No. 13,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521.
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

The crystal structure of these non-tabular grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are disclosed in British Patent No. 1,027,146, US Pat. Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58-248469.

In the present invention, a non-photosensitive fine grain emulsion having a size of 0.6 μm or less, preferably 0.2 μm or less is used for the purpose of promoting development, improving storage stability, effectively utilizing reflected light, etc. Alternatively, it may be added to the protective layer.

The tabular grains of the present invention are preferably used in color photographic light-sensitive materials.

When the tabular grains of the present invention are used in the same and / or different emulsion layers as the non-tabular monodisperse silver halide grains, the sharpness and the granularity can sometimes be improved at the same time. ..

The monodisperse silver halide emulsion (non-tabular grain) as used herein means that 95% or more of the total weight or the number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably. Defined to be within ± 30%. The fact that the graininess can be improved by using a monodisperse silver halide emulsion in a silver halide photographic light-sensitive material is described in JP-B-47-11386, JP-B-55-142329, JP-B-57-17235, and JP-A-59-72440. Have been described. In addition, the above-mentioned T. H. James, "The Theory of Photographic Process", 580-
As described on page 585, 0.3 μm to 0.8
The μm monodisperse silver halide grains have a property that they have a large light scattering property for light in a specific wavelength range, but have a relatively small light scattering property for light in other wavelength ranges. It is also known that there is.

Accordingly, the tabular silver halide emulsion and the monodisperse silver halide emulsion are appropriately arranged in consideration of the optical characteristics and graininess of each silver halide emulsion to obtain the silver halide photographic light-sensitive material. It may be possible to simultaneously improve the sharpness and granularity of the.

The light-sensitive material of the present invention may have at least one of a blue-color sensitive layer, a green color-sensitive layer and a red color-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are 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 structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are 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,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity 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. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers 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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448,
BL, GL, described in the specification of 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 RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodides. Particularly preferred is about 2 mol% to about 1
Silver iodobromide or silver iodochlorobromide containing up to 0 mol% of silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

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.
716 (November 1979), page 648, ibid. Thirty
7105 (11/1989), pages 863-865, and "The Physics and Chemistry of Photography" by Grafkeide, published by P. Glafkides, Chemieet.
Phisique Photographie, P
aul Montel, 1967), "Photographic Emulsion 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
Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in JP-A No. 1994-1999 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and No. 18716. No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity may be mixed and used in the same layer.

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.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain which is fogged inside or on the surface is described in US Pat. No. 4,626,498 and JP-A-59-214852.

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 having the inside or surface of the grain 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, and particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain need not be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The amount of silver coated on 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 the following table.

Additive type 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, page 649, right column 4. Whitening agent Page 24 Page 868 5. Fogging prevention pages 24 to 25 pages 649 right column 868 to 870 pages agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image stabilizer Page 25 Page 650 Left column Page 872 9. Hardener 26 pages 651 left column 874-875 pages 10. Binder page 26 page 651 left column 874-874 page 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 876 to 876, surfactant 13. Antistatic agent page 27 page 650 right column 876-877 page 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is fixed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62-
18539 and the mercapto compounds described in JP-A-1-283551 are preferably contained.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620,
No. 4,326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,314,
023, 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
32, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573.
No. 0, No. 55-118034, No. 60-18591
U.S. Pat. Nos. 4,500,630 and 4,540,
No. 654, No. 4,556,630, International Publication WO88
Those described in, for example, No. 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, 4,22
8,233, 4,296,200, 2,36
9,929, 2,801,171, 2,77
2,162, 2,895,826, 3,77
No. 2,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A.
No. 249,453A, US Pat. No. 3,446,6.
No. 22, No. 4,333, 999, No. 4,775, 61
No. 6, No. 4,451,559, No. 4,427,767
Nos. 4,690,889 and 4,254,212
No. 4,296,199, JP-A-61-42658.
Those described in No. etc. are preferable. Furthermore, JP-A-64-5
No. 53, No. 64-554, No. 64-555, No. 54
The pyrazoloazole couplers described in -556 and the imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
0,211, 4,367,282, 4,40
No. 9,320, No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,238,258, British Patent No. 1,14
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a 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 that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and No. 307105, V
Patents described in paragraph II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
No. 63-37346, No. 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012.
Those described in No. 1 are preferable.

RD. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using the tabular silver halide grains described above. When added, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-15763.
Those described in No. 8 and No. 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
Compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc., multi-equivalent couplers, JP-A-60-1859.
50, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or D described in JP-A No. 62-24252.
IR redox releasing redox compound, European Patent No. 17
Nos. 3,302A and 313,308A, couplers for releasing dyes that recover color after separation, US Pat.
No. 5,477, etc., ligand releasing couplers, couplers releasing leuco dyes described in JP-A-63-75747, couplers releasing fluorescent dyes described in US Pat. No. 4,774,181, and the like. Be done.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (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, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl) Phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-
p-hydroxybenzoate, etc., amides (N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 5
An organic solvent having a temperature of 0 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 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 1-80941. It is preferable to add various preservatives or antifungal agents such as 2-, 4- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

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

In the light-sensitive material of the present invention, the sum of the thicknesses 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, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ) Volume 19, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It 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 by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
Calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. 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 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, 651 left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

The color developing solution used for 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, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxy Propyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4- Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N
-Methyl-N- (3-hydroxypropyl) aniline,
4-Amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N
-Ethyl-N- (4-hydroxybutyl) aniline, 4
-Amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N
-Ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-
Methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline,
4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl), aniline, 4-amino-3- Examples thereof include propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent 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. In addition, if necessary, various preservatives such as hydroxyamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids, 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, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexyl San 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.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid from evaporating and oxidizing 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 represented 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-1-820 can be used.
Method using a movable lid described in JP-A No. 33-63, JP-A-63-
The slit development processing method described in No. 21650 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color developing step and the black and white developing step but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set within a range of 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. 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. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, an amino acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts 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. 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 lower pH can be used for speeding up the treatment.

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 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

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. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like 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 Is most commonly used, with ammonium thiosulfate being the 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, various aminopolycarboxylic acids and organic phosphonoic acids are preferably added 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 and 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering step is preferably as short as possible so long as no desilvering failure occurs. 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 concrete 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, and stirring using a rotating means of JP-A-62-183461. A method to improve the effect, further a method to improve the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution and making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such 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 effect 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 process 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 system such as countercurrent, forward flow, and other various 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 countercurrent system is described in the Journal of the Society
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly 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. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, JP-A-62-288,838 is proposed
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-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial 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 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set 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.

In some cases, the washing treatment is further followed by a stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. 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.

The silver halide color photographic material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
342,597, indoaniline compounds, 3,342,599, Research Disclosure No. 14850 and the same No. Examples thereof include the Schiff base type compound described in 15159, the aldol compound described in JP-A-13924, the metal salt complex described in US Pat. No. 3,719,492, and the urethane compound described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various treatment liquids in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit effects when applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0253]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. (Example) The silver halide emulsion of the present invention was prepared as follows. (Preparation of silver halide grains) An aqueous solution prepared by dissolving 30 g of inert gelatin and 6 g of potassium bromide in 1 liter of distilled water was stirred at 75 ° C., and 35 cc of an aqueous solution containing 5.0 g of silver nitrate and potassium bromide were added thereto. 35 g of an aqueous solution in which 3.2 g and 0.98 g of potassium iodide are dissolved is 7
After addition for 30 seconds at a flow rate of 0 cc / min, pAg was adjusted to 10
And ripened for 30 minutes to prepare a seed emulsion.

Subsequently, a predetermined amount of 1 liter of an aqueous solution in which 145 g of silver nitrate was dissolved and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature and a predetermined pAg at an addition rate near the critical growth rate. Was added to prepare a tabular core emulsion. Furthermore, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a different composition from the preparation of the core emulsion were added in equimolar amounts at an addition rate near the critical growth rate to coat the core. Then, core / shell type silver iodobromide flat plates Em 1 to 4 were prepared. Aspect ratio control was obtained by selecting pAg during core and shell preparation. The results are shown in Table 1. Also Em
In Nos. 1 to 4, 50% or more of the projected area of all grains were tabular grains.

[0255]

[Table 1] The average aspect ratio is obtained as an arithmetic mean of the aspect ratios of each grain for at least 100 silver halide grains. It can also be obtained as a ratio of the average diameter to the average thickness of the particles.

The following core / shell type silver iodobromide tabular emulsions Em-5 to 12 were prepared in the same manner as in Em-1 to 4 except that the temperature and the amounts of potassium bromide and potassium iodide were adjusted. Prepared.

[0257]

[Table 2] In Em −1 to 12, 50% or more of the projected area of all grains were tabular grains. Em -1 thus prepared
For Nos. 12 to 12, optimal emulsions of gold and sulfur were sensitized with each emulsion using sodium thiosulfate and chloroauric acid.

When the emulsion of the present invention was further prepared as described below, similar results were obtained. (1) According to the example of JP-A-2-191938, reduction sensitization is performed at the time of grain preparation using thiourea dioxide and thiosulfonic acid. (2) Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of Japanese Patent Application No. 2-34090. (3) Low molecular weight gelatin is used for the preparation of tabular grains according to the examples of JP-A-1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

Similar results were obtained not only with the core / shell double structure tabular grains as described above but also with the following uniform structure tabular grains, triple structure tabular grains and monodisperse hexagonal tabular grains. ..

[0260]

[Table 3] Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 Second layer (intermediate layer) Non-photosensitive silver iodobromide fine particles Silver 0.065 (0 0.07 μm, AgI 1.0 mol%) 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (Low-sensitivity red-sensitive emulsion layer) Emulsion silver iodobromide A silver 0.50 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-4 0.17 ExC- 7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0.87 4th layer (medium speed red-sensitive emulsion layer) Emulsion Silver iodobromide B Silver 0.7 ExS-1 3.4 × 10 ^-4 ExS-2 1.6 x 10 ^-5 ExS-3 4.9 x 10 ^-4 ExC-1 0.20 ExC-2 0.050 E xC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion silver iodobromide C silver 1.55 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 x 10 ^-4 ExS-3 3.5 x 10 ^-4 ExC-1 0.097 ExC-2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate) Layer) Cpd-1 0.040 HBS-1 0.020 Gelatin 0.80 Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion Silver iodobromide A Silver 0.30 ExS-4 2.5 × 10 ^-5 ExS-5 1.7 × 10 ^-4 ExS-6 6.9 × 10 ^-4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (medium sensitivity green emulsion layer) Emulsion Silver iodobromide B Silver 0.50 ^{ExS-4 2.1 × 10 -5 ExS} -5 1.4 × 10 -4 ExS-6 5.8 × 10 -4 ExM-2 0.094 Ex -3 0.026 ExY-1 0.018 HBS- 1 0.16 HBS-3 8.0 × 10 -3 Gelatin 0.50 9th layer (high sensitivity green-sensitive emulsion layer) Emulsion iodobromide C silver ^{1.60 ExS-4 4.6 × 10 -5} ExS- 5 1.0 × 10 ^-4 ExS-6 4.1 × 10 ^-4 ExC-1 0.015 ExM-1 0.013 ExM-4 0.065 ExM-5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloid Silver Silver 0.07 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion Silver iodobromide A Silver 0.20 ExS-7 8.6 × 10 ^-4 ExY-1 0.042 ExY-2 0.72 HBS- 1 0.28 Gelatin 1.10 12th layer (medium speed blue emulsion layer) Emulsion silver iodobromide B silver 0.50 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.15 HBS-1 0.050 gelatin 0.78 13 layers (high-sensitivity blue-sensitive emulsion layer) Emulsion silver iodobromide C silver 0.60 ExS- ^{2.8 × 10 -4 ExY-2 0.20} HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) light-insensitive silver iodobromide fine (0.07 .mu.m, AgI content of 1.0 mol%) silver 0.20 UV- 4 0.11 UV-5 0.07 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter about 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter about 1.7 μm) 0.10 B-3 0.10 Z-1 0.20 Gelatin 1.20 Furthermore, storability, processability, pressure resistance, antifungal,
To improve antibacterial property, antistatic property and coating property, W-
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. (Preparation of Samples 102 to 104) The silver iodobromide emulsions A, B and C of Sample 101 were compared with comparative emulsions EM-9, EM-5 and EM-1.
Sample Emulsion EM-10, EM-6, EM-2 of the present invention was replaced with Sample 1 in the same manner as in Sample 101.
02 was created. Similarly, EM-9 is replaced with EM-11,
EM-12, EM-5 to EM-7, EM-8, EM
-1 was replaced with EM-3 and EM-4 respectively Sample 10
3, 104 were created. (Preparation of Samples 105 to 108) Instead of the yellow colloidal silver of the tenth layer of Samples 101 to 104, the comparative dye SEN-1 was used.
Was replaced with 4 × 10 ⁻⁴ mol / m ² for Sample 101.
Samples 105 to 108 were prepared in the same manner as described above.

The dispersion method of SEN-1 was carried out as follows. Water (21.7 ml) and 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate (3 ml) and 5% aqueous solution of p-octylphenoxypoly (polymerization degree 10) oxyethylene ether (0.5 g) were used.
The mixture was placed in a 00 ml pot mill, and 1.0 g of dye and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 24 hours. The vibrating ball mill used is a BO type manufactured by Chuo Kakoki. The contents were taken out and added to 50 ml of a 10% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion. (Preparation of Samples 109 to 112) Samples 109 to 112 were prepared in the same manner as in Samples 105 to 108, except that the dye SEN-1 in the 10th layer of Samples 105 to 108 was replaced with the comparative dye SEN-2 in an equimolar amount. ..

The dispersion method of SEN-2 was carried out as follows. Dye 1.0g and tricresyl phosphate 2.0g
Was dissolved in 20 ml of ethyl acetate, this solution was mixed with 50 ml of a 10% gelatin solution containing 0.2 g of sodium dodecylbenzenesulfonate, and emulsified and dispersed using a colloid mill. (Preparation of Samples 113 to 116) Samples 113 to 116 were prepared in the same manner as Samples 109 to 112, except that the dye SEN-2 of the 10th layer of Samples 109 to 112 was replaced with the dye D-150 of the present invention in an equimolar amount. Created. The method for dispersing the dye was carried out in the same manner as in Samples 109 to 112. (Preparation of Samples 117 to 119) The dye in the tenth layer of Sample 115 was replaced by the dyes D-160, D-163, and D-16 of the present invention.
Samples 117 to 119 were prepared in the same manner as the sample 115 except that 6 was replaced with an equimolar amount.

After subjecting the above samples 101 to 119 to white imagewise exposure, the following color development processing was carried out to measure the image density obtained. Table 4 shows the relative sensitivity of the green color-sensitive layer based on the magenta image density. The decolorization / elution property of the dye during the developing process is shown by the difference (ΔDmin) from the sample 101 in Dmin (minimum image density) of the yellow density.

Also, the above samples 101 to 119 were treated at 50 ° C. and 80 ° C.
% The change in photographic characteristics after aging under temperature / humidity conditions for 3 days is shown by the relative sensitivity of the blue color-sensitive layer from the yellow image density.

The blue light absorptivity of the yellow filter after storage at 50 ° C. and 80% for 3 days was evaluated as follows. That is, it was evaluated based on the magenta color density when blue separation exposure was performed (the magenta color density is small if the yellow filter functions). A sample containing no filter in the yellow filter layer was prepared, and the blue light absorptivity thereof was set to 0%, and the blue light absorptivity of Sample 101 was expressed as 100%.

The desilvering property was evaluated by measuring the amount of residual silver in the highest density (Dmax) part of the treated sample subjected to the sensitometry by fluorescent X-ray.

As to the sharpness, the MTF value at a frequency of 40 lines per 1 mm of the cyan image of these samples was measured.

The method for measuring MTF is described in "The Theory of the Photographic Process" (The Theme), edited by T. James (TH James).
ory of the Photographic P
process 4th edition "(Mac Millan (Mac Mil
lan), 1977), pages 604 to 607. Next, the composition of the treatment liquid is shown. (Invention Developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) (unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid secondary Sodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0 (fixer) (unit g) Ethylenediaminetetraacetic acid disodium salt Salt 0.5 Ammonium sulfite 20.0 Thiosulfate Monium aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7 (Stable solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediamine Tetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

[0269]

[Table 4] From Table 4, it is clear that the present invention provides a silver halide light-sensitive material having high sensitivity and excellent in decoloring property, storability, sharpness and desilvering property.

Further, the same effect was obtained by applying it to the eleventh layer of the color reversal light-sensitive material of Example of JP-A-2-854 and performing color reversal processing.

Even when applied to the black and white silver halide light-sensitive material of Example 1 of JP-A-3-109535, excellent effects were obtained.

Similar effects were also obtained in the following color development processing.

Samples 201 to 21 produced as described above
3 was cut into a width of 35 mm, stored at 50 ° C., 80% RH for 3 days, and those not stored were processed under the following conditions using an automatic processor.

The processing steps and processing liquid compositions are shown below. (Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleaching 50 seconds 38.0 ° C 140 ml 5 liters Bleaching fixing 50 seconds 38.0 ° C 5 liters Fixed 50 seconds 38.0 ° C 420 ml 5 liters Water wash 30 seconds 38.0 ° C 980 ml 3 liters Stable (1) 20 seconds 38.0 ° C 3 liters Stable (2) 20 seconds 38.0 ° C 560 ml 3 liters Dry 1 minute 60 ° C * Replenishment amount is 1m ² of photosensitive material Amount per hit The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic developing machine and at the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the photographic material. 65
Milliliters, 50 milliliters, 50 milliliters,
It was 50 milliliters. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

As the replenishing solution, the same solution as the tank solution was replenished.

The composition of the treatment liquid is shown below. (Invention developer) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4 -(N-Ethyl-N- (β-hydroxyethyl) amino) aniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) (unit: g) 1,3-diaminopropanetetraacetic acid ferric ammonium-water Salt 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water is added to 1.0 liter pH (adjusted with ammonia water) 4.4 (Bleach-fixing solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0) (Fixer) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 liter pH (Prepared with ammonia water and acetic acid) 7.4 (Washing) Water) Tap water is used as an H-type strongly acidic kaothine exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium acid 20 mg / liter and sodium sulfate 150 mg /
1 liter was added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4 -Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 The structural formulas of the compounds used in the examples are shown below.

[0277]

[Chemical 74]

[0278]

[Chemical 75]

[0279]

[Chemical 76]

[0280]

[Chemical 77]

[0281]

[Chemical 78]

[0282]

[Chemical 79]

[0283]

[Chemical 80]

[0284]

[Chemical 81]

[0285]

[Chemical formula 82]

[0286]

[Chemical 83]

[0287]

[Chemical 84]

[0288]

[Chemical 85]

[0289]

[Chemical formula 86]

[0290]

[Chemical 87]

[0291]

[Chemical 88] Example-2 (Preparation of Sample 201) The same sample as the sample 119 of Example 1 was prepared as Sample 201. (Preparation of sample 202) ExM- of the ninth layer of sample 201
4 and ExM-5 are respectively compared to magenta coupler Cp-1,
Sample 202 was prepared in the same manner as sample 201 except that Cp-2 was replaced with an equimolar amount. (Preparation of Sample 203) Sample 203 was prepared in the same manner as Sample 201 except that the magenta coupler ExM-2 of the seventh layer and the eighth layer of Sample 201 was replaced with the magenta coupler M-69 of the present invention in an equimolar amount.

When the samples 201 to 203 were exposed to a white image and subjected to the color development processing described above, the sensitivity and desilvering property of the green color-sensitive layer were further improved in the order of samples 202, 201 and 203. ..

Samples 201 to 203 were subjected to green separation exposure, color processing was performed, and the densities of yellow, magenta, and cyan color images were measured. As a result, the ratio of the yellow density of the sub-absorption density to the magenta density of the main color was found. Sample 2
The number becomes smaller in the order of 02, 201, 203, and the color reproduction is improved. Example-3 (Preparation of Sample 301) The same sample as the sample 119 of Example 1 was prepared and designated as Sample 301. (Preparation of Sample 302) Eleventh layer, 12th layer of Sample 301,
The 13-layer yellow coupler ExY-2 was replaced with the comparative yellow coupler Cp-3. Since color development does not match if the couplers are replaced with equimolar amounts, the coupler amount was increased by 20 mol%, and the silver halide amount was increased by 15%.

The samples 301 and 302 were exposed to a white image and subjected to the above-mentioned color development processing. When the photographic performances were compared, Sample 30 was found to be sharp, the sensitivity of the green layer and desilvering.
1 was excellent.

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Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer each having at least one layer on a support.
And a hydrophilic photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a hydrophilic colloid layer containing a compound represented by the following general formula (I) and an aspect ratio (diameter equivalent to circle of silver halide / grain thickness) of 2.0 A silver halide color photographic light-sensitive material characterized in that the above-mentioned silver halide grains have an emulsion layer containing tabular silver halide grains in which 50% (area) or more of all silver halide grains in the emulsion are present. .. [Chemical 1] In the formula, R ²¹ is a hydrogen atom, alkyl, alkenyl, aryl, heterocycle, ureido, sulfonamide, sulfamoyl, sulfonyl, sulfinyl, alkylthio, arylthio, oxycarbonyl, acyl, carbamoyl, cyano, alkoxy, aryloxy, amino, or amide. Represents. Q is -O- or -NR ²² - represents, R ²²
Represents a hydrogen atom, alkyl, aryl, or heterocycle. R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom, alkyl or aryl, and R ²⁴ and R ²⁵ may form a 6-membered ring. R
²⁶ represents a hydrogen atom, alkyl, aryl, or amino. L ¹ , L ² and L ³ represent methine, and k is 0 or 1
Is. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one layer in the light-sensitive material contains a compound represented by the following general formula (M). [Chemical 2] Here, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group 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 hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one layer in the light-sensitive material contains a compound represented by the following general formula (Y). [Chemical 3] Here, R ₁₀₁ represents aryl, R ₁₀₂ and R ₁₀₃ represent a substituent, and X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. l represents an integer of 0 to 4, and when l is 2 or more, a plurality of R ₁₀₃ may be the same or different.