JP2579220B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic material, and more particularly, to sensitivity, graininess, sharpness, and the like.
The present invention relates to a silver halide color photographic material having improved edge writing fog safety and desilvering properties.

(Prior Art) In recent years, high sensitivity and small format of silver halide color photographic light-sensitive materials have been advanced, and color photographic light-sensitive materials having high sensitivity and excellent image quality have been strongly desired.

Therefore, demands for photographic silver halide emulsions are becoming more and more severe, and higher standards are required for photographic performance such as sensitivity, graininess and sharpness.

In response to such demands, use of tabular grains intended to improve sensitivity, including improvement in color sensitization efficiency by sensitizing dyes, to improve sensitivity / granularity relationship, to improve sharpness, and to increase covering power. However, U.S. Pat.Nos. 4,434,226 and 4,441,310
Nos. 4344348, 4441406, 4439520, 44593
No. 53, etc.

Also, JP-A-58-113930, JP-A-58-113934, JP-A-59-119
No. 350, each publication also discloses a multilayer color photographic light-sensitive material having high sensitivity and improved graininess, sharpness and color reproducibility using a tabular silver halide emulsion having an aspect ratio of 8 or more. ing.

According to these patents, tabular grains have low scattering properties, so sharpness is improved when used in a blue-sensitive emulsion layer, and graininess is improved when tabular grains are used in a green-sensitive or red-sensitive emulsion layer. It is described.

JP-A-61-77847 discloses a multilayer color photographic material having improved sharpness and color reproducibility using a tabular silver halide emulsion having an aspect ratio of 5 or more.

Other Research Disclosure
osure) No. 25330 shows that by adjusting the thickness of the tabular grains, the emulsion in the layer above the layer using the tabular grains increases the reflection of light that is exposed to light, thereby increasing the sensitivity of the upper layer. Disclosed is a method for minimizing reflection so as not to impair the sharpness of the upper layer.

Although such tabular grains having a high aspect ratio have various merits to utilize their characteristics,
In a so-called normal layer structure (a layer structure in which a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are arranged in order from a side farther from the support) which is most often used in a color photographic light-sensitive material, all layers have a high aspect ratio (for example, When tabular grains having an aspect ratio of 3.0 or more) are used, sharpness particularly on the low-frequency side (25 cycles / mm or less) of the green-sensitive and red-sensitive emulsion layers and fogging due to edge writing tend to be significantly deteriorated.

Furthermore, in recent years, in the industry, there has been a strong demand for faster processing, that is, a reduction in the time required for processing, and in particular, in a situation where shortening the desilvering step, which accounts for nearly half of the processing time, has become a major issue. There is a need to improve desilvering.

Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in sensitivity, granularity, sharpness, prevention of fogging by edge writing (light piping), and desilverability. Is to do.

(Means for Solving the Problems) As a result of intensive studies, the present inventor has set forth the above object of the present invention as:
It has been found that this can be achieved by the following means.

That is, the present invention provides at least one
In a color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the total projected area of all silver halide grains in all emulsion layers is determined. At least 50% is occupied by tabular grains having an average aspect ratio of 3.0 or more, and has a hydrophilic colloid layer containing at least one microcrystalline dispersion of a compound selected from the following general formulas (I) to (V): And a silver halide color photographic material.

General formula (I) General formula (II) General formula (III) A = L ₁ L ₂ = L _{3 n} A ′ General formula (IV) General formula (V) General formula (VI) (Wherein A and A ′ may be the same or different and represent a substituted or unsubstituted acidic nucleus having a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidophenyl group, a carboxyalkyl group, or a hydroxyphenyl group; The acidic nucleus is selected from the group consisting of 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine and hydroxypyridone. It is.
B represents a substituted or unsubstituted basic nucleus having a carboxyl group, a sulfamoyl group or a sulfonamide group, and the basic nucleus is selected from the group consisting of pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole. To be elected. R represents a hydrogen atom or an alkyl group; R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ are linked; A 5- or 6-membered ring may be formed. R ₃ and R ₆ represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ are each a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are connected Represents a group of non-metallic atoms necessary to form a 5- or 6-membered ring. Also B '
Represents a heterocyclic group having a carboxyl group, a sulfamoyl group or a sulfonamide group.

L ₁ , L ₂ , and L ₃ each represent a substituted or unsubstituted methine group, X and Y each represent an electron-withdrawing group, and at least one carboxyphenyl group or sulfa It has a moylphenyl group, a sulfonamidophenyl group, a carboxyalkyl group or a hydroxyphenyl group.
m represents 0 or 1, and n represents 0, 1 or 2. p
Represents 0 or 1, when p is 0, R ₃ represents a hydroxy group or a carboxy group, and R ₄ and R ₅ represent a hydrogen atom. General formula (I) General formula (II) General formula (III) A = L _1- (L ₂ = L ₃ ) _n -A ′ General formula (IV) A = (L ₁ -L ₂ ) _2-q = B General formula (V) (Where A and A ′ may be the same or different,
Each represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group.
R represents a hydrogen atom or an alkyl group; R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group; even if R ₁ and R ₂ are linked to form a 5- or 6-membered ring, Good.
R ₃ and R ₆ each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ are each a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅
Represents a group of non-metallic atoms necessary to form a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2,
p represents 0 or 1, when p is 0, R ₃ represents a hydroxy group or a carboxyl group, and R ₄ and R ₅ represent a hydrogen atom. However, the general formulas (I), (II), (III), (IV),
The compounds represented by (V) and (VI) have a pKa in a mixed solution of water and ethanol in a volume ratio of 1: 1 in one molecule.
Has at least one dissociable group in the range of 4 to 11. First, the general formulas (I), (II), (III), (IV),
The compounds represented by (V) and (VI) will be described in detail.

The acidic nucleus represented by A or A 'is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, Represents pyrazolopyridine or hydroxypyridone.

The chloride nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

B ′ is an example of a heterocyclic ring such as pyrrole, indolethiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine,
Phenoxazine, indoline, thiazole, pyridine,
Pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole and the like.

A group having a dissociable proton having a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution having a volume ratio of water to ethanol of 1 to 1 is used to make the dye molecule substantially insoluble in water at pH 6 or below pH 6. Insofar as it makes the dye molecule substantially water-soluble at pH 8 or pH 8 or higher, the type and substitution position of the dye molecule are not particularly limited, but preferably, a carboxyl group, a sulfamoyl group, a sulfonamide group, A hydroxy group is more preferred, and a carboxyl group is more preferred. The dissociable group may be substituted not only directly on the dye molecule but also via a divalent linking group (for example, an alkylene group or a phenylene group). As an example via a divalent linking group,
4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfur Huamoylphenyl,
4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-cyamibenzenesulfonamido) phenyl, 3-hydroxy Phenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4- Carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxy Butyl, 8-carboxyoctyl and the like.

The alkyl group represented by R, R ₃ or R ₆ is preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-
Groups such as propyl, isoamyl, n-octyl and the like can be mentioned.

The alkyl group represented by R ₁ and R ₂ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl,
Isopropyl) is preferable, and a substituent [eg, a halogen atom such as chlorine bromine, a nitro group, a cyano group, a hydroxy group, a carboxy group, an alkoxy group (eg, methoxy,
Ethoxy), an alkoxycarbonyl group (eg, methoxycarbonyl, i-propoxycarbonyl), an aryloxy group (eg, a phenoxy group), a phenyl group, an amide group (eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methyl Carbamoyl,
Ethylcarbamoyl) and a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R ₁ or R ₂ is preferably a phenyl group or a naphthyl group, and has a substituent [as the substituent, the groups mentioned as the substituents of the alkyl group represented by R ₁ and R ₂ and the alkyl group ( For example, methyl, ethyl). ] May be provided.

The acyl group represented by R ₁ or R ₂ is preferably an acyl group having 2 to 10 carbon atoms, for example, acetyl, propionyl, n
-Octanoyl, n-decanoyl, isobutanoyl, benzoyl and the like. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ₁ or R ₂ include methanesulfonyl, ethanesulfonyl,
Examples include groups such as n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, and o-carboxybenzenesulfonyl.

The alkoxy group represented by R ₃ or R ₆ is preferably an alkoxy group having 1 to 10 carbon atoms, for example, methoxy, ethoxy, n
-Butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, isopropoxy and the like. Examples of the halogen atom represented by R ₃ or R ₆ include chlorine, bromine, and fluorine.

As a ring formed by connecting R ₁ and R ₄ or R ₂ and R ₅
For example, a julolidine ring can be mentioned.

As a 5- or 6-membered ring formed by linking R ₁ and R ₂ ,
For example, there can be mentioned a piperidine ring, a morpholine ring and a pyrrolidine ring.

The methine group represented by L ₁ , L ₂ or L ₃ may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group which may be substituted,
For example, acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl), an arylcarbonyl group (optionally substituted arylcarbonyl group, for example, benzoyl, 4-
Ethoxycarbonylbenzoyl, 3-chlorobenzoyl), alkoxycarbonyl group (optionally substituted alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl,
-Ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2- (2- Chloroethoxy)
Ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxy] ethoxycarbonyl), an aryloxycarbonyl group (optionally substituted aryloxycarbonyl group, for example, phenoxycarbonyl, 3-ethylphenoxycarbonyl , 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl) phenoxycarbonyl), Carbamoyl group (optionally substituted carbamoyl group, for example, carbamoyl group ethyl carbamoyl,
Dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di- (t-
Amyl) phenylcarbamoyl, 2-chloro-3- (dodecyloxycarbamoyl) phenylcarbamoyl, 3
-(Hexyloxycarbonyl) phenylcarbamoyl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), and a sulfamoyl group (optionally substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl).

 Next, specific examples of the dye used in the present invention will be described.

The dyes used in the present invention are described in International Patent WO88 / 04794, European Patent EP0274723A1, EP2767566, and JP299,435.
No., JP-A-52-92716, JP-A-55-155350, JP-A-55-155351
No. 61-205934, No. 48-68623, U.S. Pat.
Nos. 3486897, 3746539, 3933798, 41304
The compounds can be easily synthesized according to the methods described in Nos. 29 and 4040841, and the like, and according to the methods.

In the present invention, the dye forms a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on the photographic element. The fine powder dispersion is obtained by precipitating a dye in the form of a dispersion and / or in the presence of a dispersing agent, by a known means of pulverization, for example, ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.).
It can be formed by sand milling, colloid milling, jet milling, roller milling, or the like. In this case, a solvent (eg, water, alcohol, or the like) may coexist. Alternatively, after dissolving the dye in an appropriate solvent, a non-solvent for the dye may be added to precipitate microcrystalline powder of the dye. In this case, a surfactant for dispersion may be used.
Alternatively, by controlling the pH of the dye,
Crystallization may be carried out by first dissolving and then changing the pH. The dye particles in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less, and particularly preferably 0.5 μm or less.
m or less, and more preferably 0.1 μm or less in some cases.

The amount of the dye used in the present invention is in the range of 1 mg to 1000 mg / m ² . Preferably it is 5 mg to 800 mg / m ² .

The dye dispersion of the present invention can be added to any layer irrespective of the emulsion layer or the intermediate layer.

The effect of the present invention is remarkable when part or all of the colloidal silver generally used for the yellow filter layer and / or the antihalation layer is used in place of the colloidal silver.

The back layer containing carbon (for example, carbon black, colloidal carbon, carbon graphite) used in the present invention may be a colloidal carbon dispersion useful for an antihalation back layer described in, for example, US Pat. No. 2,271,234. US Patent No. 2,32
Various alkali-soluble substances such as cellulose acetate phthalate described in the specification of US Pat. No. 7,828 are used as a carrier for an antihalation substance, and colloidal carbon is finely dispersed in a coating solution diluted with an organic solvent in order to obtain a desired coating density. And can be provided by applying it.

Carbon is used as a binder with a hydrophilic polymer, particularly a polymer that is soluble under high pH conditions.

As described above, when carbon is used for the back layer, it is advantageous in terms of chargeability, development suitability, and the like as compared with the case where a dye or the like is used.

The antihalation back layer used in the present invention has a density of preferably 0.1 to 2.0, more preferably 0.5 to 1.5, with respect to white light when used under normal conditions.

In the emulsion layer provided on the support, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer may be provided in this order from the support, or vice versa. Further, the same color-sensitive layer may be composed of two or three layers.

The coated silver amount of the light-sensitive material of the present invention is preferably from 1 to 15 g / m ^{2, and} more preferably from 3 to 11
g / m ² is more preferred. Here, a large amount of coated silver is not preferable in terms of desilvering when a persulfate or a metal complex of an organic iron acid is used as a bleaching agent.

A tabular silver halide grain (hereinafter, referred to as a "tabular grain") in the present invention has two opposing parallel main planes and an equivalent circle diameter of the main plane (a circle having the same projected area as the main plane). Particles whose diameters are at least twice as large as the distance between the main planes (ie, the thickness of the particles).

The average grain diameter / grain thickness ratio of the emulsion having tabular grains of the present invention is preferably from 3 to 12, and more preferably from 5 to 10.

Here, the average grain diameter / grain thickness ratio can be obtained by averaging the grain diameter / grain thickness ratio of all tabular grains. As a simple method, the average diameter of all tabular grains and the average of all tabular grains are obtained. It can also be obtained as a ratio with the thickness.

The diameter (equivalent to a circle) of the tabular grains of the present invention is 0.3 to 10 μm,
Preferably 0.5 to 5.0 μm, more preferably 0.5 to 2.0 μm
m.

The particle thickness is 0.5 μm or less, preferably 0.05 to 0.5 μm,
More preferably, it is 0.08 to 0.3 μm.

The measurement of the particle diameter and the particle thickness in the present invention can be obtained from an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226. Specific examples of the halogen composition of the tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, and silver bromoiodide silver chloroiodobromide. Further, silver thiocyanate, silver cyanate and the like may be contained.

As a method for producing tabular grains, U.S. Pat.Nos. 4,434,226, 4,439,520, 4,441,310, 4,399,215 and 443.
No. 3048, No. 4386156, No. 4400463, No. 4414306
No. 4,443,501, etc., as appropriate.

For example, in an atmosphere having a relatively high pAg value of pBr 1.3 or less, tabular grains form seed crystals in which 40% or more exist by weight, and silver and a halogen solution are added while maintaining the same or higher pBr value. It is obtained by growing a seed crystal.

In the grain growth process by adding silver and / or halogen,
It is desirable to add silver and a halogen solution so as not to generate new crystal nuclei.

The size of the tabular grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

The internal sensitivity after surface chemical sensitization of the tabular grains of the present invention can be increased by performing chemical sensitization at a stage before the completion of grain formation. Preferably, the chemical sensitization is performed at a stage prior to 80% of the silver content of the whole grains.

This chemical sensitization is described in The James of The Theory of Photographic Process, 4th Edition, Macmillan, 1977, (THJames, The Theo
ry of the Photographic Process, 4 th ed, Macmillan, 1
977) can be performed using active gelatin as described on pages 67-76, and can also be performed in Research Disclosure, Volume 120, April 1974, 12008; Research Disclosure, Volume 34, 1975. June 13452, U.S. Patent No. 2,642,3
No. 61, No. 3,297,446, No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018, and 3,904,41
No. 5, and pAg 5-10, pH 5-8 and a temperature of 30-80 ° C. as described in GB 1,315,755 for sulfur, selenium, tylyl, gold, platinum, palladium, iridium, rhodium or sensitizers thereof. Can be performed using a plurality of combinations. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and in U.S. Pat.
The reaction is performed in the presence of a sulfur-containing compound described in 7,711, 4,266,018 and 4,054,457 or a sulfur-containing compound such as hypo, thiourea-based compound, and rhodanine-based compound. Chemical sensitization can also be performed 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 capri and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038, 3,411,914, 3,554,757
No., JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Daffin, pp. 138-143. In addition to or in lieu of chemical sensitization, reduction sensitization can be used, for example, with hydrogen, as described in U.S. Pat.Nos. 3,891,446 and 3,984,249, and U.S. Pat.
Nos. 2,743,182 and 2,743,183, using stannous chloride, thiourea dioxide, polyamines and such reducing agents, or low pAg (eg, less than 5) and / or high pH (eg, 8 (Large) reduction sensitization can be achieved by the treatment. Also U.S. Patent 3,917,48
The chemical sensitization method described in No. 5 and 3,966,476 can also be applied.

Also, sensitization methods using oxidizing agents described in Japanese Patent Application Nos. 59-122981 and 59-122984 can be applied.

As another method for increasing the internal sensitivity, there is a method of introducing a gap having a halogen composition at a stage before the completion of grain formation. This is also preferably introduced at a stage prior to 80% of the total silver content of the grains.

As the gap of the halogen composition increases, the internal sensitivity increases. For example, in the case of silver iodobromide, a difference in silver iodide content of 5 mol% or more is preferably present, and more preferably 10 mol% or more. Preferably, there is a difference in content.

In the present invention, the following monodispersed hexagonal tabular grains can be used.

The emulsion is a silver halide emulsion comprising a dispersion medium and silver halide grains, wherein 70% or more of the total projected area of the silver halide grains is the maximum with respect to the length of the side having the minimum length. A hexagonal shape having a ratio of the length of the side having a length of 2 or less and occupied by tabular silver halide having two parallel surfaces as outer surfaces; Of variation in grain size distribution of silver halide grains [a value obtained by dividing the variation (standard deviation) of grain size expressed by the circle-converted diameter of the projected area thereof by the average grain size]
Has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The composition of the hexagonal tabular grains may be any of silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide.
When iodine ions are contained, the content is 0 to 30 mol%, and the crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, it is preferable that the grains contain reduction sensitized silver nuclei.

The silver halide grains can be produced by nucleation-Ostwald ripening and grain growth, the details of which are described in Japanese Patent Application No. 61-299155.

In the production of the tabular grains of the present invention, a method for increasing the addition rate, amount and concentration of a silver salt solution (for example, an aqueous solution of AgNO ₃ ) and a halide solution (for example, an aqueous solution of KBr), which are added to accelerate the grain growth, is known. It is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925
No. 3,672,900, No. 3,650,757, No. 4,
242,445, JP-A-55-142329 and JP-A-55-158124 can be referred to.

Silver halide solvents are useful for accelerating ripening.
For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent other than the halogen ion, ammonia or an amine compound, a thiocyanate salt, for example, an alkali metal thiocyanate salt, particularly a sodium and potassium thiocyanate salt, and an ammonium thiocyanate salt can be used. The use of thiocyanate ripening agents is taught in U.S. Pat. Nos. 2,222,264, 2,448,534 and 3,320,069. Also U.S. Pat.
Commonly used thioether ripening agents as described in 71,157, 3,574,628 and 3,737,313 can also be used. Or JP-A-53-82408 and JP-A-53-144319
Thione compounds such as those disclosed in US Pat.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the process of silver halide precipitation. Such compounds may be initially present in the reactor or may be added together with one or more salts according to conventional methods. United States Patent 2,
448,060, 2,628,167, 3,737,313, 3,772,0
Issue 31 and Research Disclosure, 134
Vol., June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (chalcogen compounds such as sulfur, selenium and tellurium), gold and VI.
The characteristics of silver halide can be controlled by the presence of a compound such as a compound of a Group I noble metal in the process of silver halide precipitation. As described in JP-B-58-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions form grains during precipitation. The inside can be reduced and sensitized.

In the tabular grains used in the present invention, silver halides having different compositions may be bonded by epitaxal bonding, or may be bonded to a compound other than silver halide, such as, for example, rhodan silver or lead oxide. Is also good. These emulsion grains are described in U.S. Pat.Nos. 4,094,684 and 4,142,900.
No. 4,459,353, UK Patent No. 2,038,792, U.S. Pat.Nos. 4,349,622, 4,395,478, 4,433,501, 4,4
Nos. 63,087, 3,656,962 and 3,852,067,
No. 162540 and the like.

The tabular grains of the present invention require that the surface be chemically sensitized. This is because sufficient sensitivity cannot be obtained with a normal surface developing developer due to high internal sensitivity.

Chemical sensitization is described in The James of the Theory of Photographic Process, 4th Edition.
Edition, published by Macmillan, 1977, (THJames, The Theory
of the Photographic Process, 4th ed, Macmillan, 197
7) It can be performed using active gelatin as described on pages 67-76, or can be performed using Research Disclosure.
120, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Patent No. 2,642,361
Nos. 3,297,446, 3,772,031, 3,857,711,
3,901,714, 4,266,018, and 3,904,415
P, as described in British Patent 1,315,755.
Ag 5-10, pH 5-8 and temperature 30-80 ° C. can be carried out using sulfur, selenium, chillyl, gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, as well as U.S. Patent Nos. 3,857,711;
The reaction is performed in the presence of a sulfur-containing compound described in US Pat. Nos. 6,018 and 4,054,457 or a sulfur-containing compound such as hypo, thiourea-based compound, and rhodanine-based compound. Chemical sensitization can also be performed 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 capri and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitizer modifiers are described in U.S. Pat.No.2,131,038
No. 3,411,914, No. 3,554,757, JP-A-58-126526
And Daffin, "Emulsion Chemistry", pp. 138-143. In addition to or in lieu of chemical sensitization, reduction sensitization, for example with hydrogen, as described in U.S. Pat.Nos. 3,891,446 and 3,984,249, and U.S. Pat.Nos. 2,518,698, 2,743,182 Using stannous chloride, thiourea dioxide, polyamines and such reducing agents as described in US Pat. Nos. 2,743,183; or low pAg (eg, less than 5) and / or high pAg.
Reduction sensitization can be achieved by H (for example, greater than 8) treatment. U.S. Pat.Nos. 3,917,485 and 3,966,476
The color sensitization can also be improved by the chemical sensitization method described in (1).

Also, sensitization methods using oxidizing agents described in Japanese Patent Application Nos. 59-122981 and 59-122984 can be applied.

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. Can use tabular grains and non-tabular grains in different emulsion layers and / or in the same emulsion layer. Here, as non-tabular grains, for example, cubic, octahedral, regular crystal grains such as tetradecahedron or spherical, grains having irregular crystal forms such as potatoes and the like. Can be mentioned.
As the silver halide of these grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are
Silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol% to 25 mol% of silver iodide.

The non-tabular grains used herein may be fine grains of 0.1 micron or less or large grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. An emulsion may be used.

Non-tabular grains used in the present invention are described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides,
Chimie et Physique Photographique Paul Montel, 196
7), Duffin “Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focalprene (VLZelikam et a).
l, Making and Coating Photographic Emulsion, Focal P
ress, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept 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 nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion consisting of the above-mentioned regular grains,
It is obtained by controlling pAg and pH during particle formation.
For details, see, for example, Photographic Science and Eng.
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

For monodispersed emulsions, see JP-A-48-8600 and
39027, 51-83097, 53-137133, 54-48521
Nos. 54-99419, 58-37635, 58-49938, JP-B-47-11386, U.S. Pat. No. 3,655,394, and British Patent No. 1,413,748.

The crystal structure of these non-tabular grains may be uniform, or the inside and outside may have different halogen compositions.
It may have a layered structure. These emulsion grains are described in GB 1,027,146, U.S. Pat.
No. 4,877 and Japanese Patent Application No. 58-248469.

In the present invention, a non-photosensitive fine grain emulsion having a particle size of 0.6 μm or less, preferably 0.2 μm or less is added to a silver halide emulsion layer, an intermediate layer or a protective layer for the purpose of promoting development, improving storage stability, and effectively utilizing reflected light. May be.

The tabular grains of the present invention are preferably used for a color photographic light-sensitive material.

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

Here, the monodispersed silver halide emulsion (non-tabular grains) means that the total weight or 95% or more of the silver halide grains contained therein is within ± 40% of the average grain size, more preferably ± 30%. Are defined as The use of a monodispersed silver halide emulsion in a silver halide photographic light-sensitive material can improve the granularity as described in JP-B-47-1138.
6, JP-A-55-142329, JP-A-57-17235 and JP-A-59-72440. Also, TH The James, "The Theory of Photographic Process," 580-5
As described on page 85, a monodisperse silver halide grain of 0.3 μ to 0.8 μ has a large light scattering property with respect to light in a specific wavelength range, but has a large light scattering property with respect to light in other wavelength ranges. Is also known to have the property of relatively low light scattering.

Therefore, a tabular silver halide emulsion having a grain diameter / thickness ratio of 5 or more and a monodispersed silver halide emulsion are appropriately arranged in consideration of the optical characteristics and graininess of each silver halide emulsion. Therefore, the sharpness and granularity of the silver halide photographic light-sensitive material may be improved at the same time.

Some examples of such embodiments are listed.

Example 1) In a light-sensitive material in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side, the silver halide emulsion layer constituting the blue-sensitive layer has an average grain size of silver halide grains contained therein. Is in the range of 0.3 to 0.8 μm, tabular silver halide grains are used in the emulsion layer, and when the average grain size is not in the above range, monodispersed silver halide is used. Thus, it is possible to improve the sharpness of the green and red sensitive layers and the granularity of the blue sensitive layer.

Example 2) In a light-sensitive material having the same layer arrangement as in Example 1, the average grain size of silver halide grains contained in the silver halide emulsion layer constituting the green-sensitive layer is 0.4 to 0.8.
When the average particle size is in the range of μ, the sharpness of the red-sensitive layer is improved by using a monodisperse emulsion when the average particle size is not in the above range. Further, it is possible to improve the granularity of the green sensation layer.

Example 3) In the light-sensitive material having the same layer arrangement as in Example 1, wherein the emulsion layer having the same color sensitivity comprises two or more layers having different sensitivities, the blue-sensitive layer having the highest sensitivity
If monodispersed silver halide of 1.0μ or more (especially a double structure grain is preferable) and the light scattering of the less sensitive blue-sensitive layer is large, use tabular grains for the less sensitive blue-sensitive layer to obtain The sharpness of the layer and the red-sensitive layer can be improved.

Example 4) In the case of a light-sensitive material having the same layer arrangement as in Example 3, when all of the green-sensitive layers have large light scattering, tabular grains are used for all of the green-sensitive layers, and the sharpness of the red-sensitive layer is improved. It is possible to improve the granularity of the green layer.

As in Examples 3 and 4, especially when the blue-sensitive layer, green-sensitive layer and red-sensitive layer are each composed of a plurality of emulsion layers, the emulsion layer having a large light scattering is preferably used to improve the sharpness and granularity. Consideration should be given to using monodisperse emulsions in emulsion layers which use silver halide grains and provide less light scattering. or,
In the case where tabular grains were further used in the red-sensitive layer in Example 4, light scattering between the emulsion layers became large, which sometimes deteriorated the sharpness of the green-sensitive layer on the red-sensitive layer. It may not be preferred to use tabular grains for the closest red-sensitive layer.

As described above, the tabular grains and non-tabular grains used in the present invention are usually those subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716, and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and their locations are shown in the table below.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G mentioned above.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 968, 4,314,023, 4,511,649, EP 249,473A, and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International Publication W
Those described in, for example, No. 088/04795 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643, VII-
Section G, U.S. Patent No. 4,163,670, JP-B-57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, UK Patent No. 1,14
Those described in 6,368 are preferred. Also, U.S. Pat.
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 74,181, or a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
No. 2,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
Patents described in the paragraph, JP-A-57-151944, 57-154234
And Nos. 60-184248, 63-37346 and 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618, multi-equivalent couplers described in
No. 185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A, 313,
No. 308A, couplers releasing dyes that recolor after release, RD Nos. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, etc., and ligands described in U.S. Pat.No. 4,553,477 Release couplers, couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat.
And couplers which release a fluorescent dye described in 4,181.

The coupler used in the present invention can be introduced into a 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.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method 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 ester (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 esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyluraryl) Amides, 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 derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, JP-A-63-257747
No. 62-272248, and JP-A-1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or fungicides such as 3,5-disimethylphenol, 2-phenoxyethanol, and 2- (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 that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and still more preferably 20 μm or less. 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 at 25 ° C. 55% relative humidity (2 days), film swell speed T _1/2
It can be measured according to a method known in the art. For example, a swellometer of the type described by A. Green et al. In Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, No. 2, pages 124-129. ) Can be measured, and T _1/2 is defined as 90% of the maximum swelled film thickness reached when the color developer is treated at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 90%. Defined as the time to reach 2.

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexyl Njiamin tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N, N-trimethylenephosphonic acid, ethylenediamine -N, N, N, N-tetramethylene phosphonic acid,
Ethylenediamine-di- (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

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

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

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 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 photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III) such as amino diamines 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. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
Nos. 53-72623, 53-95630, 53-95631, 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in, for example, July, 1983; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-42,434
Nos. 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,2
Compounds described in JP-A-90,812 and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing color photographic materials for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A Nos. 62-183460 and 62-183461, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material, and a method disclosed in JP-A-62-183461.
The method of increasing the stirring effect using the rotating means of No. 83461, and furthermore, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent, the stirring effect is further increased. And a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. 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 consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or 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
It is preferable to have the photosensitive material conveying means described in JP-A-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath.
The effect of preventing performance deterioration of the processing liquid is high. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

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

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (19
1986) Sankyo Publishing, Sanitary Technology Society, “Sterilization and sterilization of microorganisms,
A fungicide described in "Encyclopedia of Fungicides" (1986), "Encyclopedia of Fungicides and Antifungal Agents" (1986) edited by the Industrial Technology Association and the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

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

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

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

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056, European Patent 210,660A2 and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

Example 1 30 g of inert gelatin and 6 g of potassium bromide were added to distilled water 1
Stir the aqueous solution dissolved in
After adding 35 cc of an aqueous solution in which 5.0 g was dissolved and 3.2 g of potassium bromide and 35 cc of an aqueous solution in which 0.98 g of potassium iodide were dissolved at a flow rate of 70 cc / min for 30 seconds, the pAg was raised to 10 and aged for 30 minutes. A seed emulsion was prepared.

Subsequently, a predetermined amount of an aqueous solution 1 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, and the plate was added. A core emulsion was prepared. Subsequently, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in the preparation of the core emulsion were added in equimolar amounts at an addition rate near the critical growth rate to coat the core. Core / shell type silver iodobromide tabular emulsions Em-1 to 4 were prepared.

Aspect ratio adjustment is based on pAg during core and shell preparation.
Was obtained by selecting. The results are shown in Table 1-1.

Em-1 to 4 were tabular grains having a projected area of 85% or more of all the grains.

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

In Em-1-12, tabular grains accounted for 85% or more of the projected area of all grains. Em-1 to 12 thus prepared were optimally subjected to gold / sulfur sensitization in each emulsion using sodium thiosulfate and chloroauric acid.

On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to prepare Sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide and colloidal silver, the coating amount is expressed in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. The symbols indicating the additives have the following meanings.
However, when there are multiple utilities, only one of them is listed as a representative.

U: UV absorber, HBS: high boiling point organic solvent, EX: coupler, S: additive (Sample 101) First layer (gelatin layer) Gelatin 0.40 Second layer (intermediate layer) 2,5-di-t-pentadeci Lehydroquinone 0.18 Ex-1 0.07 Ex-3 0.02 Ex-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Silver halide emulsion I silver 0.55 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion II Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 Sensitizing dye IV 3.0 × 10 ^-5 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion III Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.4 × 10 ^-4 sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 Sixth Layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 Seventh Layer (first green-sensitive emulsion layer) Silver iodobromide emulsion I silver 0.40 Sensitizing dye V 3.0 × 10 ^{- 5} Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 8th layer (No. 2 green-sensitive emulsion layer) Silver iodobromide emulsion II silver 0.80 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX -1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 Ninth layer (third green-sensitive emulsion layer) Silver iodobromide emulsion III Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74 Layer 10 (yellow filter layer) Yellow colloidal silver Silver 0.05 EX- 5 0.08 HBS-3 0.03 Gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.24 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX -8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer) Silver iodobromide emulsion II Silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 Gelatin 0.46 13th layer (3rd blue-sensitive emulsion layer) Silver iodobromide emulsion III silver 0.77 sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 gelatin 0.69 14th layer (first protective layer) Silver iodide emulsion (silver iodide 1 mol%, average particle size 0.07μ) Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 15th layer (2nd protective layer) Polymethyl acrylate particles (about diameter) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72 In addition to the above components, gelatin hardener H-1 and a surfactant were added to each layer. The structural formulas of the compounds used are shown in Table A below.

Silver iodobromide emulsion I of the third, seventh and eleventh layers, fourth layer,
The silver / bromoiodide II of the eighth and twelfth layers and the silver / bromoiodide emulsion III of the fifth, ninth and thirteenth layers were subjected to the above-described Em-sulfur-sensitized Em- Samples 101 to 104 were prepared using 1 to 12.

Next, on the back side of the support, a back layer (16th
Layer 10), except that Sample 10 was applied.
5-108 were produced.

Sixteenth layer (back layer) Methyl methacrylate-methacrylic acid copolymer (copolymer molar ratio: 1: 1) 1.5 parts Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%, phthalyl 36 parts) 1.5 parts Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon 1.2 parts
It was applied to 1.0.

Next, samples 101 to 1 were prepared except that the first gelatin layer was replaced with the following antihalation layer containing black colloidal silver.
Samples 109 to 112 were produced in the same manner as in 04.

First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 0.40 Then, on the back side of the support, the above-mentioned back layer (16th layer)
Samples 113 to 116 were prepared in the same manner as Samples 101 to 104, except that the above-mentioned antihalation layer was replaced with the first gelatin layer.

Next, in Samples 109 to 112, the dye dispersion S-1 of the present invention was replaced with I-1 in place of the black colloidal silver added to the first layer.
Is 0.21 g / m ² , and the dye dispersion S-2 of the present invention is III-
Except that the addition amount of 3 was added to a 0.23 g / m ² sample 1
Samples 117 to 120 were produced in the same manner as in Samples 09 to 112.

Then, except that the above-mentioned back layer (16th layer) was applied to the back side of the support, samples 121 to 1 were prepared in the same manner as samples 117 to 120.
24 were produced.

Next, in Samples 117 to 120, instead of the yellow colloidal silver of the tenth layer (yellow filter layer), the dispersion S-3 of the present invention was added so that the addition amount of II-5 was 0.22 g / m ^2. Samples 125 to 128 were prepared in the same manner as Samples 117 to 120 except for the above.

Then, except that the above-mentioned back layer (16th layer) was applied to the back surface side of the support, samples 129 to 1 were prepared in the same manner as samples 125 to 128.
32 were produced.

Next, in Samples 117 to 120, Dispersion S-4 of the present invention was added in place of the yellow colloidal silver of the tenth layer (yellow filter layer) so that the addition amount of I-28 was 0.24 g / m ² . Except for the above, Samples 133 to 136 were produced in the same manner as Samples 117 to 120.

Next, samples 137 to 140 were prepared in the same manner as samples 133 to 136, except that the back layer (the 16th layer) was applied to the back surface of the support.

Preparation Method of Fine Powder Dye Dispersion S-1 The dye was dispersed in a vibration ball mill by the following method.

Water (21.7 ml) and a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate (3 ml) and a 5% aqueous solution of p-octylphenoxy poly (degree of polymerization 10) oxyethylene ether (0.5 g) were placed in a 700 ml pot mill, and the mixture of the present invention was prepared. 1.00 g of the dye (I-1) and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. The vibration ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion.

S-2 (dye III-3), S-3 (dye II-5) and S-4 (dye I-28) were prepared in the same manner.

Exposure to these samples for sensitometry (1/100 second)
And the following color development processing was performed.

Filter the processed sample with a red filter, green filter,
The density was measured with a blue filter.

The results of the photographic performance were described as relative sensitivities when the sensitivity of Sample 101 was set to 100, where the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each.

Processing Method Color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 45 seconds Rinse 1 minute 10 seconds Settle 45 seconds Rinse 1 minute 15 seconds Stabilize 1 minute 05 seconds The composition of the processing solution used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Add water 1.0 l pH 10.0 Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Bromide Ammonium 150.0g Ammonium nitrate 10.0g Add water 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid sodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyle Ether (average polymerization degree 10) Evaluation of 1.0l sharpness by adding 0.3g water was measured MTF of the green-sensitive layer and red-sensitive layer. MTF measurement is based on The Theory of Photographic Proces
s 4th edd. The method described in page 605 (published by Macmillan) was followed. The exposure was performed by applying white light, and the magenta color density was measured with a green filter, and the cyan color density was measured with a red filter. For the green sensitive layer, the MTF values for the spatial frequencies of 10 cycles / mm and 40 cycles / mm at a magenta color density of 1.4 were shown as representative values in the low frequency region and the high frequency region, respectively. With respect to the red-sensitive layer, the MTF values for a spatial frequency of 10 cycles / mm and 40 cycles / mm at a cyan color density of 1.0 are shown as representative values in a low frequency region and a high frequency region, respectively. The larger the MTF, the better.

Evaluation of fogging by edge writing (light piping) was performed as follows. Each of the samples 101 to 140 was processed into a 35 mm patrone-packed form, and a 3 cm film was taken out from the patrone mouth. The sample in the patrone form was placed under normal light room conditions for 8 hours, and the above treatment was carried out. The fog density of a portion of the patrone that was 20 cm in the patrone from the mouth was measured. (D ₁ ) As a reference, a fog density was measured by subjecting a completely dark room sample in which no part of the sample was exposed to a light room to the above-mentioned processing. (D ₂ ) and Δd = d ₁ −d ₂ was calculated as fog by edge lighting (light piping).

In the evaluation of the desilvering property, the amount of residual silver in the highest concentration (Dmax) portion of the processed sample subjected to the sensitometry was measured by X-ray fluorescence.

Summarizing the contents of samples 101 to 140 and the above test results,
The results are shown in Table 1-3.

As can be seen from Tables 1-3, the sample of the present invention has improved sharpness on the high frequency side with little loss of sharpness on the low frequency side as compared with the comparative example, and also has a good level of fogging due to edge lighting. Up to now, it is clear that the desilvering property has also been improved and that it has excellent performance.

Example 2 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multilayer manner to prepare a sample 201 as a multilayer color photosensitive material.

1st layer: gelatin layer UV absorber C-1 0.04 g / m ² UV absorber C-2 gelatin layer containing 0.18 g / m ² HBS-2 0.09 g / m ² 2nd layer; intermediate layer Compound H-1 Gelatin layer containing 0.30 g / m ² coupler C-7 0.07 g / m ² HBS-1 0.11 g / m ² HBS-2 0.01 g / m ² Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion I Amount of coated silver (the same applies hereinafter) 0.58 g / m ² Sensitizing dye I 7.0 × 10 ^-5 mol per mol of silver Sensitizing dye II 2.0 × 10 ^-5 mol per mol of silver Sensitizing dye III Silver 1 2.8 × 10 ^-4 mol per mol of sensitizing dye IV 2.0 × 10 ^-5 mol per mol of silver Coupler C-3 0.26 g / m ² Coupler C-4 0.01 g / m ² Coupler C-5 0.01 g gelatin layer a fourth layer including a / m ^2; the second red-sensitive emulsion layer silver iodobromide emulsion II 1.3 g / m ² sensitizing dye I silver 5.2 × 10 ^-5 mol sensitizing dye moles II silver 1.5 × 10 ^-5 mole per mole of sensitizing dye III 2.1 × 10 ^-4 mole per mole of silver Sensitizing dye IV per mole of silver 1.5 × 10 ^-5 mol Coupler C-12 0.06 g / m ² Coupler C-3 0.04 g / m ² Coupler C-13 0.01 g / m ² Coupler C-5 0.03 g / m ² HBS-1 0.12 g / m ² Gelatinatin layer containing HBS-2 0.11 g / m ² Fifth layer; third red-sensitive emulsion layer Silver iodobromide emulsion III 0.9 g / m ² Sensitizing dye I 5.5 × 10 ^-5 mole increase per mole of silver Sensitizing dye II 1.6 × 10 ^-5 mol per mol of silver Sensitizing dye III 2.2 × 10 ^-5 mol per mol of silver Sensitizing dye IV 1.6 × 10 ^-5 mol per mol of silver Coupler C- 12 0.04 g / m ² coupler ^{C-3 0.03g / m 2 HBS} -1 gelatin layer sixth layer containing ^{0.06g / m 2 HBS-2 0.05g} / m 2; the intermediate layer compound H-1 0.02g / m ² 7th layer; first green-sensitive emulsion layer Silver iodobromide emulsion I 1.54 g / m ² sensitizing dye V 3.8 × 10 ^-4 mole per 1 mole of silver Sensitizing dye VI 1 mole per silver Te 3.0 × 10 ^-5 mol coupler C-6 0.29g / m ² coupler C-7 0.05g / m ² coupler C-8 0.08g / m ² coupler ^{C-4 0.06g / m 2 HBS} -1 0.31g / m ² No gelatin layer eighth layer; the second green-sensitive emulsion layer Silver iodobromide emulsion II 0.61g / m 2.7 × 10 ^-4 mol sensitizing dye VI 1 mol of silver for ^two sensitizing dyes V 1 mol of silver gelatin layer ninth layer containing 2.1 × 10 ^-5 mol coupler C-6 0.03g / m ² coupler C-9 0.001g / m ² coupler ^{C-8 0.001g / m 2 HBS} -1 0.034g / m 2; the 3 Green-sensitive emulsion layer Silver iodobromide emulsion III 0.7 g / m ² Sensitizing dye V 3.0 × 10 ^-4 mol per mol of silver Sensitizing dye VI 2.4 × 10 ^-5 mol per mol of silver Coupler C -6 0.03 g / m ² Coupler C-8 0.001 g / m ² HBS-1 Gelatin layer containing 0.04 g / m ² 10th layer; Yellow filter layer Yellow colloidal silver 0.036 g / m ² Compound H-1 0.10 g / m ² coupler ^{C-7 0.08g / m 2 HBS} -1 0.09g / m 2 gelatin layer 11th layer comprising; feeling first blue emulsion layer silver iodobromide emulsion I 0.34 g / m ² coupler C-10 0.41 g / m ² coupler ^{C-14 0.03g / m 2 HBS} -1 gelatin layer 12th layer containing 0.16 g / m ^2; the second blue-sensitive emulsion layer silver iodobromide Ginchichi II 0.49 g / m ² Coupler ^{C-10 0.15g / m 2 HBS} -1 0.06g / m 2 gelatin layer 13 layer comprising; third blue-sensitive emulsion layer Silver iodobromide emulsion III 0.75 g / m ² sensitizing dye VII silver gelatin layer containing 2.3 × 10 ^-4 mol coupler ^{C-10 0.05g / m 2 HBS} -1 0.02g / m 2 moles 14th layer: first protective layer UV absorber C-1 0.05 gelatin layer 15th layer comprising g / m ² UV absorber ^{C-2 0.24g / m 2 HBS} -2 0.12g / m 2; the second protective layer of polymethyl methacrylate particles (diameter 1.5 microns) 0.05 g / m ² Gelatin layer containing In addition to the above composition, gelatin hardener C-11 and surfactant were added to each layer.

 The compounds used to make the samples are shown below.

C-3 (same as EX-2) C-6 (same as EX-6) C-8 (same as EX-7) C-10 (same as EX-9) C-11 (same as H-1) C-12 (same as EX-4) C-14 (same as EX-8) Silver iodobromide emulsion I of the third, seventh and eleventh layers, fourth layer,
The silver iodobromide II of the eighth and twelfth layers and the silver iodobromide emulsion III of the fifth, ninth and thirteenth layers contained the gold and silver of Example 1 as shown in Table 2-1.
Samples 201-204 were prepared using sulfur sensitized Em-1-12.

Next, on the back side of the support, a back layer (16th
Layer 20), except that sample 20 was applied.
5-208 were produced.

Sixteenth layer (back layer) Methyl methacrylate-methacrylic acid copolymer (copolymer molar ratio: 1: 1) 1.5 parts Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%, phthalyl 36 parts) 1.5 parts Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon 1.2 parts
It was applied to 1.0.

Next, samples 201 to 2 were prepared except that the first gelatin layer was replaced with the following antihalation layer containing black colloidal silver.
Samples 209 to 212 were prepared in the same manner as in 04.

First layer: Antihalation layer Black colloidal silver 0.18 / m ² UV absorber C-1 0.04 g / m ² UV absorber C-2 Gelatin layer containing 0.18 g / m ² HBS-2 0.09 g / m ² The back layer (the 16th layer) on the back side of the support
Samples 213 to 216 were prepared in the same manner as Samples 201 to 204, except that the first gelatin layer was replaced with the above antihalation layer.

Next, in Samples 209 to 212, instead of the black colloidal silver added to the first layer, the dye dispersion S-5 of the present invention was added in an amount of 0.22 g / m ² of VI-4 and the dispersion S-6 of the present invention was added. III-12 except that the amount of addition was added to a 0.23 g / m ² of the sample 209-2
Samples 217 to 220 were produced in the same manner as in 12.

Then, samples 221 to 224 were prepared in the same manner as samples 217 to 220 except that the back layer (the 16th layer) was applied to the back side of the support.
Was prepared.

Next, in Samples 217 to 220, the dispersion S-7 of the present invention was added in place of the yellow colloidal silver of the tenth layer (yellow filter layer) so that the addition amount of I-25 was 0.22 g / m ² . Except for the above, samples 225 to 228 were prepared in the same manner as samples 217 to 220.

Next, samples 229 to 2 were prepared in the same manner as samples 225 to 228, except that the back layer (the 16th layer) was applied to the back side of the support.
32 were produced.

Next, in Samples 217 to 220, the dispersion S-4 of the present invention was added so that the addition amount of I-28 was 0.24 g / m ² instead of the yellow colloidal silver of the tenth layer (yellow filter layer). Except for the above, Samples 233 to 236 were produced in the same manner as Samples 217 to 220.

Then, on the back side of the support, the above-mentioned back layer (16th layer)
237-240 in the same manner as Samples 133-136 except that
Was prepared.

Preparation Method of Fine Powder Dye Dispersion S-5 The dye was dispersed in a vibration ball mill by the following method.

Water (21.7 ml) and a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate (3 ml) and a 5% aqueous solution of p-octylphenoxy poly (degree of polymerization 10) oxyethylene ether (0.5 g) were placed in a 700 ml pot mill, and the mixture of the present invention was prepared. 1.00 g of dye (VI-4) and zirconium oxide beads (diameter 1
mm) was added and the contents were dispersed for 2 hours. The vibration ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion.

S-6 (dye III-12), S-7 (dye I-25) and S-4 (dye I-28) were prepared in the same manner.

Exposure to these samples for sensitometry (1/100 second)
And the following color development processing was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter.

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 201 was 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each 100.

The formulation of the processing liquid used in each processing step is as follows.

The MTF of the green-sensitive layer and the red-sensitive layer for evaluation of sharpness was measured.

MTF measurement is based on The Theory of Photographic Process
4th edd. Page 605 (Macmillan) was used. The exposure was performed by giving white light, and the magenta color density was measured with a green filter, and the cyan color density was measured with a red filter. For the green sensitive layer, the MTF values for the spatial frequencies of 10 cycles / mm and 40 cycles / mm at a magenta color density of 1.4 are shown as representative values in the low frequency region and the high frequency region, respectively. For the red sensitive layer, 10 cycles / mm at cyan color density of 1.0 and
The MTF values for a spatial frequency of 40 cycles / mm are shown as representative values in the low frequency region and the high frequency region, respectively. The larger the MTF value, the better.

The evaluation of fog by edge lighting (light piping) was performed as follows. Samples 201 to 216 above
Each was processed into a 35 mm patrone-packed form, and a 3 cm film was discharged outward from the patrone's mouth. The sample in the patrone form was placed under normal light room conditions for 8 hours, and the above treatment was performed.
The fogging density of the part where it entered was measured. (D ₁ ) As a reference, a fog density was measured by subjecting a completely dark room sample in which no part of the sample was exposed to a light room to the above-mentioned processing. (D ₂ ) and Δd = d ₁ −d ₂ was calculated as fog by edge lighting (light piping).

In the evaluation of the desilvering property, the amount of residual silver in the highest concentration (Dmax) portion of the processed sample subjected to the sensitometry was measured by X-ray fluorescence.

Summarizing the contents of samples 201 to 240 and the above test results,
The results are shown in Table 2-1.

From Table 2-1 it can be seen that the sample of the present invention has improved sharpness on the high frequency side with little loss of sharpness on the low frequency side as compared with the comparative example, and also has a good level of fogging due to edge lighting. Up to now, it is clear that the desilvering property has also been improved and that it has excellent performance.

Example 3 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and a sample 301 was prepared. The numbers represent the amount added per m ² .

First layer: Gelatin layer Gelatin 1.9 g U-1 0.40 g U-2 0.1 g U-3 0.1 g Oil-1 0.1 g Second layer: Middle layer Gelatin 0.40 g Cpd-D 10 mg Oil-3 40 mg Third layer: Intermediate layer Fogged fine-grain silver iodobromide emulsion (average particle size: 0.06μ, AgI content: 1 mol%) Silver amount: 0.05g Gelatin: 0.4g Fourth layer: low-sensitivity red-sensitive emulsion layer Sensitizing dyes S-1 and S Silver iodobromide emulsion I spectrally sensitized by -2 Silver content 0.4 g Gelatin 0.8 g Coupler C-1 0.20 g Coupler C-9 0.05 g Oil-1 0.1 cc Fifth layer: Medium-sensitivity red-sensitive emulsion layer Sensitizing dye Silver iodobromide emulsion spectrally sensitized by S-1 and S-2 II Silver amount 0.4g Gelatin 0.8g Coupler C-1 0.2g Coupler C-2 0.05g Coupler C-3 0.2g Oil-1 0.1cc 6 layers: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion III spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount 0.4g Gelatin 1.1g Coupler C-3 0.7g Coupler C-1 0.3g 7 layers: middle layer Latin 0.6g Dye D-1 0.02g Eighth layer: Intermediate layer Fogged silver iodobromide emulsion (average particle size 0.06μ, AgI content 0.3 mol%) Gelatin 1.0g Cpd-A 0.2g Ninth layer: Low sensitivity Green-sensitive emulsion layer Silver iodobromide emulsion I spectrally sensitized with sensitizing dyes S-3 and S-4 Silver amount 0.5 g Gelatin 0.5 g Coupler C-4 0.10 g Coupler C-7 0.10 g Coupler C-8 0.10 g Cpd-B 0.03 g Cpd-E 0.1 g Cpd-F 0.1 g Cpd-G 0.1 g Cpd-H 0.1 g 10th layer: middle-speed green-sensitive emulsion layer Spectral sensitized with sensitizing dyes S-3 and S-4 Silver iodobromide emulsion II Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Cpd-B 0.03 g Cpd-E 0.1 g Cpd-F 0.1 g Cpd-G 0.05 g Cpd-H 0.05 g 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 III Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.2g Coupler C-8 0.2g Cpd-B 0.08g Cpd-E 0.1 g Cpd-F 0.1 g Cpd-G 0.1 g Cpd-H 0.1 g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-2 0.05 g 13th layer: Yellow filter layer Yellow colloidal silver Silver content 0.1 g Gelatin 1.1 g Cpd- A 0.01 g Layer 14: Intermediate layer Gelatin 0.6 g Layer 15: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I sensitized with sensitizing dyes S-5 and S-6 Silver content 0.6 g Gelatin 0.8 g Coupler C-5 0.6g Sixteenth layer: Medium speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 Silver amount 0.4g Gelatin 0.9g Coupler C-5 0.3g Coupler C-6 0.3 g 17th layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 IV Silver amount 0.4 g Gelatin 1.2 g Coupler C-6 0.7 g 18th layer: 1st protective layer Gelatin 0.7g U-1 0.04g U-3 0.03g U-4 0.03g U-5 0.05g U-6 0.05g Cpd-C 0.8g Dye D-3 0.05g 19th layer : Second protective layer fogged fine particles Silver bromide emulsion (average particle size 0.06μ, AgI content 1 mol%) Silver amount 0.1g Gelatin 0.4g 20th layer: Third protective layer Gelatin 0.4g Polymethyl methacrylate (average particle size 1.5μ) 0.1g Methyl methacrylate 4: 6 copolymer of acrylic acid (average particle size 1.5μ) 0.1g Silicone oil 0.03g Surfactant W-1 0.3mg In addition to the above composition, gelatin hardener H-1 and coating agent And a surfactant for emulsification.

Oil-1 Dibutyl phthalate Oil-2 Tricresyl phosphate Cpd-C (same as S-2) Silver iodobromide emulsion I of the fourth, ninth, and thirteenth layers, the fifth layer,
The silver iodobromide II of the tenth and fifteenth layers and the silver iodobromide emulsion III of the sixth, eleventh and sixteenth layers were prepared as shown in Table 3-1.
Samples 301-304 were prepared using sulfur sensitized Em-1-12.

Next, a back layer (21st
Layer 30), except that Sample 30 was applied.
5-308 were prepared.

Layer 21 (back layer) Methyl methacrylate-methacrylic acid copolymer (copolymer molar ratio: 1: 1) 1.5 parts Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%, phthalyl 36 parts) 1.5 parts Acetone 50 parts Methanol 25 parts Methyl cellosolve 25 parts Colloidal carbon 1.2 parts
It was applied to 1.0.

Next, samples 301 to 3 were prepared except that the first gelatin layer was replaced with the following antihalation layer containing black colloidal silver.
Samples 309 to 312 were produced in the same manner as in 04.

First layer: Antihalation layer Black colloidal silver 0.25 g Gelatin 1.9 g U-1 0.04 g U-2 0.1 g U-3 0.1 g Oil-1 0.1 g Next, the above-mentioned back layer (21st layer)
Were coated in the same manner as Samples 301 to 304, except that the first gelatin layer was replaced with the above-mentioned antihalation layer.

Next, in Samples 309 to 312, the dye dispersion S-8 of the present invention was replaced with V-2 in place of the black colloidal silver added to the first layer.
Is 0.24 g / m ² , and the dye dispersion S-9 of the present invention is III-
Amount of 2 0.21 g / m ^2, the dye dispersion S-10 of the present invention III-3
Sample 3, except that the addition amount of 4 was added to a 0.23 g / m ²
Samples 317 to 320 were produced in the same manner as in 09 to 312.

Next, samples 321 to 324 were prepared in the same manner as samples 317 to 320 except that the back layer (the 21st layer) was coated on the back side of the support.
Was prepared.

Next, in Samples 317 to 320, the dispersion S-7 of the present invention was added in place of the yellow colloidal silver of the thirteenth layer (yellow filter layer) so that the addition amount of I-25 was 0.22 g / m ² . Except for the above, samples 325 to 328 were prepared in the same manner as samples 317 to 320.

Next, samples 329 to 329 were prepared in the same manner as samples 325 to 328, except that the back layer (the 21st layer) was applied to the back side of the support.
32 were produced.

Next, in Samples 317 to 320, the dispersion S-4 of the present invention was added so that the addition amount of I-28 became 0.24 g / m ² instead of the yellow colloidal silver of the 13th layer (yellow filter layer). Except for the above, Samples 333 to 336 were produced in the same manner as Samples 317 to 320.

Next, the back layer (the 21st layer) is formed on the back side of the support.
337-340 in the same manner as samples 333-336 except that
Was prepared.

Preparation Method of Fine Powder Dye Dispersion S-8 The dye was dispersed in a vibration ball mill by the following method.

Water (21.7 ml) and a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate (3 ml) and a 5% aqueous solution of p-octylphenoxy poly (degree of polymerization 10) oxyethylene ether (0.5 g) were placed in a 700 ml pot mill, and the mixture of the present invention was prepared. 1.00 g of the dye (V-2) and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. The vibration ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion.

S-9 (dye III-2) and S-10 (dye I
II-34), S-7 (dye I-25) and S-4 (dye I-28) were prepared.

Exposure to these samples for sensitometry (1/100 second)
And the following color development processing was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter.

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 301 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each set. Processing time Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ℃ 12l 2200ml / m ² First water washing 2〃 38〃 4〃 7500 〃 Inversion 2〃 38〃 4〃 1100100 Color development 6 発 38〃 12〃 2200 〃 Adjustment 1〃 38〃 4〃 1100 〃 Bleaching 3〃 38〃 12〃 220 〃 Fixed 3〃 38〃 8〃 1100 第二 Second flush 4〃 38〃 8〃 7500 〃Stable 1〃 25〃 2〃 1100 The composition of each treatment liquid was as follows.

First developer Reversal liquid Color developer Conditioning liquid Bleach Fixer Stabilizing liquid Evaluation of sharpness measured the MTF of the green sensitive layer and the red sensitive layer.

MTF measurement is based on The Theory of Photographic Process
4th edd. Page 605 (Macmillan) was used. The exposure was performed by giving white light, and the magenta color density was measured with a green filter, and the cyan color density was measured with a red filter. For the green sensitive layer, the MTF values for the spatial frequencies of 10 cycles / mm and 40 cycles / mm at a magenta color density of 1.9 are shown as representative values in the low frequency region and the high frequency region, respectively. For the red-sensitive layer, 10 cycles / mm at a cyan color density of 1.5 and
The MTF values for a spatial frequency of 40 cycles / mm are shown as representative values in the low frequency region and the high frequency region, respectively. The larger the MTF value, the better.

The evaluation of fogging by edge writing (light piping), which appears as a decrease in Dmax in reversal development as in this example, was performed as follows. Sample 301 above
~ 316 processed into 35mm patrone stuffed form,
A 3 cm film was taken out of the patrone's mouth. The sample in the patrone form was placed under normal light room conditions for 8 hours, and subjected to the above-described treatment, and the concentration of a portion Dmax of 20 cm into the patrone from the mouth of the patrone was measured. (D ₁ ) As a reference, a Dmax density was measured by performing the above-mentioned treatment on a completely dark room sample in which no part of the sample was exposed to a light room. (D ₂ ) and Δd = d ₁ −d ₂ was calculated as a decrease in Dmax of reversal development due to fogging by edge writing (light piping).

The desilvering property was evaluated by measuring the amount of residual silver in the maximum exposure portion of the processed sample subjected to the sensitometry as described above.
It was measured with a line.

Summarizing the contents of samples 301 to 340 and the above test results,
The results are shown in Table 3-1.

Table 3-1 shows that the sample of the present invention has improved sharpness on the high frequency side with little loss of sharpness on the low frequency side as compared with the comparative example, and has a Dmax of reversal development caused by fogging due to edge writing. It is clear that the desilvering property has also been improved while maintaining a good level of decrease in silver, and that it has excellent performance.

(Effect of the Invention) According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material in which the sharpness on the high frequency side is remarkably improved without deteriorating the sharpness on the low frequency side and the desilvering property is excellent.

Further, according to the present invention, fogging due to edge lighting is prevented despite the use of mainly tabular grains.

Claims (2)

(57) [Claims] 1. A color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, wherein all of the emulsion layers are used. At least 50% of the total projected area of all silver halide grains therein is occupied by tabular grains having an average aspect ratio of 3.0 or more, and at least one compound selected from the following formulas (I) to (V): A silver halide color photographic material having a hydrophilic colloid layer containing a microcrystal dispersion. General formula (I) General formula (II) General formula (III) A = L ₁ L ₂ = L _{3 n} A ′ General formula (IV) General formula (V) General formula (VI) (Wherein A and A ′ may be the same or different and represent a substituted or unsubstituted acidic nucleus having a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidophenyl group, a carboxyalkyl group, or a hydroxyphenyl group; The acidic nucleus is selected from the group consisting of 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine and hydroxypyridone. It is.
B represents a substituted or unsubstituted basic nucleus having a carboxyl group, a sulfamoyl group or a sulfonamide group, and the basic nucleus is selected from the group consisting of pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole. To be elected. R represents a hydrogen atom or an alkyl group; R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ are linked; A 5- or 6-membered ring may be formed. R ₃ and R ₆ represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ are each a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are connected Represents a group of non-metallic atoms necessary to form a 5- or 6-membered ring. Also B '
Represents a substituted or unsubstituted heterocyclic group having a carboxyl group, a sulfamoyl group or a sulfonamide group. L ₁ , L ₂ , and L ₃ each represent a substituted or unsubstituted methine group, X and Y each represent an electron-withdrawing group, and at least one carboxyphenyl group or sulfa It has a moylphenyl group, a sulfonamidophenyl group, a carboxyalkyl group or a hydroxyphenyl group. m
Represents 0 or 1, and n represents 0, 1 or 2. p represents 0 or 1. When p is 0, R ₃ represents a hydroxy group or a carboxy group, and R ₄ and R ₅ represent a hydrogen atom. ) 2. The silver halide color photographic light-sensitive material according to claim 1, further comprising a back layer containing carbon on the side of the support opposite to the emulsion layer side.