JPH05297518A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance, to improve desilverability, to enable a rapid processing, and to enhance storage stability by incorporating a specified compound. CONSTITUTION:The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer containing a compound to be allowed to release a bleach promoter by reaction with the oxidation product of an aromatic primary amine color developing agent and at least one of compounds represented by formulae I-III in which each of X1 and Y1 is cyano, carboxy, etc., and each may combine with each other to form a ring; each of L<1>, L<2>, and L<3> is a methine group; Ar is a heterocyclic group; n is 0, 1, or 2; Z is an atomic group necessary to form a 5- or 6-membered ring; each of R<1>, R<2>, R<4>, and R<5> is H or the like; R<3> is -NR<11>R<12> or the like; each of R<6>-R<9> is alkyl or the like or an atomic group necessary to combine with one another to form a 5- or 6-membered ring; Y is S or O or the like; and m is 0, 1, or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a dyed layer, containing a dye which is photochemically inert and is easily decolorized and / or eluted by photographic processing, The present invention relates to a silver halide color photographic light-sensitive material containing a compound capable of releasing a compound having a bleaching promoting action.

[0002]

2. Description of the Related Art Generally, a silver halide color photographic light-sensitive material is basically processed by a color development step and a desilvering step. In the color developing step, the exposed silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. The silver formed here is oxidized by a bleaching agent in the subsequent desilvering step, further converted into a soluble silver complex by the action of a fixing agent, and dissolved and removed. recent years,
In the industry, there is a strong demand for speeding up the processing, that is, reducing the time required for the processing, and in particular, shortening the desilvering process, which occupies almost half of the processing time, is a major issue.
As a method of increasing the bleaching power to shorten the desilvering process,
It has been proposed to add various bleaching accelerators to a bleaching bath, a bleach-fixing bath or their pre-baths. For example, JP-A-6
No. 3-88552, a method of adding a bleaching accelerator to a processing solution having a bleaching ability is known. However, these methods have a drawback that the bleaching accelerator is easily deactivated.

Further, a method is known in which a bleaching accelerator or a precursor thereof is present in a light-sensitive material and processed. However, when a bleaching accelerator is contained in a light-sensitive material, it has a great influence on photographic properties and the reason that the undeveloped portion of the silver halide in the light-sensitive material and the bleaching accelerator form a poorly soluble salt. However, this method also has many problems.
In contrast, Research Disclosure Item N
No. 24241, No. 11449 and JP-A-61-2.
No. 01247 uses a silver halide color photographic light-sensitive material containing a bleach accelerator releasing type coupler, and JP-A-2-93454 discloses compounds releasing a bleaching accelerator by a redox reaction. It is known that the desilvering property is improved by using the contained silver halide color photographic light-sensitive material.

On the other hand, a technique of incorporating a dye into a silver halide light-sensitive material for improving image quality or adjusting sensitivity has been conventionally practiced in the art. For example, photographic emulsion layers and / or other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range. When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, the filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. A coloring layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer for the purpose of preventing blurring or halation of an image based on the image. When there are a plurality of photographic emulsion layers, an antihalation layer may be placed between those layers. Coloring of the photographic emulsion layer is also carried out in order to prevent deterioration of image sharpness (usually called irradiation) due to light scattering in the photographic emulsion layer.

Recently, dyes for the purpose of substituting yellow colloidal silver (usually called Carey Lea Silver) in color photographic light-sensitive materials, dyeing dyes in crossover cut layers in X-photographic light-sensitive materials, and safe in printed photographic light-sensitive materials. The use thereof such as a dye for dyeing a non-photosensitive emulsion layer is widespread for light safety.

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

With a general so-called water-soluble dye, it is not possible to dye only a specific layer and the dye diffuses to all layers in the light-sensitive material, resulting in unnecessary reduction in sensitivity and silver halide. May have adverse effects. In order to prevent such dye diffusion, for example, a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in the layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. The method of localizing is disclosed in US Pat. Nos. 2,548,564, 4,124,386, and 3,625,694.

As a diffusion-resistant dye for dyeing a specific layer by using a water-insoluble dye solid, for example, European Patent No. 0252550B and US Pat. No. 4,420,555.
Issue No. 4,948,718 Issue No. 4,861,700
No. 61-205630, 61-20593.
No. 4, No. 62-56958, No. 62-222248.
No. 63-184749 and JP-A-3-63642.

With these diffusion-resistant dyes, it is possible to dye a specific layer and improve the above-mentioned drawbacks to some extent.
There is a problem that the decolorization and elution properties in the processing solution, which are important functions, are inferior, and the storage stability is insufficient and the sensitivity decreases over time, so new dyes are required. Was there.

To solve these problems, new dyes such as US Pat. No. 4,923,788 and JP-A-3-144438 have been proposed.
Heteroarylidene dyes described in Japanese Patent Application Nos. 3-163421 and 3-165171 are found. These dyes were improved in diffusion resistance and decolorization, but the storage stability was not sufficient.

As an attempt to prevent deterioration of storage stability when a bleaching accelerator is added to a light-sensitive material, JP-A-3-120532 describes a combination of a bleaching accelerator silver salt and a yellow filter dye. Further, a combination of a compound releasing a bleaching accelerator and a diffusion resistant / elution type dye is disclosed in JP-A-2-230140, and a combination of a compound releasing a bleaching accelerator and a microcrystalline dispersion of a specific dye is disclosed in JP-A-2-230140. It is described in JP-A-3-39954, and it is shown that improvement of desilvering property can greatly contribute to speeding up of processing, but none of them can prevent deterioration of storage stability due to a dye, and thus the conventional method cannot be used. In the technology, it was difficult to achieve both desilvering property and storage stability by combining a diffusion resistant / elution type dye and a compound that releases a bleaching accelerator.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility, good in desilvering property, capable of rapid processing, and excellent in storage stability. It is in.

[0014]

The above-mentioned problems can be solved in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support by the following general formula (I), (II) or ( At least one compound represented by III) is contained, and at least one compound capable of reacting with an oxidized product of an aromatic primary amine type color developing agent to release a residue of a compound having a bleaching promoting action is contained. And a silver halide color photographic light-sensitive material. General formula (I)

[0015]

[Chemical 4]

In the formula, X ₁ and X ₂ may be the same or different from each other, and are a cyano group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group,
It represents a sulfonyl group or a sulfamoyl group. Also,
X ₁ and X ₂ may be connected to each other to form a ring. L
¹ , L ² and L ³ each represent a methine group, Ar represents a heterocyclic group, and n represents 0, 1, or 2. General formula (II)

[0017]

[Chemical 5]

In the formula, Z represents an atomic group necessary for forming an optionally condensed 5- or 6-membered ring, and R ¹ , R ² , R
⁴ , R ⁵ are each a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group, a hydroxy group, a carboxy group, an amino group, a carbamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, and R ³ is —NR ¹¹ R
¹² , -OR ¹¹ and -SR ¹¹ are represented and L ¹ , L ² , L ³ and n are represented.
Each has the same meaning as described above, and R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group or an aryl group. General formula (III)

[0019]

[Chemical 6]

In the formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each an alkyl group, an aryl group, a hydrogen atom, or a group of atoms or a double atom necessary for each of them to form a 5- or 6-membered ring. Represents a bond, and Y represents S, O, N—R ¹³ , Se, CR ¹⁴ R ¹⁵
And L ¹ , L ² and Z have the same meanings as described above, and m
Represents 0, 1, 2 and R ¹⁰ , R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group.

Next, the general formulas (I), (II) and (III) will be described in detail. In the formula, X ₁ and X ₂ may be the same or different and each is a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl, dodecanoyl, Hexadecanoyl, 1-oxo-7
-Chloroheptyl group, etc., an arylcarbonyl group (an optionally substituted arylcarbonyl group, for example, benzoyl, 4-aminobenzoyl, 4-nitrobenzoyl, 4-methanesulfonylaminobenzoyl, 4-ethanesulfonylaminobenzoyl, 4 -Propanesulfonylaminobenzoyl, 4-trifluoromethanesulfonylaminobenzoyl, 4-trifluoroacetylaminobenzoyl, 4-trichloroacetylaminobenzoyl, 3-hydroxy-4-methanesulfonylaminobenzoyl, 3-methanesulfonylaminobenzoyl, 3-
Propanesulfonylaminobenzoyl, 2-methanesulfonylaminobenzoyl, 4-methoxybenzoyl, 3
-Nitrobenzoyl, 4-methylaminocarbonylaminobenzoyl, 4-ethylaminocarbonylaminobenzoyl, 4-ethoxycarbonylaminosulfonylaminobenzoyl, 4-methoxycarbonylaminosulfonylaminobenzoyl, 3-methylaminocarbonylaminobenzoyl, 4-methoxy- 3-Methanesulfonylaminobenzoyl, 4-ethoxy-3-methanesulfonylaminobenzoyl, 4- (2-hydroxyethoxy)-
2-hydroxybenzoyl, 3-chlorobenzoyl group and the like, alkoxycarbonyl group (alkoxycarbonyl group which may be substituted, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2
-Ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2- (2- Chloroethoxy)
Ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxy] ethoxycarbonyl group, etc., aryloxycarbonyl group (which may be substituted aryloxycarbonyl group, for example, phenoxycarbonyl, 3
-Ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-
Nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl) phenoxycarbonyl group and the like), carbamoyl group (which may be substituted, such as carbamoyl group, ethylcarbamoyl, 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- (dodecyloxycarbonyl) phenylcarbamoyl, 3- (hexyloxycarbonyl) phenylcarbamoyl group, etc.), sulfonyl group (eg, methylsulfonyl, decylsulfonyl, phenylsulfonyl group, etc.), sulfamoyl group (may be substituted) And a sulfamoyl group, for example, a sulfamoyl group or a methylsulfamoyl group).

The ring formed by combining X ₁ and X ₂ is preferably a 5- or 6-membered ring and has the same meaning as the 5- or 6-membered ring formed by Z. The 5-membered ring formed by X ₁ , X ₂ or Z is preferably pyrazolone, isoxazolone, furanone, imidazolone, oxazolone, indandione or oxazolidinedione. As a 6-membered ring, barbituric acid, thiobarbituric acid, 6-hydroxy-2-
Pyridone and the like are preferable.

The heterocyclic group represented by Ar is preferably a 5-membered heterocyclic ring, for example, pyrrole, indole, furan and thiophene are particularly preferable. Coumarin is preferred as the 6-membered heterocycle. The methine group represented by L ¹ , L ² and L ³ may have a substituent, but is preferably an unsubstituted methine group.

The halogen atom represented by R ¹ , R ² , R ⁴ and R ⁵ is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group represented by R ¹ , R ² , R ⁴ , and R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. Further, R ² and R ³ , R ⁴ and R ³ are combined to form 5 or 6
You may form a member ring. The alkoxy group represented by R ¹ , R ² , R ⁴ and R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms, and for example, methoxy, ethoxy, methoxycarbonylmethoxy, carboxymethoxy, 2-chloroethoxy and the like are preferable.

The amino group represented by R ¹ , R ² , R ⁴ and R ⁵ is preferably a dialkylamino group such as dimethylamino and diethylamino. The alkoxycarbonyl group represented by R ¹ , R ² , R ⁴ and R ⁵ is preferably an alkoxycarbonyl group having 2 to 8 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and hydroxyethoxycarbonyl. R
^The acylamino group represented by ¹ , R ² , R ⁴ and R ⁵ is preferably an acylamino group having 1 to 8 carbon atoms, and an acetylamino group, a propionylamino group, a trifluoroacetylamino group, a benzoylamino group or the like is preferable. R ¹ ,
The sulfonamide group represented by R ² , R ⁴ and R ⁵ is preferably a sulfonamide group having 1 to 10 carbon atoms, and is preferably methanesulfonamide, ethanesulfonamide, benzenesulfonamide or 3,5-bis (methoxycarbonyl) benzene. Sulfonamide and the like are preferable.

The alkyl group represented by R ¹¹ and R ¹² is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, hydroxyethyl, 2-chloroethyl,
Ethoxycarbonylethyl, ethoxycarbonylmethyl, cyanoethyl, methanesulfonamidoethyl are preferred. The aryl group represented by R ¹¹ and R ¹² is preferably an aryl group having 6 to 10 carbon atoms, for example, phenyl, 4-methylphenyl and 4-methoxyphenyl.

The alkyl group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. The aryl group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably a phenyl group.

The alkyl group represented by R ¹⁰ , R ¹³ , R ¹⁴ and R ¹⁵ is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, sulfonatopropyl, sulfonatobutyl, carboxymethyl, methanesulfonylcarbamoylmethyl. , 4-methylbenzenesulfonylcarbamoylmethyl is preferred. The compound represented by the general formula (I), (II) or (III) preferably has a group having a dissociative proton, for example, a sulfonamide group, a sulfamoyl group, a carbonimido group, an acylsulfamoyl group. Base,
A sulfonylcarbamoyl group, a sulfonimide group and a carboxy group are preferred. Next, general formulas (I), (II) and (III)
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

The bleach accelerator releasing compound used in the present invention is
Preferably, it can be represented by the following general formula (B).

General formula (B) A- (L ₁ ) _k -Z A represents a group which cleaves (L ₁ ) _k -Z by reacting with an oxidized product of a developing agent, and L ₁ is a bond with A. Represents a group that cleaves Z, then k represents 0 or 1 and Z represents a bleaching accelerator.

Next, the general formula (B) will be described.

In the general formula (B), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (eg 5-pyrazolone type, pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
No. 4,001, such as a pyrazolopyrimidine type coupler residue) and a colorless coupler residue (for example, an indanone type or acetophenone type coupler residue). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-2.
30135, 62-251746, 61-27.
8852, U.S. Pat. Nos. 3,364,022 and 3,
379,529, 3,639,417, 4,6
84,604 or J.Org.Chem., 29,588 (1
964).

In the general formula (B), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A of the compound represented by the general formula (B), and the ** mark represents the position of bonding with Z. Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ are a hydrogen atom Or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups represented by the following "Chemical formula 23" to "Chemical formula 25".

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, * and ** have the same meanings as described for general formula (T-1), and Nu represents a nucleophilic group. Represents an example of a nucleophilic species such as an oxygen atom or a sulfur atom, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu to cleave the bond with the ** mark, and Link represents that Nu and E are Represents a linking group that is sterically related so that it can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) include those represented by the following "Chemical formula 26" and "Chemical formula 27".

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
9737, 58-209738, etc.,
It is a group represented by the general formula (T-3) represented by the following "Chemical Formula 28".

[0059]

[Chemical 28]

In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). However, R ₁₁ and R ₁₂ may bond to each other to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Also, t represents 1 or 2,
t is two in the case of 2 - _{[Z 1 (R 11) x =} Z 2 (R 12) y ]
The-may be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

[Chemical formula 29] to [Chemical formula 32] below (T-
Specific examples of 3) will be given.

[0062]

[Chemical 29]

[0063]

[Chemical 30]

[0064]

[Chemical 31]

[0065]

[Chemical 32]

(4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, the following groups are the linking groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General Formula (T-4) * -OCO-** General Formula (T-5) * -SCS-** (5) Group Utilizing Cleavage Reaction of Iminoketal For example, described in U.S. Pat. No. 4,546,073. It is a certain linking group, and is represented by the general formula (T-
It is a group represented by 6).

[0067]

[Chemical 33]

In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R ₁₄ is R
It has the same meaning as ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following "Chemical Formula 34".

[0069]

[Chemical 34]

(6) A compound that becomes a coupler residue or a redox group after being cleaved from A. For example, JP-A-63-21
No. 4752 represented by B in the general formula (I), more preferably a redox group. In the general formula (B), L ₁ is preferably (T-1) to (T-5).
And particularly preferably (T-1) (T
-3) and (T-4).

As the group represented by Z in the general formula (B), specifically known bleaching accelerator groups can be mentioned. For example, U.S. Pat. No. 3,893,858, British Patent No. 1138842, JP-A-53-141623.
Various mercapto compounds as described in Japanese Patent Publication No.
Compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854
Thiazolidine derivatives as described in JP-B No. 53-94927, isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506, and JP-B-4.
9-26586, a thiourea derivative as described in JP-A-49-42349, a thioamide compound as described in JP-A-55-26506, and a dithiocarbamate salt as described in JP-A-55-26506. An arylenediamine compound as described in US Pat. No. 4,552,834. These compounds have a substitutable heteroatom contained in the molecule,
It is a preferred example to bond with A- (L ₁ ) _k- in the general formula (B).

The group represented by Z is preferably a group represented by the following general formula (V), (VI) or (VII).

[0073]

[Chemical 35]

In the formula, the asterisk * represents the position at which it bonds to A- (L ₁ ) _k- , R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and R ₃₂ represents A group having the same meaning as R ₃₁ ,
Represents a divalent aromatic group having 6 to 10 carbon atoms or a divalent heterocyclic group having a 3- to 8-membered ring, preferably a 5- or 6-membered ring, and X ₁ represents -O-, -S-,-. COO-, -SO _{2
-, - NR 33 -, -} NR 33 -CO -, - NR 33 -SO 2
-, -S-CO-, -CO-, -NR ₃₃ -COO-,-
_{N = CR 33 -, - NR} 33 CO-NR 34 -, or -NR
₃₃ SO ₂ NR ₃₄ — group, X ₂ represents an aromatic group having 6 to 10 carbon atoms, X ₃ is a 3-membered to 8-membered ring having at least one carbon atom bonded to S in the ring. And preferably represents a 5- or 6-membered heterocyclic group, Y ₁ is a carboxyl group or a salt thereof, a sulfo group or a salt thereof,
A hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (which may be substituted with an aliphatic group having 1 to 4 carbon atoms),-
NHSO ₂ —R ₃₅ or —SO ₂ NH—R ₃₅ group (salt means sodium salt, potassium salt, ammonium salt or the like), and Y ₂ has the same meaning as described for Y _1. Alternatively, it represents a hydrogen atom, r represents 0 or 1, i represents an integer of 0 to 4, j represents an integer of 1 to 4, and k represents an integer of 0 to 4. However, j Y ₁ is R ₃₁ − {(X ₁ ) _r −R ₃₂ } _i
And X ₂ -{(X ₁ ) _r −R ₃₂ } _i are bonded at substitutable positions, and k Y ₁ are X ₃ − {(X ₁ ) _r −R ₃₂ }.
_When bonded to a substitutable position of _i , when k and j are plural, k and j Y ₁ 's each represent the same or different, and when i is plural, i (X ₁ ) _r- R ₃₂ Represents the same or different. Where R ₃₃ and R ₃₄
And R ₃₅ each represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R ₃₁ to R ₃₅ represent an aliphatic group, they may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Although it is preferably unsubstituted, examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy), and an alkylthio group (eg, methylthio, ethylthio).

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. Examples of the substituent include those enumerated as the aliphatic group substituents.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₃₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. For example, pyridine, imidazole, piperidine, oxirane,
Mention may be made of sulfolane, imidazolidine, thiazepine or pyrazole. Examples of the substituent include those enumerated above as the aliphatic group substituents.

Specific examples of the group represented by the general formula (V) include the following.

[0078]

[Chemical 36]

[0079]

[Chemical 37]

Specific examples of the group represented by the general formula (VI) include the followings.

[0081]

[Chemical 38]

Specific examples of the group represented by the general formula (VII) include the followings.

[0083]

[Chemical Formula 39]

[0084]

[Chemical 40]

Next, specific examples of the bleaching accelerator-releasing compound preferably used in the present invention will be given, but the present invention is not limited thereto.

[0086]

[Chemical 41]

[0087]

[Chemical 42]

[0088]

[Chemical 43]

[0089]

[Chemical 44]

[0090]

[Chemical 45]

[0091]

[Chemical 46]

[0092]

[Chemical 47]

[0093]

[Chemical 48]

[0094]

[Chemical 49]

[0095]

[Chemical 50]

[0096]

[Chemical 51]

[0097]

[Chemical 52]

Others, Research Disclosure I
tem Nos. 24241 and 11449, JP-A-61-
201247, 63-106749, 63-121843, 63-121844, 63-1474752 and 2-93.
The compounds described in Japanese Patent No. 454 are also used in the same manner.

Further, the bleaching accelerator releasing compound used in the present invention can be easily synthesized based on the description in the above patent specification.

The amount of the compound of the general formula (B) added varies depending on the structure of the compound, but is preferably 1 × 10 ⁻⁵ to 1 mol, and particularly preferably 1 × 10 ⁵ mol per mol of silver present in the same layer or adjacent layers. ^-4 to 0.5 mol.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There are no particular restrictions on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
It is also possible to arrange the layers in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- It is preferable to dispose the donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification of 89850 adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(Nov. 1979), p. 648, ibid. No. 307105 (Nov. 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, PhotographicScience by Gatov.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the methods described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be mixed and used in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. No. 4,626,498, JP-A-59-214852, the inside of which is covered with a silver halide grain, and a colloidal silver is a photosensitive halogenated photosensitive grain. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in U.S. Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or number of silver halide grains is within ± 40% of the average grain size) It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles in the projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 page 5.fogging prevention page 24 ~ 25 page 649 page right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 page left columns 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitors 14. matting agents, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. .. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. The light-sensitive material of the present invention has the general formula (I) to
In addition to the dye represented by (III), WO88 / 04794, dyes dispersed by the method described in International Publication No. 1-502912 or EP 317,308A, U.S. Pat. twenty five
The dye described in No. 9358 can also be incorporated. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-71.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Those described in 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A 64-554, 64-555 and 64-556, and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
No., British Patent No. 1,146,368, JP-A-1-319744, 3-1.
Those described in 77836, 3-177837, and European Patent No. 423,727A are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181, and US Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in No. 77,120. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is disclosed in the above-mentioned RD 17643, VII-F and the patents described in Nos. 307105 and VII-F, JP-A-57-151944 and 57-154234.
Nos. 60-184248, 63-37346, 63-37350, and US Pat. Nos. 4,248,962 and 4,782,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and JP-A-59-170.
Those described in No. 840 are preferable. In addition, JP-A-60-10702
No. 9, No. 60-252340, JP-A No. 1-49440, No. 1-45687
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate). (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azetase Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 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 are, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 2, No. 2, pages 124 to 129 can be measured using a swellometer (swelling meter), and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after 3 minutes and 15 seconds of treatment is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 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-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers include alkali metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover 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 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration.

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodide salt described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, circulation of the entire processing solution There is a method of increasing the flow rate. 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society edited by "The Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline-based compounds described in U.S. Pat. Metal salt complexes described, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various types of 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl-3-phenyl-3-phenyl-3- (phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-fluoro-3-bromo-3-chloro-3-bromo-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-phenyl-3-phenyl-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-bromo-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-chloro-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo 3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3- did lead;
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

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

[0121]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. EXAMPLE On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The materials used for each layer are classified as follows: ExC: Cyan coupler HBS: High boiling point organic solvent ExM: Magenta coupler ExO: Color mixture inhibitor ExY: Yellow coupler W: Surfactant ExS: Sensitizing dye H: Gelatin hardening agent ExU: Ultraviolet absorber B: Polymer S: Formalin scavenger or antifoggant F: Additive (stabilizer, antifoggant, etc.) The number corresponding to each component is g / m ² unit The coating amount represented by is shown, and for silver halide, the coating amount in terms of silver is shown. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.145 Gelatin 1.2 ExM-1 2.2 × 10 ^-2 HSB-1 3.3 × 10 ^-2

[0123]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion B Silver 0.25 Emulsion D Silver 0.175 ExS-3 1.5 × 10 ^-4 ExS-4 1.8 × 10 ^-5 ExS-5 2.5 × 10 ^-4 ExC-2 0.020 ExC-3 0.17 ExC-4 0.17 ExC-5 0.020 ExM-3 0.020 ExU-1 0.070 ExU-2 0.050 ExU-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.80 ExS-3 1.0 × 10 ^-4 ExS-4 1.4 × 10 ^-5 ExS-5 2.0 × 10 ^-4 ExC-1 0.010 ExC-2 0.010 ExC-3 0.050 ExC-4 0.050 ExC-6 0.080 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.5 ExS-3 1.0 × 10 ^-4 ExS-4 1.4 × 10 ^-5 ExS-5 2.0 × 10 ^-4 ExC-1 0.050 ExC-2 0.015 ExC-3 0.20 ExC-4 0.20 ExC-7 0.20 ExC-8 0.020 ExU-1 0.070 ExU-2 0.050 ExU-3 0.070 HBS-1 0.22 HBS-2 0.10 Gelatin 1.6

6th layer (intermediate layer) ExO-1 0.040 ExM-4 0.050 HBS-1 0.020 Gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion B Silver 0.20 Emulsion D Silver 0.15 Emulsion A Silver 0.05 ExS-2 5.0 × 10 ^-5 ExS-6 3.0 × 10 ^-5 ExS-7 1.0 × 10 ^-4 ExS-8 3.8 × 10 ^-4 ExM-1 0.021 ExM-3 0.030 ExM-5 0.20 ExM-6 0.0050 ExM-7 0.10 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth layer (intermediate layer) ExM-4 0.018 ExC-8 0.040 HBS-1 0.16 HBS-3 0.0080 Gelatin 0.50

9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.84 ExS-2 0.50 × 10 ^-5 ExS-6 3.5 × 10 ^-5 ExS-7 8.0 × 10 ^-5 ExS-8 3.0 × 10 ^-4 ExM-3 0.025 ExM-8 0.015 ExM-9 0.50 ExY-1 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.5

10th layer (intermediate layer) ExO-1 0.040 HBS-1 0.020 Gelatin 0.80

Eleventh layer (donor layer having a multilayer effect on the red-sensitive layer) Emulsion A Silver 1.2 Emulsion E Silver 1.4 ExS-2 4.0 × 10 ^-4 ExC-2 0.10 ExM-2 0.10 HBS-1 0.10 HBS-2 0.10 Gelatin 0.80

12th layer (yellow filter layer) Yellow colloidal silver Silver 0.085 ExO-1 0.080 HBS-1 0.030 Gelatin 0.95

13th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion B Silver 0.080 Emulsion D Silver 0.050 Emulsion F Silver 0.070 ExS-9 3.5 × 10 ^-4 ExC-3 0.042 ExY-2 0.72 ExY-3 0.020 HBS-1 0.28 Gelatin 1.1

14th layer (medium-speed blue-sensitive emulsion layer) Emulsion A Silver 0.18 ExS-9 2.1 × 10 ^-4 ExY-2 0.15 ExC-2 0.0070 HBS-1 0.050 Gelatin 0.78

Fifteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion E Silver 0.23 ExS-9 2.2 × 10 ^-4 ExY-1 0.010 ExY-2 0.60 ExY-3 0.010 HBS-1 0.070 Gelatin 0.69

Sixteenth Layer (Protective Layer) Emulsion G Silver 0.50 ExU-4 0.11 ExU-5 0.17 HBS-1 0.050 W-1 0.020 H-1 0.40 B-1 (diameter about 1.5 μm) 0.10 B-2 (diameter about) 1.5 μm) 0.10 B-3 0.020 S-1 0.20 Gelatin 1.8

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (200 ppm average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore W
-2, W-3, B-4 to B-6, F-1 to F-
17, containing iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt.

[0139]

[Table 1]

In Table 1, (1) Emulsions F and G were prepared according to the examples of JP-A-2-91938.
It was reduction sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions F and G were prepared according to the examples of Japanese Patent Application No. 2-34090.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0141]

[Chemical 53]

[0142]

[Chemical 54]

[0143]

[Chemical 55]

[0144]

[Chemical 56]

[0145]

[Chemical 57]

[0146]

[Chemical 58]

[0147]

[Chemical 59]

[0148]

[Chemical 60]

[0149]

[Chemical formula 61]

[0150]

[Chemical formula 62]

[0151]

[Chemical 63]

[0152]

[Chemical 64]

[0153]

[Chemical 65]

[0154]

[Chemical 66]

[0155]

[Chemical 67]

[0156]

[Chemical 68]

(Preparation of Emulsion A) Lime-treated gelatin 1
Water (100 cc) is added to 2.3 g, and the mixture is swollen for 1 hour and dissolved by heating at 50 ° C. to prepare a hydrocolloid solution (solution I). Next, comparative compound A (comparative dye) 0.66 g (1.13 × 10 ⁻³
Mol), 1.0 ml of a high boiling organic solvent (HSB-1) and 0.07 g of a surfactant (W-4), and 15 ml of ethyl acetate.
Is added and dissolved by heating at 70 ° C. to prepare an organic compound solution (solution II). The above liquids I and II are added and mixed, and emulsified and dispersed for 5 minutes by a high-speed rotating homogenizer (rotation speed 15,000 rpm), and the dispersion is designated as emulsion A.

(Preparation of Emulsions B to D) The comparative compound A of the emulsion A was replaced by the following comparative compound B, dyes I-10 and II of the present invention.
Emulsions B to E were prepared in the same manner as Emulsion A, except that -7 and III-2 were replaced by equal weights. The structural formulas of the comparative compound and the surfactant used for emulsion preparation are shown below.

[0159]

[Chemical 69]

(Production of Samples 102 to 104) Sample 101
Compound B-27 0.97 g / m ² , B-32 0.10 g represented by the general formula (B) except for ExC-6 in the fourth layer of
/ Other turned into m ^2, in the same manner as Sample 101 Sample 10
2, 103 were produced. A sample 104 was prepared in exactly the same manner as the sample 101 except that the compound B-26 represented by the general formula (B) was added to the sixth layer of the sample 101 at 0.09 g / m ² .

(Production of Samples 201 to 205) Sample 101
The yellow colloidal silver contained in the 12th layer of
The coating amount of the dye contained in each emulsion is 1.
Samples 201 to 205 were prepared in the same manner as the sample 101, except that the amount was replaced so as to be 2 × 10 ⁻⁴ mol / m ² .

(Production of Samples 301 to 305) Sample 102
The yellow colloidal silver contained in the 12th layer of
The coating amount of the dye contained in each emulsion is 1.
Sample 1 except that it was replaced by 2 × 10 ^-4 mol / m ²
Samples 301 and 303 were prepared in the same manner as 02. In exactly the same manner, the yellow colloidal silver of the twelfth layer of Sample 103 was emulsified with B,
Samples 302 and 304 replaced with D, and sample 104
Sample 305 in which the yellow colloidal silver of the twelfth layer was replaced with Emulsion E was prepared. Sample 1 produced as described above
A list of compounds of the general formula (B) of the fourth or sixth layer and dyes of the twelfth layer contained in 01 to 305 is shown in Table 2.

After subjecting the above samples 101 to 305 to white imagewise exposure, an automatic developing machine was used and the following method was used (until the cumulative replenishment amount of the developing solution became three times the tank volume).
The image density obtained by processing was measured. Table 2 shows the relative sensitivity of the green-sensitive layer based on the magenta image density.

Further, the above samples 101 to 305 were treated at 50 ° C. and 80 ° C.
The change in photographic characteristics after aging for 3 days under the condition of temperature and humidity is shown in Table 3 as the relative sensitivity of the blue sensitive layer from the yellow image density.

Further, as the desilvering properties of Samples 101 to 305, white uniform exposure of 20 CMS was applied to Samples 101 to 305, the same developing treatment as above was carried out, and the measured residual silver amount is shown in Table 3.

(Treatment Method) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 20 liters Bleach 3 minutes 00 seconds 38 ° C 25 ml 40 liters Water wash 30 seconds 24 ° C 1200 ml 20 liters Settlement 3 minutes 00 seconds 38 ° C 25 ml 30 liters Washing with water (1) 30 seconds 24 ° C From (2) to (1) 10 liter countercurrent piping system Washing with water (2) 30 seconds 24 ° C 1200 ml 10 liters Constant 30 seconds 38 ℃ 25 ml 10 liter Dry 4 minutes 20 s 55 ℃ Replenishment amount is 35 mm width 1 m per length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2 -Methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric acid trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1 , 2,4-Triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Water was added 1.0 liter 1. 0 liter pH 6.0 5.7

(Fixer) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320.0 ml water 1.0 liter 1.0 liter pH 6.7 7.0

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

[0171]

[Table 2]

The results shown in Table 2 show that the combination of the dye of the present invention with a compound which releases a bleaching accelerator exhibits an unexpected effect on the storage stability. It is possible to provide a light-sensitive material having improved properties and at the same time improved storage stability.

Claims (1)

[Claims] 1. At least one photosensitive halo on a support.
Silver halide color photographic light-sensitive material having silver genide emulsion layer
Is represented by the following general formula (I), (II) or (III)
An aromatic primary amine containing at least one compound
Reacts with the oxidant of the color developing agent to accelerate bleaching.
Containing a compound capable of releasing a residue of a compound having
Characteristic silver halide color photographic light-sensitive material. General formula (I):In the formula, X₁, X₂Can be the same or different from each other
A cyano group, a carboxy group, an alkylcarbonyl group,
Arylcarbonyl group, alkoxycarbonyl group, ant
Oxycarbonyl group, carbamoyl group, sulfonyl
Group represents a sulfamoyl group. Also, X₁, X₂Are mutual
They may be linked to each other to form a ring. L¹, L², L³
Each represents a methine group, Ar represents a heterocyclic group, and n represents
Represents 0, 1, 2. General formula (II)In the formula, Z forms an optionally condensed 5- or 6-membered ring.
Represents the atomic group necessary for¹, R², R^Four, R^FiveIs each
Hydrogen atom, halogen atom, alkyl group, alkoxy
Group, hydroxy group, carboxy group, amino group, carbamo
Group, alkoxycarbonyl group, acylamino group,
Represents a ruhonamide group, R³Is -NR¹¹R ¹², -O
R¹¹, -SR¹¹Represents L¹, L², L³, N are each before
R has the same meaning as¹¹, R¹²Are hydrogen atom,
It represents an alkyl group or an aryl group. General formula (III):R in the formula⁶, R⁷, R⁸, R⁹Are alkyl and aryl
Group, hydrogen atom, or each bonded to 5 to 6
Represents a group of atoms or double bonds necessary to form a member ring
Y is S, O, N-R¹³, Se, CR¹⁴R¹⁵Represents
L¹, L², Z has the same meaning as described above, m is 0,
Represents 1, 2 and R^Ten, R¹³, R¹⁴, R¹⁵Is an alkyl group
Represent