JPH0469774B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material that can be rapidly processed in a color development step and a bleach-fixing step. Regarding the processing method. In general, silver halide color photographic light-sensitive materials have three types of silver halide photographic emulsion layers coated on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. has been done. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb blue light transmitted through the blue-sensitive emulsion layer. Furthermore, each emulsion layer has
For various special purposes, other intermediate layers and a protective layer are provided as the outermost layer. Also,
For example, in light-sensitive materials for color photographic paper, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in this order from the exposed side, and each layer has a specific purpose, just as in light-sensitive materials for color negatives. Intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent.
A dye image is formed by the reaction of the resulting oxidation product of the color developing agent with the dye-forming coupler.
In this method, cyan couplers of phenolic or naphthol type, 5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indazolone or cyanoacetyl are used to form cyan, magenta and yellow dye images, respectively. Magenta couplers and acylacetamide-based or benzoylmethane-based yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. The present invention relates to a method for processing a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive. Incidentally, in recent years, various measures have been taken to quickly perform color development. As one method, it is known to use a color development accelerator when developing an exposed silver halide color photographic light-sensitive material using an aromatic primary amine color developing agent. For example, as such a color development accelerator, US Pat. No. 2,950,970;
No. 2515147, No. 2496903, No. 4038075, No.
4119462, British Patent No. 1430998, British Patent No. 1455413,
JP-A No. 53-15831, No. 55-62450, No. 55-
No. 62451, No. 55-62452, No. 55-62453, No. 51
Compounds described in Japanese Patent Publication No. 12422, Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-49728, etc. have been investigated, but most of these compounds have insufficient development accelerating effect;
Further, even among these compounds, even those which sufficiently exhibit a development accelerating effect have the drawback of often producing fog, and are therefore impractical. Furthermore, JP-A-56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-144547 and JP-A-58-50532. No. 58-
No. 50533, No. 58-50534, No. 58-50535, No. 58
No. 50536 discloses that 1-arylpyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short development time. However, the techniques described in these publications are not necessarily satisfactory in terms of obtaining dye images with sufficient color development speed and high color density, and there is still room for improvement. . In addition, various penetrants have been studied to promote the penetration of color developing agents into silver halide photosensitive materials, and among these, a method of accelerating color development by adding benzyl alcohol to a color developer is widely used. It is being However, this method has some drawbacks in terms of rapid processing because, for example, at a processing temperature of 33° C., a sufficiently high color density cannot be obtained unless the processing is carried out for 3 minutes or more. In addition to the processing concentration, a method of color development has been proposed by increasing the pH concentration of the color developer, but for example, if the pH is increased to 10.5 or higher, the oxidation of the color developer will be significantly accelerated, or Because there is no buffer solution, the color developing agent is susceptible to PH changes, which makes it difficult to obtain stable photographic performance and increases the dependence on processing time. On the other hand, in order to speed up color development, a method is also known in which a color developing agent is incorporated into a light-sensitive material in advance, as described in, for example, US Pat. No. 3,719,492. However, this method has the drawback that the raw storage stability of the silver halide color photographic light-sensitive material is poor, and fog is likely to occur before use, and furthermore, fog is likely to occur during color development processing. Furthermore, in order to inactivate the amine moiety of a color developing agent, there is a method of incorporating the color developing agent into, for example, a Schiff salt, as disclosed in US Pat.
No. 3342559, Research Disclosure,
Described in No. 15159 of 1976. However, in these methods, color development does not start until after the color developing agent has been alkaline hydrolyzed, so that the color development is rather delayed. Furthermore, it is known that development can be accelerated by lowering the silver bromine content and increasing the silver chloride content of the silver halide used, but even with this, it is difficult to obtain the required sensitivity. . OBJECTS OF THE INVENTION An object of the present invention is to provide a method for processing silver halide color photographic materials, which enables rapid processing in the color development step and bleach-fixing step, and which provides high color density. Specific Structure of the Invention The above object of the present invention is to contain at least one compound represented by the following general formula [] and at least one compound represented by the following general formula [] in a photographic constituent layer on a support. In a method in which a silver halide color photographic light-sensitive material is imagewise exposed and then processed using a color developing solution and a bleach-fixing solution, the processing time of the color developing step and the bleach-fixing step are each 90 minutes.
This is achieved by a method for processing silver halide color photographic materials in which the processing time of the bleach-fixing step is 80% or less of the processing time of the color development step. General formula [] [In the formula, X represents a hydrogen atom or an acetyl group, R ₁ represents an aryl group, and R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group. ] General formula [ ] [In the formula, Y represents a halogen atom, R ₆ represents a halogen atom or a monovalent organic group, R ₇ represents a ballast group, and Z represents a hydrogen atom or It represents a removable group, and n represents an integer from 0 to 4. ] The present invention will be explained in more detail below. In the compound represented by the general formula [] of the present invention, X is preferably a hydrogen atom. Examples of the aryl group represented by R ₁ in the general formula [] include phenyl group, naphthyl group, etc., but phenyl group is preferable. This aryl group may have a substituent. Examples of substituents include alkyl groups (such as methyl groups,
ethyl group, propyl group, etc.), halogen atom (chlorine atom, bromine atom, etc.), alkoxy group (methoxy group,
(ethoxy group, putoxy group, etc.), sulfonyl group, amide group (methylamide group, ethylamide group, etc.). Among these substituents, a methyl group is preferred. These substituents are
For example, when the aryl group represented by R ₁ is a phenyl group, it can have one or more aryl groups and can have it at any position, but is preferably at the 4-position. The alkyl group represented by R ₂ , R ₃ , R ₄ and R ₅ in the general formula [] preferably includes an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.) . This alkyl group can have substituents. Examples of the substituent include a hydroxyl group, an amino group, and an acyloxy group. Among these substituents, preferred is an acyloxy group. Also, R ₂ , R ₃ ,
Examples of the aryl group represented by R ₄ and R ₅ include a phenyl group and a naphthyl group, with a phenyl group being preferred. This aryl group may have one or more substituents at any position, and examples of the substituent include an alkyl group (methyl group, ethyl group, propyl group, etc.), a halogen atom (chlorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, etc.), and a hydroxyl group. In the present invention, among R ₂ , R ₃ , R ₄ and R ₅ , an alkyl group having an aryl group or an acyloxy group as a substituent is preferable, and an aryl group is more preferably a phenyl group. This is the case. Particularly preferred is R ₂
or a compound in which R ₃ is a phenyl group, R ₄ or
This is a compound in which R ₅ is an alkyl group having an acyloxy group as a substituent. Typical specific examples of the compound represented by the general formula [] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

The silver halide color photographic light-sensitive material according to the present invention contains the compound represented by the above general formula [], and the layer containing this compound may be any layer of the photographic constituent layers on the support. The term "photographic constituent layers" as used herein refers to photosensitive silver halide emulsion layers and non-photosensitive layers such as interlayers, subbing layers, and protective layers. In order to add the compound represented by the general formula [] of the present invention to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, it can be directly dispersed in a hydrophilic colloid solution forming the photographic constituent layer, or For example, it may be added to the hydrophilic colloid solution after being dissolved in one or a mixture of two or more suitable solvents such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, and ethyl acetate. Alternatively, after dissolving in one or a mixed solvent of two or more high boiling point organic solvents such as dibutyl phthalate, dioctyl phthalate, dimethyl phthalate, tri-0-cresyl phosphate, trioctyl phosphate, etc., hydrophilic colloids can be prepared. It may be emulsified and dispersed in a solution. Furthermore, when the photographic constituent layer is a photosensitive silver halide emulsion layer, this compound can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution. The compound represented by the general formula [] of the present invention may be added to the coating solution at any time as long as the compound is added to the light-sensitive silver halide emulsion layer after the preparation of the light-sensitive silver halide emulsion. The period is fine. When the photosensitive silver halide emulsion is a surface latent image type emulsion that mainly forms a latent image on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. Further, when the photosensitive silver halide emulsion is an internal latent image type emulsion that mainly forms latent images inside the grains, it may be carried out at any time after the silver halide emulsion has been prepared and optically sensitized. Further, when the photographic constituent layer is a non-photosensitive layer, it may be added at any time before the non-photosensitive layer is coated, but it is preferably added immediately before coating. Compounds represented by the general formula [] are commercially available, but US Pat. No. 2,688,024,
No. 2704762, JP-A-56-64339 and JP-A-58-
It can be synthesized according to No. 50535 etc. The compound represented by the general formula [] of the present invention is
It can be added to the photographic constituent layers of the photosensitive silver halide emulsion layer and/or the non-photosensitive layer. When added to a photosensitive silver halide emulsion layer, it may be added to any of the blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers. In this case, it may be added to each of these layers, or even only to one layer. When the compound represented by the general formula [] of the present invention is added to the non-photosensitive layer, it may be added to any of the undercoat layer, intermediate layer, or protective layer, but
Generally, it is preferable to add it to the undercoat layer or the lowest layer in contact with the undercoat layer. When the compound represented by the general formula [] of the present invention is added to a photosensitive silver halide emulsion layer, the amount of addition is from 0.001 mol to 1 mol per mol of silver halide.
It is in the molar range, preferably in the range of 0.005 to 0.5 molar. When the above compound is added to two or more photosensitive silver halide emulsion layers, the amount added is 0.001.
It ranges from mol to 1 mol, preferably from 0.005 to 1 mol.
It is in the range of 0.5 mole. When the compound represented by the general formula [] of the present invention is added to the non-photosensitive layer, the amount of the compound added is generally 1 mg to 1000 mg ^per square meter, preferably 5 mg to 200 mg. When the compound is added to both the photosensitive silver halide emulsion layer and the non-photosensitive layer, the amount of the compound added is from 0.001 mol per mol of silver halide in the photosensitive silver halide emulsion layer to which it is added. 1 mole, preferably 0.005 mole to 0.5
From 1 mg per m ² of non-photosensitive layer added in moles
1000mg, preferably 5mg to 200mg. In the present invention, the cyan coupler used in the silver halide color photographic light-sensitive material is a cyan coupler having an acylamino group at the 2- and 5-positions as shown by the general formula [], but preferably the 4-position is a cyan coupler for color development. So-called 2-equivalent cyan couplers, which have a group that can be eliminated during the coupling reaction with the oxidation product of the main ingredient, are advantageous in terms of color development and other aspects. In the general formula [], Y represents a halogen atom, such as fluorine, chlorine, bromine, iodine, etc., preferably fluorine, chlorine, or bromine. Further, R ₆ represents a halogen atom or a monovalent organic group, and examples of the halogen atom include chlorine, bromine, and fluorine atoms. In addition, monovalent organic groups include nitro group, amino group,
Cyano group, hydroxy group, carboxy group, alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, octyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group) etc.), alkoxy groups (e.g. methoxy, ethoxy, benzyloxy, etc.), aryloxy groups (e.g. phenoxy,
p-nitrophenoxy, etc.), acylamino groups (e.g. acetylamino group, propionylamino group,
benzoylamino group, phenoxyacetylamino group, etc.), carbamoyl group (e.g. methylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, diphenylcarbamoyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, butanesulfonamide group) group, benzenesulfonamide group, p-toluenesulfonamide group, etc.),
Sulfamoyl groups (e.g. methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylcarbonyl groups (e.g. methylcarbonyl group, propylcarbonyl group, octylcarbonyl group, etc.), arylcarbonyl groups (e.g. enylcarbonyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, t-butyloxycarbonyl group, etc.),
Aryloxycarbonyl groups (e.g., phenyloxycarbonyl group, methoxyphenyloxycarbonyl group, etc.), alkylsulfonyl groups (e.g., methanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl groups (e.g., benzenesulfonyl group, etc.), etc. I can do it. Further, R ₇ represents a ballast group, for example, a straight chain or branched alkyl group having 4 to 30 carbon atoms (for example,
t-butyl group, n-octyl group, t-octyl group, n-dodecyl group, etc.), an alkenyl group, an aryl group, a cycloalkyl group, or a 5- or 6-membered heterocyclic group. Preferably, it is a group represented by the following general formula (). General formula () In the formula, J is an oxygen atom or a sulfur atom, _R8 is a linear or branched alkylene group having 1 to 20 carbon atoms,
R ₉ is a halogen atom (preferably chlorine, bromine),
Alkyl group {preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, tert-butyl, tert-pentyl, tert-octyl, dodecyl, pentadecyl, benzyl, phenethyl)}, aryl group (e.g. phenyl) , a heterocyclic group (preferably a nitrogen-containing heterocyclic group), an alkoxy group {preferably a linear or branched alkyloxy group having 1 to 20 carbon atoms (for example, methoxy, ethoxy,
tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy groups (e.g. phenoxy), hydroxy groups, acyloxy groups {preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (e.g. acetoxy, benzoyloxy)}, Carboxy group, alkoxycarbonyl group (preferably straight chain or branched alkyloxycarbonyl having 1 to 20 carbon atoms),
Aryloxycarbonyl group (preferably phenoxycarbonyl), mercapto group, alkylthio group {preferably a linear or branched alkylthio group having 1 to 20 carbon atoms (e.g. methylthio, octylthio, dodecylthio)}, acyl group (preferably carbon straight chain or branched alkyl carbonyl having 1 to 20 carbon atoms), acylamino group (preferably straight chain or branched alkyl carbonyl having 1 to 20 carbon atoms),
benzenecarboxamide), sulfonamide group (preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonamide group), carbamoyl group (preferably a carbon number 1 to 20),
20 alkylaminocarbonyl, phenylaminocarbonyl), and a sulfamoyl group (preferably linear or branched alkylaminosulfonyl or phenylaminosulfonyl having 1 to 20 carbon atoms). Z is a hydrogen atom or a group that can be eliminated during a coupling reaction with an oxidation product of a color developing agent (for example, a halogen atom (e.g., chlorine, bromine, fluorine, etc.), an oxygen atom or a nitrogen atom at a direct coupling position); Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, and more specific examples include:
U.S. Patent No. 3476563, Japanese Patent Publication No. 1974-37425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 10135-1971, Japanese Patent Publication No. 1983-10135,
No. 117422, No. 50-130441, No. 51-108841, No. 117422, No. 50-130441, No. 51-108841, No.
No. 50-120334, No. 52-18315, No. 53-52423,
53-105226, etc.}, m represents an integer from 0 to 4, and l represents an integer of 0 or 1, respectively. Specific examples of typical compounds represented by the general formula [] of the present invention are listed below. The compound represented by the general formula [] is well known in the photographic field, for example, JP-A No. 56-29235
No. 56-116030, No. 56-99341, No. 57-
No. 136649, No. 57-136650, No. 57-142640, No. 136649, No. 57-136650, No. 57-142640, No.
No. 57-144548, No. 57-150848, No. 57-155538
No. 57-157246, No. 57-182739, etc., and Japanese Patent Application No. 57-142839, No. 57-142840, No. 57-142840,
No. 57-149500, No. 57-149792, No. 57-152109
No. 57-153301, No. 57-153550, No. 57-
No. 172386, No. 57-172385, No. 57-180968, No. 172386, No. 57-172385, No. 57-180968, No.
No. 57-181696, No. 57-185084, No. 57-206983
No. 57-212114, No. 57-218951, No. 57-
No. 221488, No. 57-230753, No. 57-232131, No. 221488, No. 57-230753, No. 57-232131, No.
No. 57-232132, No. 58-10152, No. 58-37140,
It is described in each specification such as No. 58-38438. The compound represented by the general formula [] of the present invention is added to a photographic structure layer, particularly a red-sensitive silver halide emulsion layer. When this compound is added to a red-sensitive silver halide emulsion layer, the amount added is in the range of 5 to 100 mol%, preferably 10 to 50 mol%, particularly preferably 15 to 30 mol%, based on the silver contained in the layer. It is added at a rate of The compound represented by the general formula [] of the present invention can be incorporated into the photographic constituent layer using a conventionally known method. For example, the compound represented by the general formula [] is dissolved in a known high-boiling organic solvent with a boiling point of about 175°C or higher, if necessary in combination with a low-boiling solvent, and the surface-active compound is dissolved in an aqueous binder such as an aqueous gelatin solution. The dispersion may be finely dispersed using an agent, and this dispersion may be added to the desired hydrophilic colloid layer. Known high-boiling point solvents include phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, trioctyl phosphate, etc.), N
-Substituted acid amides (N,N-diethyllaurinamide, etc.) are representative. Each structural unit forming a dye image in the present invention consists of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers necessary for silver halide color photographic materials, including the layers of image-forming units described above, can be arranged in various orders as known in the art. A typical multicolor silver halide color photographic light-sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one
The yellow dye image-forming structural unit consisting of at least one blue-sensitive silver halide emulsion layer having two yellow dye-forming couplers is supported on a support. The treatment method of the present invention can be used particularly effectively in the following four treatment steps. (1) Color development → bleach-fixing → washing (2) color development → bleach-fixing → washing with a small amount of water → washing with water (3) color development → bleach-fixing → washing with water → stabilization (4) color development → bleach-fixing → stabilization Here, washing step This includes the multistage countercurrent water washing method described in Japanese Patent Application Laid-Open No. 57-8543. The processing temperature in the method for processing silver halide color photographic materials of the present invention may be within the range generally used in the development of silver halide color photographic materials, and is preferably in the range of 28 DEG C. to 45 DEG C.
The color developing agent contained in the color developer of the present invention is preferably an aromatic primary amine compound, particularly a P-phenylenediamine compound, and N,N-
Diethyl-P-phenylenediamine hydrochloride, N-
Ethyl-P-phenylenediamine hydrochloride, N,N
-dimethyl-P-phenylenediamine hydrochloride, 2
-Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate, N-ethyl-N- β-hydroxyethylaminoaniline, 4-amino-N-(2
-methoxyethyl)-N-ethyl-3-methylaniline-P-toluenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-
Examples include ethyl-N-(β-hydroxyethyl)-3-methyl-4-aminoaniline. These color developing agents may be used alone or in combination.
You may use combinations of more than one species. Other Photography by LFANason
Processing Chemistry (Focal Prese, 1966)
pages 226-229, U.S. Patent No. 2193013, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. The silver halide color photographic light-sensitive material used in the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor. The color developing agent precursor is under alkaline conditions.
It is a compound capable of producing a color developing agent, and includes, for example, a Schiff base precursor with an aromatic aldehyde compound, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a urethane type precursor. Precursors of these aromatic primary amine color developing agents are disclosed in U.S. Patent No. 3,342,599;
Same No. 2507114, Same No. 2695234, Same No. 3719492,
British Patent No. 803783, Japanese Patent Application Publication No. 185628/1983, No. 54
−79035, Research Disclosure Magazine
15159, 12146, and 13924. The amount of these aromatic primary amine color developing agents or their precursors to be added is generally from 0.1 mol to 5 mol, preferably from 0.3 mol to 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. To incorporate these color developing agents or precursors into light-sensitive materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. and added. It can be added as an emulsified dispersion using a high boiling point organic solvent such as ate, or as a latex polymer impregnated as described in Research Disclosure 14850. The color developing solution of the present invention includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium bicarbonate, and tribasic sodium phosphate; development inhibitors such as sodium bromide and potassium bromide; Various organic solvents such as methanol, ethanol, acetone, butanol, benzyl alcohol, phenoxybutanol, diethylene glycol, ethylene glycol, N,N-dimethylformamide, preservatives such as hydroxylamine and sodium sulfite, citradinic acid, polyethylene glycol , development regulators such as polyvinylpyrrolidone, water-soluble optical brighteners such as diaminostilbene compounds, heavy metal ion masking agents such as ethylenediaminetetraacetic acid and alkyliminodiacetic acid, and development accelerators. can be included depending on the The pH value of this color developer is usually 7 or higher, most commonly about 2.5 to about 12. The higher the PH, the faster the development speed becomes and the time for the color development step can be shortened, but it is generally not preferable to have a PH of 11 or more because the stability of the processing solution deteriorates. Regarding the temperature, the processing time of the color development process can be shortened by increasing the temperature, but if the processing temperature is too high, problems such as an increase in capri and a decrease in the stability of the processing solution occur, so it is generally not recommended to set the temperature above 40℃. Undesirable. The processing time in the color development process of the present invention is 90
The time may be within seconds, preferably between 80 and 45 seconds. In the whitening and fixing treatments performed to leave the dye image of the present invention, the bleaching treatment and the fixing treatment are performed simultaneously from the viewpoint of rapid processing. As bleaching agents, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate,
Organic complex salts of iron () or cobalt (), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid. ; persulfate, permanganate; nitrosophenol, etc. can be used. Among the bleaching agents used in the bleach-fixing process of the present invention, metal complex salts of organic acids are particularly preferred. A metal complex salt of an organic acid has the effect of oxidizing the metallic silver produced during development and converting it into silver halide. Its structure is that of aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. cobalt,
It is coordinated with metal ions such as copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is, for example, an aminopolycarboxylic acid represented by the following general formula [] or []. General formula [] HOCO−A ₁ −Z′−A ₂ −COOH General formula [] [In each of the above general formulas, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ and A ₆ are each a hydrocarbon group, Z′ is a hydrocarbon group,
It represents an oxygen atom, a sulfur atom, or N-A ₇ (A ₇ is a hydrocarbon group or a lower aliphatic carboxylic acid). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [] or [] include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Ethylenediamine-N-(β-hydroxyethyl)-N,N,N'-triacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Cyclohexanediaminetetraacetic acid Iminodiacetic acid Methyliminodiacetic acid Ethyliminodiacetic acid Hydroxyethyliminodiacetic acid Propylimino Diacetic acid Butyliminodiacetic acid Dihydroxyethylglycine Ethyl etherdiaminetetraacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Phenylenediaminetetraacetic acid Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid Pentasodium salt Ethylenediamine-N-(β-hydroxyethyl)-N,N,N'-triacetic acid sodium salt Propylenediaminetetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Cyclohexanediaminetetraacetic acid sodium salt Organic acids used in the present invention The metal in the metal complex salt is a metal capable of coordinating with an organic acid, such as chromium, manganese, iron, cobalt, nickel, copper, etc., and iron is particularly preferred in the present invention. The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as sodium iron() ethylenediaminetetraacetate, ethylenediaminetetraacetic acid Iron () ammonium. Further, metal complex salts of two or more organic acids having different structures may be used in combination. The specific amount used is approximately 5 to 400 per treatment solution.
It is particularly preferable to use an amount of about 10 to 200 g per treatment solution. The bleach-fix solution used in the present invention contains a metal complex salt of an organic acid (for example, an iron complex salt) as a bleaching agent, as well as a silver halide fixing agent such as a thiosulfate, a thiocyanate, or a thiourea. A liquid containing a composition is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound mentioned above, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can also be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide,
PH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol borates. , solubilizing agents such as alkanolamines, stain inhibitors such as organic amines, organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained. In general, in neutral or alkaline environments, the oxidizing power of metal complex salts of organic acids decreases due to alkaline hydrolysis reactions and dimerization reactions, and the diffusivity decreases, resulting in a significant decrease in silver bleaching power. Are known. Therefore, in order to increase the silver bleaching ability of a treatment solution using a metal complex salt of an organic acid, it is sufficient to lower the pH of the treatment solution and use an acidic solution. As a result of promoting the reduction reaction of coloring dyes, particularly cyan dyes, by reduced forms of acid metal complex salts and converting them into leuco, a serious problem arises in that dye images take on a reddish tinge. Furthermore, a decrease in pH is caused by an increase in the oxidizing power of the metal complex salt of an organic acid in the bleach-fix solution, which reduces the rate of redox reaction with the fixing agent and sulfite ions used as a preservative for the fixing agent. It is known that the storage stability of the bleach-fix solution decreases as a result of the disproportionation reaction caused by protons of thiosulfate ion commonly used as a fixing agent. For this reason, the bleach-fix solution has a pH of 6 to 6 PH.
Used in a range of 8. The bleach-fixing temperature of the silver halide color photographic light-sensitive material of the present invention is 50°C or less, preferably 30 to 40°C.
It is held between. The bleach-fixing treatment time is 72 seconds or less, preferably 60 seconds or less. The processing temperature of the various processing steps such as color development, bleach-fixing, washing with water, stabilization, drying, etc. performed as necessary for the silver halide color photographic light-sensitive material of the present invention is carried out at 30°C or higher from the viewpoint of rapid processing. Preferably. The photographic emulsion used in the present invention is written by P. Glaftkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a monodisperse silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more monodisperse silver halide emulsions formed separately may be mixed and used. The shape of the silver halide grains may be a cube, an octahedron, a dodecahedron due to the coexistence of these, various twin crystals, or a mixture thereof. Further, the emulsion may be composed of either coarse grains or fine grains. The emulsion used in the present invention may be doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium, copper, or the like during or after grain formation. Furthermore, unnecessary soluble salts may be removed from the emulsion used in the present invention after grain formation, or they may be left as they are contained. In the case of removing the salts, any method such as the Nudel water washing method, the dialysis method, or the coagulation water washing method, which has been known for a long time, can be used. Furthermore, the emulsions used in the present invention can be sensitized by chemical sensitization. Specifically, allylthiocarbamide, N,N-diphenylthiourea, sodium thiosulfate, sulfur sensitizers such as cystine, selenium sensitizers such as tetramethylselenurea, gold compounds, palladium compounds, platinum compounds, ruthenium compounds, Sensitization can be achieved using noble metal sensitizers such as rhodium compounds, iridium compounds, or combinations of such sensitizers. Alternatively, reduction sensitization can be performed using a reducing agent such as hydrogen gas or stannous chloride. The emulsion used in the present invention contains an appropriate sensitizing dye of 5×10 ^-8 to 3×10 ^-3 per mole of silver halide in order to impart photosensitivity to the desired wavelength range.
Optical sensitization may be achieved by adding molar amounts. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in green-sensitive emulsions, for example, U.S. Pat.
No. 2739149, No. 2945763, British Patent No.
Cyanine dyes such as those described in No. 505979, etc.
Typical examples include merocyanine dyes and complex cyanine dyes. Also,
Examples of sensitizing dyes used in red-sensitive emulsions include U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2442710, No. 2454629, No. 2776280, and the like. Additionally, U.S. Patent No.
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 2213995, No. 2493748, No. 2519001, West German Patent No. 929080, etc. can be advantageously used in green-sensitive emulsions or red-sensitive emulsions. can. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Typical examples are US Patent Nos. 2688545 and 2977229.
No. 3397060, No. 3522052, No. 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Further, the silver halide color photographic light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes,
Cyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609, British Patent No. 1177429, Japanese Patent Application Publication No. 48-85130, Japanese Patent Application Publication No. 49-99620, British Patent No. 49-114420.
No. 52-108115, U.S. Patent No. 2274782, Id.
No. 2533472, No. 2956879, No. 3148187, No.
No. 3177078, No. 3247127, No. 3540887, No.
No. 3575704, No. 3653905, No. 3718472, No.
It is described in No. 4071312 and No. 4070352. The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, the antifoggant described in Research Disclosure No. 17643,
Stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic material used in the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein, etc. proteins, hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole,
Any single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included. Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a transparent support provided with a reflective layer or a reflective material, such as a glass plate. , polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the light-sensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No.
2 by the method described in No. 2761791 and No. 2941898
Simultaneous application of more than one layer can also be used. In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but for example, in the case of a full-color photosensitive material for printing, the blue-sensitive emulsion layer, the green-sensitive emulsion layer, the green-sensitive emulsion layer, It is preferable to arrange the red-sensitive emulsion layer. Furthermore, in the photosensitive material used in the present invention,
It is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and in addition, a filter layer, an anti-curl layer,
Various layers such as a protective layer and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included as well. In the present invention, the compound represented by the general formula [] can be used alone or in combination with a conventionally known cyan coupler. As conventionally known cyan couplers, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2369929 and
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 48-59838, No. 51-26034, No. 48-5055,
No. 51-146828, No. 52-69624, No. 52-90932
No. 58-95346. For example, as a magenta coupler, the US patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
-60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 11094/1983. As yellow couplers, compounds of the benzoylacetanilide and pivaloylacetanilide series are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3408194, No. 3551155, No. 3582322, No. 3582322, No. 3551155, No. 3582322, No.
No. 3725072, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
No. 87650, No. 52-82424, No. 52-115219, No. 58
-95346 etc. Two or more of the above couplers may be contained in the same layer. Also, the same coupler may be included in two or more different layers. These couplers are generally used in an amount of 2.times.10.sup.-3 to 5.times.10.sup.-1 mol, preferably 1.times.10.sup.- ² mol to ^{5.times.10.sup. -1 mol per} mole of silver in the emulsion layer. Specific Examples of the Invention Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare a silver halide color photographic material [A]. Layer 1...30mg/ ^m2 of exemplified compound-4 and 1.0
Layer containing g/m ² gelatin. Layer 2... 1.2 g/m ² of gelatin, 0.4 g/m ² (in terms of silver) or less of the same blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol% average grain size 0.7 μm),
Layer containing 0.80 g/m ² of yellow coupler (Y-1) dissolved in 0.50 g/m ² of dioctyl phthalate. Layer 3: Intermediate layer consisting of 0.7 g/m ² of gelatin. Layer 4...1.25 g/ ^m2 gelatin, 0.43 g/ ^m2 green-sensitive silver chlorobromide emulsion (silver bromide content 60 mol%, average grain size 0.5 μm), 0.3 g/ ^m2 dioctyl phthalate 0.62g/ ^m2 dissolved in
A layer containing a magenta coupler (M-1). Layer 5: Intermediate layer consisting of 1.2 g/m ² of gelatin. Layer 6...1.4 g/ ^m2 gelatin, 0.31 g/ ^m2 red-sensitive silver chlorobromide emulsion (silver bromide content 50 mol%, average grain size 0.4 μm), 0.2 g/ ^m2 dioctyl phthalate A layer containing 0.45 g of cyan coupler (C-7) dissolved in . Layer 7: A layer containing 0.3 g of Tinuvin 328 (manufactured by Ciba Geigy) dissolved in 1.0 g/m ² of gelatin and 0.2 g/m ² of dioctyl phthalate. Layer 8: Layer containing 0.5 g/m ² of gelatin. As a hardening agent, bis(vinylsulfonylmethyl)ether was added to layers 1, 3, 5, and 8 in an amount of 0.015 g per 1 g of gelatin. In addition, Sample [B] was prepared in exactly the same manner as Sample [A] above, except that the cyan coupler (C-7) in layer 6 was changed to a comparative coupler shown below, which is not of the present invention. It was created. Sample [C] was prepared in the same manner as sample [A] above except that exemplified compound 1-4 of layer 1 was not added.
It was created. [Comparison coupler] After exposing the above photosensitive material through an optical wedge,
Processed in the next step. Processing steps (33°C) Color development 1 minute and 1 minute 30 seconds Bleach-fixing 40 seconds Washing with water 1 minute 30 seconds Drying 60-80°C 2 minutes The components of each processing solution are as follows. Color developer Pure water 800ml Benzyl alcohol 8ml Hydroxylamine sulfate 2g Potassium bromide 0.6g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate 4.5g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) (Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.)
Add 2 ml of pure water and make 1 and make 20% potassium hydroxide or
Adjust the pH to 10.1 with 10% dilute sulfuric acid. Bleach-fix solution Pure water 550ml Ammonium ethylenediaminetetraacetate 65g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetic acid 20g Sodium bromide 10.0g Add pure water to make 1, and add ammonia water or diluted Adjust the pH to 7.0 with sulfuric acid. Next, the highest reflection density of the obtained sample is shown in blue (B).
Measurements were made using green (G) and red (R) monochromatic lights.
In addition, the bleach-fixing step in the processing step was performed for 1 minute.
The maximum concentration of cyan dye was measured under red light for 30 seconds. The results are shown in Tables 1 and 2.

【table】

[Table] As is clear from the table above, the general formula []
The sample [A] of the present invention containing the compound represented by the following and the compound represented by the general formula [] includes B, G,
Although sufficient coloring density was obtained for both R and the color reproduction property was good, sample [B], which does not contain the compound represented by the general formula [], had poor color reproduction property in the treatment process of the present invention, so it was used as a cyan dye. Sample [C], which has a low color density and does not contain the compound represented by the general formula [], has insufficient developability, and neither of them can provide satisfactory photographic performance. Example 2 In sample [A] of Example 1, compounds 1 to 4
1 to 14 instead of C-
Even when C-11 was used in place of Sample No. 7, the same photographic performance as Sample [A] was obtained.

Claims (1)

[Scope of Claims] 1. A silver halide color containing at least one compound represented by the following general formula [] and at least one compound represented by the following general formula [] in a photographic constituent layer on a support. In a method in which a photographic light-sensitive material is imagewise exposed and then processed using a color developing solution and a bleach-fixing solution, the processing time of the color developing step and the bleach-fixing step are each 90 seconds or less,
A method for processing a silver halide color photographic material, characterized in that the processing time of the bleach-fixing step is 80% or less of the processing time of the color development step. General formula [] [In the formula, X represents a hydrogen atom or an acetyl group, R ₁ represents an aryl group, and R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group. ] General formula [ ] [In the formula, Y represents a halogen atom, R ₆ represents a halogen atom or a monovalent organic group, R ₇ represents a ballast group, and Z represents a hydrogen atom or It represents a removable group, and n represents an integer from 0 to 4. ]