JP2782565B2 - Processing method for color image stabilizing processing solution, stabilizing solution, stabilizing replenisher, adjusting solution, bleaching solution and silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image stabilizing processing solution used for processing a silver halide color photographic light-sensitive material (hereinafter simply referred to as a "light-sensitive material") and a processing method using the same. The present invention relates to a color image stabilizing processing solution having reduced formaldehyde vapor pressure and excellent in stabilizing a dye image, and a processing method using the same.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a silver halide color photographic light-sensitive material are a color development step and a desilvering step.
In the color developing step, the silver halide exposed by the color developing agent is reduced to form silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image. In the subsequent desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent commonly called a bleaching agent, and then dissolved by a silver ion complex ion forming agent generally called a fixing agent. You. Through this desilvering step, only a dye image is formed on the color photographic material.

Usually, after these steps, a water washing treatment is performed to remove unnecessary processing liquid components. In the case of color paper and reversal color paper, it is general that the above process is completed and the drying process is performed.However, in the case of color negative film and color reversal film, a stabilization process is additionally required. is there. It is well known that formalin is used in the stabilizing bath in the final step of these processes, and that the purpose is to prevent fading of the magenta dye due to the residual magenta coupler in the processed light-sensitive material. is there. When preparing such a stabilizing bath containing formalin or when drying the photosensitive material to which the stabilizing solution is attached, some formaldehyde vapor is generated.

[0004] Inhalation of formaldehyde is known to be harmful to the human body, and the Japan Society for Occupational Health recommends 0.5 ppm of formaldehyde as the allowable working environment concentration. For this reason, efforts have been made to reduce the formaldehyde concentration in the stabilizing bath and to switch to a formalin substitute from the viewpoint of improving the working environment.

As a formalin substitute, for example, Japanese Patent Application Laid-Open No. 63-244036 discloses a hexamethylenetetramine-based compound. When this compound is used, the formaldehyde concentration, that is, the formaldehyde vapor pressure is certainly reduced, but the original purpose of the ability to prevent the fading of the magenta dye is insufficient, and remarkable fading occurs even at room temperature within a few weeks.

[0006] On the other hand, many N-methylol compounds having a specific structure have been proposed. For example, N-methylol compounds of melamine compounds described in U.S. Pat. Nos. 2,487,569 and 2,629,660, U.S. Pat.
No. 579,435, Urea, N-methylol compound of 2-oxapropylene urea, U.S. Pat. No. 2,487,446.
No. 45-8506, N-methylol compounds of thiourea compounds, and N-methylol compounds of hydantoin compounds of U.S. Pat. No. 2,579,436 and British Patent 684,540.
Methylol compound, N-methylol compound of cyandiamide compound of British Patent No. 908,136, N-methylol compound of guanidine compound of U.S. Pat. No. 3,801,322 and JP-A-61-35447,
No. 392,134, morpholine and N of biuret compound
-Methylol compounds, N-methylol compounds of pyrrole, pyrrolidine, methylamine, glycine and ethylcarbamate disclosed in JP-A-2-153348 are known.
Regarding the use of these compounds, US Pat. Nos. 4,786,583, 4,859,574 and 4,921,779, and European Patent Publication 345,17.
No. 2, 395,442 and the like.

However, those compounds having a reduced formaldehyde vapor pressure as compared with formalin have poor image storability, while those with improved image storability have a formaldehyde vapor pressure comparable to formalin. It does not simultaneously satisfy the effect of improving storage stability and reducing the formaldehyde vapor pressure. In addition, these compounds generate stains even when the image storability of the magenta dye is improved, or adversely affect the storability of the yellow or cyan dyes and other dyes present in the light-sensitive material. It has also been found that there is a problem that the processed image is low or the processed image adheres to the photosensitive material.

[0008]

Accordingly, there has been a strong demand for the development of a compound having a sufficient ability to prevent fading of a magenta dye and having a low formaldehyde vapor pressure, ie, an effective formalin substitute. That is, a first object of the present invention is to provide a color image stabilizing processing solution which does not substantially release a compound harmful to the human body. Further, a second object of the present invention is to provide a color image stabilizing processing solution capable of providing a color image which is safe and has excellent image storability of the processed photosensitive material, and a processing method using the same. That is.
Further, a third object of the present invention is to provide a color image stabilizing processing solution which can provide an excellent color image which is excellent in image storability and does not cause adverse effects such as contamination of a photosensitive material, and a process using the same. Is to provide a way.

[0009]

Means for Solving the Problems The present inventors have studied the known N-
As a result of various investigations including a methylol-type formalin precursor, the object of the present invention was to satisfy the N-methylol compound represented by the following general formula (I) and / or the condition A below , Methylol, 1,
N-methylol of 2,4-triazole, urazole
Represented by the following formula (III):
N-methylol compound (hereinafter, may be simply referred to as the N-methylol compound of the present invention) selected from the following compounds, and this is treated with a color image stabilizing processing solution for a silver halide color light-sensitive material and / or Or processing a silver halide color photographic light-sensitive material by incorporating it into a color image stabilizing replenisher or using a color image stabilizing processing solution and / or a color image stabilizing replenisher containing the compound. Has been found to be achievable.

[0010]

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(In the formula, X represents a nonmetallic atom group necessary for forming a 1H-pyrazole ring or a 1H-1,2,4-triazole ring together with a nitrogen atom.)

(Condition A) The equilibrium constant in water at room temperature is 2 ×
It is 10 ⁻² mol / l or less, and the formaldehyde release rate constant is 1 × 10 ⁻⁵ sec ⁻¹ or more.

The color image stabilizing solution of the present invention can provide a working environment with reduced formaldehyde vapor pressure by containing the N-methylol compound of the present invention. Further, the present invention has a great feature in stabilizing a dye image without using formalin by treating a light-sensitive material with a color image stabilizing processing solution containing the N-methylol compound of the present invention. doing. Therefore, any other processing and photosensitive material can be used for the other processing of the processing solution and for the photosensitive material.

The N-methylol compound represented by the formula (I) will be described in more detail. The pyrazole ring or 1,2,4-triazole ring formed by X may be unsubstituted or substituted. When the pyrazole ring formed by X has at least two or more substituents, the substituents at the ortho positions may be bonded to each other to form a 5- to 7-membered ring. In addition, among the N-methylol compounds represented by the general formula (I), preferred compounds are those that satisfy the condition A.

Of the N-methylol compounds represented by the general formula (I), those represented by the following general formula (Ia) are more preferred.

[0016]

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In the formula, Za is -N =, -CH = or -C
(R ₂ ) =. R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a sulfo group, a carboxyl group, a phospho group An acyl group, a sulfonyl group, a sulfinyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group,
Represents a sulfamoyl group, an amino group or -YRa. Here, -Y represents -O- or -S-, and Ra represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. These groups may be further substituted with a similar group, a hydroxy group, or the like. R ₁ and R ₂ or R ₂ and R ₃ may be bonded to each other to form a 5- to 7-membered ring.

The general formula (Ia) is more specifically represented by R ₁ , R ₂
And R ₃ are each a hydrogen atom, an alkyl group (for example,
Methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl), alkenyl group (for example, allyl), aryl group (for example, phenyl, 4-tert-butylphenyl), heterocyclic group (for example, 5 -Pyrazolyl, 4-pyrazolyl), a halogen atom (eg, chlorine, bromine, fluorine), a nitro group, a cyano group, a sulfo group, a carboxyl group, a phospho group, an acyl group (eg, acetyl, benzoyl, propanoyl), a sulfonyl group ( For example, methanesulfonyl, octanesulfonyl, toluenesulfonyl), sulfinyl group (for example, methanesulfinyl), acyloxy group (for example,
Acetoxy), an alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), a carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (eg, sulfamoyl, N
-Ethylsulfamoyl), an amino group (eg, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), an alkoxy group (eg, methoxy, ethoxy), alkylthio Group (eg, methylthio, octylthio), aryloxy group (eg, phenoxy), arylthio group (eg, phenylthio), heterocyclic oxy group (eg, 1-phenyltetrazolyl-5-oxy), heterocyclic thio group ( (For example, benzothiazolylthio).

In the general formula (Ia), R ₁ , R ₂ and R
₃ is preferably a hydrogen atom, an alkyl group, an alkenyl group, a halogen atom, a sulfo group, a carboxyl group, an acyloxy group, an amino group, an alkoxy group and an alkylthio group, respectively, a hydrogen atom, an alkyl group, a halogen atom, an acyloxy group, an amino group, Alkoxy groups and alkylthio groups are more preferred, and hydrogen atoms, alkyl groups, amino groups, alkoxy groups and alkylthio groups are even more preferred. In particular, in the general formula (Ia), R ₁ , R ₂ and R ₃ are preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms from the viewpoint of thermal fading of a cyan image or prevention of yellow stain. More preferably, at _{least one} of R ₁ , R ₂ and R ₃ is a methyl group, and the other is a compound of a hydrogen atom, particularly preferably a compound of all hydrogen atoms.

When the N-methylol compound of the present invention is dissolved in water at room temperature (about 25 ° C.), the following reaction occurs, and an equilibrium is reached.

[0021]

(Equation 1)

The equilibrium constant defined in the present invention means K in the above reaction. The release rate constant of formaldehyde means kr in the above reaction. In the present invention, “water” includes heavy water in addition to ordinary water. As a method of measuring these values, the equilibrium constant K is determined by nuclear magnetic resonance absorption of a heavy aqueous solution in which the N-methylol compound of the present invention is dissolved or a heavy aqueous solution in which an amine compound and an equimolar formaldehyde (37% formalin aqueous solution) coexist. Method (NMR), N
The component generated in the solution when the change in the MR peak disappears can be obtained by calculating from the proton ratio.

The formaldehyde release rate constant k
r is the formation of the N-methylol compound by adding formaldehyde and an amine compound to water or heavy water at room temperature and following the amounts of the N-methylol compound, formaldehyde and the amine compound generated in the reaction until equilibrium is reached. The rate constant Kf was determined, and the N
-It can be determined by the product of the formation rate constant Kf of the methylol compound and the above equilibrium constant K. As means for detecting these chemical species, there are nuclear magnetic resonance absorption, ultraviolet or visible spectroscopy, high performance liquid chromatography, and colorimetry, and these detection means may be selected depending on the degree of the reaction rate. .

The equilibrium constant K is 2 × 10 ⁻² mol / l or less, preferably 1.5 × 10 ⁻² mol / l or less, more preferably 1 × 10 ⁻² mol / l or less.
The release rate constant kr of formaldehyde is 1 × 10 ⁻⁵ s
A compound having an ec ^-1 or more and 1 × 10 ⁻⁴ sec ⁻¹ or more is more preferable, and a compound having a 1 × 10 ⁻³ sec ⁻¹ or more is still more preferable and a compound having 1 × 10 ⁻² sec ⁻¹ or more. Compounds are most preferred.

Examples of the N-methylol compound satisfying the condition A in the present invention include N-methylol of pyrazole, N-methylol of 1,2,4-triazole, N-methylol of urazole and the like.

The compound satisfying the condition A in the present invention is preferably a cyclic nitrogen-containing heterocyclic amine compound in the structure of the released amine compound, and this ring is preferably an aromatic ring or a compound having an aromatic ring keto or ketoid structure. More preferred. More preferred compounds satisfying the condition A in the present invention are compounds represented by the following general formula (III).

[0027]

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(Wherein, Zb is a group of non-metallic atoms necessary to form a 4- to 8-membered ring, provided that the atom bonded to the nitrogen atom is an atom selected from a carbon atom, an oxygen atom or a sulfur atom. The ring formed by Zb may have a substituent, may be condensed with an aromatic ring, an alicyclic ring or a hetero ring, or may be a spiro ring.
Examples of the substituent which the ring formed by Zb may have include the substituents described for R ₁ in formula (Ia). Among them, compounds in which the benzene ring is fused do not have high solubility, and therefore, compounds in which the benzene ring is not fused are preferred. Among the N-methylol compounds satisfying the condition A in the present invention, a more preferred N-methylol compound is an N-methylol compound represented by the above general formula (I), and further preferably a compound represented by the above general formula (Ia). And a 1H-1,2,4-triazole-1-methanol compound in which Za is -N =.

A preferred N-methylol compound in the present invention is a pK in water at room temperature of an amine compound produced by being released together with formaldehyde when dissolved in water.
a is a compound having 8 or less, more preferably 7 or less, further preferably 6 or less. On the other hand, the lower limit is 0.0
It is 1 or more, preferably 0.1 or more, more preferably 0.5 or more, and most preferably 1 or more. N of the present invention
-The methylol compound is a water-soluble N-methylol compound, and the total number of carbon atoms is 12 or less, more preferably 10 or less, and still more preferably 6 or less. Hereinafter, specific examples of the N-methylol compound of the present invention are shown,
The present invention is not limited to these.

[0030]

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[0031]

[Table 1]

[0032]

[Table 2]

[0033]

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[0034]

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[0035]

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The N-methylol compound of the present invention can be easily synthesized by reacting an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof with formaldehyde or paraformaldehyde. These synthesis methods include, for example, U.S. Pat.
No. 883,392 and Chem.ber., 85, 820 ('52), J. Org.
m., 15, 1285 ('50), EP 60,222, Khim.Ge
terotsikl.Soedin., (2), 251 ('80) [Cemical Abstracts, 9
3: 46530W], and can be synthesized according to the method described in US Pat. On the other hand, pyrazole derivatives are available from The Chemistry of H
RHWiley "Py, Volume 22 of eterocyclic Compounds
razoles, Pyrazolines, Pyrazolidines, Indazoles and C
ondensed Ring ", INTERSCIENCE PUBLISHERS ('67) or a method analogous thereto.

The following is a synthesis example of the N-methylol compound of the present invention. Synthesis Example 1 Synthesis of Compound (I-1) Pyrazole (68.1 g), sodium hydroxide (0.14 g), and methanol (80 ml) were placed in a 500-ml three-necked flask equipped with a stirrer, a thermometer, and a condenser. 50
After warming to ° C, 90% paraformaldehyde (33 g) was added in small portions and stirred at the same temperature for 1 hour.
After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower. The obtained concentrate was crystallized from ethyl acetate (300 ml). Compound (I-1) was obtained as colorless crystals.
(Yield 72 g, melting point: 79-84 ° C.)
It was confirmed by elemental analysis and various spectra. The equilibrium constant K of this compound was 5.6 × 10 ⁻³ mol / l.
The equilibrium constant was measured by using a 25 mmol / liter heavy solution of this compound in a nuclear magnetic resonance absorption method (NMR).
The components generated in the solution at the time when the NMR peak change disappeared were calculated from the proton ratio. The compound has a formaldehyde release rate constant kr
Was 8.7 × 10 ⁻² sec ⁻¹ . The measurement of the formaldehyde release rate constant kr is performed by adding formaldehyde and pyrazole to water at room temperature, and tracking the amounts of this compound, formaldehyde and pyrazole generated in the reaction with time until equilibrium is reached. The formation rate constant kf of the compound was determined. It was calculated by the product of the formation rate constant kf of the compound thus obtained and the above-mentioned equilibrium constant K. As a means for detecting the chemical species, ultraviolet spectroscopy was used. The pKa in water at room temperature of the pyrazole released from this compound was 2.5.

Synthesis Example 2 Synthesis of Compound (I-5) 3,5-dimethylpyrazole (48.1 g) and sodium hydroxide (0.07 g) were placed in a 300 ml three-necked flask equipped with a stirrer, a thermometer, and a condenser. , Methanol (50m
l) was added thereto, and the mixture was heated to 50 ° C, 90% paraformaldehyde (16.5 g) was added little by little, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower. The obtained concentrate was crystallized from ethyl acetate (150 ml). Compound (I-5) was obtained as colorless crystals. (Yield 28 g, melting point;
111 ° C) The chemical structure was confirmed by elemental analysis and various spectra. The equilibrium constant K of this compound was 3.3 ×
It was 10 ^-3 mol / l. The pKa of 3,5-dimethylpyrazole generated from this compound in water at room temperature was 4.1.

The equilibrium constants K of typical N-methylol compounds of the present invention and comparative compounds determined according to the method of compound (I-1) are shown below.

[0040]

[Table 3]

The comparative compounds in Table 3 are as follows.

[0042]

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Among the typical N-methylol compounds of the present invention and the above-mentioned comparative compounds obtained according to the method of compound (I-1), comparative compounds having an equilibrium constant K within or close to the definition of the present invention. Rate constant k of formaldehyde in water
r.

[0044]

[Table 4]

As described above, the N-methylol compound of each of the pyrrole, imidazole and tetrazole compounds has a large equilibrium constant K and is outside the scope of the present invention. In addition, although the equilibrium constant K of the N-methylol compound of the alicyclic amide compound and the urea compound satisfies the specified value of the present invention, the release rate constant of formaldehyde is small and out of the specified value of the present invention.

The N-methylol compound of the present invention may be an isolated N-methylol compound as shown in the above-mentioned synthesis examples, or may be used without isolation in the above-mentioned synthesis examples. , Or an aqueous solution containing the N-methylol compound of the present invention obtained by adding equimolar amounts of formaldehyde or paraformaldehyde and an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof. Good. Further, similarly, formaldehyde or paraformaldehyde, pyrazole,
An amine compound such as 1,2,4-triazole or a derivative thereof is added in an equimolar amount to the same treatment bath, and the N-methylol compound of the present invention obtained in the treatment bath is used. Good.

The color image stabilizing solution in the present invention is an effect of stabilizing a dye image formed by color development by adding the N-methylol compound of the present invention (particularly, fading of a magenta dye over time). And a replenisher. Therefore, it is a processing solution after color development (including a replenishing solution).
It is a bleach-fix solution and a stop solution (including respective replenishers), and more preferably a stabilizer, an adjusting solution and a bleach solution (including respective replenishers). Particularly preferred is a stabilizing solution (including a replenishing solution). The replenisher in the present invention is a replenisher for maintaining the composition of the processing solution during continuous processing.

Hereinafter, preferred embodiments will be described. (1) A stabilizer containing at least one N-methylol compound of the present invention. (2) A stable replenisher containing at least one N-methylol compound of the present invention. (3) An adjusting solution containing at least one N-methylol compound of the present invention. (4) A bleaching solution containing at least one N-methylol compound of the present invention. (5) A method of treating with a stabilizer containing at least one N-methylol compound of the present invention. (6) A method of treating while replenishing with a stable replenisher containing at least one N-methylol compound of the present invention. (7) A method of treating with an adjusting solution containing at least one N-methylol compound of the present invention. (8) A method of treating with a bleaching solution containing at least one N-methylol compound of the present invention. Particularly preferred are (1), (2), (5) and (6).

The stabilizing solution in the present invention is a stabilizing solution or a stabilizing solution which has been conventionally used in a final processing step of a color negative film or a color reversal film. It includes the stabilizing solution used in the bath stabilization step, but is preferably used in the final step.

Conventionally, the stabilizing solution or the stabilizing replenisher used in the final processing step is a processing solution containing formalin as described above, and is a processing solution which exerts an image stabilizing effect by this formalin. The invention uses the N-methylol compound of the present invention instead of formalin,
In this method, the vapor pressure of formaldehyde was kept low and the image was stabilized. Therefore, the color image stabilizing solution of the present invention contains substantially no formalin. Here, substantially not containing formalin means that it may be contained as long as the effects of the present invention are exhibited. Specifically, it refers to the case where the total of formaldehyde and the hydrate of formaldehyde is 0.005 mol / l or less. In order to lower the vapor pressure of formaldehyde, the total of the above-mentioned formaldehyde and the hydrate of formaldehyde is preferably as low as possible, particularly preferably 0.003 mol / l or less.

Each replenisher of the present invention is used for replenishing a processing solution with a compound which decreases due to deterioration of the photosensitive material during processing or deterioration with time in an automatic processor, and conversely, the concentration of the compound eluted from the photosensitive material by processing. Is adjusted to keep the performance constant. Therefore, the decreasing compound is at a higher concentration than the treatment solution, and the latter compound is at a lower concentration. Compounds that hardly change in concentration due to treatment or aging are usually contained at approximately the same concentration as the treatment solution.

The preferable addition amount of the N-methylol compound of the present invention is from 0.003 to 0.1 mol per liter of the color image stabilizing solution, more preferably from 0.1 to 0.1 mol.
005 to 0.03 mol.

Hereinafter, the color image stabilizing solution to which the N-methylol compound of the present invention can be added and other processing solutions used in the processing method using the color image stabilizing solution of the present invention will be described. . When the N-methylol compound of the present invention is used other than the stabilizer, the stabilizer may not contain the N-methylol compound of the present invention. Although the term "stabilizing liquid" is not appropriate because it does not have a stabilizing effect, it is referred to hereinafter for convenience. Also, bleach,
Since the adjusting solution and the like also have a stabilizing effect by adding the N-methylol compound of the present invention, the names of the bleaching solution, the adjusting solution and the like are not appropriate, but for convenience, they are hereinafter referred to as these.

First, the stabilizing solution and the adjusting solution used in the final treatment step which is preferable to contain the N-methylol compound of the present invention will be described. The adjusting solution is a processing solution sometimes referred to as a bleach accelerating bath. The stabilizer used in the final treatment step may contain all the compounds that can be added to the washing water described below. In particular, various surfactants for preventing unevenness of water droplets during drying of the processed photosensitive material, various antibacterial agents for preventing generation of water residue and mold generated on the processed photosensitive material, and fungicide. Germicides, fungicides and chelating agents. Further, an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof having no N-methylol group may be added. Further, in addition to the N-methylol compound of the present invention, a compound for stabilizing a dye image, for example, hexamethylenetetramine, a hexamethylenetetramine derivative, hexahydrotriazine, a hexahydrotriazine derivative, dimethylolurea, an organic acid or a pH buffering agent. May be contained. In addition, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, a fluorescent brightener, a hardener, or an alkanolamine described in US Pat. No. 4,786,583 can be used. The pH of the stabilizer used in the final treatment step is usually in the range of 4 to 9, but is preferably 6 to 8. When the stabilizer of the present invention is used in the final processing step, the replenishing amount is preferably 200 to 1500 ml per 1 m ^{2 of the} light-sensitive material to be processed, and more preferably
~ 600 ml is more preferred. When using the stabilizer of the present invention in the final treatment step, the treatment temperature is preferably 30 to 45 ° C. The processing time is preferably from 10 seconds to 2 minutes, particularly preferably from 15 to 30 seconds.

As the adjusting bath, in addition to the N-methylol compound of the present invention, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid,
Aminopolycarboxylic acid chelating agents such as cyclohexanediaminetetraacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and various bleaching accelerators described in the context of bleaching solutions such as thioglycerin, aminoethanethiol and sulfoethanethiol. Can be.
For the purpose of preventing scum, US Pat. No. 4,839,262
No. 4,059,446 and Research Disclosure, vol. 191 and 19104.
It is preferable to include a polyoxyethylene compound described in (1980). These compounds can be used in a range of 0.1 g to 20 g per liter of the adjustment liquid, but preferably in a range of 1 g to 5 g.
The pH of the adjustment bath is usually used in the range of 3 to 11,
Preferably it is 4-9, More preferably, it is 4.5-7.
The processing time in the conditioning bath is preferably 30 seconds to 5 minutes. The replenishing amount of the conditioning bath is preferably 30 ml to 3000 ml per 1 m ² of the light-sensitive material, and particularly preferably 50 ml to 150 ml.
It is preferably 0 ml. The processing temperature of the conditioning bath is 20 ° C
The temperature is preferably from 50 to 50 ° C, particularly preferably from 30 to 40 ° C.

Usually, a silver halide color photographic light-sensitive material is subjected to imagewise exposure, and then a negative type and a direct positive type light-sensitive material are subjected to color development, and a reversal positive type photographic material is subjected to black-and-white development and reversal processing. After that, color development is performed. The color developing solution that can be used in the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Preferred color developing agents are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-1 N, N-diethyl-p-phenylenediamine D-2 2-Methyl-N, N-diethyl-p-phenylenediamine D-3 4- [N-ethyl-N- (β-hydroxyethyl) amino] Aniline D-4 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 4-Amino-3-methyl-N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline D-6 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-7 4-amino-3-methyl-N-ethyl-N-
(4-hydroxybutyl) aniline Of the above-mentioned p-phenylenediamine derivatives, particularly preferred are D-4 and D-5. Further, these p-phenylenediamine derivatives are sulfates, hydrochlorides, sulfites,
It may be a salt such as p-toluenesulfonic acid salt. The amount of the aromatic primary amine color developing agent used is preferably from 0.001 to 0.1 mol, more preferably from 0.01 to 0.06 mol, per liter of the color developing solution.

If necessary, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be used as a preservative in the color developing solution. Can be added. The preferable addition amount of these preservatives is 0.5 to 10 per liter of the color developing solution.
g, more preferably 1 to 5 g.

Further, as a compound for directly preserving the aromatic primary amine color developing agent, JP-A-63-53163
Various hydroxylamines (compounds having a sulfo group or a carboxy group are preferred) described in JP-A Nos. 41 and 63-106655, hydroxamic acids described in JP-A-63-43138, and JP-A-63-146041. Hydrazines and hydrazides; phenols described in JP-A-63-44657 and JP-A-63-58443;
Α-hydroxyketones and α described in 3-44656;
-Aminoketones and various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235 and JP-A-63-24254
No. 63-21647, No. 63-146040,
Monoamines described in JP-A-63-27841 and JP-A-63-25654; JP-A-63-30845;
Diamines described in Nos. 14640 and 63-43139, polyamines described in 63-21647, 63-26655 and 63-44655, and 6
Nitroxy radicals described in 3-53551, 6
Alcohols described in JP-A-3-43140 and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239947 can be used. Other preservatives are disclosed in
Various metals described in JP-A-7-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3582, and polyethyleneimine described in JP-A-56-94349. Or an aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, if necessary.
Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0. In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
Potassium-hydroxybenzoate (potassium 5-sulfosalicylate); The amount of the buffer added is preferably 0.1 mol or more per liter of the color developing solution, and particularly preferably 0.1 to 0.4 mol.

In addition, it is preferable to use various chelating agents in the color developing solution as an agent for preventing precipitation of calcium and magnesium or for improving the stability of the color developing solution. Organic acid compounds are preferred as the chelating agent,
Examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Representative examples of these are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid and the like. These chelating agents may be used in combination of two or more as necessary. The chelating agent may be added in an amount sufficient to block metal ions in the color developing solution, for example, about 0.1 g to 10 g per liter of the color developing solution.

An optional development accelerator can be added to the color developer if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means that the color developer contains no more than 2 ml, preferably no color developer per liter. Other development accelerators include Japanese Patent Publication No. 37-1
No. 6088, No. 37-5987, No. 38-7826
And thioether compounds described in U.S. Pat. No. 3,818,247, JP-A-52-49829 and JP-A-50-1515.
No. 554, p-phenylenediamine compounds described in JP-A-50-137726, JP-B-44-30074.
And JP-A-56-156826 and JP-A-52-43429.
Quaternary ammonium salts described in US Pat.
Nos. 94,903, 3,128,182, 4,
No. 230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 2,482,546.
No. 2,596,926, No. 3,582,34
No. 6, etc., and the amine compounds described in JP-B-37-1608.
No. 8, No. 42-25201, U.S. Pat.
No. 183, Japanese Patent Publication No. 41-11431, No. 42-238
No. 83, U.S. Pat. No. 3,532,501 and the like, and polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles and the like can be added as necessary. The addition amount of the development accelerator is about 0.01 g to 5 g per liter of the color developing solution.

In the present invention, if necessary,
Optional antifoggants can be added. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing compounds such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Heterocyclic compounds can be mentioned as typical examples. The amount of the antifoggant added is about 0.001 g to 1 g per liter of the color developing solution. The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4′-diamino-2,2′-disulfostilbene compound is preferable. The amount of the fluorescent whitening agent is 0 to 5 g, preferably 0.1 g to 4 g, per liter of the color developing solution. Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The color developing replenisher contains compounds contained in the color developing solution. The role of the color developing replenisher is to control the concentration of the compound eluted from the photosensitive material by the processing of the photosensitive material or the replenishment of the compound to the color developing solution, which is reduced by deterioration over time in an automatic processor, and vice versa. In this case, the developing performance is kept constant. Therefore, the former compound has a higher concentration than the color developing tank solution,
Also, the latter compound has a low concentration. The former compound is a color developing agent or a preservative, and the replenisher contains 1.1 to 2 times the amount of the tank solution. The latter compound is a development inhibitor typified by a halide (for example, potassium bromide).
0.6 times. The concentration of the halide in the replenisher is usually 0.006 mol / l or less, but the lower the replenishment, the lower the concentration needs to be. Compounds that hardly change in concentration due to processing or aging are usually contained at approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the replenisher for color development is 0.05 to 0.
Increase by about 5 This difference in pH also needs to increase with decreasing replenishment. The replenishment amount of the color developing solution is 3000 ml or less per 1 m ² of the light-sensitive material.
Preferably it is 1500 ml.

The processing temperature of the color developing solution is suitably from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is suitably from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds, and more preferably from 1 minute to 2 minutes and 30 seconds. Further, the color developing bath may be divided into two or more baths as necessary, and a color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and further reduce the replenishing amount.

The processing method of the present invention can be preferably used for color reversal processing. In the reversal process, after the black and white development, the reversal process is performed as necessary, and then the color development is performed. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used in a reversal process of a color photosensitive material, and is a black-and-white developing solution used in a processing solution of a black-and-white silver halide photosensitive material. Various well-known additives used in addition to the liquid can be contained.

Representative additives include 1-phenyl-
Developing agents such as 3-pyrazolidone, methol and hydroquinone; preservatives such as sulfites; accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; potassium bromide and 2-methylbenzimidazole; Examples include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

When processing is carried out by an automatic developing machine using the above black-and-white developer or color developing solution, the area (opening area) of the developing solution (color developing solution and black-and-white developing solution) in contact with air should be as small as possible. preferable. For example, opening area (cm ² )
Is divided by the volume of the developing solution (cm ³ ), and the opening ratio is preferably 0.01 (cm ⁻¹ ) or less.
005 or less is more preferable.

The developer can be regenerated and used.
Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more. As processing using developer regeneration, after regenerating the overflow solution of the developer,
Use as replenisher. As a regeneration method, it is preferable to use an anion exchange resin. Regarding the particularly preferred composition of the anion exchange resin and the method of regenerating the resin, see DIAION MANUAL (I) (198) issued by Mitsubishi Kasei Kogyo Co., Ltd.
6th, 14th edition). Among the anion exchange resins, resins having the composition described in JP-A-2-952 and JP-A-1-281152 are preferable.

In the present invention, the color-developed photosensitive material is subjected to a desilvering process. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. Typical desilvering steps include the following. Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Washing-Fixing Bleaching-Bleaching-Fixing Fixing Bleaching-Fixing Fixing-Bleach-Fixing 753
No. 52. The process is described in
No. 143755 and Japanese Patent Application No. 2-216389. The composition of the processing bath such as the bleaching bath and the fixing bath applied to the above process may be one or two or more (for example, 2 to 4 tanks, in which case a countercurrent replenishment system is preferable). Is also good. In the desilvering step, after the color development, a rinsing bath,
Although it may be carried out through a washing bath or a stop bath, it is preferably carried out immediately after color development in the case of a negative photosensitive material,
In the case of the reversal process, it is preferable to carry out the color development through an adjustment bath after the color development.

As described above, the bleaching solution contains the N-
It may contain a methylol compound. Examples of the bleaching agent contained as a main component of the bleaching solution of the present invention include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and ferric aminopolycarboxylate. Complex salts and some organic compounds of ferric aminopolyphosphonate complex salts can be mentioned. In the present invention, it is preferable to use a ferric aminopolycarboxylic acid complex salt in view of environmental protection, handling safety, metal corrosiveness and the like.

The following are specific examples of the ferric aminopolycarboxylic acid complex salt in the present invention, but the invention is not limited thereto. In addition, the oxidation-reduction potential is described. No. Compound Redox potential (mV vs. NHE, pH = 6) 1. N- (2-acetamido) iminodiacetic acid ferric complex 180 2. Methyl iminodiacetic acid ferric complex 200 3. Iminodiacetic acid second Iron complex salt 210 4. Ferric salt of 1,4-butylenediamine tetraacetic acid 230 230 5. Ferric complex of diethylene thioether diamine tetraacetic acid 230 6. Ferric complex salt of glycol ether diamine tetraacetic acid 240 7. 1,3-propylene diamine Ferric tetraacetate complex 250 8. Ferric ethylenediaminetetraacetate complex 110 9. Ferric diethylenetriaminepentaacetate complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic ferric acid salt 80

The oxidation-reduction potential of the bleaching agent is determined by the method described in Transactions of the Faraday Society, Vol. 55 (1959), pp. 1312-1313. And the redox potential obtained by the measurement.

In the present invention, the oxidation-reduction potential is 15 from the viewpoint of rapid processing and the viewpoint of effectively exerting the effects of the present invention.
A bleaching agent having a redox potential of 0 mV or more is preferred, and a bleaching agent having a redox potential of 180 mV, most preferably 200 mV or more is preferred. If the oxidation-reduction potential is too high, bleaching fog occurs, so the upper limit is 700 mV or less, preferably 500 mV or less. Among them, particularly preferred is a ferric complex of 1,3-propylenediaminetetraacetic acid of compound No. 7.

The ferric aminopolycarboxylic acid complex salt is used as a salt of sodium, potassium, ammonium or the like.
Ammonium salts are preferred because of the fastest bleaching.

The amount of the bleaching agent used in the bleaching solution is preferably 0.17 to 0.7 mol per liter of the bleaching solution.
7 mol is preferred. Particularly preferred is 0.30 to 0.6
Is a mole. The amount of the bleaching agent used in the bleach-fixing solution is from 0.01 to 0.5 mol, preferably from 0.02 to 0.2 mol, per liter of the bleach-fixing solution. In the present invention, the oxidizing agents may be used alone or in combination of two or more. When two or more are used in combination, the total concentration may be within the above-mentioned range.

When the ferric aminopolycarboxylic acid complex salt is used in the bleaching solution, it can be added in the form of a complex salt as described above. (Eg, ferric sulfate, ferric chloride,
A complex salt may be formed in the treatment solution by coexisting with ferric nitrate, ammonium ferric sulfate, and ferric phosphate. In the case of this complex formation, the aminopolycarboxylic acid may be added slightly in excess of the amount required for complex formation with ferric ions.
It is preferable to make an excess in the range of 0%.

The bleaching solution as described above generally has a pH of 2
Used in 7.0. In order to speed up the processing, the pH of the bleaching solution is preferably 2.5 to 5.0, more preferably 3.0 to 4.8, and particularly preferably 3.5 to 4.5.
It is preferable that the replenisher is usually used in the range of 2.0 to 4.2. In the present invention, a known acid can be used to adjust the pH to the above range. As such an acid, an acid having a pKa of 2 to 5.5 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and is a value determined at an ionic strength of 0.1 mol / dm and 25 ° C. It is preferred that the bleaching solution contains 0.5 mol / liter or more of an acid having a pKa in the range of 2.0 to 5.5 because bleaching fog and precipitation of the replenisher due to aging at low temperatures can be prevented. This pKa is 2.0 to 5.5.
Examples of the acid include inorganic acids such as phosphoric acid, acetic acid, malonic acid,
Although any organic acid such as citric acid may be used, an acid having a pKa of 2.0 to 5.5, which effectively exhibits the effect by the above-mentioned improvement, is an organic acid. Among the organic acids, an organic acid having a carboxyl group is particularly preferable. pKa is 2.0-
The 5.5 organic acid may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, its pKa is as defined in 2. above.
If it is in the range of 0 to 5.5, it can be used as a metal salt (for example, sodium or potassium salt) or an ammonium salt. Further, two or more organic acids having a pKa of 2.0 to 5.5 can be used in combination. However, the acid mentioned here excludes aminopolycarboxylic acid, its salt and its Fe complex salt.

The pKa2.
Preferred specific examples of the organic acid of 0 to 5.5 include acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid,
Aliphatic monobasic acids such as propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, Glycine, glutamine, cysteine, serine, methionine,
Amino acid compounds such as leucine; benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy; aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid;
Aliphatic dibasic acids such as tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid;
Various organic acids such as amino acid-based dibasic acids such as aspartic acid, glutamic acid and cystine; aromatic dibasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid can be listed. Among these, monobasic acids having a hydroxyl group and a carboxyl group are preferred, and glycolic acid and lactic acid are particularly preferred. Glycolic acid and lactic acid are used in an amount of 0.2 to 2 mol, preferably 0.5 to 1.5 mol, per liter of the bleaching solution. These acids are preferable because the effects of the present invention are more remarkably exhibited and bleaching fog is suppressed without odor. Further, the combined use of acetic acid and glycolic acid or lactic acid is preferable since the effect of simultaneously solving precipitation and bleaching fog becomes remarkable. The combined molar ratio of acetic acid and glycolic acid or lactic acid is 1: 2 to 2:
1 is preferred. The total amount of these acids used is preferably 0.5 mol or more per liter in the form of a bleaching solution. Preferably it is 1.2 to 2.5 mol / l. More preferably, it is 1.5 to 2.0 mol / liter.

When adjusting the pH of the bleaching solution to the above range, the acid and the alkali agent (for example, ammonia water, KOH,
NaOH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Among them, aqueous ammonia is preferable.

The alkaline agent used in the bleaching starter when adjusting the starting solution of the bleaching solution from the replenisher is as follows.
It is preferable to use potassium carbonate, aqueous ammonia, imidazole, monoethanolamine or diethanolamine. Further, the replenisher may be used as it is without using a bleaching starter.

In the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Such bleaching accelerators are described, for example, in US Pat.
3,858, German Patent 1,290,821
No. 1,138,842, JP-A-53-95630, and Research Disclosure No. 17129 (July, 1978) having a mercapto group or a disulfide group. Compounds, thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patent Polyethylene oxides described in Japanese Patent No. 2,748,430, JP-B-45-8836
And the like. Particularly preferred are mercapto compounds as described in British Patent No. 1,138,842 and Japanese Patent Application No. 1-11256.

In the bleaching solution of the present invention, in addition to the bleaching agent and the above compounds, a bromide such as potassium bromide, sodium bromide, ammonium bromide or a chloride such as potassium chloride, sodium chloride or ammonium chloride may be used. A halogenating agent may be included. The concentration of the rehalogenating agent is from 0.1 to 1
It is 5.0 moles, preferably 0.5 to 3.0 moles. Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

In the present invention, it is preferable to employ a replenishment method. The replenishment amount of the bleaching solution is per 1 m ² of the light-sensitive material.
It is preferably 600 ml or less, more preferably 100 to 5 ml.
00 ml. The bleaching time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less.

In the treatment, it is preferable that the bleaching solution using the aminopolycarboxylic acid ferric complex salt is subjected to aeration to oxidize the resulting aminopolycarboxylic acid iron (II) complex salt. This regenerates the oxidizing agent and the photographic performance is kept very stable.

In the processing with the bleaching solution in the present invention, it is preferable to perform so-called evaporation correction, in which water corresponding to the amount of evaporation of the processing solution is supplied. Particularly, it is preferable in a color developing solution or a bleaching solution containing a high potential bleaching agent. Although there is no particular limitation on the specific method of replenishing such water,
Above all, JP-A Nos. 1-254959 and 1-254960
No., set up a monitor tank separate from the bleach tank,
The evaporation amount of water in the monitor water tank is obtained, the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of water, and the water is replenished to the bleaching tank in proportion to the evaporation amount.
No. 3, No. 2-47777, No. 2-47778, No. 2
The evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A-47779 and JP-A-2-117972 is preferable.

In the present invention, the light-sensitive material which has been processed with the bleaching solution is processed with a processing solution having a fixing ability. The processing solution having fixing ability here is specifically a fixing solution and a bleach-fixing solution. When the processing having the bleaching ability is performed with the bleach-fixing solution, it may also serve as the processing having the fixing ability as in the above-described step. In the above-mentioned step in which the bleaching solution is processed after the bleaching process with the bleaching solution, the bleaching agent of the bleaching solution may be different from that of the bleach-fixing solution. When a water washing step is provided between the above steps, the liquid may also contain the N-methylol compound of the present invention.

The processing solution having a fixing ability contains a fixing agent. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate; thiocyanates (rodane salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; And thioethers. Among them, it is preferable to use ammonium thiosulfate. The amount of the fixing agent is from 0.3 to 3 mol, preferably from 0.5 to 2 mol, per liter of a processing solution having a fixing ability.

From the viewpoint of promoting fixing, it is also preferable to use the above-mentioned ammonium thiocyanate (rhodanammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) in combination with thiosulfate. Of these, it is most preferable to use a thiosulfate and a thiocyanate in combination. In particular, a combination of ammonium thiosulfate and ammonium thiocyanate is preferred. The amount of these compounds used in combination is from 0.01 to 1 mol, preferably from 0.1 to 1 mol, per liter of processing solution having fixing ability.
It is preferred to use 0.5 mol, but depending on the case, 1-3
The use of a mole can greatly enhance the fixing promoting effect.

In the processing solution having a fixing ability, sulfites (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (for example, sodium acetaldehyde bisulfite, particularly preferably a compound described in Japanese Patent Application No. 1-298935) or
And a sulfinic acid compound described in US Pat. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.

Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids and organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,
1-diphosphonic acid, ethylenediamine-N, N, N ',
N'-tetramethylene phosphonic acid, nitrilotrimethylene phosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,
2-propylenediaminetetraacetic acid can be mentioned.
Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred.
The addition amount of the chelating agent is 0.01 to 0.3 mol, preferably 0.1 to 0.2 mol, per liter of the treatment liquid.

The pH of the fixing solution is preferably from 5 to 9, and more preferably from 7 to 8. Further, in the bleach-fix solution, it is preferably 4.0 to 7.0, and more preferably,
5.0 to 6.5. Further, the pH of the bleach-fixing solution after being processed in the bleaching solution or the first bleach-fixing bath is 6 to
8.5 is preferable, and furthermore, 6.5 to 8.0 is preferable.

In order to adjust the processing solution having fixing ability to such a pH range, and as a buffer, pKa is 6.0.
It is preferable to contain a compound having a range of from 9.0 to 9.0. As these compounds, imidazoles such as imidazole and 2-methyl-imidazole are preferred. These compounds are preferably used in an amount of 0.1 to 1 liter of the processing solution.
It is 10 mol, preferably 0.2 mol to 3 mol.

The bleach-fixing solution may further contain compounds which can be contained in the above-mentioned bleaching solution.

In the present invention, the bleach-fix solution (start solution) at the start of processing is prepared by dissolving the compound used in the above-mentioned bleach-fix solution in water. You may mix and prepare an appropriate amount.

When the replenishment method is adopted, the replenishment amount of the fixing solution or the bleach-fixing solution is 100 per m ² of the light-sensitive material.
~ 3000ml is preferred, more preferably 300 ~
1800 ml. The replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher or disclosed in JP-A-61-143755.
And Japanese Patent Application No. 2-216389, may be used using a bleaching solution and an overflow solution of a fixing solution.

Further, as in the above-mentioned bleaching process, it is preferable to perform the bleach-fixing process while replenishing the processing solution and replenishing water corresponding to the evaporation.

In the present invention, the total processing time of the processing having the fixing ability is 0.5 to 4 minutes, preferably 0.5 to 2 minutes.
Minutes, particularly preferably 0.5 to 1 minute. In the present invention, the total processing time of the desilvering step comprising a combination of bleaching, bleach-fixing and fixing is preferably from 45 seconds to 4 minutes, more preferably from 1 minute to 2 minutes. The processing temperature is 25 to 50.
° C, preferably 35 to 45 ° C.

The processing solution having a fixing ability of the present invention can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. As a silver recovery method,
Electrolysis (described in French Patent No. 2,299,667),
Precipitation method (JP-A-52-73037, German Patent No. 2,3
31 and 220), an ion exchange method (JP-A-51-1)
No. 7114, described in German Patent No. 2,548,237) and metal replacement method (described in British Patent No. 1,353,805)
Etc. are effective. These silver recovery methods are preferably performed in-line from the tank liquid, because the rapid processing suitability is further improved.

After the processing step having the fixing ability, usually,
A water washing process is performed. After processing with a processing solution having fixing ability,
A simple treatment method of performing a stabilization treatment using the stabilizer of the present invention without substantially washing with water can also be used. The washing water used in the washing step can contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant However, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water may contain various antibacterial agents and fungicides for preventing generation of water rust and mold generated on the photosensitive material after processing. Examples of these antibacterial and antifungal agents are disclosed in
Thiazolyl benzimidazole compounds as shown in JP-A-157244 and 58-105145, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds as typified by trichlorophenol , Bromophenol compounds, organotin and organozinc compounds, acid amide compounds, diazines and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary such as benzalkonium chloride Ammonium salts, antibiotics typified by penicillin, etc., are available from Journal Antibact. Antifung.
Agents) Vol 1. No.5, p. 207-223 (198
These include the general-purpose anti-blur agents described in 3).
More than one species may be used in combination. Also, JP-A-48-83820
Various disinfectants described in the above item can also be used.

It is preferable that the washing water contains various chelating agents. Preferred chelating agents include
Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid,
Examples thereof include organic phosphonic acids such as diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345172A1. Further, it is preferable that a preservative which can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water.

The washing step and the stabilizing step are preferably performed in a multi-stage countercurrent system, and the number of stages is preferably two to four. The replenishment amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area. Tap water can be used as the water used in these washing steps, but Ca, M, etc. may be used depending on the ion exchange resin or the like.
It is preferable to use water deionized to a g ion concentration of 5 mg / liter or less, or water sterilized by halogen, an ultraviolet germicidal lamp, or the like. In addition, tap water may be used as water for correcting the amount of evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

It is preferable to use a method in which the overflow liquid in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a prebath, because the amount of waste liquid can be reduced. In processing, not only bleaching solution, bleach-fixing solution and fixing solution, but also other processing solutions (for example, color developing solution, washing water, and stabilizing solution), use an appropriate amount of water or correction solution to correct concentration due to evaporation. It is preferable to replenish the solution or the processing replenisher.

In the present invention, the effect is particularly effective when the total processing time of the processing solution from the bleaching process to the drying step is from 1 minute to 3 minutes, preferably from 1 minute to 20 seconds to 2 minutes. .

In the present invention, the drying temperature is from 50 to 65.
C is preferable, and 50 to 60 C is more preferable. The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds.

In the light-sensitive material of the present invention, it is sufficient that at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer is provided on a support. The number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited. A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. , The photosensitive layer is blue light,
A unit photosensitive layer having color sensitivity to either green light or red light.In a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally such that the red photosensitive layer is , A green color sensitive layer and a blue color sensitive layer 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 color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, see JP-A-61-4374.
No. 8, No. 59-113438, No. 59-113440
And couplers such as those described in JP-A-61-20037 and 61-20038, and may include a color-mixing inhibitor, an ultraviolet absorber, an anti-stain agent, and the like as commonly used. You may go out.

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high sensitivity emulsion layer and a low sensitivity emulsion layer. A two-layer structure of layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.
As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /
Alternatively, they can be installed in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-63.
As described in JP-A-936-936, an order of blue-sensitive layer / GL / RL / GH / RH can be arranged from the side farthest from the support. In addition, Japanese Patent Publication No. 49-15495
The upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower sensitive silver halide emulsion layer, and the lower layer is less sensitive than the middle layer as described in An example is an arrangement in which a silver emulsion layer is disposed, and the sensitivity is sequentially lowered toward the support, and the sensitivity is sequentially reduced to three layers having different sensitivities. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The dry thickness of the support of the light-sensitive material and all the constituent layers except the undercoat layer and the back layer of the support is preferably from 12.0 to 20.0 μm from the viewpoint of bleaching fog, stain over time and the like. More preferably, 12.0-18.
0μ.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
After storage of the photographic material under conditions of 5 ° C. and 50% RH, the photographic material was stored for 7 days. First, the total thickness of the photographic material was measured, and then, after removing the coating layer on the support, the thickness was measured again. The difference is used to determine the thickness of the entire coating layer excluding the support of the photosensitive material. The thickness is measured, for example, by a film thickness measuring device (Anritus Electric Co.
Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite. Further, a photograph of a cross section of the above-mentioned photosensitive material can be taken using a scanning electron microscope (preferably at a magnification of 3,000 or more), and the total thickness on the support can be measured.

In the present invention, the swelling ratio of the photosensitive material [(25
Equilibrium swollen film thickness in H ₂ O at 25 ° C., total dried film thickness at 25 ° C., 55% RH / total dried film thickness at 25 ° C., 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferred. If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the film swelling speed of the light-sensitive material in the present invention is determined by setting a saturated swelling film thickness to 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds). When the time required to reach this 1/2 film thickness is defined as the swelling speed T1 / 2, it is preferable that T1 / 2 is 15 seconds or less. More preferably, it is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the light-sensitive material used in the present invention may be any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver bromide and silver chloride. Good.
Preferred silver halides are silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 0.1 to 30 mol% of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% iodide.

The silver halide grains of the photographic emulsion are cubic,
Those having regular crystals such as octahedron and tetrahedron,
Those having an irregular crystal form such as a sphere or a plate, those having a crystal defect such as a twin plane, or a composite form thereof may be used.

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

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion preparation and types" and No. 18
716 (November 1979), p. 648, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glaf)
kides, Chimie et Physique Photographique Paul
Montel, 1967), Daffin's "Emulsion Chemistry",
Published by Focal Press (GF Duffin, Photographic
Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikman et al Making and Coating).
Photographic Emulsion, Focal Press, 1964). U.S. Pat. Nos. 3,574,628 and 3,655,39
No. 4 and British Patent No. 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science, Inc.
And Engineering (Gutoff, Photographic Sci
14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, and 4,430,048;
No. 4,439,520 and British Patent No. 2,11
2,157 and the like.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, or may have a phase structure. Further, silver halides having different compositions may be joined by an epitaxial junction,
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure No. 17643 (December 1978) and No. 17643.
18716 (November 1979) and No. 307
105 (November 1989), and the relevant locations are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures (RD), and the relevant portions described below are indicated. Type of additive [RD17643] [RD18716] [RD307105] 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right Columns 866 to 868 Super sensitizer 〜Page 649 right column 4. Brightener 24 page 647 page right column 868 5. Fogging prevention 24-25 page 649 page right column 868-870 agent, stabilizer 6. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers 7.Stain, page 25, right column, page 650, left column, page 872 Inhibitors to right column 8. Dye image, page 25 Page 650, left column, page 872 Stabilizer 9. Hardener page 26, page 651, left column, pages 874 to 875 10. Binder, page 26, page 651, left column, pages 873 to 874 11. Plasticizer, page 27, page 650, right column, page 876 Lubrication Agent 12. Coating aid, 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 Inhibitor 14.Matsuto agent, pages 878 to 879

In the present invention, various color couplers can be used in combination, and a typical example is RD No. 1 described above.
7643, VII-CG and RD No. 307105, VII-CG
The patent is described in US Pat.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620;
Nos. 4,326,024 and 4,401,752
No. 4,248,961, JP-B-58-1073
9, UK Patent Nos. 1,425,020 and 1,47
No. 6,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, EP 249,473A, and JP-A-3-131847.
And the like are preferred. Further, 1-alkylcyclopropylcarbonyl-type and indolinylcarbonyl-type yellow couplers having a high extinction coefficient of the dye and high wet heat fastness, for example, Japanese Patent Application Nos. 2-64718 and 2-3145.
No. 22, No. 2-232857, No. 2-26341,
Those described in JP-A-2-296401 are particularly preferable.

As the magenta coupler, 2-equivalent and / or 4-equivalent 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat.
No. 4,351,897, European Patent 73,636
No. 3,061,432 and US Pat. No. 3,72.
No. 5,064, RD No. 24220 (June 1984
), JP-A-60-33552, RD No. 24230
(June 1984), JP-A-60-43659, 6
No. 1-72238, No. 60-35730, No. 55-1
Nos. 18034, 60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, WO (PCT) 88/047.
No. 95 is more preferable.

In the present invention, an effective effect is exhibited when at least one of the 4-equivalent magenta couplers is used. Preferred among the 4-equivalent magenta couplers are 4-equivalent 5-pyrazolone-based magenta couplers of the following general formula (M) or 4-equivalent pyrazoloazole-based magenta couplers represented by the following general formula (m).

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In the general formula (M), R ₄ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. A
r represents a substituted or unsubstituted phenyl group. In addition, R ₄ ,
Any of Ar may be a divalent or higher polyvalent group to form a multimer such as a dimer, or form a polymer coupler by linking a polymer main chain and a coupling mother nucleus. May be. In the general formula (m), R ₅ represents a hydrogen atom or a substituent, Z represents a group of non-metallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring is It may have a substituent and may have a condensed ring. Any of the substituents on the azole ring formed by R ₅ and Z may be a divalent or higher polyvalent group to form a multimer such as a dimer. A polymer coupler may be formed by linking with a coupling mother nucleus.

The alkyl group of R ₄ represents a linear or branched alkyl group having 1 to 42 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a cycloalkenyl group, and the aryl group has 6 carbon atoms. Represents an aryl group of ~ 46, an acyl group represents an aliphatic acyl group having 2 to 32 carbon atoms or an aromatic acyl group having 7 to 46 carbon atoms,
The carbamoyl group represents an aliphatic carbamoyl group having 2 to 32 carbon atoms or an aromatic carbamoyl group having 7 to 46 carbon atoms. These groups may have a substituent, and they are an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

More specifically, R ₄ is an alkyl group (for example, methyl, ethyl, butyl, propyl, octadecyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, methoxyethyl, ethoxyethyl, t-butoxyethyl, phenoxyethyl, methanesulfonylethyl , 2
-(2,4-di-tert-amylphenoxy) ethyl), an aryl group (for example, phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3- Octadecenyl-1-succinimide) phenyl, 2-chloro-
5-octadecylsulfonamidophenyl, 2-chloro-5- [2- (4-hydroxy-3-tert-butylphenoxy) tetradecanamidophenyl]), acyl group (for example, acetyl, pivaloyl, tetradecanoyl,
2- (2,4-di-tert-pentylphenoxy) acetyl, 2- (2,4-di-tert-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-t
ert-amylphenoxyacetamide) benzoyl)
A carbamoyl group (e.g., N-methylcarbamoyl,
N, N-dimethylcarbamoyl, N-hexadecylcarbamoyl, N-methyl-N-phenylcarbamoyl, N
-[3- {1- (2,4-di-tert-pentylphenoxy) butyramide}] phenylcarbamoyl). Specific examples of the substituents that these groups may further have include, for example, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an acyl group, an aryloxycarbonyl group, Alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group,
Carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, aryloxycarbonylamino group, imide group, Alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfonyl group, sulfinyl group, azo group, phosphonyl group, azolyl group, fluorine atom, chlorine atom, and bromine atom. R ₄ is preferably an aryl group or an acyl group.

Ar represents a substituted or unsubstituted phenyl group. As the substituent, a halogen atom, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group is preferable. Specifically, Ar is, for example, a phenyl group, a 2,4,6-trichlorophenyl group,
2,5-dichlorophenyl group, 2,4-dimethyl-6-
A methoxyphenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 2,6-dichloro-4-ethoxycarbonylphenyl group, a 2,6-dichloro-4-cyanophenyl group or a 4- [2- (2,4 -Di-tert-amylphenoxy) butyramido] phenyl group. It is preferably a substituted phenyl group, and more preferably a phenyl group substituted by at least one halogen atom (particularly a chlorine atom). preferable.

Of the pyrazoloazole-based magenta couplers represented by the general formula (m), preferred are 1H-
Imidazo [1,2-b] pyrazole, 1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H- A pyrazolo [1,5-d] tetrazole skeleton, each of the following general formulas [m-1] and [m-
2], [m-3] and [m-4].

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The general formula (m) and R ₅ , R ₅₁ , R ₅₂ and R ₅₃ in these formulas will be described. R ₅ and R ₅₁ represent a hydrogen atom or a substituent.
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, hydroxy group, sulfo group, nitro group, carboxy group, amino group, alkoxy group, aryloxy group,
Acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy Group, azo group, acyloxy group, carbamoyloxy group,
Silyloxy group, aryloxycarbonylamino group,
Examples include an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group, and an azolyl group. R ₅ and R ₅₁ may form a bis form with a divalent group.

More specifically, R ₅ and R ₅₁ are each a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom),
An alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group; specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl,
3- {4-} 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl,
Cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), an aryl group (e.g., phenyl, 4
-T-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, hydroxy Group, sulfo group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, -Methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), an acylamino group (for example, acetamide,
Benzamide, tetradecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t
-Butyl-4-hydroxyphenoxy) butanamide,
2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide), an alkylamino group (for example,
Methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-
Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {α- (3-t-butyl-4-
Hydroxyphenoxy) dodecaneamide｝ anilino),
A ureido group (eg, phenylureido, methylureide, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino),
Alkylthio groups (eg, methylthio, octylthio,
Tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio groups (for example, phenylthio, 2-butoxy-5-t-octylphenyl) Ruthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio),
Alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy- 5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2 -Hydroxy-4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethyl) Silyloxy), an aryloxycarbonylamino group (for example, phenoxycarbonylamino), an imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2- Benzothiazolylthio, 2,4 Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl) A phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl) and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group which can further have a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₅ and R _5
Examples of ₅₁ include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, a urethane group, and an acylamino group.

R ₅₂ is the same group as R _51, and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group and a cyano group. is there.

R ₅₃ has the same meaning as R _51, and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or a carbamoyl group. And an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group.

The polymer of the magenta coupler represented by formula (M) or (m) is described in JP-B-2-4405.
Reference can be made to the description such as No. 1. Hereinafter, specific examples of preferable 4-equivalent magenta couplers are listed below.

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In the present invention, the effect is particularly effective when a 4-equivalent 5-pyrazolone magenta coupler of the general formula (M) is used. In the present invention, the coating amount of the 4-equivalent magenta coupler is from 0.4 × 10 ^-3 to 1 m ² of the photosensitive material.
Preferably it is 3.5 × 10 ⁻³ mol. In the present invention, there is no problem even when used in combination with a 2-equivalent magenta coupler.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622 and 4,333,99.
No. 9, 4,753, 871, 4,451, 5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,29
No. 6,199, JP-A-61-42658, JP-A-3-
What is described in 196037 etc. is preferable. Also, pyrrolotriazole, pyrroloimidazole, imidazopyrazole, imidazole, pyrazolotriazole, cyclic active methylene cyan couplers, for example, Japanese Patent Application No. 2-302
No. 078, No. 2-32051, No. 3-226325
And JP-A-3-236894, JP-A-64-32260.
And those described in JP-A-2-141745 are particularly preferable.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in RD No. 17643, Sections VII-G,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,1
38,258, British Patent No. 1,146,368 and Japanese Patent Application No. 2-50137 are preferred. Also,
A coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a dye reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910 and British Patent 2,102,173.

A coupler which releases a photographically useful residue upon coupling can also be preferably used. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
31,188, JP-A-59-157638, 59
The thing described in -170840 is preferable.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,42.
No. 7, etc., EP 173,30
No. 11449, No. 24241, couplers capable of releasing a dye which recolors after release described in JP-A No. 2A;
Bleach accelerator releasing couplers described in JP-A 1-2201247, etc., ligand releasing couplers described in U.S. Pat. No. 4,553,477, couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat. 4,774,
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a photographic material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027 and the like. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, etc.) Tridodecyl phosphate, tributoxyethyl phosphate,
Trichloropropylphosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide) , N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amyl phenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
Ert octylaniline and the like; hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used.
Butyl acetate, ethyl propionate, 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. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230 and the like.

These couplers may be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above-mentioned high-boiling organic solvent, or may be water-insoluble and organic. It can be dissolved in a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, the international publication number WO88 / 0
The homopolymers or copolymers described on pages 12 to 30 of JP-A No. 0723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

Suitable supports that can be used in the present invention are described, for example, in RD No. 17643, page 28 and RD No. 18;
716 at page 647 right column to page 648 left column. The present invention can be applied to various photosensitive materials. Especially for general or movie color negative film,
It is preferably used for a reversing film for a slide or a television.

[0163]

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. The amount of silver coverage (Composition of photosensitive layer) The silver halide and colloidal silver, expressed in units of g / m ^2, also a coupler, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2 × 10 ^-2 Second layer: Intermediate layer Fine grain silver iodobromide (AgI: 1.0 mol%, equivalent spherical diameter: 0.7 μm)
m) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent spherical diameter 0.9 μm, coefficient of variation of equivalent spherical diameter 21%, tabular grains, diameter / Thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.40 gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv- 1 0.32

Fourth Layer: Second Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, sphere equivalent diameter variation coefficient 25%, tabular grains,
Diameter / thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ^-4 mol ExS-2 1.0 × 10 ^-4 mol ExS-3 3.0 × 10 ^-5 mol ExC-1 0.13 ExC-2 6.2 × 10 ^{− 2} ExC-4 4.0 × 10 ^-2 Solv-1 0.10

Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type,
Sphere equivalent diameter 1.4 μm, coefficient of variation of sphere equivalent diameter 28%, plate-like particle, diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ^-4 mol ExS-2 6.0 × 10 ^-5 mol ExS -3 2.0 × 10 ^-5 mol ExC-2 8.5 × 10 ^-2 ExC-5 7.3 × 10 ^-2 Solv-1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 Solv- 1 8.0 × 10 ^-2

Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / Thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.16 gelatin 1.20 ExS-4 5.0 × 10 ^-4 mol ExS-5 2.0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 Solv-1 0.20 Solv- 33.0 × 10 ⁻² 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%, tabular grains ,
Diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 × 10 ^-4 mol ExS-6 7.0 × 10 ^-5 mol ExM-1 0.12 ExM-2 7.1 × 10 ^{− 3} ExM-3 3.5 × 10 ^-2 Solv-1 0.15 Solv-3 1.0 × 10 ^-2 Ninth layer: Intermediate layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2

Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type,
Sphere equivalent diameter 1.4 μm, coefficient of variation of sphere equivalent diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ^-4 mol ExS-5 8.0 × 10 ^-5 mol ExS -6 8.0 × 10 ^-5 mol ExM-4 4.5 × 10 ^-2 ExM-6 1.0 × 10 ^-2 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 Solv-1 0.25 11th layer: yellow filter Layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12 12th layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10

Thirteenth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.55 μm, coefficient of variation of equivalent spherical diameter 25%, tabular grains,
Diameter / thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver emulsion (AgI 19.0 mol%, internal high AgI type,
Sphere equivalent diameter 1.0 μm, coefficient of variation of sphere equivalent diameter 16%, octahedral particle) Silver coating amount 0.19 Gelatin 0.35 ExS-7 2.0 × 10 ^-4 mol ExY-1 0.22 Solv-1 7.0 × 10 ^-2 15th layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%) , Internal high AgI type,
Sphere equivalent diameter 1.7 μm, coefficient of variation of sphere equivalent diameter 28%, plate-like particle, diameter / thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1.00 ExS-8 1.5 × 10 ^-4 mol ExY-1 0.21 Solv-1 7.0 × 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2 18th layer: 2nd protective layer Fine grain silver chloride (sphere) Equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (1.5 μm diameter) 2.0 × 10 ^-2 B-2 (1.5 μm diameter) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H -1 0.35 Cpd-7 1.00

This sample contains 1,2-benzisothiazolin-3-one (average 200 ppm based on gelatin), n
-Butyl-p-hydroxybenzoate (about 1,000 pp
m), and 2-phenoxyethanol (about 10,000 p
pm) was added. B-4, B-5, W-2, W
-3, F-1, F-2, F-3, F-4, F-5, F-
6, F-7, F-8, F-9, F-10, F-11, F
-12, F-13 and iron, lead, gold, platinum, iridium and rhodium salts.

The compounds used above are listed below.

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The dried film thickness of the sample 101 excluding the support was 22 μm, and the swelling speed T1 / 2 was 9 seconds. The sample 101 prepared as described above was cut into a length of 2 m with a width of 35 mm, and after being exposed to white light of 50 lux for 0.01 seconds, using an automatic developing machine under the following conditions: The processing was performed until the cumulative replenishment amount of the processing solution became three times the mother liquor tank capacity. It should be noted that only the stabilizing solution was sequentially replaced, and the other processes were performed under the same conditions, and the stain of the processed sample was evaluated. Then, the sample was used as an image stability evaluation sample. The processing steps and the composition of the processing solution are shown below.

Processing step Step Processing time Processing temperature Replenishment amount * Tank capacity (° C.) (ml) (liter) Color development 3 minutes 5 seconds 38.0 600 17 Bleaching 50 seconds 38.0 140 5 Bleaching and fixing 50 seconds 38. 0-5 Settling 50 seconds 38.0 4205 Rinse 30 seconds 38.0980 3 Stable (1) 20 seconds 38.0-3 Stable (2) 20 seconds 38.0 560 3 Drying 1 minute 60 * Refill The amount was 1 m ² of the light-sensitive material. The stabilizing solution was of the countercurrent type from (2) to (1), and the overflow of washing water was all introduced into the fixing bath. For replenishment to the bleach-fix bath, a cut is provided at the top of the bleach tank and the top of the fixing tank of the automatic processor, and all the overflow generated by the supply of the replenisher to the bleach tank and the fixing tank is transferred to the bleach-fix bath. It was made to flow in. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step are each per 1 m ² of the photosensitive material. 65ml,
50 ml, 50 ml, 50 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Each replenisher was replenished with the same liquid as the respective tank liquid. The composition of the treatment liquid is shown below.

(Color developing solution) Unit (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-3.3 Sodium diphosphonic acid 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Iodide Potassium 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4- [N-ethyl-N-4.5 (β-hydroxyethyl) amino] aniline sulfate 1.0 liter of water and pH 10.05

(Bleaching solution) Unit (g) 1,3-diaminopropanetetraacetic acid 130 Ferric ammonium-water salt Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Add water and add 1.0 L pH [Ammonia water 4.2)

(Bleach-fixing solution) A mixture of the above-mentioned bleaching solution and the following fixing solution in a ratio of 15:85 (by volume) (pH 7.0)

(Fixing solution) Unit (g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution 280 ml (700 g / L) Imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 L pH [adjusted with ammonia water and acetic acid] 7.4

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by 20 mg / L of sodium diisocyanurate and 15 mg of sodium sulfate.
0 mg / liter was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing solution) Unit (g) p-Toluenesulfinic acid 0.1 sodium polyoxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Image stabilization Agent (listed in Table A) 0.01 liter with water added 1.0 liter pH 7.2

[Evaluation of Image Preservation] Each sample after the above-mentioned processing was subjected to a photographic densitometer FSD10 manufactured by Fuji Photo Film Co., Ltd.
After measuring the magenta concentration at 3, the relative humidity 55
The solution was aged for 2 months under the condition of%, and the concentration was measured again in the same manner. The evaluation was made based on the decrease in the magenta concentration over time. (M fading) The magenta density of each sample after the treatment was 1.5.

[Evaluation of Treated Stain] Each sample after the above treatment was visually observed to evaluate the stain. The evaluation criteria are as follows. Rank 1. 1. No dirt is observed. Slight contamination is observed (1/10 of the sample surface)
Below, and the dirt is slightly cloudy). 3. Clouding is observed (1/10 or more of the sample surface) 4. Adhered matter is observed (1/10 or less of the sample surface). Adhesion is observed (more than 1/10 of the sample surface)

[Measurement of Formaldehyde Vapor Pressure] Each of the stable liquids was prepared according to the following formulation, and 100 ml of each liquid was placed in a petri dish (opening area: 80 cm ² ) and placed in a 5 liter glass closed container. After aging at 20 ° C. for 7 days, the formaldehyde vapor pressure in the glass container was measured with a formaldehyde L-type direct reading gas detector tube manufactured by Gastech. (HCHO concentration) Table A shows each image stabilizer used and each evaluation result.

[0198]

[Table 5]

As can be seen from Table A, by using the N-methylol compound of the present invention, a process having a low formaldehyde vapor pressure and excellent image storability can be performed without causing stains on the processed sample. be able to.

Example 2 The following compound ExC was further added to the fifth layer of the sample 101 of Example 1.
-6 was added at 1.0 × 10 ^-2 g / m ² , and E of the tenth layer was added.
A sample 201 was prepared in the same manner except that xM-4 was replaced with ExM-4 'described below by an equal weight.

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Processing was performed in the same manner as in Example 1 except that the image stabilizer in the stabilizing solution was changed as shown in Table B, and the image storability, processed stain, and formaldehyde vapor pressure were evaluated. The results are shown in Table B.

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[Table 6]

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As can be seen from Table B, by using the compound of the present invention, it is possible to carry out processing excellent in image storability without a low formaldehyde vapor pressure and without generating stain on the processed sample. .

Example 3 In the sample 101 of Example 1, the magenta coupler Ex
The same test was performed on the same samples 201 and 202 as in Example 1 except that the magenta coupler of M-1 or M-17 was replaced with an equimolar instead of M-1, and similar results were obtained. . Further, in Samples 203 and 101 similar to Example 1 except that the magenta coupler of M-1 was replaced with an equimolar instead of the magenta coupler ExM-4 in Sample 101, the magenta coupler ExM- 4, except that the ExM-4 and M-1 magenta couplers were replaced by equimolar 1: 1 molar ratio instead of 4.
When a test was performed on the same sample 204 as in Example 1, similar results were obtained.

Example 4 The following processing steps and processing solutions were processed using an automatic developing machine until the cumulative replenishment amount of the processing solutions became three times the mother liquor tank capacity.
In the same manner as in Examples 1 and 2, each of the stable liquids was subjected to the treatment of Sample 101, and an image storability test was performed. As a result, similar results were obtained. Processing method Step Processing time Processing temperature Replenishment amount * Tank capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38 33 20 Bleaching 6 minutes 30 seconds 38 25 40 Rinse 2 minutes 10 seconds 24 1200 20 4 minutes 20 seconds 38 25 30 Rinse 1 minute 05 seconds 24-10 Rinse 1 minute 00 seconds 24 1200 10 Stable 1 minute 05 seconds 38 25 10 Dry 4 minutes 20 seconds 55 * Replenishment amount is 35mm width 1m length Counter flow piping system

Next, the composition of the processing solution will be described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene 3.0 3.2 -1,1-Diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-4.5 5.5 hydroxyethylamino]-2-methylaniline sulfate 1.0 liter 1.0 liter with water added pH 10.05 10.10

(Bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 100.0 120.0 Ferric sodium trihydrate Ethylenediaminetetraacetic acid 10.0 10.0 Disodium salt Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml 1.0 liter with water 1.0 liter pH 6.0 5.7 (fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 0.7 disodium salt sodium sulfite 7.0 8.0 sodium bisulfite 5.0 5.5 ammonium thiosulfate 170.0 ml 200.0 ml aqueous solution (700g / liter) 1.0 liter with water 1.0 liter pH 6.7 6.6

(Stabilizer) Mother liquor (g) Replenisher (g) Image stabilizer (described in Tables A and B) 2.0 ml 3.0 ml polyoxyethylene-p-0.3 0.45 monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 0.08 Disodium salt Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0

Example 5 In Example 4, the stabilizing solution was no. 1 (no image stabilizer added) and 0.1% of Exemplified Compound I-1 in the bleaching solution.
Sample 101 was processed by adding 3 mol / L. The stain and image storability of the sample after the treatment were evaluated. As good as 8, good results were obtained. Similarly, Sample 201 was treated by adding 0.3 mol / L of Exemplified Compound II-1 to the bleaching solution. When the stain and the image storability of the sample after the treatment were evaluated, No. 2 of Example 2 was evaluated. 16
Similar good results were obtained.

Example 6 A multilayer color photographic material sample 501 comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g UV absorber U-6 0.1 g High boiling organic solvent Oil-1 0.1 g

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-D 10 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: Intermediate layer Fine particles iodized on the surface and inside Silver emulsion (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%)
Silver 0.05g Gelatin 0.4g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.2 g Emulsion B silver amount 0.3 g gelatin 0.8 g coupler C-1 0.15 g coupler C-2 0.05 g coupler C-9 0.05 g compound Cpd-D 10 mg High-boiling organic solvent Oil-2 0.1 g Fifth layer: medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C -3 0.2 g High boiling organic solvent Oil-2 0.1 g Sixth layer: high sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-K 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D-1 0.02 g Eight layers: Intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06
μm, coefficient of variation 16%, AgI content 0.3 mol%)
Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixture inhibitor Cpd-J 0.1 g Color mixture inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E silver amount 0.3 g Emulsion F silver amount 0.1 g Emulsion G silver amount 0.1 g gelatin 0.5 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-D 10 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g 10th layer: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High-boiling organic solvent Oil-2 0.01 g Eleventh layer: high-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil-2 0.02g

Twelfth layer: Intermediate layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g 13th layer: Yellow filter layer Yellow colloidal silver Silver 0.1 g Gelatin 1.1 g Anti-color mixing agent Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: Low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.4 g Emulsion K Silver amount 0.1 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.6 g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L Silver content 0.1 g Emulsion M Silver content 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g 17th layer: Highly sensitive blue-sensitive emulsion layer Emulsion N Silver content 0.4 g Gelatin 1.2 g Coupler C-6 0.7 g

18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U-2 0.01 g UV absorber U-3 0.03 g UV absorber U-4 0.03 g UV absorber U -5 0.05 g UV absorber U-6 0.05 g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd-C 0.2 g Cpd-I 0.4 g Dye D-3 0.05 g

19th layer: 2nd protective layer Colloidal silver Silver content 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1
(Mol%) silver amount 0.1 g gelatin 0.4 g 20th layer: third protective layer gelatin 0.4 g polymethyl methacrylate (average particle size 1.5 μ) 0.1 g copolymer of methyl methacrylate and acrylic acid (average particle size) 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

Further, additives F-1 to F-8 were added to all the emulsion layers in addition to the above composition. Furthermore, in each layer,
In addition to the above composition, gelatin hardener H-1 and surfactants W-3 and W-4 for coating and emulsification were added. More preservative,
Phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol and butyl p-hydroxybenzoate were added as fungicides.

The silver iodobromide emulsions used are as follows. Emulsion name Average particle size Coefficient of variation AgI content (μm) (%) (%) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− A monodisperse tetrahedral particles 0.25 16 3.7 B monodisperse cubic internal latent image type particles 0.30 10 3.3 C monodisperse tetrahedral particles 0.30 18 5.0 D polydisperse twin particles 0.60 25 2.0 E Monodisperse cubic particles 0.17 17 4.0 F Monodisperse cubic particles 0.20 16 4.0 G Monodisperse cubic internal latent image type particles 0.25 11 3.5 H Monodisperse Cubic internal latent image type grains 0.30 9 3.5 I polydisperse tabular grains, 0.80 28 1.5 average aspect ratio 4.0 J monodisperse tetrahedral grains 0.30 18 4.0 K monodisperse 14 Plane particles 0.37 17 4.0 L Monodisperse cubic internal latent image type particles 0.46 14 3.5 M Monodisperse Cubic grains 0.55 13 4.0 N polydisperse tabular grains, 1.00 33 1.3 average aspect ratio 7.0-------------------------------------------------------------------------- −−−−−−−−−−−−−−−

Spectral Sensitization of Emulsions A to N Emulsion name Sensitizing dye added 1 mol of silver halide Addition amount (g) of sensitizing dye per addition ----------------- −−−−−−−−−−−−−−−−−−− A S−1 0.025 Immediately after chemical sensitization S−0.25 Immediately after chemical sensitization B S−1 0.01 End of grain formation Immediately after S-2 0.25 Immediately after completion of grain formation C S-1 0.02 Immediately after chemical sensitization S-2 0.25 Immediately after chemical sensitization DS-1 0.01 Immediately after chemical sensitization S-2 0.10 Chemistry Immediately after sensitization S-7 0.01 Immediately after chemical sensitization ES-30.5 Immediately after chemical sensitization S-4 0.1 Immediately after chemical sensitization FS-3 0.3 Immediately after chemical sensitization S-40. 1 Immediately after chemical sensitization G S-3 0.25 Immediately after grain formation was completed S-4 0.08 Immediately after grain formation was completed H S-3 0.2 During grain formation S-4 0. 6 During grain formation IS-3 0.3 Immediately before the start of chemical sensitization S-4 0.07 Immediately before the start of chemical sensitization S-8 0.1 Immediately before the start of chemical sensitization J S-6 0.2 During grain formation S- 5 0.05 During particle formation KS-6 0.2 During particle formation S-5 0.05 During particle formation LS-6 0.22 Immediately after particle formation S-5 0.06 Immediately after particle formation MS S- 6 0.15 Immediately after chemical sensitization S-5 0.04 Immediately after chemical sensitization NS-6.22 Immediately after the completion of grain formation S-5 0.06 Immediately after the grain formation is completed ---------------. −−−−−−−−−−−−−−−−−−−−−−−−−−−

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The sample 501 was exposed imagewise, and processed using a cine-type automatic developing machine according to the processing steps described below. First, each of the stabilizing solutions was sequentially treated with the bleaching solution 1 by 0.5 m ^{2, and then} treated in the same manner by using the bleaching solution 2. The same evaluation as in Example 1 was performed on the obtained sample. . Processing step Time Temperature Replenishment amount * Tank capacity (minutes) (° C) (liters) (liters) Black-white development 6 38 1.5 12 First rinse 1 38 7.5 4 Inversion 1 38 1.1 4 Color development 4 38 2.0 12 Adjustment 238 1.14 Bleaching 438 1.3 12 Settling 338 1.3 12 Second washing (1) 138 4 Second washing (2) 138 7.5 4 Stabilizing 1 38 1.1 4 drying 2 50 * replenishment rate overflow liquid amount second washing per photosensitive material 1 m ² (2) is led to the second washing (1) bath.

The composition of each processing solution was as follows. (Black and white developer) Start solution Replenisher Unit (g) Nitrilo-N, N, N 2.0 2.0-Trimethylenephosphonic acid / 5 sodium salt Diethylenetriamine 3.0 3.0 Pentaacetic acid pentasodium salt Sulfurous acid Potassium 30 30 Hydroquinone mono 20 20 Potassium sulfonate Potassium carbonate 33 33 1-Phenyl-4-me 2.0 2.0 Tyl-4-hydroxymethyl-3-pyrazolidone Potassium bromide 2.5 0.9 Thiocyanic acid Potassium 1.2 1.2 Potassium iodide 2.0 mg 2.0 mg Add water 1.0 liter 1.0 liter pH (25 ° C) 9.60 9.70 Adjust pH with hydrochloric acid or potassium hydroxide did.

(Reversal Solution) Start Solution / Replenisher Common Unit (g) Nitrilo-N, N, N 2.0-Trimethylenephosphonic acid / 5 sodium salt Stannous chloride dihydrate 1.0 p -Aminophenol 0.1 Sodium hydroxide 8.0 Glacial acetic acid 15 mL Add water 1.0 L Add ammonium sulphite 20 Water add 1.0 L pH (25 ° C) 6.60 Adjust pH with acetic acid or aqueous ammonia did.

(Color Developer) Start Solution Replenisher Unit (g) Nitrilo-N, N, N 2.0 2.0-Trimethylenephosphonic acid / 5 sodium salt Diethylenetriamine 2.0 2.0 Pentaacetic acid 5 Sodium salt Sodium sulfite 7.0 7.0 Tripotassium phosphate.12 hydrate 3636 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazinic acid 1.5 5 N-ethyl- (β-methyl 10.5 10.5 tansulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 3,6-dithiaocta 3.5 3.5 1,8-diol Water was added and 1.0 liter 1.0 liter pH (25 ° C.) 11.90 12.05 The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Adjustment solution) Start solution / replenisher common unit (g) Ethylenediaminetetraacetic acid 8.0 disodium salt dihydrate sodium sulfite 12 2-mercapto-1,3,0.5 4-triazole pH ( 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching Solution 1) Start Solution / Replenisher Common Unit (g) Ethylenediaminetetraacetic acid 3 Ethylenediaminetetraacetic acid 150 Ferric ammonium dihydrate 2-mercapto-1,3,0.5 4-triazole bromide Ammonium 120 Ammonium nitrate 25 Water was added to 1.0 liter pH (25 ° C) 4.20 pH was adjusted with acetic acid or aqueous ammonia.

(Bleaching Solution 2) Start Solution / Replenisher Common Unit (g) 1,3-diaminopropanetetraacetic acid 1,3-diaminopropane120 ferric ammonium tetraacetate ammonium dihydrate glycolic acid 40 Acetic acid 30 Ammonium bromide 120 Ammonium nitrate 25 Water was added to 1.0 liter pH (25 ° C) 4.20 pH was adjusted with acetic acid or aqueous ammonia.

(Fixing solution) Start solution / replenisher common unit (g) Ethylenediaminetetraacetic acid 1.7 · sodium dihydrate sodium benzaldehyde-20-o-sulfonate sodium bisulfite 15 ammonium thiosulfate 250 ml g / liter) 1.0 liter by adding water pH (25 ° C.) 6.00 pH was adjusted with acetic acid or aqueous ammonia.

(Stabilizing solution) Using each stabilizing solution of Example 1 or 2 (Common to start solution / replenisher)

The evaluation of the image storability was carried out at a portion where the magenta density was 0.5 in the gray coloring portion of the sample subjected to each processing. The results were the same as in Examples 1 and 2. Good results were obtained when the stabilizer containing the N-methylol compound of the present invention was used. In the above processing, the stabilizer used was a solution containing no image stabilizer, and a solution obtained by adding each of the image stabilizers in Table C to the adjustment solution at 0.03 mol / L was used. Evaluation of image storability was performed in the same manner. The results are shown in Table C.

[0249]

[Table 7]

As can be seen from Table C, the use of the N-methylol compound of the present invention in the conditioning bath also has a sufficient effect of preventing fading of the magenta dye. In particular, 1,
Good results were obtained with the use of the ferric complex of 3-diaminopropanetetraacetic acid. When the surface of each sample in Table C was observed, no stain was observed in any of the samples.

Example 7 Using photosensitive material, sample 201 of Example 2 of JP-A-2-90151, photosensitive material 1 of Example 1 of JP-A-2-93641 and photosensitive material 9 of Example 3 were used. No. 1 processing No. 1 8
And the processing No. of the second embodiment. When the treatment was carried out in No. 16, the vapor pressure of formaldehyde was low, the fastness of the dye image was excellent, and the photosensitive material did not stain.

[0252]

According to the present invention, the vapor pressure of formaldehyde is low, the effect of preventing fading of a dye image is excellent, and the photosensitive material is not stained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeru Nakamura 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fujisha Shin Film Corporation (72) Inventor Morio Yagihara 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujisha Shin Film Corporation ( 72) Inventor Hiroyuki Watanabe 210, Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. (56) References 2-220052 (JP, A) JP-A-2-27355 (JP, A) JP-A-2-153348 (JP, A) JP-A-2-89053 (JP, A) JP-A-2-503483 (JP, A) A) U.S. Pat. No. 5,348,845 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 11/00

Claims (8)

(57) [Claims] 1. A color image stabilizing processing solution for a silver halide color photographic light-sensitive material, comprising at least one N-methylol compound represented by the following general formula (I). Embedded image (In the formula, X represents a nonmetallic atom group necessary to form a 1H-pyrazole ring or a 1H-1,2,4-triazole ring together with a nitrogen atom.) 2. A composition which satisfies the following condition A, and further comprises N-methylol of pyrazole and N-methyl of 1,2,4-triazole.
A color image for a silver halide color photographic light-sensitive material, comprising at least one of a methylol compound, an N-methylol compound of urazole and an N-methylol compound selected from the compounds represented by the following general formula (III). Stabilization solution. (Condition A) Equilibrium constant in water at room temperature is 2
× 10 ^-2 mol / l or less, and the formaldehyde release rate constant is 1 × 10 ^-5 sec ^-1 or more. Embedded image (In the formula, Zb is a group of non-metallic atoms necessary to form a 4- to 8-membered ring, provided that the atom bonded to the nitrogen atom is an atom selected from a carbon atom, an oxygen atom or a sulfur atom. ) 3. An N-methylol compound represented by the general formula (I) according to claim 1 and / or an N-methylol derivative of pyrazole which satisfies the condition A according to claim 2 and
N-methylol of 1,2,4-triazole, urazo
Represented by the general formula (III):
A stabilizer for a silver halide color photographic light-sensitive material, comprising at least one N-methylol compound selected from compounds . 4. An N-methylol compound represented by the general formula (I) according to claim 1 and / or an N-methylol derivative of pyrazole which satisfies the condition A according to claim 2 and
N-methylol of 1,2,4-triazole, urazo
Represented by the general formula (III):
An adjusting solution for a silver halide color photographic light-sensitive material, comprising at least one N-methylol compound selected from compounds . 5. An N-methylol compound represented by the general formula (I) according to claim 1 and / or an N-methylol derivative of pyrazole which satisfies the condition A according to claim 2 and
N-methylol of 1,2,4-triazole, urazo
Represented by the general formula (III):
A bleaching solution for a silver halide color photographic light-sensitive material, comprising at least one N-methylol compound selected from compounds . 6. An N-methylol compound represented by the general formula (I) according to claim 1 and / or an N-methylol derivative of pyrazole which satisfies the condition A according to claim 2 , and
N-methylol of 1,2,4-triazole, urazo
Represented by the general formula (III):
A method for processing a silver halide color photographic light-sensitive material, comprising processing with a color image stabilizing processing solution containing at least one N-methylol compound selected from compounds . 7. A silver halide color photographic light-sensitive material comprising 4
7. The method according to claim 6 , wherein the material contains at least one equivalent magenta coupler. 8. An N-methylol compound represented by the general formula (I) according to claim 1, which is treated with a processing solution having a bleaching ability containing a bleaching agent having an oxidation-reduction potential of 150 mV or more. The condition A according to claim 2 is satisfied , and
N-methylol of pyrazole, 1,2,4-triazo
N-methylol body, urazole N-methylol
Of a silver halide color photographic light-sensitive material, which is processed with a color image stabilizing processing solution containing at least one of an N-methylol compound selected from a compound represented by the formula (III): Method.