JPH0534889A - Color picture stabilizing processing solution, stabilizing solution, stabilizing replenishment solution, adjusting solution and bleaching solution and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To give high discoloration preventing capacity and low vapor pressure of formalin by making include 1H-pyrazole-1-methanol compounds, 1H-1,2,4- triazole-1-methanol compounds and/or N-methylol compounds having <=2X10<-2>mol/l equilibrium constant in water at room temperature and >=1X10<-5>sec<-1> release velocity constant of formaldehyde. CONSTITUTION:N-methylol compounds represented by the formula I and/or N-methylol compounds having <=2X10<-2>mol/l equilibrium constant in water at room temperature and >=1X10<-5>sec<-1> release velocity constant of formaldehyde are made included in color image stabilizing processing solution and/or its makeup solution. Here working environment where vapor pressure of formaldehyde is reduced is provided and a pigment image is stabilized. In the formula I, X represents a nonmetallic group required for forming a 1-H-pirazole ring or a 1H-1,2,4-triazole ring together with a nitrogen atom.

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 sometimes simply referred to as a light-sensitive material) and a processing method using the same. The present invention relates to a color image stabilizing treatment liquid which has a reduced formaldehyde vapor pressure and is excellent in stabilizing a dye image, and a treatment 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 produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the subsequent desilvering step, the silver generated in the color developing step is oxidized by the action of an oxidizing agent commonly referred to as a bleaching agent, and then dissolved by a complex ion forming agent of silver ions commonly referred to as a fixing agent. It Through this desilvering process, only the dye image is formed on the color light-sensitive material.

Usually, after these steps, washing treatment is carried out to remove unnecessary treatment liquid components. In the case of color paper or reversal color paper, it is general to complete the process above and proceed to the drying process, but in the process of color negative film or color reversal film, a stabilization process is required in addition to this. is there. It is well known that formalin is used in the stabilizing bath in the final step of these processings, and its purpose is to prevent fading of magenta dye due to residual magenta coupler in the light-sensitive material after processing. is there. A slight amount of formaldehyde vapor is generated during preparation of a stabilizing bath containing such formalin and during drying of the light-sensitive material to which the stabilizing solution adheres.

It is known that inhalation of formaldehyde is harmful to the human body, and the Japan Society for Occupational Health recommends 0.5 ppm as an acceptable concentration of formaldehyde in the working environment. Therefore, from the viewpoint of improving the working environment, efforts have been made to reduce the formaldehyde concentration in the stabilizing bath and to switch to a formalin substitute.

As a formalin substitute, for example, JP-A-63-244036 describes a hexamethylenetetramine compound. When this compound is used, the formaldehyde concentration, that is, the formaldehyde vapor pressure is surely reduced, but the original purpose of the magenta dye is not sufficient to prevent fading, and remarkable fading occurs even after several weeks at room temperature.

On the other hand, many N-methylol compounds having a specific structure have been proposed. For example, N-methylol compounds of melamine compounds of US Pat. Nos. 2,487,569 and 2,629,660, US Pat.
579,435 Urea, N-methylol compound of 2-oxapropylene urea, U.S. Pat. No. 2,487,446.
N-methylol compound of thiourea compound of JP-B-458506, N-methyl compound of hydantoin compound of US Pat. No. 2,579,436, and British Patent No. 684,540.
Methylol compounds, N-methylol compounds of cyandiamide compounds of British Patent No. 908,136, N-methylol compounds of guanidine compounds of U.S. Pat. No. 3,801,322, JP-A-61-35447, British Patent No. 1,
392,134 morpholine, biuret compound N
-Methylol compounds, N-methylol compounds such as pyrrole, pyrrolidine, methylamine, glycine and ethylcarbamate described in JP-A-2-153348 are known.
Regarding the use of these compounds, US Pat. Nos. 4,786,583, 4,859,574, 4,921,779 and European Patent Publication 345,17 are also available.
No. 2, 395, 442, etc.

However, those compounds having a lower formaldehyde vapor pressure than formalin have poor image storability, and those having an improved image storability have a formaldehyde vapor pressure comparable to formalin. The effect of improving the preservability and the reduction of formaldehyde vapor pressure are not satisfied at the same time. Further, these compounds generate stains even if the image storability of the magenta dye is improved, adversely deteriorate the storability of the yellow and cyan dyes and other dyes present in the light-sensitive material, and have poor solubility. It has been found that there is a problem that it is low or that it adheres to the photosensitive material and stains the processed image.

[0008]

Therefore, it has been strongly desired to develop a compound which has a sufficient magenta dye fading preventing ability and a low formaldehyde vapor pressure, that is, an effective formalin substitute. That is, the first object of the present invention is to provide a color image stabilizing treatment liquid which does not substantially release compounds harmful to the human body. Further, a second object of the present invention is to provide a color image stabilizing treatment liquid capable of providing a color image which is safe and has excellent image storability of a processed light-sensitive material, and a treatment method using the same. That is.
Further, a third object of the present invention is to provide a color image stabilizing treatment liquid which is excellent in image storability and which can provide an excellent color image which does not cause adverse effects such as stains on the photosensitive material, and a treatment using the same. Is to provide a method.

[0009]

The present inventors have known N-
As a result of various studies including a methylol type formalin precursor, the above-mentioned object of the present invention is an N-methylol compound represented by the following general formula (I) and / or an N-methylol compound satisfying the following condition A (hereinafter, (Collectively referred to simply as the N-methylol compound of the present invention), and by incorporating this in a color image stabilizing processing solution and / or a color image stabilizing replenishing solution for a silver halide color light-sensitive material, It has also been found that this can be achieved by processing a silver halide color photographic light-sensitive material using a color image stabilizing processing solution and / or a color image stabilizing processing replenishing solution containing this compound.

[0010]

[Chemical 2]

(In the formula, X represents a nonmetal 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 / liter or less, and the formaldehyde emission rate constant is 1 x 10 ^-5 sec ^-1 or more.

The color image stabilizing treatment liquid of the present invention can provide a working environment in which formaldehyde vapor pressure is reduced by containing the N-methylol compound of the present invention. Further, the present invention is characterized in that the dye image is stabilized without using formalin by processing the light-sensitive material with the color image stabilizing processing solution containing the N-methylol compound of the present invention. is doing. Therefore, with respect to other treatments of the above-mentioned processing liquid and regarding the light-sensitive material, any treatment or light-sensitive material can be used.

The N-methylol compound represented by 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 in 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 compounds that satisfy the condition A.

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

[0016]

[Chemical 3]

In the formula, Za is -N =, -CH = or -C.
Represents (R ₂ ) =. R ₁ , R ₂ and R ₃ may be the same or different and each is 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 or a phospho group. , An acyl group, a sulfonyl group, a sulfinyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group,
It 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 or a hydroxy group. Further, R ₁ and R ₂ or R ₂ and R ₃ may combine with each other to form a 5- to 7-membered ring.

More specifically, the general formula (Ia) is 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 (eg allyl), aryl group (eg phenyl, 4-tert-butylphenyl), heterocyclic group (eg 5 -Pyrazolyl, 4-pyrazolyl), halogen atom (for example, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phospho group, acyl group (for example, acetyl, benzoyl, propanoyl), sulfonyl group ( For example, methanesulfonyl, octanesulfonyl, toluenesulfonyl), sulfinyl group (eg, methanesulfinyl), acyloxy group (eg,
Acetoxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl), sulfamoyl group (eg, sulfamoyl, N
-Ethylsulfamoyl), amino group (for example, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), alkoxy group (for example, methoxy, ethoxy), alkylthio Group (for example, methylthio, octylthio), aryloxy group (for example, phenoxy), arylthio group (for example, phenylthio), heterocyclic oxy group (for example, 1-phenyltetrazole-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, and a hydrogen atom, an alkyl group, a halogen atom, an acyloxy group, an amino group, An alkoxy group and an alkylthio group are more preferable, and a hydrogen atom, an alkyl group, an amino group, an alkoxy group and an alkylthio group are further preferable. Particularly, 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 hydrogen atom compound, and particularly preferably all are hydrogen atom compounds.

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

[0021]

[Equation 1]

The equilibrium constant defined in the present invention means K in the above reaction. The formaldehyde release rate constant refers to kr in the above reaction. In the present invention, "water" includes heavy water in addition to ordinary water. As a method for measuring these values, the equilibrium constant K is determined by nuclear magnetic resonance Method (NMR), N
The components generated in the solution when the MR peak change disappears can be calculated from the proton ratio and obtained.

Further, formaldehyde emission rate constant k
r is the formation of an N-methylol compound by adding formaldehyde and an amine compound to water or heavy water at room temperature and tracing the amounts of the N-methylol compound, formaldehyde and amine compound produced in this reaction until equilibrium is reached. The velocity constant Kf was obtained, and N thus obtained was obtained.
-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 a nuclear magnetic resonance absorption method, an ultraviolet or visible spectroscopic method, a high performance liquid chromatography method, and a colorimetric method, and these detecting means may be selected depending on the degree of reaction rate. ..

The equilibrium constant K is 2 × 10 ^-2 mol / liter or less, preferably 1.5 × 10 ^-2 mol / liter or less, and more preferably 1 × 10 ^-2 mol / liter or less.
The formaldehyde emission rate constant kr is 1 × 10 ^-5 s
A compound having ec ⁻¹ or more and 1 × 10 ⁻⁴ sec ⁻¹ or more is more preferable, and a compound having 1 × 10 ⁻³ sec ⁻¹ or more is further preferable, 1 × 10 ⁻² sec ⁻¹ or more The compound is most preferred.

Examples of the N-methylol compound satisfying the condition A in the present invention include N-methylol compound of pyrazole, N-methylol compound of 1,2,4-triazole, N-methylol compound 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 has an aromatic ring or a keto or ketoid structure of an aromatic ring. More preferable. A more preferable compound satisfying the condition A in the present invention is a compound represented by the following general formula (III).

[0027]

[Chemical 4]

(In the formula, Zb is a group of non-metal atoms necessary for forming a 4- to 8-membered ring. However, 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, and 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). Of these, a compound in which the benzene ring is condensed is reduced in solubility, and therefore, a compound in which the benzene ring is not condensed is preferable. In the N-methylol compound satisfying the condition A in the present invention, a more preferable N-methylol compound is the N-methylol compound represented by the general formula (I), and more preferably the general formula (Ia). N-methylol compound described above, particularly a 1H-1,2,4-triazole-1-methanol compound in which Za is -N =.

The N-methylol compound preferred in the present invention is a pK in water at room temperature of an amine compound formed by being released together with formaldehyde when dissolved in water.
a is a compound of 8 or less, more preferably 7 or less, and 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 further preferably 6 or less. Specific examples of the N-methylol compound of the present invention are shown below,
The present invention is not limited to these.

[0030]

[Chemical 5]

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[0035]

[Chemical 8]

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. Examples of synthetic methods thereof include, for example, US Pat.
883,392 and Chem.ber., 85,820 ('52), J. Org. Che
m., 15,1285 ('50), European Published Patent No. 60,222, Khim.Ge
terotsikl.Soedin., (2), 251 ('80) [Cemical Abstracts, 9
3: 46530W]. On the other hand, the pyrazole derivative is the Chemistry of H
The 22nd volume of eterocyclic Compounds, RHWiley "Py
razoles, Pyrazolines, Pyrazolidines, Indazoles and C
It can be synthesized by the method described in "ondensed Ring", INTERSCIENCE PUBLISHERS ('67) or a method analogous thereto.

The synthesis examples of the N-methylol compound of the present invention are shown below. 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 cooling tube. Fifty
After heating to ° C, 90% paraformaldehyde (33 g) was added little by little, and the mixture was stirred at the same temperature for 1 hr.
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). The compound (I-1) was obtained as colorless crystals.
(Yield 72 g, melting point; 79-84 ° C) The chemical structure is
Confirmed by elemental analysis and various spectra. The equilibrium constant K of this compound was 5.6 × 10 ⁻³ mol / liter.
The equilibrium constant was measured using a nuclear magnetic resonance absorption method (NMR) using a 25 mM / liter heavy aqueous solution of this compound.
And the components generated in the solution when the peak change in NMR disappeared were calculated from the proton ratio. In addition, the formaldehyde emission rate constant kr of this compound
Was 8.7 × 10 ^-2 sec ^-1 . The formaldehyde release rate constant kr was first measured by adding formaldehyde and pyrazole to water at room temperature and tracing the amounts of this compound, formaldehyde and pyrazole produced in this reaction with time until equilibrium was reached. The production rate constant kf of the compound was determined. It was calculated by the product of the formation rate constant kf of this compound thus obtained and the above equilibrium constant K. Ultraviolet spectroscopy was used to detect this chemical species. The pyrazole released from this compound had a pKa of 2.5 at room temperature in water.

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, thermometer and cooling tube. , Methanol (50m
1) was added 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 hr. After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure at 40 ° C or lower. The concentrate obtained was crystallized from ethyl acetate (150 ml). Compound (I-5) was obtained as colorless crystals. (Yield 28 g, melting point; 108-
The chemical structure was confirmed by elemental analysis and various spectra. The equilibrium constant K of this compound is 3.3 ×
It was 10 ⁻³ mol / liter. The pKa of 3,5-dimethylpyrazole released from this compound in water at room temperature was 4.1.

The equilibrium constants K of representative N-methylol compounds of the present invention and comparative compounds obtained by the method of compound (I-1) are shown below.

[0040]

[Table 3]

The comparative compounds in Table 3 are as follows.

[0042]

[Chemical 9]

Among the typical N-methylol compounds of the present invention obtained by the method of compound (I-1) and the above-mentioned comparative compounds, comparative compounds whose equilibrium constant K is within or close to the definition of the present invention. Formaldehyde emission rate constant k
Indicates r.

[0044]

[Table 4]

Thus, the N-methylol compound of each of the pyrrole, imidazole and tetrazole compounds has a large equilibrium constant K, which is outside the scope of the present invention. Further, it can be seen that the N-methylol compounds of alicyclic amide compounds and urea compounds have an equilibrium constant K that satisfies the specified value of the present invention, but the formaldehyde release rate constant is small and is outside the specified value of the present invention.

As the N-methylol compound of the present invention, an N-methylol compound obtained by isolation may be used as shown in the above-mentioned synthesis example, and it is also possible to use the N-methylol compound without isolation in the above-mentioned synthesis example. , Formaldehyde or paraformaldehyde and an aqueous solution containing the N-methylol compound of the present invention obtained by adding equimolar amounts of an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof. Good. Furthermore, formaldehyde or paraformaldehyde, pyrazole,
Even if an amine compound such as 1,2,4-triazole or a derivative thereof is added to the same treatment bath in an equimolar amount, the N-methylol compound of the present invention obtained in this treatment bath can be used. Good.

The color image stabilizing treatment liquid in the present invention contains the N-methylol compound of the present invention to stabilize the dye image formed by color development (especially, fading of magenta dye over time). And a replenisher is included. Therefore, it is a processing solution (including a replenishing solution) after color development, and specifically, a stabilizing solution, an adjusting solution, a bleaching solution,
A bleach-fixing solution and a stop solution (including respective replenishing solutions), and more preferably a stabilizing solution, an adjusting solution and a bleaching solution (including respective replenishing solutions). Particularly preferred is a stabilizing solution (including replenisher). The replenisher in the present invention is a replenisher for maintaining the composition of the treatment liquid during continuous treatment.

The preferred embodiments will be described below. (1) A stabilizing solution 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) A preparation liquid 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 stabilizing solution containing at least one N-methylol compound of the present invention. (6) A method of replenishment with a stable replenisher containing at least one N-methylol compound of the present invention. (7) A method of treating with a preparation liquid 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 substitute solution for washing with water, which is conventionally used in the final processing step of a color negative film or a color reversal film. The stabilizing solution used in the bath stabilizing step is also included, but it is preferably used in the final step.

The stabilizing solution and stabilizing replenishing solution which have been used in the final processing step in the past are processing solutions containing formalin as described above, and the processing solution that produces an image stabilizing effect by this formalin is used. The invention uses the N-methylol compound of the present invention in place of formalin,
It was possible to suppress the formaldehyde vapor pressure to a low level and stabilize the image. Therefore, the color image stabilizing treatment liquid of the present invention contains substantially no formalin. Here, the phrase “substantially free of formalin” means that the formalin 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 hydrate of formaldehyde is 0.005 mol / liter or less. In order to reduce the formaldehyde vapor pressure, the lower the total amount of the formaldehyde and the formaldehyde hydrate is, the more preferable, and 0.003 mol / liter or less is particularly preferable.

Each of the replenishers of the present invention is used for replenishing the processing solution with a compound that decreases due to processing of the light-sensitive material and deterioration over time in an automatic processor, and conversely, the concentration of the compound eluted from the light-sensitive material by the processing. It is adjusted to keep the performance constant by controlling. Therefore, the concentration of the decreasing compound is higher than that of the treatment liquid, and the concentration of the latter compound is lower than that of the treatment liquid. In addition, a compound that is unlikely to change its concentration due to treatment or aging is usually contained at almost the same concentration as the treatment liquid.

The preferred addition amount of the N-methylol compound of the present invention is 0.003 to 0.1 mol per liter of the color image stabilizing treatment liquid, and more preferably 0.003 to 0.1 mol.
It is 005 to 0.03 mol.

The color image stabilizing treatment liquid to which the N-methylol compound of the present invention can be added and other treatment liquids used in the processing method using the color image stabilizing treatment liquid of the present invention will be described below. .. When the N-methylol compound of the present invention is used in addition to the stabilizing solution, the stabilizing solution may not contain the N-methylol compound of the present invention, and in that case, the treatment liquid itself is a color image. The term "stabilizing solution" is not appropriate because it does not have the stabilizing effect of 1. Also bleach,
The adjusting solution and the like have a stabilizing effect by adding the N-methylol compound of the present invention, and therefore the names of the bleaching solution and the adjusting solution are not appropriate, but for convenience, they are referred to below.

First, the stabilizing solution and the adjusting solution which are preferably used in the final processing step for containing the N-methylol compound of the present invention will be described. The adjusting solution is a processing solution which is sometimes called a bleaching accelerating bath. The stabilizing solution 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 drops during drying of the processed light-sensitive material, various antibacterial agents for preventing generation of water stains and mold generated on the processed light-sensitive material, and antifungal agents. Agents, bactericides and chelating agents are preferably contained. Further, an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof having no N-methylol group may be added. In addition to the N-methylol compound of the present invention, a compound that stabilizes a dye image, such as hexamethylenetetramine, a hexamethylenetetramine derivative, hexahydrotriazine, a hexahydrotriazine derivative, dimethylolurea, an organic acid or a pH buffering agent is used. May be included. In addition, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, and alkanolamines described in U.S. Pat. No. 4,786,583 can be used if necessary. As the stabilizing solution used in the final treatment step, the pH is usually used in the range of 4 to 9, but 6 to 8 is preferable. When the stabilizing solution 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 particularly 300
~ 600 ml is more preferred. When the stabilizing solution of the present invention is used in the final treatment step, the treatment temperature is preferably 30 to 45 ° C. The processing time is preferably 10 seconds to 2 minutes, and particularly preferably 15 to 30 seconds.

As the conditioning bath, other than the N-methylol compound of the present invention, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid,
Aminopolycarboxylic acid chelating agents such as cyclohexanediaminetetraacetic acid; Sulfite salts such as sodium sulfite and ammonium sulfite, and various bleaching accelerators such as thioglycerin, aminoethanethiol and sulfoethanethiol explained in the bleaching solution. You can
Also, for the purpose of preventing scum, US Pat. No. 4,839,262
Sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,059,446 and Research Disclosure, Vol. 191, 19104.
It is preferable to contain the polyoxyethylene compound described in (1980). These compounds can be used in the range of 0.1 g to 20 g per liter of the preparation liquid, but preferably in the range of 1 g to 5 g.
The pH of the adjusting bath is usually in the range of 3 to 11,
It is preferably 4 to 9, and more preferably 4.5 to 7.
The treatment time in the conditioning bath is preferably 30 seconds to 5 minutes. The replenishing amount of the adjusting bath is preferably 30 ml to 3000 ml per 1 m ² of the light-sensitive material, but particularly 50 ml to 150 ml.
It is preferably 0 ml. Treatment temperature of conditioning bath is 20 ℃
˜50 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

Usually, a silver halide color photographic light-sensitive material is subjected to imagewise exposure, and then negative and direct positive light-sensitive materials are subjected to color development. 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. The preferred color developing agent is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is 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 Among the above p-phenylenediamine derivatives, D-4 and D-5 are particularly preferable. Further, these p-phenylenediamine derivatives are sulfates, hydrochlorides, sulfites,
It may be a salt such as p-toluenesulfonate. The amount of the aromatic primary amine color developing agent used is preferably 0.001 to 0.1 mol, and more preferably 0.01 to 0.06 mol, per liter of the color developing solution.

In the color developing solution, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added as necessary. It can be added. The preferred amount of these preservatives added is 0.5 to 10 per liter of color developer.
g, more preferably 1 to 5 g.

A compound which directly preserves the aromatic primary amine color developing agent is disclosed in JP-A-63-53.
41 and 63-106655, various hydroxylamines (among which, compounds having a sulfo group or a carboxy group are preferable), hydroxamic acids described in JP-A-63-43138, and 63-146041. Hydrazines and hydrazides of the same, the phenols described in Nos. 63-44657 and 63-58443, and 6
Α-hydroxyketones and α described in 3-44656
-Aminoketones, various sugars described in JP-A-63-36244, and the like can be mentioned. Further, in combination with the above compound, JP-A Nos. 63-4235 and 63-24254.
No. 63-21647, No. 63-146040,
63-27841 and 63-25654, etc., monoamines, 63-30845 and 63-
14640, 63-43139 and the like diamines, 63-21647, 63-26655 and 63-46655, and polyamines 6,
Nitroxy radicals described in 3-53551, 6
The alcohols described in 3-43140 and 63-53549, the oximes described in 63-56654 and the tertiary amines described in 63-239447 can be used. As another preservative, JP-A-5
Various metals described in 7-44148 and 57-53749, salicylic acids described in 59-180588, alkanolamines described in 54-3582, polyethyleneimine described in 56-94349. If desired, the aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained.
It is particularly preferable to add an aromatic polyhydroxy compound.

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) and the like can be mentioned. The addition amount of the buffer is preferably 0.1 mol or more, and particularly preferably 0.1 to 0.4 mol, per liter of the color developing solution.

In addition, it is preferable to use various chelating agents in the color developing solution as a precipitation preventing agent for calcium and magnesium or to improve the stability of the color developing solution. As a chelating agent, an organic acid compound is preferable,
Examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Typical 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 etherdiaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid etc. are mentioned. Two or more of these chelating agents may be used in combination, if necessary. The amount of the chelating agent added may be an amount sufficient to block the metal ions in the color developing solution, and is, for example, about 0.1 g to 10 g per liter of the color developing solution.

If desired, an arbitrary development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution in the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, "substantially" means not more than 2 ml, preferably not containing at all, per liter of color developing solution. Other development accelerators include JP-B-37-1
No. 6088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, U.S. Pat. No. 3,818,247, thioether compounds, JP-A Nos. 52-49829 and 50-15.
P-phenylenediamine compounds described in JP-A No. 554, JP-A-50-137726 and JP-B-44-30074.
No. 5, JP-A-56-156826, JP-A-52-43429.
Quaternary ammonium salts described in US Pat.
No. 94,903, No. 3,128,182, No. 4,
230,796, 3,253,919, Japanese Patent Publication No. 41-11431, and U.S. Pat. No. 2,482,546.
No. 2,596,926, No. 3,582,34
No. 6, etc., amine compounds, JP-B-37-1608
No. 8, 42-25201, U.S. Pat. No. 3,128,
No. 183, Japanese Patent Publication Nos. 41-11431, 42-238
No. 83, U.S. Pat. No. 3,532,501 and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles and the like can be added if necessary. The amount of the development accelerator added is about 0.01 to 5 g per liter of the color developing solution.

In the present invention, if necessary,
Any antifoggant can be added. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing substances such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. A heterocyclic compound can be given as a representative example. The addition amount of the antifoggant 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 added is 0 to 5 g, preferably 0.1 g to 4 g, per liter of the color developing solution. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The color developing replenisher contains a compound contained in the color developing solution. The role of the color developing replenisher is to control the concentration of the compound eluted from the light-sensitive material due to the replenishment of the compound to the color developing solution, which is reduced by the processing of the light-sensitive material and deterioration in the automatic processor over time. This keeps the developing performance constant. Therefore, the former compound has a higher concentration than the color developing tank solution,
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 (eg potassium bromide), and the replenisher contains 0 to 0% of the tank solution.
0.6 times included. The halide concentration in the replenisher is usually 0.006 mol / liter or less, but it is necessary to reduce the concentration as the replenisher is lowered, and in some cases, it may not be contained at all. In addition, a compound that is unlikely to change its concentration due to processing or aging is usually contained at almost the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the color developing replenisher is 0.05 to 0.
Increase by about 5 This difference in pH also needs to be increased as the amount of replenishment decreases. The replenishment amount of the color developing solution is 3000 ml or less per 1 m ² of the light-sensitive material, but 100 ml-
It is preferably 1500 ml.

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

The processing method of the present invention can be preferably used for color reversal processing. In the reversal processing, after black and white development, reversal processing is performed if necessary, and then color development is performed. The black-and-white developing solution used at this time is called a black-and-white first developing solution which is generally used for reversal processing of color light-sensitive materials, and it is used for black-and-white silver halide light-sensitive material processing solutions. Various well-known additives that are used by being added to the liquid can be contained.

A typical additive is 1-phenyl-
3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, potassium bromide and 2-methylbenzimidazole, methyl Examples thereof 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 with the above-mentioned black-and-white developing solution or color-developing solution in an automatic developing machine, the area (opening area) in which the developing solution (color-developing solution and black-and-white developing solution) comes into contact with air should be as small as possible. preferable. For example, opening area (cm ² )
The opening ratio is preferably 0.01 (cm ^-1 ) or less, where the value obtained by dividing the value by the volume of the developing solution (cm ³ ) is the opening ratio.
It is more preferably 005 or less.

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 processing solution called a regenerant is added to increase the activity of the developing solution and use it again as a processing solution. . In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more. As the treatment using the developer regenerator, after regenerating the developer overflow liquid,
Use as replenisher. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods are described in DIAION MANUAL (I) (198) issued by Mitsubishi Kasei Co., Ltd.
6th edition, 14th edition). Among the anion exchange resins, resins having the compositions described in JP-A-2-952 and 1-281152 are preferable.

In the present invention, the color-developed light-sensitive material is desilvered. The desilvering process here basically comprises a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these processes are carried out simultaneously and these processes. The following are typical desilvering process steps. Bleaching-fixing Bleaching-bleaching fixing Bleaching-washing-fixing Bleaching-bleaching fixing-fixing Bleaching fixing Fixing-bleaching fixing In particular, among the above-mentioned steps, the steps are preferable. 753
No. 52. Regarding the process, JP-A-61
No. 143,755 and Japanese Patent Application No. 2-216389. Further, the treatment baths such as the bleaching bath and the fixing bath which are applied to the above-mentioned steps may have one bath or two or more baths (for example, 2 to 4 baths, in which case a countercurrent replenishment system is preferable). Good. In the desilvering process, after the color development, a rinse bath,
It may be carried out through a washing bath or a stop bath, but in the case of a negative working light-sensitive material, it is preferably carried out immediately after color development,
In the case of reversal processing, it is preferable to carry out through a conditioning bath after color development.

The bleaching solution contains the N- of the present invention as described above.
It may contain a methylol compound. Examples of the bleaching agent contained as the 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 aminopolycarboxylic acid. Partially organic compounds of complex salts and ferric aminopolyphosphonate complexes can be mentioned. In the present invention, it is preferable to use the ferric aminopolycarboxylic acid complex salt from the viewpoints of environmental protection, safety in handling, corrosion of metals, and the like.

Specific examples of the ferric aminopolycarboxylic acid complex salt in the present invention are shown below, but the invention is not limited thereto. The redox potential is also shown. No. Compound Redox potential (mV vs. NHE, pH = 6) 1. N- (2-acetamido) iminodiacetic acid ferric iron complex salt 180 2. Methyliminodiacetic acid ferric iron complex salt 200 3. Iminodiacetic acid second acid Iron complex salt 210 4. 1,4-Butylenediaminetetraacetic acid ferric complex salt 230 5. Diethylene thioether diamine tetraacetic acid ferric complex salt 230 6. Glycol ether diamine tetraacetic acid ferric complex salt 240 7. 1,3-Propylenediamine Ferric tetraacetate complex salt 250 8. Ethylenediaminetetraacetic acid ferric complex salt 110 9. Diethylenetriamine pentaacetic acid ferric complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic acid ferric acid salt 80

The redox potential of the above bleaching agent is determined by the method described in Transactions of the Faraday Society, Volume 55 (1959), 1312-1313. Therefore, it is defined by the redox potential obtained by measurement.

In the present invention, the oxidation-reduction potential is 15 from the viewpoint of rapid treatment and the effect of the present invention.
A bleaching agent having 0 mV or more is preferable, a bleaching agent having a redox potential of 180 mV, and most preferably 200 mV or more. If the redox potential is too high, bleaching fog occurs, so the upper limit is 700 mV or less, preferably 500 mV or less. Of these, particularly preferred is Compound No. 7, 1,3-propylenediaminetetraacetic acid ferric complex salt.

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, which is 0.25 to 0.
7 mol is preferred. Particularly preferred is 0.30 to 0.6
It is a mole. The amount of the bleaching agent used in the bleach-fixing solution is 0.01 to 0.5 mol, preferably 0.02 to 0.2 mol, per liter of the bleach-fixing solution. Further, in the present invention, the oxidizing agents may be used alone or in combination of two or more kinds, and in the case of using two or more kinds together, the total concentration may be within the above range.

When the ferric aminopolycarboxylic acid complex salt is used in the bleaching solution, it can be added in the form of the complex salt as described above, but the aminopolycarboxylic acid which is a complex forming compound and the ferric iron salt. (For example, ferric sulfate, ferric chloride,
Ferric nitrate, ferric ammonium sulfate, and ferric phosphate) may coexist to form a complex salt in the treatment liquid. In the case of this complex formation, the aminopolycarboxylic acid may be added in a slight excess over the amount required for complex formation with ferric ion, and when added in excess, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

The bleaching solution as described above generally has a pH of from 2 to
Used in 7.0. 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 in order to accelerate the processing.
It is preferable that the replenisher is used as 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 logarithmic value of the reciprocal of the acid dissociation constant, and shows the value obtained at 25 ° C. at an ionic strength of 0.1 mol / dm. It is preferable to add 0.5 mol / liter or more of an acid having a pKa in the range of 2.0 to 5.5 to the bleaching solution because bleaching fog and precipitation of the replenisher due to low temperature aging can be prevented. This pKa 2.0 to 5.5
Examples of the acid include inorganic acids such as phosphoric acid, acetic acid, malonic acid,
Although it may be any of organic acids such as citric acid, the acid having a pKa of 2.0 to 5.5 which effectively exhibits the effect by the above improvement is an organic acid. Further, among organic acids, organic acids having a carboxyl group are 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 2.
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 kinds of organic acids having pKa of 2.0 to 5.5 can be mixed and used. However, the acid mentioned here does not include aminopolycarboxylic acids, salts thereof and Fe complex salts thereof.

PKa2. That can be used in the present invention.
Preferable 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 mono-substituted 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;
Amino acid-based dibasic acids such as aspartic acid, glutamic acid, and cystine; aromatic dibasic acids such as phthalic acid and terephthalic acid; and various organic acids such as polybasic acids such as citric acid. Among these, monobasic acids having a hydroxyl group and a carboxyl group are preferable, and glycolic acid and lactic acid are particularly preferable. The amount of glycolic acid and lactic acid used is 0.2 to 2 mol, preferably 0.5 to 1.5 mol, per liter of the bleaching solution. These acids are preferable because they exert the effect of the present invention more remarkably and suppress bleaching fog without odor. Further, it is preferable to use acetic acid and glycolic acid or lactic acid in combination because 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 suitably 0.5 mol or more per liter in the bleaching solution. It is preferably 1.2 to 2.5 mol / liter. More preferably, it is 1.5 to 2.0 mol / liter.

When adjusting the pH of the bleaching solution to the above range, the above-mentioned acid and alkaline agents (for example, aqueous ammonia, KOH,
NaOH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Of these, ammonia water is preferable.

The alkaline agent used in the bleaching starter when the starting solution of the bleaching solution is adjusted from the replenisher is
It is preferable to use potassium carbonate, aqueous ammonia, imidazole, monoethanolamine or diethanolamine. Alternatively, the replenisher may be diluted as it is without using the bleach 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. No. 3,89.
No. 3,858, German Patent No. 1,290,821
JP-B No. 1,138,842, JP-A No. 53-95630 and Research Disclosure No. 17129 (July 1978), which have 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 patents Polyethylene oxides described in Japanese Patent No. 2,748,430, JP-B-45-8836
It is possible to use the polyamine compounds described in the publication. Particularly preferred are the mercapto compounds as described in British Patent 1,138,842 and Japanese Patent Application No. 1-111256.

In the bleaching solution of the present invention, in addition to the bleaching agent and the above-mentioned compound, a re-formation of bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride and ammonium chloride. A halogenating agent can be included. The concentration of the rehalogenating agent is 0.1 to 1 liter in a state of being used as the processing liquid.
The amount is 5.0 mol, preferably 0.5 to 3.0 mol. Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

In the present invention, it is preferable to employ a replenishing system, and the replenishing amount of the bleaching solution is 1 m ² of the photographic material.
It is preferably 600 ml or less, more preferably 100 to 5
It is 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 containing the ferric aminopolycarboxylic acid complex salt is subjected to aeration to oxidize the resulting iron (II) aminopolycarboxylic acid complex salt. As a result, the oxidant is regenerated and the photographic performance is kept extremely stable.

For the treatment with the bleaching solution according to the present invention, it is preferable to carry out so-called evaporation correction by supplying water corresponding to the evaporation of the processing solution. In particular, it is preferable in a color developing solution or a bleaching solution containing a high potential bleaching agent. There are no particular restrictions on the specific method for replenishing water,
Above all, JP-A-1-254959 and 1-254960.
Installed a monitor water tank different from the bleaching tank described in the publication.
A method for determining the evaporation amount of water in the monitor water tank, calculating the evaporation amount of water in the bleaching tank from this evaporation amount, and replenishing the bleaching tank with water in proportion to this evaporation amount, and Japanese Patent Application No. 2-4674.
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 the specifications of No. 47779 and No. 2-119722 is preferable.

In the present invention, the light-sensitive material after being processed with the bleaching solution is processed with a processing solution having fixing ability. The processing solution having a fixing ability here is specifically a fixing solution and a bleach-fixing solution. When the processing having a bleaching ability is carried out with a bleach-fixing solution, it may also serve as the processing having a fixing ability as in the above-mentioned steps. The bleaching solution may be different from the bleaching agent in the bleach-fixing solution in the above-mentioned step of treating with the bleach-fixing solution after bleaching with the bleaching solution. When there is a water washing step between the steps as described above, the solution may also contain the N-methylol compound of the present invention.

A fixing agent is contained in the processing liquid having fixing ability. As a fixing agent, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates (rhodan salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiourea, Thioether etc. can be mentioned. Of these, ammonium thiosulfate is preferably used. The amount of the fixing agent is 0.3 to 3 mol, preferably 0.5 to 2 mol, per liter of the processing liquid having fixing ability.

From the viewpoint of accelerating fixing, it is also preferable to use thiosulfate together with the above-mentioned ammonium thiocyanate (rhodanammonium), thiourea and thioether (for example, 3,6-dithia-1,8-octanediol). Of these, it is most preferable to use thiosulfate and thiocyanate in combination. In particular, the combined use of ammonium thiosulfate and ammonium thiocyanate is preferable. The amount of these compounds used in combination is 0.01 to 1 mol, preferably 0.1 to 1 mol, per liter of the processing liquid having fixing ability.
It is better to use 0.5 mol, but depending on the case, 1 to 3
The fixing promotion effect can be greatly enhanced by using a molar amount.

In the processing solution having fixing ability, a sulfite (eg sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (for example, sodium acetaldehyde sodium bisulfite, particularly preferably the compound described in Japanese Patent Application No. 1-298935) or JP-A-1.
A sulfinic acid compound described in US Pat. No. 231051 may be contained. Further, various optical brighteners, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained.

Furthermore, it is preferable to add a chelating agent such as various aminopolycarboxylic acids and organic phosphonic acids to the processing solution having 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'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,
2-Propylenediaminetetraacetic acid can be mentioned.
Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable.
The amount of the chelating agent added 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 5-9, more preferably 7-8. Further, in the bleach-fixing solution, it is preferably 4.0 to 7.0, more preferably
It is 5.0 to 6.5. The pH of the bleach-fixing solution or the bleach-fixing solution after being treated in the first bleach-fixing bath is 6 to
It is preferably 8.5, more preferably 6.5 to 8.0.

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

The bleach-fixing solution may further contain a compound which can be contained in the bleaching solution described above.

In the present invention, the bleach-fixing solution at the start of processing (starting solution) is prepared by dissolving the above-mentioned compound used in the bleach-fixing solution in water. It may be prepared by mixing an appropriate amount.

When the replenishing method is adopted, the replenishing amount of the fixing solution or the bleach-fixing solution is 100 per 1 m ² of the light-sensitive material.
~ 3000 ml is preferred, more preferably 300 ~
It is 1800 ml. The bleach-fixing solution may be replenished as a bleach-fixing replenishing solution, and JP-A-61-1143755.
No. 2-216389 and Japanese Patent Application No. 2-216389, an overflow solution of a bleaching solution and a fixing solution may be used.

Further, similarly to the bleaching process described above, it is preferable to carry out the bleach-fixing process while replenishing the processing solution with replenishing the water corresponding to the evaporation amount.

In the present invention, the total processing time of the processing having fixing ability is 0.5 to 4 minutes, preferably 0.5 to 2
Min, particularly preferably 0.5 to 1 min. In the present invention, the total processing time of the desilvering process consisting of a combination of bleaching, bleach-fixing and fixing is preferably 45 seconds to 4 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 to 50.
C., preferably 35 to 45.degree.

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

After the processing step having fixing ability, usually,
Perform a washing process step. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using the stabilizing solution of the present invention is carried out without substantially washing with water. The rinsing water used in the rinsing step may contain various surfactants in order to prevent unevenness of water drops when the photosensitive material after processing is dried. These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, higher alcohol sulfate ester salt type anionic surfactants. Agents, alkylnaphthalene sulfonate type anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants However, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. The alkylphenol is particularly preferably octyl, nonyl, dodecyl or dinonylphenol, and the addition mole number of ethylene oxide is particularly preferably 8 to 14. It is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water may contain various antibacterial agents and fungicides in order to prevent the generation of water stains and the mold generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are JP-A-57 / 1982.
No. 157244 and No. 58-105145, thiazolylbenzimidazole compounds, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. , Bromophenol compounds, organic tin and organic zinc compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, and quaternary compounds such as benzalkonium chloride. Ammonium salts, antibiotics such as penicillin, etc., Journal Antibacterial & Antifungus Agent (J. Antibact. Antifung.
Agents) Vol 1. No. 5, p. 207-223 (198
Examples of the general-purpose antifungal agent described in 3) are 2
You may use together 1 or more types. Also, JP-A-48-83820
Various bactericides described in the above publication can also be used.

Further, 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 hydrolyzates of maleic anhydride polymers described in European Patent 345172A1. Further, it is preferable that the wash water contains a preservative that can be contained in the fixing solution or the bleach-fixing solution.

The washing process and the stabilizing process are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount carried in from the previous bath per unit area. As water used in these washing steps, tap water can be used, but Ca, M and
It is preferable to use water deionized to a g ion concentration of 5 mg / liter or less, water sterilized with halogen, an ultraviolet sterilization lamp or the like. The water for correcting the evaporation of each treatment liquid may be tap water, but it is preferable to use deionized water or sterilized water which is preferably used in the above washing step.

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

In the present invention, the effect is particularly effectively exhibited when the total processing time of the processing solution before the drying step after the bleaching processing is 1 minute to 3 minutes, preferably 1 minute 20 seconds to 2 minutes. ..

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

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer on a support, There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer composed of 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 light-sensitive material, the unit photosensitive layers are generally arranged in order from the support side to the red color-sensitive layer. The green color sensitive layer and the blue color sensitive layer are installed in this order. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-2374 is used.
No. 8, No. 59-113438, No. 59-113440
Nos. 61-20037, 61-20038, and the like may contain a coupler and the like, and contains a color mixing inhibitor, an ultraviolet absorber, an anti-staining agent, etc., as commonly used. You can leave.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of layers can be preferably used. Usually, it is preferable that the layers are arranged so that the photosensitivity becomes lower toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, JP-A-57-112751, JP-A-62-200350,
As described in JP-A Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.
As a specific example, from the farthest side from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL) /
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. Further, JP-A-56-25738 and 62-63.
As described in Japanese Patent No. 936, a blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. In addition, Japanese Examined Japanese Patent Publication Sho 49-15495
As described in the publication, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is a lower sensitive silver halide emulsion layer, and the lower layer is a lower sensitive silver halide emulsion. An arrangement may be mentioned in which a silver emulsion layer is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The dry film thickness of the support of the photographic material and all the constituent layers except the undercoat layer and backing layer of the support is preferably from 12.0 to 20.0 .mu. More preferably 12.0-18.
0 μ.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
The photosensitive material was stored under conditions of 5 ° C. and 50% RH for 7 days after preparation, and first, the total thickness of the photosensitive material was measured, and then the coating layer on the support was removed, and then the thickness was measured again. The thickness of the entire coating layer excluding the support of the light-sensitive material is defined by the difference. This thickness is measured, for example, by a film thickness measuring device (Anritus Electric Co.
Ltd., K-402B Stand.). The coating layer on the support can be removed using an aqueous solution of sodium hypochlorite. It is also possible to use a scanning electron microscope to take a cross-sectional photograph of the above-mentioned photosensitive material (magnification is preferably 3,000 times or more) to measure the total thickness on the support.

Swelling rate of the light-sensitive material of the present invention [(25
Equilibrium swollen film thickness in ℃, H ₂ O -25 ° C, dry total film thickness at 55% RH / dry total film thickness at 25 ° C, 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferable. If the swelling ratio deviates from the above value, the amount of the color developing agent remaining becomes large, and the photographic performance, the image quality such as desilvering property, and the film physical properties such as film strength are adversely affected.

Further, the film swelling speed of the light-sensitive material in the present invention is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swollen film thickness is When the time required to reach the film thickness of 1/2 is defined as the swelling speed T1 / 2, T1 / 2 is preferably 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.
A preferred silver halide is 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 with regular crystals such as octahedron and tetradecahedron,
It may have an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 1.
7643 (December 1978), pp. 22-23, "I. Emulsion preparation and types" and ibid.
716 (November 1979), page 648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glaf).
kides, Chimie et Physique Photographique Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin,
Published by Forcal Press (GF Duffin, Photographic
Emulsion Chemistry (Focal Press, 1966)), "Manufacturing and Coating of Photographic Emulsions" by Zelikman et al., VLZelikman et alMaking and Coating.
It can be prepared using the method described in Photographic Emulsion, Focal Press, 1964) and the like. US Pat. Nos. 3,574,628 and 3,655,39
Monodisperse emulsions described in, for example, No. 4 and British Patent No. 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gatov, Photographic Science.
And Engineering (Gutoff, Photographic Sci
ence and Engineering), Volume 14, pages 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,430,048,
U.S. Pat. No. 4,439,520 and British Patent No. 2,11.
It can be prepared by the method described in No. 2,157.

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

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure No. 17643 (December 1978) and the same No.
18716 (November 1979) and No. 307 of the same.
105 (November 1989), and the relevant parts 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 are shown below. Types of additives [RD17643] [RD18716] [RD307105] 1. Chemical sensitizer, page 23, 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right Column 866 to 868 Supersensitizer to page 649 Right column 4. Brightener page 24 647 Page right column 868 5. Fogging prevention page 24 to 25 649 Page right column 868 to 870 Agent, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber, stain 7. page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener page 26 651 Page left column 874 to 875 page 10. Binder page 26 651 Page left column 873 to 874 page 11. Plasticizer, page 27 650 page right column 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. matting agents, pages 878 to 879

Various color couplers can be used in combination in the present invention. Typical examples thereof are RD No. 1 mentioned above.
7643, VII-C to G and RD No.307105, VII-C to G
Are described in the patents listed in.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620,
No. 4,326,024, No. 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-1073.
No. 9, British Patent Nos. 1,425,020 and 1,47
6,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, European Patent 249,473A, and JP-A-3-131847.
Those described in No. etc. are preferable. Further, 1-alkylcyclopropylcarbonyl type and indolinylcarbonyl type yellow couplers having a high absorption 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 and the like are particularly preferable.

As the magenta coupler, 2-equivalent and / or 4-equivalent 5-pyrazolone type and pyrazoloazole type compounds are preferable, and US Pat. No. 4,310,619,
No. 4,351,897, European Patent No. 73,636.
U.S. Pat. Nos. 3,061,432 and 3,72.
No. 5,064, RD No. 24220 (June 1984)
Mon.), JP-A-60-33552, RD No. 24230.
(June 1984), JP-A-60-43659 and JP-A-60-43659.
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, WO (PCT) 88/087.
Those described in No. 95 and the like are more preferable.

In the present invention, an effective effect is exhibited when at least one kind of 4-equivalent magenta coupler is used. The 4-equivalent magenta coupler is preferably a 4-equivalent 5-pyrazolone-based magenta coupler represented by the following general formula (M) or a 4-equivalent pyrazoloazole-based magenta coupler represented by the following general formula (m).

[0122]

[Chemical 10]

In 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 one of Ar may become a divalent or higher polyvalent group to form a multimer such as a dimer, and a polymer main chain and a coupling mother nucleus are connected to each other to form a polymer coupler. You may. In general formula (m), R ₅ represents a hydrogen atom or a substituent, Z represents a non-metal atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring is It may have a substituent or may have a condensed ring. It should be noted that 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. The coupling mother nucleus may be connected to form a polymer coupler.

The alkyl group represented by 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 an aryl group has 6 carbon atoms. ~ 46 aryl group, the acyl group represents a C2-32 aliphatic acyl group or a C7-46 aromatic acyl group,
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 linked 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). Two
-(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) tetradecanoamidophenyl]), an 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 (for example, 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 substituent which 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, An alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an azo group, a phosphonyl group, an azolyl group, a fluorine atom, a chlorine atom and a 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. More specifically, Ar is, for example, phenyl group, 2,4,6-trichlorophenyl group,
2,5-dichlorophenyl group, 2,4-dimethyl-6-
Methoxyphenyl group, 2,6-dichloro-4-methoxyphenyl group, 2,6-dichloro-4-ethoxycarbonylphenyl group, 2,6-dichloro-4-cyanophenyl group or 4- [2- (2,4 -Di-tert-amylphenoxy) butylamido] phenyl group. A substituted phenyl group is preferable, and a phenyl group in which at least one halogen atom (especially chlorine atom) is substituted is preferable, and a 2,4,6-trichlorophenyl group or a 2,5-dichlorophenyl group is particularly preferable. preferable.

Among the pyrazoloazole type magenta couplers represented by the general formula (m), preferred one is 1H-
Imidazo [1,2-b] pyrazole, 1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H- It has a pyrazolo [1,5-d] tetrazole skeleton and is represented by the following general formulas [m-1] and [m-
2], [m-3] and [m-4].

[0128]

[Chemical 11]

[0129]

[Chemical formula 12]

[0130]

[Chemical 13]

[0131]

[Chemical 14]

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, and the substituent is
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 Group, azo group, acyloxy group, carbamoyloxy group,
Silyloxy group, aryloxycarbonylamino group,
Examples thereof 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 be a divalent group to form a bis form.

More specifically, R ₅ and R ₅₁ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom),
Alkyl group (for example, a straight chain or branched chain 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] dodecanamide} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl,
Cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4
-T-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), 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, 2 -Methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), an acylamino group (for example, acetamide,
Benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t
-Butyl-4-hydroxyphenoxy) butanamide,
2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), 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) dodecanamide} anilino),
A ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino),
Alkylthio groups (eg, methylthio, octylthio,
Tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenyl) Ruthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio),
Alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy- 5-t-butylbenzenesulfonamide), a carbamoyl group (eg, 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 (for example, 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 groups (eg, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo groups (eg, 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), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), 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 capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₅ and R
_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 , 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 or 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 carbamoyl. A group and an acyl group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group.

Regarding the polymer of the magenta coupler represented by the general formula (M) or (m), it is described in JP-B-2-4405.
The description of No. 1 etc. can be referred to. Specific examples of preferable 4-equivalent magenta couplers are listed below.

[0138]

[Chemical 15]

[0139]

[Chemical 16]

[0140]

[Chemical 17]

[0141]

[Chemical 18]

[0142]

[Chemical 19]

[0143]

[Chemical 20]

[0144]

[Chemical 21]

[0145]

[Chemical formula 22]

[0146]

[Chemical formula 23]

[0147]

[Chemical formula 24]

[0148]

[Chemical 25]

[0149]

[Chemical formula 26]

[0150]

[Chemical 27]

[0151]

[Chemical 28]

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

Examples of cyan couplers include phenol type and naphthol type couplers. US Pat.
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, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, US Patents 3,446,622, 4,433,99.
9, No. 4,753,871, No. 4,451,5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
6,199, JP-A-61-42658, JP-A-3-
Those described in 196037 and the like are preferable. In addition, pyrrolotriazole, pyrroloimidazole, imidazopyrazole, imidazole, pyrazolotriazole, cyclic active methylene cyan couplers, for example, Japanese Patent Application No. 2-302.
No. 078, No. 2-322051, No. 3-226325.
No. 3,236,894, JP-A No. 64-32260.
And those described in JP-A-2-141745 and the like are particularly preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in RD No. 17643, Item VII-G,
U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-394
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 preferable. Also,
A coupler described in U.S. Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a dye which reacts with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming

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

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910 and British Patent 2,102,173.

A coupler that releases a photographically useful residue upon coupling is also preferably used. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,1.
31,188, JP-A-59-157638, 59.
Those described in -170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in, for example, EP 7,173,30.
RD No. 11449, RD No. 24241, a coupler which releases a dye that recolors after the separation described in No.
Bleaching accelerator releasing couplers described in 1-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, leuco dye releasing couplers described in JP-A-63-75747, U.S. Pat. Fourth 4,774
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like, and specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di- 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, Tridodecyl phosphate, tributoxyethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide) , N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-).
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2) -Butoxy-5-t
ert octylaniline etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene etc.) 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, and a typical example is ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

A process of the latex dispersion method, effects and a specific example of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230.

These couplers may also 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, international publication number WO88 / 0
The homopolymers or copolymers described on pages 12 to 30 of the No. 0723 specification are used. Particularly, it is preferable to use an acrylamide polymer in terms of color image stabilization and the like.

Suitable supports which can be used in the present invention are, for example, RD No. 17643, page 28 and the same No. 18 mentioned above.
716, page 647, right column to page 648, left column. The present invention can be applied to various light-sensitive materials. Color negative film for general use or movies,
It is preferably used for a slide or a reversal film for television.

[0163]

EXAMPLES The present invention is described in detail below with reference to examples, but the present invention is not limited to these.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material 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 dye is shown by the number 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%, sphere equivalent diameter O.O7μ
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, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular grain, diameter / Thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 18%, tetradecahedral grains) 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, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 25%, tabular grains,
Diameter / thickness ratio 3.0) silver coverage 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 x 10 ^-2 Solv-1 0.10

Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type,
Equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, 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 6th layer: intermediate layer gelatin 1.00 Cpd-4 8.0 × 10 ^-2 Solv- 1 8.0 x 10 ^-2

Seventh layer: first green emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent 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, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 18%, tetradecahedral grains) 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- 3 3.0 × 10 ^-2 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 25%, plate-like grains ,
Diameter / thickness ratio 3.0) silver coverage 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 9th layer: Intermediate layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2

10th layer: third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type,
Equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere 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, spherical equivalent diameter 0.55 μm, variation coefficient of spherical equivalent 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 Iodobromide Silver emulsion (AgI 19.0 mol%, internal high AgI type,
Equivalent sphere diameter 1.0 μm, coefficient of variation of sphere equivalent diameter 16%, octahedral grain) 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 spherical diameter O.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: 3rd blue sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%) , Internal high AgI type,
Equivalent sphere diameter 1.7 μm, variation coefficient of sphere equivalent diameter 28%, plate-like particles, 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 (diameter 1.5 μm) 2.0 × 10 ^-2 B-2 (diameter 1.5 μm) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H -1 0.35 Cpd-7 1.00

This sample contained 1,2-benzisothiazolin-3-one (average 200 ppm with respect to gelatin), n.
-Butyl-p-hydroxybenzoate (approx. 1,000 pp
m) and 2-phenoxyethanol (approx. 10,000 p
pm) was added. Furthermore, 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 salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

The compounds used above will be listed below.

[0175]

[Chemical 29]

[0176]

[Chemical 30]

[0177]

[Chemical 31]

[0178]

[Chemical 32]

[0179]

[Chemical 33]

[0180]

[Chemical 34]

[0181]

[Chemical 35]

[0182]

[Chemical 36]

[0183]

[Chemical 37]

[0184]

[Chemical 38]

[0185]

[Chemical Formula 39]

[0186]

[Chemical 40]

The dry film thickness of the sample 101 excluding the support was 22 μm, and the swelling speed T 1/2 was 9 seconds. The sample 101 produced as described above was cut into a length of 2 m with a width of 35 mm, exposed to white light of 50 lux for 0.01 second, and then, using an automatic processor, under the following conditions. The treatment was carried out until the cumulative replenishment amount of the treatment liquid became three times the capacity of the mother liquor tank. Incidentally, only the stabilizing solution was sequentially replaced, and the other treatments were performed under the same conditions, and after the treatment, the stain of the sample was evaluated, and the sample was used as an image stability evaluation sample. The treatment process and the treatment liquid composition are shown below.

Processing Steps Processing Time Processing Temperature Replenishment Amount * Tank Capacity (° C) (ml) (L) Color Development 3 min 5 sec 38.0 600 17 Bleach 50 sec 38.0 140 5 Bleach Fix 50 sec 38. 0-5 Settling 50 seconds 38.0 420 5 Washing with water 30 seconds 38.0 980 3 Stable (1) 20 seconds 38.0-3 Stable (2) 20 seconds 38.0 560 3 Dry 1 minute 60 * Replenishment The amount is per 1 m ² of the light-sensitive material. The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic developing machine and at the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65 ml,
50 ml, 50 ml, 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Further, each replenisher was replenished with the same liquid as each tank liquid. The composition of the treatment liquid is shown below.

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

(Bleach) Unit (g) 1,3-Diaminopropanetetraacetic acid 130 Ferric ammonium-hydrochloride Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water is added to 1.0 liter pH [ammonia water Adjust with] 4.2

(Bleaching Fixing Solution) A mixture solution of 15:85 (volume ratio) of the above bleaching solution and the following fixing solution (pH 7.0).

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

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IRA-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / l, followed by 20 mg / l sodium isocyanurate dichloride and 15 sodium sulfate
0 mg / l 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 mol Add water 1.0 liter pH 7.2

[Evaluation of Image Preservability] Each of the samples after the above-mentioned treatment was used as a photographic densitometer FSD10 manufactured by Fuji Photo Film Co., Ltd.
After measuring the magenta density at 3
% For 2 months, and the concentration was measured again in the same manner. The evaluation was made based on the amount of decrease in magenta density over time. (M fading) The magenta density of each sample after the treatment was 1.5.

[Evaluation of Treatment Contamination] Each sample after the above treatment was visually observed to evaluate the contamination. The evaluation criteria are as follows. Rank 1. No dirt is observed 2. Slight stain is observed (1/10 of the sample surface)
Below, and to the extent that dirt is also slightly clouded) 3. Clouding is observed (1/10 or more of the sample surface) 4. 4. Adherence is recognized (1/10 or less of the sample surface) 5. Adherence is recognized (more than 1/10 of the sample surface)

[Measurement of Formaldehyde Vapor Pressure] Each stabilizing solution was prepared according to the following formulation, 100 ml of each was placed in a Petri dish (opening area: 80 cm ² ) and placed in a glass closed container having a volume of 5 liters. After aging for 7 days at 20 ° C., the formaldehyde vapor pressure in the glass container was measured with a formaldehyde L-type direct-reading gas detector tube manufactured by Gastec. (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, the formaldehyde vapor pressure is small, and the sample after the treatment is processed without stains and excellent in image storability. 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 in an amount of 1.0 × 10 ^-2 g / m ² , and E of the 10th layer was added.
Sample 201 was prepared in the same manner except that xM-4 was replaced with the following ExM-4 ′ in the same weight.

[0201]

[Chemical 41]

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

[0203]

[Table 6]

[0204]

[Chemical 42]

[0205]

[Chemical 43]

As can be seen from Table B, by using the compound of the present invention, the formaldehyde vapor pressure is small, and the processed sample can be processed with excellent image storability without causing stains. ..

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

Example 4 The following processing steps and processing solutions were used in an automatic developing machine until the cumulative replenishment amount of the processing solutions reached 3 times the mother liquor tank capacity.
Similar to Examples 1 and 2, the sample 101 was treated with each stabilizing solution, and the image storability was tested. Similar results were obtained. Treatment method Treatment time Treatment temperature Replenishment amount * Tank capacity (℃) (ml) (liter) Color development 3 minutes 15 seconds 38 33 20 Bleach 6 minutes 30 seconds 38 25 40 Water wash 2 minutes 10 seconds 24 1200 20 Fixed arrival 4 minutes 20 seconds 38 25 30 30 minutes water washing 1 minute 05 seconds 24-10 water washing 1 minute 00 seconds 24 1200 10 stability 1 minute 05 seconds 38 25 10 dry 4 minutes 20 seconds 55 * Replenishment amount is 35 mm width 1 m length Counter-flow piping system

Next, the composition of the processing liquid will be described. (Color developer) 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 Water was added to 1.0 liter 1.0 liter pH 10.05 10.10

(Bleach) 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 Add water 1.0 liter 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 (700 g / liter) Add water 1.0 liter 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 the Exemplified Compound I-1 was added to the bleaching solution in an amount of 0.
Sample 101 was processed by adding 3 mol / liter. When the stain and image storability of the sample after the treatment were evaluated, No. 1 of Example 1 was evaluated. Good results were obtained as in No. 8. Similarly, Sample 201 was processed by adding 0.3 mol / liter of Exemplified Compound II-1 to the bleaching solution. When the stain and 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 light-sensitive material sample 501 consisting of layers having the following compositions 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 described use.

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 Ultraviolet absorber U-6 0.1 g High boiling point 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 Surface and inner fogged fine grain iodobromide Silver emulsion (average grain size 0.06μm, coefficient of variation 18%, AgI content 1 mol%)
Silver amount 0.05 g Gelatin 0.4 g

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 point organic solvent Oil-2 0.1 g Fifth layer: Medium-speed 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 Silver iodobromide emulsion with a fogged surface and inside (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 mixing inhibitor Cpd-J 0.1 g Color mixing 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 sensitivity 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 point organic solvent Oil-2 0.01 g 11th 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 point organic solvent Oil-1 0.02 g High boiling point 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 Thirteenth layer: Yellow filter layer Yellow colloidal silver 0.1 g gelatin 1.1 g Color mixture inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g 14th 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 Sixteenth layer: Medium-speed blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-6 0.7 g

Eighteenth layer: First 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 Ultraviolet absorber U-6 0.05 g High boiling point 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

Layer 19: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain 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 polymethylmethacrylate (average particle size 1.5 μ) 0.1 g copolymer of methylmethacrylate and acrylic acid 4: 6 (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

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, a gelatin hardening agent H-1 and coating and emulsifying surfactants W-3 and W-4 were added. More antiseptic,
Phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-hydroxybenzoic acid butyl ester were added as a fungicide.

The silver iodobromide emulsion used is as follows. Emulsion name Average grain 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 crystal 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 grain 0.30 9 3.5 I polydisperse tabular grain, 0.80 28 1.5 average aspect ratio 4.0 J monodisperse 14-sided grain 0.30 18 4.0 K monodisperse 14 Hedron grains 0.37 17 4.0 L monodispersed cubic internal latent image type grains 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 Silver Halide Sensitizing Dye Addition amount (g) Timing when added ------------- −−−−−−−−−−−−−−−−−−− A S-1 0.025 Immediately after chemical sensitization S-2 0.25 Immediately after chemical sensitization B S-1 0.01 Grain formation completion Immediately S-2 0.25 Immediately after grain formation C S-1 0.02 Immediately after chemical sensitization S-2 0.25 Immediately after chemical sensitization D S-1 0.01 Immediately after chemical sensitization S-2 0.10 Chemistry Immediately after sensitization S-7 0.01 Immediately after chemical sensitization E S-3 0.5 Immediately after chemical sensitization S-4 0.1 Immediately after chemical sensitization F S-3 0.3 Immediately after chemical sensitization S-4 0. 1 Immediately after chemical sensitization G S-3 0.25 Immediately after completion of grain formation S-4 0.08 Immediately after completion of grain formation H S-3 0.2 During grain formation S-4 0. 6 During grain formation I S-3 0.3 Just before starting chemical sensitization S-4 0.07 Just before starting chemical sensitization S-8 0.1 Just before starting chemical sensitization J S-6 0.2 During grain forming S- 5 0.05 During particle formation K S-6 0.2 During particle formation S-5 0.05 During particle formation L S-6 0.22 Immediately after completion of particle formation S-5 0.06 Immediately after completion of particle formation M S- 6 0.15 Immediately after chemical sensitization S-5 0.04 Immediately after chemical sensitization N S-6 0.22 Immediately after completion of grain formation S-5 0.06 Immediately after completion of grain formation -------- −−−−−−−−−−−−−−−−−−−−−−−

[0226]

[Chemical 44]

[0227]

[Chemical 45]

[0228]

[Chemical 46]

[0229]

[Chemical 47]

[0230]

[Chemical 48]

[0231]

[Chemical 49]

[0232]

[Chemical 50]

[0233]

[Chemical 51]

[0234]

[Chemical 52]

[0235]

[Chemical 53]

[0236]

[Chemical 54]

[0237]

[Chemical 55]

[0238]

[Chemical 56]

Image exposure was applied to the above sample 501, and processing was performed using a cine type automatic developing machine in accordance with the processing steps shown below. First, each of the stabilizers was sequentially treated with 0.5 m ² using the bleaching solution 1, and then similarly treated with the bleaching solution 2, and the obtained sample was evaluated in the same manner as in Example 1. .. Treatment process time Temperature Replenishment amount * Tank capacity (min) (° C) (liter) (liter) Black and white development 6 38 1.5 12 First washing with water 1 38 7.5 4 Inversion 1 38 1.1 4 Color development 4 38 2.0 12 Adjusting 2 38 1.1 4 Bleaching 4 38 1.3 12 Stationary 3 38 1.3 12 Second washing (1) 1 38 ── 4 Second washing (2) 1 38 7.5 4 Stability 1 38 1.1 4 Drying 250 * Replenishment amount per 1 m ² of light-sensitive material The overflow solution of the second washing (2) was introduced into 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 pentasodium pentasodium salt Sulfite Potassium 30 30 Hydroquinone mono 20 20 Potassium sulphonate Potassium carbonate 33 33 1-Phenyl-4-me 2.0 2.0 Cyl-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 pH adjusted 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 Water added 1.0 liter Ammonium sulfite 20 Water added 1.0 liter pH (25 ° C) 6.60 pH adjusted with acetic acid or ammonia water 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 36 36 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazic acid 1.5 1. 5 N-ethyl- (β-me 10.5 10.5 tansulphonamide ethyl) -3-methyl-4-aminoaniline sulphate 3,6-dithiaocta 3.5 3.5 3.5-1,8-diol 1.0 liter 1.0 liter pH (25 ° C.) 11.90 12.05 pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation Solution) Common for Start Solution / Replenishment Solution Unit (g) Ethylenediaminetetraacetic acid 8.0 · 2 sodium salt / dihydrate sodium sulfite 12 2-mercapto-1,3,0.5 4-triazole pH ( 25 ° C.) 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching Solution 1) Common for Start Solution / Replenishing Solution 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 / Replenishing Solution Common Unit (g) 1,3-Diaminopropan 3 Tetraacetic Acid 1,3-Diaminoprop 120 120 Ferric 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 / Replenishing Solution Common Unit (g) Ethylenediaminetetraacetic Acid 1.7 · 2 Sodium Dihydrate Benzaldehyde-20-o-Sulfonate Nalium Sodium Bisulfite 15 Ammonium Thiosulfate 250 ml (700) 1.0 liter pH (25 ° C.) 6.00 pH was adjusted with acetic acid or aqueous ammonia.

(Stabilizing Solution) Each stabilizing solution of Example 1 or 2 was used (common to starting solution / replenishing solution).

The evaluation of the image storability was carried out by using the portion where the magenta density was 0.5 in the gray color-developed portion of the sample subjected to each treatment. The results are similar to those in Examples 1 and 2, and good results were obtained when the stabilizing solution containing the N-methylol compound of the present invention was used. In addition, in the above treatment, a stabilizer containing no image stabilizer was used, and a liquid prepared by adding 0.03 mol / liter of the image stabilizer shown in Table C to the adjusting liquid was used. Similarly, the image storability was evaluated. The results are shown in Table C.

[0249]

[Table 7]

As can be seen from Table C, even when the N-methylol compound of the present invention is used in the conditioning bath, it has a sufficient effect of preventing fading of the magenta dye. Especially as a bleach
Good results were obtained with the ferric 3-diaminopropanetetraacetic acid complex salt. When the surface of each sample in Table C was observed, no stain was found.

Example 7 As a light-sensitive material, a sample 201 of Example 2 of JP-A-2-90151, a photosensitive material 1 of Example 1 of JP-A-2-93641 and a photosensitive material 9 of Example 3 were used. Process No. 1 8
And the process No. of Example 1. When treated with 16, the formaldehyde vapor pressure was low, the fastness of the dye image was excellent, and the light-sensitive material was not stained.

[0252]

By carrying out the present invention, the vapor pressure of formaldehyde is small, the effect of preventing discoloration of dye images is excellent, and the light-sensitive material is not stained.

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[Procedure amendment]

[Submission date] February 3, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

More specifically, the general formula (Ia) is 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 (eg allyl), aryl group (eg phenyl, 4-tert-butylphenyl), heterocyclic group (eg 5 -Pyrazolyl, 4-pyrazolyl), halogen atom (for example, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phospho group, acyl group (for example, acetyl, benzoyl, propanoyl), sulfonyl group ( For example, methanesulfonyl, octanesulfonyl, toluenesulfonyl), sulfinyl group (eg, methanesulfinyl), acyloxy group (eg,
Acetoxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl), sulfamoyl group (eg, sulfamoyl, N
-Ethylsulfamoyl), amino group (for example, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), alkoxy group (for example, methoxy, ethoxy), alkylthio Group (for example, methylthio, octylthio), aryloxy group (for example, phenoxy), arylthio group (for example, phenylthio), heterocyclic oxy group (for example, 1-phenyltetrazolyl-5-oxy), heterocyclic thio group ( (For example, benzothiazolylthio).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0251

[Correction method] Change

[Correction content]

Example 7 As a light-sensitive material, a sample 201 of Example 2 of JP-A-2-90151, a photosensitive material 1 of Example 1 of JP-A-2-93641 and a photosensitive material 9 of Example 3 were used. Process No. 1 8
And the process No. of Example 2. When treated with 16, the formaldehyde vapor pressure was low, the fastness of the dye image was excellent, and the light-sensitive material was not stained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shigeru Nakamura 210 Naka Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Morio Yagihara 210, Nakanuma Minami Ashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor Hiroyuki Watanabe 210 Nakanishuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (13)

[Claims] 1. A color image stabilizing treatment liquid for a silver halide color photographic light-sensitive material comprising at least one N-methylol compound represented by the following general formula (I). [Chemical 1] (In the formula, X represents a group of nonmetal atoms necessary for forming a 1H-pyrazole ring or a 1H-1,2,4-triazole ring together with a nitrogen atom.) 2. A color image stabilizing processing liquid for silver halide color photographic light-sensitive materials, which contains at least one N-methylol compound satisfying the following condition A. (Condition A) The equilibrium constant in water at room temperature is 2 × 10 ⁻² mol / liter or less, and the formaldehyde release rate constant is 1 × 10 ⁻⁵ sec ⁻¹ or more. 3. Containing at least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2. A stabilizing solution for silver halide color photographic light-sensitive materials, characterized by: 4. An N-methylol compound represented by the general formula (I) according to claim 1 and / or at least one N-methylol compound satisfying the condition A according to claim 2 is contained. A stable replenisher for silver halide color photographic light-sensitive materials. 5. An N-methylol compound represented by the general formula (I) according to claim 1 and / or at least one N-methylol compound satisfying the condition A according to claim 2 is contained. A preparation liquid for silver halide color photographic light-sensitive materials, characterized by: 6. An N-methylol compound represented by the general formula (I) according to claim 1 and / or at least one N-methylol compound satisfying the condition A according to claim 2 is contained. A bleaching solution for silver halide color photographic light-sensitive materials, characterized by: 7. A color containing at least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with an image stabilizing processing solution. 8. A stable composition containing at least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a liquid. 9. A stable composition containing at least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2. A method of processing a silver halide color photographic light-sensitive material, which comprises replenishing with a replenisher. 10. At least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2.
A method of processing a silver halide color photographic light-sensitive material, which comprises processing with an adjusting solution containing a seed. 11. A bleaching solution containing at least one N-methylol compound represented by the general formula (I) according to claim 1 and / or N-methylol compound satisfying the condition A according to claim 2. A method for processing a silver halide color photographic light-sensitive material, characterized in that 12. A silver halide color photographic light-sensitive material comprising:
8. The method for processing a silver halide color photographic light-sensitive material according to claim 7, which contains at least one 4-equivalent magenta coupler. 13. A treatment liquid having a bleaching ability containing a bleaching agent having an oxidation-reduction potential of 150 mV or higher is treated with the treatment liquid.
And a color image stabilizing treatment containing at least one N-methylol compound represented by formula (I) according to claim 1 and / or N-methylol compound satisfying condition A according to claim 2. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a liquid.