JPH0534886A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent stain and light discoloration by processing photosensitive material containing a pyrazoloazole base coupler or 5-pyrazolon polymer coupler with processing solution including compounds selected from N-methyrol compounds, such as pyrazole base, triazole base or urazol base, or azole methylamine compounds after imagelike exposure. CONSTITUTION:Silver halide color photographic sensitive material is processed with processing solution containing compounds represented by the formula I and/or II. In the formula I, X is a nonmetallic atom group required for forming a four- to eight-numbered ring on condition that an atom combined with a nitrogen atom is the one selected from a carbon atom, oxygen atom or sulfur atom. In the formula II, X0 represents a nonmetallic atom group required for forming a nitrogen containing aromatic heterocycle. Ra and Rb may be the same or different and represent an alkyl or alkenyl radical.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method for improving the storability of a color image after processing of a silver halide color photographic light-sensitive material using a pyrazoloazole type coupler or a 5-pyrazolone type polymer coupler.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) generally has a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion on a support. In the emulsion layer, a color image is reproduced by a so-called subtractive color method, in which three types of couplers develop colors in a relationship of complementary colors with colors felt by the respective layers.

Generally, the basic steps of forming a color image on a silver halide color photographic light-sensitive material are a color developing 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 next 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 ion 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 performed to remove unnecessary treatment liquid components. In the case of color paper and reversal color paper, it is general to complete the process and proceed to the drying process, but in the process of color negative film and color reversal film, a stabilization process is required in addition to this. is there. However, the dye image thus obtained is not always stable to light and heat and humidity.

In photographic materials, 5 as a magenta coupler
-Pyrazolone couplers are the mainstream, and their 4 equivalents are 5-
Formalin is contained in the stabilizer for the pyrazolone-based coupler to prevent fading of the magenta dye due to the residual coupler in the processed light-sensitive material during dark heat storage. However, even in the case of the same 5-pyrazolone type coupler, not only the effect of preventing fading during storage in dark heat but also the effect of fastness to light was not effective for polymer couplers.

Further, a pyrazoloazole type coupler excellent in color reproducibility as a magenta coupler has been rapidly developed. For example, US Pat. No. 3,725,067,
No. 4,562,146, No. 4,607,002
Issue No. 4,675,280 Issue No. 4,840,88
No. 6, and U.S. Pat. Nos. 4,621,046 and 4,4.
659,652, JP-A-61-65243 and 61.
-65245, 61-65246, 61-65
No. 247, No. 64-554, No. 64-555, and No. 6
Pyrazolotriazole couplers described in JP-A-4-556, JP-A-60-33552 and 64-553.
Pyrazolotetrazole couplers described in Japanese Patent
Examples thereof include pyrazolopyrazole couplers described in Nos. 0-43659 and 64-555.

These couplers give various colored images from magenta to cyan region depending on the introduced substituents, and their absorption spectra can be seen in the absorption spectra of the various colored images obtained from the above-mentioned 5-pyrazolone type couplers. It has one major feature that there is no second absorption peak on the short wavelength side and the absorbance on the short wavelength side of the blue light region is small. Therefore, it can be said that the coupler is excellent in color reproducibility.

However, even with this pyrazoloazole coupler, the storability of the color image with respect to the light obtained by processing, especially the stain, is not always satisfactory. Many proposals have been made for improving the color image storability of pyrazoloazole couplers. For example, JP-A-60-97353 and JP-A-60-262159.
No. 62-92945, JP-A-2-217845.
U.S. Pat. Nos. 4,623,617 and 4,67
The compounds described in 5,275, 4,639,415 and the like can be used, and as to the prevention of stain, for example, JP-A-62-143048 and 62-229.
The compounds described in No. 145, No. 62-283338 and the like can be used. The use of these compounds is certainly effective in preventing discoloration and stains, but the introduction of these compounds into the light-sensitive material increases the film thickness of the light-sensitive material, reduces the sharpness, or reduces the sensitivity of the light-sensitive material during processing. It takes time to wash out the incorporated processing additive, which is not always a preferable solution.

Further, the use of the processing solution containing formalin, which was effective for the above-mentioned 5-pyrazolone type couplers, makes the pyrazoloazole type couplers both fast against dark heat and fast to light. It was almost invalid.

As described above, in the current photographic materials in which the 5-pyrazolone-based coupler is the mainstream of the magenta coupler, the color image fading to the light obtained from the 5-pyrazolone-based polymer coupler and the pyrazoloazole-based coupler described above is faded. There is an urgent need to develop compounds that replace formalin that also have a preventive effect.

Further, the use of a stabilizing bath using formalin has a problem that formaldehyde vapor is generated during the preparation of the stabilizing bath and the drying of the light-sensitive material to which the stabilizing solution adheres. It is recommended to use 0.5 ppm as an acceptable working environment concentration of formaldehyde, which is harmful to the human body. For this reason, efforts have been made to reduce the concentration of formalin in the stabilizing bath and to switch to a formalin substitute from the viewpoint of improving the working environment.

As a formalin substitute, for example, JP-A-63-244036 describes a hexamethylenetetramine compound. If this compound is used, the formaldehyde concentration, that is, the formalin vapor pressure will certainly decrease, but the original purpose of the magenta dye is insufficient in its ability to prevent fading during dark heat storage, resulting in significant fading even after several weeks at room temperature. To do.

Also, 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 compounds of thiourea compounds of JP-B No. 458506, N-methyl compounds of hydantoin compounds 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 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, among these compounds, those having a reduced formalin vapor pressure as compared with formalin have poor image preservability during dark heat preservation, and conversely those having improved image preservability during dark heat preservation. It has a formalin vapor pressure similar to that of formalin, and does not satisfy both the improvement effect of image storability and the reduction of formalin vapor pressure at the same time, and much less effect on color image fastness to light was not found.

[0014]

DISCLOSURE OF THE INVENTION As described above, a color image obtained from a pyrazoloazole-based magenta coupler or a 5-pyrazolone-based polymer coupler, which is satisfactory in the preservation of a color image relating to stain and photobleaching, can be satisfied. Moreover, there is a strong demand for the development of a formalin substitute effective for improving the preservation of color images, which has a low vapor pressure of formalin in place of formalin. Therefore, the first object of the present invention
It is an object of the present invention to provide a processing method for improving stain and color image storability of a light-sensitive material after processing. Second object of the present invention
Is to provide a treatment method that reduces the emission of formaldehyde, which is harmful to the human body, and enhances the safety of the working environment.

[0015]

As a result of various studies including the above-mentioned known N-methylol type compounds, the present inventors have found that they can be achieved by the following treatment methods. That is, a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [M] and / or a polymer coupler having a constitutional unit formed from a monomer represented by the general formula (PA) is prepared as follows. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution containing a compound represented by the formula (A) and / or a compound represented by the general formula (X). General formula (A)

[0016]

[Chemical 7]

(In the formula, X is a group of non-metal atoms necessary for forming a 4- to 8-membered ring. However, the atom bonded to each nitrogen atom is selected from a carbon atom, an oxygen atom or a sulfur atom. A general formula (X)

[0018]

[Chemical 8]

(In the above general formula (X), X ₀ represents a non-metal atom group necessary for forming a nitrogen-containing heteroaromatic ring. Ra and Rb may be the same or different and each is an alkyl group or an alkenyl. Represents a group, Ra and R
b may combine with each other to form a 4- to 8-membered ring. )

General formula [M]

[0021]

[Chemical 9]

(In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms. May have a substituent (including a condensed ring), Y represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. PA)

[0023]

[Chemical 10]

(In the formula, R ₁₂₁ is a hydrogen atom and has 1 to 4 carbon atoms.
Represents an alkyl group or chlorine, and -D- is -COO.
-, -CON (R ₁₂₂ )-or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and -F- represents -CON (R ₁₂₂ )-, -N (R ₁₂₂ ) C
ON (R ₁₂₂ )-, -N (R ₁₂₂ ) COO-, -N (R
₁₂₂ ) CO-, -OCON ( _R122 )-, -N
(R ₁₂₂ )-, -COO-, -OCO-, -CO-,-
O -, - S -, - SO 2 -, - N (R 122) SO 2 -,
Or -SO ₂ N (R ₁₂₂₎ - represent. R ₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic group or aryl group. When two or more R _122's are present in the same molecule, they may be the same or different. T represents a 5-pyrazolone magenta coupler residue. p, q, and r represent 0 or 1. However, p, q, and r are never 0 at the same time. )

The present invention will be described in detail below. First, the compound represented by the general formula (A) of the present invention (hereinafter referred to as the N-methylol compound of the present invention) will be described. The N-methylol compound of the present invention is a water-soluble compound and preferably has a total number of carbon atoms of 12 or less, more preferably 10 or less, and further preferably 6 or less. X by -N (CH ₂ O
The 4- to 8-membered ring formed together with (H) -N- is preferably a 5- to 6-membered ring, and more preferably a 5-membered ring. Of these, a pyrazole ring, a 1,2,4-triazole ring and a urazole ring are preferable. Thus -N by X (CH ₂ OH) -N-
The 4- to 8-membered ring formed therewith may be saturated or unsaturated, but an unsaturated ring is preferable, and a pyrazole ring and a 1,2,4-triazole ring are particularly preferable.

[0026] -N (CH ₂ OH) -N- together with the carbon atom and a nitrogen atom on the ring formed of the X may be substituted or an unsubstituted. These substituents include an alkyl group (eg, methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl), an alkenyl group (eg, allyl), an aryl group (eg, phenyl, 4-tert-). Butylphenyl), heterocyclic group (for example, 5-pyrazole, 4-pyrazole), 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 (eg, methanesulfonyl, octanesulfonyl, toluenesulfonyl), sulfinyl group (eg, dodecanesulfinyl), acyloxy group (eg, acetoxy), alkoxycarbonyl group (eg, methoxycarbonyl, butoxycal) Nil), a carbamoyl group (for example, carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (for example, sulfamoyl, N-ethylsulfamoyl), an amino group (for example, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), alkoxy group (eg, methoxy, ethoxy), alkylthio group (eg, methylthio, octylthio), aryloxy group (eg, phenoxy),
Examples thereof include an arylthio group (eg, phenylthio), a heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy), a heterocyclic thio group ((eg, benzothiazolylthio), etc. Also, at least two or more substituents. When it has a group, the substituents at the ortho positions may be bonded to each other to form a 5- to 7-membered aromatic ring, alicyclic ring or heterocyclic ring, or a spiro ring. Among them, the compound in which the benzene ring is condensed has a reduced solubility, and therefore, the compound in which the benzene ring is not condensed is preferable.The compound represented by the general formula (A) of the present invention undergoes the following reaction when dissolved in water. Occurs and equilibrium is reached.

[0027]

[Equation 1]

The equilibrium constant 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 absorption of a heavy aqueous solution in which the N-methylol compound of the present invention is dissolved or a heavy aqueous solution in which an equimolar formaldehyde (37% formalin aqueous solution) coexists with an amine compound. Method (NMR), and the component generated in the solution when the peak change in NMR disappears can be calculated from the proton ratio.

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, a colorimetric method, and these detecting means may be selected depending on the degree of reaction rate. .

The equilibrium constant K is preferably not more than 2 × 10 ^-2 mol / liter, more preferably at most 1 × 10 ^-2 mol / liter. The formaldehyde emission rate constant Kr is 1
× 10 ⁻⁵ sec ⁻¹ or more is preferable, a compound having 1 × 10 ⁻⁴ sec ⁻¹ or more is more preferable, a compound having 1 × 10 ⁻³ sec ⁻¹ or more is further preferable, 1 × 10 ⁻² sec ⁻ Most preferred are compounds of ¹ or more.

In the present invention, a compound having a pKa of 8 or less in water at room temperature of the released amine compound is preferable, more preferably 7 or less, further preferably 6 or less. On the other hand, the lower limit is 0.01 or more, preferably 0.1 or more, more preferably 0.5 or more, and most preferably 1 or more. Among the compounds represented by the general formula (A), the compounds represented by the following general formula (AI) are more preferable. General formula (AI)

[0032]

[Chemical 11]

In the formula, Xa is = C (R ₆₂ )-or = N-
Represents R ₆₁ , R ₆₂ and R ₆₃ 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,
It represents an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an amino group or -YRc. Where -Y
Represents -O- or -S-, Rc represents an alkyl group,
It represents an alkenyl group, an aryl group or a heterocyclic group. These groups may be further substituted. Also R ₆₁ and R ₆₂
Alternatively, R ₆₂ and R ₆₃ may combine with each other to form a 5- to 7-membered ring.

More specifically, R ₆₁ , R ₆₂ and R ₆₃ are each a hydrogen atom or an alkyl group (eg, methyl, ethyl,
n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl), alkenyl group (eg allyl), aryl group (eg phenyl, 4-tert-)
Butylphenyl), heterocyclic group (for example, 5-pyrazole, 4-pyrazole), halogen atom (for example, chlorine,
Bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phospho group, acyl group (eg, acetyl, benzoyl, propanoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, toluenesulfonyl), sulfinyl group ( For example, dodecanesulfinyl), acyloxy group (eg acetoxy), alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), carbamoyl group (eg carbamoyl, N-ethylcarbamoyl), sulfamoyl group (eg sulfamoyl, N-ethyl). Sulfamoyl), amino group (for example, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), alkoxy Group (e.g., methoxy, ethoxy), an alkylthio group (e.g., methylthio, octylthio), an aryloxy group (e.g., phenoxy),
Represents an arylthio group (eg, phenylthio), a heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy), a heterocyclic thio group ((eg, benzothiazolylthio). R ₆₁ , R ₆₂ and R ₆₃ are From the viewpoint of preventing stain and discoloration of a color image, a hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms is preferable, and more preferably,
At most one of R ₆₁ , R ₆₂ and R ₆₃ is a methyl group,
Others are compounds of hydrogen atoms, and particularly preferably all are compounds of hydrogen atoms. Specific examples of the compound represented by formula (A) are shown below, but the invention is not limited thereto.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

The compound represented by the general formula (A) of the present invention can be easily synthesized by reacting an amine compound having no methylol group with formaldehyde or paraformaldehyde. As the method for synthesizing the amine compound and the N-methylol compound of the present invention,
For example, European Published Patent No. 60,222 and Khim.Getero
tsikl.Soedin., (2), 251 ('80) [Cemical Abstracts, 93: 46
530W], U.S. Pat. No. 2,883,392 and Chem.ber.,
85,820 ('52), J.Org.Chem., 15,1285 ('50), The Chemis
RHWi, Vol. 22 of try of Heterocyclic Compounds
ley "Pyrazoles, Pyrazolines, Pyrazolidines, Indazole
s and Condensed Ring ", INTERSCIENCE PUBLISHERS ('67)
It can be synthesized by the method described in 1) or a method similar thereto.

An example of the synthesis is shown below. Synthesis Example 1 Synthesis of Compound (A-1) Pyrazole (68.1 g), sodium hydroxide (0.14 g) and methanol (80 ml) were put into a 500 ml three-necked flask equipped with a stirrer, a thermometer, and a cooling tube. 50 ° C
After heating up to 90% paraformaldehyde (3
3 g) was added little by little, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, filtration was performed, and the filtrate was concentrated under reduced pressure at 40 ° C or lower. The concentrate obtained was crystallized from ethyl acetate (300 ml). The compound (A-1) was obtained as colorless crystals. (Yield 72 g, melting point; 79 to 84 ° C.) The chemical structure was confirmed by elemental analysis and various spectra. The equilibrium constant K of this compound was 5.6 × 10 ⁻³ mol / liter. In addition,
The equilibrium constant was measured by measuring a 25 mM / liter heavy aqueous solution of this compound by a nuclear magnetic resonance absorption method (NMR), and calculating a component generated in the solution from the proton ratio when the peak change of NMR disappeared. I asked. The formaldehyde release rate constant kr of this compound was 8.
It was 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 over 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 (A-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. After adding methanol (50 ml) and heating 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 resulting concentrate was washed with ethyl acetate (15
(0 ml) for crystallization. Compound (A-5) as colorless crystals
Got (Yield 28 g, melting point; 108 to 111 ° C.) The chemical structure was confirmed by elemental analysis and various spectra. In addition,
The equilibrium constant K of this compound was 3.3 × 10 ⁻³ mol / liter. Also, the pKa of 3,5-dimethylpyrazole released from this compound in water at room temperature
Was 4.1.

The N-methylol compound of the present invention may be a compound obtained by isolation by the above-mentioned synthetic method or the like,
Alternatively, an aqueous solution containing the N-methylol compound of the present invention obtained by adding equimolar amounts of formaldehyde and an amine compound having no methylol group may be used as it is without isolation. Further, similarly, formaldehyde and an amine compound having no methylol group may be directly added to the same treatment bath to use the N-methylol compound obtained in this treatment bath.

The content of the compound represented by the general formula (A) of the present invention is 1 × 10 ⁻³ mol to 5 per liter of the treatment liquid.
The mole is appropriate, preferably 5 × 10 ⁻³ mol to 3 mol, particularly preferably 1 × 10 ⁻² mol to 1 × 10 ⁻¹ mol.

In the treatment liquid of the present invention, it is preferable to excessively contain the amine compound in which the methylol group is not substituted in the general formula (A) since the formalin vapor pressure can be lowered. It is preferable that these are contained in an amount of 10 times mol or less with respect to the N-methylol compound.
It is more preferably 2 to 5 times.

Next, the compound represented by formula (X) will be described. In the general formula (X), X ₀ represents a group of non-metal atoms necessary for forming a nitrogen-containing heteroaromatic ring, and the resulting nitrogen-containing heteroaromatic ring is, for example, a pyrrole ring, a pyrazole ring or an imidazole ring. , Triazole ring, tetrazole ring, rings in which benzene is condensed to these rings (eg, indazole ring, indole ring, isoindole ring, benzimidazole ring, benztriazole ring), rings in which hetero ring is condensed (eg, purine ring ), A ring in which an alicyclic ring is condensed (for example, a 4,5,6,7-tetrahydroindazole ring), and the like. These nitrogen-containing heteroaromatic rings may have a substituent, and examples of the substituent include an alkyl group (eg, methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl). , An alkenyl group (eg,
Allyl), aryl groups (eg phenyl, 4-ter)
t-butylphenyl), heterocyclic group (eg, 5-pyrazole, 4-pyrazole), halogen atom (eg, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group, carboxyl group, phospho group, acyl group (For example, acetyl, benzoyl, propanoyl) or a sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), a sulfinyl group (for example, dodecanesulfinyl), an acyloxy (for example, acetoxy), an alkoxycarbonyl group (for example, Methoxycarbonyl, butoxycarbonyl), carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl), sulfamoyl group (eg, sulfamoyl, N-ethylsulfamoyl), amino group, alkylamino group (eg, methylamino). Amino, dimethylamino),
Acylamino group (eg acetylamide, benzoylamide), sulfonamide group (eg methanesulfonamide), imide group (eg succinimide), ureido group (eg methylureido), sulfamoylamino group (eg N- Methylsulfamoylamino),
Urethane group (eg methoxycarbonylamino), alkoxy group (eg methoxy, ethoxy), alkylthio group (eg methylthio, octylthio), aryloxy group (eg phenoxy), arylthio group (eg phenylthio), heterocyclic thio Groups (eg,
Benzothiazolylthio) and a heterocyclic oxy group (1-phenyltetrazole-5-oxy).

Ra and Rb may be the same or different and each represents an alkyl group (eg, methyl, ethyl, n).
-Propyl, butyl, cyclopropyl, hydroxyethyl, methoxyethyl) and alkenyl groups (eg allyl). These groups may be substituted with a substituent, and examples thereof include the substituents listed as the groups which may be substituted on the ring formed by X, and further include a hydroxyl group and a trialkylsilyl group. Ra and R
b may combine with each other to form a 4- to 8-membered ring. Ra
And Rb are bonded to each other to form a 4- to 8-membered ring, the alkyl group and alkenyl group of Ra and Rb may be directly bonded, or may be bonded via an oxygen atom, a nitrogen atom, a sulfur atom or the like. You may. As a typical example, a pyrrolidine ring, a piperidine ring, a morpholine ring, a piperazine ring, a pyrroline ring, a pyrrole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a 1,4-oxazine ring, 1,4.
-A thiazine ring, an azetidine ring, etc. are mentioned. These rings may also be substituted with the substituents listed as the groups which may be substituted by the above Ra group.

Among the compounds represented by the general formula (X), X
_The nitrogen-containing heteroaromatic ring formed by ₀ is preferably a non-condensed monocycle, and more preferably a pyrazole ring or a triazole ring. 1,2,4 if it is a triazole ring
-It is preferably a triazole ring. These nitrogen-containing heteroaromatic rings are preferably unsubstituted or substituted with a group selected from an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a halogen atom and an amide group. Unsubstituted ones are particularly preferred. on the other hand,
Ra and Rb are acid dissociation constants p of secondary amines represented by the following general formula (Y) corresponding to -N (Ra) (Rb).
It is preferable that Ra and Rb are secondary amines having a Ka (value in water at room temperature (about 25 ° C.)) of 8 or more. General formula (Y)

[0048]

[Chemical 14]

Specific examples of the compound represented by formula (Y) and pKa thereof are shown below, but the invention is not limited thereto.

[0050]

[Chemical 15]

[0051]

[Chemical 16]

[0052]

[Chemical 17]

[0053]

[Chemical 18]

Among Ra and Rb, more preferred is the case where Ra and Rb are bonded to each other to form a 5- or 6-membered ring, and more preferred is the case where a 5- or 6-membered saturated ring is formed. Particularly preferably, the formed ring is a pyrrolidine ring, a piperidine ring, a morpholine ring or a piperazine ring, and most preferably a piperazine ring. Among the compounds represented by the general formula (X), those excellent in the effect of the present invention can be represented by the following general formula (XI). General formula (XI)

[0055]

[Chemical 19]

In the above general formula (XI), X ₀ represents X ₀ defined in the general formula (X), and X ₀ 'has the same meaning as X ₀ . The compound represented by the general formula (X) is preferably water-soluble, and the total carbon number thereof is preferably 30 or less, more preferably 20 or less, and particularly preferably 16 or less. Specific examples of the compound represented by formula (X) of the present invention are shown below, but the present invention is not limited thereto.

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

[0067]

[Chemical 30]

The compound represented by the general formula (X) of the present invention is described in J. Org. Chem., Vol. 35, P883 (1970), Chem. Be.
r., vol.85, P820 (1952), US Pat. No. 4,599,427, or the like, or a method analogous thereto. The compound represented by the general formula (X) is a compound represented by the general formula (Y), a compound represented by the general formula (Z) described later and formaldehyde (or a compound that releases formaldehyde) in a solution. It can be easily generated simply by mixing with.

The content of the compound represented by the general formula (X) is preferably 1.0 × 10 ^{−4 to} 0.5 mol, and more preferably 0.001 to 0.1 mol, per liter of the treatment liquid. And more preferably 0.001 to 0.03 mol.

In the present invention, it is preferable to use the compound represented by the following general formula (Z) together with the compound represented by the general formula (X). In this case, the vapor pressure of formaldehyde can be further reduced, and the effect of the present invention becomes more remarkable. General formula (Z)

[0071]

[Chemical 31]

In the general formula (Z), X ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing heteroaromatic ring,
Examples of the nitrogen-containing heteroaromatic ring obtained as a result include those listed as the nitrogen-containing heteroaromatic ring formed by X ₀ described above. These nitrogen-containing heteroaromatic rings may also have a substituent, and examples of these substituents also include those listed as the substituents that the nitrogen-containing heteroaromatic ring formed by X ₀ may have. .

Among the compounds represented by the general formula (Z), those having a total carbon number of 20 or less are preferable, more preferably 15 or less, still more preferably 10 or less. Also, X
_The nitrogen-containing heteroaromatic ring formed by ₁ is preferably a non-fused monocyclic ring, more preferably a pyrazole ring or a triazole ring. 1,2,4 if it is a triazole ring
-It is preferably a triazole ring. These rings are preferably unsubstituted or substituted with a group selected from an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a halogen atom and an amide group. Unsubstituted ones are particularly preferred. Specific examples of the compound represented by formula (Z) of the present invention are shown below, but the present invention is not limited thereto.

[0074]

[Chemical 32]

[0075]

[Chemical 33]

[0076]

[Chemical 34]

[0077]

[Chemical 35]

[0078]

[Chemical 36]

These compounds are commercially available and can be easily obtained.

The content of the compound represented by the general formula (Z) is 0. 1 with respect to 1 mol of the compound represented by the general formula (X).
01 to 100 mol is preferable, and 0.1 to 100 mol is more preferable.
It is 20 mol, most preferably 1 to 10 mol. The compound represented by the general formula (X) of the present invention may partially undergo hydrolysis in an aqueous solution. The treatment liquid of the present invention may contain these hydrolyzates, and further condensates thereof.

When the compound of the general formula (Y) has two secondary amines per molecule, that is, in the case of 2 equivalents, the compound of the general formula (Y) is
The number of moles may be half, for example, when Y-22 is used, formaldehyde, Y-22, and Z-4 are each 2
X-35 is produced at a ratio of 1 mol by reacting with 1 mol and 2 mol. Therefore, in order to obtain the embodiment of the present invention, at least the compound represented by the general formula (Z) may be added in excess (1.01 to 100 times mol) with respect to formaldehyde. Further, the compound represented by the general formula (Y) is preferably added in an amount of ½ mol or more with respect to formaldehyde. Therefore, the compound represented by the general formula (Z) is represented by the general formula (Y). 2.02 for the compound represented
A 200-fold molar amount may be added.

The compounds represented by the general formula (A) and / or the general formula (X) of the present invention (hereinafter sometimes collectively referred to as the compound of the present invention) are used in combination in a bath. You may use. The processing liquid containing the compound of the present invention, by containing the compound of the present invention, has the effect of stabilizing the dye image formed by color development (in particular, the effect of preventing fading of the magenta dye over time). This is the processing liquid that it has. It is preferably a processing solution after color development, specifically, a stabilizing solution, a controlling solution, a bleaching solution, a bleach-fixing solution and a stopping solution, and more preferably a stabilizing solution, a controlling solution and a bleaching solution. Particularly preferred is a stabilizing solution.

The above-mentioned stabilizing solution is a stabilizing solution which is conventionally used in the final processing step of a color negative film or a color reversal film, and when the final step is a washing step or a rinsing step, it is used in a stabilizing step of the prebath thereof. Although the stabilizer used is included, it is preferably used in the final step. Conventionally, the stabilizing solution and the stable replenishing solution used in the final processing step are a processing solution containing formalin, which is a processing solution that produces an image stabilizing effect by the formalin, but the present invention replaces formalin. By using the compound of the present invention, it was possible to suppress the formalin vapor pressure to a low level and to perform image stabilization, and the processing 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 vapor pressure of formalin, the lower the total amount of formaldehyde and the hydrate of formaldehyde, the more preferable, and 0.003 mol / liter or less is particularly preferable. By the method of using the N-methylol compound of the general formula (A) of the present invention described above, even when the formaldehyde and the amine compound having no methylol group are directly added to the same treatment bath and used, Due to the equilibrium reaction, the treatment liquid of the present invention has a range in which formalin is not substantially contained.

The treatment liquid of the present invention is preferably replenished with a replenisher containing the compound of the present invention in continuous treatment. The replenishing solution is replenished to the processing solution with a compound that decreases due to processing of the light-sensitive material and deterioration in the automatic processor over time, and conversely by controlling the concentration of the compound eluted from the light-sensitive material during processing, the performance is improved. Is adjusted to keep it constant. 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. Also,
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.

By adding an alkanolamine to the treatment liquid containing the above-mentioned compound of the present invention, the effect of improving the storage stability of the color image of the present invention becomes more remarkable. As the alkanolamine, any of primary, secondary or tertiary amines may be used, but tertiary amines are particularly preferable. Preferable total carbon number of alkanolamine is 2 to 1
It is 0, and particularly preferably 4 to 8. In the alkanolamine, it is sufficient that the hydroxy group is directly substituted with the alkyl group, and the number of hydroxy groups per molecule is preferably 1 to 3, and most preferably 3. The alkyl group of the alkanolamine may be linear or branched, and may be substituted with a substituent other than the hydroxy group. Examples of the substituent of the alkanolamine include a halogen atom, a nitro group, an amino group, a sulfamoyl group and a carbamoyl group, but an unsubstituted alkanolamine is preferable. Specific examples of the alkanolamine include: monoethanolamine diethanolamine triethanolamine N- (3-chloropropyl) -N, N-bis (2-hydroxyethyl) -amine N, N, N-tris (3-hydroxypropyl) ) Amine However, the preferred alkanolamines of the present invention are not limited to these. A particularly preferred alkanolamine is triethanolamine. The preferable amount of alkanolamine added to the stabilizer is 0.001
0.05 mol / liter, particularly preferably 0.005
~ 0.02 mol / l. This added amount is also applied to the replenisher.

The treatment liquid containing the above-mentioned compound of the present invention in the present invention further contains at least one compound represented by the following general formula (B) or general formula (C) to further improve the present invention. The effect of improving the storability of the color image is more remarkably exhibited. General formula (B)

[0087]

[Chemical 37]

In the formula, R ₄₁ is a hydrogen atom, an alkyl group or an alkoxy group, and R ₄₂ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group or a nitro group. Represent. R ₄₁ is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n
-Butyl group, tert-butyl group, tert-octyl group, n-dodecyl group, n-heptadecyl group, n-octadecyl group, etc., and the alkyl group is a sulfo group, a carboxyl group or a halogen atom (for example, chlorine atom). Atom, bromine atom, fluorine atom).
R ₄₂ , R ₄₃ , and R ₄₄ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), and a linear or branched alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group,
iso-propyl group, n-propyl group, n-butyl group,
sec-butyl group, tert-butyl group, tert-amino group, n-hexyl group) or an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group,
n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, n-pentyloxy group, i
so-pentyloxy group). General formula (C)

[0089]

[Chemical 38]

In the formula, R ₅₁ is a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, an aryl group, a —CONHR ₅₄ group (R ₅₄ is an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkyl group. Represents a sulfonyl group or an arylsulfonyl group) or a heterocyclic group, and R ₅₂ and R ₅₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group,
It represents an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfinyl group or an alkylsulfonyl group.

In R ₅₁ of the general formula (C), the alkyl group and the alkenyl group have 1 to 36 carbon atoms, and more preferably 1 to 18 carbon atoms. The cyclic alkyl group has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. These alkyl groups may have a substituent on the alkenyl group, cyclic alkyl group, aralkyl group, aryl group, and heterocyclic group, and as the substituent, a halogen atom, nitro, cyano, thiocyano, aryl, alkoxy, Aryloxy, carboxy, sulfoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide, heterocyclic group, aryl Sulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialky Amino, anilino, N- alkyl anilino, N- arylanilino, selected from such as N- acylamino, hydroxy and mercapto groups. In R ₅₂ and R ₅₃ of the general formula (C), the alkyl group has 1 to 18 carbon atoms, and more preferably 1 to 9 carbon atoms. The number of carbon atoms in the cyclic alkyl group is 3 to 12, more preferably 3
~ 6. These alkyl group, cyclic alkyl group and aryl group may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a sulfone group, an aryl group and a hydroxy group.

It is known that the compound represented by the general formula (B) or the general formula (C) is added to a photographic light-sensitive material as a preservative of a hydrophilic colloid of a silver halide photographic light-sensitive material. In the invention, the storability of color images is improved by adding these compounds to a processing solution containing the compound of the present invention. The compounds represented by the general formula (B) are disclosed in JP-A Nos. 54-27424 and 59-13192.
9, 59-142543, Research Disclosure 17146, and 22875. The compound represented by the general formula (C) is disclosed in JP-A-58-16634.
3, 59-131929, 59-142543, 59-226343, 59-226344, 59-.
228247.

Typical specific examples of the compound represented by the general formula (B) are shown below, but the invention is not limited thereto.

[0094]

[Chemical Formula 39]

These exemplified compounds are generally well known, and some of them are commercially available from IC Japan Co., Ltd. and Dainippon Ink and Chemicals Co., Ltd.

Next, typical examples of the compound represented by the general formula (C) are shown below, but the invention is not limited thereto.

[0097]

[Chemical 40]

[0098]

[Chemical 41]

[0099]

[Chemical 42]

[0100]

[Chemical 43]

[0101]

[Chemical 44]

[0102]

[Chemical formula 45]

[0103]

[Chemical formula 46]

[0104]

[Chemical 47]

[0105]

[Chemical 48]

[0106]

[Chemical 49]

[0107]

[Chemical 50]

Synthetic methods of these exemplified compounds represented by the general formula (C) are described in French Patent No. 1555416, etc., and a part of them is described by Rohm and Haas.
It is commercially available from Japan.

The compounds represented by the general formula (B) and the general formula (C) of the present invention are added to a treatment liquid containing the compound of the present invention. Therefore, it is desirable that the compound be water-soluble. Therefore, in the case of a compound which does not form a salt or does not have a water-soluble group such as a carboxylic acid group, the total number of carbon atoms is preferably 12 or less, more preferably 10 or less. It is more preferably 8 or less. In the present invention, the general formula (B) and the general formula (C)
Among the exemplified compounds represented by, more preferable compounds include B-1, C-1, C-40, C-45, C-47 and C-48. More preferably B-
1 and C-45, with B-1 being most preferred. The compounds represented by the general formulas (B) and (C) may be used alone or in combination of two or more kinds.

In the present invention, the amount of the compounds represented by the general formulas (B) and (C) added to the treatment liquid is 500 mg or less per liter of the treatment liquid. Preferably 1-2
The range is 00 mg, and the particularly preferred range is 10 to 100.
mg. This addition amount includes the replenisher.

The processing solutions to which the compound of the present invention can be added and the other processing solutions used in the processing method using the processing solution containing the compound of the present invention will be described below. When the compound of the present invention is used in addition to the stabilizer, the stabilizer does not need to contain the compound of the present invention, and in that case, the processing liquid itself has a color image stabilizing effect. The name "stabilizing solution" is not appropriate because it is not used, but for convenience sake, the same name will be used hereinafter.

First, preferable stabilizing solutions and adjusting solutions containing the compound of the present invention will be described. The adjusting solution is a processing solution which is sometimes called a bleaching accelerating bath.

In the stabilizing solution of the present invention, in addition to the compound of the present invention, a compound that stabilizes a dye image, such as hexamethylenetetramine, hexamethylenetetramine derivative, hexahydrotriazine, hexahydrotriazine derivative, dimethylolurea, organic It may contain an acid or a pH buffering agent. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, Bi, A
A metal compound such as 1 or the like, an optical brightener, a hardener, etc. can be used.

In order to improve the stability of the liquid, p
-Sulfinic acid compounds such as sodium toluenesulfinate and sodium benzenesulfinate are preferably added. The preferable addition amount of the sulfinic acid compound is 0.0001 mol to 0.01 per 1 liter of the stabilizing solution.
Mol, and particularly preferably 0.0005 to 0.00
It is 5 mol.

The stabilizing solution of the present invention preferably contains various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. As these surfactants,
Polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type There are anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants, but there are nonionic surfactants. It is preferable to use, and particularly preferable is an alkylphenol ethylene oxide adduct. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The stabilizing solution may contain various antibacterial agents and fungicides in order to prevent water stains and molds on 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, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds. Compounds, diazines and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts represented by benzalkonium chloride,
Antibiotics such as penicillin, journal Antibacteria and Antifungus
Agent (J. Antibact. Antifung. Agents) Vol
1. No. 5, p. The general-purpose antifungal agents described in 207 to 223 (1983) and the like may be used in combination of two or more kinds. Further, various bactericides described in JP-A-48-83820 can also be used.

It is preferable that the stabilizing solution contains various chelating agents. As a preferred chelating agent,
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.

In the stabilization process using the stabilizing solution, a multi-stage countercurrent system is preferable, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 of the amount brought in from the previous bath per unit area.
Times, preferably 2 to 30 times, more preferably 2 to 15 times. As the water used in this stabilizing step, tap water can be used, but Ca,
It is preferable to use water deionized to a Mg ion concentration of 5 mg / liter or less, water sterilized with halogen, an ultraviolet sterilizing lamp or the like.

In the present invention, after the desilvering treatment, it is preferable to carry out the stabilizing treatment using the above stabilizing solution immediately without washing with water. It is preferable to use a method in which the overflow liquid in the stabilizing step is caused to flow into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced. In the processing, an appropriate amount of water or a correction solution or a processing replenishing solution is replenished to correct the concentration of each processing solution including the stabilizing solution of the present invention (eg, color developing solution, bleaching solution, washing water) due to evaporation. Preferably.

The stabilizing solution of the present invention has a pH of usually from 4 to 10, and preferably from 5 to 9.5, and particularly preferably from 6 to 9. The replenishing amount of the stabilizing solution is 20 per 1 m ^{2 of the} light-sensitive material processed.
0 to 1500 ml is preferable, 300 to 1200 ml, particularly 500 to 1000 ml is preferable. The processing temperature of the stabilizing solution is preferably 30 to 45 ° C. The processing time is 10 seconds ~
2 minutes is preferable, and 15 to 90 seconds is particularly preferable.

As the conditioning bath, in addition to the compounds of the present invention, an aminopolycarboxylic acid chelating agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid and cyclohexanediaminetetraacetic acid; sodium sulfite, Sulfites such as ammonium sulfite and thioglycerin, aminoethanethiol,
Various bleaching accelerators described in the bleaching solution such as sulfoethanethiol may be contained. Also, for the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure 191, 19104 (1980).
It is preferable to contain the polyoxyethylene compound described in 1 above. These compounds can be used in the range of 0.1 g to 20 g per liter of the preparation liquid, but are preferably in the range of 1 g to 5 g. PH of adjusting bath
Is usually used in the range of 3 to 11, but preferably 4
-9, more preferably 4.5-7. The treatment time in the conditioning bath is preferably 30 seconds to 5 minutes. Also,
The replenishing amount of the adjusting bath is 30 ml to 300 per 1 m ² of the light-sensitive material.
0 ml is preferable, but 50 ml to 1500 ml is particularly preferable. The treatment temperature of the conditioning bath is preferably 20 ° C to 50 ° C, and particularly preferably 30 ° C to 40 ° C.

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, and a reversal positive light-sensitive material is subjected to black-and-white development and reversal processing. After that, color development is performed. The color developing solution that can be used in the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Preferred color developing agents are p-phenylenediamine derivatives, representative examples of which are shown below, but 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-6 4-Amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline D-7 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-8 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline Among the above p-phenylenediamine derivatives, D-4 and D-6 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, sulfite salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adduct may be 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, and more preferably 1 to 5 g.

Further, 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 them, 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, and the phenols described in Nos. 63-44657 and 63-58443, 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, and the like monoamines, 63-30845, 63-
14640, 63-43139, and the like diamines, 63-21647, 63-26655, and 63-46655, and the polyamines 6,
Nitroxy radicals described in 3-53551, 6
It is preferable to use the alcohols described in 3-43140 and 63-53549, the oximes described in 63-56654, and the tertiary amines described in 63-239447. 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. And aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 and the like may be contained if necessary.
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, 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 an agent for preventing the precipitation of calcium or magnesium or for improving 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 ortho-hydroxyphenylacetic 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 necessary, any 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 that the amount of the developer is not more than 2 ml, preferably not at all, per liter of the 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 and the like, thioether compounds, JP-A Nos. 52-49829 and 50-15.
P-phenylenediamine compounds described in JP-A No. 554, JP-A-50-137726, 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
Amine compounds described in No. 6, etc., JP-B-37-1608
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 other polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as 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, further, 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 antifoggant 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 0.01 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, 4,4′-diamino-2,2′-disulfostilbene compound is preferable. The amount of the fluorescent whitening agent added is 0 to 5 g, preferably 0.
It is 1 g to 4 g. 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 replenishing 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 appropriately 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. Further, in the present invention, prior to the color development step, various surfactants and alkali metals having a buffering capacity of pH 8 or higher, preferably pH 8.5 to 12.0, which can be used in the washing water described later, are used. The treatment may be carried out with a treatment liquid containing a sulfate or a nitrate.

The processing method of the present invention can be preferably used for color reversal processing. In the reversal process, after the black and white development, the reversal process is performed if necessary, and then the 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 is the black-and-white developing solution 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, 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, when the value obtained by dividing the opening area (cm ² ) by the volume of the developing solution (cm ³ ) is the opening ratio, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, more preferably 0.005 or less.

The developer can be regenerated and used.
As a process using the regenerating of the developing solution, the replenishing solution is used after regenerating the overflow solution of the developing solution.

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 performed 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 Particularly preferred among the above-mentioned steps is, for example, JP-A-61- 753
No. 52. Regarding the process, JP-A-61
No. 143,755 and Japanese Patent Application No. 2-216389. Further, the bleaching bath, the fixing bath, and the like, which are applied to the above-mentioned steps, may have one or more treatment 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 may contain the compound of the present invention as described above. The bleaching agent contained as the main component of the bleaching solution of the present invention, red blood salt, ferric chloride,
Examples thereof include inorganic compounds such as dichromate, persulfate, and bromate, and some organic compounds of ferric aminopolycarboxylic acid complex salts and ferric aminopolyphosphonic acid complex salts. In the present invention, it is preferable to use the ferric aminopolycarboxylic acid complex salt from the viewpoints of environmental protection, safety in handling, metal corrosiveness, 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 complex 200 3. Iminodiacetic acid ferric iron complex salt 210 4.1,4-butylenediaminetetraacetic acid ferric iron complex salt 230 5. Diethylene thioether diamine tetraacetic acid ferric iron complex salt 230 6. Glycol ether diamine tetraacetic acid ferric iron complex salt 240 7.1,3-Propylene diamine tetraacetic acid ferric iron complex salt 250 8. Ferric ethylenediamine tetraacetic acid complex salt 110 9. Ferric acid diethylenetriamine pentaacetate complex 80 10. Ferric acid trans-1,2-cyclohexanediaminetetraacetic acid 80

The redox potential of the bleach described above is measured by the method described in Transactions of the Faraday Society, Volume 55 (1959), pages 1312 to 1313. It is defined by the redox potential obtained by In the present invention, a bleaching agent having an oxidation-reduction potential of 150 mV or more is preferable, a bleaching agent having an oxidation-reduction potential of 180 mV or more, and most preferably 200 mV or more is preferable from the viewpoint of rapid processing and the effect of the present invention. is there. If the redox potential is too high, bleaching fog will occur, so the upper limit is 700 mV or less, preferably 500.
It is mV or less. Among these, particularly preferred is compound No. 7, 1,3-propylenediaminetetraacetic acid ferric complex.

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 bleach used in the bleaching solution is 0.01 per 1 liter of the bleaching solution.
-1 mol is suitable, preferably 0.17-0.7 mol, and 0.25-0.7 mol is preferable for speeding up the treatment and reducing stain over time. Particularly preferred is 0.30 to 0.6 mol. The amount of the bleaching agent used in the bleach-fixing solution is 0.01 to 0.1 per liter of the bleach-fixing solution.
It is 5 mol, preferably 0.02 to 0.2 mol. Further, in the present invention, the oxidizing agents may be used alone or in combination of two or more kinds, and when two or more kinds are used in combination, 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. (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 excessively, 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. In order to accelerate the processing, the bleaching solution preferably has a pH of 2.5 to 5.0, more preferably 3.0 to 4.8, and particularly preferably 3.5 to 4.5.
It is preferable that the replenisher is 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 determined at 25 ° C. at an ionic strength of 0.1 mol / dm. The acid having a pKa of 2.0 to 5.5 may be any of inorganic acids such as phosphoric acid and organic acids such as acetic acid, malonic acid and citric acid, but organic acids having a pKa of 2.0 to 5.5. Is preferred. Further, among the organic acids, organic acids having a carboxyl group are particularly preferable. However, the acid mentioned here excludes 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. Further, the combined use of acetic acid and glycolic acid or lactic acid is preferable because the effect of simultaneously solving precipitation and bleaching fog becomes remarkable. The combined 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 a 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.

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

In the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Such bleaching accelerators are described, for example, in US Pat. No. 3,89.
No. 3,858, German Patent No. 1,290,821
No. 1,138,842, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group, Thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No. 2 , 748,430, polyethylene oxides, JP-B-45-8836
It is possible to use the polyamine compounds described in the publication. Particularly preferred are 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, ammonium chloride, etc. A halogenating agent can be included. The concentration of the rehalogenating agent is 0.1 to 1 liter in the state of being used as the treatment 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 6 per 1 m ² of the light-sensitive material.
It is preferably less than 00 ml, more preferably 100 to 500
ml. The bleaching time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less. During the treatment, the bleaching solution containing the ferric aminopolycarboxylic acid complex salt is preferably aerated 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 in the present invention, it is preferable to carry out so-called evaporation correction by supplying water corresponding to the amount of 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.

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 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 agent 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 contain the compound of the present invention.

The processing solution having fixing ability contains a fixing agent. As the 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 the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) in combination with thiosulfate. Of these, it is most preferable to use thiosulfate and thiocyanate together. 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 0.5 mol, per liter of the processing liquid having fixing ability, but depending on the case, 1 to 3 mol may be used. The fixing promoting effect can be greatly enhanced by using a molar amount.

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

Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or 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 may 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. In the bleach-fixing solution, it is preferably 4.0 to 7.0, and 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 from 6 to
8.5 is preferable and 6.5 to 8.0 is more preferable.

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 to 1 m ² of the light-sensitive material.
3000 ml is preferred, more preferably 300-18
It is 00 ml. The replenishment of the bleach-fixing solution may be conducted as a bleach-fixing replenishing solution, or as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389, an overflow solution of a bleaching solution and a fixing solution is used. May be.

Further, like the bleaching treatment described above, it is preferable to carry out the bleach-fixing treatment while replenishing the processing solution with replenishing 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 5
The temperature is 0 ° C, preferably 35 to 45 ° C.

The processing solution having fixing ability of the present invention can be subjected to silver recovery by a known method, and the reclaimed solution subjected to such silver recovery can be used.

After the processing step having fixing ability, usually,
Perform a washing process. 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 droplets during drying of the processed light-sensitive material. These surfactants include polyethylene glycol-type nonionic surfactants, polyhydric alcohol-type nonionic surfactants, alkylbenzene sulfonate-type anionic surfactants, higher alcohol sulfate ester-type anionic surfactants. Agents, alkyl naphthalene 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. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, the rinsing water may contain various antibacterial agents and fungicides in order to prevent water stains and molds on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are JP-A-57 / 1982.
-157244 and JP-A-58-105145, thiazolylbenzimidazole compounds, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. Quaternary compounds such as bromophenol compounds, organotin compounds, zinc compounds, acid amide compounds, diazine compounds, triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, and benzalkonium chlorides. Ammonium salts, antibiotics such as penicillin, etc., Journal Antibacterial & Antifungus Agent (J. Antibact. Antifung.
Agents) Vol 1. No. 5, p. 207-223 (198
The general-purpose antifungal agents described in 3) and the like can be mentioned as 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 to add various chelating agents to the washing water. As a preferred chelating agent,
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 amount of replenishment is 1 to 50 times, preferably 2 to 30 times, 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 sterilizing lamp or the like. Further, tap water may be used as water for correcting the evaporation of each treatment liquid, but deionized water or sterilized water which is preferably used in the above washing step is preferable.

Further, it is preferable to use a method in which the overflow liquid in the water 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 processing, not only bleaching solution, bleach-fixing solution, fixing solution, but also other processing solutions (for example, color developing solution, washing water, stabilizing solution), in order to correct concentration by evaporation, appropriate amount of water or correction It is preferred to replenish the solution or processing replenisher.

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

In the present invention, the drying temperature is 50-80.
C. is preferable, and particularly 50 to 70.degree. C. is more preferable. The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds.

Next, the coupler represented by the general formula [M] of the present invention will be described in detail. Among the skeletons of the coupler represented by the general formula [M], 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
-Pyrazolo [1,5-d] tetrazole of the formulas [MI], [M-II], [M-III] and [M-III], respectively.
-IV].

[0168]

[Chemical 51]

Substituents R ₁ , R ₁₁ and R in these formulas
₁₂ , R ₁₃ and Y will be described in detail. R ₁ and R
₁₁ represents a hydrogen atom or a substituent, specifically, a hydrogen atom, a halogen atom, 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 alkoxy group, an aryloxy group. 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, hetero Ring oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁ or R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁ and R ₁₁ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms). Group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, and specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-penta Decylphenoxy) 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), a heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, Alkoxy groups (eg methoxy, ethoxy, 2-
Methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3 -Methoxycarbamoyl), 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), alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (eg, 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 group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy))
Propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-tylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), an alkoxycarbonylamino group (for example, Methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide,
2-methyloxy-5-t-butylbenzenesulfonamide), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecyl) Carbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N
-Dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl),
Sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyl Tetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (For example,
Acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide A group (for example, N-succinimide, N-
Phthalimide, 3-octadecenylsuccinimide),
A heterocyclic thio group (eg, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl,
Octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (for example, 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 ₁ and R
_Examples of ₁₁ 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 ₁₂ has the same meaning as R _11, and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group,
A sulfinyl group, an acyl group and a cyano group. R ₁₃ has the same meaning as R _11, 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, a carbamoyl group or an acyl group. And more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group.

Y represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The splitting group (referred to as splitting group) is a halogen atom, an alkoxy group, Aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 member Alternatively, there are 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, the leaving group is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy,
Methylsulfonylethoxy, ethoxycarbonylmethoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-
Carboxyphenoxy), acyloxy groups (eg acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg dichloroacetylamino, heptafluoro) Butyrylamino), alkyl or aryl sulfonamide groups (eg methanesulfonamino, trifluoromethanesulfonamino, p
-Toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy),
Alkyl, aryl or heterocyclic thio groups (eg,
Dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio,
Tetrazolylthio), carbamoylamino group (for example,
N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl,
Tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (for example, succinimide, hydantoinyl), arylazo group (for example, phenylazo,
4-methoxyphenylazo) and the like. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, Y may contain a photographically useful group such as a development inhibitor or a development accelerator.
Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Examples of the magenta coupler compound represented by formula [M] are shown below, but the invention is not limited thereto.

[0176]

[Chemical 52]

[0177]

[Chemical 53]

[0178]

[Chemical 54]

[0179]

[Chemical 55]

[0180]

[Chemical 56]

[0181]

[Chemical 57]

[0182]

[Chemical 58]

[0183]

[Chemical 59]

[0184]

[Chemical 60]

[0185]

[Chemical formula 61]

[0186]

[Chemical formula 62]

[0187]

[Chemical formula 63]

[0188]

[Chemical 64]

References which describe a method for synthesizing the coupler represented by the formula [M] are listed below. The compound of the formula [M-I] is represented by the formula [M-I] such as in US Pat. No. 4,500,630.
The compounds of I] are described in U.S. Pat.
The compound of the formula [M-III] is disclosed in JP-B-47-27411,
The compound of the formula [M-IV] such as US Pat. No. 3,725,067 can be synthesized by the method described in JP-A-60-33552.

The coupler represented by the general formula [M] of the present invention is used by being added to the green-sensitive emulsion layer and / or its adjacent layer and the red-sensitive emulsion layer and / or its adjacent layer. In the coupler represented by the formula [M] of the present invention, the same coupler can be divided into two or more layers and used.
It is also possible to use a mixture of two or more species. The total amount added is 0.01 to 2.00 g / m ² , preferably 0.05 to
It is 1.5 g / m ² . More preferably 0.10 to 1.0
It is 0 g / m ² . The coupler represented by the general formula [M] is preferably a magenta coupler and a green-sensitive emulsion layer and / or
Or it is used for the adjacent layer.

The method of adding the coupler represented by the general formula [M] of the present invention to the light-sensitive material can be carried out according to the method of adding a coupler described below. Is in the range of 0 to 4.0, preferably 0 to 2.0, more preferably 0.1 to 1.5, still more preferably 0.1 to 1. The weight ratio range is 0.

Stain generated after the processing of the silver halide color photographic light-sensitive material incorporating the coupler represented by the general formula [M] of the present invention (magenta stain in the case of showing a magenta color and cyan stain in the case of showing a cyan color) And the fading of the color image can be reduced by treating with a treatment liquid containing the compound of the present invention. Further, at least one of the alkanolamines and / or the compound represented by the general formula (B) or the general formula (C) is used.
The use of seeds further improves the storage stability of this color image. This will be clarified in the examples described later.

Next, the polymer coupler having a constitutional unit formed from the monomer represented by the general formula (PA) (hereinafter sometimes referred to as the magenta polymer coupler of the present invention) will be described. General formula (PA)

[0194]

[Chemical 65]

(In the formula, R ₁₂₁ is a hydrogen atom and has 1 to 4 carbon atoms.
Represents an alkyl group or chlorine, and -D- is -COO.
-, -CON ( _R122 )-, or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and -F- represents -CON ( _R122). )-, -N (R ₁₂₂ ) CON
(R ₁₂₂ )-, -N (R ₁₂₂ ) COO-, -N (R ₁₂₂ ) CO
-, -OCON ( _R122 )-, -N ( _R122 )-, -COO
-, - OCO -, - CO -, - O -, - S -, - SO 2
_{-, - N (R 122)} SO 2 - or -SO ₂ N (R _122),
Represents-. R ₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic group or aryl group. Two or more R _122's in the same molecule may be the same or different. T represents a 5-pyrazolone magenta coupler residue. p, q, and r represent 0 or 1. However, p,
q and r are never 0 at the same time. )

The general formula (PA) will be described in more detail below. T is represented by the following general formula (PB) 5
-A coupler residue of a pyrazolone magenta coupler.

[0197]

[Chemical formula 66]

* Indicates D, E or F in the general formula (PA).
Represents a bond that is bonded to the vinyl moiety via any of the following.

In the formula, Ar ₅₁ is 1 of the 5-pyrazolone coupler.
Represents a well-known type substituent at the position, for example, an alkyl group, a substituted alkyl group (eg, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), a substituted or unsubstituted heterocyclic group (eg, 4-pyridyl, 2 -Thiazolyl), a substituted or unsubstituted aryl group [as the substituent of the heterocyclic group and the aryl group, an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenyloxy), Alkoxycarbonyl group (eg methoxycarbonyl), acylamino group (eg acetylamino), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl, ethylcarbonyl), dialkylcarbamoyl group (eg dimethylcarbamoyl), arylcarbamoyl Group (eg phenylcarbamoyl), alkylsulfonyl group (eg methylsulfonyl), arylsulfonyl group (eg phenylsulfonyl), alkylsulfonamide group (eg methanesulfonamide), arylsulfonamide group (eg phenylsulfonamide), sulfamoyl group, Alkylsulfamoyl group (eg ethylsulfamoyl), dialkylsulfamoyl group (eg dimethylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), cyano group, nitro group,
Examples thereof include a halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different. Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group. ]] Is represented.

Z ₅₁ represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidation product of an aromatic primary amine color developing agent, and specifically, a hydrogen atom, a halogen atom (eg, chlorine, bromine). ), A coupling-off group linked by an oxygen atom (eg acetoxy, propanoyloxy,
Benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-
Cyanophenoxyl, 4-titanium sulfonamide phenoxy, α-naphthoxy, 4-cyanoxyl, 4-methanesulfonamide-phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyl Oxy,
2-phenethyloxy, 2-phenoxy-ethoxy, 5
-Phenyltetrazolyloxy, 2-benzothiazolyloxy), those described in the coupling-off group linked by a nitrogen atom (for example, JP-A-59-99437), specifically benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide,
2,3,4,5,6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido,
N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxozolidinyl, 1-benzyl-5-ethoxy-3-hydantoinyl, 2-oxo-1,2- Dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-
1,2,4-triazol-1-yl, 5- or 6-
Bromo-benzotriazol-1-yl, 5-methyl-
1,2,3,4-triazol-1-yl group, benzimidazolyl), a coupling-off group linked by a sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4- Methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl). It is preferably a coupling-off group linked by a nitrogen atom, and particularly preferably a pyrazolyl group.

-E- represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group, or a phenylene group, and the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene,
Examples of tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups include benzylidene, and examples of phenylene groups include p-phenylene and m.
-Phenylene, methylphenylene and the like. Also −E
The substituent of the alkylene group, aralkylene group or phenylene group represented by-is an aryl group (eg phenyl) nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (eg methoxy), an aryloxy group (eg phenoxy), an acyloxy group. Group (eg acetoxy), acylamino group (eg acetylamino), sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine, chlorine, bromine), carboxy group, carbamoyl group (Eg, methylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), a sulfonyl group (eg, methylsulfonyl) and the like. When there are two or more substituents, they may be the same or different. -E
-Is preferably an alkylene group or a phenylene group.

R ₁₂₁ is preferably a hydrogen atom and a carbon number of 1.
~ 4 alkyl groups. Particularly preferred are hydrogen atom and methyl group. -D- is preferably -COO- and -CON ( _R122 )-, particularly preferably -CO.
N (R ₁₂₂ )-. R ₁₂₂ is preferably a hydrogen atom or an aliphatic group, and particularly preferably a hydrogen atom. -F- is preferably -CON ( _R122 )-, -N ( _R122 ) CON ( _R122 ).
_{-, - N (R 122)} - and -SO ₂ N (R ₁₂₂₎ - a.
Particularly preferred is -CON (R ₁₂₂ )-. R ₁₂₂ is preferably a hydrogen atom or an aliphatic group, and particularly preferably a hydrogen atom. p, q, r are preferably p = q = 1, r = 0; p =
0, q = r = 1; p = 1, q = r = 0; p = q = 0, r
= 1. It is particularly preferable that p = 1 and q = r = 0.

The addition-polymerizable ethylenically unsaturated compound (monomer) of 5-pyrazolone magenta color-forming represented by the general formula (PA) may be used alone or in a non-color-forming (oxidizing form of an aromatic primary amine developing agent and a cup). (No ring reaction) forms a polymer coupler of a copolymer with an ethylene type monomer. Preferred is a polymer coupler which is a copolymer with a non-color forming ethylene type monomer. Examples of the non-color-forming ethylene type monomer include acrylic acid ester, methacrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, acrylamides, methacrylamides, vinyl ethers. , Styrenes, and the like.

Specific examples of these monomers will be given below. As the acrylic ester, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
Examples thereof include acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2- (2-methoxyethoxy) ethyl acrylate and the like. As the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-
Butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate and the like can be mentioned. Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diester include diethyl itaconic acid, dimethyl itaconic acid and dibutyl itaconic acid. Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide,
2-methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, phenyl acrylamide, etc. are mentioned. Examples of methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide and diethyl methacrylamide.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether. As styrenes, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, vinyl benzoate. Examples thereof include acid methyl ester and 2-methylstyrene.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocyclic compounds (eg, vinyl pyridine), glycidyl esters (eg, glycidyl acrylate), unsaturated compounds. Nitriles (eg acrylonitrile), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (eg monomethyl itaconate), monoalkyl maleate (eg monomethyl maleate), citraconic acid, vinyl sulfonic acid, acryloyloxy Examples thereof include alkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid), acrylamido alkyl sulfonic acid (for example, 2-acrylamido-2-methylethane sulfone), and the like. These acids may be salts of alkali metals (eg Na, K) or ammonium ions. Among these monomers, comonomers preferably used include acrylic acid ester, methacrylic acid ester, styrenes, maleic acid ester,
Acrylamides and methacrylamides are included. Two or more kinds of these monomers may be used in combination. When two or more kinds are used in combination, examples thereof include n-butyl acrylate and styrene, n-butyl acrylate and butyl styrene, t-butyl methacrylamide and n-butyl acrylate.

The proportion of the 5-pyrazolone magenta coupler represented by the general formula (PA) in the magenta polymer coupler is usually preferably 5 to 80% by weight.
3 in terms of color reproducibility, color development, processing dependence and stability
0 to 70% by weight is preferred. In this case, the equivalent molecular weight (gram of polymer containing 1 mol of monomer coupler) is about 2
It is 50 to 4,000 but is not limited to this. The magenta polymer coupler of the present invention is based on the coupler monomer, and when the same layer as silver halide is used, silver 1 is used.
0.005 to 0.5 mol per mol, preferably 0.0
It is preferable to add 3 to 0.25 mol. When the magenta polymer coupler of the present invention is used in the non-photosensitive layer, the coating amount is 0.01 to 1.0 g / m ² , preferably 0.1 to 1.0 g / m ² .
It is in the range of 0.5 g / m ² .

The magenta polymer coupler of the present invention is prepared by dissolving a lipophilic polymer coupler obtained by copolymerization of a monomer coupler as described above in an organic solvent and emulsifying and dispersing in an aqueous gelatin solution in the form of a latex. Maybe,
Alternatively, it may be directly produced by an emulsion polymerization method. U.S. Pat. No. 3,451,820 for a method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, and U.S. Pat. No. 4,080,211 for emulsion polymerization.
No. 3,370,952 and European Patent No. 341,0.
The method described in No. 88A2 can be used. In the synthesis of the magenta polymer coupler, a polymerization initiator and a polymerization solvent are used in JP-A-56-5543 and JP-A-5757.
-94752, JP-A-57-176038, JP-A-57.
-204038, JP-A-58-28745, and JP-A-58.
-10738, JP-A-58-42044, JP-A-58-58
It is carried out using the compound described in 145944. The polymerization temperature must be set in relation to the molecular weight of the polymer produced, the type of initiator, etc.
Although the above is possible, the polymerization is usually performed in the range of 30 ° C to 100 ° C. Next, specific examples of the magenta polymer coupler of the present invention will be given, but the present invention is not limited thereto. (The subscripts represent the molar ratio.)

[0208]

[Chemical formula 67]

[0209]

[Chemical 68]

[0210]

[Chemical 69]

[0211]

[Chemical 70]

[0212]

[Chemical 71]

[0213]

[Chemical 72]

[0214]

[Chemical formula 73]

[0215]

[Chemical 74]

The magenta polymer coupler of the present invention is added and used in the green-sensitive emulsion layer and / or its adjacent layer, preferably the green-sensitive emulsion layer. It can be introduced into the light-sensitive material according to the method described for the coupler represented by the general formula [M], and the addition amount thereof is also the same.

The stain and the fading of the color image generated after the processing of the light-sensitive material using the magenta polymer coupler of the present invention can be reduced by the processing with the processing liquid containing the compound of the present invention. Furthermore, alkanolamines and /
Alternatively, the storage stability of the color image is improved by using at least one kind of the compounds represented by the general formula (B) or the general formula (C).

Among the couplers represented by the general formula [M] and the polymer coupler having a magenta color-forming moiety represented by the general formula (PA) in the present invention, the coupler represented by the general formula [M] is limited to the magenta coupler. In this case, when treated with a treatment liquid containing the compound represented by the general formula (A) and / or (X) of the present invention, the storability of the color image has a great effect of improving the storability, which is a preferred embodiment.

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 provided on a support, There are no particular restrictions on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. 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, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. 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. For the intermediate layer, JP-A-64-1374 is used.
No. 8, No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038 may contain a coupler and the like, and include 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 sensitivities are gradually lowered 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 side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL /
It can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH. In addition, Japanese Examined Japanese Patent Publication 55-349
As described in Japanese Patent Publication No. 32, No. 32, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in 63936. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest light sensitivity, the middle layer is a silver halide emulsion layer having a lower light sensitivity, and the lower layer is more than the middle layer. An example is an arrangement in which a silver halide emulsion layer having low photosensitivity 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 / It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The dry film thickness of the support of the light-sensitive material and all the constituent layers of the support except the undercoat layer and back layer of the support are 18.0 μm.
m or less is preferable, and 12 to 16 μm is particularly preferable.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
The photosensitive material was stored under the conditions of 5 ° C. and 50% RH for 7 days, 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 above light-sensitive material is determined by the difference. The thickness can be measured by, for example, 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 or more) to measure the total thickness on the support.

Swelling rate of the light-sensitive material of the present invention [(25
° C., the equilibrium swollen film thickness -25 ° C. in in H ₂ O, dried whole thickness / 25 ° C. at 55% RH, dry whole thickness at 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferable. If the swelling ratio is out of the above range, the residual amount of the color developing agent increases, and the photographic performance, image quality such as desilvering property, and 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 swelling film thickness reached when processed in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swelling 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. It is more preferably 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% silver iodide.

The silver halide grains of the photographic emulsion are cubic,
Having regular crystals such as octahedron, 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.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types"
And No. 18716 (November 1979), 648.
P.Glafkides, Chimie et Physique Photograph, "Physics and Chemistry of Photography" by Graphide
ique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making and Coatin
g Photographic Emulsion, Focal Press, 1964) and the like. U.S. 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 Scie
nce and Engineering), Volume 14, pp. 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, may have a phase structure, and silver halide having different compositions may be bonded by epitaxial bonding. May have been
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The 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), 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 in the table below. Types of additives [RD17643] [RD18716] [RD307105] 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right Column 866 to 868 Supersensitizer to page 649 Right column 4. Brightener 24 pages 647 page Right column 868 5. Fogging prevention 24 to 25 pages 649 Right column 868 to 870 Agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dye, ultraviolet absorber 7.Stain, 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 26 Page 651 Page Left 874 to 875 Page 10. Binder 26 Page 651 Left column 873 to 874 11. Plasticizer, Page 27 Right Page 650 Page 876 Lubrication Agent 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent 13. Static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Various color couplers can be used in the present invention, and specific examples thereof are described in the above-mentioned RD No.
17643, VII-CG and RD No. 307105,
It is described in the patents described in VII-C to G.

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
Preferred are those described in US Pat. No. 6,760, US Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and European Patent 249,473A.

As the magenta coupler, a coupler which can be used in combination with the coupler represented by the general formula [M] and / or the general formula (PA) is 2 equivalents and / or 4
Equivalent amounts of 5-pyrazolone type couplers are preferred, and US Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
32, No. 3,725,064, RD No. 2422
0 (June 1984), JP-A-60-33552, R
D No. 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573.
No. 0, No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,54
0,654, 4,556,630, WO (PC
Those described in T) 88/04795 and the like are more preferable.

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, U.S. Patents 3,446,622, 4,433,99.
No. 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
Those described in JP-A No. 6,199 and JP-A No. 61-42658 are 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,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237, British Patent 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 as described in No. 7 and the like, European Patent No. 173,30
RD No. 11449, RD No. 24241, a coupler which releases a dye that recolors after the separation described in No.
Bleach 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 light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
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 etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 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), 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) and 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. Typical examples are ethyl acetate,
Examples thereof include butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
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 in water-insoluble organic solvent. It can be dissolved in a 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. In particular, use of an acrylamide polymer is preferable in terms of color image stabilization and the like.

Suitable supports which can be used in the present invention are, for example, the above-mentioned RD No. 17643, page 28 and the same RD No. 17643.
716, right column, page 647 to left column, page 648. 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.

[0244]

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

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0x10 ^-3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.05

Third Layer (First Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing Dye I 6.9 × 10 ⁻⁵ Sensitizing Dye II 1.8 × 10 ⁻⁵ Sensitizing Dye III ^3.1x10-4 EX-2 0.17 EX-10 0.020 EX-11 0.09 EX-14 0.08 U-1 0.070 U-2 0.050 U-3 0. 070 HBS-1 0.060 Gelatin 0.85 Fourth layer (second red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ⁻⁴ EX-2 0.20 EX-3 0.050 EX-10 0.015 EX-13 0.145 EX-14 0.10 EX-15 0.050 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.30

Fifth Layer (Third Red Sensitive Emulsion Layer) Emulsion D Silver 1.60 Sensitizing Dye I 5.4 × 10 ⁻⁵ Sensitizing Dye II 1.4 × 10 ⁻⁵ Sensitizing Dye III 2.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.79

Seventh Layer (First Green Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing Dye IV 3.0 × 10 ⁻⁵ Sensitizing Dye V 1.0 × 10 ⁻⁴ Sensitizing Pigment VI 3.8 × 10 ⁻⁴ EX-1 0.021 EX-7 0.030 EX-8 0.025 M-22 0.23 HBS-1 0.29 HBS-3 0.004 Gelatin 0.70 Eight layers (second green-sensitive emulsion layer) Emulsion C Silver 0.45 Sensitizing dye IV 2.1 × 10 ⁻⁵ Sensitizing dye V 7.0 × 10 ⁻⁵ Sensitizing dye VI 2.6 × 10 ⁻⁴ EX -7 0.026 EX-8 0.018 M-22 0.083 HBS-1 0.27 HBS-3 5.0 × 10 ^-3 gelatin 0.62

Ninth Layer (Third Green Sensitive Emulsion Layer) Emulsion E Silver 1.20 Sensitizing Dye IV 3.5 × 10 ⁻⁵ Sensitizing Dye V 8.0 × 10 ⁻⁵ Sensitizing Dye VI 3.0 × 10 ^-4 EX-1 0.013 M-31 0.065 M-36 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.53 10th layer (yellow filter layer) Yellow colloidal silver Silver 0 .050 EX-5 0.080 HBS-1 0.030 gelatin 0.92

Eleventh Layer (First Blue Sensitive Emulsion Layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 Sensitizing Dye VII 3.5 × 10 ⁻⁴ EX-8 0.042 EX -9 0.72 HBS-1 0.28 Gelatin 1.13 12th layer (2nd blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VII 2.1 × 10 ^-4 EX-9 0.15 EX −10 7.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78 13th layer (3rd blue emulsion layer) Emulsion H Silver 0.77 Sensitizing dye VII 2.2 × 10 ⁻⁴ EX-9 0.20 HBS-1 0.070 gelatin 0.71

14th Layer (First Protective Layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.02 15th Layer (2nd Layer) Protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 gelatin 1.12.

Furthermore, all layers have preservability, processability, pressure resistance,
W-1, W-2, W-3, B-4, B-5, F- for improving antifungal / antibacterial properties, antistatic properties and coating properties.
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 structural formulas of the silver halide emulsions and compounds used are shown below.

[0254]

[Table 3]

[0255]

[Chemical 75]

[0256]

[Chemical 76]

[0257]

[Chemical 77]

[0258]

[Chemical 78]

[0259]

[Chemical 79]

[0260]

[Chemical 80]

[0261]

[Chemical 81]

[0262]

[Chemical formula 82]

[0263]

[Chemical 83]

[0264]

[Chemical 84]

[0265]

[Chemical 85]

[0266]

[Chemical 86]

[0267]

[Chemical 87]

[0268]

[Chemical 88]

Subsequent to Sample 101, the main magenta couplers used in the 7th, 8th and 9th layers were changed as shown in Table 4 below, and the HBS-1 / coupler weight ratio was changed to Sample 101. Samples were prepared with the same adjustments as above, but otherwise unchanged.

[0270]

[Table 4]

[0271]

[Chemical 89]

These samples prepared were white light (color temperature: 48
After a wedge exposure of 00 ° K) was applied, the stabilizing solution was changed in the following treatment. The processing steps and processing solutions are shown below.

[Processing process] Process Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 05 seconds 38.0 ℃ 600ml 5000ml Bleach 50 seconds 38.0 ℃ 140ml 3000ml Bleach fixing 50 seconds 38.0 ℃ − 3000ml Fixed 50 seconds 38.0 ℃ 420ml 3000ml water wash 30 seconds 38.0 ℃ 980ml 2000ml stable (1) 20 seconds 38.0 ℃ − 2000ml stable (2) 20 seconds 38.0 ℃ 560ml 2000ml dry 1 minute 60 ℃ * Replenishment amount per 1m ² of photosensitive material Is a countercurrent method from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. To replenish the bleach-fix bath, connect the upper part of the bleaching tank of the automatic processor and the bottom of the bleach-fixing tank, and the upper part of the fixing tank and the bottom of the bleach-fixing tank with a pipe, and supply the replenisher to the bleaching tank and the fixing tank. All the overflow solution generated was allowed to flow into the bleach-fix bath. 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, 5
It was 0 ml. The crossover time is 5 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 2.0 2.2   1-hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3   Sodium sulfite 3.9 5.2   Potassium carbonate 37.5 39.0   Potassium bromide 1.4 0.4   Potassium iodide 1.3 mg −   Hydroxylamine sulfate 2.4 3.3   2-Methyl-4- [N-ethyl-N- (β-hydro     Xyethyl) amino] aniline sulfate 4.5 6.0   1.0 liter with water added 1.0 liter     pH 10.05 10.15

[0275] (Bleach) Mother liquor (g) Replenisher (g)   1,3-Propylenediaminetetraacetic acid ferric ammonium     Um-water salt 144.0 206.0   Ammonium bromide 84.0 120.0   Ammonium nitrate 17.5 25.0   Hydroxyacetic acid 63.0 90.0   Acetic acid 54.2 80.0   1.0 liter with water added 1.0 liter     pH [adjusted with ammonia water] 3.80 3.60

(Bleach-fixing solution mother liquor) A mixture of the bleach-fixing solution mother liquor and the following fixing solution mother liquor in a ratio of 15:85.

[0277] (Fixer) Mother liquor (g) Replenisher (g)   Ammonium sulfite 19.0 57.0   Ammonium thiosulfate aqueous solution (700g / l) 280ml 840ml   Imidazole 28.5 85.5   Ethylenediaminetetraacetic acid 12.5 37.5   1.0 liter with water added 1.0 liter     pH [adjusted with ammonia water and acetic acid] 7.40 7.45

(Washing Water) Mother liquor and replenisher common tap water were prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-type). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium isocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

[0279] (Stabilizer) Common for mother liquor and replenisher (Unit: g)   Additive (see Table 5 and Table 6)   sodium p-toluenesulfinate 0.3 g   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization: 10) 0.2   Ethylenediaminetetraacetic acid disodium salt 0.05   1.0 liter with water     pH 7.2

The sample obtained by the processing was subjected to the following experiment in order to evaluate the stability of the image. (1) In order to evaluate magenta stain, the treated sample was stored under the condition of 40 ° C and 80% RH for 90 days, and the minimum concentration value measured by green light (G) after the test completion and before the test start The difference (ΔGmin) was calculated. (2) In order to evaluate the light fastness of a magenta color image, a fluorescent lamp fading tester was used and irradiation was performed at 10,000 lux for 7 days.
At this time, the relative humidity in the fluorescent lamp fading tester is 75% (30%
C.). Evaluation of light fastness of the color image is tested before starting to measure the concentration after completion of the test where the exposure giving a density of minimum density + concentration of 2.0 as measured by G light that concentration difference (△ D _G) Was calculated. These results are summarized in Table 5 together with stabilizer additives.
And shown in Table 6.

[0281]

[Table 5]

[0282]

[Table 6]

As is clear from Tables 5 and 6, samples 101 and 102 using the coupler represented by the general formula [M] of the present invention, samples 103 and 104 using the magenta polymer coupler of the present invention, and Sample 105, in which the coupler represented by the general formula [M] and the magenta polymer coupler of the present invention were mixed, was excellent in suppression of stain increase under high humidity and light fastness when the compound of the present invention was used in the stabilizing solution. You can see that Further, in the compound represented by the general formula (A) of the present invention, (A
It is also clear that (A-1) is superior when -1) and (A-34) are compared, and this shows that the unsaturated heterocyclic ring system compound gives better results. I understand. Further, treatment liquids No. 1 and No. 2 using the compound represented by the general formula (A) of the present invention, and treatment liquids No. 7 and No. 7 using the compound represented by the general formula (X).
No. 8 had no formaldehyde odor as compared with Comparative Treatment Solution No. 5. Therefore, the working environment can be improved.

Example 2 Based on the above-mentioned Example 1 and Sample 101, the compounds used in each layer were not changed and only the amount of gelatin used was reduced to prepare a support and a base coat of the support. Samples were prepared by changing the total dry film thickness excluding the layers and the back layer as shown in Table 7 below.

[0285]

[Table 7]

The samples 201 to 203 thus produced were subjected to white light wedge exposure together with the sample 101, and the same treatment was carried out using the stabilizing solution of the treatment No. 2 shown in Example 1. The color image stability of the obtained sample was determined by the same method as in Example 1. The results are shown in Table 8.

[0287]

[Table 8]

From the results of Table 8, Samples 201 to 203 in which the dry film thickness of all layers except the support, the undercoat layer and the back layer of the support were thinned by reducing the amount of gelatin were clearly observed under high humidity. It can be seen that the light fastness of the magenta stain and magenta color image in FIG. Further, it is clear from the mutual comparison of Sample 101 and Samples 201 to 203 that the stability of the color image is further improved by further reducing the film thickness, and it is more preferable that the thickness is 16.0 μm or less. . Further, when the dependency of the film thickness was similarly examined by using the treatment Nos. 7 and 8 of Example 1, similar results were obtained.

Example 3 Using the sample 203 produced in Example 2, in the treatment of the stabilizing solution in the treatment of Example 1, No. 2 and No. 3 of the stabilizing solution, as shown in Table 9, 0.01 mol of triethanolamine / 25 mg / liter of each of (B-1) and (C-45) as a compound represented by liter and the general formula (B) or the general formula (C).
The same treatment as in Example 1 was carried out using the stabilizing solution containing 1 liter, and the stability of the color image was examined in the same manner. The results are shown in Table 9.

[0290]

[Table 9]

As is apparent from Table 9, the light-sensitive material containing the coupler represented by the general formula [M] of the present invention was used as a processing stabilizing solution in the formaldehyde-releasing compound represented by the general formula (A) of the present invention. By containing alkanolamine or the compound represented by the general formula (B) or the general formula (C) in the stabilizing solution, the light fastness of magenta stain and color image under high humidity conditions can be improved. It can be seen that the color image is further improved and exhibits excellent color image storability. It is also apparent that the combined use of the alkanolamine and the compound represented by the general formula (B) or the general formula (C) shows a further better storability of a color image. Further, when a similar test was performed using the sample 103 instead of the sample 203, the same effect was observed.
Furthermore, in the above test, the stabilizing solution was treated with
When the effects of the alkanolamine or the compound represented by the general formula (B) or the general formula (C) were investigated in o. 7 and 8, the same effect as the stabilizing solution No. 2 was obtained. .

Example 4 No. 7 according to Sample 101 of Example 1 of JP-A-2-854.
Sample 401 was prepared by substituting the coupler (C-3) in the layer with the coupler (M-35) represented by the general formula [M] of the present invention in an equimolar amount. The coupler (C-3) corresponds to the coupler (C-4) in addition to the exemplary coupler (M-7) of the present invention.
Corresponds to the exemplary coupler (P-3) of the present invention. In addition,
The film thickness of each layer was set to the following film thickness constitution by reducing the gelatin amount. 1st layer 1.5 μm 2nd layer 0.8 μm 3rd layer 0.6 μm 4th layer 1.5 μm 5th layer 1.5 μm 6th layer 0.8 μm 7th layer (no change) 8th layer 1.2 μm 9 layers 1.2 μm 10th layer 0.8 μm 11th layer 0.8 μm 12th layer 1.2 μm 13th layer 2.8 μm 14th layer 1.5 μm 15th layer 0.6 μm 1st to 15th layers at this time Total dry film thickness up to layer is 17.
It is 5 μm. The sample 401 was subjected to white light wedge exposure, and the following treatment was performed.

[Treatment Process] Treatment Process Time Temperature Tank Capacity Replenishment Volume [L] [L / m ² ] Black and White Development 6 minutes 38 ° C. 12 2.2 First Washing 2 〃 38 〃 4 7.5 Reversal 2 〃 38〃 4 1.1 Color development 6〃 38〃 12 2.2 Adjustment 2〃 38〃 4 1.1 Bleaching 4〃 38〃 12 0.22 Constant 3〃 38〃 8 1.1 Second water wash 4〃 38〃 8 7.5 Stability 1〃 25〃 2 1.1 Dry 2〃 50〃 --- The composition of each treatment solution was as follows.

[0294] (Black and white developer)                                             Start solution Replenisher   Nitrilo-N, N, N-trimethylene phospho 2.0 g 2.0 g     Acid ・ 5 sodium salt   Sodium sulfite 30g 30g   Hydroquinone / potassium monosulfonate 20g 20g   33 g of potassium carbonate 33 g   1-phenyl-4-methyl-4-hydroxy 2.0 g 2.0 g     Methyl-3-pyrazolidone   Potassium bromide 2.5g 1.4g   Potassium thiocyanate 1.2g 1.2g   Potassium iodide 2.0 mg −     Add water 1 liter 1 liter     pH 9.60 9.60     The pH was adjusted with hydrochloric acid or potassium hydroxide.

[0295] (Reversal liquid)                                             Start solution Replenisher   Nitrilo-N, N, N-trimethylene phospho 3.0g Same as mother liquor     Acid ・ 5 sodium salt   Stannous chloride / dihydrate 1.0 g   p-aminophenol 0.1g   Sodium hydroxide 8g   Glacial acetic acid 15 ml   1 liter with water     pH 6.00   The pH was adjusted with hydrochloric acid or sodium hydroxide.

[0296] (Color developer)                                             Start solution Replenisher   Nitrilo-N, N, N-trimethylene phospho 2.0 g 2.0 g     Acid ・ 5 sodium salt   Sodium sulfite 7.0g 7.0g   Trisodium phosphate dodecahydrate 36g 36g   Potassium bromide 1.0 g −   Potassium iodide 90mg −   Sodium hydroxide 3.0g 3.0g   Citrazine acid 1.5g 1.5g   N-ethyl- (β-methanesulfonamidoe 11g 11g     Tyl) -3-methyl-4-aminoaniline     Sulfate   3,6-dithia-1,8-octanediol 1.0 g 1.0 g   Add water 1 liter 1 liter     pH 11.80 12.00   The pH was adjusted with hydrochloric acid or potassium hydroxide.

[0297] (Preparation liquid)                                             Start solution Replenisher   Ethylenediaminetetraacetic acid, disodium salt, 8.0 g Same as mother liquor     Dihydrate salt   Sodium sulfite 12g   1-thioglycerin 0.4 ml   Sorbitan ester * 0.1 g   Additive (See Table 10)   1 liter with water     pH 6.20   The pH was adjusted with hydrochloric acid or sodium hydroxide.

[0298] (Bleaching solution)                                             Start solution Replenisher   Ethylenediaminetetraacetic acid ・ Disodium salt ・ 2.0g 4.0g     Dihydrate salt   Ethylenediaminetetraacetic acid ・ Fe (III) ・ 120g 240g     Ammonium dihydrate   Potassium bromide 100g 200g   Ammonium nitrate 10g 20g   Add water 1 liter 1 liter     pH 5.70 5.50   The pH was adjusted with hydrochloric acid or sodium hydroxide.

[0299] (Fixer)                                             Start solution Replenisher   Ammonium thiosulfate 8.0g Same as mother liquor   Sodium sulfite 5.0g   Sodium bisulfite 5.0g   1 liter with water     pH 6.60   The pH was adjusted with hydrochloric acid or aqueous ammonia.

[0300] (Stabilizer)                                             Start solution Replenisher   Additive (see Tables 10 and 11) Same as mother liquor   Polyoxyethylene-p-monononylphenyl 0.5 ml     Ether (average degree of polymerization 10)   1 liter with water     without adjusting pH   Sorbitan ester *

[0301]

[Chemical 90]

The sample obtained by the processing was subjected to the storability of the color image, ΔGmin and ΔD according to the method described in Example 1.
_G was evaluated. The results are also shown in Table 10.

[0303]

[Table 10]

[0304]

[Table 11]

As is clear from Tables 10 and 11, the coupler represented by the general formula [M] and the general formula (P
A light-sensitive material using a polymer coupler having a constitutional unit formed from a monomer represented by A) is a processing solution containing the compound represented by the general formula (A) or the general formula (X) of the present invention. It can be seen that the processing improves the lightfastness of magenta stain and magenta color images. Processing No. 4-2, 4-3 and processing No. 4-4,
From the relative comparison of 4-5, it can be seen that the photographic material of the present invention has no effect on the storability of the color image by formalin. It can also be seen that when the treatment liquid containing the compound represented by the general formula (A) or the general formula (X) is the final bath in the treatment step, the effect of preserving the color image is great.

Example 5 In the sample 401 prepared in Example 4, 1/5 molar amount of the coupler (C-1) in the third layer was replaced by the coupler (M-34) represented by the above general formula [M] of the present invention. ), The whole amount of the coupler (C-2) was replaced with the same amount (M-33), and Sample 501 was prepared without any change. The sample 501 and the sample 401 were subjected to the white light wedge exposure as before, and then the treatment No. 4-1 of Example 4 was performed.
Processes 4-8 and 4-12 were performed. The light fastness (ΔD _R ) and cyan stain (ΔD _R ) of the cyan image of the obtained color image
Rmin) was evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0307]

[Table 12]

As is clear from Table 12, even if the coupler represented by the above general formula [M] of the present invention is a coupler which gives a cyan image of long wavelength absorption, the above general formula (A) or It is clear that the treatment with the treatment liquid containing the compound represented by the general formula (X) produces a small amount of cyan stain and enhances the light fastness of the color image, which is clearly effective.

[0309]

The color light-sensitive material containing the coupler represented by the general formula [M] and / or the polymer coupler having a constitutional unit formed from the monomer represented by the general formula (PA) of the present invention is an image. After the same exposure, color development processing is performed, and when the obtained color image is stored under high humidity conditions,
The stain and the photobleaching of the color image generated are treated by a treatment liquid containing the compound represented by the general formula (A) and / or the general formula (X) of the present invention to prevent the stain and the photobleaching. You can Further, the treatment liquid using the compound represented by the general formula (A) and / or the general formula (X) of the present invention does not give off a formaldehyde odor at all, and also provides a treatment method with an improved working environment. To do.

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [M] and / or a polymer coupler having a constitutional unit formed from a monomer represented by the general formula (PA). , The following general formula (A)
And / or a processing solution containing a compound represented by the general formula (X) is used for processing a silver halide color photographic light-sensitive material. General formula (A): (In the formula, X is a group of non-metal atoms necessary for forming a 4- to 8-membered ring. However, the atom bonded to each nitrogen atom is an atom selected from a carbon atom, an oxygen atom or a sulfur atom. General formula (X): (In the general formula (X), X ₀ represents a group of non-metal atoms necessary for forming a nitrogen-containing heteroaromatic ring. Ra and Rb may be the same or different and each represents an alkyl group or an alkenyl group. Ra and Rb may combine with each other to form a 4- to 8-membered ring.) General formula [M] (In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of nonmetal atoms necessary for forming an azole ring containing 2 to 3 nitrogen atoms, and the azole ring is a substituent (condensed ring). Y represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidation product of an aromatic primary amine color developing agent.) General formula (PA) (In the formula, R ₁₂₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or chlorine, and -D- represents -COO- or -CON.
(R ₁₂₂ )-or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and -F-
Is -CON ( _R122 )-, -N ( _R122 ) CON (R
₁₂₂ )-, -N ( _R122 ) COO-, -N ( _R122 ) C
O-, -OCON ( _R122 )-, -N ( _R122 )-,-
COO-, -OCO-, -CO-, -O-, -S-,-
_{SO 2 -, - N (R} 122) SO 2 -, or -SO ₂ N
_Represents (R ₁₂₂ )-. R ₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic group or aryl group. R
_{When 122} are two or more in the same molecule, they may be the same or different. T represents a 5-pyrazolone magenta coupler residue. p, q, and r represent 0 or 1. However, p, q, and r are never 0 at the same time. ) 2. The dry film thickness of all the layers of the silver halide color photographic light-sensitive material except the support, the undercoat layer and the back layer of the support is 18.0 μm or less.
5. A method for processing a silver halide color photographic light-sensitive material described in. 3. The general formula (A) and / or the general formula (X)
The processing method for a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution containing the compound represented by the following is a processing solution used in the processing step after the color development step. 4. General formula (A) and / or general formula (X)
4. The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the processing liquid containing the compound represented by the above formula further contains an alkanolamine compound. 5. The general formula (A) and / or the general formula (X)
The silver halide color photograph according to claim 4, wherein the processing solution containing the compound represented by the formula (1) further contains at least one kind of the compound represented by the following formula (B) or (C). Method of processing photosensitive material. General formula (B) (In the formula, R ₄₁ represents a hydrogen atom, an alkyl group or an alkoxy group, and R ₄₂ , R ₄₃ and R ₄₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group or a nitro group.) Formula (C) (In the formula, R ₅₁ is a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, an aryl group, or —CO
An NHR ₅₄ group (R ₅₄ represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, or an arylsulfonyl group) or a heterocyclic group, and R ₅₂ and R ₅₃ are each a hydrogen atom, It represents a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfooxide group, an alkylsulfinyl group or an alkylsulfonyl group. )