JPH10123678A - Processing method of silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the sudden reduction of pH without reducing developablility even by a long-term processing by performing a processing with a developer containing a specified compound or benzenesulfonamide and having an ascorbic acid as developing agent. SOLUTION: A processing is performed with a developer containing at least one of a compound represented by the formula I and benzenesulfonamide or its derivative and having ascorbic acid or its derivative as developing agent. In the formula, R1 -R4 represent hydrogen atom, -OH, -SO3 X, a halogen atom, or an alkyl group, X represents hydrogen atom or a cation. The compound is contained in an amount of 0.5-30g per litter of the used developer, more preferably 5-15g. The benzenesulfonamide or its derivative is particularly preferably a compound represented by the formula II, and it is preferably used in an amount of 0.1-15g per litter of the used developer. In the formula II, R5 -R7 represent hydrogen atom, -OH, -SO3 X or the like. X represents hydrogen atom or a cation such as alkali metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a silver halide light-sensitive material. More specifically, the present invention relates to a method for stably developing a silver halide photosensitive material over a long period of time using a developing solution containing ascorbic acid as a developing agent.

[0002]

2. Description of the Related Art After a latent image is formed on a silver halide photosensitive material by exposure, a developing step is essential for obtaining an image. In this processing step, the processing method and processing agent differ depending on the type of the silver halide photosensitive material. For example, typical processing steps for black-and-white photographic light-sensitive materials are development, fixing, washing with water, and drying. In addition, steps such as bleaching and stabilization may be required.

In the black-and-white developing solution used for processing the silver halide light-sensitive material, hydroquinone is generally used as a developing agent usually used. However, in recent years, hydroquinone has caused concerns about its harm and
COD, BOD) are becoming a problem. When using hydroquinone, not only hydroquinone itself, but also solvents such as diethylene glycol and triethylene glycol used when making a concentrate of a treating agent kit containing the same,
Sulfite, which is indispensable as an antioxidant for hydroquinone, further increases COD and BOD, and as a result, greatly increases the load on the environment.

Therefore, in recent years, a developing solution using ascorbic acid as a developing agent (hereinafter referred to as ascorbic acid developing solution) has attracted attention. When ascorbic acid is used as a developing agent, its toxicity is low, its water solubility is higher than that of hydroquinone, and it is not necessary to use a solvent such as diethylene glycol.

However, in the case of ascorbic acid developer, a problem different from hydroquinone occurs. That is, the pH of a developing solution containing hydroquinone as a developing agent (hereinafter referred to as a hydroquinone developing solution) increases, whereas the pH of an ascorbic acid developing solution decreases by air oxidation. Moreover, the decrease in the pH of the ascorbic acid developer is more steep than the increase in the pH of the hydroquinone developer. For this reason, if left in an automatic developing machine, the developing activity is reduced in a shorter time than the hydroquinone developer, and the photographic characteristics are deteriorated. For example, the sensitivity is lowered and the maximum density is greatly reduced.

To solve this problem, see, for example,
In No. 3318, the pH value is monitored using a pH electrode, and the pH value is controlled using an alkaline solution. This method uses pH
When the pH of the electrode decreases due to air oxidation during long-term stoppage, or when only the pH is restored with alkali, the concentration of the developing agent cannot be compensated for, and the activity of development is reduced. . JP-A-6-19069 states that carbonate ion is added in an amount of 0.5 mol / liter or more. However, when a large amount of a carbonate is added, the progress of development of the silver halide light-sensitive material tends to decrease. In Japanese Patent Application Laid-Open No. 7-92627, the pH of the replenisher is maintained at a value higher than that of the start solution by 0.5 or more to maintain the pH during running. However, in this method, the replenishment interval and the replenishment amount must be determined in detail, and there is a problem that the method of use becomes complicated. Further, as to the preservative of ascorbic acid, JP-A-5-210220 discloses a method of adding a salicylic acid derivative to an ascorbic acid developer having a pH of more than 12, and a method of adding a hydrazine compound as disclosed in JP-A-7-287364. It is shown. Although this method improves storage, it is not enough to withstand practical use.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developing solution for a silver halide photosensitive material containing ascorbic acid or a derivative thereof as a developing agent without deteriorating the developing property even if the developing process is carried out for a long period of time. An object is to provide a simple method in which the pH does not drop rapidly.

[0008]

An object of the present invention is to provide a silver halide photographic light-sensitive material comprising ascorbic acid or a derivative thereof containing at least one compound represented by the formula (2) or benzenesulfonamide or a derivative thereof. This was achieved by using a developing method characterized by processing with a developing solution as a developing agent.

Embedded image In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are a hydrogen atom, —OH, —SO ₃ X,
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different in a halogen atom or an alkyl group (having 1 to 10 carbon atoms, which may be substituted). X represents a hydrogen atom or a cation.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the compound represented by Chemical formula 2 included in the present invention are shown below, but are not limited thereto.

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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Among the above compounds used in the present invention, R
₁ , R ₃ and R ₄ are hydrogen atoms and R ₂ is a hydrogen atom, -OH, -SO
₃ X and X are preferably a compound represented by a hydrogen atom or a cation.

The compound used in the present invention is preferably contained in an amount of 0.5 to 30 g, more preferably 5 to 15 g, per liter of the developer used.

Particularly preferred as the benzenesulfonamide or a derivative thereof included in the present invention is a compound represented by the following formula.

Embedded image In the formula, R ₅ , R ₆ , and R ₇ represent a hydrogen atom, —OH, —SO ₃ X, or an alkyl group (1 to 10 carbon atoms, which may be substituted). X represents a hydrogen atom, an alkali metal atom, or a cation such as ammonium. R ₅ , R ₆ and R ₇ may be the same or different.

Next, the compound of the formula (15) is shown, but is not limited thereto.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The benzenesulfonamide or a derivative thereof used in the present invention is used in an amount of 0.1 per liter of a developer used.
The content is preferably 1 to 15 g, and more preferably 3 to 10 g.

The silver halide photosensitive material used in the present invention is a black-and-white photographic material (for example, a medical or industrial X-ray photographic material, a lithographic photographic material such as a lithographic photographic material, a micro photographic material, a micro photographic material for X-rays). Reversal photographic materials, computerized typesetting paper, negative photographic materials for general photography, photographic paper, etc.).

In the field of graphic arts, an image generating system capable of obtaining ultra-high contrast photographic characteristics is required in order to improve continuous tone reproduction by a halftone image, and a hydrazine compound is added to an emulsion or a developing solution. It is known to add. JP-A-7-258782 describes a method in which hydrazine or a substance promoting nucleation thereof is contained in a photosensitive material, and the photosensitive material is processed with a developing solution containing ascorbic acid. These photosensitive materials can be used for the developer of the present invention.

The hydrazine derivatives used in the present invention include hydrazine sulfate, hydrazine hydrochloride and the like, and US Pat. Nos. 4,224,401 and 4,243,734;
Nos. 4,272,614 and 4,385,108
No. 4,269,929 and 4,323,64
No. 3, 4,798,780, 4,998,604
Nos. 4,994,365 and 5,104,769
JP-A-59-106244, JP-A-60-106244
No.179734, No.61-267759, No.61-2
No. 30145, No. 62-270953, No. 62-17
Nos. 8246, 62-180361, 62-275
No. 247, No. 63-253357, No. 63-2652
39, JP-A-2-271351, JP-A-2-2770
There are hydrazine derivatives described in the specification such as JP-A No. 48, No. 8-6-1193, etc., which can be used in the present invention.

Photosensitive materials to which the above-mentioned hydrazine compound is added are susceptible to the pH of the developing solution, and photographic characteristics such as sensitivity and gamma greatly vary only by increasing or decreasing about 0.2 from the initial pH. In a developing solution containing ascorbic acid as a developing agent, the pH is significantly lowered by air oxidation. However, by using the method of the present invention, a photosensitive material to which a hydrazine compound is added can be processed without changing photographic characteristics.

The silver halide used in the light-sensitive silver halide emulsion layer of the above light-sensitive material is not particularly limited, and silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. Although silver bromoiodide or silver bromoiodide can be used, the content of silver iodide is preferably 5 mol% or less. The form, habit crystal, size distribution and the like of the silver halide grains are not particularly limited, but those having an average grain size of 0.7 μm or less, particularly preferably 0.5 μm or less, are preferable, and the total number of grains is 90 μm or less. % Or more is ± 1 of the average particle diameter
Those having a particle size in the range of 0% are preferred. The method for preparing the silver halide emulsion may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

Ascorbic acid or a derivative thereof used in the developer of the present invention includes, for example, L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, D-glucoascorbic acid, 6-deoxy-L-ascorbic acid , L-rhamnoascorbic acid, D-glucoheptoascorbic acid, imino
-L-erythroascorbic acid, imino-D-glucoascorbic acid, imino-6-deoxy-L-ascorbic acid, imino
-D-glucoheptoascorbic acid, glycoascorbic acid, D-galactascorbic acid, L-araboascorbic acid, sorbascorbic acid, sodium isoascorbate, sodium ascorbate and the like. These compounds may be salts of alkali metals and the like.

In the ascorbic acid developer used in the present invention, it is preferable to use a super-additive developing agent as an auxiliary. Examples of this include 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl
-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl -
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) , 1-aryl-3-aminopyrazolidones (eg, 1- (p-hydroxyphenyl) -3-aminopyrazolidone, 1- (p-methylaminophenyl) -3-aminopyrazolidone, 1- ( p-amino-m-methylphenyl) -3-aminopyrazolidone or the like, or a mixture thereof. The combination of ascorbic acids and 1-phenyl-3-pyrazolidones is most preferred for the developing agent used in the black-and-white developer used in the present invention because good performance is easily obtained. In addition, a p-aminophenol-based developing agent may be contained.

Further, a dihydroxybenzene-based developing agent which is less harmful in environmental measures may be added. For example,
Hydroquinone monosulfonate described in JP-A-8-179481 is exemplified.

The LFMason Photographic Process
ing Chemistry (Focal Press, 1966) 226-229
And those described in JP-A-48-64933 may be used.

These developing agents are generally used in an amount of about 0.1 to 80 g / l, preferably about 0.2 to 50 g / l. Of these, the auxiliary developing agent exhibiting superadditivity is preferably contained at 1 to 10% by weight based on the main developing agent.

In the developer of the present invention, sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde sodium bisulfite and the like can be used as preservatives. Usually, in the case of a developing solution containing ascorbic acid as a developing agent, even if the concentration of sulfite ion is added at 0.1 mol or more per liter, the preservability is hardly changed. Therefore, the sulfite ion concentration in the ascorbic acid developer is generally about 0.1 mol / liter. However, when containing the compound defined in claim 2,
It has been found that an additional effect of more than 0.2 mol / liter of sulfite ion can provide an even more stabilizing effect of pH. In this case, a concentration range that does not affect the developability is more preferable, and it is preferable to add the compound in a range of 0.2 to 1.0 mol / liter.

The pH of the developer used in the present invention is preferably in the range of 9.0 to 12.0. More preferably, pH 9.5 to 11.
The range is up to 0. Compounds used for adjusting the pH include inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic; Compounds such as Japanese Patent Publication No. Hei 6-77139 may be included.

Additives other than the above-mentioned components include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol. And an organic solvent such as a color tone agent, an antifoaming agent, a water softener, and the like, if necessary.

[0049]

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

Example 1 Developer water 600 ml Sodium sulfite 10 g Potassium carbonate 50 g Ascorbic acid 30 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 0.7 g Benzotriazole 0.2 g KBr 5 g Disodium ethylenediaminetetraacetate 1 g of salt was added to make up to 1 L with water, and the pH was adjusted to 10.50 with KOH.
(25 ° C.).

The above developer is referred to as Comparative Example 1. Further, Comparative Examples 2, 3, and 4 were added to the developer of Comparative Example 1 by adding 5 g per liter of the following Chemical Formulas 25, 26, and 27 (compounds described in JP-A-5-210220). Chemical formula 3,
Chemical formula 4, Chemical 6, Chemical 10, Chemical 11, Chemical 12, Chemical 16, Chemical 1
The present inventions 1 to 11 are obtained by adding 5 g per liter of 7, 7, 18 and 24. 13 L of each of these developers was prepared.

[0052]

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[0053]

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[0054]

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The developing solutions of the comparative example and the present invention were put in a 15-liter plastic bucket and allowed to stand at room temperature (25 ° C.) for air oxidation. On the first, second, third, fourth, and fifth days, the pH was measured with a pH meter. Water was added so that the amount of the evaporated water became the above-mentioned volume (13 L). Table 1 shows the results
Shown in

[0056]

[Table 1]

In the developer of Comparative Example 1 shown in Table 1, the pH continued to drop sharply and dropped by about 0.6 in 5 days.
Comparative Example 2, to which the compound described in No. 210220 was added,
In Comparative Examples 3 and 4, there was almost no difference from Comparative Example 1. On the other hand, the developing solution of the present invention was extremely stable without a decrease in pH of 0.15 or more over 5 days. In particular, the compounds of the present inventions 5 and 6 were effective because the decrease in pH was within 0.05.

Example 2 A cubic monodispersed silver iodobromide emulsion containing iridium and having an average particle diameter of 0.25 μm was prepared by a pAg controlled double jet method, and desalted, washed with water, and redispersed by a flocculation method. Dissolved. The content of silver iodide is 1.5
Mol%.

This emulsion was sulfur sensitized by a conventional method, and
-Phenyl-5-mercaptotetrazole, and anhydrous -5,5'-dichloro-9-ethyl-3,3 'as a sensitizing dye.
-Di- (3-sulfopropyl) -oxacarbocyanine sodium hydroxide was added and the emulsion was dried at about 40 ° C for 45 minutes.
After allowing to stand for 5 minutes to stabilize the spectral sensitizing effect, 5-methylbenzotriazole, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzenesulfonate were added. Thereafter, the mixture was coated on a polyethylene terephthalate film with silver nitrate at 5 g / m ² and gelatin at 3 g / m ² . As a protective layer, 1 g / m ^{2 of} gelatin, a surfactant, a matting agent, and a hardening agent were added thereto, followed by coating and drying to prepare a sample.

An automatic processor (LD, manufactured by Dainippon Screen Co., Ltd.)
The developing solutions of Comparative Examples 1 to 4 and the present inventions 1 to 11 were placed in the developing tank of No. 221), and CF901 manufactured by Mitsubishi Paper Mills, Ltd. was charged as the fixing solution in the fixing tank. Expose the sample to LD2
The developing process was performed at 38 ° C. for 20 seconds using No. 21, and the sensitivity value, the minimum density (Dmin), and the maximum density (Dmax) were measured. For light exposure, use a light source with a color temperature of 5400 ° K.
Exposure was performed through a red filter (Ratten No. 29) and a step wedge, and the sensitivity value was determined as an exposure amount necessary to obtain a transmission density of 3.0. In Table 3, the sensitivity value of the sample when processed with the solution immediately after preparation of Comparative Example 1 was set to 100, and the sensitivity value when developed by air oxidation for 6 days was expressed as a relative value. For air oxidation, the automatic processor was operated at the above processing temperature for 6 days for 10 hours per day. No processing was performed except for the photosensitive material to be tested.

[0061]

[Table 2]

As can be seen from Table 2, the sensitivity of the developer of Comparative Example 1 decreases after being left for 6 days, and the developer of Comparative Examples 2 and 3 has almost the same tendency as Comparative Example 1, whereas In the developer of the present invention, the change in pH was small, and the sensitivity and the maximum density were hardly changed. Particularly, in the present inventions 5 and 6, a remarkable effect was confirmed.

Example 3 4 × 10 ^-7 mol of iridium hexachloride (II) per mol of silver
I) 97 mole% AgB in the presence of potassium and ammonia
r, average particle size 0.25μ with 3 mol% AgI
Was prepared by the double jet method. The emulsion was desalted by flocculation, and 40 g of inert gelatin was added per mole of silver. This emulsion was kept at 50 DEG C., and 5,5'-dichloro-9-ethyl-3,3'-bis (4
(Sulfobutyl) oxacarbocyanine was added, and the mixture was aged for 20 minutes and then cooled. Using this emulsion,
Compounds of the formulas (9), (30), (31) and (32) are added in an amount of 0.4 × 10 ⁻³ mol per mol of silver, and 5-methylbenzothiazole, 2-methyl-4-hydroxy-1,3,3a, 7 are further added.
-Tetraazaindene was added. Further, 30 mg / m ^{2 of the following} chemical formula was added to each sample as a contrast enhancement accelerator, and 1,3
-Divinylsulfonyl-2-propanol was added, and the amount of silver was 3.7 g / m 2 on a polyethylene terephthalate film.
² was applied. A gelatin was applied thereon as a protective layer so as to be 1.5 g / m ² to obtain a sample.

[0064]

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[0069]

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The coated sample was exposed to tungsten light at 3200 ° K through a step wedge, and Comparative Examples 1, 2, and 3 of Example 1 and the developing solutions of Examples 3, 6, 8, and 10 of the present invention were used. Processing was carried out using the same automatic processor as described above. Thereafter, the film was left in an automatic developing machine under the same conditions as in Example 1 for 6 days, and then processed again. The sensitivity value of the sample when processed with the developer immediately after preparation of Comparative Example 1 was 1
The sensitivity value when developed by air oxidation for 6 days was expressed as a relative value. Table 3 shows the results.

[0071]

[Table 3]

As can be seen from Table 3, the developing solutions of Comparative Examples 1 to 3 showed a sharp decrease in the maximum density and sensitivity after standing for 6 days, whereas the developing solutions of the present invention showed photographic images irrespective of the type of human peroxidation. The properties hardly changed. In particular, it was confirmed that the developer of the present invention 6 maintained stable photographic characteristics.

Example 4 In the developing solution of Comparative Example 1 of Example 1, the concentration of sodium sulfite was 12.6 g / liter (0.1 mol), 25.2 g / liter (0.2 mol), 5%.
What added 0.4 g / l (0.4 mol) and 100.8 g / l (0.8 mol) is referred to as Comparative Examples 5-1, 5-2, 5-3 and 5-4. On the other hand, those obtained by adding the compound of formula 11
The present invention 13-1, 13-2, 13-3, 13-4, which is obtained by adding -2, 12-3, 12-4 and Chemical formula 12,
Compounds of the present invention 14-1 and 14
-2, 14-3, 14-4, and 4
-1, 15-2, 15-3, 15-4. These comparative examples and the developing solution of the present invention were placed in a 1-liter beaker and left in a constant temperature bath at 35 ° C. for 10 days while being in contact with air. On the second, fourth, sixth, and eighth days On day 10, the pH was measured. Table 4 shows the results.

[0074]

[Table 4]

The developing solutions of Comparative Examples 5-1 to 5-4 shown in Table 4
The pH continued to drop sharply regardless of the amount of ON added. one
On the other hand, among the compounds of the present invention,₁,
R_Three, R _FourIs a hydrogen atom and R_TwoIs a hydrogen atom, -OH, -SO_ThreeX, X
Represents a hydrogen atom or a compound represented by a cation,
By containing sulfate ion 0.2 mol / l or more,
Can improve pH stability over a long period of time
You. Further, with respect to these developers, the photosensitive material of Example 3 was used.
Processed, the degree of pH decrease and the photographic properties
There is a correlation between the degradation, and in the present invention, the sulfite ion-rich
With the developer, stable photographic characteristics could be obtained.

[0076]

According to the present invention, in a developing solution containing ascorbic acid as a developing agent for a silver halide light-sensitive material, the development activity due to air oxidation is prevented from largely changing, and a stable pH is maintained. By doing so, the photosensitive material can be processed stably. In particular, in a super-high contrast photosensitive material containing a hydrazine compound, ultra-high contrast characteristics can be stably reproduced.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material is processed with a developing solution containing at least one of the compound represented by the chemical formula 1 or benzenesulfonamide or a derivative thereof, wherein the developing agent is ascorbic acid or a derivative thereof. A processing method characterized in that: Embedded image In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are a hydrogen atom, —OH, —SO ₃ X,
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different in a halogen atom or an alkyl group (having 1 to 10 carbon atoms, which may be substituted). X represents a hydrogen atom or a cation. 2. The method according to claim 1, wherein R ₁ , R ₃ , and R ₄ are hydrogen atoms, R ₂ is a hydrogen atom, —OH, —SO ₃ X, and X are a hydrogen atom and a cation. . 3. A processing method according to claim 2, wherein the sulfite ion concentration of the developer is 0.2 mol or more per liter.