JPH07168325A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image free from residual silver, residual thiosulfate, and residual dye stains even in the case of ultra-rapid mass processing using an automatic developing machine and superior in image quality by incorporating a specified compound in a developing solution and a fixing solution. CONSTITUTION:This photosensitive material is processed with the developing solution and the fixing solution each containing the compound represented by formula I in a content ratio of 2:1-1:1 for the total processing times of 20-33 sec. In formula I, each of X and Y is H, hydroxy, alkyl, amino, aminosulfonyl, or the like; each of R1 and R3 is alkylene optionally having an ether bond; R2 is R5-CO-NH-R6-NO-CO-R7 or same as R1; R6 is a group of formula II; each of R5 and R7 is same as R1 each of R8-R10 is H or alkyl; and each of n1-n4 is an integer of 1-5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a processing method for promoting development and fixing in rapid processing of a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, it has been desired to process silver halide light-sensitive materials rapidly.

For example, in a silver halide photographic light-sensitive material for X-ray photography, the so-called Dry to D is used mainly in the ortho system.
It started to be processed by ry in 30 seconds. In such a case, the time allotted for developing and fixing processing is about 5 to 10 seconds,
With such short-time processing, deterioration of the finished image quality (sensitivity,
Inevitable deterioration of gamma, deterioration of graininess, residual color, residual silver, etc.).

In order to solve this, use of a development accelerator has been proposed. For example, polyonium salt described in U.S. Pat.No. 2,188,226, polyethylene oxide described in 2,708,162, linear thioether described in 3,046,132, cyclic thioether described in JP-A-62-85239, etc. are disclosed, but mainly in light-sensitive materials. It is added to obtain a development-accelerating action, and no improvement in sensitivity is observed in the ultra-rapid processing.

Further, sodium sulfite, potassium sulfite and the like used as preservatives in the developing solution have a dissolving effect on silver halide, and when the silver halide photographic light-sensitive material is processed, sulfite and silver complex salt are formed. It is produced in a large amount and is eluted in the developer. The eluted silver complex is easily reduced by the developing agent, accumulating deposited silver called so-called silver sludge and floating in the developing solution and adhering to the processed film, or adhering to the roller of the automatic developing machine and adhering to the film. It has a drawback that it gives a so-called silver stain that causes yellowish brown streaks and scratches.

Similarly, as a fixing processing accelerator, for example, thiourea derivatives described in JP-A-45-35754, JP-B-58-122535 and JP-A-58-122536, alcohols having a triple bond in the molecule, and US Although thioethers and the like described in Japanese Patent No. 4,126,459 are disclosed, residual silver, residual hypo, and residual color property due to fixing failure are extremely deteriorated in ultra-rapid processing.

Therefore, it is urgent to accelerate development and fixing in ultra-rapid processing of silver halide photographic light-sensitive materials, and development of these materials has been desired.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide residual silver, residual hypo, and residual color contamination even in an extremely rapid mass processing by an automatic processor with a total processing time (Dry to Dry) of 20 to 33 seconds. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material capable of obtaining an image of excellent quality without any defects.

[0009]

The above objects of the present invention are as follows.
In the processing method of a silver halide photographic light-sensitive material, a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support is developed using an automatic processor, fixed, washed with water, and dried. 1] is contained in the developing solution and the fixing solution, and the ratio of the content of the compound in the developing solution to the content of the compound is in the range of 0.5 to 1.0, and the total processing time (Dry It was achieved by a processing method of a silver halide photographic light-sensitive material characterized by processing in a range of 20 to 33 seconds.

That is, in the ultra-rapid processing of the present invention, when the compound represented by the general formula [1] is added to the developing solution, a remarkable development-accelerating effect is obtained, and when it is contained in the fixing solution at the same time, a surprising fixing is achieved. It was unexpected by the present inventors that the accelerating effect and the improvement in the residual color property were found. These are not found even if they are contained only in the fixing solution, and when they are added to both the developing solution and the fixing solution and in the ratios of the present invention, the fixing is promoted and the residual color is greatly improved. Further, these fixing acceleration effect and residual color improvement can be found by the ultra-rapid processing of the present invention in the total processing time of 20 to 33 seconds.

Usually, various inhibitors are contained in the developing solution in order to suppress fog and adjust the shape of the characteristic curve of the obtained image. All of these inhibitors in the developer adsorb to the fog nucleus, latent image nucleus or sublatent image nucleus of the silver halide grains in the silver halide photographic light-sensitive material to suppress the development reaction. (For that reason, sensitivity and fog are reduced.) Also, it is involved in the growth of developed silver and affects the covering power and the curve shape.

[0012] As a result of investigating the characteristics with respect to the treatment time, paying attention to the adsorption of the inhibitor, it was found that the characteristic (fogging) significantly increases when the treatment with the inhibitor added in a short time of 33 seconds or less. I found it. It is considered that the adsorption of the inhibitor is insufficient in the ultra-rapid treatment. The compound of the present invention does not provide a sufficient fixing-promoting effect even when added alone to the fixing solution, and the effect of the inhibitor is reduced by the short-time treatment as described above. It is considered that the effect of the compound of (1) is large in the processing solution and the effect is increased by processing in the fixing solution while impregnating the compound of the present invention in the developing solution.

The present invention will be specifically described below.

First, the compound represented by the general formula [1] will be described.

[0015]

[Chemical 3]

In the formula, X and Y, which may be the same or different, each represents a hydrogen atom, a hydroxyl group, an alkyl group, an amino group, an ammonio group, a carboxyl group, a sulfo group, an aminocarbonyl group or an amisulfonyl group. X and Y may form a ring. As the substituents of X and Y, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, for example, a methyl group, an ethyl group, an amino group which may have a substituent,
For example, dimethylamino group, diethylamino group, di-cyanoethylamino group, morpholino group, ammonio group such as trimethylammonio group, aminocarbonyl group such as dimethylaminocarbonyl group, aminosulfonyl group,
For example, a dimethylaminosulfonyl group is preferable.

The compound represented by the general formula [1] may be a salt of an inorganic or organic acid. Preferred salts include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.

R ₁ and R ₃ represent an alkylene group, and these alkylene groups may have an ether bond.

R ₂ represents R ₅ —CO—NH—R ₆ —NH—CO—R ₇ or an alkyle group which may have an ether bond.

R ₆ is

[0021]

[Chemical 4]

R ₅ and R ₇ are alkylene groups which may have an ether bond, R ₈ , R ₉ and R ₁₀ are hydrogen atoms or alkyl groups, and n ₁ , n ₂ , n ₃ and n ₄ are 1 Represents an integer of 5;

Specific examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited to these compounds.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

The compound represented by the general formula [1] can be synthesized by a very general method, for example. US Patent
3,021,215, British Patent 950,089, Journal of
Organic Chemistry Vol. 26, pp. 1991-1995 (1961
New Experimental Chemistry Course, Vol. 14, 1713-1726, Maruzen (published in 1978).

These compounds of the present invention may be used in combination.

The amount of the compound of the present invention added to the developer is 1.
6 × 10 ^{-6 to} 1.6 × 10 ^-1 mol / liter is preferable, and 1.6 × 10 ^{-4 to} 7.8 × 10 ^-2 mol / liter is particularly preferable, and 3.0 × 10 ^{-5 to} 3.0 × 10 ^-1 for the fixing solution. Mol / l is preferred,
Particularly preferably, it is 3.0 × 10 ^{-4 to} 1.5 × 10 ^-1 mol / liter.

In the present invention, the content ratio of the compound represented by the general formula [1] (developing solution addition amount / fixing solution addition amount) means the addition amount ratio per 1 liter of each of the developing solution and the fixing solution. The content ratio of the developing solution and the fixing solution is 0.5 to 1.0, preferably 0.7 to 1.0.

That is, when the addition amount ratio of the developing solution / fixing solution is less than 0.5, the range of improvement in residual color property, which has been improved by treatment with the developing solution / fixing solution of the present invention, is extremely small,
When the content ratio is higher than 1.0, the action of the compound of the present invention in the developing solution is strongly exerted, so that the fixability (residual silver, residual hypo) and the improvement in residual color are reduced. In particular, it has a strong influence on the fixing effect.

As described above, simply increasing the addition amount has the drawbacks that the silver sludge is generated in the developing solution and the fluctuation range to sensitometry is large, and the fixing property is decreased in the fixing solution. Harmful manifestation.

That is, the effect is exhibited by the balance of the addition amount of the compound of the general formula [1] of the present invention to the developing solution and the fixing solution.

The developing agent of the developing solution according to the present invention is
It is preferable to use dihydroxybenzenes, 3-pyrazolidones described in JP-A-4-15641 and JP-A-4-16841, or a combination thereof. Also, para-aminophenols and 3-aminopyrazolones may be used.

The total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones is preferably 0.1 mole / liter or less.

Preservatives may include sulfites such as calcium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. Further, addition of a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

Further, borate described in JP-A-61-28708, sucrose, acetoxime described in JP-A-60-93439,
A buffering agent such as 5-sulfosalicylic acid, phosphate and carbonate may be used. The content of these agents is such that the pH of the developer is 9.0.
~ 13, preferably pH10 ~ 12.5.

Polyethylene glycols and their esters are used as dissolution aids in the developing solution, and quaternary ammonium salts, development accelerators, hardeners, surfactants and the like are contained as sensitizers. be able to. Further, as a silver sludge inhibitor, for example, a silver stain inhibitor described in JP-A-56-106244, a sulfide described in JP-A-3-51844, a disulfide compound, a cystine derivative described in Japanese Patent Application No. 4-92947, or a triazine compound. Etc. may be used.

As the antifoggant, for example, an indazole type, imidazole type, benzimidazole type, triazole type, benztriazo type, tetrazole type, thiadiazole type compound or the like may be used in the developing solution.
Also, as an inorganic inhibitor, sodium bromide, potassium bromide,
You may use potassium iodide etc. In addition, pages 226 to 229 of "Photographic Processing Chemistry" by LFA Menson, published by Focal Press (1966),
U.S. Patents 2,193,015 and 2,592,364, JP-A-48-54933
You may use those described in No.

Further, as a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, for example, as an organic chelating agent, a chelate stabilizing constant with iron described in JP-A 1-193853 is 8 or more. The chelating agent of is preferably used. Further, as the inorganic chelating agent, there are sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like.

The preferred processing conditions for the development of the present invention are a development temperature of 25 to 50 ° C, more preferably 30 to 40 ° C. The developing time is 5 to 10 seconds, more preferably 8 to 9.8 seconds. The total treatment time is preferably 20-33 seconds, more preferably
23 to 30 seconds.

The replenisher used in the present invention is composed of the same components as the developer described later, and the replenisher replenishes the amounts corresponding to processing fatigue and oxidation fatigue. As the replenishment method, there are width replenishment described in JP-A-55-126243, replenishment by feeding speed, area replenishment described in JP-A-60-104946, and controlled area replenishment by continuous processing number described in JP-A-1-149156. Well, the preferred replenishment rate is 500-150 ml / m ² .

The fixing agent of the present invention may be a commonly used fixing material, for example, an aqueous solution containing thiosulfate. The pH of the fixing solution is 3.8 or more, preferably 4.2 to 5.5.

As a fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of the fixing speed.

The fixing solution may contain a fixing hardener such as an aluminum salt.

The concentration of thiosulfate in the fixer is preferably
The range is preferably from 0.1 to 5 mol / liter, more preferably from 0.8 to 3 mol / liter.

The pH of the fixing solution is preferably 3.8 to 5.8, particularly preferably 4.5 to 5.1. The higher the pH, the higher the fixability but the poorer the dryness.

The processing conditions of the fixing solution of the present invention are preferably a fixing time of 3.6 to 6.0 seconds and a processing temperature of 15 to 45 ° C, particularly preferably 25 to 38 ° C.

A surfactant may be added to the fixing solution of the present invention. Preferred surfactants include, for example, anionic surfactants such as sulfate ester and sulfonate, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. To be

The fixer contains various acids in addition to the above compounds.
Additives such as salts, chelating agents and wetting agents can be included.

Examples of the acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferable. The preferable additive amount of the additive is 0.5 to 20 g / liter.

Drying is usually 35 to 100 ° C., preferably 40 to 8
The automatic developing machine may be provided with a drying zone in which a hot air of 0 ° C. is blown or a heating means by far infrared rays is provided.

The automatic developing machine has a function of applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the developing, fixing and washing steps. Kaihei 3-264953) may be used. Further, the automatic developing machine may include a device capable of preparing a developing solution and a fixing solution.

The processing agents of the present invention are various black and white silver halides for X-rays, printing plates, general black and white, films for laser light sources, CRT photography, duplication, II or mirror indirect photography light-sensitive materials. It can be applied to photographic materials.

The silver halide emulsion which can be applied to the processing method of the present invention has any halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. However, silver chloroiodobromide is preferable from the viewpoint of high sensitivity, and the average silver iodide content is particularly preferably 0 to 4.0 mol%.
0.2-3.0 mol%, average silver chloride content 0-5.0 mol%
Is.

In the silver halide emulsion, the halogen composition may be uniform within the grain or silver iodide may be localized, but the one localized in the central portion is preferably used. .

Further, the method for producing a silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like. As a method for producing a monodisperse tabular silver halide emulsion, reference can be made to JP-A No. 61-6643.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

In the silver halide emulsion of the silver halide photographic light-sensitive material applicable to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research
Day Closure No.17643 (December 1978), No.187
16 (November 1979), and No. 308119 (December 1989). The types of compounds shown in these three Research Disclosures and their locations are listed below.

Additives RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 to 4 XXII Support 28 XVII 1009 XVII Used for photosensitive materials Examples of the support that can be used include those described in RD-17643, page 28 and RD-308119, page 1009.

A suitable support is polyethylene terephthalate or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

[0069]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of Developer of the Present Invention The developer of the present invention comprises the following formulation (12 liter formulation) with the addition amount of the exemplified compound of the general formula [1] as the development accelerator of the present invention and the fixing solution. The addition amount ratio of is shown in Table 1.

Developer formulation (12 liter formulation) Part-1 Potassium hydroxide 700 g Potassium sulfite (50% solution) 2280 g Diethylenetetramine pentaacetic acid 120 g Exemplified compound of general formula [1] Amount shown in Table 1 Sodium bicarbonate bicarbonate 132 g Boric acid 200g 5-Methylbenzotriazole 1.2g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 390g Add water to make 5000ml Part-2 Glacial acetic acid 170g Triethylene glycol 310g 1-Phenyl-3-pyrazolidone 25g Part-3 Glue Tar aldehyde (50% solution) 15 g Preparation of starter solution Glacial acetic acid 120 g Potassium bromide 225 g Preparation of fixing solution of the present invention by adding water to 1000 ml The fixing solution of the present invention has the following formulation (12 liter formulation). Table 1 shows the amount of the exemplary compound of the general formula [1] added as a fixing accelerator and the ratio of the amount added to the developing solution. .

Fixer formulation (12 liter formulation) Ammonium thiosulfate 6000 g Sodium sulfite 150 g Sodium acetate trihydrate 450 g Glutaraldehyde bisulfite adduct 15 g Exemplified compound of general formula [1] Amount shown in Table 1 Tartaric acid 20 g Sodium citrate 50g Gluconic acid 70g 1- (n, n-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Glacial acetic acid 150g Part-B Aluminum sulphate 800g 50% Sulfuric acid 100g Preparation of the developing solution to about 5 liters of water Patr-A, Part -B was added at the same time, and while stirring and dissolving, water was added to make 12 liters and the pH was adjusted to 10.68. The developer replenisher is also used, and 20 ml of the starter is added to 1 liter of the developer to adjust the pH to 10.55 to obtain a working solution.

The fixing solution was prepared by adding Patr-to about 5 liters of water.
Add A and Part-B at the same time, add water while stirring and dissolve to make 18 liters, and use sulfuric acid and NH ₄ OH to adjust the pH to 4.4.
Adjusted to. This fixer was used as the fixer replenisher.

<Preparation of silver halide photographic light-sensitive material> Preparation of seed emulsion containing gelatin treated with hydrogen peroxide vigorously stirred at 40 ° C.
A double-jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution, and the temperature was 25 ° C for 1.5 minutes to 30 minutes.
After the liquid temperature was lowered to 80 ml, ammonia water (28%) of 80 ml per mol of silver nitrate was added and stirring was continued for 5 minutes.

Then, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added and redispersed. The resulting seed emulsion has an average grain size of 0.23 μm and a coefficient of variation
It was 0.28 spherical particles.

Growth from Seed Emulsion Grains were grown as follows using the seed emulsion described above. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method to an aqueous solution containing ossein gelatin and propyloxy polyethyleneoxy disuccinate disodium salt vigorously stirred at 75 ° C. During this time pH
= 5.8 and pAg = 9.0. After the addition was completed, the pH was adjusted to 6.0 and GD-1 was added at 400 mg / mol AgX. 40 ° C
After desalting with an aqueous solution of Demol N manufactured by Kao Atlas Co., a gelatin aqueous solution was added and redispersed. By this method, the average silver iodide content is 0.5 mol% and the projected area diameter is 0.96μ.
A tabular silver iodobromide emulsion having m, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0 was prepared.

Sample Preparation The obtained emulsion was mixed with GD-1 at 55 ° C. and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4- Anhydrous of (sulfobutyl) benzimidazolocarbocyanine sodium salt (weight ratio of 200: 1) was added at 500 mg per mol of silver halide.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added at 3 × 10 ^-2 mol per mol of silver halide and dispersed in an aqueous solution containing 70 g of gelatin.

For ripened emulsions, JP-A-2-301744,
Additives as shown on page 95, line 16 to page 96, line 20 were added.

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved in a solvent composed of 28 liters of tricresylphosphite and 85 liters of ethyl acetate at 55 ° C.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 Kg of anionic surfactant AS is called an aqueous solvent.

Next, the oil-based solvent and the water-based solvent were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C.

[0083]

[Chemical 10]

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (Matting agent having an area average particle size of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent)
500 mg

[0086]

[Chemical 11]

The emulsion layer is 1.7 g in terms of silver per side.
/ M ² , the amount of gelatin applied is 2.5 g / m ² , and the protective layer has an amount of gelatin applied of 0.99 g / m ² with two slide hopper type coaters at a speed of 90 m / min. Acrylic-butylmethacrylate copolymer (50: 10: 40wt%) was diluted to a concentration of 10wt% and the aqueous copolymer dispersion was applied onto a 175μm polyethylene terephthalate base coated as an undercoating liquid. The emulsion layer and the protective layer were coated on both sides simultaneously and dried for 2 minutes and 15 seconds to obtain a sample film.

<Evaluation of Photographic Performance (Sensitivity, Gamma)> A sample film was used as a fluorescent intensifying screen KO-250 (manufactured by Konica Corporation) with a tube voltage of 90 KVP and 20 mA for 0.05 seconds for X-ray irradiation. The sensitivity and the gamma (γ) were determined by performing the measurement and shown in Table 1. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0, and the result was expressed as relative sensitivity when the sensitivity of Sample No. 1 was 100.

The value of gamma is the density of the characteristic curve from 1.0 to 2.0.
It was shown by the value of gamma. That is, tan θ was defined as gamma (γ), where θ was the inclination of the straight line connecting the density 1.0 and density 2.0 points.

For processing, an automatic processor SRX-503 was used, and the above-mentioned developing solution (a compound containing the exemplified compound as a development accelerator was added as shown in Table 1), a starter, and a fixing solution (the exemplified compound as a fixing accelerator were listed in Table 1). Was added as described above).

First, 16.5 liters of the developing solution was filled in the development processing tank, and 330 ml of a starter was added. The pH of the developing processing solution at the start was 10.55. The fixing tank was filled with a fixing solution having a pH of 4.4, and the processing was performed by changing the total processing time as shown in Table 1.

The above developing solution and fixing solution were used as the replenishing solution. The processing equilibrium of the processing solution is exposed and exposed to give an optical density of 1.1.
2000 sheets were processed to obtain a running equilibrium state. At this time, the pH of the developing solution was 10.55 and the pH of the fixing solution was 4.53.

The processing conditions are shown below.

(Treatment Process) Process Treatment temperature (° C.) Treatment time (sec) Replenishment amount (ml / m ² ) Insertion − 0.8 − Development + crossover 35 9.7 270 Fixing + crossover 35 5.5 430 Washing + crossover 18 4.8 70 Squeeze 40 3.8-Dry 45 5.4-Total-30.0- <Processability test> Evaluation of residual color property A film obtained by treating the prepared sample film without exposing it under the same conditions as the above sensitometry was used as a light source for photographic observation.
The evaluation was visually performed on (Shoukasten) in the following five grades.

Evaluation Criteria 5: No Contamination of Residual Color 4: Slight Contamination of Residual Color 3: Slight Contamination of Residual Color but No Practical Problem 2: Slight Contamination of Residual Color but Limit of Practical Range 1: Contamination of Residual Color Evaluation of residual silver that is not practically possible Under the same processing conditions as above, the unexposed film was processed without exposure to obtain a residual silver evaluation sample. The residual silver was evaluated by the following method.

Residual silver evaluation liquid (sodium sulfide 2.6 × 10
^-3 mol / liter aqueous solution) is added drop by drop to five points on the residual silver evaluation film.

After being left for 3 minutes, the liquid was wiped off thoroughly and left at room temperature and normal humidity for 15 hours, and then left with an interference filter of spectral filter 436 ± 10 nm using a photo densitometer PDA-65 (manufactured by Konica Corporation). The blue light transmission densities of the portion below the silver evaluation droplet and the portion not dropped were measured, and the difference was used as a measure of the residual silver. That is, the larger this difference is, the higher the residual silver concentration in the processed film is.

Evaluation Method for Residual Hypo Residual hypo detection liquid (7 g of silver nitrate, 30 ml of glacial acetic acid and 1000 of pure water.
(dissolved in ml) is added drop by drop to 5 points on the above-mentioned treated test film.

After standing for 3 minutes, the solution was wiped off thoroughly with a filter paper, and after standing for 15 hours at room temperature and normal humidity, the silver sulfide produced was analyzed by a photographic densitometer PDA-65 and used as a spectral filter 436 ± 1.
The blue light transmission densities of the lower drop portion and the non-drop portion were measured with an interference filter of 0 nm, and the difference was averaged to calculate the residual hypo amount from a calibration curve obtained from a standard sample. The results thus obtained are shown in Tables 1 and 2 below.

[0100]

[Table 1]

[0101]

[Table 2]

As is clear from Tables 1 and 2, the samples according to the present invention have less residual silver and less residual hypo than the comparative samples even after rapid processing, and have high sensitivity and high gamma without residual color contamination. It can be seen that the photographic performance of is obtained.

[0103]

According to the present invention, a silver halide capable of obtaining high sensitivity and high gamma photographic performance with little residual silver, residual hypo and residual color contamination even during ultra-rapid processing with a total processing time of 20 to 33 seconds. A method of processing a photographic light-sensitive material has been provided.

Claims (1)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material, which comprises developing, fixing, washing with water and drying the silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support using an automatic processor. In the following general formula [1]
The developing solution and the fixing solution contain the compound represented by, and the ratio of the content of the compound in the developing solution to the content of the compound in the fixing solution is in the range of 0.5 to 1.0, and the total processing time (Dry to Dry )
The method for processing a silver halide photographic light-sensitive material is characterized in that the processing is carried out for 20 to 33 seconds. General formula [1] In the formula, X and Y may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an amino group, an ammonio group, a carboxyl group, a sulfo group, an aminocarbonyl group, or an aminosulfonyl group. R ₁ and R ₃ represent an alkylene group, and these alkylene groups may have an ether bond. R ₂ represents an alkylene group which may have _{R 5 -CO-NH-R 6} -NH-CO-R 7, or an ether bond. R ₆ is R ₅ and R ₇ are an arylene group which may have an ether bond, R
₈ , R ₉ and R ₁₀ represent a hydrogen atom or an alkyl group, and n ₁ ,
n _2, n _3, n ₄ represents an integer of 1 to 5.