JP2681161B2 - Processing solution and processing method for silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a processing solution and a processing method for a silver halide color photographic light-sensitive material. More specifically, it relates to a processing solution for a silver halide color photographic light-sensitive material (hereinafter also referred to as "light-sensitive material") and a method for processing the light-sensitive material, in which the fixability is remarkably improved.

[Background of the Invention]

In recent years, with the development of automatic processors, rapid processing progresses,
Also in the fixing step, a rapid fixing solution containing ammonium thiosulfate as a main component has come to be used. The use of fixing accelerators has become more common as the speed has increased. For example, JP-B-45-35754 describes a combination of a thiourea derivative and a potassium-containing developer, and US Pat. No. 3,854,947 describes a thiocyanate or an alkali metal thiosulfate and an anion. No. 3,961,958 describes N-methylpyrrolidone, and No. 4,138,257 describes a pyrrolidone-containing polymer, and 4,126,45.
No. 9 describes thioether.
All of these were effective means for accelerating the fixing process, but as the accelerating process further progressed, they could not be said to be sufficient.

When a silver halide photographic light-sensitive material is processed by an automatic developing machine, if the processing amount is increased, the fixing solution becomes fatigued, the fixing speed is delayed, and eventually the rapid fixing ability is lost. In particular, a film sensitive material having a large amount of coated silver is susceptible to this influence. Therefore, it has been required to prevent the fixing speed from decreasing when the liquid is fatigued and to improve the processing capacity.

Further, since the concentration of the fixing agent is increasing, crystal precipitation is likely to occur in the tank during the processing for a long period of time. Therefore, prevention of such crystal precipitation has been required.

[Object of the invention]

An object of the present invention is to provide a processing solution in which the fixing speed of a silver halide photographic light-sensitive material is improved.

Another object of the present invention is to provide a treatment liquid which prevents crystal precipitation on the vessel wall of the processing tank of the automatic developing machine.

[Configuration of the invention]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, the above object of the present invention was achieved by a processing solution for a color light-sensitive material containing the following components and having a pH value of 5-8. It was

Thiosulfate as a fixing agent Compound represented by the following general formula (A): General formula (A) In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group which may have a substituent. R ₁ and R ₃ may be linked to form a heterocycle.

Further, the method for processing a light-sensitive material of the present invention which achieves the above object is characterized in that a processing solution containing the above-mentioned components and in the processing step and having a pH value of 5 to 8 is used.

[Specific configuration of the invention]

 Hereinafter, the present invention will be described more specifically.

As the thiosulfate as the fixing agent used in the present invention, for example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate and the like can be used. The amount of addition is preferably 0.5 mol to 3 mol, more preferably 0.9 mol to 2.5 mol, and most preferably 1.1 mol to 2.0 mol per treatment liquid.

Next, the compound represented by formula (A) will be described in detail. R _{1 to} R ₄ may be the same or different and each is a hydrogen atom or an alkyl group which may have a substituent, and R ₁ and R ₃ may be linked to form a heterocycle. Examples of the alkyl group which may have a substituent, for example, _{-CH 2 NHCONH 2, -CH 2 CH} 2 OH,
It can be mentioned -CH ₂ CH ₂ NHCONH ₂ and the like. More preferably, a hydrogen atom, R ₁ and R ₃ are linked to form a 5-membered ring, and most preferably a hydrogen atom.

Specific preferred examples of the compound represented by formula (A) are shown below.

(A-1) NH ₂ CONH ₂ (A-2) (CH ₃ ) ₂ NCONH ₂ (A-8) N ₂ NCONHCH ₂ CH ₂ NHCONH ₂ (A-9) (CH ₃ ) ₂ NCONHCH ₃ (A-10) (HOCH ₂ CH ₂ ) ₂ NCON (CH ₂ CH ₂ OH) _{2 The} present invention has been established. Although a remarkable effect is obtained in the solution, a preferable effect can be obtained also in the bleach-fixing solution.

When the processing solution having the fixing ability according to the present invention is a bleach-fixing solution, the bleaching agent used in the bleach-fixing solution is preferably a ferric complex salt of aminocarboxylic acid or aminophosphonic acid. The aminocarboxylic acid and aminophosphonic acid each represent an amino compound having at least two carboxylic acid groups and an amino compound having at least two phosphonic acid groups, and preferably the following general formula [I] And a compound represented by [II].

General formula [I] General formula (II) Wherein, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene _{group, -R 83 OR 83 OR 83 -} , - R 83 ZR 83 - represents, Z is> N-R
₈₃ -A _{6, represents> N-A 6, R 79} ~R 83 represents an alkylene group having a substituted or unsubstituted, A ₂ to A ₆ is a hydrogen atom, -OH, -CO
OM, represents -PO ₃ M _2, M represents a hydrogen atom, an alkali metal atom.

Next, preferable specific exemplary compounds of the compounds represented by the general formulas [I] and [II] are listed below.

(Exemplified Compound) (I-1) Ethylenediaminetetraacetic acid (I-2) Diethylenetriaminepentaacetic acid (I-3) Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid (I-4 ) 1,3-Propylenediaminetetraacetic acid (I-5) Triethylenetetramine hexaacetic acid (I-6) Cyclohexanediaminetetraacetic acid (I-7) 1,2-Diaminopropanetetraacetic acid (I-8) 1,3- Diaminopropan-2-ol-tetraacetic acid (I-9) Ethyletherdiaminetetraacetic acid (I-10) Glycoletherdiaminetetraacetic acid (I-11) Ethylenediaminetetrapropionic acid (I-12) Phenylenediaminetetraacetic acid (I- 13) Ethylenediaminetetraacetic acid disodium salt (I-14) Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt (I-15) Ethylenediaminetetraacetic acid 4-na Thorium salt (I-16) Diethylenetriaminepentaacetic acid pentasodium salt (I-17) Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid sodium salt (I-18) Propylenediaminetetraacetic acid Sodium salt (I-19) Ethylenediaminetetramethylenephosphonic acid (I-20) Cyclohexanediaminetetraacetic acid sodium salt (I-21) Diethylenetriaminepentamethylenephosphonic acid (I-22) Cyclohexanediaminetetramethylenephosphonic acid (II-1) ) Nitrilotriacetic acid (II-2) Methyliminodiacetic acid (II-3) Hydroxyethyliminodiacetic acid (II-4) Nitrilotripropionic acid (II-5) Nitrilotrimethylenephosphonic acid (II-6) Iminodimethylenephosphonic acid (II-6) II-7) Hydroxyethyliminodimethylenephosphonic acid (II-8) nit Lilotriacetic acid trisodium salt Among these aminocarboxylic acids and aminophosphonic acids, compounds (I-1), (I-2) and (I-4) which are particularly preferably used from the viewpoint of the effects of the present invention are preferred. ,
(I-6), (I-7), (I-10), (I-19),
(II-1) and (II-5) are mentioned. Among these, (I-4) is particularly preferable from the viewpoint of the effect of the present invention.

The ferric iron complex salt of an organic acid according to the present invention is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt such as triethanolamine salt. The potassium salt, sodium salt and ammonium salt are preferably used. At least one kind of these ferric complex salts may be used, but two or more kinds may be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the silver amount of the light-sensitive material to be processed and the silver halide composition. For example, it can be used in an amount of 0.01 mol or more per bleach-fixing solution, preferably from 0.05 to Used at 1.9 mol.
In the replenisher, it is desirable to use the replenisher concentrated to the full solubility in order to reduce the concentration.

In carrying out the method of the present invention, silver may be recovered from the fixing solution or the bleach-fixing solution by a known method. For example, electrolysis method (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,331,220), ion-exchange method (described in Japanese Patent Application Laid-Open No. 51-17114) And the metal substitution method (described in British Patent 1,353,805) can be effectively used.

It is particularly preferable to recover silver in-line from the tank liquid, because the suitability for rapid processing is further improved. However, silver may be recovered from the overflow waste liquid and reused.

The fixing solution and the bleach-fixing solution according to the present invention exhibit the effects of the present invention more favorably when the replenishing amount is 800 ml or less per 1 m ^{2 of the} light-sensitive material. Especially 20ml ~ ⁶ per m2 of photosensitive material
Significant effects are obtained at 50 ml, especially at 30 ml to 400 ml.

The processing time of the fixing solution according to the present invention needs to be 3 minutes and 10 seconds or less in total, and the total time is preferably 20 seconds to
The effect of the object of the present invention is satisfactorily achieved when it is in the range of 3 minutes and 20 seconds or less, particularly preferably 40 seconds to 3 minutes, and particularly preferably 60 seconds to 2 minutes 10 seconds. Further, the processing time of the bleach-fixing solution is preferably 3 minutes and 45 seconds or less, more preferably 20 seconds to 3 minutes 20 seconds, and particularly preferably 40 seconds to 3 minutes. Good effect.

In the processing method of the present invention, it is preferable to apply forced agitation to the bleaching solution, the fixing solution and the bleach-fixing solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability.

Here, the forced liquid stirring means that the liquid is not normally diffused and moved, but is forcibly stirred by adding a stirring means.

 Forcible stirring means include the following methods.

1. High-pressure spray treatment method or spray stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method The high-pressure spray treatment method is a spray nozzle that applies a discharge output pressure of 0.1 kg / cm ² or more. Refers to a method in which the processing liquid is directly sprayed onto the photosensitive material in the processing liquid, and the spraying and stirring method is a process in which the processing liquid is directly applied in the processing liquid by applying a pressure of 0.1 kg / cm ² or more from the nozzle. A method of spraying on a photosensitive material to perform processing, and a pressure pump or a liquid feed pump is generally used as a pressure source. Pressure pumps include plunger pumps, gear pumps, magnet pumps,
There is a cascade pump, for example, Maruyama Seisakusho 15-LP
M type, 10-BFM type, 20-BFM type, 25-BFM type and the like are known as examples.

Further, as a liquid sending pump, for example, MD-8 manufactured by Iwaki Co., Ltd.
Type, MD-10 type, MD-20R type, MD-30R type, MD-55R type, MDK
-25 type and MDK-32 type.

On the other hand, nozzles and spray nozzles have straight-line type, fan type,
There are a circular type, a full type, a ring type, etc., which have a strong impact force and are more effective as the microscopic vibration is applied to the processed photosensitive material. The impact force of the spray is mainly determined by the flow rate (/ min) and the sprue pressure (kg / cm ² ). Therefore, there is a need for a pressurizing device capable of adjusting the pressure in proportion to the number of spray nozzles so as to sufficiently exert the effect. The most preferable pressure is
In 0.3~10kg / cm ^2, the effect can not be obtained with less than this,
If it is too large, the photosensitive material may be scratched or damaged.

Next, with the air bubbling method, a sparger is installed at the bottom of the lower transfer roller of the processing liquid tank, air or an inert gas is sent to the sparger, and the photosensitive material is vibrated by the bubbles discharged from its mouth. In addition, the processing liquid is effectively contacted with the front surface, the back surface, and the side surface of the photosensitive material.

As the material of the sparger, hard polyvinyl chloride, stainless steel coated with polyethylene, corrosion resistant ones such as sintered metal are suitable, and the perforation diameter is such that the discharged bubbles are perforated to be 2 mm to 30 mm. Even better results can be obtained by adjusting the distance from 5 mm to 15 mm. Examples of the method of sending air include an air compressor, for example, a Bebicon (0.4KW, BU7TL) manufactured by Hitachi, Ltd., and an air pump, for example, an air pump (Ap220 type) manufactured by Iwaki.
The air volume is 2 / m for each rack of the automatic processor.
In is required 30 / min, and 5 / min to 20 / min gives more preferable results. The amount of air or inert gas must be adjusted according to the size of the processing solution tank and the amount of photosensitive material, but the air or inert gas must be adjusted so that the vibration width of the photosensitive material due to air bubbles is from 0.2 mm to 20 mm. It is preferred to send the quantity.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the space of the bottom or the side wall in the processing liquid tank of the automatic developing machine and the photosensitive material is irradiated with ultrasonic waves to increase the development promotion efficiency. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type) or a magnetostrictive barium titanate vibrator (holder type) manufactured by Ultrasonic Industrial Co., Ltd. is used.

The oscillator frequency of the ultrasonic oscillator is 5-1000KHz
Of these, those having a frequency of 10 to 50 KHz are particularly preferred in view of the effects of the present invention and damage to the equipment of the automatic developing machine. As the method of irradiating the photosensitive material with the ultrasonic wave, the photosensitive material may be irradiated directly or indirectly by providing a reflection plate. However, since the ultrasonic wave is attenuated in proportion to the irradiation distance, the direct irradiation may be performed. It is more preferable to do so. The irradiation time is preferably at least one second. In the case of partial irradiation, any of the initial stage, intermediate stage, and late stage of the treatment process may be performed.

Further, the vibration processing method is a method in which vibration is applied to the photosensitive material between the upper roller and the lower roller in the processing tank of the automatic developing machine to effectively carry out the immersion processing. As the vibrator of the vibration source, for example, V-2B or V-4B type manufactured by Shindo Electric Co., Ltd. is generally used. The vibrator is installed in such a manner that the vibrator is fixed on the upper part of the immersion processing tank of the automatic developing machine, and the vibrator is applied from the back side of the photosensitive material. The frequency of the vibrator is preferably 100 to 10,000 times / min. The most preferred range is 500-6000 cycles / min. The amplitude of the light-sensitive material to be processed is 0.2 mm to 30 mm, preferably 1 mm to 20 mm. If it is lower than this, there is no effect, and if it is too large, the photosensitive material may be damaged. The number of oscillators varies depending on the size of the automatic developing machine. However, when the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing one or more at least one processing tank in each processing tank.

The color developer according to the present invention may contain an alkali agent usually used in the developer, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfite. You may.

Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylfarmamide, dimethylsulfoxide and the like can be appropriately contained.

Further, the pH of the developer according to the present invention is preferably 7 or more, more preferably about 9 to 13.

In the color developer used in the present invention, hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,3
-Dimethyl ether or the like may be contained.

Further, various chelating agents can be used in combination as a sequestering agent in the color developer according to the present invention. For example, as the chelating agent, ethylenediaminetetraacetic acid, aminopolycarboxylic acid such as diethylenetriamidopentaacetic acid, organic phosphonic acid such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid)
Or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid Etc.

The replenishing amount of the stabilizing solution according to the present invention is 1 per unit area of the color photographic light-sensitive material for photography to be processed, which is brought in from the previous bath.
The concentration of the pre-bath component (bleach-fixing solution or fixing solution) in the stabilizing solution in the present invention is preferably 80 to 80 times, particularly preferably 2 to 60 times. More preferably 1/500 or less in the tank, particularly preferably 1/100
It is 0 or less. Furthermore, from the perspective of low pollution and storage stability of liquid, 1/5
00 to 1/10000 is preferable, more preferably 1/2000 to 1/50
Configure the stabilization treatment tank to be 000.

The stabilizing tank is preferably composed of a plurality of tanks, and the plurality of tanks is preferably 2 or more and 6 or less.

This is a case where the number of stabilizing treatment tanks is two or more and six or less, and it is preferable to use a counter current method (a method of supplying to the rear bath and causing an overflow from the front bath). Particularly preferably, two or three tanks are used, and more preferably two tanks.

The carry-in amount varies depending on the type of photosensitive material, the transport speed of the automatic developing machine, the transport method, the squeeze method of the surface of the photosensitive material, etc., but usually a color film (roll film for shooting)
For normal amount carried is ^{50ml / m 2 ~150ml / m 2} ,
Is remarkable replenishing amount than the effect of the present invention for this amount carried is in the range of ^{50ml / m 2 ~4.0 / m 2} , the effect is particularly noticeable replenishing amount is in the range of 200ml / m ² ~1500ml / m ² .

The treatment temperature of the treatment with the stabilizing solution is preferably 15 to 60 ° C,
The temperature is more preferably in the range of 20 to 45 ° C.

The silver halide emulsion that can be used in the present invention is preferably a tabular silver halide emulsion, but in addition to this, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, Any silver halide such as silver iodobromide and silver chloroiodobromide may be used. As the protective colloid of silver halide, various kinds of synthetic colloids can be used in addition to natural substances such as gelatin. For silver halide emulsions, coupler stabilizers, sensitizers, hardeners, sensitizing dyes,
Conventional photographic additives such as surfactants may be included.

As the photosensitive material used in the present invention, any of color negative film, color paper, color reversal film, color reversal paper and the like can be used.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

In Example 1 all examples, the amount of silver halide photographic light-sensitive material is particularly shows the g per 1 m ² unless otherwise noted.
Further, silver halide and colloidal silver are shown in terms of silver.

On a triacetylcellulose film support, each layer having the following composition was sequentially formed from the support side to prepare Sample 1 of a multilayer color photographic light-sensitive material.

Sample 1 (Comparison) 1st layer: Antihalation layer (HG-1) Black colloidal silver ...... 0.22 UV absorber (UV-1) ...... 0.20 Colored coupler (CO-1) ...... 0.06 Colored coupler (CM-2) ) …… 0.05 High boiling point solvent (oil-1) …… 0.19 Gelatin …… 1.3 Second layer: Intermediate layer (IL-1) UV absorber (UV-1) …… 0.01 High boiling point solvent (oil-1) …… 0.01 Gelatin ...... 1.4 Third layer: Low sensitivity red sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) …… 1.1 Silver iodobromide emulsion (Em-2) …… 0.5 Sensitizing dye (S -1) ...... 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) …… 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) …… 0.5 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-4 ') ... 1.1 Cyan coupler (C-2') ... 0.07 Colored cyan coupler (Ce-1) ... 0.05 DIR compound (D-1) ) …… 0.002 High boiling point solvent (oil-1) …… 0.5 Gelatin …… 1.3 4th layer: High sensitivity red sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) …… 2.0 Sensitizing dye (S -1) ...... 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) …… 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) …… 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1 ') ... 0.15 Cyan coupler (C-2') ... 0.02 Cyan coupler (C-3 ') ... 1.15 Colored cyan coupler (CC- 1) ...... 0.02 DIR compound (D-2) ...... 0.05 High boiling point solvent (oil-1) ...... 0.5 Gelatin ...... 1.4 Fifth layer: Intermediate layer (IL-2) Gelatin ・ ・ ・ 0.4 Sixth layer: Low Sensitive green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) …… 1.1 Sensitizing dye (S-4) …… 5.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) ) …… 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) …… 0.5 Colored magenta coupler (CM-1) …… 0.05 DIR compound (D-3) …… 0.015 DIR compound (D-4) …… 0.020 High boiling solvent (oil-2) …… 0.5 Gelatin ...... 1.0 Seventh layer: Intermediate layer (IL-3) Gelatin ・ ・ ・ 0.9 High boiling point solvent (oil-1) ・ ・ ・ 0.2 Eighth layer: High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) …… 1.2 Sensitizing dye (S-6) …… 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) …… 2.5 × 10 ^-4 (mol / silver 1 mol) Molar) Sensitizing dye (S-8) ...... 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-2) ...... 0.06 Magenta coupler (M-3) ...... 0.18 Colored magenta coupler (CM- 2) …… 0.05 DIR compound (D-3) …… 0.01 High boiling point solvent (oil-3) …… 0.5 Gelatin …… 1.0 9th layer: Yellow filter layer (YC) Yellow colloid De silver …… 0.1 Color stain inhibitor (SC-1) …… 0.1 High boiling point solvent (oil-3) …… 0.1 Gelatin …… 0.8 10th layer: Low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) ...... 0.25 Silver iodobromide emulsion (Em-2) ...... 0.25 Sensitizing dye (S-10) …… 7.0 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) …… 0.6 Yellow coupler (Y-2) …… 0.12 DIR compound (D-2) …… 0.015 High boiling point solvent (oil-3) …… 0.14 Gelatin …… 1.1 11th layer: High-sensitivity blue-sensitive emulsion layer (BH ) Silver iodobromide emulsion (Em-4) ...... 0.53 Silver iodobromide emulsion (Em-1) ...... 0.20 Sensitizing dye (S-9) ...... 1.0 × 10 ^-4 (mol / silver 1 mol) increase Sensitizing dye (S-10) …… 3.0 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) …… 0.36 Yellow coupler (Y-2) …… 0.10 High boiling point solvent (oil-3) …… … 0.07 Gelatin …… 1.1 12th layer: Protective layer (pro-1) Fine grain silver iodobromide emulsion ...... 0.4 (Average particle size 0.08μm, AgI 2mol%) UV absorber (UV-1) ...... 0.10 UV absorber (UV-2) ...... 0.05 High boiling point solvent (oil-1) …… 0.15 High boiling point solvent (oil-4) …… 0.1 Formalin scavenger (HS-1) …… 0.5 Formalin scavenger (HS-2) …… 0.2 Gelatin …… 0.9 13th layer: Second protective layer (Pro-2) Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) …… 0.10 Cyan dye (AIC-1) …… 0.01 Magenta dye (AIM -1) ...... 0.02 Sliding agent (WAX-1) ...... 0.04 Gelatin ...... 0.9 In addition to the above composition in each layer, coating aid Su-2, dispersion aid Su-3, hardener H -1 and H-2, preservative DI-
1. Stabilizer Stab-1 and antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.46 μm, average silver iodide content 7.5% Monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.32 μm, average silver iodide content 2.0% Monodisperse Emulsion of uniform composition Em-3 Average grain size 0.78 μm, average silver iodide content 6.0% Monodisperse surface low silver iodide-containing emulsion Em-4 Average grain size 0.95 μm, average silver iodide content 8.0% Monodispersed surface silver iodide-containing emulsions Em-1, Em-3 and Em-4 are disclosed in JP-A-60-138538.
It is a silver iodobromide emulsion having a multilayer structure adjusted with reference to each publication of JP-A No. 61-245151 and mainly comprising an octahedron.

Further, in each of Em-1 to Em-4, the average value of particle diameter / particle thickness is 1.0, and the width of particle distribution is 14, 1 respectively.
0, 12 and 12%.

The thus-prepared sample was exposed to wedges using white light, and then subjected to the following development processing.

[Experimental treatment]

 Processing time Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38 ° C Bleaching (1 tank) 45 seconds 35 ° C Fixed (2 tanks) 1 minute 30 seconds 35 ° C (2 tanks cascade) Stabilization 1 minute 35 ℃ (3-tank cascade) Drying 45 seconds (40 ℃ to 80 ℃) The composition of the treatment liquid used is as follows.

(Color developing solution)

Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.0 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl ) Aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1 and adjust to pH10.06 with potassium hydroxide or 50% sulfuric acid.

(Color development replenisher)

Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 6.0 g Water Potassium oxide 2 g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

(Bleach)

1,3 Diaminopropane-N, N, N ', N'-ferric acid ferric ammonium salt 0.23 mol Ethylenediamine-N, N, N', N'-ferric acid ferric ammonium salt 0.25 mol Hydroxyethylethylenediamine Acetic acid 10 g Ammonium bromide 150 g Glacial acetic acid 30 ml Ammonium nitrate 30 g Add water to make 1 and adjust to pH 5.3 with ammonia water or glacial acetic acid.

[Bleach replenisher]

1,3 Diaminopropane-N, N, N ', N'-tetraacetic acid ferric ammonium salt 0.33 mol Ethylenediamine-N, N, N', N'-ferric acid ferric ammonium salt 0.36 mol Hydroxyethylethylenediamine ternary Acetic acid 2 g Ammonium bromide 178 g Glacial acetic acid 21 ml Ammonium nitrate 35 g Add water to 1 and adjust to pH 5.0 with aqueous ammonia or glacial acetic acid.

(Fixing solution)

Ammonium thiosulfate 250 g Ammonium sulfite 20 g Ethylenediaminetetraacetic acid 0.5 g Exemplified compound A (described in Table 1) Add water to make 1 and use acetic acid and aqueous ammonia to obtain ph
Adjust to 7.0.

[Fixing replenisher]

 Ammonium thiosulfate 250 g Ammonium sulfite 20 g Ethylenediaminetetraacetic acid 0.5 g Exemplified compound A (described in Table 1) Add water to adjust to pH 7.0.

[Stabilizing solution and stabilizing replenisher]

Formaldehyde (37% solution) 2ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.05g Ermagen 810 1ml Formaldehyde bisulfite adduct Sodium 2g Add water to make 1 and add ammonia water and 50% sulfuric acid.
Adjusted to ph7.0.

However, each replenishing amount was 650 ml of color developing replenishing liquid, 140 ml of bleaching replenishing liquid, 815 ml of fixing replenishing liquid and 1000 ml of stabilizing replenishing liquid per 1 m ² of light-sensitive material, and running test was conducted.

The running treatment was carried out for 10 days until the amount of the fixing replenisher solution which was twice the volume of the fixing tank tank was replenished.

After the running was completed, the fixing processing time was changed in units of 10 seconds and the fixing was carried out for up to 6 minutes until the derailment was completed (when the amount of residual silver in the Dmax portion and Dmin portion was 0.5 mg / 10 in fluorescent X-ray silver amount analysis).
Table 1 shows the time when it became 0 cm ² or less). Further, after the running was completed, the degree of crystal precipitation on the inner wall of the fixing tank of the tank was observed and evaluated in three grades of good ◯, slightly good Δ, and bad x.

Example 2 A sample prepared in the same manner as in Example 1 was wedge-exposed with white light, and then subjected to the following development processing.

[Experimental treatment]

 Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38 ° C Bleach fixing (2 tanks) 2 minutes 30 seconds 35 ° C (2 tank cascade) Stabilization 1 minute 35 ° C (3 tank cascade) Drying 45 seconds (40 ° C to 80 ° C) The composition of the treatment liquid used is as follows.

(Color developing solution)

Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.0 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl ) Aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1 and adjust to pH10.06 with potassium hydroxide or 50% sulfuric acid.

[Color development replenisher] potassium carbonate 40 g sodium hydrogen carbonate 3 g potassium sulfite 7 g sodium bromide 0.5 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.0 g Potassium hydroxide 2 g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

[Bleach-fixing solution and bleach-fixing replenisher]

Ferric ammonium salt of 1,3-propylenediaminetetraacetic acid
0.25 mol Hydroxyethyl ethylenediamine triacetic acid 10 g Glacial acetic acid 30 ml Ammonium thiosulfate 200 g Ammonium sulfite 20 g Exemplified compound (A) (described in Table 1) Add water to 1 and use acetic acid and aqueous ammonia.
Adjust to ph7.0.

[Stabilizing solution and stabilizing replenisher]

Formaldehyde (37% solution) 2ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.05g Ermagen 810 1ml Formaldehyde bisulfite adduct Sodium 2g Add water to make 1 and add ammonia water and 50% sulfuric acid.
Adjusted to ph7.0.

However, each replenishing amount was 650 ml of color developing replenisher, 1000 ml of bleach-fixing replenisher, and 775 ml of stabilizing replenisher for a running test per 1 m ² of the light-sensitive material.

The running process was carried out for 10 days until the amount of the bleach-fix replenisher solution which was twice the capacity of the bleach-fix tank was replenished.

After the running is completed, the same evaluation as in Example 1 is performed,
The results are shown in Table 2.

Continuation of front page (56) Reference JP-A-61-250647 (JP, A)

Claims (2)

(57) [Claims] 1. A composition comprising the following components and 5 to 8
A processing solution for a silver halide color photographic light-sensitive material, which has a pH value. Thiosulfate as a fixing agent Compound represented by the following general formula (A): General formula (A) [In the formula, each of R ₁ , R ₂ , R ₃ and R ₄ represents a hydrogen atom or an alkyl group which may have a substituent. R ₁ and R ₃ may be linked to form a heterocycle. ] 2. A processing method for a silver halide color photographic light-sensitive material, which comprises using the processing liquid according to claim 1.