JP3248009B2 - Processing method of silver halide photographic material - Google Patents

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 which is processed with a low replenishing amount of a processing solution.

[0002]

BACKGROUND OF THE INVENTION When a photographic light-sensitive material is processed using an automatic processor, it is known that each processing solution used is deteriorated in use. In the case of the developing solution, the deterioration of the processing solution is caused by the components contained in the photosensitive layer of the photosensitive material reacting with the components of the developing agent and being consumed (processing fatigue).
And degradation (air oxidation fatigue) caused by the oxidation of constituent chemicals by oxygen or by a decrease in pH due to absorption of carbon dioxide in the air.

[0003] In particular, oxidation fatigue due to air oxidation, and halogen ions which are constituents of the photosensitive material are eluted in a developer, and among these eluted halogen ions, iodide ions are replaced by the eluted bromide ions of silver bromide. Therefore, it is known that only bromine ions are mainly accumulated in the developing solution and act as a suppressing component to affect photographic characteristics.

In order to perform stable processing of a silver halide photographic light-sensitive material, a considerable amount of replenisher is supplied to supply useful substances and dilute unnecessary substances in order to compensate for the deterioration in development and fixing efficiency due to these deteriorations. And the photographic performance is maintained.

As a replenishing method, Japanese Patent Application Laid-Open No. 55-126242
No. 55-126243, No. 57-195245, No. 57-195246,
No. 59-195247, No. 60-104946, No. 62-238559, and JP-A-1-140156, the development replenisher is continuously or intermittently replenished according to the development processing amount to reduce fatigue. Means for recovery are disclosed.

[0006] Further, these photographic processing waste liquids are conventionally discharged as they are into sewers, causing water pollution of rivers, lakes, marshes and seawater.

In recent years, it has been desired to reduce the amount of waste photographic processing liquid in order to reduce the environmental pollution load and simplify the processing operation. As a means to reduce the amount of waste photographic processing liquid,
There is a method of reducing the replenisher or regenerating and reusing it.

However, during processing in an automatic developing machine, if the amount of the developing solution is reduced, there arises a problem that development unevenness occurs.

[0009] In order to solve this problem, the addition of a surfactant or the like has been studied. However, a sufficient effect has not been obtained, and a sufficient result has not yet been obtained.

[0010]

The object of the present invention is to provide a developer replenishing amount of 300 ml /
An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material that does not cause development unevenness when processing is performed in a processing step of m ² or less.

[0011]

The above object of the present invention DETAILED DESCRIPTION OF THE INVENTION, a one-side photosensitive material having a silver halide emulsion layer on one side of the support, the emulsion side, the average particle size is not selected chemical ripening 0.8~2.0μm of containing silver halide grains, and a developer replenishing amount of the silver halide photographic light-sensitive material is 300 ml / m ² or less to 0.2~100mg / m ² containing a fluorine-containing surfactant to a hydrophilic colloid layer of the emulsion side This is achieved by a processing method for a silver halide photographic light-sensitive material which is processed in the following processing step.

Hereinafter, the present invention will be described in detail.

The unchemically ripened silver halide grains according to the present invention are grains which have been subjected to only physical ripening for grain formation.
Generally, it refers to silver halide grains in which the second ripening (chemical ripening) after desalting excess salts is omitted. The average particle size of the silver halide grains in the present invention 0.8~2.0μm der
The addition amount is preferably 0.1 to 1 g / m ^{2 in} terms of silver amount.

Next, the fluorine-containing surfactant used in the present invention will be described.

Examples of the above fluorine-containing surfactant include compounds described in JP-B-56-44411, pp. 58-61, and JP-A-49-4.
6733, 51-32322, 56-19042, 57-11341,
No. 55-7762, No. 56-34856, No. 54-111330, No. 61-47948
No., JP-B-52-25087, JP-B-47-9303, U.S. Patent 3,775,1
No. 26, 3,589,906, RD-16630 and the like. Representative examples of these are given below.

[0016]

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[0017]

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The fluorine-containing surfactant used in the present invention is preferably contained in the hydrophilic colloid layer on the emulsion surface side in an amount of 0.2 to 1%.
200 mg / m ² is contained. Further, the above-mentioned fluorinated surfactant may be contained in the backing layer as required.

The silver halide composition of the silver halide emulsion subjected to chemical ripening used in the present invention may be, for example, silver bromide,
Any silver halide such as silver iodobromide and silver chloroiodobromide may be used. Preferred silver halide compositions include silver iodobromide emulsions containing 30 mol% or less of silver iodide.

The halogenated grains may be of any crystal type as long as they have the constitution of the present invention. For example, they may be single crystals such as cubic, octahedral, and tetrahedral, and may have various shapes. May be a multiple twin particle having

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention are described in, for example, "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Paul Montel (1967) or VLZelikman et al. “Makin
g And Coating Photographic Emulsion "by Focal Press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The average grain size of the silver halide grains subjected to chemical ripening is 0.1 to 0.6 μm, and may be a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a wide grain size distribution. Here, the monodisperse emulsion means a silver halide emulsion having a coefficient of variation of 0.20 or less with respect to the grain size defined in, for example, JP-A-60-162244.

Monodisperse emulsions include silver halide grains having an average grain size of more than 0.1 μm, wherein at least 95 wt% of the grains are within ± 40% of the average grain diameter. In addition, the average particle size is 0.25μm ~ 2μm, at least 9
Also included are silver halide emulsions in which 5 wt% or at least 95% of silver halide grains are in the range of an average grain size of ± 20%.

The average particle size referred to here is the diameter when spherical silver halide grains are used, or when the projected image is converted into a circular image having the same area for cubic or spherical particles other than spherical particles. When the diameters, each of which is ri and the number is ni, the average particle size is defined by the following equation:

Average particle size = Σniri / Σni The method for producing the above monodisperse emulsion is known, for example, J. Phot. Sci, 1
2.242-251, (1963), JP-A-48-36890, JP-A-52-16364
No. 55-142329, No. 58-49938, UK Patent 1,413,748
And U.S. Pat. Nos. 3,574,628 and 3,655,394.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is prepared by, for example, using a seed crystal as a method for obtaining the above monodisperse emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. An emulsion that has been grown may be used. The silver halide composition of the unchemically ripened silver halide emulsion used in the present invention is, for example, silver bromide, silver iodobromide,
Any silver halide such as silver chloroiodobromide may be used. Preferred silver halide compositions include silver iodobromide emulsions containing 30 mol% or less of silver iodide.

The average size of the silver halide grains of the non-chemical ripening is 0.8Myuemu～2.0Myuemu, or a broad polydisperse emulsion narrow monodisperse emulsion or particle size distribution particle size distribution.

The silver halide grains may be of any crystal type as long as they have the constitution of the present invention, and may be, for example, single crystals such as cubic, octahedral, and tetrahedral, and various shapes. May be a multiple twin particle having

Unchemically ripened silver halide grains can be prepared by the same method as the above-mentioned chemically ripened grains according to the present invention. The crystal structures of the chemically ripened silver halide grains and the unchemically ripened silver halide grains of the emulsion according to the present invention may have different silver halide compositions on the inside and outside, and form a layered structure. May be. A particularly preferred embodiment of the emulsion is a silver halide grain having substantially two distinct layered structures (core / shell structure) comprising a high iodine core portion and a low iodine shell layer.

The high iodine core portion is silver iodide, and the silver iodide content is 20 to 40 mol%, preferably 20 to 30 mol%.

The silver halide composition other than silver iodide in the core may be either silver bromide or silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The outermost shell layer is a silver halide containing 5 mol% or less of silver iodide, preferably 2 mol%.
The layer contains the following silver iodide. The silver halide other than silver iodide in the outermost layer may be any of silver chloride, silver bromide and silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The method for producing the above-mentioned core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
Nos. 250, 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B No. 35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, the aforementioned (RD) No. 17643, (RD) No. 18716 and (RD) N
o. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are shown in the following table.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B 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 Brightener 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 right 1005-6 XI Plasticizer 27 XII 650 right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the present invention Examples of the support used for the silver photographic light-sensitive material include those described in the above RD,
A suitable support may be a plastic film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The silver halide photographic light-sensitive material according to the present invention comprises a hydrophilic colloid such as a silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an ultraviolet absorbing layer, an antistatic layer, an antihalation layer and a backing layer. It may be composed of layers.

In these hydrophilic colloid layers, various synthetic high molecular compounds such as gelatin can be used as a binder or protective colloid.

As gelatin, lime-processed gelatin, acid-processed gelatin or gelatin derivative may be used. Examples of synthetic polymers other than gelatin include cellulose derivatives such as hydroxyethyl cellulose,
A homo- or copolymer such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polyacrylamide and the like can be used. The photographic processing of the light-sensitive material of the present invention can be performed, for example, by the methods described in RD-17643, XX to XXI, pp. 29 to 30, or 308119.
XX to XXI, pages 1011 to 1012, may be treated with a treatment solution. This processing may be either black-and-white photographic processing for forming a silver image or color photographic processing for forming a dye image. The processing temperature is usually in the range of 18 ° C to 50 ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

[0044] Note that the developer replenishing amount used in process step of the present invention is 300 ml / m ² or less.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0046]

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

Example 1 (Preparation of unchemically ripened emulsions C and D)
A silver iodobromide emulsion (emulsion C) having an average grain size of 1.0 μm (emulsion C) and 1.5 μm (emulsion D) was prepared using a 3 μm silver iodobromide emulsion (silver iodide content: 2 mol%) by the ammonia method. (3 mol%) was grown. The coefficient of variation (σ / r) was in the range of 0.15 to 0.20.

[Preparation of Emulsions A and B] A having an average particle size of 0.1 μm
Using a gBrI (AgI content 2 mol%) seed emulsion, an aqueous solution of ammoniacal AgNO _{3 and an} aqueous solution of potassium bromide were added by a double jet method, and AgBr having an average particle size of 0.25 μm was used.
A cubic monodisperse emulsion of I (average AgI content 0.4 mol%) was grown. The coefficient of variation (σ / r) was 0.17.

After this emulsion was divided, one was dissolved immediately before chemical ripening and when the temperature became constant, the following dye (1) was added to obtain emulsion (A), and the other was the following dye (2) Was added to obtain an emulsion (B). The dye amounts were each 90 mg / mol silver halide. Next, ammonium thiocyanate, chloroauric acid and hypo were added and subjected to chemical sensitization,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

[0050]

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(Backing layer) Backing lower layer coating solution Gelatin 400 g Sodium i-amine-n-decylsulfosuccinate
0.4g Antihalation dye (1)
10g Diethylene glycol 5.0g Glyoxal 2.0g Dye emulsified dispersion (as shown below) 33g

[0052]

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Finish to 7 liters with water.

[Preparation method of dye emulsion dispersion] The following dyes
10Kg of tricresyl phosphate 28l and ethyl acetate 85l
At 55 ° C. This is called an oil-based solution. On the other hand, 270 l of a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) was prepared. This is called an aqueous solution. Next, the oil-based solution and the aqueous-based solution were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water.

[0055]

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Backing upper layer coating solution Gelatin 400 g i-Amyl-n-decylsulfosuccinate sodium salt 10 g Antihalation dye (1) 10 g Polythymer methacrylate 12 g SAM-1 3.0 g SAM-2 0.75 g Glyoxal 13.6 g Fluorine-containing interface Activator Amount shown in Table 1

[0057]

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Finish to 7 liters with water.

Red-Sensitive Silver Halide Emulsion Layer Coating Solution The above emulsions A and B and the unchemically ripened emulsion were added so that the silver amounts shown in Table 1 were obtained.
The following was added to prepare a red-sensitive silver halide emulsion coating solution.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-nitromethane 10mg

[0061]

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Emulsion side protective layer coating solution A solution having the following composition was added in an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium i-amyl-n-decylsulfosuccinate 1.4 g Polymethyl methacrylate (particle size: 4 μm) 0.15 g Silicon dioxide particles (area average particle size: 1.2 μm) 0.5 g Ludox AM (colloidal silica (Dupont))
30g 2-4-Dichloro-6-hydroxy-1,3,5-triazine sodium (2% aqueous solution) 10ml Formalin (35%) 2ml Glyoxal (40%) 5ml Topside 300 (manufactured by Permchem Asia Ltd.) 45mg SAM- 1 1.0g SAM-2 0.4g Fluorinated surfactant Amount shown in Table 1

[0064]

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Preparation of Support A polyethylene terephthalate support having a thickness of 180 μm was biaxially stretched and heat-set on both sides, and then subjected to a corona discharge treatment. An undercoat latex (Compound of Synthesis Example 1) described in Example 1 of JP-A-59-18945 was further applied thereon.

Then, on one surface of the upper layer, the following compound described in JP-A-4-80744 by the same applicant as the present invention was applied as an antistatic layer.

Water-soluble conductive polymer (Ex. P4) 0.6 g / m ² Hydrophobic polymer (Ex. HP1) 0.5 g / m ² Curing agent (Ex. AH5) 2 × 10 ⁻³ mol / dm ² Application is 30 m / min. After application at a speed by a roll-fit coating pan and an air knife, activation treatment by corona discharge was performed again in the same manner as described above to obtain a support.

Coating of Sample The above-mentioned support was coated with the above-mentioned silver halide emulsions A and B according to the present invention and a coating solution for an emulsion surface protective layer on the side on which the antistatic layer was not coated.

On the side where the antistatic layer was applied, the lower and upper backing layers described above were applied.

The amount of gelatin in the backing layer was 3.0 g in the lower layer.
/ m ² and the upper layer was simultaneously coated by a slide hopper method at a speed of 90 m / min so that the upper layer became 1.2 g / m ² . The emulsion layer was coated so that the amount of gelatin was 2.4 g / m ² , the protective layer was 1.2 g / m ² , and the amount of silver was as shown in Table 1, to obtain a sample.

(Adjustment of Processing Solution) The compositions of the developing solution and the fixing solution used in the present invention are shown below.

Developer Formulation Part-A (for 15 liter finishing) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Diethylenetriaminepentaacetic acid 45 g Sodium bicarbonate 150 g 5-Methylbenzenetriazole 2.0 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 390g Add water to make 5000ml.

Part-B (for finishing 15 L) Glacial acetic acid 220 g Triethylene glycol 200 g 1-phenyl-3-pyrazolidone 27 g 5-nitroindazole 0.45 g n-acetyl-D, L-penicillamine 0.15 g Fixer prescription Part-A ( Ammonium thiosulfate (70wt / vol%) 4000g Sodium sulfite 175g Sodium acetate / trihydrate 400g Sodium citrate 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (for 19l finishing) Aneniminium sulfate 65g Sulfuric acid (50wt %) 105g Starter formula (for 1 liter finishing) (2 liters per liter of developer)
Add 0 ml and use. ) Glacial acetic acid 138g Potassium bromide 325g 5-Methylbenzotriazole 1.5g Make up to 1 liter with pure water.

The obtained sample was evaluated by the following evaluation method.

<Evaluation Method of Sample> A sample was exposed to tungsten light at a density of 1.5 ± 0.2 so as to be uniform, and the above-mentioned developing solution and fixing solution were mixed in an SRX-501 (manufactured by Konica) for 45 seconds. Processed. The replenishment amount per unit m ^{2 of the} film was as shown in Table 1 for development, and the fixing solution was 400 ml / m ² .

The unevenness of development of the obtained sample was visually evaluated.

(Evaluation rank) 5: Very good 4: Good 3: No problem in practical use 2: Poor 1: Very poor The results are shown in Table 1.

[0078]

[Table 1]

As is evident from Table 1, the present invention is superior to the comparative example in the development unevenness at a low replenishing amount of the developing solution.

Example 2 A sample was prepared in the same manner as in Example 1. However, samples were prepared and evaluated in the same manner as in Example 1 except that the chemically ripened silver halide grains had a particle size of 0.3 μm and the spectral sensitizing dye was exemplified as 2 (emulsion E). Summarized.

[0081]

[Table 2]

As can be seen from Table 2, according to the present invention, a silver halide photographic light-sensitive material having no development unevenness can be obtained in the same manner as in Example 1 even if the grain size of the chemically ripened emulsion is increased and the spectral sensitizing dye is changed. Obtained.

[0083]

According to the method for processing a silver halide photographic light-sensitive material of the present invention, when processing is performed in a processing step in which the replenishing amount of a developing solution is 300 ml / m ² or less, an excellent image without developing unevenness can be obtained. Can be.

Claims (1)

(57) [Claims] 1. A on one side of the support a single-sided photosensitive material having a silver halide emulsion layer, the emulsion side, the average particle diameter 0.
Contains unchemically aged silver halide grains of 8 to 2.0 μm ,
And that the silver halide photographic material 0.2~100mg / m ² containing a fluorine-containing surfactant to a hydrophilic colloid layer of the emulsion side volume developer replenishing is treated with 300 ml / m ² or less is process A method for processing a silver halide photographic material.