JPH08137059A - Processing method for silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide a method for processing a silver halide photographic material, by which the amounts of waste processing liquids are reduced through a reduction in the amount of replenishment and, even in the case of super fast processing, high sensitivity and low fog are ensured. CONSTITUTION: A silver halide photographic material containing at least one kind of compound represented by the formula is processed by means of an automatic developing machine in which a developing solution is replenished by not more than 20ml per quarto. In the formula, Z1 and Z2 each represent the nonmetallic atom required to complete a five- or six-membered heterocycle, and R1 and R2 each represent a substituted or unsubstituted alkyl group; R3 and R4 each represent hydrogen atom, an alkyl group or an aryl group, at least either of R3 or R4 being an alkyl group or an aryl group; m1 and m2 each represent 0 or 1, and X1 represents a counterion; (n) represents 0 or 1, and is 0 if an intramolecular salt is to be formed.

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 specifically, it is capable of obtaining high sensitivity and low fog even in rapid processing in which processing waste liquid is reduced by reducing replenishment. It relates to a method of processing a material.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of protecting the global environment, technological development for reducing and detoxifying industrial waste has been promoted. In the photographic industry as well, there is a strong demand for reduction of processing waste liquid (developing liquid, fixing liquid, etc.) both inside and outside the industry.

The photographic processing waste liquid is mainly a liquid discharged from a processing tank mounted in an automatic developing machine, and it can be said that the amount of the replenishing liquid replenished during the running processing process greatly influences the discharged liquid amount.

On the other hand, there is a great demand for rapid processing that shortens the development processing time and obtains information at an early stage, and is particularly remarkable for medical X-ray films that require urgent information.

However, in order to speed up the processing of the silver halide photographic light-sensitive material, the processing time of each of development, fixing, washing and drying is shortened, and in order to reduce the amount of processing waste liquid, for example, the amount of development replenisher is reduced. Causes the following problems.

(1) Contamination of residual color increases due to insufficient development, fixing and washing time, and high image quality cannot be obtained. (2) Fatigue of the developing solution (balance of the developing solution composition is lost) causes increase of fog, and as a result, high sensitivity cannot be obtained.

Many proposals have hitherto been made to improve the rapid processability of silver halide photographic light-sensitive materials. For example, the iodine content of silver halide grains may be lowered to improve developability and fixability. Various techniques have been disclosed, such as reducing the amount of binder to improve drying properties and processability.

Further, for the purpose of reducing the replenishment amount of the developing solution, for example, the swelling ratio of the hydrophilic colloid layer is made small.
No. 80 and No. 6-10263 are disclosed.

However, many of these prior arts are not sufficient when a large size object such as a quartet film for medical use is rapidly processed (Dry to Dry time is within 90 seconds). It deteriorated, and further improvement was desired.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to process a silver halide photographic light-sensitive material capable of reducing processing waste liquid by reducing the replenishment rate and obtaining high sensitivity and low fog even during running by ultra-rapid processing. Is to provide a method.

[0011]

The objects of the present invention have been achieved by the following.

A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [I] is processed in an automatic processor having a developer replenishing amount of 20 ml or less per sheet. A method of processing a silver halide photographic light-sensitive material, comprising:

[0013]

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Z ₁ and Z ₂ represent a non-metal atom necessary for completing a 5- or 6-membered heterocycle, and R ₁ and R ₂ represent a substituted or unsubstituted alkyl group. R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group, and at least one is an alkyl group or an aryl group. m ₁ and m ₂ represent 0 or 1, and X ₁ represents a counter ion. n represents 0 or 1, and n is 0 when forming an intramolecular salt.

The present invention will be described in detail below.

In the above general formula [I], the 5- or 6-membered heterocycle represented by Z ₁ and Z ₂ is, for example, thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole or benzoselena. Examples thereof include sol, naphthoselenazole, 2,3-dialkylindolenine, imidazole, benzimidazole, naphthimidazole and quinoline nuclei, and particularly preferable nuclei include benzoxazole nuclei. Each of these nuclei may have a usual substituent such as a halogen atom, an alkyl group, an aryl group, an alkoxy group, a cyano group or a trifluoromethyl group, which is used for a spectral sensitizing dye.

In the above general formula [I], R ₁ and R ₂ are each an alkyl group having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, etc.). These alkyl groups may have a substituent, and examples of the substituted alkyl group include an aralkyl group (eg, benzyl, phenethyl, etc.), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl, etc.), a carboxyalkyl group. (Eg 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl group (eg 2-methoxyethyl, 2- {2-methoxyethoxy})
Ethyl, etc.), sulfoalkyl groups (eg 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 4-sulfo-3-methylbutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-) Sulfopropyl, 3-sulfopropoxyethoxyethyl etc.), sulfatoalkyl group (eg 3-sulfatopropyl, 4-sulfatobutyl etc.), heterocyclic substituted alkyl group (eg 2- {pyrrolidin-2-one-yl}) Ethyl, tetrahydrofurfuryl, etc.), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group and the like.

Preferred as the alkyl group for R ₁ and R ₂ are those having 5 or less carbon atoms, and particularly preferred are those having 1 to 4 alkyl groups (eg, methyl, ethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl group) and the like.

The alkyl group represented by R ₃ and R ₄ has 1 to 1 carbon atoms.
There may be mentioned 18, preferably 1 to 7, particularly preferably 1 to 4 alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.). These alkyl groups may have a substituent, and examples of the substituted alkyl group are the same as those of R ₁ and R ₂ described above. Examples of the aryl group include phenyl and 2-naphthyl, and examples of the substituted aryl group include such as 3-chlorophenyl and 3-methylphenyl group.

Specific examples of the dye compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0021]

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[0022]

[Chemical 4]

[0023]

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[0024]

[Chemical 6]

[0025]

[Chemical 7]

The above-mentioned dyes are described in “Heterocyclic” by FM Hamer.
Compounds-Cyanine Dyes and Related Compounds '' John
Wiley & Sons. New York, London, 1964 or DMS Turmer, "Heterocyclic Compounds-Specia"
l topics in Heterocyclic Chemistry "John Wiley & So
ns company. New York, London, 1977, Chapter 18,
Section 14, pp. 482-515. , "Rodd's Chemistry of Carb
on Compounds ”2nd.Ed.vol.IV, part B, 1977. 15th
Chapter, pp. 369-422: 2nd.Ed.vol.IV, part B, 1985.
Chapter 15, pp. 267-296. Elsvier Science Publishing C
It can be synthesized by the method described in Ompany Inc, New York, etc.

The sensitizing dye of the above-mentioned general formula [I] according to the present invention may be dissolved in water or a hydrophilic organic solvent such as methanol or ethanol and added to the silver halide emulsion at the time of use. Alternatively, it may be added to the emulsion by a method in which it is solid-dispersed in an aqueous system in which an organic solvent or a surfactant does not exist.

The amount used is not uniform depending on the type of dye or silver halide grains, but it is usually 1 × 10 ^-4 mol to 4 × 10 ^-3 mol per mol of silver halide.
It is more preferably 2 × 10 ⁻⁴ mol to 2 × 10 ⁻³ mol.

The addition may be carried out at any time in the production process of the silver halide emulsion, but it is preferably from the physical ripening step to before the completion of chemical ripening.

In addition to the dye represented by the general formula [I] of the present invention, other known dyes may be used in combination.

The present invention is characterized in that after the silver halide photographic light-sensitive material thus spectrally sensitized is exposed, it is processed in an automatic developing machine in which the replenishing amount of the developing solution is cut into four and 20 ml or less per sheet. . The developer replenishment amount referred to here is the amount of developer replenishment for obtaining stable photographic characteristics by replenishing the amount consumed in the course of running processing in an automatic processor and adjusting the amount of developer and fatigue to a constant level. Refers to. The developing replenisher is generally a new one having the same composition as the developer used in running, but a replenisher having a different composition may be used.

In the present invention, from the viewpoint of eliminating pollution, the developing replenishing solution per quadrant film after exposure is 20 ml or less, more preferably 17 ml or less, and particularly preferably 14 ml. That is, when the amount is 20 ml or less, the developer discharged is eliminated and the object of the present invention can be achieved.

In the method of developing a silver halide photographic light-sensitive material according to the present invention, it is preferable to complete the steps from development to drying within 90 seconds by processing with an automatic processor. That is, the time from the time when the tip of the photosensitive material begins to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry time) is within 90 seconds. It is preferably within 30 seconds.

The fixing temperature and time are about 20 ° C to 50 ° C for 4 seconds to
20 seconds is preferable, and 30 seconds to 40 ° C. is more preferably 4 seconds to 15 seconds. The developing time is 5 to 45 seconds, preferably 8 to 30 seconds. The development temperature is preferably 25 ° C to 50 ° C, more preferably 30 ° C to 40 ° C. The drying time is usually 35 to 100 ° C, preferably 40
The automatic developing machine may be provided with a drying zone in which hot air of -80 ° C is blown or a heating means by far infrared rays is provided.

The automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the steps of developing, fixing and washing with water (Japanese Patent Laid-Open No. 3-30083).
264953) may be used. Furthermore, a device capable of preparing a developing solution and a fixing solution may be incorporated. The silver halide composition of the emulsion used in the silver halide photographic light-sensitive material of the present invention may be arbitrary, and any silver halide such as silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide, etc. may be used. May be. A preferable silver halide composition is a silver iodobromide emulsion containing 30 mol% or less of silver iodide.

The halogenated grain may be of any crystal type, for example, a single crystal such as a cube, octahedron, or tetrahedron, and is a polytwinned grain having various shapes. May be.

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
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

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

The silver halide grains may be fine grains having a grain size of 0.1 μm or less or large grains having a projected area of 10 μm, and may be a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a wide grain size distribution. . The monodisperse emulsion referred to herein means a silver halide emulsion having a grain size variation coefficient of 0.20 or less as defined in JP-A-60-162244.

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

The method for producing the above monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (grain diameter) / (grain thickness) of 3
The tabular grains described above may be used.

Preferred tabular grains have an aspect ratio of 5 or more and 50 or less, more preferably 5 or more and 20 or less. The equivalent spherical diameter of the particles is 0.2 μm to 30 μm,
More preferably, it is 0.4 μm to 10 μm. Further, the thickness of the particles is preferably 0.5 μm or less, more preferably 0.3 μm or less.

The advantages of such tabular grains are that they can improve spectral sensitization efficiency and image graininess and sharpness. For example, British Patent No. 2,112,157, US Patent Nos. 4,414,310, and 4,434,226. Is disclosed in
The emulsion can be prepared by the methods described in these publications. The crystal structure of silver halide may have a different silver halide composition from the inside to the outside, or may have a layered structure. A particularly preferred embodiment of the emulsion is silver halide grains having substantially two distinct layered structures (core / shell structure) consisting of a high iodine core portion and a low iodine shell layer.

The high-iodity 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 portion 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%.
It is a layer containing the following silver iodide. 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.

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

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. Preferred water washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using a polymer flocculant such as exemplified G-3 and G-8 described in JP-A-2-7037.

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

Examples of the compound used in such a process include Research Disclosure (RD) No. 17643.
(December 1978), (RD) No.18716 (November 1979) and (RD) No.3
Various compounds described in 08119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are listed below.

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 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 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 Examples of the support used in the silver halide photographic light-sensitive material of the present invention include those described in the above RD,
A suitable support is a polyethylene terephthalate film or the like, and the surface of the support 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 photographic processing of the light-sensitive material of the present invention is carried out, for example, by XX-XXI of RD-17643, pages 29-30 or XX-XX of 308119.
Treatment with a treatment solution as described in I, pages 1011-1010 may be performed. This process may be either a black and white photographic process for forming a silver image or a color photographic process for forming a dye image.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants,
A defoaming agent, a toning agent, a water softening agent, a dissolution aid, a viscosity imparting agent and the like may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution 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.

[0058]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 <Preparation of Support> (Dispersion of Dye Fine Particles) 5 g of the following dye (dried powder) was added to 500 ml of water and dispersed at 25 ° C. and 1500 rpm for 8 hours. The average particle size and distribution of the dispersion were measured with a laser analysis / scattering particle size distribution analyzer LA-700 (manufactured by Horiba Ltd.). The average particle size of the obtained particles was 0.2 μm, and the dispersity of the particles was within 20% in terms of coefficient of variation.

(Creation of crossover cut layer) A crossover cut layer was coated on both surfaces of a 175 μm-thick polyethylene terephthalate support colored in blue so that the coating amount per one surface would be the following composition. .

The following fine particle disperse dyes 0.030 g / m ² gelatin 0.4 g / m ² nonylphenol polyethylene glycol (polymerization degree = 10) 0.006 g / m ²

[0062]

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<Preparation of Emulsion> Preparation of Seed Emulsion A hexagonal tabular seed emulsion was prepared by the following method.

Solution A Ossein gelatin 60.2g Distilled water 20l Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% ethanol solution) 5.6ml KBr 26.8g 10% H ₂ SO ₄ 144ml Solution B 2.5N AgNO ₃ solution 3500 ml solution C KBr 1029 g KI 29.3 g Distilled water to 3500 ml Solution D 1.75 N KBr aqueous solution At the following silver potential control amount of 35 ° C, the mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289 is used. Solution A to solution B and solution C respectively
Nucleation was carried out by adding 64.1 ml by the double jet method over 2 minutes.

After stopping the addition of Solution B and Solution C, 60
It takes 6 minutes and the temperature of solution A is raised to 60 ° C, and solution B and solution C are mixed again by the simultaneous mixing method at 68.5 ml / min.
For 50 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mv using the solution D.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. The obtained emulsion was used as seed emulsion E.
m-0. In this emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.07 μm and an average diameter (circle diameter conversion) of It was found to be 0.5 μm by an electron microscope.

(Preparation of tabular emulsion) A tabular silver iodobromide emulsion Em-1 was prepared using the following four kinds of solutions.

Solution E Ossein gelatin 29.4 g Seed emulsion Em-0 1.6 mol equivalent Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.5 ml Distilled water to 1400 ml.

Solution F 3.5N AgNO ₃ aqueous solution 2360 ml Solution G KBr 974 g KI 11.0 g Distilled water to 2360 ml Solution H 1.75 N KBr aqueous solution At the following silver potential control amount 60 ° C. 58-582
The total amount of solution F and solution G was added to solution E by the simultaneous mixing method at a flow rate of 21.26 ml / min over 111 minutes using a mixing stirrer shown in No. 89 to grow.

During this period, the silver potential was controlled to +5 mv using the solution H. Then to remove excess salts,
Precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate, and an aqueous gelatin solution containing 92.2 g of ossein gelatin was added and dispersed by stirring.
The particles of Em-1 obtained here have an average projected area diameter of 0.
85μm, thickness 0.20μm, aspect ratio 4.3, silver iodide content
It was 0.8 mol% of tabular silver iodobromide.

Pure water was added to each of the obtained silver halide emulsions of Em-1 so that the volume per mol of silver was 300 ml, the temperature was raised to 55 ° C., and the spectral sensitizing dyes shown in Table 1 were added. . The spectral sensitizing dye was added as a 0.5% methanol solution.

After 10 minutes, ammonium thiocyanate was added in an amount of 2 × 10 ^-3 mol per mol of silver, and an appropriate amount of chloroauric acid and hypo were added to start chemical ripening. P at this time
H was 6.15 and the silver potential was 50 mv. Chemical aging completed
70 minutes before, 4.0 g was added per 1 mol of fine silver iodide grains,
Then, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to complete the chemical ripening. An emulsion additive described below was added to the obtained emulsion to prepare a preparation liquid. The pH of the photographic emulsion coating solution after preparation was 6.20 and the silver potential was 80 mv (35 ° C.) using sodium carbonate and potassium bromide.

Using this emulsion coating solution, a sample was prepared as follows. That is, the photographic emulsion layer is equivalent to metallic silver on one side.
The amount of gelatin was set to 1.7 g / m ² and the amount of gelatin was set to 2.0 g / m ² per side.

A protective layer solution was prepared using the additives described below. The protective layer is a support having the above-mentioned crossover cut layer at a speed of 80 m / min using two slide hopper type coaters together with the emulsion layer prepared as described above so that the amount of gelatin per side is 0.9 g / m ^2. Both sides were simultaneously coated on the body and dried for 2 minutes and 20 seconds to obtain a sample.

Additives used in the emulsion (light-sensitive silver halide coating solution) are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 10 mg t-Butyl-catechol 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.0 g Nitrophenyl-triphenylphosphonium chloride 5.0 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g 2-Sodium mercaptobenzimidazole-5-sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1- Phenyl-5-mercaptotetrazole 15mg Methacrylic acid-ethyl acrylate copolymer 18g

[0077]

[Chemical 9]

Next, the additives used in the protective layer liquid are shown. The weights given are given in quantities per liter of coating liquid.

Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethylmethacrylate, matting agent with area average particle size 3.5 μm 0.4 g Silicon dioxide particles Area average particle size 1.2 μm Matting agent 0.7 g Ludox AM (DuPont) (colloidal silica) 3.0 g Hardener 5.5 g C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 3.0 g Bis (vinylsulfonylmethyl) ether 2,4- Dichloro-6-hydroxy-1,3,5-triazine sodium salt (2% aqueous solution)
5 ml

[0080]

[Chemical 10]

Each of the obtained samples uses the standard light B described in "New Edition, Data Book of Illumination" (Corporation of Illuminating Engineering, Ed., 1st edition, 2nd edition), page 39 as a light source, and exposes the samples for 0.1 seconds. Then, a so-called white light exposure was carried out by exposing with 3.2 CMS with a non-filter. Here, this exposure was performed from both sides of the film so that both sides of the film had the same amount of light.

The development is performed by an automatic processor SRX-502 (Konica Corporation)
Made by using a developer and a fixer having the following composition, a developing temperature of 35 ° C., a fixing temperature of 33 ° C., and washing water of 5.0 liters per minute at a temperature of 18 ° C. and a drying temperature of 50 ° C. The processing steps were processed in 30 second mode.

A running solution was used for both the developing solution and the fixing solution. In other words, 1000 pieces of quartet-sized sample No. 1 exposed to a density of 1.2 ± 0.1 after development processing
After processing one sheet, the exposed sample No. 1 was developed and the fog and sensitivity were measured. Sample No. 2 to No.
6 was similarly evaluated.

In Table 1, the sensitivity is represented by the reciprocal of the exposure amount that gives the density of fog +1.0, and is represented by the relative sensitivity when the sensitivity of Sample No. 1 is 100.

(Processing step) Process Processing temperature (° C) Processing time (sec) Replenishment amount Insertion-0.8 Development + crossover 35 9.7 Fixing + crossover 33 5.5 22 ml / quarter cut 1 sheet Wash + crossover 18 4.8 5.0l / min Squeeze 40 3.8 Dry 50 5.4 Total-30.0 Developer formulation Part-A (for finishing 15 liters) Potassium hydroxide 470g Potassium sulfite (50% solution) 3000g Sodium hydrogencarbonate 150g Diethylenetriamine pentaacetic acid 5 sodium 45g 1-Phenyl -5-Mercaptotetrazole 0.2g Hydroquinone 390g Add water to finish to 5000ml Part-B (for 15 liter finish) Glacial acetic acid 220g Triethylene glycol 200g 1-Phenyl-3-pyrazolidone 27g 5-Nitroindazole 0.45g n-acetyl- DL-Penicillamine 0.15g Add water to finish to 5000ml Starter (for 1 liter finish) Glacial acetic acid 138g Potassium bromide 325g 5-me Lubenzotriazole 1.5 g Add water to make 1 liter (Add 20 ml of this starter solution to 1 liter of developing solution) Fixer formulation Part-A (for finishing 19 liters) Ammonium thiosulfate (70 wt / vol%) 4000 g Sulfurous acid Sodium 175 g Sodium acetate trihydrate 400 g Sodium citrate 50 g Gluconic acid 38 g Boric acid 30 g Glacial acetic acid 140 g Part-B (for finishing 19 liters) Aluminum sulfate (anhydrous salt equivalent) 65 g Sulfuric acid (50 wt%) 105 g It is shown in Table 1 below. The sensitizing dyes a and b used for comparison had the following structures.

[0086]

[Table 1]

As is apparent from the table, the sample of the present invention shows less fog and high sensitivity even if the developer replenishment amount is reduced.

[0088]

[Chemical 11]

Example 2 Preparation of emulsion 16 g of gelatin was dissolved in 1 liter of water, and 0.4 g of potassium bromide, 6 g of sodium chloride and 10 parts of sodium salt of polyisoprene polyoxyethylene disuccinate were placed in a container heated at 53 ° C. % 0.8% ethanol solution, then 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride are added by a double jet method to form a core portion of 20 mol% of silver chloride. Then 500 ml of an aqueous solution containing 100 g of silver nitrate and 40 potassium bromide.
g, 14 g of sodium chloride, and 500 ml of an aqueous solution containing 0.7 mol of potassium hexachloroiridium (III) in a molar ratio to silver are added by the double jet method to give silver chloride of 40
A cubic monodispersed silver chlorobromide emulsion Em-2 having a mol% shell portion and a silver chloride content of 30 mol% and an average particle size of 0.35 μm
Was prepared.

After desalting this emulsion, 30 g of gelatin was added and maintained at 55 ° C., the sensitizing dyes shown in Table 2 were added as a methanol solution, and then ammonium thiocyanate, gold chloride and sodium thiosulfate were added to chemically enhance the emulsion. After giving a feeling,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added.

Preparation of coating liquid <Backing lower layer coating liquid> Gelatin 400 g i-amyl-n-decylsulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Diethylene glycol 5.0 g Glyoxal 40% aqueous solution (hardening agent)
5.0 ml

[0092]

[Chemical 12]

Finish with water to 7 liters <Backing top coating solution> Gelatin 400g i-Amine-n-decylsulfosuccinate sodium 10g Antihalation dye (1) 10g Polymethylmethacrylate 12g SAM-1 3.0g SAM-2 0.75g Glyoxal 40% aqueous solution (hardener) 34.0 ml Make up to 7 liters with water.

<Silver Halide Emulsion Layer Coating Solution> A silver halide emulsion coating solution was prepared by adding the following to the above emulsion per mol of silver halide.

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

[0096]

[Chemical 13]

<Coating Solution for Protective Layer on Emulsion Side> In the solution having the following composition, the addition amount is shown per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g i-amine-n-decylsulfosuccinate sodium 1.4 g Polymethylmethacrylate (particle diameter 4 μm) 0.15 g Silicon dioxide particles (area average particle diameter 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% aqueous solution 5.0ml Topside 300 ( Permchem Asia Ltd.) 45mg SAM-1 1.0g SAM-2 0.4g

[0099]

Embedded image

Coating of Sample A silver halide emulsion layer and an emulsion protective layer solution were coated on the same support as used in Example 1. Further, the backing lower layer and the upper layer described above were coated on the surface side coated with the antistatic layer.

The amount of gelatin in the backing layer was 3.0 in the lower layer.
g / m ^2, the upper layer was simultaneously coated by a slide hopper method at 90m / min so that the 1.2 g / m ^2. A sample was obtained by coating the emulsion layer so that the amount of gelatin and the amount of silver were 2.0 g / m ² , respectively. The gelatin for the protective layer was 0.9 g / m ² .

The obtained sample was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0103]

[Table 2]

As can be seen from the table, even when the silver chlorobromide emulsion is used, the sample of the present invention has less fog and high sensitivity even if the developer replenishing amount is reduced.

[0105]

According to the present invention, a method of processing a silver halide photographic light-sensitive material having a reduced fog and a high sensitivity even when the processing speed is rapidly reduced can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [I]:
A method for processing a silver halide photographic light-sensitive material, characterized in that processing is carried out by an automatic developing machine in which the replenishing amount of the developing solution is cut into four and is 20 ml or less per sheet. Embedded image Z ₁ and Z ₂ represent a non-metal atom necessary for completing a 5- or 6-membered heterocycle, and R ₁ and R ₂ represent a substituted or unsubstituted alkyl group. R ₃ and R ₄ represent a hydrogen atom, an alkyl group or an aryl group, and at least one is an alkyl group or an aryl group. m ₁ and m ₂ represent 0 or 1, and X ₁ represents a counter ion. n represents 0 or 1, and when forming an intramolecular salt, n
Is 0.