JPH08262654A - Processing method of silver halide photographic material - Google Patents

Abstract

PURPOSE: To provide a processing method of silver halide photographic material in which liquid blurring and fog are reduced and a high sensitivity can be provided by processing a specified silver halide photographic material with an alkaline developer containing a specified compound or its salt. CONSTITUTION: A silver halide photographic material in which the silver halide particle in a silver halide emulsion layer has an average aspect ratio of 3 or more, the average silver chloride content is 30mol% or more, and the hardening degree is 50 minutes to 200 minutes is processed with an alkaline developer containing a compound represented by the formula or its salt. In the formula, R represents a hydrogen atom or hydroxyl group, and (n) represents an integer of 1 to 4. This developer is an alkaline developer containing reductones represented by the formula. These reductones are preferably used in 1-100g per litter of the developer, and more preferably 5-50g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material in which fog and roller marks are not generated even at high temperature rapid processing.

[0002]

2. Description of the Related Art In recent years, in the processing of silver halide photographic light-sensitive materials, rapid processing at high temperature has rapidly become widespread, and the processing time for processing by an automatic processor has been greatly shortened. For this reason, in order to obtain sufficient sensitivity in a short time, a method for processing a silver halide photographic light-sensitive material that does not increase fog even when it is rapidly processed at high temperature, and a halogenation method that quickly dries in a drying step after washing with water. A method of processing silver photographic light-sensitive materials is required.

As one of means for improving the drying property of silver halide photographic light-sensitive materials, there is a method of reducing the water content immediately before the start of drying in the drying step after the washing step. For example, it is possible to reduce the amount of gelatin as a binder, which is a hydrophilic substance coated on a silver halide photographic light-sensitive material. However, the reduction of gelatin causes deterioration of graininess of the silver halide photographic light-sensitive material. , It will significantly deteriorate photographic performance and processing performance such as generation of roller marks.

A method of adding glutaraldehyde as a hardening agent to a developing solution is generally used. However, rapid processing has problems in developability and fixability, and the odor of glutaraldehyde significantly deteriorates the working environment. There is a drawback.

A method of processing with a developer containing ascorbic acid, which is one of the reductones, is disclosed in US Pat. No. 5,264,323,
Although it is disclosed in European Patent No. 9,202,849, high temperature treatment can provide high sensitivity but has a drawback of increasing fog.

As means for achieving high sensitivity, Japanese Patent Laid-Open No. 3-2526
No. 49 and No. 3-288243 disclose a method of using tabular grains having a silver chloride content of 80 mol% or more, but the tabular grains have low pressure resistance and a liquid pressure effect (liquid pre) or a roller mark. Is likely to occur. When the amount of gelatin as a binder is increased to improve the pressure resistance and the degree of hardening is increased, the processability is deteriorated. Japanese Unexamined Patent Publication Nos. 6-82954 and 6-82938 disclose means for achieving rapid processability by increasing the degree of film hardening, but they have the drawback of degrading sensitivity.

Therefore, there has been a demand for a processing method of a silver halide photographic light-sensitive material which can be processed at high temperature and at high speed, achieves high sensitivity without increasing fog, and does not generate liquid pre-prints or roller marks.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a development processing method for a silver halide photographic light-sensitive material capable of obtaining high sensitivity with reduced liquid pre-fog and fog.

[0009]

At least one on a support
In a silver halide photographic light-sensitive material having a silver halide emulsion layer, the silver halide grains in the silver halide emulsion layer have an average aspect ratio of 3 or more and an average silver chloride content of
A silver halide photographic light-sensitive material having a hardness of 30 mol% or more and a hardness of 50 minutes or more and 200 minutes or less is prepared by the following general formula [1].
A method for processing a silver halide photographic light-sensitive material, which comprises processing with an alkaline developing solution containing a compound represented by: or a salt thereof.

[0010]

Embedded image

(Wherein R represents a hydrogen atom or a hydroxyl group,
n represents an integer of 1 to 4. The developer of the present invention is characterized in that it is an alkaline developer containing a reductone represented by the general formula [1].

As the reductones contained in the alkaline developer of the present invention, enediol type, enaminol type, enediamine type, thiolenol type and enaminethiol type compounds are generally known. Examples of these compounds are described in US Pat. No. 2,688,549 and JP-A-62.
-237443 and the like. Methods for synthesizing these reductones are also well known, and are described in detail in, for example, Yuji Nomura and Hirohisa Omura, "Chemistry of Reductones" (Uchida Lao Tsukuba Shinsha 1969).

The preferred specific examples of the reductones of the present invention are shown below.

[0014]

Embedded image

The reductone compounds of the present invention can also be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. These reductones are developers 1
It is preferable to use 1 to 100 g, preferably 5 to 50 g per liter.

As the developing agent constituting the developing treatment agent of the present invention, in addition to the above-mentioned reductones, the developing agents preferably used in combination are the dihydroxy compounds described in JP-A-4-15641 and JP-A-4-16841. Benzene (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfinate, sodium hydroquinone monosulfinate , Catechol, pyrazole, etc.),
Examples of 3-pyrazolidones include (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone,
Phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl
-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl
-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-
p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4
-Dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-
4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., 3-aminopyrazolines (for example, 1- (p
-Hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.) and phenylenediamine (For example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4 -Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methoxyethylaniline, etc.), and further aminophenols (eg, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diamino) Phenol, N- (4-hydroxyphenyl) glycine, N- (2'-hydroxyethyl) -2
-Aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl) -4- (N-methyl) aminophenol, etc.) and the hydrochlorides or sulfates of these compounds can be used.

It is also preferable to use three or more of these in combination.

The above-mentioned para-aminophenols and 3-aminopyrazolones can be used in combination with the reductones of the present invention.

The amount of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones to be used in combination is preferably 0.004 mol / liter, more preferably 0.0
It is 4 to 0.12 mol / liter.

The amount of 3-aminopyrazolidones used is preferably 0.001 to 0.1 mol / liter, more preferably 0.005 to 0.05 mol / liter. In addition to the developer, a preservative (eg, sulfite, bisulfite, etc.) and a buffer (eg, carbonate, boric acid,
Borate, alkanolamine, etc.), alkaline agent (eg carbonate, etc.), solubilizing agent (polyethylene glycols and their esters etc.), pH adjuster (eg organic acid such as citric acid), sensitizer ( For example, a quaternary ammonium salt or the like), a development accelerator, a hardener (for example, dialdehydes such as glutaraldehyde), a surfactant and the like can be contained. Further as an antifoggant azole-based organic antifoggant (for example, indazole-based,
(Imidazole-based, benzimidazole-based, triazole-based, benztriazo-based, tetrazole-based, thiadiazole-based), a masking agent for masking calcium ions mixed in tap water used for treatment liquids sodium hexametaphosphate, calcium hexametaphosphate, poly There are phosphates and the like.

The fixing agent preferably contains thiosulfate. Thiosulfate is supplied as a solid,
Specifically, it is supplied as a salt of lithium, potassium, sodium, or ammonium, preferably sodium thiosulfate or ammonium thiosulfate is supplied and dissolved, and more preferably supplied as an ammonium salt and dissolved and used. As a result, a fixing solution having a high fixing rate can be obtained, but sodium is preferable from the viewpoint of retention.

The concentration of thiosulfate is preferably 0.1 to 5 mol / liter, more preferably 0.5 to 2 mol / liter, and further preferably 0.7 to 1.8 mol / liter. Other fixing agents such as iodide salts and thiocyanates can also be used.

The fixing agent contains a sulfite, and the concentration of the sulfite is 0.2 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent.
As the sulfite, solid lithium, potassium, sodium, ammonium salt or the like is used, and it is used by dissolving with the solid thiosulfate.

The fixer preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof.

Examples of these salts include potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate and ammonium tartrate. Potassium, potassium sodium tartrate, sodium malate, ammonium malate, sodium succinate,
Lithium, potassium, sodium, ammonium salts, etc. (represented by ammonium succinate, etc.) are mentioned as preferable salts, and one kind or a combination of two or more kinds thereof can be used.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, etc. are supplied as solids and are used by dissolving them in an aqueous solvent. The preferable content in the fixing solution after dissolution is 0.05 mol / liter or more, The preferred content is 0.2-
It is 0.6 mol / liter. Examples of the acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid, with boric acid and aminopolycarboxylic acids being preferred. Such as acids and salts. The preferable addition amount is 0.5 to 20 g / liter.

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

Examples of the surfactant include anionic surfactants such as sulfate ester compounds and sulfonate compounds, nonionic surfactants such as polyethylene glycol and ester compounds, and amphoteric surfactants described in JP-A-57-6840. And so on.

Examples of the wetting agent include alkanolamine and alkylene glycol.

As the fixing accelerator, for example, JP-A-45-357 is used.
No. 54, JP-B-58-122535 and JP-A-58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, and thioethers described in US Pat. No. 4,126,459.

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

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

In addition, “The theory of the ph” by TH James
otographic process ”4th edition, published by Macmillan (1977) 38
~ Method described on page 104, GF Daufin "Photoemulsion Chemistry"
“Photographic Emulsion Chemistry”, Focal press
Published by the company (1966), P. Glafkides "Physics and Chemistry of Photography""C
himie et physique photographique ”Paul Montel (1967), VL Zelikman et al.,“ Making and Coating photographic Emulsion ”Fo
It is prepared by the method described in Cal Press (1964).

That is, a solution method such as a neutral method, an acid method or an ammonia method is mixed under conditions such as a forward mixing method, a back mixing method, a double jet method, a controlled double jet method, a conversion method, a core / shell method. It can be produced using the particle preparation conditions such as and the like and a combination method thereof.

The silver halide emulsion of the present invention is preferably a monodispersed silver halide emulsion, and silver halide emulsions containing 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size are preferably used. Particularly preferably used.

The average grain size of the tabular grains in the present invention is 0.
2 to 2.5 μm is preferable, and 0.5 to 2.0 μm is particularly preferable.

In the tabular silver halide emulsion, the average value of grain diameter / thickness (called aspect ratio) (called average aspect ratio) is 3 or more, preferably 4 to 50, more preferably 5 Is ~ 20.

The average thickness is preferably 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05 to 0.25 μm.

In the present invention, the diameter of the silver halide grain is defined as the equivalent spherical diameter of the grain from the observation of an electron micrograph of the silver halide grain. The thickness of the silver halide grain is defined as the minimum distance between the two parallel planes forming the tabular silver halide grain.

The thickness of the tabular silver halide grains can be determined from an electron micrograph of a silver halide grain shaded, or an electron micrograph of a sample slice obtained by coating a silver halide emulsion on a support and drying. .

To obtain the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

As the tabular silver halide emulsion, those having monodispersity are preferably used, and those having 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size are particularly preferable. It is preferably used.

The tabular emulsion of the silver halide photographic light-sensitive material of the present invention is silver chlorobromide from the viewpoint of obtaining high sensitivity, and is a silver halide grain having an average silver chloride content of 30 mol% or more, It is preferably 40 mol% or more and 80 mol% or less.

The silver halide emulsion and the non-photosensitive hydrophilic colloid layer of the present invention are prepared by using the above-mentioned MT with an inorganic or organic hardener.
Is cured for 50 minutes or more and 200 minutes or less. Examples of hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,
3-dihydroxydioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-S-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinyl. Gelatinized gelatin or the like can be used alone or in combination. Especially JP-A-53-412
21, the active vinyl compounds described in Nos. 53-57257, 59-162546, and 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferable. In the present invention, the term "hardness" means a silver halide photographic light-sensitive material at 60 ° C.
Time required for the emulsion layer or the non-photosensitive hydrophilic colloid layer to start to dissolve when immersed in 1N sodium hydroxide solution (MT [melting time])
It is represented by.

MT of the emulsion layer and the non-photosensitive hydrophilic colloid layer of the present invention is in the range of 50 minutes to 200 minutes. Generally, when MT at 60 ° C. is 200 minutes or more, the drying property and the transporting property are improved but the developing property is deteriorated, and when the MT is 50 minutes or less, the developing property is improved but the transporting property is drastically deteriorated. In that case, the developability and the transportability are improved without deteriorating the developability.

Drying is usually 35 to 100 ° C., preferably 40
The automatic developing machine may be provided with a drying zone in which hot air at a temperature of 80 ° C. to 80 ° C. is blown or a heating means by far infrared rays is provided.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like. Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

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

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution.

The average silver chloride content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to chloride.

When producing tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used if necessary.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
The method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A No. 35-16086 or the method using G-3, G-8, etc., as an aggregation polymer agent described in JP-A-2-7037 is particularly preferable. The salt method can be mentioned.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, RD No.176
43 (December 1978), No.18716 (November 1979) and No.308
119 (December 1989). The following table lists the types of compounds and the locations where they are described in these three Research Disclosures.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII 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 Examples of the support that can be used in the light-sensitive material according to the present invention include the above-mentioned RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9. A suitable support is a plastic film or the like, and an undercoat layer may be provided on the surface of these supports in order to improve adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like may be applied.

[0057]

Embodiments of the present invention will be described below. Of course, the present invention is not limited to the examples described below.

Example 1 Preparation of EM-1 (AgBr _0.20 Cl _0.80 tabular grains) <Solution A> High methionine gelatin (methionine 59.7 mM per 1 g gelatin) 30 g 4,5,6-triaminopyrimidine 100 g NaCl 246 g NaBr 108 g Distilled water to 6000 ml <Solution B> Silver nitrate 893 g Distilled water to 2000 ml At 40 ° C, the pH of solution A in the mixing stirrer shown in JP-B-58-58288 is adjusted to 5.6, and solution B is 6 ml. Was added over 1 minute. Next, the solution was further linearly accelerated over 55 minutes (9.8 times from the start to the end), and the whole amount of the solution B was added during that time. 120 ml of the gelatin solution was added 1, 15 and 18 minutes after the start of addition of the solution B. 4M after 5 minutes and 18 minutes
400 g of NaCl solution and 100 g of 20 mM 4,5,6-triaminopyrimidine solution. During the addition of the above raw materials, the inflow of silver nitrate was stopped for 1 minute, and the additives were uniformly mixed. During this period p
H was controlled to be constant by adding caustic soda or nitric acid.

Approximately 3000 particles of EM-1 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 1.8.
The average particle thickness was 0.12 μm, the average aspect ratio was 15, the sphere-equivalent particle size was 0.67 μm, and the coefficient of variation was 18%.

EM-2 (AgBr _0.50 Cl _0.50 tabular grains)
Preparation of EM-2 EM-2 was prepared in the same manner as EM-1 except that 162 g of NaBr was added to the mixer and the amount of NaCl was reduced to 154 g.

Approximately 3000 particles of EM-2 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 2.0.
The average particle thickness was 0.13 μm, the average aspect ratio was 15, the equivalent spherical diameter was 0.74 μm, and the coefficient of variation was 18%.

EM-3 (AgBr _0.80 Cl _0.20 tabular grains)
Preparation of EM-3 was prepared in the same manner as EM-1, except that NaBr was further reduced to 433 g and NaCl was reduced to 61 g in the mixer.

Approximately 3000 particles of EM-3 were observed and measured by an electron microscope, and the shape was analyzed. The average particle diameter was 2.0.
The average particle thickness was 0.13 μm, the average aspect ratio was 15, the equivalent spherical diameter was 0.74 μm, and the coefficient of variation was 18%.

After the completion of addition, each emulsion was desalted by precipitation using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts, and an aqueous gelatin solution containing 92.2 g of ossein gelatin was added. The mixture was redispersed with stirring as 2500 ml.

Next, each emulsion thus obtained was heated to 50 ° C., and then the spectral sensitizing dye 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium was added. After adding 300 mg of each salt anhydride per mol of silver, 7.0 × 10 ^-4 mol of ammonium thiocyanate per mol of silver was added, and chloroauric acid and sodium thiosulfate were added for optimum chemical ripening. -Hydroxy-6-methyl 1,3,3a, 7-tetrazaindene (TAI) stabilized with 3 × 10 ^-2 mol.

Preparation of comparative emulsion (A) Preparation of seed emulsion Iodibromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling 60 ° C., pAg = 8 and pH = 2.0. Monodisperse cubic particles of silver were prepared.

The resulting reaction solution was desalted at 40 ° C. with an aqueous solution of Demol N (manufactured by Kao Atlas Co.) and an aqueous solution of magnesium sulfate, and then an aqueous solution of gelatin was added and redispersed to obtain a seed emulsion.

Growth from Seed Emulsion Grains were grown as follows using the seed emulsion described above. First, disperse the seed emulsion in a gelatin aqueous solution kept at 40 ° C,
Further, the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. To this solution, an aqueous solution of ammoniacal silver nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method.
During the addition, the pH was controlled to 7.3 and the pH was controlled to 9.7, and the silver iodide content was 35.
A mol% layer was formed. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method.

Up to 95% of the target particle size, keep pAg = 9.0,
Was continuously changed from 9.0 to 8.0. Then pAg 1
It was adjusted to 1.0 and grown to a target particle size while maintaining pH 8.0. Subsequently, it was lowered to pH = 6.0 with acetic acid and the spectral sensitizing dye 5,5 '
400 mg / mol A of anhydrous di-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt
gX was added, desalting was performed using the demole N aqueous solution and magnesium sulfate aqueous solution described above, and then a gelatin solution was added and redispersed.

By this method, a comparative emulsion (A) of monodisperse silver iodobromide having an average silver iodide content of 2.0 mol, a rounded apex tetrahedron with an average grain size of 0.74 μm and a coefficient of variation of 0.16 was prepared. .

(Preparation of Sample) Various additives described below were added to each emulsion to prepare emulsion coating solutions. The amount of addition is shown in an amount per mole of silver halide.

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-dihydroxybenzene-4- Ammonium sulfonate 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg Formalin Amount shown in Table 1

[0073]

[Chemical 4]

NC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g (Preparation of Protective Layer Solution) The additives used in the protective layer are as follows. The addition amount is shown as the amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg Formalin

[0076]

Embedded image

The above coating solution was uniformly coated on both sides of a blue-colored polyethylene terephthalate film having a thickness of 175 μm and subjected to undercoating, and dried.

The coating amount was 2.25 g / m ^{2 in} terms of silver equivalent on one side of the emulsion layer, and 2.5 g / m ^{2 on} one side as gelatin coating amount.
m ² , the protective layer is 90 g / min with two slide hopper type coaters so that the amount of gelatin attached is 0.99 g per side.
A sample was obtained by simultaneously coating both sides of the emulsion layer and the protective layer at a speed of m.

(Preparation of Processing Agent) Developer Formulation Part-A (10.8 ml for finishing) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetriamine pentasodium pentasodium 32.3 g Sodium hydrogencarbonate 108 g 1-phenyl-5-mercapto Tetrazole 15mg 5-Methylbenzotriazole 150mg 1,4-Dihydroxybenzene 135g Add water to make 3600ml Part-B (for 10.8ml finish) Reductones of the present invention Glacial acetic acid (90%) 150g Triethylene Glycol 144g 1-Phenyl-3-pyrazolidone 19.5g 5-Nitroindazole 0.32g n-Acetyl-D, L-penicillamine 0.11g Mixing method for each part Add 5 liters of water at 25 ℃ to a 50 liter tank and stir it The above Part-A was added, then Part-B was added, and finally water was added to make 10.8 liters. This developing solution was allowed to stand at 25 ° C. for 24 hours and then adjusted with potassium hydroxide or acetic acid so that the pH at 25 ° C. was 10.45.

The above developing solution was used as a replenishing solution as it was, and the following starter was added to the developing tank at the start of use at a rate of 20 ml per liter of the developing solution.

Starter solution formulation Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Fixer formulation to add water to 1.0 l (For 38 liters finish) Ammonium thiosulfate (70% solution) 4100g Sodium sulfite 410g Sodium acetate 250g Glacial acetic acid 365g Tartaric acid 52.5g Boric acid 82g Aluminum sulfate (anhydrous equivalent) 156g Add water to finish to 5ml Hardness (MT) Evaluation The obtained sample was dipped in a 1N NaOH aqueous solution at 60 ° C., the time until the beginning of melting of the emulsion layer was measured, and this melting time was defined as the hardness (MT).

Evaluation of Sensitivity and Fog For the obtained sample, a fluorescent intensifying screen for X-ray photography SRO-2 was used.
After sandwiching with 50 and irradiating with X-ray through Penetrometer B type, automatic developing machine SRX-503, developing and fixing are processed with the above processing agent according to the present invention for 45 seconds to give a base density + fog + 1.0 density. The reciprocal of the X-ray irradiation energy required for the sensitivity was taken as the sensitivity, and the sensitivity was expressed as a relative sensitivity value with the sensitivity of Sample 1 being 100, and the fog was shown by the value obtained by subtracting the support concentration.

Evaluation of roller mark The sample was cut into 127 × 305 mm and the density after development was 1.0, 0.6,
The sample film was pre-exposed so as to have a density of three steps by giving an exposure of 0.4, and each sample film was treated in the same manner as described above. evaluated.

5: No spotted mark is observed at all 4: Spotted mark is slightly observed 3: Spotted mark is observed but practically usable 2: Spotted mark is generated Unusable due to a large number of spots 1: Spots markedly generated

[0085]

[Table 1]

[0086]

[Table 2]

From Tables 1 and 2, the processing methods of silver halide photographic light-sensitive materials using the developer containing the reductone of the present invention, Sample Nos. 1 to 3 and 6 are comparative Samples Nos. 4, 5 and 7, respectively. By comparison, it can be seen that the sensitivity, fog and liquid pre are excellent.

[0088]

According to the present invention, there is provided a method for developing a silver halide photographic light-sensitive material in which liquid pre-print and fog are reduced and high sensitivity is obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photograph in which the silver halide grains in the silver halide emulsion layer have an average aspect ratio of 3 or more, an average silver chloride content of 30 mol% or more, and a hardening degree of 50 minutes or more and 200 minutes or less. A method of processing a silver halide photographic light-sensitive material, which comprises processing the light-sensitive material with an alkaline developer containing a compound represented by the following general formula [1] or a salt thereof. Embedded image (In the formula, R represents a hydrogen atom or a hydroxyl group, and n is 1 to 4
Represents the integer. )