JPH09146230A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve contamination due to remaining colors in the initial period of running, to reduce the amt. of residual sodium thiosulfate (hypo) and to easily prepare the treating liquid for running start. SOLUTION: A liquid prepared by diluting a replenisher of a fixing liquid with water by >=4/3 times is used as a fixing liquid for the initial period of running. This fixing liquid to be used in the initial period of running has >=0.5mol/l concn. of thiosulfate ion. In this process, while a photosensitive material is carried on rollers in a fixing bath, the fixing liquid sucked from the fixing bath is injected in the transverse direction to the travelling direction of the photosensitive material so as to circulate the fixing liquid in the fixing bath. The amt. of the liquid injected is controlled to 50-150% of the amt. of the liquid in the fixing bath per one min. The flow rate (m/min) defined by ((the sum of the charged and circulated liquid (m<3> /min))/((the sum area (m<2> ) of apertures of the circulation and charge port for the liquid)) is controlled to 60 to 5(m/min).

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 light-sensitive material, and more particularly to a fixing processing method for improving residual color contamination and residual hypo at the initial stage of running.

[0002]

2. Description of the Related Art With the improvement of medical diagnostic technology, it is strongly demanded to always obtain a stable and rapid image having excellent image quality in a process for forming an image with a medical light-sensitive material.

In general, as the fixing solution is brought into the developing solution as the photosensitive material is subjected to continuous running processing, the pH thereof rises, and the concentration of silver ions and halogen ions rises due to the fixing reaction. In such a fixing process, the fixing solution in the initial stage of running is more active than the fixing solution at the time of running equilibrium, but since the pH is low, the dye remains on the photosensitive material easily. In particular, when the replenishment is low, that is, when the replenishment amount is relatively small, the amount of the developer brought in is large relative to the amount of the fixer to be replenished. Addition of a starter to the fixing solution as a means for solving such a dye residue at the initial stage of running is disclosed in JP-A-3-68937 and the like, but it complicates the work. On the other hand, the fixing active initial fixer tends to leave hypo in the processed film, which tends to cause image deterioration during long-term storage. From the above background, it is strongly desired to solve the residual dye and residual dye in the early stage of running.

[0004]

SUMMARY OF THE INVENTION Therefore, the problems to be solved by the present invention are to improve the residual color contamination in the initial stage of running, to reduce residual hypo, and to add a starter to the fixer solution for replenishment in the early stage of running. It is an object of the present invention to provide a method of processing a silver halide light-sensitive material, which can improve the complexity of the work in the method of using a fixing solution.

[0005]

The above-mentioned objects of the present invention have been achieved by the following processing methods.

In a method for processing a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one layer of a support, a fixing solution used at the initial stage of processing is replenished with water to prepare a fixing solution with a ratio of 4/3 times. A method of processing a silver halide photographic light-sensitive material, which is a liquid diluted as described above.

The method for processing a silver halide photographic light-sensitive material as described above, wherein the fixing solution used at the initial stage of processing has a thiosulfate ion concentration of 0.5 mol / l or more.

In the fixing bath, the silver halide photographic light-sensitive material is subjected to development processing by using a roller-conveying type automatic developing machine, and the fixing solution sucked from the fixing bath is discharged from a side lateral to the transfer direction of the light-sensitive material. The fixing solution is circulated, and the discharge amount of the fixing solution circulation is 5 times the fixing solution amount of the fixing bath per minute.
0 to 150%, and the flow rate represented by the following definition is 60 to 5 m / min.

Flow velocity (m / min) = total discharge circulation flow rate (m
⁽³ / min) / total diameter area of liquid circulation discharge port (m ² ) Here, the fixer used in the initial stage of the process means the repetitive use of the fixer that is repeatedly used by supplementing the replenisher. This is the fixer of time.

The present invention will be described in detail below.

In the present invention, the fixing solution used at the initial stage of processing is a solution obtained by diluting the fixing solution used for replenishment with water by 4/3 or more. This dilution ratio is preferably 4/3 times to 5/2 times. The term "diluted 4/3 times" as used herein means that water is added so that the volume becomes 4/3 times the original fixing solution.

In the present invention, the fixing agent used for replenishment contains thiosulfate. The thiosulfate is specifically supplied as a salt of lithium, potassium, sodium or ammonium, preferably sodium thiosulfate or ammonium thiosulfate, more preferably an ammonium salt is used, whereby the fixing speed is high. A fixer is obtained.

The concentration of the thiosulfate is preferably 0.5 mol / l or more, more preferably 0.5 to 5 mol / l, still more preferably 0.5 to 2 mol in the fixing solution used at the initial stage of processing. / L, and particularly preferably 0.7 to 1.8 mol / l. In the fixing solution used in the present invention, an iodide salt or a thiocyanate can also be used as a fixing agent.

In the present invention, the fixing solution preferably contains sulfite, and the concentration of sulfite is 0.2 mol when thiosulfate and sulfite are dissolved and mixed in an aqueous solvent.
/ L or less is preferable. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is used, which is dissolved and used together with the solid thiosulfate.

In the present invention, the fixing solution preferably contains a carboxylic acid such as acetic acid, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof as a buffer agent.

Further, in the present invention, the fixing solution preferably contains a compound represented by the following general formula (I).

General Formula (I) R ₁ — (B) _n —CH ₂ —COOH In the general formula (I), R ₁ is at least 1 selected from a hydroxyl group, an amino group, a sulfo group, a nitro group and a halogen atom. Represents an alkyl group or an aryl group each substituted with one substituent, B is a carbonyloxy group,
It represents a carbonylimino group, an oxy group or a thio group, and n represents 0, 1 or 2.

In the general formula (I), R ₁ is preferably a hydroxyl group, an amino group, a sulfo group or an alkyl group having 5 or less carbon atoms substituted with a halogen atom, and the substituent of the alkyl group is an amino group. Is more preferable. n is 0
It is preferred that

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

I-1 HO-CH ₂ -CH ₂ COOH I-2 HO-CH ₂ -CH ₂ -CH ₂ COOH I-3 HO-CH ₂ -CH ₂ -CH ₂ -CH ₂ COOH I-4 CH _{3 -CH (OH) -CH 2 COOH I} -5 CH 3 -CH (OH) -CH 2 -CH 2 COOH I-6 H 2 N-CH 2 -CH 2 COOH I-7 H 2 N-CH 2 -CH _{2 -CH 2 COOH I-8 H} 2 N-CH 2 -CH 2 -CH 2 -CH 2 COOH I-9 HO 3 S-CH 2 -CH 2 COOH I-10 HO 3 S-CH 2 -CH 2 - _{CH 2 COOH I-11 HO 3} S-CH 2 -CH 2 -CH 2 -CH 2 COOH I-12 O 2 N-CH 2 -CH 2 COOH I-13 O 2 N-CH 2 -CH 2 -CH 2 _{COOH I-14 O 2 N-} CH 2 -CH 2 -CH 2 -CH 2 COOH I- _{5 Cl-CH 2 -CH 2 COOH} I-16 Cl-CH 2 -CH 2 -CH 2 COOH I-17 Cl-CH 2 -CH 2 -CH 2 -CH 2 COOH I-18 Br-CH 2 -CH 2 _{COOH I-19 Br-CH 2} -CH 2 -CH 2 COOH I-20 CH 3 -CHBr-CH 2 COOH I-21 Br-CH 2 -CH 2 -CH 2 -CH 2 COOH I-22 I-CH 2 _{-CH 2 COOH I-23 H 2} N-CH 2 -CH (OH) -CH 2 -CH 2 COOH I-24 HO-CH 2 -C (CH 3) 2 -CH (OH) -CO-NH-CH ₂ COOH I-25 H ₂ N—CH (OH) —CH ₂ —CH ₂ —CH ₂ COOH The compound represented by the general formula (I) is easily prepared by a method described in a publicly known or new experimental chemistry course (Maruzen). Can be synthesized.

The compound represented by the general formula (I) may be added as a salt, for example, as a lithium, potassium, sodium or ammonium salt, and one kind or a combination of two or more kinds thereof can be used.

The content of the compound represented by the general formula (I) is such that the pH of the compound is 0.
It is preferable that the amount is such that it has a buffering capacity not to increase by 3 or more. The above content is preferably 0.0
5 mol / l or more, and most preferably 0.2 to 0.
It is 6 mol / l.

The fixing solution of the present invention may contain an acid and its salt, a water-soluble aluminum salt acting as a hardener, a chelating agent, a surfactant, a wetting agent, a fixing accelerator and the like.

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 aminopolyacid being preferred. Acids such as carboxylic acids and salts thereof. The preferable addition amount is 0.5 to 20 g / l.

Examples of the water-soluble aluminum salt acting as a hardening agent include aluminum chloride, aluminum sulfate, potassium alum and the like.

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

As the surfactant, for example, anionic surfactants such as sulfuric acid esterified products and sulfonated products, nonionic surfactants such as polyethylene glycol-based and ester-based surfactants, 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-
No. 35754, Japanese Patent Publication No. 58-122535, No. 58-
No. 122,536, thiourea derivative, alcohol having a triple bond in the molecule, US Pat. No. 4,126,459
And the like.

In the present invention, the pH of the fixing solution used for replenishment is preferably 3.8 or higher, and 4.1 to 4.1
A range of 5.5 is especially preferred.

The replenishing rate of the fixing solution of the present invention is 350 ml / m.
^It is preferably ² or less, and particularly preferably in the range of 50 to 250 ml / m ² .

Next, the developing solution used in the processing method of the present invention will be described.

The developing solution used in the processing method of the present invention is not particularly limited, and a known developing solution for a silver halide photographic light-sensitive material can be used.

The developer may contain the following developing agents. As a black and white developing agent, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone,
Bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,
3-Dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc. 3-Pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl) -3-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl 4,4-dimethyl-3
-Pyrazolidone, 1- (2-benzothiazole) -3-
Pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-
o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-allyl-3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline) , 1- (p-methylaminophenyl) -3-aminopyrazoline, 1-
(P-amino-m-methylphenyl) -3-aminopyrazoline, etc.), pyrazolones (eg, 4-aminopyrazolone), etc., or a mixture thereof. Further, reductones described in JP-A-7-84343 may be used as a developing agent.

In the developing solution, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine, etc.) and alkaline agents (eg, Carbonates, etc.), solubilizers (polyethylene glycols and their esters, etc.), pH adjusters (eg organic acids such as citric acid), sensitizers (eg quaternary ammonium salts), development accelerators, hardeners Membrane agents (for example, dialdehydes such as glutaraldehyde), surfactants and the like can be contained. Further, as an antifoggant, an azole organic antifoggant (for example, indazole-based, imidazole-based, benzimidazole-based, triazole-based, benztriazole-based, tetrazole-based, thiadiazole-based), calcium ions mixed in tap water used in the treatment liquid are added. Hiding agents for hiding include sodium hexametaphosphate, calcium hexametaphosphate, polyphosphates and the like.

An anti-silver agent for the developing solution, for example, JP-A-56
The compounds described in No. 24347 can be used.

P of the developer used in the processing method of the present invention
H is preferably in the range of 9 to 13, and more preferably in the range of 10 to 12.

An amino compound such as an alkanolamine described in JP-A-56-106244 can be used in the developer.

In addition to this, L. F. A. Mason, "Photographic Processing Chemistry," published by Focal Press, Inc. (1966), pages 22-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
And those described in JP-A-48-64933 can be used.

The roller-conveying type automatic developing machine preferably used in the present invention has a mechanism of fixing the light-sensitive material in the fixing bath while transferring it with a roller. The fixing solution sucked from the fixing bath is moved in the transfer direction of the light-sensitive material. On the other hand, by discharging from the lateral side, the fixing liquid in the fixing bath is circulated to efficiently agitate the fixing liquid to reduce the residual dye and improve the fixing property. The present inventors have found that when a fixing solution having a relatively low salt concentration, such as the fixing solution in the early stage of processing used in the present invention, is used, the effect of stirring is particularly large for a fixing solution having a relatively low salt concentration. It was

The agitation of the fixing solution is usually carried out by circulating the fixing solution by sucking and discharging the fixing solution in a pump installed in an automatic developing machine. Excessive agitation accelerates the evaporation and oxidation of the fixing solution, and the pump is installed. It is not preferable in terms of space inside the automatic processor. Therefore, as the circulating liquid amount, it is preferable to circulate 50% to 150% of the fixing bath liquid amount in one minute, and more preferably 60% to 120% liquid amount in one minute. It is to be.

Under such an amount of circulating liquid, the flow rate represented by the above definition is 60 to 5 m / min, preferably 50 m / min.
By adjusting the length to 10 m, the residual dye can be reduced and the fixability can be improved.

For the stirring of the fixing solution according to the method of the present invention, there may be two or more solution inlets or solution discharging in the same fixing bath, and there may be a plurality of circulation pumps. . Therefore, the discharge amount of the fixing liquid circulation of the present invention is the total amount thereof.

The stirring in the fixing bath may be performed in a developing bath or a water washing bath, in addition to the fixing bath. The drying system of the drying section of the automatic processor used in the present invention may be any of drying systems using warm air, infrared radiation, and a heat roller, or may be used in combination.

Next, the silver halide light-sensitive material processed by the processing method of the present invention will be described. The silver halide emulsion in the photosensitive silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention may be a single emulsion or a mixture of two or more kinds of emulsions. The emulsion to be mixed may be either tabular grains or normal grains or twin grains having an aspect ratio of less than 2. The emulsion layer may be composed of one layer or a plurality of layers. As the silver halide emulsion, grains having an average grain size or a thickness of 0.3 μm or less are preferably used. Here, the thickness of silver halide grains constitutes tabular grains 2
The smallest distance between two parallel principal planes. The thickness of the tabular silver halide grains is calculated by depositing a metal from a diagonal direction of the grain together with a comparative latex, measuring the shadow length on an electron microscope, and referring to the shadow length of the latex. Alternatively, it can be determined from an electron micrograph of a sample slice obtained by coating and drying a silver halide emulsion on a support.

A silver halide emulsion having a monodispersion property is preferably used, and a silver halide emulsion having 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size is particularly preferably used. To be

The silver halide emulsion may have any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, but from the viewpoint of high sensitivity, silver bromide or Silver iodobromide is preferred, and the average silver iodide content is preferably 0 to 5.0 mol%, particularly preferably 0.1 to 3.0 mol%.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926 and 58-113927,
Nos. 58-113934 and 62-1855, European Patents 219,849, and 219,850 can also be referred to. Further, as a method for producing a monodisperse tabular silver halide emulsion, JP-A-61-6643 can be referred to. As a method of producing a tabular silver iodobromide 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 a pBr of 2 or less to generate seed crystals, Then, it can be obtained by 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 addition rate of silver salt and halide aqueous solution. The aspect ratio can be controlled by the method of preparing the seed crystal, the thickness and pAg at the time of growth, pH, the halogen composition, the aging time and the temperature. The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the added halide aqueous solution, that is, the ratio of bromide to iodide. In addition, a silver halide solvent such as ammonia, thioether or thiourea can be used, if necessary, during the production of tabular silver halide grains. The grains may be grown by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, and a silver ion-containing solution can be supplied.

As the silver halide emulsion, core / shell type or double structure type grains having a silver halide composition in which the inside and the surface of the grain are different are also preferably used. As a method for obtaining a core / shell type emulsion, for example, US Pat.
No. 505,068, No. 4,444,877, British Patent No. 1,027,146, and JP-A-60-14331. In the core / shell type grains of the silver halide emulsion, the silver iodide content of the outermost shell layer of the grains is preferably less than 5 mol%, more preferably 3 mol%.
Is less than.

The silver iodide content of the outermost shell layer of silver halide grains can be detected by various surface elemental analysis means. XP
S (X-ray Photoelectron Spe
It is useful to use methods such as ctrocopy), Auger electron spectroscopy, and ISS. XPS is the simplest and highly accurate means, and the silver iodide content of the outermost shell layer can be defined by the value measured by this method.

The depth analyzed by the XPS surface analysis method is said to be about 10Å. For the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, refer to “Electron spectroscopy” by Soichi Aihara (Kyoritsu Library 16, published by Kyoritsu Publishing, 1978). You can

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the surface of the grain, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. In these emulsions, a cadmium salt, a lead salt, a zinc salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, etc. may be used at the stage of physical ripening or grain preparation.

The silver halide emulsion may be subjected to a water washing method such as a Noudel water washing method and a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method,
For example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or an example of an aggregated polymer agent G described in JP-A-63-158644
A particularly preferable desalting method is a method using 3, G8 or the like.

As the chemical sensitization, so-called sulfur sensitization, S
Sensitization by e compound, sensitization by Te compound, gold sensitization,
Noble metals from Group VIII of the Periodic Table (eg Pd, Pt, Id, etc.)
The sensitization method according to the above method, and the sensitization method using a combination thereof can be used. Among them, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and Se compound sensitization is preferable. It is also preferable to carry out the reaction in combination with the reduction sensitization.

It is preferable to supply iodide ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and dye adsorption. Particularly, a method of adding silver iodide in the form of fine grains is preferable. It is also preferable to carry out chemical sensitization in the presence of a compound having adsorptivity to silver halide. As the compounds, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, and particularly compounds having a mercapto group and compounds having a benzene ring are preferable.

Reduction sensitization can be used as the chemical sensitization. The reduction sensitization is carried out by adding a reducing compound, a method called silver ripening, a method of allowing a silver ion excess state of pAg = 1 to 7 to pass, and a high pH aging called high pH of 8-11.
It is applied to a silver halide emulsion by a method such that the H state is passed. Further, these two or more methods can be used in combination. The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be any of inorganic or organic compounds, thiourea dioxide, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives,
Examples of the sulfite include thiourea dioxide, stannous chloride and dimethylamine borane. The amount of these reducing compounds added varies depending on the reducing properties of the compound and the type of silver halide, the emulsion production conditions such as the dissolution conditions, and is 1 × 10 1 per mol of silver halide.
A range of ^-8 to 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains. It is also preferable to subject any portion and / or shell layer other than the outermost shell layer of the silver halide grain to a reduction treatment and further grow the grain as it is. From the viewpoint of effect control, the surface of the inner shell layer to be laminated in multiple stages, for example, seeds It is preferably applied to the surface of the emulsion grains or the surface of the shell layer at the time of growth suspension. The reduction treatment may be carried out in the presence of a thiosulfonic acid compound as disclosed in JP-A-2-135439 and JP-A-2-136852.

The silver halide emulsion can be spectrally sensitized with methine dyes and other spectral sensitizing dyes. The sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, horoboler cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These sensitizing dyes can apply any of the commonly used nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.,
A nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has pyrazoline-containing nuclei having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes are exemplified by German Patent No. 929,080, US Pat. No. 2,231,658,
No. 2,493,748, No. 2,503,776
No. 2,519,001, No. 2,912,32
No. 9, No. 3,655,394, No. 3,656,9
No. 59, No. 3,672,897, No. 3,649,
No. 217, British Patent No. 1,242,588, Japanese Patent Publication No. 4
No. 4-14030.

The sensitizing dyes may be used alone or in combination. Sensitizing dyes are often used in combination. Typical examples thereof are U.S. Pat. Nos. 2,688,545 and 2,977,299.
No. 3,397,060, No. 3,522,05
No. 2, No. 3,527, 641, No. 3, 617, 2
No. 93, No. 3,628,964, No. 3,666
No. 480, No. 3,679, 428, No. 3,70
No. 3,377,863,862, British Patent No. 1,344,281, Japanese Patent Publication No. 43-4936, and the like.

The sensitizing dye may be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and before coating, but it is preferably added at several points.

The silver halide photographic light-sensitive material may have a crossover cut layer provided between the support and the emulsion layer. This layer may be an undercoat layer provided between the support and the hydrophilic colloid layer, or a dye layer may be provided between the undercoat layer and the emulsion layer. Examples of the dye used in the undercoat layer include an oxonol dye having a pyrazolone nucleus and a barbituric acid nucleus, an azo dye, an azomethine dye, an anthraquinone dye, an arylidene dye, a styryl dye, a triarylmethane dye, a merocyanine dye, and a cyanine dye. . The dye used in the dye layer may be dispersed in the form of fine particles. Specific examples of the dyes include the exemplified compounds (I-2, 4, 6, 8, 9, 10, 11, 12, 13-, described in JP-A-2-264247, pages 6-12.
27, II-2, 5, 6, III-3, 4, 6, 8, 9, 1
0, 11, 12, 14-28, IV-3, 5, 6, 8, 1
0-16, V-3, 5, 6, 7) and the like can be used. These compounds are described in International Patent Publication 88/087.
94, European Patent Nos. 0274723A1 and 27
6,566, 299,435, JP-A-52-92.
No. 716, No. 55-155350, No. 55-1553.
No. 51, No. 61-205934, No. 48-68623.
U.S. Pat. Nos. 2,527,583 and 3,486.
No. 897, No. 3,746, 539, No. 3,933, 7
98, 4,130,429, 4,040,84
It can be easily synthesized according to the method described in No. 1 and the like.

In the silver halide emulsion, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. A hydrazine compound may be added to the silver halide emulsion, and the compounds described in Japanese Patent Application No. 5-134743 are preferable, and the compounds represented by the general formula (5) and the nucleation accelerators represented by the general formulas (7) and (8) are particularly preferable. Compounds are preferred. A tetrazolium salt may be added to the silver halide emulsion, and the compounds described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure (hereinafter sometimes referred to as “RD”) No. No. 17643 (December 1978);
No. 18716 (November 1979) and the same No. 3081
19 (Dec. 1989). The types and locations of the compounds shown in these three Research Disclosures are listed below.

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 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 Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 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 Support 28 XVII 1009 XVII Used in the silver halide photographic light-sensitive material of the present invention Examples of the support that can be used include the above-mentioned RD-17643.
28, and RD-308119, page 1009. Further, polyethylene-2,6-naphthalate may be used as the support. 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 the adhesion of the coating layer, or corona discharge or ultraviolet irradiation may be applied.

[0065]

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

Example 1 Preparation of light-sensitive material <Preparation of seed emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide Potassium 841 g Water 2825 ml D1 1.75 N potassium bromide aqueous solution Silver potential control amount at 42 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solutions B1 and C1 was stopped, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. Diameter (converted to circle diameter)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

<Preparation of Em-1> A tabular silver halide emulsion Em-1 was prepared by using seed emulsion-1 and the following four kinds of solutions.
Was prepared.

A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Equal to 3150 ml with water B2 potassium bromide 1734 g 3644 ml with water C2 Silver nitrate 2478 g Finish with water 4165 ml D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) Equivalent to 0.080 mol * 0.06 mol iodide To 6.64 liters of a 5.0 wt% gelatin aqueous solution containing potassium, 2 liters of an aqueous solution each containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After forming the particles, p using an aqueous solution of sodium carbonate
H was adjusted to 6.0.

Solution A2 was vigorously stirred in the reaction vessel while keeping it at 60 ° C., and a part of solution B2, a part of solution C2 and half of solution D2 were added thereto by a simultaneous mixing method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 is continuously added over 37 minutes, and then a part of the solution B2, a part of the solution C2 and the remaining whole amount of the solution D2 are added over 15 minutes, and finally, The remaining total amount of the solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was 8.8.
I kept it at 8. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

Further, the solution D2 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent.

After the addition is complete, the emulsion is cooled to 40.degree.
1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate 90%) was added as an aggregating polymer agent, and the mixture was stirred for 3 minutes. afterwards,
A 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.6. After stirring for 3 minutes, the emulsion was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Thereafter, 9.0 l of distilled water at 40 ° C. was added, and after stirring and standing, the supernatant was drained. Further, 11.25 l of distilled water was added, and after stirring and standing, the supernatant was drained. Subsequently, a gelatin aqueous solution and a 10% (weight) aqueous sodium carbonate solution were added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was 5.80 at 40 ° C,
The pAg was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio of about 4.5, width of particle size distribution 1
It was 8.1% of tabular silver halide grains. The average of the distance between twin planes was 0.020 μm, and the grains having a ratio of the distance between twin planes to the thickness of 5 or more accounted for 97% (number) of all tabular silver halide grains and 10 or more grains. Occupied 49%, and 15% or more of the particles occupied 17%.

Next, after the above emulsion (Em-1) was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and thiol were added. Add a mixed aqueous solution of sodium sulfate and a dispersion of triphenylphosphine selenide,
After 60 minutes, a silver iodide fine grain emulsion was added, and ripening was carried out for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.

It should be noted that the above-mentioned additive and its addition amount (AgX1
Per mole) is shown below.

5,5′-Dichloro-9-ethyl-3,3′-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydride 2.0 mg 5,5′-di- (butoxycarbonyl) -3, 3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydrate 120 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0.4 mg iodine Silver halide fine particles 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 500 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-994.
Prepared by a method according to the method described in No. 37. That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes.

The above selenium sensitizer dispersion was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Immediately after that, the residual concentration of ethyl acetate was reduced to 0.3 under reduced pressure.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

The average iodine content on the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the above silver iodide fine grains was about 4 mol%.

Next, the emulsions thus sensitized were added with the additives described below to prepare an emulsion layer coating solution. At the same time, a coating solution for the protective layer was prepared.

Next, from below, on both sides of the support, the following transverse light-shielding layers were previously coated on both sides of a polyethylene terephthalate film base for X-rays (thickness: 175 μm) colored blue with a concentration of 0.15. The emulsion layer coating solution and the protective layer coating solution were simultaneously multilayer coated so as to have the following prescribed coating amounts, and dried to prepare a silver halide photographic light-sensitive material.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Each emulsion obtained above various additives compound added following (G) 0.5mg / m ² 2,6- bis (hydroxyamino) -4-diethylamino - 1,3,5-triazine 5 mg / m ² t-butyl - catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 8 0 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-ammonium sulfonate 500 mg / m ² 2-mercaptobenzimidazole- Sodium 5-sulfonate 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² However, as gelatin, 1.0 g / m Adjusted to ² .

[0084] The third layer (protective layer) matting agent 50 mg / m ² consisting of gelatin 0.8 g / m ² Polymethyl methacrylate (area average particle diameter 7.0 .mu.m) Formaldehyde 20 mg / m ² 2,4-dichloro-6- Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² polyacryl Sodium acid 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50mg / m ² compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 -H 3mg / m 2 _{8 F 17 SO 2 N (C} 3 H 7) _{[(CH 2 CH 2 O) 15} H ] _{^{2mg / m 2 C 8 F 17}} SO 2 N (C 3 H 7) _{[(CH 2 CH 2 O) 4} - (CH ₂ ) ₄ SO ₃ Na] 1 mg / m ^{2 The} coating amount of the material was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

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The silver halide photographic light-sensitive material for evaluation thus obtained was developed by the following method.

Formulation of Developer Part A (for 12 l finishing) Potassium hydroxide 600 g Potassium sulfite (50% solution) 2180 g Diethylenetetraamine pentaacetic acid 100 g Sodium bicarbonate 240 g 5-Methylbenzotriazole 1.2 g 1-phenyl-5- Mercaptotetrazole 0.2 g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 200 g Hydroquinone 360 g Water is added to make 5000 ml.

Part B (for 12 l finishing) Glacial acetic acid 170 g Triethylene glycol 324 g 1-Phenyl-3-pyrazolidone 21.6 g n-Acetyl-D, L-penicillamine 2.4 g The developer was prepared by mixing Part A and about 5 l of water. PartB
Was added at the same time, water was added while stirring and dissolving to make 12 l, and the pH was adjusted to 10.60 with KOH.

2.4 g of glacial acetic acid was added to 1 liter of this developer.
/ L and 7.9 g / l of potassium bromide, KOH
The pH was adjusted to 10.45 to prepare a developing solution.

Fixing solution Pure water 2600 g Sodium sulfite 450 g Boric acid 108 g Acetic acid 490 g β-alanine 600 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Aluminum sulfate 800 g Ammonium thiosulfate (70 wt / vol%) Table 1 amount (listed as the concentration of the fixing solution in the initial stage of the process (starting running) in Table 1) It was diluted with water while stirring to obtain a final fixing solution of 18 liters.
It should be noted that sulfuric acid or NaOH was added in an amount such that the final pH was 4.45 before being diluted with water.

The above fixing solution was diluted as shown in Table 1 and used as a fixing solution for starting running in a fixing bath of an automatic processor. The automatic processor is SRX503 (Konica Corporation)
DR) to make the flow rate of the fixer variable,
What was made possible to be processed by Y-TO-DRY (dry-dry) for 30 seconds was used. The flow rate (l / min) of the circulating fluid of the fixing solution and the flow rate were the amounts shown in Table 1. The flow rate was adjusted by changing the diameter of the circulating fluid discharge port. Processing time is DRY-TO-D
RY for 30 seconds, development temperature and fixing temperature both 35 ℃,
The residual dye and residual hypo at the beginning of running were evaluated.

Evaluation of Dye Residue An unexposed light-sensitive material having a four-section size (10 inches × 12 inches) developed under the above conditions was visually evaluated.

Evaluation Criteria 5: No Occurrence 4: Occurrence is Minor, No Problems at All 3: Occurs, but No Problems or Practical Problems in Practice 2: Occurrence and Problems in Practical Practice 1: Occurrence is remarkable, Evaluation of residual hypo that cannot withstand use 0.1 mg of silver nitrate in the above unexposed photosensitive material
1 aqueous solution was dropped as a residual hypo evaluation solution, left for 3 minutes, wiped well and dried, and the concentration of silver sulfide produced was measured with a photographic densitometer PDA-65 (manufactured by Konica Corporation) using a spectral filter 436 ±. It measured using the interference filter of 10 nm. Table 1 shows the difference in blue light transmission density between the portion below the residual hypo evaluation droplet and the portion not dropped. That is, the larger this difference is, the higher the residual hypo concentration in the processed photosensitive material is. If the amount of residual hypo is large, it becomes a problem that the color tends to change to a sepia tone when the photo is saved.

Evaluation of Residual Silver 2.6 parts of sodium sulfide were added to the above unexposed light-sensitive material.
A × 10 ^-3 mol / l aqueous solution was dropped as a residual silver evaluation solution, left for 3 minutes, wiped off well and dried, and the concentration of the produced silver sulfide was measured by a photographic densitometer PDA-65 (manufactured by Konica Corporation). ), Using an interference filter of spectral filter 436 ± 10 nm. Table 1 shows the difference in blue light transmission density between the portion below the residual silver evaluation droplet and the portion not dropped. That is, the larger the difference, the higher the residual silver concentration in the processed film.

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[Table 1]

(Note) Dilution ratio = volume of fixer after dilution / volume of fixer before dilution As is clear from Table 1, according to the present invention, the dye remains and remains at the initial stage of running without deteriorating the residual silver. The hypo has been improved. Further, it can be seen that the fixing solution obtained by diluting the replenishing solution as the fixing solution at the initial stage of the treatment has a greater effect of improving the residual dye and residual dye by stirring.

[0099]

EFFECTS OF THE INVENTION According to the present invention, the work in the method of improving the residual color contamination in the early stage of running, reducing the amount of residual hypo, and adding a starter to the replenishing fixer to obtain the fixer in the early stage of running There is provided a method for processing a silver halide light-sensitive material in which the complexity of the above is improved.

Claims (3)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one layer of a support, wherein the fixing solution used in the initial stage of processing is 4 / water. A method of processing a silver halide photographic light-sensitive material, which is a liquid diluted three times or more. 2. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the thiosulfate ion concentration of the fixing solution used at the initial stage of processing is 0.5 mol / l or more. 3. A silver halide photographic light-sensitive material is subjected to development processing using a roller-conveying type automatic developing machine, and a fixing solution sucked from a fixing bath is discharged from a side lateral to the transfer direction of the light-sensitive material. The fixer in the bath is circulated, and the discharge amount of the fixer circulated is 50 times the fixer in the fixer for 1 minute.
3. The method for processing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the flow rate represented by the following definition is 60 to 5 m per minute. Flow rate (m / min) = total discharge circulation flow rate (m ³ / min) / total diameter area of liquid circulation discharge port (m ² )