JP2000181005A - Silver halide photographic sensitive material and its development processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and its development processing method which is free of occurrence of film stains and uneven development and uneven drying and opacification at the time of development processing and occurrence of stains in a rinsing bath by incorporating a polysaccharides in a specified range of average molecular weight, in at least one layer on the side of the silver halide emulsion layers of the photosensitive material. SOLUTION: This photosensitive material, containing in at least one of the layers on one side of a support same as the silver halide emulsion layers the polysaccharides, having a weight average molecular weight of 50,000-200,000, is imagewise exposed and processed with a developing solution containing as a developing agent a compound which is represented by the formula, in which each of R1 and R2 is independently, an optionally substituted alkyl or such alkylthio grain or the like, and each of they may combine with each other, and where (k) is 0 or 1: and when k=1, X is a -CO- or -CS- group; and each of M1 and M2 is an H or alkali metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof, and more particularly to a silver halide photographic light-sensitive material having good processability even in rapid processing, and a development processing method thereof.

[0002]

2. Description of the Related Art In recent years, silver halide photographic materials have been
In addition to photographic performance, the film to be processed is required to have a property of preventing the occurrence of stains, development unevenness, drying unevenness, etc. in addition to rapid processing.

As a corresponding technique, it is known to use a polysaccharide, particularly dextran or dextrin, as a binder component of a light-sensitive material.

For example, Japanese Patent Application Laid-Open No. 6-43571 discloses the use of dextrans in a photosensitive material layer for the purpose of improving the ultra-rapid processability of a medical X-ray film. However, although this technique has an accelerating effect, it has the drawback that dextran is eluted during the treatment, and the film is easily stained, and the drying property is further deteriorated. JP-A-6-43571 does not disclose the relationship between the molecular weight of dextrans and the processability.

Further, for the purpose of improving the drying property of a photosensitive material, Japanese Patent Application Laid-Open No. Hei 7-301876 discloses a method in which a branched polysaccharide and a vinylidene chloride-based polymer latex are used in combination. There was also a bad effect that chlorine was sometimes generated, and it was not a practical method.

Incidentally, Japanese Patent Application Laid-Open Nos. 8-328183 and 9-304855 using an organic contrasting agent and dextrans are known, each of which aims at improving aging characteristics and improving scratch resistance. Further, Japanese Unexamined Patent Publication No.
No. 179254 discloses a developing method in which a photosensitive material containing dextrans is mainly used as a reductone.

However, when a photosensitive material containing an organic contrasting agent is processed with a developing solution containing a reductone as a main agent, high contrast and improved physical properties can be obtained, but uneven drying tends to occur during processing. Had.

[0008] A new technology which has a rapid processing property, and also has no stain, development unevenness, drying unevenness or film devitrification even in a long-time running process, and no generation of stains in a washing tank. The development of was desired.

[0009]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material which is free from film stains, development unevenness, drying unevenness, devitrification and stains in a washing tank during processing. An object of the present invention is to provide a developing method. A second object of the present invention is to provide a silver halide photographic light-sensitive material having the above-mentioned performance and suitable for printing plate making, and a method for developing the same.

[0010]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
The problem has been solved by the following configuration.

(1) A photosensitive material having a photosensitive silver halide emulsion layer on one side of a support, wherein at least one layer on the emulsion layer side contains a polysaccharide having a weight average molecular weight of 50,000 to 200,000. A silver halide photographic light-sensitive material, which comprises subjecting the material to imagewise exposure and then treating the material with a developing solution containing a compound represented by the following formula (A) as a developing agent.

[0012]

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(Wherein R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. Or R ₁ and R ₂ may be bonded to each other to form a ring, k represents 0 or 1, and when k = 1, X represents-
Represents CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. (2) In at least one layer on the emulsion layer side of the light-sensitive material,
The silver halide photographic material as described in the above item (1), further comprising an organic contrast agent.

(3) A polysaccharide having a weight-average molecular weight of 50,000 to 200,000 and at least one organic compound in at least one of the emulsion layers of a light-sensitive material having a light-sensitive silver halide emulsion layer on one side of the support. After the photosensitive material containing the agent is exposed imagewise, the pH of the compound represented by the above general formula (A) is adjusted to 9.0 as a developing agent.
A process for developing a silver halide photographic material, wherein the process is performed with a developing solution of 10.0.

(4) The developing method of (3), wherein the replenishing amount of the washing water is 10 to 500 ml / m ^2. Processing method.

Hereinafter, the present invention will be described in detail.

The term "polysaccharide" as used in the present invention is a generic term for compounds in which a monosaccharide has a unit. Preferred polysaccharide units constituting the polysaccharide of the present invention include D-mannose and D-mannose.
-Glucose, D-glucuronic acid, D-glucosamine,
D-galactosamine and the like.

As preferred polysaccharides, dextran, dextrin, xanthan gum guar gum, pullen, chitosan, carboxymethylcellulose, hydroxypropylcellulose and the like are used. More preferred polysaccharides are dextran and dextrin,
Particularly preferred is dextran.

In the present invention, the polysaccharide has a weight average molecular weight of 5
In the case of 10,000 to 200,000, the object effect of the present invention is selectively exerted. Particularly preferred polysaccharides have a weight average molecular weight of 50,000 to 80,000.

In GPC, the weight average molecular weight is 2
The fraction of fractions of 10,000 or less is preferably 40% or less, and
% Or less is preferable.

In the present invention, the addition position of these polysaccharides is not particularly limited, but is preferably a light-sensitive emulsion layer or a non-light-sensitive emulsion layer coated on a support, particularly a hydrophilic colloid layer (e.g. Protective layer) is preferred.

The added amount of the polysaccharide of the present invention is from 0.05 g to
1.5 g / m ² is preferable, and 0.1 g is more preferable.
1.0 g / m ² , more preferably 0.1 g to 0.3 g / m ^2.
g / m ² .

In the present invention, the organic contrasting agent may be a hydrazine derivative or a hydrazine derivative described in JP-A-10-10680.
It is preferable to use a tetrazolium compound which is a nitrogen-containing heterocyclic derivative having 6 to 6 members, and it is particularly preferable to use a hydrazine derivative.

An object of the present invention is to form a high-contrast image using the above-mentioned organic high-contrast agent. The light-sensitive material of the present invention is exposed and developed. The inclination (γ) is to be 10 to 100.

Examples of the hydrazine derivative include those represented by the following general formula (H).

[0026]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) n-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ⁵² — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino A carbamoyl group or an oxycarbonyl group. R ⁵² represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, and amino group.

Among the compounds represented by the general formula (H), a compound represented by the following general formula (Ha) is more preferred.

[0029]

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In the formula, R ¹¹ represents an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Furthermore, the R ¹¹ preferably contains at least one ballast group or a silver halide adsorption accelerating group.

As the ballast group, those commonly used in immobile photographic additives such as couplers are preferable, and those having 8 carbon atoms are preferable.
For example, alkyl, alkenyl, alkynyl, alkoxy, phenyl, phenoxy, alkylphenoxy and the like which are relatively inert to the above photographic properties can be mentioned.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula (Ha), A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula (H), and both are preferably hydrogen atoms.

In the general formula (Ha), G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula (Ha), R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, allyl group, heterocyclic group, alkoxy group, hydroxyl group, amino group, carbamoyl group, Represents an oxycarbonyl group. Desirable R ¹² is a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, a —COOR ¹³ group, and a —CON
(R ¹⁴⁾ (R ¹⁵⁾ group (R ¹³ represents an alkynyl group or a saturated heterocyclic group, R ¹⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ¹⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group). More preferably, it represents a substituted alkyl group substituted by two electron-withdrawing groups, particularly preferably three electron-withdrawing groups. R ¹²
The electron withdrawing group for substituting the carbon atom substituted with G preferably has a σp value of 0.2 or more and a σm value of 0.3 or more, for example, halogen, cyano, nitro, nitrosopolyhaloalkyl, polyhaloaryl, Alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyloxy group,
A carbamoyl group, an alkyl or aryl sulfinyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfonyloxy group, a sulfamoyl group, a phosphino group, a phosphine oxide group, a phosphonate ester group, a phosphonamide group, an arylazo group,
It represents an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group.

R ^{12 in the} formula (Ha) particularly preferably represents a fluorine-substituted alkyl group, a monofluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Next, specific examples of the compound represented by the general formula (H) are shown below, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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Specific examples of other preferred hydrazine compounds are described in US Pat. No. 5,229,248, columns 4 to 60 (1) to (252).
It is.

These hydrazine compounds can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in column No. 9,248, column 59 to column 80.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. The hydrazine compound is added to at least one layer on the silver halide emulsion layer side, preferably to the silver halide emulsion layer and / or a layer adjacent thereto, more preferably to the emulsion layer. The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers is 0% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. .2
0.8 molar equivalent. Preferably, it is 0.4 to 0.6 molar equivalent. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

When the above-mentioned high contrast agent is used in the light-sensitive material to be processed, it is preferable to use a nucleation accelerator in order to accelerate the high contrast.

As the nucleation accelerator, a compound represented by the following general formula [Na] or [Nb] is preferably used.

[0056]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
_{And 13} represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group, and R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable,
A molecular weight of 300 or more is particularly preferred. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group, a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of these nucleation accelerators [Na] are shown below.

[0059]

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[0060]

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[0061]

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[0062]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group,
Ar and R ₁₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide-adsorbing group include groups having the same meaning as the silver halide-adsorbing group of the compound represented by formula (H).

Specific examples of the compound represented by the general formula [Nb] include the following.

[0065]

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[0066]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5;
No. 8 thiosulfonic acid compound.

The nucleation accelerator used in the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. Is preferred. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably in the range of 10 ^-5 to 10 ^-2 mol.

In the present invention, the halogen composition of the silver halide in the silver halide emulsion of the light-sensitive material to be processed is not particularly limited. It is preferable to use a silver halide emulsion having a composition of silver chlorobromide containing silver chloride of at least mol% and silver chloroiodobromide containing silver chloride of at least 60 mol%.

The average grain size of silver halide is 1.2 μm.
m or less, particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG. Mees & T. H. Ja
by mes: The theory of the ph
otographic process, 3rd edition, 36
Pp. 43 (1966, published by Mcmillan).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

In the present invention, the method of reacting the soluble silver salt with the soluble halide salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

The silver halide emulsion contains tabular grains,
It is preferred that 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used are tabular grains having an aspect ratio of 2 or more. In particular, the ratio of tabular grains is 60 to
More favorable results are obtained with an increase to 70% and even to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Of these tabular grains, tabular grains having a (100) plane having a silver chloride content of 50 mol% or more and having a (100) plane as a main plane are preferably used.
264,337, 5,314,798, 5,3
20, 958, etc., and the desired tabular grains can be easily obtained.

In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled on specific surface portions. In order to control the photosensitive nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to provide a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodine ions. The preparation of the particles can be appropriately selected from an acid method, a neutral method, an ammonia method and the like. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5.

In order to control the growth of grains during the formation of tabular grains, for example, ammonia, thioether, thiourea compounds, thione compounds and the like can be used as a silver halide solvent. As thioether compounds, 3,6,9,15,1 described in German Patent 1,147,845
8,21-hexoxa-12-thiatricosan, 3,
9,15-trioxa-6,12-dithiaheptadecane; 1,17-dioxy-3,9-15-trioxa-
6,12-dithiaheptadecane-4,14-dione;
1,20-dioxy-3,9,12,18-tetroxa-6,15-dithiaeicosan-4,17-dione;
7,10-dioxa-4,13-dithiahexadecane-
2,15-dicarboxamide; JP-A-56-94347
Oxathioether compounds described in JP-A-1-121847; JP-A-63-259563; 63-30
And a cyclic oxathioether compound described in No. 1939. Particularly, thiourea is disclosed in JP-A-53-82408.
What is described in the specification is useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea;
1,3-dimethylimidazole-2-thione; 1,3-
Dimethylimidazole-4-phenyl-2-thione; tetrapropylthiourea and the like.

At the time of physical ripening or chemical ripening, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. In order to obtain high illuminance characteristics, iridium is preferably doped in a range of 10 ^<-9> to 10 ^{< -3 >} mol per mol of silver halide. In order to obtain a high-contrast emulsion, rhodium, ruthenium, osmium and / or rhenium is preferably doped in a range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated.

The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A-2-2082 and JP-A-2-2082.
Nos. 20853, 2-20854, 2-20855
The hexadentate ligands and alkali complex salts described in the specification include common sodium salts, potassium salts, cesium salts or primary, secondary and tertiary amine salts. Also, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these include, for example, K ₂ [RuCl ₆ ], (NH ₄ ) ₂
[RuCl ₆ ], K ₂ [Ru (NO) Cl ₄ (SC
N)], K ₂ [RuCl ₅ (H ₂ O)] and the like. Ru is replaced by Rh, Os, Re, Ir, Pd
And Pt.

Rhodium, ruthenium, osmium and / or
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

It is often better to have more of these in the shell. In addition, instead of being localized in a discontinuous layer configuration, a method of increasing the abundance as the particles are continuously outside the particles may be used. The addition amount can be appropriately selected from the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
176: 17643, pp. 22-23 (Dec. 1978
Mon)) or in the literature cited.

The silver halide emulsion may or may not be chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499, JP-A-50-7132
Compounds described in Nos. 5, 60-150046 and the like can be preferably used.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-
Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3). 3a, 7-tetrazaindenes), pentazaindenes and the like; addition of many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. it can.

It is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As the gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

An inorganic or organic hardener can be added to the photosensitive photographic emulsion and the non-photosensitive hydrophilic colloid layer according to the present invention as a crosslinking agent for a hydrophilic colloid such as gelatin. Examples of these compounds include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N
-Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-
Dihydroxydioxane), 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.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ) Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardeners and the like can be used alone or in combination. These hardeners are (RD) 176 vol.
7643 (issued in December 1978), page 26, paragraphs A to C.

Various other additives can be used in the light-sensitive material according to the present invention, and examples thereof include a desensitizer, a plasticizer, a slipping agent, a development accelerator, and oil.

The support used for the light-sensitive material is transparent,
It may be either non-permeable but is preferably a permeable plastic support. For plastic supports,
A support made of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound, or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after forming the film. The most preferable time is after film formation and after emulsion coating, but may be after emulsion coating. The heat treatment is preferably performed at a temperature of 45 ° C. or higher and a glass transition temperature of 1 second to 10 days. It is preferable to set the time within one hour from the viewpoint of productivity.

Further, it is preferred that the following compounds are contained in the constituent layers of the silver halide photographic material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, page 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (11) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described, for example, in (RD) No. 17643 (December 1978),
No. No. 18716 (November 1979) and the same No.
308119 (December 1989).

In the present invention, the processing is preferably carried out by employing an automatic developing machine having at least four processes of development, fixing, washing (or stabilization) and drying.

As the developer used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (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, etc.), aminophenols (o-aminophenol,
p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc., ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.)
And metal complex salts (iron salt of EDTA, iron salt of DTPA, nickel salt of DTPA, etc.) can be used alone or in combination. Among them, it is preferable to use a developing agent represented by the following general formula (A).

[0097]

Embedded image

In the general formula (A), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and k =
When it is 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

In the compound represented by the general formula (A),
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is particularly preferred.

[0100]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the formula (A) or the formula [Aa] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Preferred examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or [Aa] according to the present invention are shown below.
The present invention is not limited to these.

[0104]

Embedded image

[0105]

Embedded image

These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

The developing agent as used herein refers to a compound capable of developing silver halide in a developer of 5 moles.
It occupies 0% or more.

In the present invention, a developing agent represented by the general formula (A) and a 3-pyrazolidone (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)
And aminophenols (o-aminophenol, p-aminophenol, N-methyl-o-aminophenol,
N-methyl-p-aminophenol, 2,4-diaminophenol, etc., and dihydroxybenzenes substituted with a hydrophilic group (hydroquinone monosulfonate, sodium salt of hydroquinone monosulfonic acid, potassium salt of 2,5-hydroquinone disulfonic acid, etc.) It is more preferred to use the developing agents in combination. When used in combination, the developing agents of 3-pyrazolidones, aminophenols, and dihydroxybenzenes substituted with a hydrophilic group are usually 0.01 to 0.2 per liter of developer.
It is preferably used in less than a molar amount. In particular, a combination of ascorbic acid or a derivative thereof with 3-pyrazolidones and a combination of ascorbic acid or a derivative thereof with 3-pyrazolidones and a dihydroxybenzene substituted with a hydrophilic group are preferably used.

In the present invention, the developing solution contains an alkaline agent (such as sodium hydroxide and potassium hydroxide) and a pH buffer (such as carbonate, phosphate, borate, boric acid, acetic acid, citric acid, and alkanolamine). Preferably, it is added. p
As the H buffer, a carbonate is preferable, and the added amount thereof is 1
It is preferably from 0.2 mol to 1.0 mol per liter, more preferably from 0.3 mol to 0.6 mol.

When the compound represented by formula (A) is used as a developing agent, it preferably contains a sulfite as a preservative. As a preferable addition amount, 0.02 to
0.3 mol / l is preferred, and particularly preferably 0.1 mol / l.
1-0.2 mol / l is preferred.

If necessary, dissolution aids (polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants ,
Antifoaming agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or Alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (US Pat. No. 2,304,025, JP-B-47-455).
No. 41), a hardening agent (glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, pH8.
5 or more and 10.2 or less.

As the fixing solution, those having a commonly used composition can be used. Fixers generally have a pH of 3
８8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum, or an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde) can be added to the fixing solution.

The fixing solution may contain, if desired, a preservative (sulfite, bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening ability. And the like.

In the present invention, the concentration of ammonium ions in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The concentration of ammonium ion is particularly preferably in the range of 0 to 0.05 mol per liter of the fixing solution. Sodium thiosulfate may be used instead of ammonium thiosulfate as the fixing agent, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the acetate ion concentration in the fixing solution is preferably less than 0.33 mol / l. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution.However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less per liter of the fixing solution,
Particularly preferably, it is 0.13 mol or less, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The fixing solution includes citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. Salts such as lithium salt, potassium salt, sodium salt, ammonium salt and the like, lithium hydrogen tartrate,
Potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartaric acid, sodium potassium tartaric acid, and the like may be used. Among these, preferred are citric acid, malic acid, succinic acid and salts thereof. Most preferred are malic acid and its salts.

In the method for developing a silver halide photographic light-sensitive material of the present invention, the replenishing amount of washing water is used to process 1 m of the photographic material.
It is preferably 10 to 500 ml per ² and more preferably 50 to 200 ml.

The washing water in the present invention is preferably subjected to a washing treatment with a washing water containing a purifying agent containing an oxidizing agent and a bactericide.

The oxidizing agent used here includes metal or nonmetal oxides, oxyacids or salts thereof, peroxides,
Compounds containing an organic acid system are exemplified. From the viewpoint of discharging to drainage pipes, the oxyacids include sulfuric acid,
Nitrous acid, nitric acid, hypochlorous acid and the like are preferable, and as the peroxide, hydrogen peroxide solution and fentonic acid are particularly preferable. Most preferred is aqueous hydrogen peroxide.

These oxidizing agents are preferably supplied in the form of a concentrate or a solid agent from the viewpoint of physical distribution. As a preferred form, a concentrated solution is preferred, and a concentrated solution having an oxidizing agent component of 0.1 to 10 mol / l is preferable, and particularly preferably 0.5 to 2.0 mol / l.

In the present invention, a concentrated liquid or solid agent containing an oxidizing agent can be supplied by mixing with washing water. The mixing may be performed before entering the washing tank, or the concentrated liquid or solid agent and the washing water may be directly mixed in the washing tank.

The replenishment timing of the oxidizing agent-containing concentrated liquid or solid agent and water may be replenished at a constant rate every unit time, or may be replenished according to the processing amount by detecting the processing amount of the photosensitive material.

The amount of the oxidizing agent added to the washing tank is preferably in the range of 1/2 to 10 molar equivalents, and particularly preferably in the range of 1/2 to 3 molar equivalents with respect to the thiosulfate brought into the photosensitive material. Is preferred.

In the water washing of the present invention, in order to make the oxidizing agent act effectively, it is also a preferable embodiment to coexist with compounds such as a preservative and a bactericide.

The bactericide used in the present invention may be any as long as it does not adversely affect the photographic performance. Specific examples thereof include thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, and bromophenol compounds. Compounds, thiocyanic acid and isothianoic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organic tin and organic zinc compounds,
Cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds,
There are various antibacterial agents and fungicides such as active halogen compounds such as chlorinated sodium isocyanurate, chelating agents, sulfite compounds, and antibiotics represented by penicillin. Other L. E. FIG. West. “Water Qu
ality Criteria "Photo.Sci.a
nd Eng,. Vol 9 No. 6 (1965); Japanese Unexamined Patent Publication (Kokai) Nos. 57-8542 and 58-105.
No. 145, No. 59-126533, No. 55-1119
No. 42 and Nos. 57-157244; "Antibacterial and Fungicide Chemistry" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7) Chemicals such as those described in the "Handbook of Bactericidal and Fungicide Technology", Japan Society of Bactericidal and Fungicide (Hyohodo) (Showa 61) can be used.

Specific examples are shown below, but the present invention is not limited to these.

1.5-chloro-2-methyl-4-isothiazolin-3-one 2.2- (4-thiazolyl) -benzimidazole 6. methyl isothianoate 4.3,5-dichloro-4'-fluoro-thiocarbanilide 5.4-chloro-3,5-dimethylphenol 6.2,4,6-trichlorophenol 7. 7. Sodium dehydroacetate 9. Sulfanilamide 9.3,4,5-tribromosalicylanilide Potassium sorbate 11. 12. Benzalkonium chloride 12.1-bromo-3-chloro-5,5-dimethylhydantoin 13. Monochloroacetamide 14. Monobromoacetamide 15. Monoiodoacetamide 16. Benzimidazole 17. Cyclohexylphenol 18.2-octyl-isothiazolin-3-one 19. Ethylenediaminetetraacetic acid 20. 21. Nitrilo-N, N, N-trimethinephosphonic acid 21.1-Hydroxyethane-1,1-diphosphonic acid 18. ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid Chlorinated sodium isocyanurate 24.2-methyl-4-isothiazolin-3-one 25.10,10'-oxybisphenoxyarsine 26.1,2-benzisothiazolin-3-one 27. Thiosalicylic acid These exemplified compounds are described in US Pat. No. 2,767,1.
No.72, No.2,767,173, No.2,767,17
Nos. 4,870,015 and British Patent 848,13
No. 0, French Patent No. 1,555,416, and the like, describe their synthesis methods and examples of application to other fields. Some are commercially available, and Predentol O
N, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600
(Permachem Asia Co., Ltd.), Fine Side J-7
00 (manufactured by Tokyo Fine Chemical Company) ProzelGXL
(Manufactured by ICI Company).

When the above disinfectant is supplied into the washing water, it is preferably 0.01 to 50 g / l, more preferably 0.05 to 20 g / l. When contained as a detergent, 0.1 to 50 g based on the detergent.
/ Liter, more preferably 1 to 20 g / liter.

In the present invention, a compound having a polyalkylene oxide chain represented by the following general formula (Po) is preferable as a preservative which may be used for washing water.

Formula (Po) HO (C ₂ H ₄ O) _a (C ₃
H ₆ O) _b (C ₂ H ₄ O) _c H (where a, b, and c are positive integers) The compound represented by the general formula (Po) has ethylene oxide added with propylene glycol as a hydrophobic group. Compound. In the present invention, the average molecular weight is 2,000 to 850.
0, polypropylene glycol (PPG) molecular weight 14
In the general formula, a + c is preferably about 150 and b is preferably about 30 in the general formula. As such compounds, commercially available products include, for example, nonionic surfactants of "Pluronic series" manufactured by Asahi Denka Co., Ltd., and the following compounds are specifically preferable.

[0134]

[Table 1]

The compound having a polyalkylene oxide chain is added in an amount of 1 ppm to 1000 p with respect to the washing water.
pm, more preferably 10 ppm to 100 ppm, and when contained as a purifying agent,
It is 0.01% to 10%, preferably 0.1% to 5%. Other preservatives include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline, salicylic acid, quinolinic acid and their derivatives and salts thereof, and preferably salicylic acid and their derivatives and salts thereof. is there.

The purifying agent used in the washing water according to the present invention preferably contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. The chelate stability constant with calcium is the logarithm of the formation constant when one chelating agent binds to one calcium ion and is measured at a temperature of 20 ° C. and an ionic strength of 0.2. is there. Specifically, organic acids such as maleic acid, glycolic acid, gluconic acid, glucoheptanoic acid, tartaric acid, citric acid, succinic acid, salicylic acid, ascorbic acid, and erythorbic acid, glycine, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilo3 Aminopolycarboxylic acids such as acetic acid and derivatives thereof, and salts thereof. Among the organic acids, gluconic acid and citric acid are preferable, and as the aminopolycarboxylic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are preferable.

These compounds are used in an amount of about 0.005 to 0.2 mol, preferably 0.005 to 1 mol per liter of washing water.
Used at ~ 0.1 mol.

In the present invention, when the washing time is less than 20 seconds, the effect of the present invention is remarkable, preferably less than 16 seconds, more preferably less than 12 seconds.

In the present invention, a developing and fixing replenisher prepared from a solid processing agent can be used. The term "solid processing agent" as used herein means a powder processing agent, a tablet, a pill, a granule, etc., which is subjected to a moisture-proof treatment as required. Pastes and slurries are semi-liquid, have poor storage stability, and are not included in the solid processing agents of the present invention if they have a shape that is regulated with a risk of transportation.

Here, the powder refers to an aggregate of fine-grained crystals. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. Tablets are obtained by compressing powder or granules into a certain shape.

Among the above-mentioned solid processing agents, tablets are preferably used because they have high replenishment accuracy and are easy to handle.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is temporarily added to the surface of the photographic processing agent. Any means such as forming a coating layer by spraying can be adopted.

A preferred tablet production method is a method in which a powdery solid processing agent is granulated, followed by a tableting step and molding. Compared with a solid processing agent formed by a tableting step by simply mixing a solid processing agent component, there are advantages in that solubility and storage stability are improved and photographic performance is stabilized.

Granulation methods for tablet molding include rolling granulation,
Known methods such as extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet molding, the average particle size of the obtained granules is 100 to 800 in that, when the granules are mixed and compressed under pressure, non-uniformity of components, that is, so-called segregation hardly occurs.
μm, more preferably 2 μm.
It is 00 to 750 μm. Further, the particle size distribution is preferably such that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
For example, Japanese Unexamined Patent Publication Nos.
No. 3, 3-39735, 3-39939 and the like. Furthermore, powder processing agents can be manufactured by a general method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. can do.

[0147] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the solid material obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The solid processing agent is used at least for the developer and the fixing agent, but can be used for other photographic processing agents such as other rinsing agents. In addition, it is the developer and the fixing agent that can exclude the regulation of liquid dangerous substances. Most preferably, all the processing agents are solidified, but it is preferable that at least the developer and the fixing agent are solidified.

The solid treating agent can be solidified as only one part of a certain treating agent, but it is preferable that all components are solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

When the developer is solidified, it is preferable that all of the alkali agent and the reducing agent are solidified, and in the case of tablets, it is preferable to use at least three agents, most preferably one agent.

When a solid processing agent is divided into two or more agents, it is preferable that the plurality of tablets and granules are packaged in the same manner.

When the fixing agent is solidified, the main agent, preservative,
It is preferable to solidify all of the hardeners such as aluminum salts, and in the case of tablets, to use at least 3 or less, most preferably 1 or 2 drugs. When the solid treatment is performed by dividing into two or more agents, it is preferable that these tablets and granules are packaged in the same manner. In particular, it is preferable in terms of handling that the aluminum salt be solid.

Examples of the package of the solid processing agent include polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, and nylon (stretched or unstretched). , Polyvinylidene chloride, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PE
T), other polyesters, hydrochloride rubber, acrylonitrile butadiene copolymer, epoxy-phosphate resin (polymers described in JP-A-63-63037,
And a pulp.

These are preferably made of a single material. When used as a film, the films are laminated and adhered, but may be used as a coating layer or a single layer.

Further, for example, an aluminum foil or an aluminum vapor-deposited synthetic resin is used between the above synthetic resin films.
It is more preferable to use various gas barrier films.

In order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ²・ 24hr ・ atm or less (20 ℃ 65% RH
), More preferably 30 ml / m ² · 24 hr · at
m or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
μm, and more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

When the treating agent is packaged or bound or covered with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, Hydroxypropyl cellulose type,
Film or binder composed of pullulan, dextran or gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline or polyethylene glycol base Agents are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of the effect of coating or binding.

The thickness of the water-soluble film is preferably from 10 to 120 μm, particularly preferably from 15 to 80 μm, in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film and the precipitation of crystals in an automatic developing machine. Is preferably used, and especially those having a size of 20 to 60 μm are preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

Further, the tensile strength of the water-soluble film is 0.3.
Preferably ^{5 × 106~50 × 106kg / m 2} , especially 1 × 106~25 × 106kg / m ² are preferred, especially preferably ^{1.5 × 106~10 × 106kg / m 2} . These tensile strengths are measured by the method described in JISZ-1521.

The photographic processing agent packaged or bound or coated with the water-soluble film or binder can be used during storage, transportation, and handling to prevent atmospheric humidity such as high humidity, rain and fog, and water. It is preferable that the moisture-proof packaging material has a film thickness of 10 to 15 in order to prevent damage from sudden contact with water due to splashing or wet hands.
A film of 0 μm is preferable, and the moisture-proof packaging material is polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, which can have a moisture-proof effect with polyethylene,
Polyvinylidene chloride, polyamide, polycarbonate,
It is preferably at least one selected from acrylonitrile-based and metal foils such as aluminum, and metalized polymer films, and may be a composite material using these.

Further, when the moisture-proof packaging material is a degradable plastic,
It is particularly preferable to use a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include those composed of natural polymers, polymers produced from microorganisms, synthetic polymers having good biodegradability, and blending of biodegradable natural polymers with plastics. And those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability can be used favorably. To give specific examples of each of these,
It looks like this:

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers PHB-PHV (3-hydroxybutyrate and 3-hydroxyvale) Of “Bio”) as a component
pol ", microbial-produced cellulose, etc. Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or copolymers or mixtures thereof Mixing of biodegradable natural polymers into plastics As natural polymers with good biodegradability , Starch and cellulose, which have shape disintegration in addition to plastics.As photodegradable plastics, the introduction of carbonyl groups for photodisintegration, etc. is there.

For such degradable plastics,
"Science and Industry", Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July, 1990, No. 23
~ 34 pages and the like can be used. Biopol (manufactured by ICI), E
co (eco) (manufactured by Union Carbide), E
colite (Eco Plastic)
Co., Ltd.), Ecostar (St. Law)
Commercially available decomposable plastics such as R. Starch (manufactured by Rence Starch) and Knuckle P (manufactured by Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² · 24 hr or less.
It is more preferably 5 g · mm / m ² · 24 hr or less.

In view of the demand for reducing the amount of waste liquid, the present invention is processed while replenishing a fixed amount in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² .

Preferably, 30 to 250 ml per m ²
It is. The amount of replenishment for development is preferably 250 ml or less per m ² , more preferably 30 to 30 ml per m ^2.
200 ml. Here, the fixing replenishment amount and the development replenishment amount indicate the replenishment amount. Specifically, it is the replenishing amount of each of the developing mother liquor and the fixing mother liquor when the same liquor is replenished. And the total amount of water, and the total volume of the solid processing agent and the volume of water when the solid developing agent and the solid fixing agent are replenished with a solution prepared by dissolving in water. And the total volume of each solid processing agent and water when the solid fixing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

Due to the demand for shortening the development time, when processing is performed using an automatic developing machine, the total processing time (Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone.
(ToDry) is preferably 70 seconds or less and 10 seconds or more. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing with water, stabilizing processing,
Time including all the time of the process such as drying, that is, Dry
It is the time of to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30.
~ 60 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the effect of the present invention was significant when the washing time was less than 20 seconds.

In order to remarkably exert the effects of the present invention, a heat transfer material (for example, 60.degree.
~ 130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc.) Those that transmit heat energy to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat or emit infrared rays) and have a drying zone are preferably used.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Waste liquid treatment method: JP-A-2-64638, 388
(2) Lower left column of page 391 (5) Lower left column of page (3) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(4) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (5) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) lower right column to page 501 (7) Lower right column and JP-A-2-10805
No. 1, page 588 (2), lower left column to page 589 (3), lower left column (6) Method for recovering fixing waste silver: JP-A-6-27623, page (4), "0012" to page (7), "0071".

[0176]

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

Example 1 (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and Na
A water-soluble halide solution C composed of Cl and KBr is adjusted to pH 3.
The mixture was added at a temperature of 0, 40 ° C. and a constant flow rate in Solution A for 30 minutes by the simultaneous mixing method, and 0.20 μm of AgCl 70 mol%, AgBr 3
0 mol% of cubic crystals were obtained. At this time, the silver potential (EAg) was 160 mV at the start of mixing and 100 mV at the end of mixing. Unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin per mol of silver was added to adjust the pH to 5.7, followed by dispersion at 55 ° C. for 30 minutes. After dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per mol of silver. The silver potential of the resulting emulsion is 190 mV (40 ° C.)
Met.

A: Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion exchange water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg B: Silver nitrate 170 g Nitric acid (5%) 4.5 ml Ion exchange water 200 ml C: 47.5 g of NaCl 51.3 g of KBr 6 g of ossein gelatin 0.15 mg of Na ₃ [IrCl ₆ ] 200 ml of deionized water 200 ml of 4-hydroxy-6 per mole of silver in the obtained emulsion.
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
× 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. Next, the sulfur dispersed in the form of fine particles was converted into sulfur atoms by 2 × 10
^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid were added and chemically ripened at a temperature of 50 ° C. for 60 minutes, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrahydrofuran was added. Seindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and 1.5 × 10 ⁻³ mol of potassium iodide. Then, after the temperature was lowered to 40 ° C., 2 × 10 ⁻⁴ mol of sensitizing dyes S-1 and S-2 were added per mol of silver.

Using the obtained emulsion, one side of the undercoated support was adjusted so that the coating weight per 1 m ² was as follows.
From the support side, the following first and second layers were simultaneously coated in multiple layers and cooled and set (emulsion formulation A). Thereafter, the following backing layer was coated on the undercoating layer having the antistatic layer on the opposite side at a coating speed of 200 m / min using the dye formulation shown in Table 1,
A sample was obtained by cooling and setting at 1 ° C. and drying both sides simultaneously. The emulsion formulation B was exactly the same as the emulsion formulation A except that it did not contain the hydrazine derivative.

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was applied to both sides. And dried at 100 ° C. for 1 minute.

Copolymer of 2-hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) (numbers are by weight) 0.5 g / m ² surfactant A 3.6 mg / m ² Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ² (Antistatic layer) Corona discharge of 10 W / (m ² · min) was performed on a polyethylene terephthalate support provided with an undercoat layer. Thereafter, an antistatic layer having the following composition was applied on one surface at a speed of 70 m / min using a roll-fit coating pan and an air knife, dried at 90 ° C. for 2 minutes, and then dried at 140 ° C.
For 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² hydrophobic polymer particles C 0.4 g / m ² polyethylene oxide compound (MW 600) 0.1 g / m ² Curing agent E 0.1 g / m ² First layer (Emulsion layer) Gelatin 1.0 g Silver halide emulsion A 3.3 g as silver amount Hydrazine derivative H-34 0.015 g Hydrazine derivative H-39 0.020 g 5-Nitroindazole 0.01 g 2-Mercaptohypoxanthine 0.02 g Suspended polymer of colloidal silica 75% by weight, vinyl acetate 12.5% by weight, and vinyl pivalinate 12.5% by weight 1.4 g Polysaccharide Amount shown in Table 2 4-mercapto-3,5,6-fluoro Phthalic acid 0.05 g Sodium polystyrene sulfonate (average molecular weight 500,000) 0.015 g The pH of the coating solution was 5.2.

Second layer (protective layer) Gelatin 0.9 g Polysaccharide Amount shown in Table 2 Nucleation promoter Na-21 0.15 g Colloidal silica 0.10 g Fungicide Z 0.005 g Sodium polyoxyethylene lauryl ether sulfonate 0.001 g Sodium dihexylsulfosuccinate 0.015 g Silica (average particle size 5 μm) 0.015 g Silica (average particle size 8 μm) 0.15 g Hardener (1) 0.15 g Backing layer Gelatin 1.8 g F-10. 01g F-2 0.03g F-3 0.10g Suspended polymer of 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, and 12.5% by weight of vinyl pivalinate 0.7g Sodium polystyrene sulfonate 0 0.010 g Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 3 μm 0.045 g Hard Agent (2) 0.05 g Backing protective layer Gelatin 1.8 g Matting agent: Monodisperse polymethyl methacrylate having an average particle diameter of 3 μm 0.045 g Sodium polyoxyethylene lauryl ether sulfonate 0.005 g Sodium dihexyl sulfosuccinate 0.005 g Hard film Agent (1) 0.15g

[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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The following processing was performed on the obtained film sample.

(Per liter of development start solution) Diethylene triamine pentaacetic acid 1 g Sodium sulfite 30 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4'-hydroxylmethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 40 g 1-phenyl-5-mercaptotetrazole 0.025 g potassium bromide 4 g 5-methylbenzotriazole 0.21 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.07 g KOH In addition, it was finished to 1 liter.

(Development replenisher: 2-fold concentrated solution) Diethylenetriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium carbonate 70 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 1.5 g 1-phenyl -5-mercaptotetrazole 0.03 g potassium bromide 1 g 5-methylbenzotriazole 0.30 g 2,5-dihydroxybenzoic acid 5 g 8-mercaptoadenine 0.10 g KOH was added in such an amount that the pH of the working solution became 10.15. To 0.5 liter.

(Per liter of fixing start solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Na gluconate 5 g Citric acid 3Na · 2H ₂ O 12 g Citric acid 12 g Adjusted to pH 5.4 with sulfuric acid so that the pH of the working solution becomes 5.4. To 1 liter.

(Washing water) To 1 liter of tap water, 8.8 ml of the following purifying agent was added and placed in a washing tank to prepare washing water.

(Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35% by weight hydrogen peroxide water 171 g Pluronic F-68 3.1 g Hoksite F-150 15 g DTPA · 5Na 10 g Finished to 1 liter with pure water.

[0195] (Amount of replenishment of processing solution) A developer, a fixing replenisher, a purifying agent, and tap water for dilution of the above-mentioned formulation are respectively supplied to a developing tank, a fixing tank,
The washing tank was replenished directly under the following conditions.

Developer replenishment amount Working solution 65 ml / m ² dilution water 65 ml / m ² Fixer replenishment rate Concentrate 65 ml / m ² dilution water 65 ml / m ² Rinse water replenishment amount Tap water 2.3 L / m ² Purifying agent 20 ml / m ² (running processing conditions) The developing solution, fixing solution and washing water prepared according to the above-mentioned formulation were filled in an automatic developing machine LD-T1060 (manufactured by Dainippon Screen Mfg. Co., Ltd.). In this state, the light-sensitive material prepared above was processed at a rate of 30 m ² per day and run for one week. Evaluation was made on sensitivity, γ (gamma), haze, film stain, uneven development, stain in a washing tank, and drying property.

<Measurement of Sensitivity and γ> The obtained silver halide photosensitive material was subjected to wedge exposure using a semiconductor laser of 633 nm, and then processed with the above-mentioned processing solution and processing conditions to obtain sensitivity and γ. The sensitivities in the table indicate the sample Nos. 100
Is expressed as a relative value when the sensitivity is set to 100, and γ was obtained from the slope of a characteristic curve giving densities of 1.0 and 3.0.

<Haze> After the unexposed film was developed, the degree of devitrification of the film was visually evaluated on a 5-point scale.
Rank 5 is the best, and 3 or more is a practical level.

<Film Stain> After running for one week under the above conditions, the stain attached to the treated film was visually evaluated comprehensively. The evaluation was performed in five ranks, with rank 5 being the best and 3 or more being a level that could withstand practical use.

<Uneven Development> After running for one week under the above conditions, a film sample exposed to light so as to have a density of 1.0 was developed, and the uneven development of the obtained sample was visually evaluated. The evaluation was performed in five ranks, with rank 5 being the best and rank 3 or higher being a level that can withstand practical use.

<Stain of Washing Tank> The stain of the scale of the washing tank after running for one week under the above conditions was visually evaluated.

The evaluation is performed in five ranks. Rank 5 is the best, and rank 3 or higher is a level that can withstand practical use.

Rank 1: There is scale on the roller and the washing tank wall, and the scale is floating in the liquid. Rank 2: There is scale on the roller and the washing tank wall, but there is no suspended matter in the liquid. Rank 3: The roller is slimy, but no scale is attached to the washing tank wall. Rank 4: Part of the roller is slimy. Rank 5: No scale is generated.

<Evaluation of Drying Property> At the end of one week running under the above conditions, the drying property of the treated film was visually evaluated according to the following five grades.

Rank 5: Completely dry, warm film Rank 4: Completely dry, cool film Rank 3: Slightly wet out, but films are not sticky Rank 2: Partly Comes out wet, but the films stick slightly. Rank 1: More than half of the film is wet.

The obtained results are shown in Tables 2 and 3 below.

[0207]

[Table 2]

[0208]

[Table 3]

As can be seen from the table, the sample of the present invention has no sensitivity and gamma deterioration during running processing, and has little film stain, development unevenness, drying unevenness and washing tank stain, and a silver halide photographic material. It can be seen that a processing method can be obtained. The haze was also at a level that could withstand practical use.

Example 2 Emulsion A prepared in Example 1 was used. However, sensitizing dye S
Emulsion B was prepared by adding sensitizing dyes S-3 and S-4 in an amount of 1 × 10 ^-4 mol per mol of silver, instead of -1 and S-2.

The obtained emulsion B was coated with the first layer and the second layer simultaneously from the support side so as to have the following formulation per 1 m ² , and was cooled and set. On the other side, the following backing layer and backing protective layer were applied.

First layer (emulsion layer) Gelatin 1.0 g Silver halide emulsion B 3.3 g in terms of silver amount Hydrazine derivative H-34 0.015 g Hydrazine derivative H-39 0.020 g 5-Nitroindazole 0.01 g 2- Mercaptohypoxanthine 0.02 g Suspended polymer of 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, and 12.5% by weight of vinyl pivalinate 1.4g Polysaccharide Table 4 Quantity 4-mercapto-3, 5,6-fluorophthalic acid 0.05 g Sodium polystyrene sulfonate (average molecular weight: 500,000) 0.015 g The coating solution pH was 5.8.

Second layer (protective layer) Gelatin 0.90 g Polysaccharide Table 2 Nuclear nucleation promoter Na-21 0.20 g Colloidal silica 0.10 g Fungicide Z 0.005 g Sodium polyoxyethylene lauryl ether sulfonate 0 0.010 g sodium dihexylsulfosuccinate 0.015 g silica (average particle size 5 μm) 0.01 g silica (average particle size 8 μm) 0.015 g hardener (1) 0.15 g (backing layer) gelatin 1.8 g F-10 0.02 g F-4 0.05 g Suspension polymer of colloidal silica 75% by weight, vinyl acetate 12.5% by weight, and vinyl pivalinate 12.5% by weight 0.7 g Sodium polystyrene sulfonate 0.010 g Hardener (2) 0.05 g (backing protective layer) 1.8 g of gelatin Matting agent: having an average particle diameter of 3 μm Monodispersed polymethyl methacrylate 0.045 g Sodium polyoxyethylene lauryl ether sulfonate 0.005 g Sodium dihexyl sulfosuccinate 0.005 g Hardener (1) 0.15 g The obtained sample was treated in the same manner as in Example 1. At this time, the washing tank was modified into a three-stage countercurrent system and treated with the following washing liquid.

(Rinse solution) Pure water DTPA · 5Na Benzoisothiazoline salicylate Sodium sulfite 30 g Sodium chloride 53 g Dipropylene glycol 17 g Adjusted to pH 5.0 with sulfuric acid, and finished to 1 liter.

(Processing conditions) Temperature Processing time Developing 38 ° C for 15 seconds Fixing 37 ° C for 15 seconds Rinse with water (three-stage countercurrent washing tank) 25 ° C for 20 seconds Drying 50 ° C for 10 seconds (Replenishing amount of processing solution) Same as in Example 1. The replenisher for developing and fixing was replenished, and the rinse solution having the above formulation was directly replenished to the third washing tank under the following conditions.

Rinse water: Rinse solution 150 ml / m ² <Evaluation> The performance before and after the running was evaluated under the same conditions as in Example 1. The sensitivity and γ are the results of exposure through a 780 nm interference filter. The results obtained are shown in Table 4 below.

[0219]

[Table 4]

As is evident from Table 4, the sample of the present invention can obtain a sample with little film stain, development unevenness and washing tank stain.

[0219]

According to the present invention, there is provided a silver halide photographic light-sensitive material which is free from deterioration in sensitivity and gamma even during running processing, and has little film stain, uneven development, uneven drying, devitrification and stain in a washing tank. A processing method was obtained.

Claims (4)

[Claims] 1. A light-sensitive material comprising a light-sensitive material having a light-sensitive silver halide emulsion layer on one side of a support and a polysaccharide having a weight average molecular weight of 50,000 to 200,000 in at least one of the emulsion layers. Is treated with a developer containing a compound represented by the following formula (A) as a developing agent after imagewise exposure. Embedded image (Wherein R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group; ₁ and R ₂ may combine with each other to form a ring, k represents 0 or 1, and when k = 1, X represents —CO— or —CS—, and M ₁ and M ₂ are each hydrogen. Represents an atom or an alkali metal.) 2. The method according to claim 1, wherein at least one of the photosensitive materials on the emulsion layer side
The silver halide photographic material according to claim 1, wherein the layer contains an organic contrast agent. 3. A polysaccharide having a weight average molecular weight of 50,000 to 200,000 and an organic toning agent in at least one of the emulsion layers of a light-sensitive material having a light-sensitive silver halide emulsion layer on one side of a support. After the imagewise exposure of the photosensitive material containing the compound represented by the formula (A), the compound represented by the general formula (A) is used as a developing agent at a pH of 9.0 to 9.0.
A process for developing a silver halide photographic material, wherein the process is performed with a developing solution of 10.0. 4. A method according to claim 3, wherein the replenishing amount of the washing water is 10 to 500 ml / m ^2. .