JPH11271944A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high max. density and low fog contrasty good image quality and to improve the stain of a silver halide photographic sensitive material and contamination with fur, algae, a dye, etc., by supplying an oxidizing agent- contg. thick soln. or solid agent while mixing with water in a washing tank after a fixing step when the sensitive material contg. a specified spectral sensitizing dye is washed after it is imagewise exposed, developed and fixed. SOLUTION: When a silver halide photographic sensitive material contg. a spectral sensitizing dye represented by the formula is washed with oxidizing agent-contg. washing water after it is imagewise exposed, developed and fixed, an oxidizing agent-contg. thick soln. or solid agent is supplied while mixing with water in a washing tank after the fixing step. In the formula, each of R11 and R12 is alkyl, R13 is H, alkyl or alkoxy, D11 is a group of nonmetallic atoms required to complete a divalent ethylene bond, each of Z11 and Z12 is a group of nonmetallic atoms required to complete a 5- or 6-membered nitrogen- contg. heterocycle, X1 is an acid anion and (n) is 1 or 2.

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 material (hereinafter simply referred to as a "photosensitive material"), and more particularly to an image forming method using a black-and-white silver halide photographic material. The silver halide photographic light-sensitive material for printing plate making which has both high fog and little change with the passage of time is highly improved. The stains of the photosensitive material after processing, such as stains and dyes, are remarkably improved. The present invention also relates to a treatment method in which stains such as pigments and the like are significantly improved.

[0002]

2. Description of the Related Art A printing plate making operation includes a step of faithfully reproducing a halftone image. In order to produce an excellent printed matter, it is necessary that a target halftone dot is faithfully reproduced on a plate-making photosensitive material.

In recent years, in the field of printing plate making, there has been a demand for an improvement in dot quality. For example, in a method called FM screening which is constituted by a high-definition printing of 600 lines / inch or more or a random pattern of uniform minimum points. , 25μ
It is necessary to reproduce a minute point of m or less.

In the printing plate making process, in recent years, with the progress of digitization, a form of direct output from an image setter after editing on a system has become widespread.

[0005] Therefore, in addition to the generally required characteristics such as ultra-high contrast and little deterioration over time, a photographic material for plate making is particularly suitable for exposure with an image output machine equipped with a laser light source, a so-called plate making scanner. When performed, it is necessary that minute dots are faithfully reproduced.

[0006] By the way, the silver halide black-and-white photographic light-sensitive material is processed in the steps of developing, fixing, washing and drying using an automatic developing machine (hereinafter also referred to as an automatic developing machine) after imagewise exposure. However, when processing is performed using an automatic developing machine, dirt (Ag sludge, scale, algae, etc.) in the washing tank is likely to occur. Washing of the washing rack is necessary due to this dirt, and improvement of maintenance is desired in a demand for labor saving. A concentrated solution of the oxidizing agent is diluted with water and supplied to the washing tank as washing water. Purifying agent MB-1 (containing an oxidizing agent; anti-scale kit) manufactured by Co., Ltd. is marketed as a product. As a result, dirt (Ag sludge, water scale, algae, etc.) in the washing tank can be significantly reduced, and the maintenance performance has been improved.

[0007]

However, in such a system, a silver halide emulsion photographic material using a dye to spectrally sensitize the exposure light source of an image setter or a plate-making scanner so as to have sensitivity is used. In this case, a phenomenon in which the dye decolorized in the development and fixing processes gradually recovers with the elapse of time after the process and becomes a color stain is observed, and the amount of the dye used is restricted, which is a hindrance to high sensitivity.

Particularly, in a system for printing plate making, it is necessary to reduce the effects of halation and irradiation as much as possible, and this problem has been a major obstacle.

The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a high-contrast and good image quality with high maximum density and low fog even in a very short exposure such as laser exposure. In addition, it is an object of the present invention to provide an image forming method in which stains of a photosensitive material after processing are remarkably improved, and stains such as scales, algae, and pigments in a washing tank during processing are also significantly improved.

[0010]

An object of the present invention is to provide a silver halide photographic material containing at least one of the spectral sensitizing dyes represented by the above general formulas (1) to (3). After the post-development process and the fixing process, and further performing the washing process with the washing water containing the oxidizing agent, the concentrated solution or the solid agent containing the oxidizing agent is mixed with the water in the washing tank after the fixing process of the automatic developing machine. Image forming method, the capacity of the washing tank is less than 20 L, the oxidizing agent is hydrogen peroxide, the washing water contains a germicide, and the washing water is represented by the general formula (A). The washing water contains a compound selected from salicylic acid and its derivatives and salts thereof, and the washing water contains a silver sludge inhibitor represented by the general formula (B). Containing, The washing water contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions, and the silver halide photographic material is exposed by a printing plate making scanner or an exposure device of an imagesetter. Achieved by

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material processed in the present invention is spectrally sensitized by spectral sensitizing dyes represented by the general formulas (1) to (3).

In the general formulas (1) to (3), R ₁₁ and R
_The alkyl groups represented by ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ may be the same or different, and are preferably a methyl group having 1 to 8 carbon atoms, an ethyl group, a propyl group, It also includes those having a substituent such as a butyl group, a pentyl group and a heptyl group. Examples of the substituent include a carboxy group, a sulfo group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom,
A bromine atom, a hydroxy group, an alkoxycarbonyl group (having 8 or less carbon atoms, for example, a methoxycarbonyl group,
An ethoxycarbonyl group, a benzyloxycarbonyl group or the like), an alkoxy group (having 7 or less carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a benzyloxy group, etc.), an aryloxy group (a phenoxy group,
p-tolyloxy group, etc., acyloxy group (3 or less carbon atoms, for example, acetyloxy group, propionyloxy group, etc.), acyl group (8 or less carbon atoms, for example, acetyl group, propionyl group, benzoyl group, mesyl group) Carbamoyl group (carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.) , Aryl group (phenyl group, p
-Hydroxyphenyl group, p-carboxyphenyl group,
p-sulfophenyl group, α-naphthyl group, etc.). In the case of a substituted alkyl group, those having 6 or less carbon atoms in the alkyl portion are preferred. Further, it may have two or more substituents.

R ₂₃ , R ₂₄ and R ₃₃ each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group, and R ₃₃ is preferably a lower alkyl group or a benzyl group.

The alkyl group represented by W ₁ and W ₂ has 1 carbon atom.
To 18 are preferable, and especially 1 to 4.

D ₁₁ represents a group of nonmetallic atoms necessary to complete a divalent ethylene bond, for example, ethylene or triethylene, wherein the ethylene bond has one, two or more suitable groups, for example, It may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or the like.

The 5- or 6-membered nitrogen-containing heterocyclic nucleus completed by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ and Z ₃₁ includes a thiazole nucleus, [benzothiazole nucleus, 4-chlorobenzothiazole nucleus, 5-chlorobenzothiazole nucleus, 6-chlorobenzothiazole nucleus, 7-chlorobenzothiazole nucleus, 4-methylbenzothiazole nucleus, 6-methylbenzothiazole nucleus, 6-methylbenzothiazole nucleus, 5-bromobenzothiazole nucleus, 6 -Bromobenzothiazole nucleus, 5-iodobenzothiazole nucleus, 5-phenylbenzothiazole nucleus, 5-methoxybenzothiazole nucleus, 6
-Methoxybenzothiazole nucleus, 5-ethoxybenzothiazole nucleus, 5-carboxybenzothiazole nucleus, 5-
Ethoxycarbonylbenzothiazole nucleus, 5-phenethylbenzothiazole nucleus, 5-fluorobenzothiazole nucleus, 5-trifluoromethylbenzothiazole nucleus, 5,
6-dimethylbenzothiazole nucleus, 5-hydroxy-6
-Methylbenzothiazole nucleus, tetrahydrobenzothiazole nucleus, 4-phenylbenzothiazole nucleus, naphtho [2,1-d] thiazole nucleus, naphtho [1,2-d] thiazole nucleus, naphtho [2,3-d] thiazole nucleus , 5-
Methoxynaphtho [1,2-d] thiazole nucleus, 7-ethoxynaphtho [2,1-d] thiazole nucleus, 8-methoxynaphtho [2,1-d] thiazole nucleus, 5-methoxynaphtho [2,3-d Thiazole nucleus], selenazole nucleus [benzoselenazole nucleus, 5-chlorobenzoselenazole nucleus, 5-methoxybenzoselenazole nucleus, 5-methylbenzoselenazole nucleus, 5-hydroxybenzoselenazole nucleus, naphtho [2, 1-d] selenazole nucleus, naphtho [1,2-d] selenazole nucleus, etc., oxazole nucleus [benzoxazole nucleus, 5-chlorobenzoxazole nucleus, 5-methylbezooxazole nucleus, 5-bromobenzoxazole nucleus, 5 -Fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxybenzoxazole nucleus, - trifluoro benzoxazole nucleus, 5-hydroxy benzoxazole nucleus, 5-
Carboxybenzoxazole nucleus, 6-methylbenzoxazole nucleus, 6-chlorobenzoxazole nucleus, 6-
Methoxybenzoxazole nucleus, 6-hydroxybenzoxazole nucleus, 4,6-dimethylbenzoxazole nucleus, 5-ethoxybenzoxazole nucleus, naphtho [2,
1-d] oxazole nucleus, naphtho [1,2-d] oxazole nucleus, naphtho [2,3-d] oxazole nucleus and the like],
Quinoline nucleus [2-quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus, 6-methyl-2-
Quinoline nucleus, 8-fluoro-2-quinoline nucleus, 6-methoxy-2-quinoline nucleus, 6-hydroxy-2-quinoline nucleus, 8-chloro-2-quinoline nucleus, 8-fluoro-4-
Quinoline nucleus, etc.), 3,3-dialkylindolenine nucleus [3,3-dimethylindolenine nucleus, 3,3-diethylindolenine nucleus, 3,3-dimethyl-5-cyanoindolenine nucleus, 3,3-dimethyl -5-methoxyindolenine nucleus, 3,3-dimethyl-5-methylindolenine nucleus,
3,3-dimethyl-5-chloroindolenine nucleus, etc.], imidazole nucleus [1-methylbenzimidazole nucleus, 1-
Ethylbenzimidazole nucleus, 1-methyl-5-chlorobenzimidazole nucleus, 1-ethyl-5-chlorobenzimidazole nucleus, 1-methyl-5,6-dichlorobenzimidazole nucleus, 1-ethyl-5,6-dichlorobenzo Imidazole nucleus, 1-alkyl-5-methoxybenzimidazole nucleus, 1-methyl-5-cyanobenzimidazole nucleus, 1-ethyl-5-cyanobenzimidazole nucleus, 1-methyl-5-fluorobenzimidazole nucleus,
1-ethyl-5-fluorobenzimidazole nucleus, 1-
Phenyl-5,6-dichlorobenzimidazole nucleus, 1
Allyl-5,6-dichlorobenzimidazole nucleus, 1
-Allyl-5-chlorobenzimidazole nucleus, 1-phenylbenzimidazole nucleus, 1-phenyl-5-chlorobenzimidazole nucleus, 1-methyl-5-trifluoromethylbenzimidazole nucleus, 1-ethyl-5-trifluoromethyl Benzimidazole nucleus, 1-ethylnaphtho [1,2-d] imidazole nucleus, etc.], pyridine nucleus [pyridine nucleus, 5-methyl-2-pyridine nucleus, 3-methyl-4
-Pyridine nucleus and the like].

Of these, thiazole nuclei and oxazole nuclei are preferred, and benzothiazole nuclei, naphthothiazole nuclei, naphthoxazole nuclei and benzoxazole nuclei are particularly preferred.

The specific examples of the spectral sensitizing dyes represented by formulas (1) to (3) are shown below, but the present invention is not limited to these.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The oxidizing agent used in the present invention includes metal or non-metal oxides, oxyacids or salts thereof, peroxides, compounds containing organic acid systems, and the like. From the viewpoint of discharging to the drainage pipe, the oxyacid is preferably sulfuric acid, nitrous acid, nitric acid, hypochlorous acid and the like, and the peroxide is particularly preferably hydrogen peroxide solution, fentonic acid drug and the like. Most preferred is hydrogen peroxide.

It is preferable to dilute these oxidizing agents by replenishing them in a concentrated state or solid state in a washing tank. The timing of replenishment may be fixed replenishment every unit time, or replenishment may be performed according to the amount of processing by detecting the processing amount of the photosensitive material. The amount of the oxidizing agent to be added is in the range of モ ル to 10 molar equivalents, and particularly preferably １ ／ to 3 molar equivalents, with respect to the thiosulfate brought into the photosensitive material.

In the present invention, the capacity of the washing tank is preferably less than 20 L from the viewpoint of making the effects of the present invention uniform.

In the present invention, it is necessary to supply the concentrated liquid or solid agent containing the oxidizing agent while mixing it with water.
The term "while mixing with water" as used herein refers to a form in which the concentrated liquid and the water are separately supplied to the washing tank, and a form in which the water and the concentrated liquid are mixed immediately before being supplied to the washing tank. The term “immediately before” as used herein refers to a time after two minutes before the concentrated liquid and water are mixed and finally diluted to a concentration to be introduced into the washing tank.

The form in which the washing water obtained by diluting the oxidizing agent-containing concentrated liquid with water in the dilution tank and thereafter introducing the washing water into the washing tank is not included in the present invention.

In the present invention, it is a preferable embodiment that the oxidizing agent coexists with a compound such as a preservative or a bactericide so that the oxidizing agent works effectively (hereinafter, also referred to as a purifying agent).

Preservatives used in the present invention include, for example, phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline, salicylic acid, quinolinic acid and derivatives thereof, and salts thereof. And their salts.

The washing water of the present invention preferably contains a bactericide. The disinfectant may be any as long as it does not adversely affect the photographic performance.Specifically, thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothianoic acid compounds, acids Azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, chlorinated isocyanuric compounds There are various antibacterial agents and fungicides such as active halogen compounds such as sodium acid salts, chelating agents, sulfite compounds, and antibiotics represented by penicillin. Other L. E. FIG. Wes
t. “Water Quality Criteri
a "Photo. Sci. and Eng. Vol.
No. No. 6 (1965);
No. 542, No. 58-105145, No. 59-1265
Nos. 33, 55-111942, and 57-157
No.244 various anti-bacterial agents; described in "Bactericidal and Fungicide Chemistry" written by Hiroshi Horiguchi and published by Sankyo Publishing Co., Ltd. (Showa 57); Chemicals and the like as described above can be used.

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

1. 1. 5-chloro-2-methyl-4-isothiazolin-3-one 2. 2- (4-thiazolyl) -benzimidazole 3. methyl isothiocyanate 3,5-dichloro-4'-fluoro-thiocarbanilide 4-chloro-3,5-dimethylphenol 2,4,6-trichlorophenol 7. 7. Sodium dehydroacetate 8. Sulfanilamide 3,4,5-tribromosalicylanilide Potassium sorbate 11. 11. Benzalkonium chloride 1-Bromo-3-chloro-5,5-dimethylhydantoin Monochloroacetamide 14. Monobromoacetamide 15. Monoiodoacetamide 16. Benzimidazole 17. Cyclohexylphenol 18. 19. 2-octyl-isothiazolin-3-one Ethylenediaminetetraacetic acid 20. Nitrilo-N, N, N-trimethinephosphonic acid 21. 1-hydroxyethane-1,1-diphosphonic acid 18. ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 23. chlorinated sodium isocyanurate 2-methyl-4-isothiazolin-3-one 25. 10,10'-oxybisphenoxyarsine 1,2-Benzisothiazolin-3-one These exemplary compounds are described in U.S. Pat. No. 2,767,
172, 2,767,173, 2,767,1
74, 2,870,015, British Patent 848,
No. 130, French Patent No. 1,555,416
In each specification, the synthesis method and examples of application to other fields are described. There are also those that are commercially available, Predentol ON, Permachem PD, Topside 800,
Topside EG5, Topside 300, Topside 600 (from Permachem Asia), Fineside J-700 (Tokyo Fine Chemical), Proz
It can be obtained under the trade name of elGXL (manufactured by ICI).

When the above disinfectant is supplied into the washing water, the disinfectant 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.

The compound represented by the general formula (A) having a polyalkylene oxide chain used in the present invention is a compound obtained by adding propylene glycol as a hydrophobic group to ethylene oxide. In the present invention, the average molecular weight is 2000
~ 8500, polypropylene glycol (PPG) molecular weight of 1400-2400, ethylene oxide weight% in the total molecule of about 40-85% is preferable, and particularly, in the general formula, n + 1 is 150 and m is about 30. 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.

[0048]

[Table 1]

The addition amount of the compound having a polyalkylene oxide chain is 1 ppm to 1000 p based on 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%.

The washing water according to the present invention has the general formula (B)
It is preferable to contain a silver sludge inhibitor represented by

In the general formula (B), the alkyl group represented by Z ¹ preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms. And it may have a substituent in addition to the above substituents. The aromatic group represented by Z ¹ preferably has 6 to 3 carbon atoms.
It is a monocyclic or condensed ring and may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ¹ is preferably a monocyclic or fused ring having 1 to 32 carbon atoms,
It is a 5- or 6-membered ring having 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur, and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent. Among the compounds represented by the general formula (B), a compound in which Z ¹ is preferably a heterocyclic group having two or more nitrogen atoms.

In the formula, Z ¹ is a hydroxyl group, —SO ₃ M
Selected from the group consisting of a group, a —COOM group (where M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonium group. It is substituted by at least one or a substituent having at least one selected from this group. M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate). The ammonio group preferably has 20 or less carbon atoms and the substituent is a substituted or unsubstituted linear, branched or cyclic alkyl group (for example, methyl, ethyl, benzyl, ethoxypropyl, cyclohexyl) Etc.), substituted or unsubstituted phenyl groups,
Represents a naphthyl group.

Further, among the compounds represented by the general formula (B), more preferred are the compounds represented by the following general formula (Ba).

[0054]

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In the formula, Z is a group necessary for forming an unsaturated 5- or 6-membered heterocyclic ring having a nitrogen atom (for example, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine and the like). Yes, R ¹¹ , R
¹² is a hydrogen atom, -SM ¹ group, halogen atom, alkyl group (including those having a substituent), alkoxy group (including those having a substituent), hydroxyl group, -COOM
Group, -SO ₃ M group, an alkenyl group (including those having a substituent), amino group (including those having a substituent), (including those having a substituent) carbamoyl group, a phenyl group (the substituent and those in the containing) having, in the formula has at least one -SM group or thione group and a hydroxyl group, -COOM group, -SO ₃ M group, a substituted or unsubstituted amino group, a substituted or unsubstituted It has at least one substituent selected from the group consisting of substituted ammonium groups. In the formula, R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5- or 6-membered ring, and is preferably a nitrogen-containing heterocycle. M and M ¹ are the same as those in the general formula (B)
It is the same as M ¹ defined in a compound represented by. Preferably, Z is a group forming a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the aforementioned -SM group or thione group. As the substituent, a halogen atom ( For example, fluorine, chlorine, bromine, a lower alkyl group (including those having a substituent, preferably those having 5 or less carbon atoms such as a methyl group and an ethyl group), and a lower alkoxy group (including those having a substituent) Those having 5 or less carbon atoms, such as methoxy, ethoxy and butoxy, are preferred.),
Lower alkenyl groups (including those having a substituent, preferably those having 5 or less carbon atoms), carbamoyl groups, phenyl groups and the like are mentioned. Further, compounds represented by the following general formulas A to F in the general formula (Ba) are particularly preferable.

[0056]

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In the formula, each of R ¹ , R ² , R ³ , and R ⁴ represents a hydrogen atom, a —SM ₁ group, a halogen atom, a lower alkyl group (including those having a substituent; a methyl group, an ethyl group, etc. those having 5 or less carbon atoms is preferred.), including those with lower alkoxy group (substituent. those having 5 or less carbon atoms is preferred.), hydroxy group, -COOM _2, -SO ₃ M ₃ group,
A lower alkenyl group (including a group having a substituent, preferably a group having 5 or less carbon atoms), an amino group, a carbamoyl group and a phenyl group, at least one of which is a -SM ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different. In particular, a substituent other than -SM ₁ is hydroxy group, -COOM _2, -SO ₃ M ₃ group, it preferably has a water-soluble group such as an amino group. The amino group represented by R ¹ , R ² and R ³ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by the general formula (B) as a silver sludge inhibitor are shown below, but the present invention is not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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In the present invention, the amount of the compound represented by the general formula (B) is from 10 ^-6 to 10 per liter of washing water.
^-1 mol, more preferably 10 ^-5 to 10 ^-2.
Preferably it is molar.

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,
It was measured under conditions of ° C and an ionic strength of 0.2.
Specifically, maleic acid, glycolic acid, gluconic acid,
Organic acids such as glucoheptanoic acid, tartaric acid, citric acid, succinic acid, salicylic acid, ascorbic acid, and erythorbic acid; glycine; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid; and derivatives thereof. Salt. 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 0.1 per liter of washing water.
About 005 to 0.2 mol, preferably 0.005 to 0.5 mol.
Used in 1 mole.

In the image forming method of the present invention, various known light sources can be used. The effect of the present invention can be fully demonstrated in performing an extremely short exposure of 10 ^-6 seconds or less by a laser beam using an infrared laser light source, particularly in output by an image setter.

The image forming method of the present invention is preferably carried out in an automatic developing machine having at least four processes of development, fixing, washing (or stabilizing bath) 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 developer containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as developing agents, for example, US Pat. Nos. 2,688,548 and 2,68.
8,549, 3,022,168, 3,51
Nos. 2,981, 4,975,354 and 5,32
No. 6,816 can be used.

In the present invention, a developing agent of ascorbic acid or a derivative thereof and a 3-pyrazolidone (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3) are used.
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
Pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (o-aminophenol,
p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like, and dihydroxybenzenes substituted with a hydrophilic group (hydroquinone monosulfonate, hydroquinone monosulfone) It is more preferable to use a developing agent such as sodium acid salt or potassium 2,5-hydroquinonedisulfonate 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 and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

In the present invention, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid,
Alkanolamine) is preferably added.
As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less per 1 L,
More preferably, it is in the range of 0.75 mol or more and 1.5 mol or less. If necessary, dissolution aids (polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (nonionic surfactants including 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 Its alkali metal salts, nitrilotriacetates, polyphosphates, etc.) and development accelerators (U.S. Pat. No. 2,304,025, JP-B-47-45).
No. 541), a hardening agent (glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent. PH of developer is 7.5 or more and 1
Preferably, it is adjusted to less than 0.5. More preferably, the pH is 8.5 or more and 10.4 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.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (such as glutaraldehyde and a sulfurous acid adduct of glutaraldehyde) and the like.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent capable of softening water. A compound such as an agent can be included.

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. Particularly preferably, it is in the range of 0 to 0.05 mol. 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 concentration of acetate ions 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, but 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, particularly preferably 0.13 mol or less, per liter of the fixing solution, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The fixer includes citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. These salts include 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, citric acid, isocitric acid, malic acid, succinic acid and salts thereof are more preferred. Most preferred are malic acid and its salts.

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 means an aggregate of fine 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 solid processing agents, tablets are preferably used because of their high replenishment accuracy and simple handling.

In order 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 added to the surface of the temporarily formed photographic processing agent. Any means such as forming a coating layer by spraying can be adopted (Japanese Patent Application Nos. 2-135887 and 2-20).
No. 3165, No. 2-203166, No. 2-20316
No. 7, 2-203168 and 2-300409).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Further, the particle size distribution is
% Is preferably within 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, for example, in 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.

[0087] 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 a developer and a 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 processing agent can be solidified only for one part of a certain processing agent, but it is preferable that all the 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 the solid processing agent is divided into two or more agents, it is preferable that these 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, aluminum foil or aluminum vapor-deposited synthetic resin is used between the above-mentioned synthetic resin films.
It is more preferable to use various gas barrier films.

Further, in order to preserve the solid processing agent and prevent generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ² 24 hr · atm or less (at 20 ° C. and 65% RH),
More preferably, it is preferably 30 ml / m ² 24 hr · atm 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, 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 consisting 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 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.
5 × 10 ⁶ to 50 × 10 ⁶ kg / m ² is preferable, and
It is preferably from × 10 ^{6 to} 25 × 10 ⁶ kg / m ² , and particularly preferably from 1.5 × 10 ⁶ to 10 × 10 ⁶ kg / m ² . These tensile strengths are measured by a method described in JIS Z-1521.

The photographic processing agent packaged or bound or coated with a 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 metallized polymer films, and may be a composite material using these.

The moisture-proof packaging material is made of 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.

Specific examples of these are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial-produced 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 transmission 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 m per 1 m ² each
l. The replenishment amount for development is preferably 250 ml or less per m ² , more preferably 30 ml per m ^2.
~ 200 ml. The fixing replenishing amount and the developing replenishing amount referred to herein indicate the replenishing amounts. 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 processor, the total processing time (Dry) from the insertion of the leading edge of the film into the automatic processor until it comes out of the drying zone.
to Dry) is preferably 60 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, stabilization, and drying. Time including all process time, ie Dr
It is the time of y 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 15 to 50 seconds. Further, in order to stably process a large amount of photosensitive material of 100 m ² or more, the developing time is preferably 18 seconds or less and 2 seconds or more.

In order to remarkably exert the effects of the present invention, a heat transfer material of 60 ° C. or higher (for example, 60 ° C.
~ 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) Bottom left column to page 391 (5) Bottom left column (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".

It is preferable to employ the following techniques for the silver halide photographic light-sensitive material to be processed.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Page [0042] (2) Compound Having an Acid Group JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(17) page [0062] (4) Supersensitizer JP-A-6-347938 (3) page [0011]
(16) Page [0066] (5) Hydrazine derivative JP-A-7-114126 (23) Page [0111]
(6) Nucleation accelerator JP-A-7-114126, page (32) [0158]
-(36) [0169] (7) Tetrazolium compound JP-A-6-208188, (8) page [0059]-
(10) Page [0067] (8) Pyridinium Compound JP-A-7-110556, (5) Page [0028] to
(29) [0068] (9) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) page (10) SPS support JP-A-3-131843, pages 324 (2) to 327
(5) For other known additives, for example, Research Disclosure No. 17643 (December 1978
No.), and No. 18716 (November 1979) and the same No. 308119 (December 1989).

[0117]

EXAMPLES Example 1 <Preparation of a photosensitive material> (Preparation of a silver halide emulsion) An average diameter of 0.09 .mu.m composed of 70 mol% of silver chloride and the remainder of silver bromide by a double jet method.
m of silver chlorobromide core particles were prepared. K when mixing core particles
₃ Rh (NO) ₄ (H ₂ O) ₂ was added at 40 ° C. and p in the presence of 80 μg per mol of silver per mol of silver per mol of silver.
While maintaining H3.0 and the silver potential (EAg) at 165 mV, an aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed. The core particles were shelled using a double jet method with EAg reduced to 125 mV with saline. At that time, K
20 μg of ₃ RhCl ₆ was added to 1 mol of silver. Further, KI conversion was performed using silver iodide fine particles, and the resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (70 mol% silver chloride, iodine iodine) having an average diameter of 0.15 μm. (Consisting of 0.2 mol% of silver bromide and the remainder being silver bromide).

Next, JP-A-2-280139, 287
Desalting was performed using denatured gelatin G-8 (having the amino group in gelatin replaced with phenylcarbamyl) described on page (3). The EAg after desalting was 190 mV at 50 ° C.

To the obtained emulsion, potassium bromide (100 mg / mol silver) and citric acid were added to adjust the pH to 5.6.
EAg was adjusted to 123 mV, and sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added to silver 1
The reaction was performed by adding 170 mg to the mole. And
Inorganic sulfur (S ₈ ) compound dispersed in a solid (Seisin Enterprise Co., Ltd .; saponin added using PM-1200 and dispersed to an average of 0.5 μm) was added in an amount of 0.6 to 1 mol of silver.
mg and 6 mg of chloroauric acid, and chemically ripened at a temperature of 55 ° C until the maximum sensitivity was obtained. Then, at 40 ° C, 300 mg of a sensitizing dye shown in Table 2 was added, and 4-hydroxy-6 was added.
-Methyl-1,3,3a, 7-tetrazaindene was converted to silver 1
600 mg per mole, 20 mg of 1-phenyl-5-mercaptotetrazole and 300 mg of potassium iodide
After the addition, the pH was adjusted to 5.1 with citric acid.

(Preparation of a silver halide photographic light-sensitive material) Coating solutions of a gelatin undercoat layer of Formula 1 below, a silver halide emulsion layer of Formula 2 and a protective layer of Formula 3 below on a support, and vice versa A backing layer of the following formula 4 and a formula 5
Backing protective layer of 200m / m by curtain coating method
In, the emulsion layer side was simultaneously layer-coated at the speed of in, cooled and set.
The sample is cooled and set on both sides and dried on both sides simultaneously.
1 to 106 were obtained.

Formulation 1 (Gelatin undercoat layer) Gelatin 0.55 g / m ² 1-phenyl-5-mercaptotetrazole 2.0 mg / m ² Fungicide Z 0.5 mg / m ² Solid disperse dye 1-25 30 mg / m ² Prescription 2 (Composition of silver halide emulsion layer) Silver halide emulsion Silver amount 3.3 g / m ² equivalent amount Gelatin 1 g / m ² Hydrazine compound H1 10 mg / m ² Amine compound Na21 13 mg / m ² SA (sodium-iso -Amyl-n-decylsulfosuccinate) 1.7 mg / m ² 2-mercaptohypoxanthine 2 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² polymer latex L1 0.25 g / m ² polymer latex L6 1.0 g / m ² dye k 10 g / m ² gelatin coating solution pH using phthalated gelatin was 4.8.

Formulation 3 (Emulsion protective layer composition) Gelatin 0.6 g / m ² SA 12 mg / m ² Matting agent: spherical polymethyl methacrylate having an average particle diameter of 3.5 μm 15 mg / m ² average particle diameter 8 μm irregular silica 13 mg / m ² surfactant S1 30 mg / m ² slip agent (silicone oil) 10 mg / m ² compound a 50 mg / m ² polymer latex L6 0.3 g / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardness Membrane h4 60 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ² 2-Mercaptohypoxanthine 30 mg / m ² Formulation 4 (backing layer composition) Gelatin 1.5 g / m ² surfactant S1 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 100 m g / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Prescription 5 (backing protective layer) Gelatin 0.8 g / m ² Matting agent: Monodisperse polymethyl methacrylate 50 mg / m ^{2 with} average particle size of 5 μm Variable silica with average particle size of 3 μm 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant S1 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Compound a 50 mg / m ² hardener h2 20 mg / m ² sodium polystyrenesulfonate 10 mg / m

[0123]

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[0124]

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[0125]

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[0126]

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Preparation of solid processing agent <Preparation of solid developer kit> (for use in 10 liters of liquid) (Pretreatment of material) Hydroquinone was converted to MIKRO-PULVERIZER AP-B manufactured by Hosokawa Micron Corporation.
The powder was pulverized with a pulverizer at a mesh of 8 mm and a rotation speed of 25 Hz. 8-Mercaptoadenine was crushed by the same crusher at a mesh of 8 mm and a rotation speed of 50 Hz. KBr was crushed with the same crusher at a mesh of 8 mm and a rotation speed of 50 Hz.

(Mixing of Raw Materials) The following formulation was mixed for 10 minutes using a commercially available V-type mixer (capacity: 200 liters).

Hydroquinone (pulverized material) 65 kg Elbit N 16 kg Dimezone S 3.5 kg 8-mercaptoadenine (pulverized material) 0.3 kg DTPA. 5H 11 kg KBr (the above ground material) 6.5 kg Sorbitol 5 kg From arbitrary points (5 places) of the obtained mixture, 50 g samples were sampled and analyzed, and the concentration of each component was within ± 5% of the above prescribed value. , And were sufficiently homogeneously mixed.

(Molding) Using a compression granulator Briquetter BSS-IV manufactured by Shinto Kogyo Co., Ltd., the above mixture was subjected to a pocket shape of 5.0 mmΦ × 1.2 mm (Depth), a roller rotation speed of 20 rpm, Feeder rotation speed 50rpm
Molded at The obtained plate-like molded product was crushed by a classifier, and divided into 2.4 to 7.0 mm granules and 2.4 mm or less fine powder (one having a size of 7.0 mm or more was crushed). 2.4
The fine powder having a diameter of not more than mm was mixed with the above mixture and returned to the compression molding machine to be molded again. Thus, granules DA
Was obtained in an amount of about 95 kg.

(Preparation of Raw Materials) The following raw materials are prepared,
Pretreatment was performed.

<< Mixing of sodium sulfite / 1-phenyl-5-mercaptotetrazole / benzotriazole >> 18 g of 1-phenyl-5-mercaptotetrazole and 78 g of benzotriazole were dissolved in 400 ml of ethyl alcohol. The resulting solution was added dropwise in small amounts to 20 kg of sodium sulfite rotating with a mixer, and the rotation was continued until the solution was sufficiently dried. When sampling and analyzing 10 g each from an arbitrary point (5 places) of the obtained mixture,
1-phenyl-5mercaptotetrazole and benzotriazole were sufficiently homogeneously mixed. Let the obtained mixture be M-1.

<< potassium carbonate / sodium carbonate / anhydrous /
Mixing of lithium hydroxide and 1H ₂ O >> Potassium carbonate 56k using a commercially available V-type mixer (capacity 200 liters)
g, sodium carbonate 42 kg, lithium hydroxide 1H ₂
22 kg of O was mixed for 10 minutes. The resulting mixture is
-2.

(Packaging (10-liter solution for use)) A raw material mixture and a molded product were filled in a standing pouch in the following order and sealed with a heat sealer.

Mixture M-2 600 g (bottom layer) Mixture M-1 663.2 g (middle layer) Granules DA 399 g (top layer) This kit was dissolved in 10 liters of pure water.

<Preparation of solid fixing agent kit>
(Liter amount) (Pretreatment of material) Sodium 1-octanesulfonate was added to MIKRO-PULVERI manufactured by Hosokawa Micron Corporation.
With a ZER AP-B crusher, mesh 4 mm, rotation speed 6
Milled at 0 Hz.

(Mixing of Materials) A commercially available V-type mixer (capacity 2
00 liters) was mixed for 10 minutes.

91 kg of ammonium thiosulfate (10% sodium salt) 7.5 kg of sodium metabisulfite 1 kg of sodium 1-octanesulfonate (the above-mentioned ground product) was added to the obtained mixture and mixed for further 5 minutes.

(Molding) Using a compression granulator Briquetta BSS-IV manufactured by Shinto Kogyo Co., Ltd., the above mixture was used to form a pocket having a shape of 5.0 mmΦ × 1.2 mm (Depth) and a roller rotation speed of 30 rpm. , Feeder rotation speed 67rpm
Molded at The obtained plate-like molded product was crushed by a classifier, and divided into 2.4 to 7.0 mm granules and 2.4 mm or less fine powder (one having a size of 7.0 mm or more was crushed). 2.4
The fine powder having a diameter of not more than mm was mixed with the above mixture and returned to the compression molding machine to be molded again. Thus, about 95 kg of granule FA was obtained.

(Mixing of Materials) A commercially available V-type mixer (capacity 2
00 liters) was mixed for 10 minutes.

Sodium acetate / anhydrous 80 kg dehydrated aluminum sulfate 19 kg succinic acid 2 kg sodium gluconate 1 kg (molding) Shape 5.
Molding was performed at 0 mmΦ × 1.2 mm (Depth), at a roller rotation speed of 30 rpm, and at a feeder rotation speed of 67 rpm. The obtained plate-like molded product is crushed by a classifier, and
The powder was divided into 7.0 mm granules and 2.4 mm or less fine powder (fractions of 7.0 mm or more were crushed). The fine powder having a size of 2.4 mm or less was mixed with the above-mentioned mixture and returned to the compression molding machine to be molded. Approximately 95 kg of granules FB
Obtained.

(Packaging) The moldings were filled in the form of a standing pouch in the following order.

Granule FB 620 g (bottom layer) Granule FA 1610 g (top layer) This kit was made up to 10 liters with pure water. pH 5
It was adjusted to 4.70 with a 0% sulfuric acid aqueous solution and NaOH.

<Preparation of Purifier M1> Pure water 800 g per liter of concentrated liquid Salicylic acid 0.1 g 35% by weight hydrogen peroxide solution 171.5 g Pluronic F-68 3.1 g Hocside F-150 15 g DTPA · 5Na 10 g Pure water <Processing conditions> The processing was performed under the following processing conditions using automatic developing machines A and B having different tank capacities.

[0145] The tank capacity of the washing tank was 25 L for the automatic developing machine A and B for the automatic developing machine.
Is 18 L, and the oxidizing agent-containing concentrated solution (purifying agent M1) of the present invention is 20 ml per 1 m ² of the processed photosensitive material,
2.3 L of water are each supplied and mixed in the washing tank.

The obtained photosensitive material sample was used as a light source for 78
1. A laser sensitometer using a semiconductor laser of 0 nm
Perform step exposure while changing the light amount in 5 × 10 ^-7 seconds,
Processing was performed under the above conditions using an automatic developing machine shown in Table 2.

The obtained developed sample was subjected to the maximum blackening density (Dma) using a PDA-65 (Konica Digital Densitometer).
x) and fog density (Dmin) were measured and evaluated. Sensitivity is the sample No. The sensitivity at a density of 2.0 was 100
And expressed as relative sensitivity.

A 50% halftone dot image was output to each sample using FT-R1050 (manufactured by Dainippon Screen).
Processing was performed under the above conditions. Halftone dots of the obtained developed sample were observed with a 100-power loupe, and visual evaluation of image quality was performed in five stages. Rank 5 is the highest level, rank 3 is the lowest limit where practical problems do not occur, and rank 2 and lower are levels that have practical problems.

Further, stains and dye stains adhering to the processed film were visually evaluated in five steps. Rank 5 is the highest level, rank 3 is the lowest limit where practical problems do not occur, and rank 2 and lower are levels that have practical problems.

Table 2 shows the obtained results.

[0151]

[Table 2]

[0152]

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Example 2 <Preparation of Purifying Agents M2 to M5>
Except for 5Na, the purification agent M2 was exactly the same as M1.
Was prepared.

In addition, the purifying agent M2 is used to convert Pluronic F-6.
Purification agent M3 was prepared in exactly the same manner as M2 except for excluding 8.

Hereinafter, similarly, the purifying agent M3 is converted to the hocside F-
Purification agent M4 exactly like M3 except for 150
And purifying agent M5 by further removing salicylic acid from purifying agent M4.
Was produced respectively.

Using Samples 105 and 106, 100 m ^{2 of} each of the oxidizing agent-containing concentrated solutions M1 to M5 for washing water was used in the automatic developing machine B under the same conditions as in Example 1 as shown in Table 3. Was processed and stains and dye stains attached to the film after the treatment were visually evaluated in five stages. Rank 5 is the highest level, rank 3 is the lowest limit where practical problems do not occur, and rank 2 and lower are levels that have practical problems.

The stain on the wall surface of the washing tank of the automatic developing machine and the stain on the dye, and the stain on the squeeze roller were also visually evaluated in the same manner in five steps.

Table 3 also shows the obtained results.

[0159]

[Table 3]

[0160]

As demonstrated in the examples, the image forming method of the present invention realizes excellent image quality, and is excellent in that there is little stain on the film and stains on the automatic developing machine, especially on the dye stain.

Claims (10)

[Claims] 1. A silver halide photographic material containing at least one of spectral sensitizing dyes represented by the following general formulas (1) to (3): after imagewise exposure, developing and fixing, and further comprising an oxidizing agent. Forming a concentrated solution or a solid agent containing an oxidizing agent while mixing with water in a washing tank after a fixing step of an automatic developing machine when performing a washing treatment with washing water containing Method. Embedded image [In the formula, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , and R ₃₂ each represent an alkyl group. R ₁₃ represents a hydrogen atom, an alkyl group or an alkoxy group. R ₂₃ , R ₂₄ and R ₃₃ each represent a hydrogen atom,
Represents a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group. R ₂₅ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or Represents Here, W ₁ and W ₂ each represent an alkyl group or an aryl group, and may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. D ₁₁ represents a group of nonmetallic atoms necessary for completing a divalent ethylene bond. D ₁₂ and D ₁₃ represent a hydrogen atom. However, the D ₁₂ and D ₁₃ may form a divalent ethylene bond having the same meaning as D ₁₁ jointly. Z ₁₁ ,
Z ₁₂ , Z ₂₁ , Z ₂₂ and Z ₃₁ each represent a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. X
₁ , X ₂ and X ₃ each represent an acid anion. m and n represent 1 or 2. V is a lower alkyl group, an alkoxy group,
Represents a halogen atom. ] 2. The image forming method according to claim 1, wherein the capacity of the washing tank is less than 20 L. 3. The image forming method according to claim 1, wherein the oxidizing agent is hydrogen peroxide. 4. The image forming method according to claim 1, wherein said washing water contains a bactericide. 5. The image forming method according to claim 1, wherein the washing water contains a compound having a polyalkylene oxide chain represented by the following general formula (A). Formula _{(A) HO- (C 2 H} 4 O) n- (C 3 H 6 O) m- (C 2 H 4 O)
1H [wherein, n, m, and l represent positive integers. ] 6. The image forming method according to claim 1, wherein the washing water contains a compound selected from salicylic acid and its derivatives and salts thereof. 7. The image forming method according to claim 1, wherein the washing water contains a silver sludge inhibitor represented by the following general formula (B). . General formula (B) Z ¹ -SM ¹ [wherein, Z ¹ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ² group, a —COO
At least one selected from the group consisting of an M ² group (M ² represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, a substituted or unsubstituted ammonium group; And those substituted with at least one substituent selected from this group. M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate). ] 8. The method according to claim 1, wherein the washing water contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. 8. The image forming method according to item 7. 9. An image according to claim 1, wherein said silver halide photographic material is exposed to a semiconductor laser having a wavelength in an infrared region. Forming method. 10. The method according to claim 1, wherein the silver halide photographic light-sensitive material is exposed by a printing plate making scanner or an image setter exposing device.
9. The image forming method according to 6, 7, or 8.