JP3261641B2 - Processing method of silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to a method for processing a silver halide photographic light-sensitive material for printing plate making capable of obtaining a high-contrast image.

[0002]

2. Description of the Related Art A lith-type silver halide light-sensitive material is well known in the art for forming a photographic image having a very high contrast using a certain kind of silver halide. Since it cannot be performed, there is a disadvantage that it is unstable against air oxidation. For this reason, an image forming system which eliminates the instability of the image forming method by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. Requested, U.S. Pat.Nos. 4,166,742 and 4,168,977
Nos. 4,221,857, 4,224,401, 4,243,739,
A surface latent image type silver halide photographic material to which a specific hydrazine compound is added as disclosed in JP-A-4,272,606 and JP-A-4,311,781, containing 0.15 mol / l or more of a sulfite preservative at pH 11.0 to 12.3 There has been proposed a system for forming a negative image with a super-high contrast of more than 10 by processing with a developer having excellent storage stability. However, this new image forming system has a drawback in that the nucleation effect of the hydrazine compound causes the nucleation effect to reach the non-exposed area around the exposed area and the image is substantially enlarged, so that it is impossible to faithfully reproduce the image. Was. For this reason, for example, enlargement (expansion) and reduction (reduction) of a net photograph in the line drawing photographing process
In fields where particularly strict quality is required, such as quality or clearness of reproducibility, blank character quality in a return process, or scanner output in a color separation process, image quality is insufficient. Also, in this new image forming system, the pH of the developing solution is high, so that it is easily affected by air oxidation, and the preservability of the developing solution is not sufficient. So p
Highly active hydrazine compounds which harden even in a developer having a pH of around 10.5 are disclosed in U.S. Pat. Nos. 167,814, 4,988,604 and 4,994,
No. 346, JP-A-63-234244, JP-A-63-249838 and the like.

However, there has been a problem that the stability in running is deteriorated due to the low activity of the developer.
On the other hand, from the viewpoint of global environment conservation, reduction of photographic processing waste liquid is desired. However, in order to maintain stability, it is necessary to increase the replenishment amount of a developing solution to perform processing, and these improvements have been greatly desired. It has been greatly desired to improve this.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a high contrast even at a low developer pH, no sensitivity fluctuation in running, and a good replenishment rate and good processing even when rapid processing is performed. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which provides photographic performance.

[0005]

An object of the present invention is to provide a support having at least one silver halide emulsion layer on a support,
And a silver halide photographic material containing a hydrazine derivative in at least one hydrophilic colloid layer,
The maximum density of the blackened part when developed using the following developer
This is achieved by a method for processing a silver halide photographic light-sensitive material in which a light-sensitive material having a pH of 4.5 to 6.0 is processed with a developing solution having a pH of 9.0 to 11.0 having the following developing solution composition using an automatic developing machine.

[0006] 0.2 to 1.5 mol / liter as a carbonate is contained. At least one of the above general formulas [1] and [2] is contained. At least one of the above general formulas [3a], [3b] and [3c] One type is 1.0 × 10 ^-3 mol / L or more and 5.0 × 10 ^-3 mol
The content of the hydroquinone is 15 to 60 g / L. The content of the 3-pyrazoline developing agent is 0.1 to 10 g / L. The present invention will be specifically described below. As the hydrazine derivative used in the present invention, a compound represented by the following general formula [H] is used.

[0007]

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In the formula, A represents an aliphatic group, an aromatic group, or a heterocyclic group, and the aliphatic group represented by A preferably has 1 to 1 carbon atoms.
30, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-
A butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like, which are further substituted with suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group, a sulfonamide group, an acylamino group, Sulfamoyl group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] includes at least nitrogen, sulfur,
Hetero ring containing one hetero atom selected from oxygen is preferable, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring. No.

Particularly preferred as A are an aryl group and a heterocyclic group. The aryl group and the heterocyclic group of A are
It may have a substituent. A preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof 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.

B is specifically an acyl group (eg, formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc., alkylsulfonyl group (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (such as methanesulfinyl), an arylsulfinyl group (such as benzenesulfinyl), a carbamoyl group (such as methylcarbamoyl and phenylcarbamoyl), an alkoxycarbonyl group (such as methoxycarbonyl and methoxyethoxycarbonyl). For example, phenoxycarbonyl, etc.), a sulfamoyl group (eg, dimethylsulfamoyl), a sulfinamoyl group (eg, methylsulfoyl) Namoyl), an alkoxysulfonyl group (eg, methoxysulfonyl), a thioacyl group (eg, methylthiocarbonyl), a thiocarbamoyl group (eg, methylthiocarbamoyl), an oxalyl group (eg, a methyloxalyl group, an ethoxyzaryl group), or a heterocyclic group (eg, Pyridine ring, pyridinium ring, etc.).

As B, an acyl group or an oxalyl group is particularly preferred.

D ₁ and D ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Ethoxalyl).

In the present invention, when an amino group or an onium salt is contained in a part of the structure of A or B, the effect of preventing image enlargement is large, which is particularly preferable. The onium salt referred to in the present invention means a quaternary ammonium salt, a phosphonium salt, a sulfonium salt, and an iodonium salt.

When the light-sensitive material according to the present invention is processed with a developer having a pH of about 10.5, a hydrazine derivative represented by the following general formula [Ha] is particularly preferable because it easily exhibits high contrast.

[0018]

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In the formula, R ₄ is 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),
As these groups, those further substituted with a suitable substituent are preferably used. It is preferred that R ₄ contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. Or those containing a repeating structure of an alkyleneoxy unit described in JP-A-5-61143,
A structure containing a quaternary ammonium salt is also preferably used.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof 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. X represents various substituents which can be substituted, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different.

In the general formula [Ha], D ₁ and D ₂ have the same meaning as in the general formula [H]. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and particularly preferably a carbonyl group. R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group, or an oxycarbonyl group.

In the general formula [Ha], the most preferable R
₅ includes an oxycarbonyl group, a -COOR ₆ 'group and -CO
An N (R ₇ ′) (R ₈ ′) group (R ₆ ′ represents an alkynyl group or a saturated heterocyclic group, and R ₇ ′ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; A ring group, and R ₈ ′ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

In the general formula [Ha], it is preferable that a part of the structure of R ₄ , R ₅ and X contains an amino group or an onium group (quaternary ammonium salt, phosphonium salt, sulfonium salt, iodonium salt).

Next, specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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In addition, JP-A-4-76532 and JP-A-5-88288,
The hydrazine derivatives described in JP-A-5-61144, JP-A-2-1223 and JP-A-4-306664 are preferably used.

It is preferable to use a nucleation accelerator in order to effectively promote the contrast enhancement by hydrazine. Examples of the nucleation accelerator include those represented by the following general formula [Na] or [Nb].

[0031]

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In the general formula [Na], R ₁ , R ₂ , R ₃
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. R ₁ , R ₂ and R ₃ can form a ring. Particularly preferred are aliphatic secondary and 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, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

A compound represented by the following general formula [Na ₂ ] is a more preferable type of the general formula [Na].

[0034]

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In the general formula [Na ₂ ], R ₄ , R ₅ , R ₆
And R ₇ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, a substituted aryl group, a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Further, R ₄ and R ₅ and each set of R ₆ and R ₇ are not hydrogen atoms at the same time. X is O,
Represents S, Se and Te atoms. L ₁ and L ₂ represent a divalent linking group. Specific examples include a linking group comprising a combination of the groups shown below.

[0036] _{-CH 2 -, - CH = CH} -, - C 2 H 4 -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an aliphatic group or an aromatic group), - O -, - S -, - (CO) -, - (SO 2)
-, - CH ₂ N-addition, preferably contains at least one or more of the following structure in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ ) HCH ₂ O]-,-[O
_{C (CH 3) HCH 2 O} ] -, - [OCH 2 C (OH) HCH 2] - Specific examples of these nucleation accelerator (Na) below.

[0038]

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[0039]

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[0040]

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In addition, compounds described in JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 9 are also preferably used.

A compound represented by the following general formula [Nb] is a more preferable type of the general formula [Na].

[0043]

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In the formula, Ar is a substituted or unsubstituted aryl group,
Represents a heterocyclic group or an aromatic ring group. R represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, or aryl group. Ar and R may be linked by a linking group to form a ring.

These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. The molecular weight is preferably 120 or more, particularly preferably 300 or more, in order to impart a preferable resistance to diffusion groups. As the silver halide adsorbing group, those having the same meaning as those in formula [H] are preferably used.

Specific compounds of the general formula [Nb] include the following.

[0047]

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[0048]

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Next, the general formulas (1) and (2) will be described.

In the general formula (1), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group aryl group, an aralkyl group, a hydroxyl group, a mercapto group, a carboxyl group , A sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group. Where R ₁₁ or R ₁₂
At least one is a mercapto group or a droxyl group. R ₁₃ and R ₁₄ may combine with each other to form a saturated or unsaturated ring. The substituent in the compound has at least one mercapto group and one hydroxyl group.

In the general formula [2], R ₂₁ , R ₂₂ , R ₂₃ , R
₂₄ and R ₂₅ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, and an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbamoyl group or sulfamoyl group. R ₂₄ and R ₂₅ may combine with each other to form a saturated or unsaturated ring. The substituent in the compound has at least one mercapto group and one hydroxyl group. The above compound is 10-500m
Used in developer at g / l. Preferably 50-2
00 mg / liter.

Specific compounds are shown below, but are not limited to these compounds.

[0053]

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The general formulas [3a], [3b] and [3c] will be described. In the general formulas [3a], [3b] and [3c], Y ₁ represents a hydrogen atom, an alkali metal atom or a mercapto group, and R ₄ and Y ₂ each represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group. Group, hydroxyl group, mercapto group, sulfo group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, hydroxycarbonyl group, alkylcarbonyl group Or an alkoxycarbonyl group, wherein n is 1 to
Represents an integer of 4. General formulas [3a], [3b], [3c]
Typical examples represented by are shown below, but are not limited thereto.

3a-1 5-nitroindazole 3a-2 6-nitroindazole 3a-3 5-sulfindazole 3a-4 5-cyanoindazole 3a-5 6-nitroindazole 3a-6 5-mercaptoindazole 3b-1 benzotriazole 3b-2 5-methylbenzotriazole 3b-3 5-chlorobenzotriazole 3b-4 5-nitrobenzotriazole 3b-5 5-ethylbenzotriazole 3b-6 5-carboxybenzotriazole 3b-7 5-hydroxybenzotriazole 3b- 8 5-aminobenzotriazole 3b-9 5-sulfobenzotriazole 3b-10 5-cyanobenzotriazole 3b-11 5-methoxybenzotriazole 3b-12 5-ethoxybenzotriazole 3b-13 5-mercaptobenzotriazole 3c-1 benzimida 3c-2 5-sulfobenzimidazole 3c-3 5-methoxybenzimidazole 3c-4 5-chlorobenzimidazole 3c-5 5-nitrobenzimidazole 3c-6 2-mercapto-5-benzimidazole In the present invention, General formulas [3a], [3b], [3c]
If the in compound represented by adding to the developing solution, the amount added, the decrease in sensitivity is greater is greater than the amount in the developer 1l per ^{1.0 × 10 -3 mol~5.0 × 10 -3} mol. Preferably a developer 1l per ^{2.0 × 10 -3 mol~3.0 × 10 -3} mol.

The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, particularly preferably 0.5 to 0.1 μm. 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

[0057]

(Equation 1)

Is the particle size. Determined by algebraic or geometric mean based on the average grain projected area. For details on how to determine the average particle size, see Mees, James: The Theory of the Photographic Process (CEMe).
es & T.H.James: The theory of the photographic pro
cess), Third Edition, pp. 36-43 (1966 (Macmillan "Mcmi
llan ”company))).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, the narrower the particle size distribution is, the more preferable is 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.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen 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 grains used in the silver halide emulsion may be cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt or at least one of them during grain formation or growth. It is preferable to add a complex salt containing the following element. For details of the silver halide emulsion and its preparation method, see Research Disclosure No. 176 No. 17
643, pages 22-23 (December 1978). The halogen composition of the silver halide in the silver halide emulsion is not particularly limited, but is preferably silver chloride or silver chlorobromide (preferably 50 mol% or less of silver bromide).
Alternatively, it is silver chloroiodobromide. The silver halide emulsion may or may not be chemically sensitized. As methods for chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these methods may be used alone or in combination. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanines, polysulfide compounds and the like can be used in addition to the sulfur compounds contained in gelatin.

The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

As the reduction sensitizer, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used. The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog 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, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Benzenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzene Luffin acid, can be added to many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, 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, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be coated with various additives for various purposes such as a coating aid, antistatic, improvement of slipperiness, emulsification dispersion, prevention of adhesion and improvement of photographic properties. May be used.

It is advantageous to use gelatin as a 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-vinylpyrrolidone polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole polyvinylpyrazole and the like can be used as a single or copolymer and various kinds of synthetic hydrophilic polymer materials can be used. .

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

The photographic emulsion of the present invention 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 or the like alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate,
A polymer having a combination of sulfoalkyl (methacrylate, styrene sulfonic acid and the like) as a monomer component can be used.

The silver halide emulsion of the present invention is preferably spectrally sensitized with various sensitizing dyes. Preferred sensitizing dyes include Research Disclosure 176, 197
8th edition (17643) pp. 23-24 and 346 (1993) (346
85) Those described can be used. Various other additives are used in the photosensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, dyes and the like.

As these additives and the above-mentioned additives, those described in Research Disclosure No. 176 (supra), pages 22 to 31, and the like can be used.

In the light-sensitive material used in the present invention, the emulsion layer and the protective layer may be a single layer or a multilayer composed of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one or both sides of a flexible support usually used for the light-sensitive material. Those useful as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and polyethylene terephthalate.

The developing agent used in the present invention is mainly composed of hydroquinone. In addition, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5 -Dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like may be used in combination. When hydroquinone is used in combination with other hydroquinones, the molar ratio of the sulfite / hydroquinone is calculated with respect to the total number of moles of the hydroquinone.

The amount of hydroquinone used is 15 g to 60 g per liter of developer. Particularly preferred is 18 to 30 g.

The 3-pyrazolidone developing agents used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4-
Dimethyl 3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3
-Pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-
Pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc., each of which is 0.1 g to 10 g per liter of a developing solution.
g / l.

In addition, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, p-aminophenol-based developing agents
N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol may be used in combination.

In the present invention, silver sludge inhibitors are disclosed in JP-B-62-4702, JP-A-3-51844, JP-A-4-26838,
The compounds described in JP-A Nos. 4-362942 and 1-319031 are exemplified. These silver sludge inhibitors are preferably added to the developing solution, but may be added to the photosensitive material.

Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium metabisulfite, formaldehyde, and sodium bisulfite. Sulfite is
It is preferably at least 0.3 mol / l, particularly preferably at least 0.35 mol / l. The upper limit is up to 2.0 mol / l, especially 1.0 mol / l
Preferably up to liters.

The counter cation of the carbonate of the present invention is preferably an alkali metal or an alkaline earth metal. Particularly preferred cations are sodium and potassium. The carbonate concentration of the present invention is 0.2 to 0.15 mol / l, but if the concentration is too low, the developing solution is oxidized by oxygen in the air to affect photographic performance. On the other hand, if the carbonate concentration is too high, precipitation of the developer at a low temperature occurs, which affects photographic performance.

The preferable range is from 0.25 to 0.1 mol / l, and the developing performance is particularly stable from 0.3 to 0.1 mol / l.
0.6 mol / liter.

In the developing solution, if necessary, an alkaline agent (pH buffer such as sodium hydroxide or potassium hydroxide (for example, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.)), a dissolution aid ( For example, polyethylene glycols, esters thereof, alkanolamines, etc., sensitizers (eg, nonionic surfactants including polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, antifoggants (eg, Halides such as potassium bromide and sodium bromide, tetrazoles, thiazoles, etc., chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerators (eg, US Patent No. 2,304,025, compounds described in JP-B-47-45541, etc.), and hardeners (for example, glutaraldehyde or It can be added, such as sulfate adduct), or antifoaming agents.

The pH of the developing solution and the replenishing solution of the present invention is 9.0 to 9.0.
When it is less than 9.0, the preservability of the solution is remarkably good, but on the contrary, the developing activity is lowered and softened, which is not practical. A preferred range is 10.0 to 10.5. Also, the pH of the developing solution of the starting solution
And the pH of the developing replenisher may be the same or different.

The development temperature of the present invention is preferably in the range of 25 ° C. to 45 ° C., more preferably 30 ° C. to 38 ° C.

The replenishment amount of the present invention is a value obtained by developing a photosensitive material which has been exposed to 50% per unit area and developing it. When the blackening ratio is from 10% to 100%, the replenishment amount is determined according to the ratio. Is done. The present invention has a remarkable effect in 100 to 35
0 ml / m ² , and a preferred range is 150 to 250 ml / m ^2.
It is.

The compound of the present invention contains a developing agent in a light-sensitive material, for example, an emulsion layer, as a special type of development processing.
It may be used as an activator processing solution for processing a photosensitive material in an alkaline aqueous solution to perform development. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.
In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and others, and has a pH of usually 3.8 to 5.8.
Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents 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 and the like.

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

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid in a semi-kneaded state having a high viscosity. Further, it may be used after being diluted at the time of use, or may be used as it is.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence from the drying zone when processing using the automatic developing machine is 20 in order to reduce the developing time. It is preferably up to 120 seconds. 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. This is the time including the entire process time, that is, Dry to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 80 seconds.

[0091]

EXAMPLES The effects of the present invention will be specifically illustrated by examples.

Example 1 (Preparation of silver halide emulsion) Silver chloride 70 mol%, silver bromide 30
A silver nitrate grain was grown by mixing a silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr by a controlled double jet method so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pAg 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of Na ₂ RhCl ₆ was added per mol of silver during grain formation. Thereafter, desalting was performed using modified gelatin treated with phenyl isocyanate, and the following compounds [A], [B] and [C]
Add a fungicide consisting of a mixture of and ossein gelatin,
Redistributed. The resulting emulsion has an average particle size of 0.2 μm, coefficient of variation
The emulsion consisted of 10% cubic grains. 50 mg of S-1 and 4-mercapto-2,3,5,6-tetrafluorobenzoic acid per mol of silver were added to the emulsion thus obtained,
Further, 5 mg of chloroauric acid and 0.5 mg of sulfur per 1 mol of silver were added, and the mixture was chemically ripened at 60 ° C. for 80 minutes at pH 5.8 and pAg 7.0. After aging, 4-methyl-6-hydroxy-1,3,3a, 7-
900 mg of tetrazaindene was added per 1 mol of silver, and 300 mg of KI and 350 g of S-2 were further added.

(Preparation of silver halide photographic light-sensitive material) One of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) on the subbing layer, the amount of gelatin silver halide emulsion layer is 2.0 g / m ² of the following formulation (1), amount of silver 3.2 g / m ²
And a protective layer of the following formula (2) is further coated thereon so that the amount of gelatin becomes 1.5 g / m ^2, and on the other undercoat layer on the opposite side, According to the following formula (3), a backing layer is coated so that the amount of gelatin is 2.4 g / m ^2, and a protective layer having the following formula (4) is further coated thereon so that the amount of gelatin is 1 g / m ^2. To obtain a sample.

Formula (1) (Silver halide emulsion layer composition) Gelatin 2.0 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: Adenine 25 mg / m ² Stabilizer: 1-phenyl-5- Mercaptotetrazole 2 mg / m ² 5-Nitroindazole 10 mg / m ² Hydrazine derivative: H-12 3 × 10 ⁻⁵ mol / m ² Nucleation accelerator: Na-10 1 × 10 ⁻⁴ mol / m ² Polymer latex 1.0 g / M ² Compound K 45 mg / m ² Surfactant: saponin 0.1 g / m ² : Sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Hardener: 2-hydroxy-4,6-dichloro-1,3, 5-triazine 60 mg / m ² formulation (2) [Emulsion protective layer composition] Gelatin 1.5 g / m ² Matting agent: silica having an average particle size of 3.5 μm 20 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² surfactant S 2 mg / m ² promoter: hydroquinone 50 mg / m ² 1-phenylene 4-hydroxy-4'-methyl-pyrazolidone 5 mg / m ² Hardener: Formalin 45 mg / m ²

[0095]

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Formulation (3) (backing layer composition)

[0097]

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Gelatin 2.4 g / m ² Surfactant: sodium dodecylbenzenesulfonate 50 mg / m ² (4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: 50 mg / polymethyl methacrylate having an average particle size of 4.0 μm m ² surfactant: sodium sulfosuccinate and di (2-ethylhexyl) ester 10 mg / m ² hardener: glyoxal 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3,5-triazine 35 mg / m ^{2 The} obtained sample was prepared by modifying Konica's automatic developing machine GR-27 so as to meet the following processing conditions with a developing solution and a fixing solution having the following composition. (80% exposed) 200
The photographic performance and silver sludge were evaluated when a total of 800 sheets (running processing) were processed for a day.

Developer formulation Pure water 280 g Sodium sulfite 52 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 850 mg Diethyltriamine pentaacetic acid 1.5 g Boric acid 8 g Potassium bromide 4.5 g Potassium carbonate Amount shown in Table 1 Diethylene glycol 40g General formula [3a-3c] Amount shown in Table 1 Hydroquinone 20g 1-Phenyl-2-mercaptotetrazole 35mg Compound of general formula [1] Amount shown in Table 1 Compound of general formula [2] Amount shown in Table 1 Hydroxide Potassium Potassium pH in Table 1 Water was added at the time of use to make up to 1 liter.

Fixing solution formulation Ammonium thiosulfate (72.5% w / v aqueous solution) 200 ml pure water 140 g ethylenediaminetetraacetic acid disodium salt 100 mg sodium sulfite 25 g boric acid 10.0 g acetic acid (90% w / v aqueous solution) 15.5 g sodium acetate trihydrate 36.5 g tartaric acid (50% w / v aqueous solution) 6 ml aluminum sulfate (aqueous solution with 8.1% w / v content in terms of Al2O3) 25 ml sodium hydroxide (50% w / v aqueous solution) Amount to bring pH to 4.8 when using Water was added to make up to 1 liter.

(Processing conditions) (Process) (Temperature) (Time) (Amount of replenishment) Current image 35 ° C for 30 seconds Amount shown in Table 1 Fixation 33 ° C for 20 seconds 400ml / m ² Rinse with water Room temperature 15 seconds -Drying at 40 ° C for 15 seconds-(Sensitivity and gamma) The obtained sample was brought into close contact with a step wedge, exposed to 3200 ° K tungsten light for 3 seconds, developed and fixed, and the sensitivity was determined. The sensitivity is fog density + 4.
0 The reciprocal of the exposure amount that gives the transmission density
The relative value under each condition was determined as 100. Gamma was determined from the slope of the characteristic curve at transmission densities 1 to 3. Gamma needs to be 10 or more in practical use.

(Evaluation of black spots) An unexposed film was processed under the above-mentioned developing and fixing conditions, and
Observation was made with a double loupe to evaluate the degree of occurrence of black pots. A dot having no black spots in the halftone dots is assigned the highest rank "5", and ranks "4", "3", "2", "1" according to the degree of occurrence of black spots occurring in 2 mm x 2 mm. The evaluation was sequentially lowered. In the ranks "1" and "2", black spots are also large, which is not a practically preferable level.

(Evaluation of Silver Sludge) After the completion of running, the inside of the developing tank of the automatic developing machine was visually observed to evaluate the rank. Those having no blackened silver were ranked as the highest rank "5", and the ranks "4", "3", "2", and "1" were sequentially reduced according to the degree of occurrence, and evaluated. In addition, rank "1" and "2"
In this case, silver stains are remarkably generated on the processed film, and the level is not practical.

Table 1 shows the results.

[0105]

[Table 1]

From the results shown in Table 1, it is understood that the processing method of the present invention is excellent in running stability. In particular, it can be seen that this effect is surprisingly exhibited when the replenishment amount of development is reduced.

Example 2 (Preparation of silver halide emulsion) Silver chloride 68 mol%, silver bromide 30
An aqueous silver nitrate solution and a mixed aqueous solution of NaCl, KBr and KI were mixed by a controlled double jet method so that the silver halide composition was 2 mol% and 2 mol% of silver iodide to grow silver halide grains. At this time, mixing was performed at 36 ° C, pAg 7.8, and pH 3.0.
Performed under the conditions of, Na ₃ RhC _l6 per mole silver 2 × 10 ^-7 mol, and the K ₂ IrC _l6 8 × 10 ^-7 mol was added during grain formation. Thereafter, desalting and redispersion were performed in the same manner as in Example 1. The resulting emulsion was an emulsion composed of cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%. The emulsion thus obtained was added with 3 mg of chloroauric acid and 1.2 mg of sodium thiosulfate per mole of silver, and chemically ripened at 60 ° C. for 40 minutes at pH 5.4 and pAg 7.0. After aging, 4-methyl-6-hydroxy-1,3,3a, 7-
Add 900 mg of tetrazaindene per mole of silver, add 50 mg of 1-phenyl-5-mercaptotetrazole and add KI150
mg and 200 mg of S-3 were added.

Formulation (1) (Silver halide emulsion layer composition) Gelatin 1.8 g / m ² Silver halide emulsion Silver amount 3.5 g / m ² Antifoggant: 2-mercaptoxanthine 2 mg / m ² 5-methylbenzotriazole 10 mg / M ² hydrazine derivative: H-13 40 mg / m ² Nucleation accelerator: Na-10 20 mg / m ² Polymer latex 1.0 g / m ² Polyethylene glycol molecular weight 4000 30 mg / m ² Surfactant: saponin 0.1 g / m ² : Sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Hardener: 2-hydroxy-4,6-dichloro-1,3,5-triazine 60 mg / m ² Formula (2) [Emulsion protective layer composition] Gelatin 1.5 g / m ² matting agent: silica having an average particle diameter of 3.5 μm 20 mg / m ² surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² surfactant S 2 mg / m ² accelerator: hydroquinone 50 mg / m ² 1-phenyl-4-hydroxy-4'- Chirupirazoridon 5mg / m ² hardener: formalin 50mg / m ²

[0109]

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Formulation (3) (Backing layer composition) D-2 50 mg / m ² D-3 40 mg / m ² D-4 80 mg / m ² Gelatin 2.4 g / m ² Surfactant: sodium dodecylbenzenesulfonate 50 mg / m ² hardener: H-1

[0111]

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(4) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: polymethyl methacrylate 50 mg / m ^{2 having an} average particle size of 4.0 μm Surfactant: sodium sulfosuccinate and di (2-ethylhexyl) ester 10 mg / m ² hardener: bisvinylsulfomethyl ether 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3,5-triazine 35 mg / m ^{2 The} obtained sample was evaluated by the following method.

The same running as in Example 1 was performed. However, the exposure area of the processed film was 50% of the total area.

Table 2 shows the results.

[0115]

[Table 2]

From the results shown in Table 2, it is understood that the processing method of the present invention is excellent in running stability.

Example 3 The maximum density of the light-sensitive material was changed by adjusting the composition of silver chloride / silver bromide and the amount of coated silver in the silver halide grains of the light-sensitive material of Example 2 and the amount of hydroquinone in the developer. The same evaluation as in Example 2 was performed.

Table 3 shows the results. Example 2 experiment with developer
Nos. 48 to 50 were used.

[0119]

[Table 3]

From the results shown in Table 3, it can be seen that the running stability is remarkably excellent in the maximum density range of the light-sensitive material of the present invention.

[0121]

According to the present invention, there is provided a method for processing a silver halide photographic light-sensitive material which exhibits a high contrast even at a low developing solution pH, has no fluctuation in sensitivity during running, and provides good photographic performance even when the replenishing amount is reduced and rapid processing is carried out. Could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 5/29 G03C 1/06

Claims (3)

(57) [Claims] 1. A method for processing a silver halide photographic light-sensitive material comprising a support having at least one silver halide emulsion layer and at least one hydrophilic colloid layer containing a hydrazine derivative. A photosensitive material having a maximum density of a blackened portion of 4.5 to 6.0 when subjected to development processing using a developer containing a composition is developed using an automatic developing machine with a developer having a pH of 9.0 to 11.0 having the following developer composition. A method for processing a silver halide photographic light-sensitive material, characterized by processing. It contains 0.2 to 1.5 mol / l as a carbonate. It contains at least one of the following general formulas [1] and [2]. Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom,
Halogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, hydroxyl group, mercapto group, carboxyl group, sulfo group, phosphono group, amino group, nitro group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Or a sulfamoyl group. However, at least one of R _{11 and} R ₁₂ is a mercapto group or a hydroxyl group. R ₁₃ and R ₁₄ may combine with each other to form a saturated or unsaturated ring.
The substituent in the compound has at least one mercapto group and one hydroxyl group. [Chemical formula 2] [Wherein, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfo group , A phosphono group, an amino group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group. R ₂₄ and R ₂₅ may combine with each other to form a saturated or unsaturated ring. The substituent in the compound has at least one mercapto group and one hydroxyl group. ] At least one of the compounds represented by the following general formulas [3a], [3b], and [3c] contains not less than 1.0 × 10 ⁻³ mol / l and not more than 5.0 × 10 ⁻³ mol / l. 3] Wherein Y ₁ represents a hydrogen atom, an alkali metal atom or a mercapto group, and R ₄ and Y ₂ each represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, a mercapto group, a sulfo group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a hydroxycarbonyl group, an alkylcarbonyl group or an alkoxycarbonyl group, wherein n is 1 to
Represents an integer of 4. Containing 15 to 60 g / l of hydroquinones and 0.1 to 10 g / l of 3-pyrazolinic developing agent 2. A method for processing a silver halide photographic light-sensitive material, wherein the amount of replenishment for development in the processing according to claim 1 is 100 to 350 ml / m ² . 3. The processing method for a silver halide photographic material according to claim 1, wherein the total processing time of the developing, fixing, washing and drying steps is from 20 seconds to 120 seconds. The method for processing a silver halide photographic light-sensitive material described in the above.