JPH10153837A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method having ultrahigh contrast photographic characteristics and stability during long time running stability and capable of rapid processing and stable in storage stability of the photosensitive material by processing the photosensitive material containing a specified hydrazine derivative and a specified nucleation accelerator with a specified developing solution. SOLUTION: The silver halide photographic sensitive material containing the hydrazine derivative represented by formula I and the nucleation accelerator represented by formula II or the like and a golf compound and/or selenium compound is processed with the developing solution containing p-hydroxybenzene in an amount of 0.27-0.55mol/l and potassium ions in an amount of 0.01-1.3mol/l. In the formula, R1 is an aliphatic group or the like substituted by a sulfonamido group; both of A1 and A2 are each an H atom or one of them is an H atom and the other is an alkylsulfonyl group of the like. In formula II, each of R1 -R3 is an alkyl or aryl group of the like; (m) is an integer of 1-4; L is an m-valent organic group; (n) is an integer of 1-3; and X is an n-valent anion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 excellent in running stability and ultra-rapid processing.

[0002]

2. Description of the Related Art In a photoengraving process in the field of printing and duplication, a photosensitive material used in a plate collecting and returning process has an image portion and a non-image portion in order to improve reproduction of a line image and a halftone image. What has a so-called ultra-high contrast photographic characteristic having a clearly distinguished high blackening density has been demanded.
In particular, when a halftone dot image as a return document and a line image document are overlapped and exposed (so-called cut character image formation is performed), a silver halide photographic light-sensitive material (hereinafter referred to as a silver halide photographic material) having good line drawing reproduction performance (cut character quality). , Photosensitive materials).

[0003] As a method of imparting ultra-high contrast photographic characteristics to a photosensitive material, a method of incorporating a hydrazine derivative or a tetrazolium compound into the photosensitive material is known.

[0004] Recently, it has been desired to reduce the processing time in terms of work efficiency.

[0005] However, if the processing time is simply shortened, there arises a problem that good line drawing reproduction performance is lost.

[0006] As a technique that does not lose good line drawing reproduction performance even if the processing time is shortened, a combination of a hydrazine derivative having higher activity and a nucleation accelerator has been proposed. is not. Further, it has been found that in the ultra-rapid processing, when a hydrazine derivative is combined with a nucleation accelerator, a problem occurs that the long-term storage stability of the photosensitive material is reduced.

[0007]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a photographic material having ultra-high contrasting photographic characteristics and stability in long-term running, capable of ultra-rapid processing, An object of the present invention is to provide a method for processing a photosensitive material having excellent storage stability.

[0008]

The above objects of the present invention have been attained by the following means.

In a method for processing a light-sensitive material having a silver halide emulsion layer on a support, at least one hydrazine derivative represented by the following general formula [1] is added to the silver halide emulsion layer or another hydrophilic colloid layer. A silver halide photographic light-sensitive material containing a seed and at least one nucleation accelerator represented by the following general formulas [2] to [5] and containing at least one gold compound and / or selenium compound: , P
-0.27 to 0.55 mol / l of hydroxybenzene
And a developing solution containing 0.01 to 1.3 mol / l of potassium ions.

[0010]

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[In the formula, R ₁ represents an aliphatic group or an aromatic group substituted by a sulfonamide group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group. Represents a group, an amino group or a hydrazino group. A ₁ and A _{2 each} represent a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. ]

[0012]

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[Wherein R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic group, and these may further have a substituent. Good. m represents an integer of 1 to 4;
Represents an m-valent organic group bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L. ]

[0014]

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[In the formula, A represents an organic group for completing a heterocyclic ring. B and D each represent a divalent group.
R ₁ and R ₂ each represent an alkyl group or an aryl group;
R ₃ and R ₄ represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anionic group, but X is not necessary in the case of an internal salt. In a method for processing a light-sensitive material having a silver halide emulsion layer on a support, at least one of the silver halide emulsion layer and the other hydrophilic colloid layer may have the formula (1)
And at least one nucleation accelerator represented by the above general formulas [2] to [5], and at least one gold compound and / or selenium compound. The photosensitive material is treated with a developer containing 0.1 to 0.5 mol / l of a compound represented by the following general formula [6] and 0.01 to 1.3 mol / l of potassium ion. Processing method of photosensitive material.

[0016]

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[Wherein R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. And R ₁ and R ₂ may combine with each other to form a ring.

K represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. The processing method for a photosensitive material as described in the above item or item, wherein the total processing time of the automatic developing machine is 20 to 60 seconds.

When the developer replenishment rate is 100 to 200 ml /
m ² and the replenishing rate of the fixing solution is 100 to 400 ml /
method of processing the photographic material of the above terms or claim wherein a is m ^2.

Hereinafter, the present invention will be described specifically.

The hydrazine derivative used in the present invention is
A compound represented by the general formula [1].

In the formula, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, R ₂ represents a hydrogen atom,
Represents an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. A ₁ and A _{2 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula [1], the aliphatic group substituted by a sulfonamide group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms. It is a branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent.

In the general formula [1], the aromatic group substituted by the sulfonamide group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. here,
The unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. Among them, those containing a benzene ring are preferable. Among them, an aryl group is particularly preferred.

In the general formula [1], the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a benzene ring.
As the unsaturated heterocyclic group, a compound having a 5- or 6-membered ring containing at least one nitrogen, oxygen and sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, And a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic one, and the amino group is an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, or an aryl group. Amino groups are preferred.

R ₂ may be substituted. Preferred representative substituents include, for example, alkyl, alkenyl, alkynyl, aryl, heterocyclic, pyridinium, hydroxy, alkoxy, aryloxy and the like. Group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureide group, semicarbazide group, thiosemicarbazide group, urethane group, group having hydrazide structure, quaternary ammonium structure Group, alkyl or arylthio group, alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen Child, a cyano group, a phosphoric acid amide group,
Examples include a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure. Preferred substituents are straight-chain, branched or cyclic An alkyl group (preferably having 1 to 20 carbon atoms),
An aralkyl group (preferably having 1 to 4 carbon atoms in the alkyl moiety)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric amide group (Preferably having 1 to 3 carbon atoms)
0).

Among the groups represented by R ₂ , preferred are
A hydrogen atom, an alkyl group (eg, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (eg, an o-hydroxybenzyl group, etc.), Aryl group (for example, phenyl group, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom and a trifluoromethyl group. R ₂ is CO-
The R ₂ moiety may be split from the residual molecule to cause a cyclization reaction to generate a cyclic structure containing an atom of the —CO—R ₂ moiety. And those described in JP-A-63-29751.

A ₁ and A _{2 each} represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett having a sum of substituent constants of-
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ and A ₂ are most preferably hydrogen atoms.

The substituents of R ₁ and R _{2 in} the general formula [1] may be further substituted, and preferred examples include those exemplified as the substituent of R ₂ . Further, the substituent may be multiple-substituted, such as the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, and preferred examples also include those exemplified as the substituent of R ₂ .

R ₁ or R _{2 in} the general formula [1] may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group has a carbon number of 8 or more and is relatively inert to photographic properties. For example, an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl, a phenoxy group, an alkylphenoxy group, etc. You can choose from. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula [1] may have a group in which a group which enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include U.S. Pat. Nos. 4,385,108 and 4,459,347 such as alkylthio, arylthio, thiourea, heterocyclic thioamide, mercapto heterocyclic, and triazole groups.
And JP-A-59-195233 and JP-A-59-20023.
No. 1, No. 59-201045, No. 59-201046
Nos. 59-201047 and 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
The group described in 3-234246 is mentioned.

Particularly preferred hydrazine derivatives in the present invention are those wherein R ₁ is a ballast group, a group which promotes adsorption on the surface of silver halide grains, a group having a quaternary ammonium structure, or a phenyl group having an alkylthio group.
A hydrazine derivative in which R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position as a substituent). It should be noted that any combination of the options of R ₁ and R ₂ described above is possible, and particularly, R ₁ is a phenyl group having a group that promotes adsorption to the surface of silver halide grains or an alkylthio group, and R ₂ is a substituted alkyl group. The hydrazine derivative is preferred.

Specific examples of the compound represented by the general formula [1] are shown below. However, the present invention is not limited to the following compounds.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The hydrazine derivatives used in the present invention include, in addition to the above, RESEARCH DISC
LOSURE Item 23516 (November 1983, P. 346) and references cited therein, as well as JP-A-5-45761, JP-A-5-45762, and JP-A-5-4762.
Nos. 5763, 5-45764, 5-45765 and others can be used in combination.

In the present invention, the hydrazine derivative is preferably added in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, particularly 1 × 1 ^-6 mol, per mol of silver halide.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, and methylcellosolve. It can be used by dissolving it in, for example. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, the hydrazine derivative powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The nucleation accelerator used in the present invention is a compound represented by the general formulas [2], [3], [4] and [5].

The general formula [2] will be described in detail.

In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may have a substituent. Good. m represents an integer, L represents an m-valent organic group bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents L
May be connected.

Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te
rt-butyl group, octyl group, 2-ethylhexyl group,
Linear or branched alkyl groups such as dodecyl group, hexadecyl group and octadecyl group; aralkyl groups such as substituted and unsubstituted benzyl groups; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group, and phenyl Aryl groups such as a group, naphthyl group and phenanthryl group; alkenyl groups such as an allyl group, vinyl group and 5-hexenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group; pyridyl group, quinolyl group,
Furyl, imidazolyl, thiazolyl, thiadiazolyl, benzotriazolyl, benzothiazolyl,
Examples include a heterocyclic residue such as a morpholyl group, a pyrimidyl group, and a pyrrolidyl group. Examples of the substituents on these groups include, in addition to the groups represented by R ₁ , R ₂ , and R ₃ , a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a nitro group, 1,2, tertiary amino group, alkyl or aryl ether group, alkyl or aryl thioether group, carbonamido group, carbamoyl group, sulfonamido group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group , A cyano group or a carbonyl group. Examples of the group represented by L include, in addition to the groups having the same meanings as R ₁ , R ₂ and R ₃ , polymethylene such as trimethylene, tetramethylene, hexamethylene, pentamethylene, octamethylene and dodecamethylene. Group, phenylene group, biphenylene group, divalent aromatic group such as naphthylene group, polyvalent aliphatic group such as trimethylenemethyl group, tetramethylenemethyl group, phenylene-1,3,5-toluyl group, phenylene-1, Examples include a polyvalent aromatic group such as a 2,4,5-tetrayl group.

Examples of the anion represented by X include halogen ions such as chloride ion, bromine ion and iodine ion, carboxylate ions such as acetate ion, oxalate ion, fumarate ion and benzoate ion, and p-toluene. Sulfonate ions such as sulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate; sulfate ions; perchlorate ions; carbonate ions; and nitrate ions.

In the general formula [2], R ₁ , R ₂ and R ₃ are preferably a group having 20 or less carbon atoms, and particularly preferably an aryl group having 15 or less carbon atoms. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or an aryl group having 15 or less total carbon atoms. When m represents 2, 2 represented by L
Valent organic group is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, yet these groups and -CO- group, -O- group, -NR ₄ - group ( However, R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R _{3. When a} plurality of R ₄ are present in a molecule, they may be the same or different, and furthermore, it may be bonded to), - S- group, -SO- group, -SO ₂ -
It is a divalent group formed by combining groups. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less bonded to a P atom at its carbon atom. When m represents an integer of 2 or more, R ₁ in the molecule, R _2, R ₃ is present in plural, but a plurality of R _1, R _2, even if R ₃ is optionally substituted by one or more identical respectively good. n is preferably 1 or 2, m is preferably 1 or 2, X is R ₁ , R ₂ ,
It may combine with R ₃ or L to form an inner salt.

In order to be added as a part of the substituents of R ₁ , R ₂ and R ₃ to a specific layer of the light-sensitive material, it has a ballast group for decreasing the diffusivity or a group for promoting adsorption to silver halide. Is preferred. As the ballast group, those having a total number of carbon atoms of 15 or more and used in a silver halide photographic coupler are preferable. As the group for promoting adsorption to silver halide, thioamides (eg, thiourethane, thioureido, thioamide), mercaptos (eg, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-) are preferable. 1,
3,4-thiadiazole, 2-mercapto-1,3,4
Heterocyclic mercapto such as oxadiazole, alkyl mercapto, aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocyclic ring which forms imino silver (eg, benzotriazole).

Many of the compounds represented by the general formula [2] of the present invention are known and are commercially available as reagents. As a general synthesis method, there is a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method.

Specific examples of the compound represented by the general formula [2] are shown below, but the present invention is not limited to the following compounds.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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Next, the general formula [3], the general formula [4],
The general formula [5] will be described in more detail.

In the formula, A represents an organic group for completing a hetero ring, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a benzene ring may be condensed. . Preferred examples of A include a 5- to 6-membered ring, and more preferred examples include a pyridine ring, a quinoline ring and an isoquinoline ring. A may be substituted, and preferred substituents include
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.) A substituted or unsubstituted aryl group (for example, phenyl group, tolyl group, p-chlorophenyl group, furyl group,
Thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group) Group), an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. Particularly preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. 2 represented by B and D
The valence group is alkylene, arylene, alkenylene, -S
It is preferable that O ₂ —, —SO—, —O—, —S—, and —N (R ₆ ) — are used alone or in combination. Here, R ₆ represents an alkyl group, an aryl group, or a hydrogen atom.
As particularly preferred examples, B and D include those constituted by an alkylene, an arylene, -O-, -S- alone or in combination.

R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, and may be the same or different. The alkyl group may be substituted with a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom) and a substituted or unsubstituted aryl group (eg, phenyl, tolyl, p-chlorophenyl). , A furyl group, a thienyl group, a naphthyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), a sulfo group, a carboxy group, a hydroxy group, an alkoxy group (eg, Methoxy, ethoxy, etc.),
Represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. Particularly preferred examples include R ₁ and R ₂
Represents an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group.

R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents described above as the substituents for the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R _{4 each} have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and may be a linear or branched alkyl group or a cyclic alkyl group. The alkyl group may be substituted with a substituent, and examples of the substituent are selected from the substituents described above as the substituent for the alkyl group of R ₁ and R ₂ .
X represents an anionic group, but X is not necessary in the case of an internal salt. Examples of X represent chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonic acid ion, and oxalate.

As a part of the substituents of R ₃ , R ₄ and R ₅ ,
In order to be added to a specific layer of the light-sensitive material, it is preferable to have a ballast group for reducing diffusibility or a group for promoting adsorption to silver halide. As the ballast group, those having a total number of carbon atoms of 15 or more and used in a silver halide photographic coupler are preferable. As the group for promoting adsorption to silver halide, thioamides (eg, thiourethane, thioureido, thioamide), mercaptos (eg, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-) are preferable. 1,
3,4-thiadiazole, 2-mercapto-1,3,4
Heterocyclic mercapto such as oxadiazole, alkyl mercapto, aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocyclic ring which forms imino silver (eg, benzotriazole).

The compounds represented by the general formulas [3], [4] and [5] of the present invention can be easily synthesized by generally well-known methods (for example, Q
UART. Rev .. , 16, 163 (1962)).

Specific examples of the compounds represented by the general formulas [3], [4] and [5] are shown below. However,
The present invention is not limited to the following compounds.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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The amount of the compound represented by the general formula [2], the general formula [3], the general formula [4] or the general formula [5] of the present invention is not particularly limited. 1x
It is preferably contained in an amount of 10 ^-5 to 2 × 10 ^-2 mol,
In particular, the range of 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is a preferable addition amount. The nucleation accelerator particularly preferably used in the present invention is a compound represented by the general formula [4].

When the compounds of the general formulas [2], [3], [4] and [5] of the present invention are contained in a light-sensitive material, they may be water-soluble if they are water-soluble. As water-insoluble alcohols (eg, methanol, ethanol), esters (eg, ethyl acetate),
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ketones (for example, acetone). In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, a fine dispersion can be used by a method known as a solid dispersion method.

Next, in the developing solution of the present invention using p-hydroxybenzene as a developing agent, the amount of p-hydroxybenzene is 0.27 to 0.55 mol / l. When the amount of p-hydroxybenzene is less than 0.27 mol / l, running stability is deteriorated due to oxidative deterioration and fatigue deterioration due to oxygen in the air. Further, even if it is more than 0.55 mol / l, the running stability does not change much and the cost increases.

Further, when a large amount is added, there is a possibility that a developer component is precipitated, which is not preferable.

The gold compound of the present invention includes gold chloride, chloroauric acid, ammonium chloroaurate and the like.
The addition amount is 10 ^-5 to 10 ^-7 mol per mol of silver halide.
l is preferred. The addition may be carried out at any time from the time of particle formation to the preparation of the coating solution, but more preferably at the time of chemical ripening or the preparation of the coating solution. Also, it is preferable to add to the emulsion,
A hydrophilic colloid layer such as a protective layer may be used. When added during chemical ripening, it is preferable to use it in combination with thiosulfates, thioureas, thiazoles, rhodanines and the like.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
Preferably, the emulsion is used by stirring the emulsion at 40 ° C. or higher for a certain period of time. As the unstable selenium compound, compounds described in JP-B-44-15748 and JP-B-43-13489 are preferably used. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropionic acid, 2-selenobutyric acid), selenoesters,
Diacyl selenides, such as bis (3-chloro-2,
6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Further, as the non-labile selenium compound, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide,
Dialkyl diselenide, 2-selenazolidinedione, 2
-Selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas [7] and [8] are preferred.

[0085]

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In the formula, Z ₁ and Z ₂ may be the same or different, and include an alkyl group (eg, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group) and an alkenyl group (eg, , Vinyl, propenyl), aralkyl (eg, benzyl, phenethyl), aryl (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoyl) Phenyl group, α-
A naphthyl group), a heterocyclic group (eg, a pyridyl group, a thienyl group, a furyl group, an imidazolyl group), —NR ₁ (R ₂ ),
It represents the -OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R ₄
May be the same or different, and each represents an alkyl group,
Represents an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, an aralkyl group, the aryl group or heterocyclic group include the same examples as Z _1. Where R ₁ and R
₂ is a hydrogen atom or an acyl group (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl). You may.

In the general formula [7], preferably, Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the general formula [7], more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, -Alkyl-N-aryl-arylselenoamide.

[0088]

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each represents an aliphatic group, an aromatic group, a heterocyclic group, —OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ , -Se
R ₁₁ , X represents a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom , X represents a halogen atom.

In the general formula [8], Z ₃ , Z ₄ , Z ₅ ,
The aliphatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n -Propyl group, isopropyl group, t-butyl group,
n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group,
Aryl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula [8], Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-chlorophenyl,
Sulfophenyl group, α-naphthyl group, 4-methylphenyl group).

In the general formula [8], Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Group (for example, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula [8], cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and a halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom Or represents an iodine atom.

[0094] In the general formula (8), preferably Z _3, Z ₄ or Z ₅ represents an aliphatic group, an aromatic group, or -OR _7, R ₇
Represents an aliphatic group or an aromatic group.

In the general formula [8], a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate is more preferable.

Specific examples of the compounds represented by the general formulas [7] and [8] are shown below, but the present invention is not limited thereto.

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like. 1x per mole
It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher.
More preferably, it is 50 ° C. or more and 80 ° C. or less. pAg
And the pH is arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9. Selenium sensitization is more effective when performed in the presence of a silver halide solvent.

Next, the general formula [6] will be described.

In the general formula [6], a compound represented by the following general formula [6-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0105]

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In the general formula [6-a], R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, Represents a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁ represents O or S,
Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The alkyl group in the general formula [6] or the general formula [6-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkoxy group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, even if these groups have a substituent. Preferred substituents that can be substituted include a hydroxy group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom, preferably a sodium atom or a potassium atom.

The formula [6] or the formula [6]
Specific examples of the compound represented by -a] are shown below by showing the substituents of the respective general formulas, but the present invention is not limited thereto.

[0110]

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[0111]

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These compounds are typically ascorbic acid, or erythorbic acid and its salts (sodium, potassium, lithium salts, etc.), or derivatives derived therefrom, and are easily available as commercial products, Alternatively, it can be easily synthesized by a known synthesis method.

In the present invention, examples of the auxiliary developer exhibiting super additivity include 3-pyrazolidone derivatives and p-aminophenol derivatives. These compounds have heretofore been well known as auxiliary developing agents, and specific examples of these compounds will be shown below, but the present invention is not limited thereto.

1-phenyl-3-pyrazolidone 1-phenyl-4,4'-dimethyl-3-pyrazolidone 1-phenyl-4-methyl-4-hydroxymethyl-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 N-methyl-p-aminophenol N- (β-hydroxyethyl) -p-aminophenol N- (4-hydroxyphenyl) glycine 2-methyl-p-aminophenol p-benzylaminophenol The amount of the auxiliary developer exhibiting the synthesizing property is 0.005 to 0.8 mol / l, preferably 0.01 to 0.5 mol / l, as a development replenisher.

The potassium ion in the developer is from 0.01 to
1.3 mol / l. More preferably, 0.1-1.
0 mol / l. Potassium ions are added as preservatives, buffers and pH adjusters. For example, it is added as potassium sulfite, potassium carbonate, or potassium hydroxide.
When the amount of potassium ion exceeds 1.3 mol / l, the fixing speed is deteriorated, and the photographic characteristics are also deteriorated.

The developer preferably contains a sulfite and / or metabisulfite as a preservative. Examples of the sulfite and metabisulfite include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. 0.25 mol / l of sulfite
It is preferably at least 0.4 mol / l.

In the developing solution, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) , Dissolution aids (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent. The pH of the developer is preferably adjusted to 9.5 to 10.5.

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 other components, 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, such as aluminum chloride, aluminum sulfate and potassium alum.

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

The total processing time of the automatic processor refers to the time from when the leading end of the film is inserted into the automatic processor to when it comes out of the drying zone, that is, the so-called Dry to Dry time. Further, the total processing time includes all the steps necessary for processing the photosensitive material, and specifically includes the time required for the processing, such as development, fixing, bleaching, washing, stabilization, and drying. This is the time of dry to dry.

In the present invention, the dr
The processing time of y to Dry is 20 to 60 seconds.

The replenishing amounts of the developing solution and the fixing solution of the present invention are each 10 m ² per 1 m ² of the light-sensitive material in order to reduce the amount of waste liquid.
0 to 200 ml, preferably 100 to 400 ml, more preferably 150 to 200 ml and 150 to 30, respectively.
0 ml.

Examples of the silver halide of the silver halide emulsion used in the present invention include ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. Any used can be used. Silver chlorobromide or silver chloride containing 50 mol% or more of silver chloride is preferred.

Further, it was determined from the grain size of silver halide grains measured by electron micrograph (standard deviation of grains).
/ (Average particle size) × 100 has a variation coefficient of 15
% Or less are preferred.

The average grain size of silver halide is 0.7 μm.
m, particularly 0.3 to 0.1 μm
Is preferred. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details on how to find the average particle size, see James:
The Theory of the Photographic Process (edited by TH James: The theory of
the photographic processes
s), Third Edition, pp. 36-43 (1966, published by McMillan "Mcmillan").

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

In the production of a silver halide emulsion, a method of reacting a soluble silver salt with a soluble halide salt may be any of a normal mixing method, a simultaneous mixing method, a combination thereof and the like.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which the pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. A silver halide emulsion having a uniform grain size is obtained.

The silver halide grains used in the silver halide emulsion may be cadmium salt, zinc salt, lead salt, thallium salt, ruthenium salt, osmium salt, iridium in at least one of the steps of forming or growing the grains. It is preferable to add a Group 8 transition metal such as a salt or a rhodium salt, or a complex salt containing these elements. The preferable addition amount is 10 ^-8 mol or more and 10 ^-4 mol per mol of silver.
Mol or less. Particularly preferred transition metals include Rh
And Re.

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

The silver halide emulsion is preferably 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. A preferred chemical sensitization method is sulfur sensitization. Examples of the sulfur sensitizer include, in addition to a sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, rhodanines, and polysulfide compounds. Can be used.

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.

Examples of the reduction sensitizer include stannous salts, amines,
Formamidine, sulfinic acid, silane compounds, ascorbic acid and the like can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength by using a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus And a quinoline nucleus. These nuclei may be substituted on carbon atoms. As a core having a ketomethylene structure in the merocyanine dye or composite merocyanine dye,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5- to 6-membered heterocyclic ring such as a 2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, the aforementioned (RD) 176, 17643 (December, 1978), pp. 23-24, (RD) 34686 (19)
93), U.S. Patent Nos. 4,425,425 and 4,42.
No. 5,426 can be used. In the present invention, a sensitizing dye sensitive to light having a relatively long wavelength of 600 nm or more has a large effect of stabilizing the performance. Particularly effective sensitizing dyes include:
JP-A-6-194777, JP-A-6-194774
JP-A-6-242533, JP-A-5-11942
5, JP-A-5-158181, Japanese Patent Application No. 6-1955
No. 78 sensitizing dyes.

A method for dissolving or dispersing a sensitizing dye in an emulsion is described in US Pat. No. 3,482,981.
Nos. 3,585,195 and 3,469,987
Nos. 3,425,835 and 3,342,605
No., British Patent Nos. 1,271,329 and 1,038,0
Nos. 29 and 1,121,174; U.S. Pat.
Nos. 0,101 and 3,658,546 can be used. U.S. Pat. No. 3,485,634
The dissolution may be carried out using ultrasonic vibration described in the above item.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.
Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in (RD) 176, 17643 (Jan. 1978).
(Published in February) on page 23.

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 (eg, benzothiazoliums, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, etc.), mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines (for example, thioketo compounds such as oxazolinethione), azaindenes ( For example, triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3a, 7-
Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like, such as tetrazaindenes and pentazaindenes, can be added.

The photographic emulsion and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide] and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like) ), Mucohalogenic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin or DE 2,225,230, JP-A-1-19
8774, JP-A-5-61139, JP-A-8-62
758 or the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer may be coated with various known additives for various purposes such as coating aid, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties. Surfactants 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-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

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

The photographic emulsion used in the present invention may contain a dispersion of a water-insoluble or poorly-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 (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used.

The photosensitive material used in the invention preferably has at least one conductive layer on a support.
Typical methods for forming the conductive layer include a method using a water-soluble conductive polymer and a hydrophobic polymer curing agent, and a method using a metal oxide. For these methods, for example, the method described in JP-A-3-265842 can be used.

When the swelling percentage of the light-sensitive material processed in the present invention is 250% or less, 30% or more, preferably 180% or less, 50% or more, the effects of the present invention can be further exhibited. The swelling percentage here means that the photosensitive material is 3%.
After incubation at 8 ° C. and 50% RH for 3 days, the thickness (d0) of the hydrophilic colloid layer was measured, the photosensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and again the thickness (d0) of the hydrophilic colloid layer was measured. ) Is measured and the ratio of the swelling is represented from the swelled thickness. That is, swelling percentage = (d−d0) / d × 100.

Various techniques and additives known in the art can be used for the silver halide emulsion of the present invention. For example, the silver halide emulsion and the backing layer used in the present invention contain various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, ultraviolet absorbers. ,
An antiirradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, the silver halide emulsion and the backing layer may contain a polymer latex.

These additives are more specifically described in the above (R
D) Volume 176, 7643 (December 1978) and Ibid. 1
87, 8716 (November 1979), and the relevant portions are summarized below.

Types of Additives RD / 7643 RD / 8716 1. Chemical sensitizer page 23, page 648, right column Sensitivity increasing agent Same as above 3. 3. Spectral sensitizer page 23-24 page 648 right column Supersensitizer 頁 page 648 right column Brightener page 24 5. 5. Antifoggant page 24-25 page 649 6. Light absorber Filter dyes 25 to 26 pages 649 to UV absorbers 650 left side 7. 7. Stain inhibitor 25 page right column 650 page left to right 8. Hardener 26 pages 651 left side Binder page 26 Same as above 10. 10. Plasticizer, lubricant page 27, page 650, right column Coating aids, surfactants 26-27 Same as above 12. Antistatic agent, page 27 As above 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.

Examples of the support that can be used include cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass, and metal. it can.
These supports are subjected to a subbing process as required.

[0150]

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

Example 1 <Preparation of Emulsion> (Emulsion A) A solution containing sodium chloride kept at 40 ° C. and 3 × 10 ^-5 mol of sodium benzenethiosulfonate per mol of silver and having pH = 2.0 and 1.5. % Gelatin aqueous solution and an aqueous sodium chloride solution containing 3.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Ru (NO) Cl ₅ per mol of silver at a potential of 95 mV by a double jet method.
In 30 minutes, half of the silver content of the final particles was simultaneously added to prepare 0.12 μm of core particles. Thereafter, an aqueous silver nitrate solution was added to 10.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ R per mol of silver.
An aqueous sodium chloride solution containing uCl ₅ is
Min. To prepare silver chloride cubic grains having an average grain size of 0.15 μm (coefficient of variation: 12%).

Thereafter, the resultant was washed with water by a flocculation method well-known in the art to remove soluble salts, and gelatin was added thereto. Chemically aged, 4 × 10 ^-5 mol / AgXmo of gold or selenium
1 and sodium thiosulfate at 6 × 10 ⁻⁵ mol / AgXm
ol was added and chemically aged at 60 ° C. for 30 minutes. In addition, when the coating solution was prepared at the addition position, the material was not chemically aged, and the above amount of gold or selenium was added.

Compound-A and phenoxyethanol were used as preservatives in an amount of 50 mg / mol of silver, respectively.
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 10 ^-3 mol per mol of silver.

As final particles, pH = 5.7, pAg =
7.5, Ru = 7 × 10 ⁻⁵ mol / Ag mol.

<Preparation of Emulsion Layer Coating Solution and Its Coating>
The following compounds were added to the emulsions shown in Examples ² and ^3, and halogen was applied onto the following support including an undercoat layer so that the gelatin coating amount was 1.1 g / m ² and the silver coating amount was 2.5 g / m ^2. A silver halide emulsion layer was coated.

Gold or selenium compound 4 × 10 ⁻⁵ mol / AgX mol 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl- as shown in Tables 1, 2 and 3 N-methyltaurine sodium salt 35 mg / m ² Compound-B 10 mg / m ² Compound-C 20 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² Compound-D (hardener) 150 mg / m ² Further, a nucleation accelerator and a hydrazine derivative of the present invention were added so as to be applied as shown in Tables 1, 2, and 3.

An emulsion protective lower layer and upper layer were coated on the above emulsion layer.

<Preparation of Emulsion Protection Lower Layer Coating Solution and Its Coating>
The following compound in an aqueous gelatin solution was added, and the mixture was coated so that the coated amount of gelatin was 0.7 g / m ² .

Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² Sodium p-dodecylbenzenesulfonate 15 mg / m ² Compound-A 5 mg / m ² Compound-E 10 mg / m ² Compound-F 20 mg / m ² <Preparation of Emulsion Protection Upper Layer Coating Solution and Its Coating> The following compound was added to a gelatin aqueous solution, and the gelatin coating amount was 0.8 g / g.
It was applied as a m ^2.

Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 μ, pore diameter 25 °, surface area 700 m ² / g) amorphous silica mat Agent 10 mg / m ² (average particle size 2.5 μ, pore diameter 170 °, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound -A 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ² Then, the following conductive layer and back layer were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Solution for Conductive Layer and Its Coating> The following compound was added to an aqueous gelatin solution, and the coating amount of gelatin was 77
mg / m ² .

SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ² gelatin (Ca ⁺⁺ content 300 ppm) 77 mg / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² dihexyl-α -Sodium sulfosuccinate 40 mg / m ² Sodium polystyrene sulfonate 9 mg / m ² Compound-A 7 mg / m ² <Preparation of coating solution for back layer and its coating> The following compound was added to an aqueous gelatin solution, and the amount of gelatin applied was 2. 92 g / m
² was applied.

Gelatin (Ca ⁺⁺ content: 30 ppm) 2.92 g / m ² Polymethyl methacrylate fine particles (average particle size: 3.4 μ) 54 mg / m ² compound-H 140 mg / m ² compound-I 140 mg / m ² compound- J 40 mg / m ² Sodium dodecylbenzenesulfonate 75 mg / m ² Sodium dihexyl-α-sulfosuccinate 20 mg / m ² Compound-K 5 mg / m ² N-Perfluorooctanesulfonyl-N-propylglycine potadium 5 mg / m ² Sodium sulfate 50 mg / m ² Sodium acetate 85 mg / m ² (Support, undercoat layer) On both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), the first and second undercoat layers having the following composition are applied. did.

<One Layer of Undercoat Layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle diameter 3 μm) 0.05 g Compound-L 0.20 g Colloidal silica (Snowtex ZL; particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g with water added Further, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was dried. At a temperature of 180 ° C. for 2 minutes, a dry film thickness of 0.
It was applied to 9 μm.

<Second Layer of Undercoat Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-M 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-A 3.5 × 10 ^-3 g Acetic acid 0.2 g Water was added to 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm. Thus, samples 1 to
25 were produced.

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<Evaluation Method> [Photographic Properties] The sample thus obtained was exposed through an optical wedge with a P-627FM printer manufactured by Dainippon Screen, and processed under the following conditions, and the following items were evaluated.

1) Sensitivity (S): This is represented by the reciprocal of the exposure amount that gives a density of 4.0. It is shown as a relative value when 1 is set to 100. The running sensitivity was shown as the difference in sensitivity from the new solution after 30 m ² treatment with the replenishing amounts shown in Tables 1 and ² .

2) γ: (1.5-0.1) / ｛log
(Exposure to give a density of 1.5)-log (Exposure to give a density of 0.1)｝ However, when evaluating γ, the coating sample was treated with a replenishment amount of Tables 1 and ² by 30 m ² I went after running.

The sample was stored at 55 ° C. and 80% for 3 days.
This is a value obtained by performing the processing described in the evaluation of photographic characteristics after standing for a day.

[Fixing property] A sample having a size of 4
This is the number of sheets that have suffered a fixing defect when 10 sheets are processed at intervals.

<Developer 1 (using p-hydroxybenzene)> Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfite 40.0 g p-hydroxybenzene Amount shown in Tables 1 and 2 5-methylbenzotriazole 0.08 g 4- Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazalinone 0.04 g 2-mercaptobenzimidazole Sodium-5-sulfonate 0.15 g Sodium ersorbate 3.0 g Potassium hydroxide / sodium hydroxide and potassium carbonate / sodium carbonate were used to adjust the amount of potassium ions as shown in Tables 1 and 2, and the pH was 10.3. And finished to 1 liter.

<Developer 2 (using general formula [6])> Diethylenetriamine-pentaacetic acid 4.0 g Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate Potassium hydrogen carbonate shown in Tables 1 and 8 8 shown in Tables 1 and 8 -Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.5 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 2.7 g Compound of general formula [6] Finished. PH of the working solution is 9.8
It was 0.

<Fixing solution> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Glucon Sodium acid 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 g 1 liter with water 2 liters of water was added to 1 liter of the above fixing solution.

<Processing Conditions> As an automatic developing machine, a prototype machine having a developing and fixing tank capacity of 5 l each was used, and both the developing solution and the fixing solution were processed at 35 ° C.

Processing time Insert Development 2 seconds 4 seconds Fixing 15 seconds 30 seconds Rinsing 6 seconds 12 seconds Drying 11 seconds 22 seconds Total 45 seconds 90 seconds The results of the above evaluation are shown in Table 3.

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[Table 1]

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[Table 2]

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[Table 3]

As is clear from the results of Tables 1, 2 and 3, in the case of the present invention, the contrast is high, the running stability and the raw preservability are good, and the fixability is excellent. It can be seen that there is almost no deterioration in

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According to the present invention, it is possible to provide a method for processing a light-sensitive material which has ultra-high contrast photographic characteristics and stability in long-term running, is capable of transcendental quick processing, and is excellent in preservability of the light-sensitive material. did it.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/31 G03C 5/31 5/395 5/395

Claims (4)

[Claims] 1. A method for processing a silver halide photographic material having a silver halide emulsion layer on a support, wherein said silver halide emulsion layer or another hydrophilic colloid layer is represented by the following general formula [1]: At least one of the hydrazine derivatives
Silver halide photographic light-sensitive material containing a seed and at least one nucleation accelerator represented by the following general formulas [2] to [5] and containing at least one gold compound and / or selenium compound: From 0.27 to p-hydroxybenzene
0.55 mol / l and potassium ion from 0.01 to
A method for processing a silver halide photographic light-sensitive material, characterized by processing with a developer containing 1.3 mol / l. Embedded image [Wherein, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group. Or a hydrazino group. A ₁ , A ₂
Each represents a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. [Chemical formula 2] [Wherein, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
Represents a heterocyclic group, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents Is L
May be connected. [Chemical formula 3] [In the formula, A represents an organic group for completing a heterocycle. B and D each represent a divalent group. R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anionic group, but X is not necessary in the case of an internal salt. ] 2. A method for processing a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layer and another hydrophilic colloid layer has the general formula [1] ] And at least one nucleation accelerator represented by the general formulas [2] to [5], and at least one gold compound and / or selenium compound. Of a silver halide photographic material containing 0.1 to 0.5 mol / l of a compound represented by the following general formula [6] and 0.01 to 1.3 mol / l of potassium ion. A method for processing a silver halide photographic light-sensitive material, characterized by processing. Embedded image [Wherein, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group; ₁ and R ₂ may combine with each other to form a ring.
k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 3. The processing method for a silver halide photographic light-sensitive material according to claim 1, wherein the total processing time of the automatic developing machine is 20 to 60 seconds. 4. A developer replenishing amount of 100 to 200 ml / m.
² , and the replenishment rate of the fixing solution is 100 to 400 ml / m ²
4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein