JP2002169244A - Silver halide photographic sensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having good dot quality and excellent in original reproducibility (halftone reproducibility), to provide a silver halide photographic sensitive material having high practical Dmax, which is stable even when the amount of a developing solution replenished is reduced and to provide a processing system for the sensitive material. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support and containing at least one redox compound which releases a development inhibitor when oxidized, at least one hydrazine nucleus forming agent and a nucleus formation accelerator in the emulsion layer or at least one of other hydrophilic colloidal layers, the pKa of the redox compound and the pH of a developing solution used for processing have the relation of the expression (the pKa of the redox compound)<=(the pH of the developing solution)+1.0. A processing method for the sensitive material is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same. The present invention relates to a negative photosensitive material and an image forming method using the same.

[0002]

2. Description of the Related Art In a photoengraving process in the field of graphic arts, a continuous tone photographic image is converted into a so-called halftone dot image in which the density of the image is expressed by the size of a halftone dot area, and an image obtained by photographing a character or a line drawing. A method of making a printing original plate in combination with a printing method has been performed. The silver halide light-sensitive material used in such applications has ultra-high contrast photographic characteristics in which image parts and non-image parts are clearly distinguished in order to improve the reproducibility of characters, line drawings and halftone images. It has been required to have. In particular, in the reproducibility of halftone images when enlarging (expanding) or shrinking (reducing) halftone photographs, and the reproducibility of characters in originals with mixed Mincho / Gothic characters,
There has been a demand for an image forming method having a wide latitude that can reproduce not only ultra-high contrast photographic characteristics but also fine line drawing and faithful reproduction from a large dot to a small dot image. As a system that responds to the demand for a wide latitude, a silver halide photographic material composed of silver chlorobromide is processed with a hydroquinone developer having an extremely low effective concentration of sulfite ions to form an image having a high contrast. The squirrel developing method was known.
However, in this method, since the sulfite ion concentration in the developer is low, the developer is extremely unstable against air oxidation, and a large amount of replenishment is required to keep the activity of the solution stable.

As an image forming system which eliminates the instability of image formation in the lith developing system and is processed with a developing solution having good storage stability to obtain ultra-high contrast photographic characteristics, for example, US Pat. No. 4,166 No. 742, No. 4, 16
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
Nos. 269,922, 4,272,606, 4,311,781, 4,332,878, 4,618,574, 4,634,661,
Nos. 4,681,836 and 5,650,746. These include a surface latent image type silver halide photographic material to which a hydrazine derivative has been added and a pH of 11.0 to 12 containing a sulfurous acid preservative of 0.15 mol / L or more.
3 was treated with a developing solution containing hydroquinone / methol or hydroquinone / phenidone as a developing agent, and γ was 1
This is a system for forming a negative image having a super-high contrast exceeding zero. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and a high concentration of sulfite can be added to the developing solution. And improve dramatically. In order to sufficiently exhibit a super-high contrast image using a hydrazine derivative, it was necessary to perform processing with a developer having a pH of 11 or more, usually 11.5 or more. Although it was possible to increase the stability of the developer by using a high-concentration sulfurous acid preservative, it was necessary to use a developer having a high pH value as described above in order to obtain a super-hard photographic image. In addition, even if a preservative is present, the developer is liable to be oxidized by air and is unstable. Therefore, in order to further improve the stability, attempts have been made to realize a super-high contrast image at a lower pH.

For example, US Pat. No. 4,269,929 (JP-A-61-267759) and US Pat.
7,452 (JP-A-60-179934), U.S. Pat. Nos. 5,104,769 and 4,798,780, JP-A-1-179939, JP-A-1-179940, U.S. Pat. 604, 4,994,365,
JP-A-8-272023 discloses a method using a highly active hydrazine derivative and a nucleation accelerator in order to obtain a super-high contrast image using a developer having a pH of less than 11.0. In the processing by such an image forming system,
Although sharp halftone dot quality and processing stability were improved,
Further improvements were required from the viewpoint of original reproducibility and wide exposure latitude.

As methods for improving the original reproducibility, JP-A-3-39952, JP-A-3-174143, and JP-A-3-174143.
In 19647, a super-high contrast silver halide photosensitive material having a multilayer structure comprising a layer containing a redox compound which releases a development inhibitor by oxidation and a photosensitive silver halide emulsion layer containing a hydrazine derivative is treated with a developing solution having a pH of 11 or more. A method for doing so is disclosed. Also, JP-A-4-122926,
JP-A-7-43867 and JP-A-7-261310 disclose a double-layered photosensitive composition comprising a layer containing a redox compound which releases a development inhibitor by oxidation and a photosensitive silver halide emulsion layer containing a hydrazine derivative and a nucleation accelerator. PH 1
A method for forming an image with improved original reproducibility by processing with one or less developer is disclosed. However, this method has a problem that the practical skill Dmax is low and the practical skill Dmax is further reduced when the replenishment amount of the developer is reduced.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to provide good dot quality and original reproducibility (halftone reproducibility).
To provide an excellent silver halide photographic light-sensitive material. A second object of the present invention is to provide a silver halide photographic light-sensitive material having a high practical Dmax and a stable practical Dmax even when the replenishing amount of the developer is reduced, and a processing system therefor. .

[0007]

The above object has been achieved by the following inventions. (1) A redox compound having at least one silver halide emulsion layer on a support and releasing at least one kind of a development inhibitor by being oxidized in at least one of the emulsion layer and at least one hydrophilic colloid layer. , And at least one hydrazine nucleating agent, and a silver halide photographic material containing a nucleation accelerator, wherein the pKa of the redox compound is related to the pH of a developer used for processing by the following formula. A silver halide photographic light-sensitive material, characterized in that: Redox compound pKa ≦ pH value of developer + 1.0 (2) The nucleation accelerator is represented by the following general formula (a), (b),
The silver halide photographic material as described in the item (1), which is represented by (c), (d), (e) or (f).

[0008]

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In the general formula (a), Q ₁ represents a nitrogen atom or a phosphorus atom, and R ₁₀₀ , R ₁₁₀ and R ₁₂₀ each represent an aliphatic group, an aromatic group or a heterocyclic group, which are bonded to each other. An annular structure may be formed. M represents an m _10- valent organic group bonded to Q ₁ ⁺ at a carbon atom contained in M;
Here m ₁₀ represents an integer of 1 to 4. In the general formula (b), the general formula (c) or the general formula (d), A ₁ , A ₂ , A
₃ , A ₄ and A ₅ each represent an organic residue for completing an unsaturated heterocycle containing a quaternized nitrogen atom;
₁₀ and L ₂₀ represent a divalent linking group, and R ₁₁₁ , R ₂₂₂ , R
₃₃₃ represents a substituent. The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c) or the general formula (d) has a repeating unit of an ethyleneoxy group or a propyleneoxy group in a molecule of 20 units in total. Although it has more than one, it may be substituted over a plurality of places.

[0010]

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In the general formula (e), Q ₂ represents a nitrogen atom or a phosphorus atom. R ₂₀₀ , R ₂₁₀ and R ₂₂₀ represent the same groups as R ₁₀₀ , R ₁₁₀ and R _{120 in the} general formula (a). In formula (f), A ₆ represents a group having the same meaning as A ₁ or A ₂ in formula (b). However, the nitrogen-containing unsaturated hetero ring formed by A ₆ may have a substituent, but does not have a primary hydroxyl group on the substituent. In the general formulas (e) and (f), L ₃₀ represents an alkylene group, and Y represents —C (= O) —
Or —SO ₂ —, and L ₄₀ represents a divalent linking group containing at least one hydrophilic group. In the general formulas (a) to (f), X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when an anion group is separately formed in the molecule to form an inner salt with Q ₁ ⁺ , Q ₂ ⁺ or N ⁺ , X ^n- is not necessary. (3) After the image exposure, the silver halide photographic material described in the above items (1) and (2) is developed with a developing solution having a pH of 9.0 to 11.0, and the replenishing amount of the developing solution is 1 square meter. A method for processing a silver halide photographic light-sensitive material, wherein the amount is 250 ml or less.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The redox compound of the present invention which can release a development inhibitor by being oxidized will be described. There is no particular limitation as long as the pKa of the redox compound used in the present invention matches the following formula. Redox compound pKa ≦ developing solution pH value + 1.0 For example, when the pH of a developing solution in which a silver halide photographic light-sensitive material containing the redox compound of the present invention is developed is 10.6,
The pKa of the redox compound is 11.6 or less. Here, the pKa value is a pKa value determined by a pH meter according to an acid-base rule using a 1: 1 mixed solution of acetonitrile and water as a solvent. The lower limit of the pKa value is practically 8.0 or more, more preferably 8.5 or more, from the viewpoint of the stability of the compound. Further, the pH value of the developer refers to the pH value of the Fr (fresh) solution that has not been treated at all.

The redox compound will be described in more detail. The redox group of the redox compound is preferably a hydroquinone, a catechol, a naphthohydroquinone group, an aminophenol, a pyrazolidone, a hydrazine, a hydroxylamine, or a reductone, and more preferably a hydrazine.
The hydrazine of the present invention used as a redox compound capable of releasing a development inhibitor by being oxidized is preferably represented by the general formula (R-1), the general formula (R-2) or the general formula (R-3). Is represented. The compound represented by formula (R-1) is particularly preferred.

[0014]

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In the formula, R ₁ represents an aliphatic group or an aromatic group. G ₁ represents a —CO— group, a —COCO— group, a —CS— group,
Represents a —C (＝ NG ₂ R ₂ ) — group, a —SO— group, a —SO ₂ — group or a —P (O) (G ₂ R ₂ ) — group. G ₂ represents a simple bond, —O— group, —S— group or —N (R ₂ ) — group, R ₂ represents a group defined as R ₁ or a hydrogen atom, and a plurality of R _{When two} are present they can be the same or different. A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is A ₁
Synonymous or -CH ₂ CH (A ₄₎ - represents the (Time) _t -PUG. A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfonyl group or -G ₁ -G ₂ -R ₁ (in this case, two -G ₁ in the molecule
-G ₂ -R ₁ may be the same or different. ). Time represents a divalent linking group, and t represents 0 or 1
Represents PUG represents a development inhibitor.

Formulas (R-1), (R-2) and (R-
3) will be described in more detail. The general formula (R-
In 1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly has a straight or branched chain having 1 to 20 carbon atoms. Or a cyclic alkyl group. This alkyl group may have a substituent. In formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an aromatic heterocyclic group. Here, the aromatic heterocyclic group may be condensed with an aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring and the like. Among them, those containing a benzene ring are preferred. Particularly preferred as R ₁ is an aryl group. The aryl group or aromatic heterocyclic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido, thioureido, isothioureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl , An acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a carboxyl group, a phosphoric acid amide group, and the like. Preferred substituents are straight-chain, branched or cyclic alkyl Group (preferably having 1 carbon atom)
To 20), an aralkyl group (preferably having 7 to 7 carbon atoms)
30), an alkoxy group (preferably having 1 to 3 carbon atoms)
0), a substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with an alkyl group), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 carbon atom) To 40), a sulfamoylamino group (preferably having 1 to 40 carbon atoms), a phosphoric amide group (preferably having 1 to 40 carbon atoms) and the like.

Formulas (R-1), (R-2) and (R-
G ₁ in 3) is preferably a —CO— group or a —SO ₂ — group, and most preferably a —CO— group. A ₁ and A ₂ are preferably hydrogen atoms, and A ₃ is a hydrogen atom, —CH ₂ —CH (A
₄ )-(Time) _t -PUG is preferred.

Formulas (R-1), (R-2) and (R-
In 3), Time represents a divalent linking group.
It may have a tuning adjustment function. Represented by Time
Divalent linking group is released from the oxidized form of the redox nucleus.
One or more steps from Time-PUG
Represents a group capable of releasing PUG through the reaction of Tim
Examples of the divalent linking group represented by e
No. 4,248,962 (Japanese Patent Laid-Open No. 54-145,135)
No.) etc., the intramolecular closure of the p-nitrophenoxy derivative
Release of PUG by a ring reaction; US Pat.
310,612 (JP-A-55-53,330) and
In the molecule after ring cleavage described in JP-A-H11-4358 and JP-A-4,358,525, etc.
Release of PUG by ring closure reaction; U.S. Pat.
No. 4,330,617, No. 4,446,216, No.
4,483,919, JP-A-59-121,328
Of succinic acid monoester or its analogs described in
Formation of acid anhydride by intramolecular ring closure of ruboxyl group
With release of PUG; US Pat. No. 4,40
9,323, 4,421,845, Research
Disclosure Magazine No. 21, 228 (December 1981)
), U.S. Pat. No. 4,416,977 (Japanese Unexamined Patent Publication No.
135,944), JP-A-58-209,736,
Aryloxy groups described in JP-A-58-209,738 and the like
Or through a double bond conjugated to a heterocyclic oxy group.
Produce quinomonomethane or its analogs by child transfer
To release PUG; US Patent No. 4,420,5
No. 54 (JP-A-57-136,640) and JP-A-57-136,640.
-135,945, 57-188,035, 5
Nos. 8-98,728 and 58-209,737
Of the portion having an enamine structure of the nitrogen-containing heterocycle described in
Releases PUG from the γ-position of enamine by electron transfer
A nitrogen-containing heterocyclic compound described in JP-A-57-56,837.
By electron transfer to the carbonyl group conjugated to the ring nitrogen atom
PUG is released by an intramolecular ring closure reaction of the generated oxy group.
No. 4,146,396 (Japanese Unexamined Patent Publication No.
52-90932), JP-A-59-93,442,
JP-A-59-75475, JP-A-60-249148
And aldehydes described in JP-A-60-249149
Which release PUG with formation of a class;
146,828, 57-179,842, 59
-Decarboxylation of carboxyl group described in No. 104,641
With accompanying release of PUG; -O-COOCR_aR_b-PUG
(R _a, R_bRepresents a monovalent group. Decarburized)
Releases PUG with acid and subsequent formation of aldehydes
The isocyanate described in JP-A-60-7,429
Release of PUG with formation of naat; US Patent
Oxidation of color developer described in 4,438,193 and the like
Releases PUG by coupling reaction with body
And so on. These are represented by Time
For specific examples of divalent linking groups, see JP-A-61-23.
No. 6,549, JP-A-1-269,936, 3-6
No. 7,246 and the like.

Formulas (R-1), (R-2) and (R-
In 3), PUG is a development inhibitor. PUG has a hetero atom, and has a general formula (R-1) via the hetero atom;
It is bonded to other parts of the compound represented by (R-2) and (R-3). Examples of commonly known development inhibitors are described, for example, in The James of The Theory of the Photographic Process (THJames).
Theoryof the Photographic Process), 4th edition, 19
1977, published by Macmillan, 396 pages to 39
9 and on pages 56 to 69 of JP-A-3-67,246. These development inhibitors may have a substituent. Useful substituents include, for example, mercapto, nitro, carboxyl, sulfo, phosphono, hydroxy, alkyl, aralkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, amino groups An acylamino group, a sulfonylamino group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a halogen atom, a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, Examples include an acyloxy group, a carbonamido group, a sulfonamido group, a phosphonamido group and the like, and these groups may be further substituted.

The development inhibitor represented by PUG used in the present invention is preferably a compound that suppresses nucleation and development. Nucleation Nucleation Infectious Development is a new development chemistry used for the image forming method of the Fujifilm GRANDEX system (Fuji Photo Film Co., Ltd. and Kodak Ultratec system (Eastman Kodak Co., Ltd.). As described in The Photographic Society of Japan, Vol. 52, No. 5, pp. 390-394 (1989) and "Journal of Photographic Science", Vol. 35, p. A nucleation active species is generated based on the development process by the main agent and the cross-oxidation of the oxidizing product of the developing agent and the nucleating agent generated by the development process, and the surrounding unexposed to weakly exposed halogenation by the active species. Nucleation of silver particles
Consists of two processes. Therefore, the whole development process
Since it consists of the sum of the normal development process and the nucleation development process, in addition to the usual development inhibitor conventionally known as a development inhibitor, a compound that newly suppresses the nucleation transmission development process has an inhibitory effect. Can demonstrate. The latter is referred to herein as a nucleation development inhibitor. The development inhibitor represented by PUG used in the present invention is preferably a nucleation development inhibitor. As a compound acting as a nucleation development inhibitor, a conventionally known development inhibitor is also effective. Particularly effective compounds are compounds having at least one or more nitro group or nitroso group, pyridine and pyrazine. , Quinoline, quinoxaline,
Alternatively, a compound having a nitrogen-containing heterocyclic skeleton such as phenazine, particularly a compound having a 6-membered nitrogen-containing heteroaromatic ring skeleton, a compound having an N-halogen bond, quinones, tetrazoliums, amine oxides, azoxy compounds, and oxidizing ability And coordination compounds. Among them, compounds having a nitro group and compounds having a pyridine skeleton are particularly effective.

These nucleating development inhibitors may have substituents, and the properties of the substituents, for example, electron-withdrawing, electron-donating, hydrophobic, hydrophilic, electric charges, and adsorptivity to silver halide Various properties such as the strength of development suppression and the ease of diffusion can be controlled by such properties. Examples of useful substituents include those listed above as examples of substituents of general development inhibitors. Specific examples of these nucleation development inhibitors useful in the present invention are described in detail in JP-A-4-136839, JP-A-2665693, and the like.
Japanese Patent No. 2631162, Japanese Patent No. 2725088, Japanese Patent Application Laid-Open No. 4-283743, and Japanese Patent No. 2779712
Ind. Further, as another series of nucleation development inhibitors, an adsorptive compound to silver halide grains having an anionic charged group or a dissociable group capable of dissociating in a developer to generate an anionic charge is also effective. These are also described in detail in Japanese Patent No. 2694373.

Formulas (R-1), (R-2) and (R-
In 3), R ₁ or Time is a ballast group commonly used in immobile photographic additives such as couplers or a general formula (R-1), (R-2) or (R-3). A group which promotes the adsorption of the compound represented by silver halide may be incorporated. The ballast group has the general formula (R
-1), an organic group giving a molecular weight sufficient to prevent the compounds represented by (R-2) and (R-3) from substantially diffusing into another layer or the processing solution, A linear or branched alkyl group (or alkylene group), an alkoxy group (or alkyleneoxy group), an alkylamino group (or alkyleneamino group), an alkylthio group or an alkylthio group having a carbon number, Alkyl group, aryl group, heterocyclic group, -CO
-, -CONH-, -NHCONH-, -NHCSNH
_{-, - SO 2 NH -,} - represents a combination consisting of groups of the group NHSO ₂ NH- like. The ballast group is preferably a group in which an alkyl group having 6 to 30 carbon atoms is combined, and particularly preferably a group in which an alkyl group having 7 to 24 carbon atoms is combined.

Specific examples of the group which promotes adsorption to silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- A cyclic thioamide group such as imidazoline-2-thione, a chain thioamide group, an aliphatic mercapto group, an aromatic mercapto group, a heterocyclic mercapto group (when a nitrogen atom is next to a carbon atom to which a -SH group is bonded, This is synonymous with the cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz Imidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, ox 5- or 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon such as sol, oxazoline, thiadiazole, oxathiazole, triazine and azaindene, and heterocyclic quaternary such as benzimidazolinium And the like. These may be further substituted with a suitable substituent. Examples of the substituent include those described as the substituent of R ₁ .

Formulas (R-1), (R-2) and (R-
In 3), R ₁ or Time may include a specific group described below therein. That is, a cationic group (specifically, a group containing a quaternary ammonium group, a group containing a quaternized phosphorus atom, or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, etc.), ethylene A group containing a repeating unit of an oxy group or a propyleneoxy group, (alkyl,
Aryl or heterocycle) a thio group, a dissociative group (a group or partial structure having a low acidity proton which can be dissociated in an alkaline developer, or a salt thereof,
Specifically, for example, carboxyl group / -COOH, sulfo group / -SO ₃ H, a phosphonic acid group / -PO ₃ H, phosphoric acid group /
-OPO ₃ H, hydroxy group / -OH group, mercapto group / -SH, -SO ₂ NH ₂ group, N- substituted sulfonamide group / -SO ₂ NH- group, -CONHSO ₂ - group, -SO ₂
NHSO ₂ — group, —CONHCO— group, active methylene group, —NH— group existing in a nitrogen-containing heterocyclic group, or a salt thereof). The compound represented by the general formula (R-1) also has a hydrazine group / —N (A ₁ )
A multimer with respect to the partial structure of —N (A ₂ ) —
To a hexamer).

The compounds represented by the following general formulas (R-1) and (R-
Specific examples of the compounds represented by 2) and (R-3) are listed, but the present invention is not limited thereto.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

Among the compounds represented by the general formula (R-1) of the present invention, more preferred compounds are those represented by the following general formula (1a)
It is represented by

[0035]

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In the general formula (1a), PUGN represents a development inhibitor and represents a nitrogen-containing heterocyclic residue bonded to an adjacent carbonyl group by a nitrogen atom. However, the heterocyclic group represents a heterocyclic group having at least one nitro group as a substituent thereof, directly or indirectly, and capable of giving a pKa value of 9 to 11. ph represents a phenyl group and has at least one dissociative group directly or indirectly as a substituent. Z represents a substituent capable of substituting on a benzene ring, and p represents 0
Represents an integer of 1 to 4.

Next, the compound represented by formula (1a) of the present invention will be described in detail. In the general formula (1a)
Z represents any substituent that can be substituted on the benzene ring.
Examples of the optional substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (including an aralkyl group, a cycloalkyl group, and an active methine group), an alkenyl group, an alkynyl group, and an aryl group. Group, heterocyclic group, quaternized nitrogen-containing heterocyclic group (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acyl group Rucarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy unit), aryloxy group , A heterocyclic oxy group, Siloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone An amide group, a ureido group, a thioureido group, an imide group, an (alkoxy or aryloxy) carbonylamino group,
Sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto Group, (alkyl, aryl or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, sulfo group Or a salt thereof, a group having a phosphate amide or phosphate ester structure, and the like.

These substituents may be further substituted with these substituents. The phenyl group represented by ph in the general formula (1a) has at least one dissociative group directly or indirectly as a substituent. Here, the dissociable group means a group or a partial structure having a low acidity proton which can be dissociated in an alkaline developer, or a salt thereof. Specifically, for example, a carboxy group (—COOH), phosphonic acid group (-PO ₃ H), phosphoric acid group (-OPO ₃ H), aryl sulfonamide group, an alkylsulfonamido group, a sulfamoyl group, an acylsulfamoyl group, carbamoyl sulfamoyl group, sulfonyl ureido group, a sulfonyl A carbamoyl group, a sulfamoylcarbamoyl group, an acylcarbamoyl group, a sulfonylsulfamoyl group, an active methylene group, or a salt thereof. However, sulfo group (—SO ₃ H), mercapto group (—SH), and —NH—
Groups and hydroxy groups (-OH groups) are not included. The arylsulfonamide group is limited to a benzenesulfonamide group having at least one electron-withdrawing group as a substituent. Here, the electron-withdrawing group means a substituent having a positive Hammett's substituent constant σp value for the ortho- or para-position substituent on the benzene ring of the benzenesulfonamide group, The substituent at the position means a substituent having a positive σm value. Here, the substituent in which σp takes a positive value is specifically a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxyl group, a cyano group,
(Alkyl or aryl) sulfonyl groups, sulfo groups or salts thereof, sulfamoyl groups, nitro groups, thioureido groups, sulfonamide groups, imide groups, alkyl groups substituted with a plurality of halogen atoms (such as -CF ₃ groups) and the like. The substituent having a positive value of σm includes the same substituents as those described above as a substituent having a positive value of σp, and further includes an acylamino group, a ureido group, (alkoxy or aryloxy) carbonyl Amino group, sulfamoylamino group, (alkyl, aryl, or heterocycle)
A thio group, an alkoxy group, an aryloxy group and the like. Two or more of these electron-withdrawing groups may be substituted on the benzene ring, and the benzene ring may have any substituent other than the electron-withdrawing group.

When the dissociative group represents an active methylene group, the active methylene group means a methylene group or a methine group sandwiched between two or three electron-withdrawing groups, and the electron-withdrawing group is a substitution of Hammett. An atomic group in which the base constant σp can take a positive value, which is specifically as described above. Two or three electron-withdrawing groups may be bonded to each other to form a cyclic structure. In the present invention, the salt of the dissociative group specifically refers to an alkali metal ion, an alkaline earth metal ion, an organic ammonium ion, an organic ammonium ion such as a sodium cation, a potassium cation, a lithium cation, a magnesium cation, and a tetrabutylammonium cation. And phosphonium ions.

In the general formula (1a), the case where the ph group has at least one dissociable group indirectly means that the dissociable group is substituted with the ph group via a divalent or higher linking group. Say if you have. Here, the divalent or higher linking group is specifically represented by the following general formula. {(*) M-L1} n-L2-** wherein L1 represents an alkylene group or a phenylene group,
L2 represents -O-, -NR _N- , -S-, -C = O-,-.
SO _2- , -SO-, -C = S-, -P = O- alone,
Or a group consisting of a combination of these groups,
_N represents a hydrogen atom, a monovalent alkyl group or a monovalent aryl group. * Indicates a bonding position with a dissociable group, and ** indicates a bonding position with a ph group in the general formula (1a). m represents 1 or 2, and n represents 1 or 2. Group represented by L1 or R _N may have a substituent include the same substituents described for the group represented by Z in the general formula (1a) is specifically .

In the general formula (1a), the ph group may have any substituent at the same time as the substituent in addition to the dissociative group or the substituent containing the dissociable group. Specific examples thereof include the same substituents as described for the substituent represented by Z in the general formula (1a). The nitrogen-containing heterocyclic group represented by PUGN in the general formula (1a) represents a development inhibitor, which is represented by the general formula (R-
It is a group having the same meaning as the development inhibitor represented by PUG in 1).
The nitrogen-containing heterocyclic group represented by PUGN in the general formula (1a) is a nitrogen-containing heterocyclic group having a nitrogen atom and bonding to an adjacent carbonyl group via the nitrogen atom to give a pKa value of 9 to 11. And a nitrogen-containing heterocyclic group having at least one nitro group directly or indirectly as a substituent thereof. Here, the pKa value refers to acetonitrile and water 1:
It is a pKa value determined by a pH meter using an acid-base rule with one mixed solution as a solvent. In general formula (1a), P
The nitrogen-containing heterocyclic group represented by UGN is a 5- to 7-membered
Aromatic or non-aromatic, monocyclic or condensed, nitrogen-containing heterocyclic group, specifically, benzotriazoles, benzimidazoles, indazoles, phthalimides, succinimides , Hydantoins, urazoles, o-sulfobenzimides, isatins and the like. In the general formula (1a), when the nitrogen-containing heterocyclic group represented by PUGN indirectly has at least one nitro group as a substituent thereof, the nitro group is linked to the nitrogen-containing heterocyclic group represented by PUGN. As a substituent having at least one arylene group
A valent linking group, an alkylene group, -O-, -NR
_{N '-, - S -,} - C = O -, - SO 2 -, - SO -, -
It may contain a group consisting of C = S- and -P = O- alone or a combination of these groups. Here, R _{N ′} represents a hydrogen atom, a monovalent alkyl group or a monovalent aryl group.

Next, preferred ranges of the compound represented by formula (1a) of the present invention will be described. General formula (1a)
In Z, preferred examples of Z include an alkyl group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide group, a hydroxy group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl Group, carbamoyl group,
(Alkyl, aryl, or heterocycle) thio, sulfamoyl, halogen, cyano, nitro and the like. In the general formula (1a), p is preferably 0 or 1, and more preferably 0.

In the general formula (1a), the dissociable group of the ph group is preferably a carboxy group (—COO).
H), an arylsulfonamide group, an alkylsulfonamide group, a sulfamoyl group, an acylsulfamoyl group,
A carbamoylsulfamoyl group, a sulfonyluureido group, a sulfonylcarbamoyl group, a sulfamoylcarbamoyl group, an acylcarbamoyl group, a sulfonylsulfamoyl group, an active methylene group, or a salt thereof.
Particularly preferred are a carboxy group or a salt thereof, an arylsulfonamide group, a sulfonyluureido group, a sulfonylcarbamoyl group, and a sulfamoylcarbamoyl group. Here, the arylsulfonamide group has at least one
It is limited to a benzenesulfonamide group having two electron-withdrawing groups as substituents, and the electron-withdrawing group is preferably an ortho- or para-position substituent on the benzene ring of the benzenesulfonamide group. , A halogen atom, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, a sulfamoyl group, a nitro group, a thioureido group, a sulfonamide group, an imide group, an alkyl group substituted with a plurality of halogen atoms (such as a —CF ₃ group) Examples of the substituent at the meta position include, in addition to the substituents at the ortho or para position, an acylamino group, a ureido group, an (alkoxy or aryloxy) carbonylamino group, a sulfamoylamino group, And an alkoxy group.

In the general formula (1a), the ph group is divalent
Or at least indirectly through a further linking group.
When it has one dissociable group, it is preferred as the linking group.
For example, * -alkylene group -CONH-, *
-Alkylene group -NHCONH-, * -alkylene group-
SO_TwoNH-, * -alkylene group-NHSO_TwoNH-, *
-Alkylene group -NHCO-, * -alkylene group -OC
O-, * -phenylene group -CONH-, * -phenylene
Group -NHCONH-, * -phenylene group -SO _TwoNH
-, * -Phenylene group -NHCO-, * -phenylene group
-NHSO_TwoNH-, * -phenylene group -OCO-, etc.
Is mentioned. Here, * indicates the bonding position to the dissociable group.
You. Heterocyclic group represented by PUGN in general formula (1a)
May preferably give a pKa value of 9.5 to 11.0
A heterocyclic group, more preferably a pKa value of 9.8 to 10.
A heterocyclic group capable of giving a value of 8. In general formula (1a)
Preferably, the heterocyclic group represented by PUGN is
Nsimidazoles, indazoles, benzotriazo
It is a class. Represented by PUGN in general formula (1a)
When a heterocyclic group is indirectly substituted with a nitro group
Is a phenyl group substituted by at least one nitro group
Is a hetero bond through a single bond or a divalent linking group.
It is preferably linked to a group. As its linking group
Is -NHCO-, -NHCONH-, -O-alkyl
-, -NHSO_Two-, -O-, -S-, -S-alkyl
A linking group such as ren- is preferred. General formula (1a)
When PUGN represents benzotriazoles, the nitro group is
Is preferably indirectly substituted, and at least
The phenyl group substituted by one nitro group is Btr-NH
CO-, Btr-NHCONH-, Btr-O-alkylene
-, Btr-NHSO_Two-, Btr-O-, Btr-S-, Btr-
Linked via a linking group such as S-alkylene-, etc.
Is preferred. Where Btr is benzotriazoles
Represents the substitution position of

As the heterocyclic group represented by PUGN in the general formula (1a), indazoles are particularly preferred. Further, indazoles in which one nitro group and one or two electron-withdrawing substituents other than the nitro group are simultaneously directly substituted are particularly preferable. In this case, pKa 9-11
Specific examples of the electron-withdrawing substituent other than a nitro group include a halogen atom (chloro atom, bromo atom, fluorine atom, and iodine atom), an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, and a sulfone. Examples include an amide group, a cyano group, a carbamoyl group, a trifluoromethyl group, a carboxy group, a sulfo group or a salt thereof, an acyl group, and a formyl group. Among them, a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, and a carbamoyl group are more preferable, and an alkoxycarbonyl group,
A carbamoyl group is particularly preferred, and an alkoxycarbonyl group (especially a methoxycarbonyl group) is most preferred.

The compound of the present invention represented by the general formula (1a) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. Particularly, those containing a ballast group are one of preferred examples of the present invention. The ballast group has already been described in the description of the general formulas (R-1) to (R-3). The ballast group has the general formula (1a)
May be substituted at any position of the compound represented by the formula, but is preferably directly or indirectly substituted by the group represented by the ph. Examples of the polymer include those described in JP-A-1-100530.

The compound represented by the general formula (1a) contains a cationic group (specifically, a group containing a quaternary ammonium group, a group containing a quaternized phosphorus atom, or a quaternary group). A nitrogen-containing heterocyclic group containing a modified nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, or an (alkyl, aryl, or heterocyclic) thio group. Examples of these groups include, for example, JP-A-7-234471 and JP-A-5-3
No. 33466, JP-A-6-19032, JP-A-6-1
No. 9031, JP-A-5-45761, U.S. Pat.
No. 4365, U.S. Pat. No. 4,988,604, JP-A-7-5
No. 610, JP-A-7-244348, German Patent 4006
No. 032 and the like. The general formula (1
A compound represented by a) containing a (alkyl, aryl, or heterocyclic) thio group is one of preferred examples of the present invention. When the compound represented by the general formula (1a) contains an (alkyl, aryl, or heterocycle) thio group, the group represented by ph in the general formula (1a)
Preferably, it is directly or indirectly substituted.

The compound represented by the general formula (1a) may have a built-in adsorptive group that adsorbs to silver halide. Such an adsorbing group is represented by the general formula (R-1)
(R-3) has already been described.

Hereinafter, specific examples of the compound represented by formula (1a) of the present invention will be listed, but the present invention is not limited thereto.

[0050]

[Table 9]

[0051]

[Table 10]

[0052]

[Table 11]

[0053]

[Table 12]

[0054]

[Table 13]

[0055]

[Table 14]

[0056]

[Table 15]

[0057]

[Table 16]

[0058]

[Table 17]

As the redox compound used in the present invention, in addition to those described above, for example, JP-A-61-213,8
No. 47, 62-260, 153, JP-A-3-39,
No. 953, No. 3-39, 951, No. 3-39, 949
Nos. 3-67,246, 4-13639, 4-136840, 4-136841, and 4-2
Nos. 83743 and 4-278939, JP-A-4-33
No. 0432, Patent No. 2779712, Patent No. 2676
No. 439 and Japanese Patent No. 2709760 can be used. Furthermore, Japanese Patent Application No. 11-26383
3, Japanese Patent Application No. 11-263901, Japanese Patent Application No. 11-26
No. 3997 and Japanese Patent Application No. 11-2887 can be used.

The methods for synthesizing the redox compound used in the present invention are described in the above-mentioned documents, and are described in, for example, US Pat. No. 4,684,604 and JP-A-1-269,936.
Nos. 3,379,529 and 3,620,
746, 4,377,634, 4,332,8
No. 78, JP-A-49-129,536 and JP-A-56-15
3,336, 56-153,342 and the like.

The redox compound of the present invention is used in the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. . Further, two or more kinds of redox compounds can be used in combination. The redox compound of the present invention is dissolved in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. Can be used. Also, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It is also possible to dissolve using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, the powder of the redox compound is ball milled in water,
A colloid mill or a dispersion using an ultrasonic wave can be used.

The redox compound of the present invention is added to a silver halide emulsion layer or another hydrophilic colloid layer. Further, it may be added to at least one of a plurality of silver halide emulsion layers. Although some configuration examples are given, the present invention is not limited to these. Structural Example 1) A silver halide emulsion layer containing the redox compound of the present invention and a protective layer are provided on a support. These emulsion layers or protective layers may contain the hydrazine derivative of the present invention as a nucleating agent. Structural Example 2) On a support, a first silver halide emulsion layer and a second silver halide emulsion layer are provided in this order, and the first silver halide emulsion layer or the adjacent hydrophilic colloid layer And the hydrazine derivative, and the redox compound in the second silver halide emulsion layer or the adjacent hydrophilic colloid layer. Structural Example 3) In the structural example 2), the order of the two emulsion layers is reversed. In the structural examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (such as polyvinyl acetate or polyvinyl alcohol) may be provided between the two photosensitive emulsion layers. Structural Example 4) A hydrophilic layer containing the redox compound is provided on a support having a silver halide emulsion layer containing the hydrazine derivative, on the emulsion layer or between the support and the silver halide emulsion layer. Having a colloidal layer. A particularly preferred configuration is Configuration Example 2) or 3).

The photographic material of the present invention preferably contains at least one hydrazine derivative represented by the general formula (D) as a nucleating agent.

Formula (D)

[0065]

Embedded image

In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, and G ₁₀ represents —CO—, —COCO—, —C (= S)-,
_{-SO 2 -, - SO -,} - PO (R 30) - group (. R ₃₀ is selected from the same range as the groups defined in R _10, may be different from R _10), or an iminomethylene group Represents A ₁₀ ,
A ₂₀ represents a hydrogen atom, or one of them 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 formula (D), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted, straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. is there. In the general formula (D), R ₂₀
Is a monocyclic or condensed-ring aryl group, for example, a benzene ring and a naphthalene ring. R
_{As the} heterocyclic group represented by ₂₀ , a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, Examples include a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring, and a triazine ring. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

The group represented by R ₂₀ may be substituted. Typical examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group) , An active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl Group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group Or contain propyleneoxy group units repeatedly ), An aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, an (alkyl, aryl, or heterocyclic) amino group, -Substituted nitrogen-containing heterocyclic groups, acylamino groups, sulfonamide groups, ureido groups, thioureido groups, isothioureido groups, imide groups, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium, oxamoylamino, (alkyl or aryl) sulfonyluureido, acylureido, N-acylsulfamoylamino, nitro, mercapto, (alkyl, aryl, or heterocycle) thio, An alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an N-acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphate amide or a phosphate ester structure. Groups, and the like. These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group,
Acylamino group, sulfonamide group, ureido group, sulfamoylamino group, imide group, thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocyclic) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group and the like. .

In the general formula (D), R ₁₀ represents a hydrogen atom or a block group, and the block group is specifically an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

The alkyl group represented by R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group,
Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group,
Examples include a hydroxymethyl group, a methoxymethyl group, a methylthiomethyl group, a phenylsulfonylmethyl group, an o-hydroxybenzyl group, and the like. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, such as a vinyl group, a 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. Examples include a phenyl group, a 3,5-dichlorophenyl group, a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group, and a 2-hydroxymethylphenyl group. Preferably, the heterocyclic group is a 5- to 6-membered, saturated or unsaturated, containing at least one nitrogen, oxygen, and sulfur atom.
It may be a monocyclic or condensed-ring heterocyclic group, and may be a heterocyclic group containing a quaternized nitrogen atom, for example, a morpholino group, a piperidino group (N-substituted), a piperazino group, an imidazolyl group, an indazolyl group ( 4-nitroindazolyl group, pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group, pyridyl group, pyridinio group (N-methyl-3-pyridinio group, etc.), quinolinio group,
And a quinolyl group. Morpholino group, piperidino group,
A pyridyl group, a pyridinio group and the like are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. As the aryloxy group, a phenoxy group is preferable, and as the amino group, an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom). Examples of the amino group include 2,2,6,6-tetramethylpiperidine-
4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-
And a 3-pyridinioamino group. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

R_TenThe group represented by may be substituted
And preferred substituents are R₂₀Exemplified as a substituent of
That applies. In the general formula (D), R_TenIs G_Ten
-R_TenIs split from the residual molecule, and -G _Ten-R_TenDepartment
Initiate a cyclization reaction that produces a cyclic structure containing a minute atom
May be such as, for example,
And those described in JP-A-63-29751.
You. The hydrazine derivative represented by the general formula (D) is
Incorporates an adsorptive group that adsorbs silver silver
You may. Such adsorbing groups include alkylthio groups, a
Reelthio group, thiourea group, thioamide group, mercapto
U.S. Pat. No. 4,38 for heterocyclic groups, triazole groups, etc.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948, 63-234244
No., 63-234245, 63-234246
And the groups described in the above. These silver halides
The adsorptive group to may be a precursor. That
Such precursors are disclosed in Japanese Patent Application Laid-Open No. 2-285344.
And the groups described in the above.

R ₁₀ or R _{20 in} the formula (D) may contain a ballast group or a polymer commonly used in immobile photographic additives such as couplers. In the present invention, the ballast group means a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio group having 6 or more carbon atoms. Represents a group or a group having these as a partial structure, and more preferably a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group) having 7 or more and 24 or less carbon atoms, It represents an alkylamino group (or an alkyleneamino group), an alkylthio group, or a group having these as a partial structure. Examples of the polymer include those described in JP-A-1-100530.

R ₁₀ or R ₂₀ in the general formula (D) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (D) is a polymer having a hydrazino group. Represents, for example, JP-A-64-86134
No., JP-A-4-16938, JP-A-5-97091, WO95-
No. 32452, WO95-32453, JP-A-9-1792
No. 29, JP-A-9-235264, JP-A-9-235265, JP-A-9-235
235266 and JP-A-9-235267.

In the general formula (D), R ₁₀ or R ₂₀ represents a cationic group (specifically, a group containing a quaternary ammonium group, a group containing a quaternized phosphorus atom, or A quaternized nitrogen-containing heterocyclic group containing a nitrogen atom, a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, or a dissociative group (alkaline Groups or partial structures having low acidity protons that can be dissociated in the developer,
Alternatively it means a salt thereof, specifically, for example, carboxyl group / -COOH, sulfo group / -SO ₃ H, a phosphonic acid group / -PO ₃ H, phosphoric acid group / -OPO ₃ H, hydroxy group / - OH group, a mercapto group / -SH, -SO ₂ NH ₂
Group, N-substituted sulfonamide group / —SO ₂ NH— group,
—CONHSO ₂ — group, —CONHSO ₂ NH— group, —N
HCONHSO ₂ — group, —SO ₂ NHSO ₂ — group, —CO
An NHCO- group, an active methylene group, a -NH- group inherent in a nitrogen-containing heterocyclic group, or a salt thereof). Examples of these groups include, for example, JP-A-7-234471, JP-A-5-333466,
JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Patent No. 4,994,365, U.S. Patent No. 4,988,604, JP-A-7-259240,
The compounds described in JP-A-7-5610, JP-A-7-244348, German Patent 4006032, JP-A-11-7093 and the like can be mentioned.

In the general formula (D), A ₁₀ and A ₂₀ 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 -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

Next, particularly preferred hydrazine derivatives in the present invention will be described. R ₂₀ is particularly preferably a substituted phenyl group. Examples of the substituent include a sulfonamide group, an acylamino group, an ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group,
-Acylsulfamoylamino group and the like are particularly preferred, furthermore a sulfonamide group and a ureido group are preferred, and a sulfonamide group is most preferred. The hydrazine derivative represented by the general formula (D) has a substituent at R ₂₀ or R ₁₀
Directly or indirectly, a ballast group, an adsorption group to silver halide, a group containing a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, or a group containing a repeating unit of an ethyleneoxy group , (alkyl, aryl or heterocyclic) thio group, an alkali dissociative group capable of dissociation by developing solution or hydrazino group (group represented by -NHNH-G ₁₀ -R ₁₀ capable of forming a multimer, It is particularly preferred that at least one of) is substituted. Moreover,
As the substituent of R _20, directly or indirectly, preferably have any one group described above, most preferably represents a phenyl group R ₂₀ is substituted by a benzene sulfonamide group, the sulfonic This is the case where any one of the aforementioned groups is directly or indirectly substituted as a substituent on the benzene ring of the amide group.

Preferred groups among the groups represented by R ₁₀ are
When G ₁₀ is a —CO— group, a hydrogen atom, an alkyl group,
An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent); Most preferably, it is a hydrogen atom or an alkyl group. When G ₁₀ is a —COCO— group, an alkoxy group, an aryloxy group, or an amino group is preferable, and a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is preferable. . Also G ₁₀
Is a —SO ₂ — group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (D), G ₁₀ is preferably-
It is a CO- group or a -COCO- group, particularly preferably a -CO- group. Next, specific examples of the compound represented by the formula (D) are shown below. However, the present invention is not limited to the following compounds.

[0081]

[Table 18]

[0082]

[Table 19]

[0083]

[Table 20]

[0084]

[Table 21]

[0085]

[Table 22]

[0086]

[Table 23]

[0087]

[Table 24]

[0088]

[Table 25]

[0089]

[Table 26]

[0090]

[Table 27]

[0091]

Embedded image

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following patent publications.

(Formula 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, from pages 8 to 1 of the publication
Compounds 1 to 38 described on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H described on pages 8 to 15 of the same publication
-1 to H-44. A compound described in JP-A-9-22082, which is characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. , A compound represented by the general formula (B), the general formula (C), the general formula (D), the general formula (E), or the general formula (F), specifically, the compound N-1 described in the same publication. ~ N-30. JP-A-9-2
A compound represented by the general formula (1) described in No. 2082,
Specifically, compounds D-1 to D-55 described in the publication. In addition, WO95-32452, WO95-32453
No., JP-A-9-179229, JP-A-9-235264, JP-A-9
No.-235265, JP-A-9-235266, JP-A-9-235267,
JP-A-9-319019, JP-A-9-319020, JP-A-10-13
No. 0275, JP-A-11-7093, JP-A-6-332096, JP-A-7-209789, JP-A-8-6193, JP-A-8-248549
No., JP-A-8-248550, JP-A-8-262609, JP-A-8
No.-314044, JP-A-8-328184, JP-A-9-80667,
JP-A-9-127632, JP-A-9-146208, JP-A-9-160
No. 156, JP-A-10-161260, JP-A-10-221800, JP-A-10-213871, JP-A-10-254082, JP-A-10-25
4088, JP-A-7-120864, JP-A-7-244348, JP-A-7-333773, JP-A-8-36232, JP-A-8-36233
No., JP-A-8-36234, JP-A-8-36235, JP-A-8-2
Hydrazine derivatives described in 72022, JP-A-9-22083, JP-A-9-22084, JP-A-9-54381, JP-A-10-175946.

In the present invention, the hydrazine-based nucleating agent may be a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, It can be used by dissolving it in methylcellosolve or the like. Also, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, hydrazine derivative powder is ball milled in water,
It can be dispersed and used by a colloid mill or an ultrasonic wave. In the present specification, the amount of each compound added per mol of silver halide means per mol of the total silver applied.

In the present invention, the hydrazine nucleating agent may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support, or to any of the other hydrophilic colloid layers. It is preferable to add to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. Also, two or more hydrazine-based nucleating agents can be used in combination. In the present invention, the addition amount of the nucleating agent is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and more preferably 2 × 10 ⁻⁵ mol per mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred. In the present specification, the amount of each compound added per mol of silver halide means per mol of the total silver applied.

In the present invention, a nucleation accelerator is incorporated in the light-sensitive material. Examples of the nucleation accelerator used in the present invention include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, pages 49 to 5
Compounds A-1) to A-73) described on page 8. JP-A-7-
Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in No. 84331, specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426.
-1 to Na-22 and Nb-1 to Nb-12
Compound. The general formulas (1), (2), (3), (4) described in JP-A-8-272023
Compounds represented by the general formulas (5), (6) and (7), specifically, 1-1 to 1 described in the same specification.
-19 compound, 2-1 to 2-22 compound, 3-1 to
3-36 compound, 4-1 to 4-5 compound, 5-1 to
5-41 compounds, 6-1 to 6-58 compounds, and 7-1 to 7-38 compounds. JP-A-9-297377, p55, column 108, line 8 to p69, column 136
The nucleation promoting agent according to line 44.

The nucleation accelerator used in the present invention includes:
Quaternary salt compounds represented by the general formulas (a) to (f) are preferred, and compounds represented by the general formula (b) are most preferred. The aliphatic groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in the general formula (a) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec group.
A linear or branched alkyl group such as -butyl group, tert-butyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; Cycloalkyl groups such as propyl group, cyclopentyl group and cyclohexyl group; alkenyl groups such as allyl group, vinyl group and 5-hexenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group; alkynyl groups such as phenylethynyl group. No. As the aromatic group, a phenyl group, a naphthyl group, an aryl group such as a phenanthryl group, and as a heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, Examples include a benzothiazolyl group, 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 ₁₀₀ , R ₁₁₀ and R ₁₂₀ , a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Nitro group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, ureido group, thioureido group, sulfonyluureide group, sulfonamide group, sulfamoyl group, Hydroxyl group, sulfonyl group, carboxyl group (including carboxylate), sulfo group (including sulfonate), cyano group, oxycarbonyl group, acyl group, heterocyclic group (heterocyclic group containing quaternized nitrogen atom And the like). These substituents may be further substituted with these substituents. The groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in the general formula (a) may be bonded to each other to form a cyclic structure.

[0099] Examples of the group represented by M in the general formula (a) is When m ₁₀ represents 1 include groups of _{R 100, R 1 10, R} 120 synonymous. When m ₁₀ represents an integer of 2 or more, M is M
Represents an m _10- valent linking group that bonds to Q ₁ ⁺ at the carbon atom contained in Group,
-N (R _N) - group, -S- group, -SO- group, -SO ₂ -,
-P = O-represents a m ₁₀ divalent linking group formed by combining groups (R _N represents a hydrogen atom or R _100, R _110, R ₁₂₀ group having the same meaning as in multiple in the molecule R _N When they are present, they may be the same or different and may even be linked to each other). M may have an optional substituent, and the substituent includes R ₁₀₀ , R ₁₁₀ , R ₁₂₀
The same substituents as the substituents that the group represented by may have.

In the general formula (a), R₁₀₀, R₁₁₀, R
₁₂₀Is preferably a group having 20 or less carbon atoms,₁But
When representing an aryl atom, an aryl group having 15 or less carbon atoms is particularly preferred.
Best, Q₁Represents a nitrogen atom,
Alkyl, aralkyl and aryl groups are particularly preferred.
m_TenIs preferably 1 or 2, m_TenIs 1 when M is
Preferably, it is a group having 20 or less carbon atoms, and a total of 15 or less carbon atoms.
The alkyl, aralkyl, or aryl groups below are
Preferred. m_TenRepresents 2 when divalent represented by M
The organic group is preferably an alkylene group, an arylene group,
Has these groups and -CO- group, -O- group, -N (R_N)
-Group, -S-group, -SO_Two-Formed by combining groups
Is a divalent group. m_TenRepresents 2 and M is included in M
Q₁ ⁺Divalent with a total carbon number of 20 or less
It is preferably a group. M or R₁₀₀, R
₁₁₀, R₁₂₀Is an ethyleneoxy group or a propylene
In the case of including a plurality of repeating units of the xy group,
The preferred range of the carbon number is not limited thereto. Also m_Ten
Is an integer of 2 or more,₁₀₀, R₁₁₀, R
₁₂₀Is a plurality of each, and the plurality of R₁₀₀, R
₁₁₀, R₁₂₀May be the same or different
No.

The quaternary salt compound represented by the general formula (a) is
The molecule has a total of 20 or more ethyleneoxy or propyleneoxy repeating units, which may be substituted at one position or may be substituted over a plurality of positions. When m ₁₀ represents an integer of 2 or more, M
It is more preferred that the linking group represented by has a total of 20 or more ethyleneoxy or propyleneoxy repeating units.

In the general formulas (b), (c) and (d), A ₁ , A ₂ , A ₃ , A ₄ and A _{5 each} represent a substituted or unsubstituted quaternary nitrogen atom. Represents an organic residue for completing a substituted unsaturated heterocyclic ring, which may contain a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrogen atom, and may have a benzene ring fused. A ₁ ,
Examples of the unsaturated hetero ring formed by A ₂ , A ₃ , A ₄ and A ₅ include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring and a pyrimidine. ring,
Pyrazole rings and the like can be mentioned. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.
The unsaturated hetero ring formed by A ₁ , A ₂ , A ₃ , A ₄ , and A ₅ together with the quaternized nitrogen atom may have a substituent. In this case, examples of the substituent include R in the general formula (a).
_The same substituents as the substituents which the groups represented by ₁₀₀ , R ₁₁₀ and R ₁₂₀ may have are exemplified. The substituent is preferably a halogen atom (especially a chloro atom), an aryl group having 20 or less carbon atoms (especially a phenyl group), an alkyl group, an alkynyl group, a carbamoyl group, an (alkyl or aryl) amino group, an (alkyl or aryl) ) Oxycarbonyl group, alkoxy group, aryloxy group,
(Alkyl or aryl) thio group, hydroxy group, mercapto group, carbonamide group, sulfonamide group, sulfo group (including sulfonate), carboxyl group (including carboxylate), cyano group, and the like. Particularly preferred are a phenyl group, an alkylamino group, a carbonamido group, a chloro atom, an alkylthio group and the like, and most preferred is a phenyl group.

The divalent linking groups represented by L ₁₀ and L ₂₀ include alkylene, arylene, alkenylene, alkynylene,
A divalent heterocyclic _{group, -SO 2 -, - SO -} , - O -, -
Those composed of S-, -N ( _RN ')-, -C (= O)-and -PO- alone or in combination are preferable. However R _N 'represents an alkyl group, an aralkyl group, an aryl group, a hydrogen atom. The divalent linking group represented by L ₁₀ and L ₂₀ may have an arbitrary substituent. Examples of the substituent include the same substituents that the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in the general formula (a) may have. L ₁₀ , L
_As particularly preferred examples of ₂₀ , alkylene, arylene,
-C (= O) -, - O -, - S -, - SO 2 -, - N
(R _N ')-alone or in combination.

R₁₁₁, R₂₂₂, R₃₃₃Has 1 to 20 carbon atoms
An alkyl group or an aralkyl group is preferable, and
May also be different. R₁₁₁, R₂₂₂, R₃₃₃Is a substituent
And the substituent is represented by the general formula (a)
R₁₀₀, R₁₁₀, R₁₂₀The group represented by may have
The same substituents can be mentioned. Particularly preferably, R
₁₁₁, R₂₂₂, R₃₃₃Is an alkyl group having 1 to 10 carbon atoms
Or an aralkyl group. Examples of preferred substituents thereof
Carbamoyl group, oxycarbonyl group, acyl
Group, aryl group, sulfo group (including sulfonate),
Boxyl group (including carboxylate), hydroxy group,
(Alkyl or aryl) amino group, alkoxy group
Can be mentioned. Where R₁₁₁, R₂₂₂, R₃₃₃To etch
A repeating unit of a renoxy group or a propyleneoxy group
When including a plurality of positions, the above R₁₁₁, R₂₂₂, R₃₃₃Nitsu
The preferred range of carbon number mentioned above is not limited
No.

The quaternary salt compound represented by the general formula (b) or (c) has a total of 20 or more ethyleneoxy or propyleneoxy repeating units in the molecule. A ₁ , A ₂ , A ₃ , A ₄ , R
_111, R _222, L _10, may be substituted in any of the L ₂₀ but, preferably, the linking group represented by L ₁₀ or L _20,
It is preferable to have a total of 20 or more repeating units of an ethyleneoxy group or a propyleneoxy group. The quaternary salt compound represented by the general formula (d) has a total of 20 or more repeating units of an ethyleneoxy group or a propyleneoxy group in the molecule. _May be substituted with any of A ₅ or R _333. Preferably, the group represented by R ₃₃₃ has a total of 20 repeating units of an ethyleneoxy group or a propyleneoxy group. It is preferable to have the above.

The quaternary salt compounds represented by the general formulas (a), (b), (c) and (d) repeatedly contain an ethyleneoxy group and a propyleneoxy group simultaneously. You may go out. When a plurality of repeating units of an ethyleneoxy group or a propyleneoxy group are contained, the number of repeating units may be strictly one, or may be given as an average value. The compound is a mixture having a certain molecular weight distribution. In the present invention, it is more preferable to have a total of 20 or more ethyleneoxy group repeating units, and it is more preferable to have a total of 20 to 67 total repeating units.

In the general formula (e), Q ₂ , R ₂₀₀ ,
R ₂₁₀ and R ₂₂₀ are each represented by Q ₁ ,
It represents a group having the same meaning as R ₁₀₀ , R ₁₁₀ and R _120, and the preferred range is also the same. In the general formula (f), A ₆ is
Represents a group having the same meaning as A ₁ or A ₂ in the general formula (b),
The preferred range is also the same. However, the nitrogen-containing unsaturated hetero ring formed by A ₆ in the general formula (f) together with the quaternized nitrogen atom may have a substituent,
It has no substituent containing a primary hydroxyl group. In the general formulas (e) and (f), L ₃₀ represents an alkylene group. The alkylene group is a linear, branched, or cyclic, substituted or unsubstituted alkylene group having
1-20 are preferred. Not only saturated ones represented by ethylene groups, but also -CH ₂ C ₆ H ₄ CH ₂ -and -CH ₂ CH = CHCH ₂
A compound containing an unsaturated group represented by-may be used. When L ₃₀ has a substituent, examples of the substituent include the substituents that the groups represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in formula (a) may have. The L ₃₀ 1 to 10 carbon atoms, groups of saturated straight or branched is preferred. More preferably, it is a substituted or unsubstituted methylene group, ethylene group or trimethylene group, particularly preferably a substituted or unsubstituted methylene group or ethylene group, and most preferably a substituted or unsubstituted methylene group.

In the general formulas (e) and (f), L ₄₀ represents a divalent linking group having at least one hydrophilic group. Here -SO the hydrophilic group _{2 -, - SO -, -} O
-, - P (= O) =, - C (= O) -, - CONH -, - SO 2
_{NH -, - NHSO 2 NH -} , - NHCONH-, represents an amino group, guanidino group, an ammonio group, each group or a group composed of a combination of these groups, the heterocyclic group containing a quaternized nitrogen atom. These hydrophilic group and an alkylene group, an alkenylene group, an arylene group, L ₄₀ is constructed by combining appropriate heterocyclic group. Groups such as an alkylene group, an arylene group, an alkenylene group, and a heterocyclic group that constitute L ₄₀ may have a substituent. Examples of the substituent include the same as the examples of the substituent which the group represented by R ₁₀₀ , R ₁₁₀ and R ₁₂₀ in the general formula (a) may have. Also the hydrophilic group in L ₄₀ is present in the form of dividing the L _40, it may be present as part of a substituent on L _40, but it is present in the form of dividing the L ₄₀ Is more preferred. For example -C (= O) -, - SO 2 -, - SO -, - O -, - P (=
O) =, - CONH -, - SO 2 NH -, - NHSO 2 NH -, - NHCONH-, 4 salt structure of nitrogen or phosphorus cationic group (specifically, or a quaternary nitrogen atom nitrogen-containing hetero ring), including a case where an amino group, each group of guanidino group or a divalent group comprising a combination of these groups, are present in the form of dividing the L _40.

One of the preferred examples of the hydrophilic group contained in L ₄₀ is a combination of an ether bond and an alkylene group.
A group having a plurality of repeating units of an ethyleneoxy group or a propyleneoxy group. The degree of polymerization or the average degree of polymerization is preferably from 2 to 67. The hydrophilic group L _{40 has, -SO 2 -, - SO -} , - O -, - P (= O) =, - C
(= O) -, - CONH -, - SO 2 NH -, - NHSO 2
NH-, -NHCONH-, an amino group, a guadinino group,
Ammonio group, as a result combining group such as a heterocyclic group containing a quaternized nitrogen atom or or L _40,
It is also preferred that the compound has a dissociable group as the substituent. Here, the dissociable group means a group or a partial structure having a proton having a low acidity that can be dissociated in an alkaline developer, or a salt thereof. Specifically, for example, a carboxy group / —COOH, / -SO ₃ H, a phosphonic acid group / -PO ₃ H, phosphoric acid group / -OPO ₃ H, hydroxy group / -OH group, mercapto group / -SH, -SO ₂
NH ₂ group, N-substituted sulfonamide group / —SO ₂ NH—
Based on, -CONHSO ₂ - group, -SO ₂ NHSO ₂ - group, -
A CONHCO- group, an active methylene group, an -NH- group existing in a nitrogen-containing heterocyclic group, or a salt thereof.

L ₄₀ is preferably an alkylene group or an arylene group, and —C (= O) —, —SO ₂ —, —O—, —CONH—, —SO ₂ NH
_{-, - NHSO 2 NH -,} - NHCONH-, and is used a combination of amino group as appropriate. More preferably an alkylene group having 2 to 5 carbon atoms -C (= O) -, - SO 2 -, - O -, - CONH -, - SO 2 NH
-, -NHSO ₂ NH- and -NHCONH- appropriately combined are used. Y is -C (= O) - or -SO ₂ - represents a. Preferably -C
(= O)-is used.

In the general formulas (a) to (f), X ^n-
Examples of the counter anion represented by are a chloride ion, a bromide ion, a halogen ion such as an iodine ion, an acetate ion, an oxalate ion, a fumarate ion, a carboxylate ion such as a benzoate ion, p-
Examples include sulfonate ions such as toluenesulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate, sulfate ions, perchlorate ions, carbonate ions, and nitrate ions. The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion, or a sulfate ion, and n is preferably 1 or 2. As X ^n- , a chloro ion or a bromo ion is particularly preferable, and a chloro ion is most preferable. However, there is another anion group in the molecule, and Q ₁ ⁺ , Q ₂ ⁺
Or when forming an inner salt with N ⁺ , X ^n- is not required.

The quaternary salt compound of the present invention has the general formula
(B), quaternary salts represented by general formula (c) and general formula (f)
Compounds are more preferred, among which the compounds of the general formula (b)
The quaternary salt compound represented by the formula (f) is particularly preferred. Further
In general formula (b), L _TenThe linking group represented by
When there are 20 or more repeating units of a thyleneoxy group
Is preferable, and the case of having 20 to 67 is particularly preferable.
Good. In the general formula (f), A₆Form
Unsaturated heterocyclic compound is 4-phenylpyridine, isoquino
Particularly preferred is phosphorus or quinoline.

Next, specific examples of the quaternary salt compounds represented by formulas (a) to (f) will be shown. (In the formula, Ph represents a phenyl group.) However, the present invention is not limited to the following compound examples.

[0114]

[Table 28]

[0115]

[Table 29]

[0116]

[Table 30]

[0117]

[Table 31]

[0118]

[Table 32]

[0119]

[Table 33]

[0120]

[Table 34]

[0121]

[Table 35]

The quaternary salt compounds represented by the general formulas (a) to (f) of the present invention can be easily synthesized by a known method. Examples of the synthesis are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 3) Polyethylene glycol (average molecular weight: 2000, 800 g),
After mixing thionyl chloride (584 ml) and DMF (4 ml) at room temperature, the mixture was heated to 90 ° C. and stirred for 5 hours. After distilling off excess thionyl chloride, 4-phenylpyridine (372 g) was obtained.
Was added and reacted at 150 ° C. for 7 hours. The reaction mixture was made into a solution of ethyl acetate / 2-propanol (10/1), cooled, and the precipitated solid was collected by filtration. This was dried to obtain the desired Exemplified Compound 3. (584 g, 62% yield)

Synthesis Example 2 (Synthesis of Exemplified Compound 6) Polyethylene glycol (average molecular weight: 2000, 10 g), thionyl chloride (7.3 ml) and DMF (0.1 ml) were mixed at room temperature, then heated to 90 ° C. and stirred for 5 hours. did. After the excess thionyl chloride was distilled off, isoquinoline (4.0 g) was added and
The reaction was performed at 50 ° C. for 7 hours. The reaction mixture was treated with ethyl acetate / 2
-The solution was made into a solution of propanol (10/1), cooled, and the precipitated solid was collected by filtration. This was dried to obtain the desired Exemplified Compound 6. (7.1 g, 60% yield)

Synthesis Example 3 (Synthesis of Exemplified Compound 4) Exemplified Compound 1 was prepared in the same manner as in Synthesis Example 1 except that polyethylene glycol (average molecular weight: 3,000) was used instead of polyethylene glycol (average molecular weight: 2,000). 4 was obtained. Synthesis Example 4 (Synthesis of Exemplified Compound 65) 1,10-diamino-4,7-dioxadecane (17.6 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), ethyl acetate (100 ml), and water (50 ml) The mixture was stirred vigorously at room temperature, and chloroacetyl chloride (34 g, 0.3 mol) was added dropwise thereto. The reaction solution was separated, the ethyl acetate layer was dried over sodium sulfate, and concentrated to give 1,10-bis (chloroacetylamino) -4,7-dioxadecane (23 g, yield 70).
%). 3.3 g of this compound and triphenylphosphine (7.9
g) was mixed and heated at 150 ° C. for 5 hours. The reaction mixture was cooled and washed three times with ethyl acetate to obtain 5.4 g (yield 63%) of Exemplified Compound 65 as a brown viscous liquid.

Synthesis Example 5 (Synthesis of Exemplified Compound 62) Instead of triphenylphosphine in Synthesis Example 4, 4-
Except that phenylpyridine was used, the same operation was performed to obtain Exemplified Compound 62.

Synthesis Example 6 (Synthesis of Exemplified Compound 71) Instead of 1,10-diamino-4,7-dioxadecane in Synthesis Example 4, O, O'-bis (2-aminopropyl) polyethylene glycol 800 was used, and Exactly the same operation was performed, except that 4-phenylpyridine was used instead of phenylphosphine, to obtain Exemplified Compound 71.

The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave and used by a method known as a solid dispersion method.

The nucleation accelerator of the present invention is preferably added to a non-photosensitive layer comprising a hydrophilic colloid layer containing no silver halide emulsion on the side of the silver halide emulsion layer with respect to the support. It is preferably added to a non-photosensitive layer consisting of a hydrophilic colloid layer between the silver halide emulsion layer and the support. The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ^-6 to 2 × 10 ^-2 mol, and more preferably 1 × 1 ^-6 to 2 × 10 ^-2 mol per mol of silver halide.
0 ^{-5 to} 2 × 10 ^-2 mol is more preferable, and 2 × 10 ^-5 to 1 is preferable.
X 10 ^-2 mol is most preferred. Also, two or more nucleation accelerators can be used in combination.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide. Silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide, silver iodobromide However, silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are preferable. The shape of the silver halide grains may be any of a cubic, a tetradecahedron, an octahedron, an irregular shape, and a plate shape, but a cube is preferred. The average grain size of the silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.1 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100. It is preferable that the expressed coefficient of variation is 15% or less, more preferably 10% or less, with a narrow particle size distribution. In the silver halide grains, the inside and the surface layer may have a uniform phase or may be different. Further, a localized layer having a different halogen composition may be provided inside or on the surface of the grain. The photographic emulsion used in the present invention is P. Gla
fkides Chimie et Physique Photographique (Paul
Montel, 1967), Photographic Em by GF Dufin
ulsionChemistry (The Forcal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c It can be prepared by the method described in Emulsion (The Forcal Press, 1964). That is,
Any of an acidic method, a neutral method and the like may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be any of a one-side mixing method, a double-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 keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains by using a so-called silver halide solvent such as ammonia, thioether and tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, which are described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-dimethyl-
2-imidazolidinethione. The amount of the silver halide solvent to be added varies depending on the kind of the compound used, the intended grain size, and the halogen composition, but is preferably from 10 ^-5 to 10 ^-2 mol per mol of silver halide.

According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. Also, in order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate, or a method disclosed in British Patent No. 4,242,445, JP-A-55-15812
It is preferable to use a method of changing the concentration of the aqueous solution as described in No. 4 to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In particular, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, etc. in order to achieve high contrast and low fog. In addition, K ₄ [Fe (C
Doping of a metal hexacyanoide complex such as N) ₆ ], K ₄ [Ru (CN) ₆ ] or K ₃ [Cr (CN) ₆ ] is advantageously performed.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalato, aquo, etc. as ligands, for example, hexachlororhodium (III) complex, pentachloroacolodium complex, tetrachlorodiacolate Rhodium complex salt, hexabromorhodium (II
I) Complex salts, hexaamine rhodium (III) complex salts, trizalatrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the rhodium compound is generally used, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg, KCl, NaCl, KBr, Na
(Br or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042 and JP-A-Hei.
Nos. -285941 and 2-20852, 2-208
No. 55, etc. in the form of a water-soluble complex salt. Particularly preferred are hexacoordinate complexes represented by the following formula. [ML ₆ ] ^n- where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4. In this case, the counter ion is not important and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) ₃ Cl _3] ^2- [Ru (CO) Cl _5] ^2- [Ru (CO) Br _5] ^2- [OsCl _6] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (CN) ₆ ] ^4- [Os (O) ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. As the iridium compound used in the present invention
Is hexachloroiridium, hexabromoiridium
 , Hexaammineiridium, pentachloronitrosi
Louisiridium and the like. Ironification used in the present invention
Compounds include potassium hexacyanoferrate (II),
Ferrous cyanate;

The silver halide emulsion used in the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

The sulfur sensitization used in the present invention is usually carried out by
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ° C or more.
It is performed by stirring for a while. Public sulfur sensitizer
Known compounds can be used, for example, in gelatin
In addition to the sulfur compounds contained in, various sulfur compounds,
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature and the size of silver halide grains during chemical ripening.
Changes under various conditions such as
10 per mole ^-7-10^-2Mole, more preferably
10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
The compounds described in JP-A-4-109240 and JP-A-4-324855 can be used. In particular, JP-A-4-3
It is preferable to use the compounds represented by formulas (VIII) and (IX) in 24855.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in No. 31284.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, edited by The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company.
rganic Serenium and Tellunium Compounds), Vol1 (1
986) and Vol. 2 (1987). Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-4-324855 are preferred.

[0142] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having different chemical habits, Those having different conditions and those having different sensitivities) may be used in combination. Among them, in order to obtain a high contrast, it is preferable to coat an emulsion having a higher sensitivity as it is closer to the support, as described in JP-A-6-324426.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength of blue light, green light, red light or infrared light by a sensitizing dye. It is preferable that the dye is spectrally sensitized by a spectral sensitizing dye having a wavelength of from 600 to 600 nm. Further, Japanese Unexamined Patent Publication No.
The compound of the general formula [I] described in JP-A-5-45015 and the compound of the general formula [I] described in JP-A-9-160185 are preferable, and particularly, the compound of the general formula [I] described in JP-A-9-160185. The compound of I] is preferred. In particular,
(1) to (19) described in JP-A-55-45015
And the compounds of I-1 to I-40 and the compounds of I-56 to I-85 described in JP-A-9-160185.

Other sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Other useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17643 IV-A (19
December 1978 p. 23), Item 18341X (19
August 1979, p. 437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example, A) Japanese Patent Application Laid-Open No.
Compounds (I) -1 to (I) -8 described in JP-A-162247 and I-1 to I described in JP-A-2-48653.
-28, a compound represented by I described in JP-A-4-330434.
-1 to I-13, U.S. Pat. No. 2,161,33
Example 1 to Example 14 described in No. 1
Compounds 1 to 7 described in West German Patent 936,071; B) For helium-neon laser light source, I-1 to I- described in JP-A-54-18726.
Compound No. 38, I-1 described in JP-A-6-75322
To I-35 and the compounds of I-1 to I-34 described in JP-A-7-287338; C) For the LED light source, the dyes 1 to 20 described in JP-B-55-39818; Compounds I-1 to I-37 described in JP-A-62-284343 and compounds I-1 to I-34 described in JP-A-7-287338; Compounds of I-1 to I-12 described in JP-A-1901032, JP-A-60-80841
Compounds of I-1 to I-22 described in JP-A No.
Compounds I-1 to I-29 described in JP-A-35342 and I-1 to I-29 described in JP-A-59-192242.
Compound No. 18; E) For tungsten and xenon light sources of a plate making camera, in addition to the compounds described above, the compounds I-41 to I-55 and I-86 to I- described in JP-A-9-160185. 97 and the compounds of 4-A to 4-S, the compounds of 5-A to 5-Q, and the compounds of 6-A to 6-T described in JP-A-6-242547 can also be advantageously selected. it can.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Volume 176, 17643 (issued December 1978), 23rd
Section J on page IV or the aforementioned JP-B-49-25500
No. 43-4933, JP-A-59-19032,
No. 59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by using water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-51-723, and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion.
As disclosed in Japanese Patent No. 74624, a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion at any stage of the emulsion preparation which has been found to be useful.
For example, US Patent Nos. 2,735,766 and 3,62
No. 8,960, No. 4,183,756, No. 4,2
25,666; JP-A-58-184142;
As disclosed in the specification such as -196749,
The timing before the silver halide grain formation step and / or before desalting, the timing during and / or after the desalting step and before the start of chemical ripening, and the specification of JP-A-58-113920 are disclosed. As described above, it may be added at any time during the process immediately before or during chemical ripening, or at any time before the application of the emulsion after chemical ripening and before coating. Further, as disclosed in U.S. Pat. No. 4,225,666 and JP-A-58-7629,
The same compound may be used alone or in combination with a compound having a different structure. The compound to be divided and added and the combination of the compounds may be changed and added.

In the present invention, the amount of the sensitizing dye to be added depends on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like.
It can be used in an amount of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. 0.5 × 10 ^{-7 to} 2.0 × 10 ^-6
A molar amount is more preferable. There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5. Specifically, compounds (III) -1 to 25 described in the publication. JP-A-1-118
A compound represented by the general formula (I) described in JP-A-832 and having substantially no absorption maximum in the visible region. Specifically, compounds I-1 to I-26 described in the publication. Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line. JP-A-2-
No. 103536, page 18, lower left, line 12 to lower left, line 20 of the same polymer latex. JP-A-9-17
No. 9228, a polymer latex having an active methylene group represented by the general formula (I), specifically, compounds I-1 to I-16 described in the same specification. JP-A-9-179
A polymer latex having a core / shell structure described in No. 228, specifically the compound P-1 described in the same specification
~ P-55. The acidic polymer latex described in JP-A-7-104413, page 14, left line 1 to page 30, right line, specifically compound II-1) described in page 15 of the same publication.
~ II-9).

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15; Hardening agents described in JP-A-2-103536, page 18, upper right line, 5th line to upper right line, 17th line. Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line. Conductive substances described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7; Specifically, the metal oxide described in page 2, lower right line 2 to the lower right line 10 of the same publication, and compound P-1 described in the same publication
To P-7. JP-A-2-10353
The water-soluble dyes described in JP-A-6 No. 6, page 17, lower right line, line 1 to upper right line, line 18 thereof.

Solid disperse dyes represented by formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112. JP-A-2-
Solid disperse dyes described in JP-A-294638 and JP-A-5-11382. Surfactants described in JP-A-2-12236, page 9, upper right, line 7 to lower right, line 3; PEG surfactants described in JP-A-2-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-3
No. 9948, page 12, lower left line, line 6 to page 13, lower right line, line 5 described above. Specifically, compounds VI-1 to VI-15 described in the publication. The binder described in the first line to the twentieth line at the lower right of page 3 of JP-A-2-18542.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 80.
To 150%, more preferably 90 to 1%.
It is in the range of 40%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material, and distilling the silver halide photographic material at 25 ° C. After immersion in water for 1 minute, the swollen thickness (Δd) was measured, and the swelling ratio (%) =
It is determined by the formula of (Δd ÷ d ₀ ) × 100.

The surface pH of the silver halide photographic light-sensitive material of the present invention on the side where the silver halide emulsion layer is coated is 4.5.
-7.5, preferably 4.8-7.0, particularly preferably 5.0-6.0. Examples of the support that can be used in carrying out the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material. Also, JP-A-7-234478
And a support made of a styrene polymer having a syndiotactic structure described in US Pat. No. 5,589,795. Hereinafter, processing agents such as a developing solution and a fixing solution, a processing method, and the like in the present invention will be described. However, needless to say, the present invention is not limited to the following description and specific examples.

In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. There are no particular restrictions on the developing agents used in the developer used in the present invention (hereinafter, both the development start solution and the development replenisher are collectively referred to as a developer), but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone It preferably contains a monosulfonate, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent showing superadditivity with the dihydroxybenzene-based developing agent, and a combination of a dihydroxybenzene or an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone, or a dihydroxybenzene or the like. Examples include a combination of an ascorbic acid derivative and a p-aminophenol. As the developing agent used in the present invention, dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, and the like.
Particularly, hydroquinone is preferred. Ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention; There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol and the like. Among them, N-methyl-p-aminophenol, Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferred.

The dihydroxybenzene-based developing agent is usually 0.1.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / L to 0.6 mol / L, preferably 0.10 mol / L to 0.5 mol / L, The latter is preferably used in an amount of not more than 0.06 mol / l, preferably from 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.1
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or a p-aminophenol is used, the ascorbic acid derivative may be used in an amount of 0.01 to 0.5 mol / l, 1-phenyl-3-pyrazolidone or p-aminophenol. -Aminophenols
It is preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited to these. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259,
No. 0-93433, saccharides (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt) and the like are preferably used. Is carbonate or boric acid. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, especially 0.2 to 1.5 mol / l.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. Sulfite is preferably used in an amount of 0.2 mol / l or more, particularly 0.3 mol / l or more. However, if added in an excessive amount, it causes silver stain in the developer.
Desirably, it is 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of additives other than those described above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and dimethylformamide.
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-
Nitroindazole, 5-nitrobenzimidazole, 2
-Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,3,4
Sodium-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like. it can. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various organic and organic compounds are contained in the developer of the present invention.
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelinic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc.
And JP-B-57-102624 and JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in, for example, US Pat.
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid,
Aminotrimethylene phosphonic acid, etc.
Compounds described in 208554, 54-61125, 55-29883, 56-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, and JP-A-55-102127.
-4024, 55-4025, 55-126241, 55-65955, 55-65
956 and the compounds described in Research Disclosure 18170 described above.

These organic and / or inorganic cleans
The agent is not limited to those described above. Also,
Can be used in the form of alkali metal salt or ammonium salt
No. The addition amount of these chelating agents is
Preferably 1 × 10 per title ^-Four~ 1 × 10^-1Mole, more
Preferably 1 × 10^-3~ 1 × 10^-2Is a mole.

Further, as a silver stain preventing agent in the developing solution,
For example, JP-A-56-24347, JP-B-56-46585, JP-B-62
-2849, compounds described in JP-A-4-362942, JP-A-8-6215, and triazines having at least one mercapto group (for example, Japanese Patent Publication No. 6-23830, JP-A-3-282457, JP-A-7-17517).
8), the pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,
4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine, compounds described in JP-A-9-274289, and the like pyridine (for example, 2-mercaptopyridine) , 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, the compounds described in JP-A-7-248587, and the like pyrazines (eg, 2-mercaptopyrazine, 2, 6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc. , 3,4,6-trimercaptopyridazine, etc.)
Compounds described in 7-175177, polyoxyalkyl phosphonates described in US Pat. These silver stain inhibitors can be used alone or in combination of two or more.
1010 mmol is preferred, and 0.1-5 mmol is more preferred. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a toning agent,
It may contain a surfactant, an antifoaming agent, a hardener and the like.

The preferred pH of the developer is 9.0 to 12.0, particularly preferably 9.0 to 11.0, and more preferably 9.5 to 12.0.
It is in the range of 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As a cation of the developing solution, potassium ions do not inhibit the development as compared with sodium ions, and have less jaggedness around a blackened portion called a fringe. Further, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions.Therefore, if the potassium ion concentration of the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range with a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution is 3 per m ² of the photosensitive material.
90 ml or less, preferably 325 to 30 ml, more preferably 250 ml or less, 250 to 12
0 ml is most preferred. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration than the start solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are used as an aluminum ion concentration of 0.01 to 0.15 mol /
It is preferably contained in liters. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts having a hardening agent and the like as separate parts, or may be of a one-part type containing all components.

If desired, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) may be used in the fixing treatment agent at 0.015%.
Mol / l or more, preferably 0.02 mol / l or more
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / l to 1 mol / l, preferably 0.2 mol / l, of phosphoric acid, succinic acid, adipic acid and the like
0.7 mol / liter), compounds with aluminum stabilizing or water softening ability (eg gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid) 0.005% of benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.00
5 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide, a polyethylene-based surfactant, and an amphoteric surfactant described in JP-A-57-6840. You can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754, 58-12253.
5, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.No. 4,216,459, JP-A-64-4739, JP-A-1-4739, and 1-159
645 and the mercapto compound described in 3-101728, 4-1
70539, which may comprise a thiocyanate.

In the present invention, the pH of the fixing solution is preferably 4.0 or more, more preferably 4.5 to 6.0. The pH of the fixing solution is raised by mixing with the developing solution due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less, preferably 6.7 or less for the non-hardened fixing solution. The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml per 1 m ² of the photosensitive material. The replenisher is
It may have the same composition and / or concentration as the starting liquid, or may have a different composition and / or concentration from the starting liquid. The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration. Even when the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained. However, the solid processing agent will be described below. The solid agent in the present invention,
Known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3
You can refer to the 13th line.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991. The bulk density of the solid processing agent is preferably 0.5 to 6.0 g / cm ³ , and in particular, the tablet
Preferably to 5.0 g / cm ^3, the granules is preferably 0.5 to 1.5 g / cm ^3.

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-328
37, 4-78848, 5-93991, JP-A-4-85533, 4-8553
4, 4-85535, 5-134362, 5-97070, 5-04098,
5-224361, 6-138604, 6-138605, 8-286329 and the like can be referred to. More specifically, rolling granulation,
Extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, briquetting, roller compacting, and the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granules having different compositions on the surface and inside may be used.

The packaging material of the solid preparation is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, 6-301189,
The foldable shape as disclosed in 7-5664, 7-5666 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. For these packaging materials, screw caps, pull tops, aluminum seals may be attached to the processing agent outlet, or the packaging materials may be heat sealed,
Other known materials may be used, and there is no particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolution apparatus having a stirring function, and a method disclosed in
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a completed liquid as described in 9-80718 and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102, JP-A-7
A method of dissolving and replenishing by adding a processing agent to the circulating system of an automatic developing machine as described in -261357, dissolving by inputting a processing agent according to the processing of photosensitive material in an automatic developing machine with a built-in dissolution tank However, any other known method can be used. Further, the processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in JP-A-9-138495. The latter is preferred from the point of view. Specifically, a method of piercing the outlet, a peeling method, a cutting method, a pushing method,
2, the method described in 6-95331, and the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization processing is carried out. The liquid used for these is water or washing water. ). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be less. In particular, when the replenishment amount is 3 liters or less (including 0; that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0183] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the older are known, washing replenishing amount is preferably photosensitive material 1 m ² per 200 to 50 ml. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, means for preventing water scale may be provided in the washing step. Known means can be used as the scale preventive means, and is not particularly limited, but a method of adding a sunscreen (a so-called scale preventive agent), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method for energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, 4-189
The method described in 80 or the like can be used.

In addition, known water-soluble surfactants and defoamers may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

As described in JP-A-60-235133, a part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by adding a compound to the mixture to precipitate silver and filtering the precipitate with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment.
A bath containing the compounds described in JP-A-35-101, JP-A-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains ammonium compounds, metal compounds such as Bi and Al, fluorescent brighteners, various chelating agents, membrane pH regulators, hardeners, bactericides, deterrents, alkanolamines and surfactants. Agents can also be added. Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents may be solid agents as in the above-mentioned developing and fixing processing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439560
It is also possible to dispose after concentrating or solidifying with a concentrating device as described in US Pat.

In order to reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of the liquid and the oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to herein as roller transport type automatic developing machines. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. Furthermore, during development and fixing and
A rinsing bath may be provided between the fixing and washing with water.

In the development processing of the present invention, the time from the start of processing to the time after drying (dry to dry) is preferably 25 to 160 seconds, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds. 25 to 50 ° C is preferred, and 30 to 40 ° C is preferred. The temperature and time of the water washing are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material that has been developed, fixed, and washed may be washed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C,
The drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.Hot air drying and JP-A-4-15534, JP-A-5-2256, and JP-A-5-2256
There are heat roller drying and far infrared drying as disclosed in 89294, and a plurality of methods may be used in combination.

[0191]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 <Preparation of silver halide emulsion A> 500 ml of an aqueous silver nitrate solution in which 150 g of silver nitrate was dissolved, and (NH ₄ ) ₂ RhCl equivalent to 2 × 10 ^-7 mol per mol of silver after grain formation.
₅ (H ₂ O) and K ₃ IrCl ₆ equivalent to 1 × 10 ⁻⁷ mol
Of bromide containing 44 g of potassium bromide and 34 g of sodium chloride in 500 ml of an aqueous solution of 3 g of sodium chloride, 0.02 g of 1,3-dimethyl-2-imidazolithione, 0.5 g of citric acid and 4 mg of benzenethione Sodium sulfonate and 1 mg of sodium benzenesulfinate dissolved in 1 liter of a 2% aqueous gelatin solution were added by a double jet method at 34 ° C. for 20 minutes while stirring to give an average particle size of 0.18 μm and a silver chloride content of 58 mol%. Nucleation was performed by obtaining silver chlorobromide particles. Subsequently, 200 ml of an aqueous silver nitrate solution in which 50 g of silver nitrate was dissolved, 12 g of potassium bromide containing potassium hexacyanoferrate (II) equivalent to 1 × 10 ^-5 mol per mol of silver of the whole emulsion, and a halogen in which 13 g of sodium chloride were dissolved 200 ml of an aqueous salt solution was added over 10 minutes by the double jet method.

Thereafter, a conversion was carried out by adding a KI solution of 1 × 10 ⁻³ mol per mol of silver, followed by washing with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 40 ° C., 3 g of the anionic precipitant-1 shown below was added, and p was added using sulfuric acid until the silver halide precipitated.
H was lowered. (PH was in the range of 2.9 ± 0.2)
Next, about 3 liters of the supernatant was removed (first water washing). An additional 3 liters of distilled water was added, and then sulfuric acid was added until the silver halide precipitated. Again, 3 liters of the supernatant was removed (second washing). Perform the same operation as in the second washing for one more time.
The washing and desalting processes were completed by repeating the process three times (third washing).
40 g of gelatin per mole of silver in the emulsion after washing and desalting
Was adjusted to pH 5.9 and pAg 7.5, and then sodium benzenethiosulfonate 16 per mole of silver was added.
mg, 4 mg of sodium benzenesulfinate, 2 mg of sodium thiosulfate, 2 mg of triphenylphosphine selenide and 8 mg of chloroauric acid, and heated at 55 ° C. for 60 minutes to perform chemical sensitization. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and Proxel as a preservative (trade name,
ICI Co. , Ltd. 100 mg and 1N
Of NaOH solution was added. The resulting grains were cubic silver iodochlorobromide grains having an average grain size of 0.20 μm, a coefficient of variation of 10%, and a silver chloride content of 60 mol%. (Finally, the emulsion had pH = 6.1, pAg = 7.2, conductivity = 37 μS / m, density = 1.20 × 10 ³ kg / m ³ , and viscosity = 20 mPa · s.)

<Preparation of Emulsion B> 250 ml of an aqueous silver nitrate solution in which 75 g of silver nitrate was dissolved and (NH ₄ ) ₂ RhCl ₅ (H) equivalent to 4 × 10 ⁻⁷ mol per mol of silver of the whole emulsion.
₂ O) and 1 × 10 halogen salt solution 250ml were dissolved potassium bromide 16g sodium chloride 20g containing K ₃ IrCl ₆ corresponding to ^-7 mol, of 4g sodium chloride and 0.02g of 1,3-dimethyl -2-Imidazolithione, 0.5 g of citric acid, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate dissolved in 1 liter of a 2% aqueous gelatin solution by stirring at 45 ° C. for 12 minutes at 45 ° C. by a double jet method. With an average grain size of 0.20 μm and a silver chloride content of 7
Nucleation was performed by obtaining 0 mol% of silver chlorobromide grains. Subsequently, an aqueous silver nitrate solution 4 in which 125 g of silver nitrate was dissolved was used.
00 ml, potassium bromide 26 g and sodium chloride 34
g of a halogen salt aqueous solution in an amount of 400 g was added over 20 minutes by a double jet method. Then silver 1
Conversion was performed by adding 1 × 10 ⁻³ mol of KI solution per mol, and the resultant was washed with flocculation according to a conventional method. The specific method was the same as that for Emulsion A.
40 g of gelatin per mole of silver in the emulsion after washing and desalting
And adjusted to pH 6.0 and pAg 7.5, and 7 mg of sodium benzenethiosulfonate per mole of silver.
And sodium benzenesulfinate 2mg, chloroauric acid 8
mg and 5 mg of sodium thiosulfate were added, and heated at 60 ° C. for 60 minutes to perform chemical sensitization. Thereafter, 250 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were used.
g was added. The resulting particles have an average particle size of 0.28μ
m, a coefficient of variation of 10%, and silver iodochlorobromide cubic grains having a silver chloride content of 70 mol%. (Finally, as an emulsion, pH
= 6.1, pAg = 7.5, conductivity = 46 μS / m, density = 1.20 × 10 ³ kg / m ³ , viscosity = 62 mPa · s
It became. )

<Preparation of Coated Sample> On a polyethylene terephthalate film support having a moisture-proof layer undercoated with vinylidene chloride on both sides shown below, an UL layer / a hydrazine-containing EM layer / intermediate layer / a redox compound-containing EM layer / protective layer A sample was prepared by applying such a composition as described above. The preparation method, application amount and application method of each layer are shown below. (UL layer) Gelatin as UL layer (containing Proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative)
0.3 g / m ² , 7.5% of the nucleation accelerator No. 3 of the present invention.
× 10 ^-6 mol / m ² , 0.25 g / m ^{2 of} a polyethyl acrylate dispersion, and 1,2-
50 m of bis (vinylsulfonylacetamido) ethane
g / m ² was applied. The pH of the coating solution was adjusted to 5.8. (Hydrazine-containing EM layer) <Preparation of hydrazine-containing layer emulsion coating solution> 5 × 10 ⁻⁴ mol of a compound of the following structural formula (s-1) per mol of silver was added to Emulsion A as a sensitizing dye, and further 1 × 10 ⁻³ mol of potassium bromide, 9 × 10 ⁻⁴ mol of a mercapto compound represented by the structural formula (a), and a mercapto compound represented by the structural formula (b), 1 × 10 ⁻⁴ mol of the structural formula The triazine compound represented by (c) and the hydrazine nucleating agent-A were 2 × 1
0 ^-5 mol / m ² , and 0.2 parts of hydrazine nucleating agent-B.
× 10 ^-5 mol / m ² was added. Further, 500 mg of colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.)
m ² , 500 mg / dispersion of polyethyl acrylate
A hydrazine-containing layer coating solution was prepared by adding so as to apply m ² . The pH of the solution was adjusted to 5.8.

[0196]

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The resulting silver halide emulsion coating solution was coated so that the silver amount was 3.4 g / m ² and the gelatin amount was 1.6 g / m ² .

(Intermediate Layer) <Preparation of Coating Solution for Intermediate Layer> Sodium ethanethiosulfonate was added to a gelatin solution containing proxel as a preservative.
mg / m ^2, dye 50 mg / m ² expressed by (e), hydroquinone 100mg / m ^2, 5- chloro-8-hydroxyquinoline 10 mg / m ^2, a dispersion 100 mg / m of polyethyl acrylate ² was added so as to be applied to prepare an intermediate layer coating solution. The pH of the solution was adjusted to 7.0. The intermediate layer was coated so as to have a gelatin content of 0.7 g / m ² .

(Preparation of Redox Compound-Containing Layer Emulsion Coating Solution) <Preparation of Redox Compound-Containing Layer Emulsion Coating Solution> The structure shown above was 1 × 10 ^-4 mol per mol of silver of the redox compound-containing layer emulsion as a sensitizing dye in Emulsion B. The compound of the formula (s-1) is added, and 5 × 10 ⁻⁴ mol of the mercapto compound represented by the structural formula (a), 1 × 10 ⁻⁴ mol of the structural formula (c)
, A dye represented by the following structural formula (f): 5 mg / m ² , a dispersion of polyethyl acrylate: 100 mg / m ² , and 1,2-bis ( (Vinylsulfonylacetamido) ethane was added so that 50 mg / m ^{2 was} applied. Further, the redox compound shown in Table 36 was converted to 2.1 × 10 ⁻⁴ mol /
By adding m ² , a redox compound-containing layer emulsion coating solution was prepared. The pH of the solution was adjusted to 5.4. Table 36 shows the pKa of the added redox compound. The pKa value was determined using a 1: 1 mixed solution of acetonitrile and water as a solvent.
It is a pKa value determined by a pH meter according to the base specification.

At this time, as the redox compound, an emulsion prepared as follows was dissolved at 60 ° C. and added to the coating solution. (Preparation of redox emulsion) 8 g of the above-mentioned redox compound (S ₈ content is 5 ppm) and 0.3 g of sodium p-dodecylbenzenesulfonate in 30 ml of ethyl acetate, the following structural formulas (P-1) and (P-2) 4) each oil
g was added and dissolved at 60 ° C. to obtain solution A. 8.5 g of gelatin in 170 g of water, Proxel (trade name, ICI C)
o. , Ltd. Was added at 0.05 ° C. and dissolved at 60 ° C. to obtain a solution B. The solution A and the solution B were mixed and emulsified and dispersed at 60 ° C. with a high-speed homogenizer. After emulsification and dispersion, 60
The solvent was removed under reduced pressure at a temperature of 4 ° C. to obtain a 4% by mass emulsified dispersion of a redox compound. The resulting redox compound-containing layer emulsion coating solution was applied so that the silver amount was 0.4 g / m ² and the gelatin amount was 0.5 g / m ² .

(Protective layer) An amorphous SiO ₂ matting agent 5 having a gelatin of 0.2 g / m ² and an average particle size of about 3.5 μm 5
0 mg / m ² , colloidal silica (Snowtex C manufactured by Nissan Chemical) 60 mg / m ² , liquid paraffin 50 mg /
m ² , 1 mg / m ^{2 of} a fluorine surfactant represented by the following structural formula (g) and 10 mg / m ^{2 of} sodium p-dodecylbenzenesulfonate were applied as coating aids. The viscosity of the coating liquid for each layer was adjusted by adding a thickener represented by the following structural formula (Z).

[0202]

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The back layer was applied according to the following formulation. <Back layer> Gelatin 2.8 g / m ² surfactant p-dodecylbenzenesulfonic acid sodium salt 40 mg / m ² dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² gelatin hardener 1,2-bis (vinylsulfonyl) Acetamido) ethane 200 mg / m ² SnO ₂ / Sb (mass ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye The following dyes (h-1), (h-2), (h-3) Mixture of (h-4) Dye (h-1) 20 mg / m ² Dye (h-2) 50 mg / m ² Dye (h-3) 20 mg / m ² Dye (h-4) 30 mg / m ² Preservative ( Proxel) 10 mg / m ²

[0204]

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<Back protective layer> Gelatin 1.1 g / m ² polymethyl methacrylate fine particles (average particle size 2.5 μm) 20 mg / m ² p-dodecylbenzenesulfonic acid sodium salt 15 mg / m ² dihexyl-α-sulfosuccinate Sodium salt 15 mg / m ² Sodium acetate 60 mg / m ² Preservative (Proxel) 1 mg / m ²

<Support> The first and second undercoat layers having the following composition on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied.

<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 (i 0.20 g colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g by adding water and 10% by mass of KOH to adjust the pH to 6 The drying temperature is 180 ° C for 2 minutes, and the dry film thickness is 0.
It was applied so as to have a thickness of 9 μm.

<Second Layer of Undercoat Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (j) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Preservative (Proxel) 3.5 × 10 ^-3 g 0.2 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.

[0209]

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<Coating method> On the support on which the above-mentioned undercoat layer has been formed, first, the UL layer, the hydrazine-containing EM layer, the intermediate layer, and the redox compound-containing E
Five layers in the order of M layer and protective layer were simultaneously coated by a slide bead coater while adding a hardener solution while maintaining the temperature at 35 ° C., and after passing through a cold air set zone (5 ° C.), On the other side, the back layer from the side closer to the support,
In the order of the back protective layer, simultaneous multi-layer coating was performed by adding a hardener solution by a curtain coater method, and a cold air set zone (5 ° C.) was applied. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and others until winding up. The coating speed at this time was 120 m / min.

<Drying Conditions> After setting, the mixture was dried with a drying air at 30 ° C. until the mass ratio of water / gelatin became 800%.
Dry 200 to 200% with dry air at 35 ° C. and 30% RH, apply air as it is, 30 seconds after the surface temperature reaches 34 ° C. (assuming that drying is completed), and then 1 minute with 48 ° C. 2% air. Dried. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800%, and 800 to 200%.
To 35 seconds, and from 200% to the end of drying is 5 seconds.

The photosensitive material was wound up at 25 ° C. and 55% RH, cut in the same environment, and conditioned in a barrier bag conditioned for 6 hours at 25 ° C. and 50% RH for 8 hours.
Seal with cardboard conditioned for 2 hours at 0% RH.
The sample shown in No. 6 was prepared.

When the relative humidity in the barrier bag was measured, it was 53%. The pH of the film surface on the emulsion layer side of the obtained sample was 5.5 to 5.8.

The evaluation was performed by the following method. The obtained sample was exposed to a contact screen gray scanner negative No. 2 (manufactured by Dainippon Screen Mfg. Co., Ltd.) of 150 lines / inch through a step wedge, and exposed to light with a tungsten light source. Then, using a developer (A) ((A1) to (A3)) and a fixer (B) having the following prescription, developing was performed at 35 ° C. for 30 seconds with an FG-710F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.). Processed in time.

Developer (A1) Formulation The composition per liter of the concentrated solution is shown. Potassium hydroxide 60.0 g Diethylenetriamine pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-Methylbenzotriazole 0.53 g 4-Hydroxymethyl-4- 8. Methyl-1-phenyl-3-pyrazolidone 2.3 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.15 g 2-mercaptobenzimidazole-5-sodium sodium 5-sulfonate 0.45 g sodium erythorbate 9. 0 g Diethylene glycol 7.5 g pH 10.79 In use, the mother liquor was prepared by adding 1 part of water to 2 parts of the above concentrated liquid.
The mother liquor was diluted at a ratio of 10.65 parts by weight and the replenisher was diluted at a ratio of 3 parts of water to 4 parts of the above concentrated solution, and the pH of the replenisher was 10.62.

Fixing Solution (B) Formulation The formula per liter of the concentrated solution is shown. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metabisulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8. 7 g sodium gluconate 5.1 g aluminum sulfate 25.2 g pH 4.85 In use, 1 part of the above concentrated liquid is diluted with 2 parts of water. The pH of the working solution is 4.8.

<Halftone> Halftone (9) of the obtained halftone image
The ratio of the amount of exposure that gives a 5% halftone dot area to the amount of exposure that gives a 5% halftone dot area is expressed in logarithm. The larger the numerical value, the wider the exposure latitude and the better the image reproducibility. <Grayscale> γ is ((1.5-0.3) / log (density 1.
5) -log (exposure to give a density of 0.3)).

<Practical Dmax> 1) Creation of manuscript Monochrome scanner SCA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and the special photosensitive material SP-100WP, a step wedge was prepared in which the screen percentage was changed stepwise. The exposure was performed at a screen ruling of 150 lines / inch. 2) Photographing and processing The original and the sample were set at predetermined positions on a plate making camera C-690 (Auto Companica) manufactured by Dainippon Screen Co., Ltd., and the reflective original was irradiated with light to photograph. At this time, 80% of the step wedge on the original is 2% on the sample.
Exposure was performed while adjusting to be 0%. Then, using the developing solution (A1) and the fixing solution (B), FG-4
The film was processed with a 60A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) for a developing time of 35 ° C. for 30 seconds, and the density of the blackened portion was set as the practical skill Dmax. Also, in addition to the developer (A1), the following fatigue developers (A2) and (A3) were prepared, exposed in the same manner, and the practical skill Dmax was evaluated. The above-mentioned developer (A1) was used to process 20 large-sized images of Fuji Photo Film Co., Ltd. with 80% blackening per day while replenishing 50 ml of the used solution per large-sized (50.8 cm × 61 cm). Was run six days a week for 15 consecutive weeks, whereby a small amount of film was processed to obtain a developer in which the concentration of sulfurous acid was reduced to one third. (Developer A2) (pH = 10.55) Further, using the above-mentioned developer (A1), a photographic film YS manufactured by Fuji Photo Film Co., Ltd., which is 80% blackened per day, is converted into a large total size (50.8 cm × 61 cm). Use liquid 50m per
By processing 200 sheets of large-to-all size with replenishment, and performing this process continuously for 4 days, a large number of films were processed to obtain a developer in which the pH dropped to 10.5 and the bromine ion concentration increased. . (Developer A3)

Table 36 shows the obtained results. Example 1
Samples (2 to 6) in which the relationship between the pH of the developing solution used in Example 1 and the pKa of the redox compound satisfies the following formula, have a wide halftone gradation and a high practical Dmax. In addition, fatigue developers A2, A3
Also has a high practical skill Dmax. In the sample 1, the pKa of the redox compound used was higher than (pH of the developing solution + 1), and therefore, the practical skill Dmax was low.

[0220]

[Table 36]

Example 2 An experiment similar to that of Example 1 was performed using the following solid developer (C) and solid fixing agent (D). Performance.

Formulation of solid developer (C) Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) Diethylenetriamine / pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 4- (N-carboxymethyl -N-methylamino) -2,6-dimercaptopyrimidine 0.2 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g sodium erythorbate 6.0 g potassium bromide 6.6 g Dissolve in water to make 1 liter. pH 10.65

Here, in the form of raw materials, raw powders were used as general industrial products, and beads of alkali metal salts were commercially available. When the raw material was in the form of a briquette, a plate-shaped material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For the minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, JP-A-9-80718 and JP-A-9-9-1
A dissolution replenisher with an automatic opening mechanism as disclosed in US Pat.

Formulation of solid fixing agent (D) Formulation A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw) Powder) 42.0 g Agent B (liquid) Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make up to 50 ml. . The fixing agent (D) was prepared by dissolving the agent A and the agent B in water and adjusting the solution to 1 liter. pH was 4.8.

The ammonium thiosulfate (compact) was obtained by compressing and compressing a flake product prepared by a spray-drying method with a roller compactor and crushing into an amorphous chip having a size of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. For dissolving and replenishing, a dissolving and replenishing apparatus having an automatic opening mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Example 3 In place of the developer (A) of Example 1, the following developer (E)
When the same experiment as in Example 1 was performed using, the photosensitive material having the constitution of the present invention showed good performance as in Example 1.

The composition of the developer (E) per liter of the concentrated solution is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.25 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0.3 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.45 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 Before use, dilute the concentrate at a ratio of 2 parts of water to 1 part of the concentrated liquid. PH of the working solution is 10.5

Example 4 Using the developing solution (A) of Example 1, a scanner film HL manufactured by Fuji Photo Film Co., Ltd., which was blackened by 20% per day, was used in a 50 m solution per large total size (50.8 cm × 61 cm).
By processing 20 sheets of large and full size while replenishing l, and running this for 6 consecutive days with 15 days of running, the concentration of sulfurous acid was reduced to 1/3 by processing a small amount of film. A developer was obtained. (PH = 1
0.55) Using the developer (A) of Example 1 and a scanner film HL (manufactured by Fuji Photo Film Co., Ltd.) with 80% blackening per day, using 50% of working solution per large total size (50.8 cm × 61 cm).
Process 200 pieces of the total size while replenishing the
By performing the process continuously for a day, a large amount of film was processed to obtain a developer in which the pH was lowered to 10.5 and the bromine ion concentration was increased. The same experiment as in Example 1 was performed using the above-mentioned fatigue developing solution or the developing solution in the middle of fatigue, and the photosensitive material having the constitution of the present invention showed good performance as in Example 1. .

Example 5 When the image quality of the light-sensitive material of the present invention of Example 1 was evaluated by the following method, good performance was obtained.

[0230] 1. Evaluation of the image quality of the eye-drawing (1) Manuscript creation Monochrome scanner SCA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special photosensitive material SF-100,
A stepped wedge was created in which the transmission image of a person consisting of halftone dots and the halftone percentage were changed gradually. At this time, the screen line frequency was set to 150 lines / inch. (2) Shooting Fine plate making camera Fine Zoom C manufactured by Dainippon Screen
The evaluation sample was exposed by irradiating with a Xe lamp after setting the original at -880 (processed with a camera-integrated automatic processing machine LD-281Q) so that the magnification was equal, and irradiating with an Xe lamp. At this time, the exposure was performed such that 90% of the step wedge of the original became 10%. (3) Evaluation Adjust the exposure amount as in (2) and adjust to the small dot side (highlight part)
The tone reproducibility of the shadow portion of the sample (halftone dot collapse resistance) was evaluated by visual observation.

[0231] 2. Evaluation of copy dots (1) Original creation Fuji Photo Film Co., Ltd. monochrome scanner SCA
Using NART30 and the special photosensitive material SP-100WP, a step wedge was prepared in which the screen percentage was changed stepwise. The exposure was performed at a screen ruling of 150 lines / inch. (2) Photographing The original and the sample were set at predetermined positions on a plate making camera C-690 (Auto Companica) manufactured by Dainippon Screen Co., Ltd., and the reflected original was irradiated with light to photograph. At this time, 80% of the step wedge on the original is 2% on the sample.
Exposure was performed while adjusting to be 0%. Then, using the developing solution (A) and the fixing solution (B) of Example 1, FG-
Processing was carried out using a 460A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with a developing time of 35 ° C. for 30 seconds. (3) Evaluation Adjust the exposure time as described in (2) to adjust the halftone dot percentage on the small dot side.
The tone reproducibility (the difficulty of crushing halftone dots) of the shadow portion of the sample combined with was visually evaluated.

[0232]

The silver halide photographic light-sensitive material of the present invention is super-hard and has good halftone dot quality, and has excellent original reproducibility (halftone reproducibility). Further, the practical skill Dmax is high, and the practical skill Dmax can be stabilized even when the replenishment amount of the developer is reduced. Therefore, according to the processing method of the present invention, an image forming system having excellent quality as described above is formed.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Mitsunori Hirano 210-Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H016 AE00 BD00 BD06 CA04 2H023 CD10 CD11 CD15

Claims (3)

[Claims] 1. A support having at least one silver halide emulsion layer on a support and releasing a development inhibitor by at least one kind of oxidation in at least one of said emulsion layer and other hydrophilic colloid layers. In a silver halide photographic light-sensitive material containing a redox compound, at least one hydrazine nucleating agent, and a nucleation accelerator, the pKa of the redox compound is changed by the pKa of a developing solution used for processing.
A silver halide photographic light-sensitive material having a relationship represented by the following formula: Redox compound pKa ≦ developing solution pH value + 1.0 2. The nucleation promoter according to the following general formula (a):
The silver halide photographic material according to claim 1, which is represented by (b), (c), (d), (e) or (f). Embedded image In the general formula (a), Q ₁ represents a nitrogen atom or a phosphorus atom, and R ₁₀₀ , R ₁₁₀ , and R ₁₂₀ each represent an aliphatic group, an aromatic group, or a heterocyclic group, which are bonded to each other to form a cyclic structure. It may be formed. M represents a m ₁₀ monovalent organic group bonding to Q ₁ ⁺ a carbon atom contained in M, here m ₁₀ represents an integer of 1 to 4. In the general formula (b), the general formula (c) or the general formula (d), A ₁ , A ₂ , A ₃ , A ₄ , A ₅
Each represents an organic residue for completing an unsaturated heterocyclic ring containing a quaternized nitrogen atom, L ₁₀ and L ₂₀
Represents a divalent linking group, and R ₁₁₁ , R ₂₂₂ and R ₃₃₃ represent a substituent. The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c) or the general formula (d) has a repeating unit of an ethyleneoxy group or a propyleneoxy group in a molecule of 20 units in total. Although it has more than one, it may be substituted over a plurality of places. Embedded image In the general formula (e), Q ₂ represents a nitrogen atom or a phosphorus atom. R ₂₀₀ , R ₂₁₀ and R ₂₂₀ are R ₁₀₀ , R in the general formula (a)
₁₁₀ represents R ₁₂₀ group having the same meaning as. In the general formula (f), A
₆ represents a group having the same meaning as A ₁ or A ₂ in the general formula (b). However, the nitrogen-containing unsaturated hetero ring formed by A ₆ may have a substituent, but does not have a primary hydroxyl group on the substituent. In general formulas (e) and (f), L
₃₀ represents an alkylene group, Y represents —C (= O) — or —SO ₂ —, and L ₄₀ represents a divalent linking group containing at least one hydrophilic group. In the general formulas (a) to (f), X
^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, there is another anion group in the molecule, and Q ₁ ⁺ , Q _1
When forming an inner salt with ²⁺ or N ⁺ , ^Xn- is not required. 3. The silver halide photographic light-sensitive material according to claim 1, after image exposure, is developed using a developing solution having a pH of 9.0 to 11.0. A method for processing a silver halide photographic light-sensitive material, wherein the amount is 250 ml or less.